CA2617591A1 - Methods and systems for controlling mold temperatures - Google Patents

Abstract

Disclosed is a preferred mold design for producing plastic, molded preforms, which may be blow-molded into a container of a final, desired shape. A
preferred mold includes a temperature control system for maintaining the preform mold at a desired temperature. The temperature control system can pass fluid through channels (302, 330, 403) within the preform mold to cool plastic that is injected into the preform mold. The mold comprises a neck finish mold (402) , the neck finish mold configured to transfer heat away from the molding surface toward a channel (403) conveying a working fluid. A heat transfer member (212) may be at least partially positioned within the channel to transfer heat to the working fluid. In some embodiments, the mold comprises a high heat transfer material .

Description

METHODS AND SYSTEMS FOR CONTROLLING MOLD TEMPERATURES
Related Applications [0001] This application claims the priority benefit under 35 U.S.C. 119(e) of U.S. Provisional Application No. 60/712,352, filed Augi.lst 30, 2005, which is hereby incorporated by reference in its entirety.
Background of the Inventions Field of the Inventions [0002] The inventions relate to molds for producing articles. More specifically, these inventions relate to methods and systems for controlling mold temperatures.
Description of the Related Art [0003] The use of plastic containers as a replaceinent for glass or metal containers in the paclcaging of beverages has become increasingly popular. The advantages of plastic packaging include lighter weight, decreased brealcage as compared to glass, and potentially lower costs. The most common plastic used in malcing beverage containers today is PET. Virgin PET has been approved by the FDA for use in contact with foodstuffs. Containers made of PET are transparent, thin-walled, lightweight, and have the ability to maintain their shape by withstanding the force exer-ted on the walls of the container by pressurized contents, such as carbonated beverages. PET
resins are also fairly inexpensive and easy to process.

[0004] Most PET bottles are made by a process that includes the blow-molding of plastic prefonns, which have been made by processes including injection and compression molding. For exa.mple, in order to increase the through-put of an injection molding machine, and thereby decrease the cost of each individual prefoim, it is desirable to reduce the cycle time for each inj ection and cooling cycle. However, the injected prefonn inust cool sufficiently to inaintain its molded dimensions before it is reinoved from the injection mold. Tlierefore, it would be desirable to utilize a cooling system that can rapidly cool the injected prefomz. Typically, the temperature of the mold is controlled by pumping cooled water through passages whi.ch are within the znold. The temperature of the mold is thus controlled by the teinperature of the water flowing through the water passages. The water typically flows continuously throughout the molding operation and may cause condensation to fonn on the mold. For example, when the mold is cooled by utilizing chilled water, the moisture in the air surrounding the inold can condense, thereby forming condensation on the nlolding surfaces. The condensation nZay interfere with the molding operation by reducing preforni production and decreasing prefoiin quality. As a result, the potential of znold cooling systems has izot been realized.
Suininary of the Inventions [0005] In some embodiments, a mold is configured to mold an ai-ticle. The mold cail have a mold cavity or mold space for receiving and znolding moldable material.
The mold can be configured to mold either a single article or a plurality of articles. The mold may coinprise a neck finish mold that conlprises a higli heat transfer material. The neck finish mold can be a thread split, split ring, etc.

[0006) In some einbodiments, if a high heat transfer material is used to form a thread split having a traditional configuration (e.g., thread splits with several intern.al cooling chamzels for carrying a chilled fluid), the full potential of the high heat transfer material may not be realized. That is, in coinparison to the heat transferred to a chilled worlcing fluid flowing through the traditional steel thread split, there may be a minimal increase of heat delivered tlirough a similarly configured tluead split coinprised of a high heat transfer material. To increase heat transfer tlirougll a thread split, the thread split can be exposed to a chilled fluid flowing at a relatively high vohunetric flow rate as compared to the voluinetric flow rate of a cooling fluid used in tradition internal chaiuiel arrangements.

[0007] The cooling of a molding maclline (e.g., an injection inoldiiig machine) can be regarded as a serial arrangeinent of therinal resistances. Heat given off by the cooling polyiner in the mold can pass consecutively tlirough these thermal resistances.
This serial arrangement can include a large heat resistance of the polymer itself, heat transfer from the polymer to the mold wall, heat resistance of the mold material, and heat traiisfer from the mold material to the coolant fluid. In suc11 a serial arrangement, the hi.gliest resistance can constitute a bottleneck (i.e., the limiting resistance) to the overall lleat flow. Although substitution of a steel thread-split by, e.g., a copper alloy tluead-split of the same design, which potentially increases heat trazisport through the mold, may result in an inadequate heat transfer rate from the mold material to the coolant. The heat transfer from the thread-split to the coolant becomes the bottleneck of the system, tllus resulting in only a small improvement of overall heat transport when utilizing a high heat transfer material.
[00081 Heat trazlsfer from the mold to the coolant depends on a nuinber of variables, predominantly the temperature and flow rate of the cooling medium, the coefficient of heat transfer, and surface which is used for heat transfer. The coefficient of heat transfer is a fiinction of the flow characteristics of the cooling medium and the surface quality of the cooling passage. A high heat transfer material can be used witli a tluead split having a different coiifiguration from a traditional steel thread split to account for these variables. For exatnple, a thread split coinprised of a high heat transfer inaterial can have a different size and position of cooling chamlels from a traditional steel thread split.
[0009] Mold parts, such as mold cores and tluead splits, made of a low heat conductivity material (e.g., steel) often have reduced wall tliickliesses.
These components often have an intenlal systein of one or more intenlal cooling channels. The intenial channels may result in a more coinplicated geometry which in most cases is difficult to machine. Tluead splits with asyinmetrical geometries may be especially difficult to machine. Due to the asymmetrical geonletry and the compact body shape of a thread split, the machiniulg of such channels is coinplicated and expensive.
Moreover, the stufaces for heat transfer of these chamlels result in inadequate heat transfer.
[0010] Aii aspect of at least one of the einbodiments disclosed herein includes the realization that the external surfaces of mold components (e.g., cores;
tluead splits, etc.), which are not in contact witli the polymer in the mold, are often larger than the surfaces which may be fonned by channels within these components, and it is desirable to use these external surfaces for heat transfer to a cooling fluid. In some embodiments, one or more components of a mold can be in extenlal contact with the worlcing fluid such that the worlcing fluid flows along the surface of the component. The worlcing fluid can sometimes flow through mold plates, or other portions of the mold suitable for transporting fluids at high flow rates. In some einbodiments, the mold plates can suppoi-t the mold component being cooled. Advantageously, the configuration and design of these mold components can be greatly simplified because of the extenlal contact between the working fluid and the part. For example, a mold component comprising a thread split can be effectively cooled by fluid flowing across at least a portion of the thread split. The threat split can have one or more heat transfer members, each adapted to be in fluidic contact witll the working fluid. The heat transfer meinbers can have a simpler design as compared to small internal cooling channels. Iii some einbodiinents, the heat transfer member is a protrusion that extends outwardly from the thread split.
[0011] Furthermore, the mold plates provide suitable space for having one or more relatively large cooling chaiuzels capable of delivering a sufficient amount of fluid to rapidly absorb and carry away heat. Also, the arrangenient of the cooling chaiuiels in the mold plates can also be tuicomplicated for convenient manufacttuing.
Otlier sufficiently large components of the mold can have relatively large chamiels as compared to traditional internal channels of a tluead split.
[0012] In some einbodiments, a mold comprises a mold cavity or mold space configured to receive inoldable nlaterial. A mold plate has a chamzel configured to pass therethrough. The mold also comprises a neck finish mold comprising a molding surface, a heat transfer meinber, and a neck finish mold body. The molding surface defines a portion of the mold cavity. The heat transfer member is disposed witliiii the chaiulel of the mold plate. The neck finish mold body extends between the molding stuface and the heat transfer element. At least a portion of the neck finish mold body comprises a higli heat transfer material. In some arrangements, the mold further comprises high wear materials (e.g., hardened materials) configured to reduce wear when the neck finish mold is moved between a first position to mold a portion of a prefonn and a second position to permit removal of the prefonn.
[0013] In some embodiments, a mold is movable between an open position and close position. The mold comprises a mold cavity or space, a mold plate, and a neck finish mold. The mold cavity is configured to receive moldable material when the mold is in a closed position. The mold plate has at least one channel configured to pass fluid therethrough. The neck finish mold colnprises a neck molding surface, a heat transfer ineinber, and a neck finish mold body. The neck molding surface defines at least a portion of the mold cavity. The heat transfer member is disposed within tlie channel of the mold plate. The neck finished mold body extends between the molding surface and the heat transfer member. In some embodiments, the mold coinprises a plurality of channels and a plurality of heat transfer members. Each heat transfer member can be in at least one of the channels.
[0014] In some einbodiments, a metliod is provided for cooling a neck finish mold. The method comprises passing working fluid through a channel and a mold plate.
The working fluid flows around a portion of the neck finish mold, wlierein the portion is positioned within the chasnZel. Heat is transferred from a molding surface of the neck finish mold to the portion of the neck finish mold positioned within the cllannel, such that the working fluid absorbs heat from the neck finish mold. Iii some embodiunents, the neck flnish mold coniprises a heat transfer meinber and a neck finish mold body. The neck finish mold body extends between the molding surface and the heat transfer member. hl some aiTangeinents, at least a portion of the neclc finish mold body comprises a high heat transfer material.
[0015] In some enibodiments, the heat transfer meinber comprises one or more heat transfer enhancers, such as for exainple, an elongated member. The heat transfer ei-Aiancers can comprise one or more of the following: fins, chaiulels, bores, slots, grooves, and combinations th.ereof.
[0016] In one einbodiment, an injection mold comprises a core section having a core surface and a cavity section having a cavity surface. The inj ection mold further coinprises a plurality of fluid charnlels proximate to the cavity surface and a valve proximate to the cavity surface. The valve is configured to allow fluid to flow into the fluid charuzels while causing a pressure drop of the fluid across the valve to cool the cavity surface as the fluid passes through the fluid chaiulels and cools the cavity surface.
[0017] In some einbodiments, a mold comprises a cavity section and a core section. The core section is configured to mate witll the cavity section to fonn a mold cavity and comprises a core that defines an intei7ial surface of the mold cavity. The core is configured to receive refrigerant to control the ten7perature of the core.
In some embodiments, at least a portion of the refiigerant is vaporized within the core. In some einbodiments, at least a portion of the refrigerant is vaporized within the core by passing througll one or more pressure reducing elements positioned within the core.
[0018] In some embodiments, a mold temperature control asseinbly comprises a cavity section and a core section. The core section is coilfigured to mate with the cavity section to fonn a mold cavity or mold cavity and coinprises a core that defines an intei71a1 surface of the mold cavity. A tube within the core extends from the proxiinal end of the core to an expansion valve at the distal end of the core. The expansion valve is configured to receive fluid that comprises substantially liquid from the tube and is configured to deliver fluid comprising substantially gas to a chaiulel within the core. In some embodiments, gas is at a temperature less than temperature of the internal surface of the mold cavity.
[0019] In another embodiment, a mold teinperature control asseinbly comprises a cavity section, a plurality of fluid chamiels, and a valve system.
The cavity section defines a cavity surface. The plurality of fluid channels sulTotulds a portion of the cavity surface, and a portion of the fluid chaslnels is within the cavity section. The valve system is located upstream of the fluid chaiulels and is configured to receive fluid at a first teinperature and deliver the fluid at a second temperature, which is less than the first temperature, to the fluid chaiu-iels to cool the cavity surface. In some embodiments, the valve system coinprises a single pressure reducing elenient. In some embodiments, the valve system comprises a plurality of pressure reducing elements.
[0020] In one einbodinzent, a method of controlling the tenlperature of a mold comprises providing a core section having a core mold surface and a cavity section having a cavity mold surface and chaiuiels. Fluid is delivered at a first temperature to a valve systein within the cavity section, the valve system otitputs the fluid at a second temperature, which is less than the first temperature and the teniperature of tlie cavity mold surface, to the channels to cool the cavity mold surface. In soine embodiments, the valve system conlprises one or more pressure reducing elements.
[0021] hi some embodiments, a mold is configured to mold an article. In some embodiments, the mold is coarlfigtired to produce prefonns, containers, trays, closures, and the like. h1 some embodiments, the mold comprises a temperature control eleinent configured to affect the temperature of the mold. The tenzperature control element can comprise one or more of the following: fluid passageways, channels, teinperature control rod (e.g., heating/cooling rods), and heater (e.g., resistance heater).
The mold caii be an intrusion mold, compression mold, blow mold, injection mold, or other type of molding system for forming articles. h1 some einbodiments, the blow mold can be a stretch blow mold for stretch blow molding a prefonn. hi sonle embodiments, the blow mold can be an extrusion blow mold.
[0022] In some embodiinents, a mold comprises a core section that has a core surface. A cavity section has a cavity surface. A mold cavity or mold space is defined by the core section and the cavity section when the mold is in a closed position.
In some einbodiments, a temperature control element, such as a fluid clzaimel, is disposed within one of the core section and the cavity section. A pressure reducing device is configured to receive and vaporize at least a portion of a refrigerant. In some embodiments, the pressure reducing device is in fluid commLuiication with the fluid channel.
The one of the core section and the cavity section comprises high heat transfer material. The high heat transfer material is positioned between the fluid channel and the mold cavity.
In some embodiments, the mold does not comprise high heat transfer material.
[0023] In some embodimeiits, a molding system coinprises a first mold section and a second mold section movable between an open position and a closed position. A mold cavity or mold space is defined between the first mold section and the second mold section wlien the first mold section and the second mold section occupy the closed position. At least one of the first mold section and the second mold section coniprises higli heat transfer material and at least one fluid chaiulel. A
fluid source is in fluid conimunication with the at least one fluid channel. The fluid source contains a worlcing fluid (e.g., a refrigerant). A pressure reducing eleinent is in fluid communication wit11 the at least one fluid channel and the fluid source. The presstue reducing element is configured to reduce a pressure of the refrigerant fiom the fluid source to a second pressl.tre equal to or less than a vaporization pressure of the refrigerant.
In some embodiments, the molding systein comprises a plurality of pressure reducing eleinents.
[0024] In some embodiments, one or more temperature sensors are inteiposed between a molding surface of a mold and at least teniperature control element of the mold. In some einbodinients, one or more teinperature sensors are positioned somewhat proximate to the mold surface. The temperature sensors can aecurately meastue the temperature of the mold. Iii some embodiments, a controller is in communication witli the temperature sensor. The controller can be configLUed to selectively control the operation of a valve (e.g., a pressure reducing elenzent) in response to a signal from the temperature sensor. In some embodiments, a mold has a plurality of temperature sensors.
The sensors can be positioned at various locations within the material forining the mold.
[0025] In some embodiments, a mold for molding an article coinprises a cavity section and a core section. The core section is configured to mate with the cavity section to fonn a mold cavity. The core section coinprises a core that defines an intenlal surface of the mold cavity. A tube is disposed within the core. The tube extends fiom a proximal end of the core to a pressure reducing valve at a distal end of the core. The pressure reducing valve is configured to receive fluid from the tube and to deliver at least partially vaporized fluid to a chai.nel within the core. The partially vaporized fluid in the core is at a temperature less than a temperature of the internal surface of the mold cavity when melt fills the mold cavity.
[0026] In some embodiments, a mold asseinbly comprises a core section and a cavity section. The cavity section defines a cavity surface that is configured to mold at least a portion of an article. The cavity section cooperates with the core section to form a space. A plurality of fluid chaiulels surrounds a portion of the cavity surface. The plurality of fluid channels is positioned within a portion of the cavity section and has a high thennal conductivity. A valve system is located upstream of the fluid chamiels. The valve system receives fluid at a first teinperature a1d delivers the fluid at a second temperatLire, which is less than the first temperature, to the plurality of fluid cha.miels. In some einbodiments, the fluud is a cryogenic fluid. In some embodiinents, the cryogenic refrigerant is a higlz teinperature range cryogenic fluid. Ii1 some embodinlents, the cryogenic refrigerant is a mid teinperature range cryogenic. In soine embodiinents, the cryogenic refrigerant is a low temperature range cryogenic fluid.
[0027] hl some embodiments, a mold is configured to utilize a worlcing fluid.
In some ernbodiments, the working fluid is a refiigerant. In some enlbodiments, the working fluid is a cryogenic fluid. In some embodiments, the fluid is a cryogenic fluid.
In some embodiments, the cryogenic refrigerant is a hig11 temperature range cryogenic fluid. hi some einbodiments, the cryogenic refrigerant is a niid temperature range cryogenic. Iti some embodiments, the cryogenic refrigerant is a low temperature range cryogenic fluid.
[0028] Ii1 some embodiments, a method of controlling the teniperature of a mold for molding a preform comprises providing a core section having a core mold surface. A cavity section having a cavity mold surface and fluid chaiuzels is provided. A
refrigerant is delivered at a first teinperattire to a valve systein. The valve system outputs the refrigerant at a second teinperature, which is less than the first temperature and a temperature of the cavity mold surface. The refrigerant is passed from the valve system through at least one of the cavity section and the core section to reduce the teinperature of polyzner material disposed between the core mold surface and the cavity mold surface. In some embodiments, the polymer material is in the shape of a prefortn or closure.
[0029] In some embodiments, a molding system 'coinprises a first mold section and a second mold section movable between an open position and a closed position. A mold cavity or space is defined between the first mold section and the secarld mold section when the first mold section and the second mold section occupy the closed position. The mold cavity has a shape of a prefonn. A neclc finish mold is interposed between the first mold section and the second mold section. The neck finish mold has a neck molding surface configured to mold a portion of melt disposed in the mold cavity.
The neck finish mold comprises higli heat transfer material and a teinperattire control element configured to selectively control the teinperature of the neck molding surface. In some embodiments, the high heat transfer material is positioned between the neck molding surface and the temperature control element. At least a portion of the temperature control element may or may not be embedded in the hig11 heat transfer material.

[0030] In some einbodinients, a neck finlsh mold is configured to mold at least a potion of aii article. In some einbodiments, the neck finish mold coinprises a higli heat transfer material. The high heat transfer material may or may not form a niolding surface that can engage melt injected into a cavity of a mold. In some embodiments, the necle finish mold is a split ring inovable between two or more positions. Tii some embodinients, the neclt finish mold coinprises a temperatlire control element, such as one or more fluid passageways, heat/cooling rods.
[0031] hi some embodiments, a mold teinperature control system coarnprises a first mold section and a second mold section movable between an open position and a closed position. A lnold cavity is defined between the first mold section and the second mold section when the first mold section and the second mold section occupy the closed position. A means for passing a refrigerant through at least one of the first mold section and the second mold section for controlling the temperature of moldable material is positioned within the mold cavity. A means for vaporizing at least a portion of the refrigerant that subsequently passes through the means for passing the refrigerant is provided. A means for delivering the refrigerant to the means for vaporizing at least the portion of the refrigerant is provided.
[0032] In some einbodiments, a inethod for making a preform comprises providing a cavity mold half and a core mold half. The cavity mold half and the core mold half define a space in the shape of a preform. A first material is deposited into the space. A sufficient amount of refrigerant to reduce the temperature of the refrigerant is vaporized. The refrigerant is circulated within one of the cavity mold half and the core mold half to cool the first material to form a preform. In some embodiments, the method fiu-ther coinprises removing the preform from the cavity mold half. The prefonn is placed into a second cavity mold half. A second material is injected tl-uough a gate of the second cavity mold half into a second space defined by the second cavity mold half and the preform to form a multilayer preform. A second fluid is circulated through at least one of the second cavity mold half and the core mold half to cool a multilayer preforin.
[0033] In some embodiments, a prefoi7n conlprises a body coinprising a wall and an end cap portion. The wall has a dimensionally stable outer layer suitable for demoldiilg the preform and an interior portion adjacent the outer layer that comprises soft warm polyiner material. A neck portion is cozmected to the body. hi some embodiinents, the interior portion is positioned between the dimensionally stable outer layer and a second dimensionally stable outer layer. The outer layers forin an exterior surface and an interior surface of the preforin. In some embodinients, the heat from the prefonn is transferred through high heat transfer material and to a refrigerant. The refrigerant can coniprise cryogenic fluid. til some embodiments, the prefoim has an eggshell finish.
[0034] In some einbodiments, a mold apparatLis coinprises high heat transfer material. In some embodiments, the high heat transfer material has a thennal conductivity greater than the therinal conductivity of iron. h1 some embodiments, the high heat transfer material has a thennal conductivity selected from one of a thennal conductivity greater than the therinal conductivity of iron, a then.nal conductivity at least two times greater than the thernzal conductivity of iron, a thermal conductivity at least three times greater tllan the thennal conductivity of iron, and a tllermal conductivity at least four times greater than the tllermal conductivity of iron. In some embodiments, the higli heat transfer material has a thermal conductivity selected from one of a thennal conductivity greater tlian the thermal conductivity of iron and less than two times the thennal conductivity of iron, a thennal conductivity at least two times greater than the thennal conductivity of iron and less than tluee times the tllermal conductivity of iron, a tllennal conductivity at least tluee tiines greater than the thennal conductivity of iron and less than four times the tllermal conductivity of iron, and a tllennal conductivity at least four times greater than the thennal conductivity of iron. Tii some embodiments, the high heat transfer material comprises hardened copper alloy.
[0035] In some einbodiments, molding systems can utilize highly conductive alloys and refrigerants. The coinbination of hig11 heat transfer materials and refrigerants can provide efficient cooling, or heating, and can minimize cycle time. The high heat transfer materials and refrigerants can be used to cool rapidly molded articles in the mold.
The combination of high heat transfer materials and refrigerants can provide efficient and rapid heating of the mold, especially when the mold surfaces are at a low temperature.
For example, the mold surfaces can be at a low temperature at the end of a cooling cycle.
In some embodiments, the mold surfaces can be warmed so that melt can spread easily tluougli a lnold cavity of the mold.
[0036] In some embodiments, a mold is configured to mold an article. At least a portion of the article can have a hardened outer surface. The outer surface can be in the form of a somewliat eggshell lilce layer. In some embodiinents, substantially the entire exterior surface and/or interior surface of an article comprise a hardened outer surface. The interior portions of the articles can be warm and soft when the preform is deinolded.

[0037] Iii some embodiments, a mold can have one or more mold cavities configured to receive moldable material. The mold can have one or more of the following: a core, a cavity section, a gate msert, and a neck finish mold.
These coinponents can be heated or cooled by employing a worlcing fluid. The worlcing fluid can be a refrigerant. The worlcing fluid can be used to cool a moldable material positioned within the mold. When the molded article is removed, the worlcing fluid can preheat the mold surfaces so that moldable material, such as a molten polymer, can spread easily through the mold cavity or space.
[0038] In one embodiment, a mold which defines a mold space for receiving a moldable material comprises a first mold por-tion having one or more channels configured to convey a fluid and a second mold portion. Iii some einbodiments, the second mold portion comprises a molding surface that at least partially defines the mold space, a heat transfer nleinber and a mold body extending between the molding stu=face and the heat transfer meniber. In some embodiments, the heat transfer znember at least partially extends into the channel of the first portion. In yet other einbodiments, the heat transfer member is configured to transfer heat between the molding surface and a fluid being conveyed witliin the channel.
[0039] In another einbodiment, at least a portion of the secorid tnold poi-tion comprises a high heat transfer material. h-i one einbodiment, at least a portion of the heat transfer ineinber comprises a high heat transfer material. h-i other einbodiments, a substantial portion of the mold body of the second mold portion and the heat transfer member coinprise a high heat transfer material. In yet anotller embodiment, at least 50%
of the mold body is a high heat transfer material. In some embodiments, the second mold portion can comprise more thail abotit 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99%, or ranges encompassing such percentages of high heat transfer material by weight and/or volume. Iii other embodiments, the second mold portion may coinprise less than about 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2%, 1%, or ranges encompassing such percentages. h-i yet other arrangements, the neck finish mold 2002 may not comprise any hig11 heat transfer materials by weight and/or volume.
[0040] In one einbodiment, the second mold portion ftirther coinprises at least on.e hardened material configured to reduce wear when the second mold portion is inoved relative to an adjacent surface. h-i still another embodinlent, the second mold portion fui-tller comprises a thermal insulating material configured to fonn a thennal barrier. In yet other embodiments, the second mold portion is part of a mold cavity section. In one embodiment, the second mold portion is part of a neck finish mold. Iii another embodiment, the neck finish mold includes a tluead split movable between a closed position and an open position. In other embodiments, the first mold portion forins pai-t of a mold plate which is configured to receive a section of the neck finish mold.
In one embodunent, the second mold portion fornis an area of a mold core section.
[0041] Iii one einbodiment, the heat transfer nieniber coinprises an elongated nienlber that extends at least partially into the channel. In another embodiment, the heat transfer meinber comprises at least one heat transfer enhancer, said enhancer configured to increase the ratio of surface area to volume of the heat transfer member.
In other embodiments, the heat transfer eilllancer includes one or more of the following: a fin, protn.ision, slit, bore, chaiuiel, groove, opening, recess, indentation, mesh structure and combinations tllereof. Iii still another einbodinlent, the first mold portion and the second mold portion are part of single unitary stiltcture.
[0042] In one embodiment, a mold which defines a mold space configi.ired to receive a moldable material coinprises a mold plate having a channel configured to convey a fluid and a neck finish mold. In some embodiments, the neck finish mold comprises a mold body that includes a molding surface, which at least partially defines the mold space, and a heat transfer member at least partially disposed witllin the chaiuiel.
In other embodiments, a portion of the heat transfer n7ember is in thermal communication with a fluid w11en a fluid is being conveyed within the chamlel. Iii yet other embodiinents, at least a portion of the neck finish mold comprises a high heat transfer material. In still another embodiment, at least a portion of the heat transfer member comprises a high heat transfer material. In some einbodiments, a substantial portion of the neck finish mold comprises a high heat transfer material.
[0043] In some embodiments, the neck finish mold fi,trther comprises at least one hardened material configured to reduce wear when the neck finish mold is moved relative to an adjacent surface. In other enibodiments, the neclc finish mold additionally coinprises a tllennal insulating material configured to fonn a thennal baiTier. In one einbodiinent, the neck fmish mold comprises a thread split movable between a closed position and an open position. In another embodiment, the heat transfer member coinprises one or more heat transfer enhancers configured to increase the ratio of surface area to volume of the heat transfer meinber.
[0044] In some embodiments, a mold that is moveable between an open position and a closed position comprises a mold space configured to receive moldable nlaterial when the mold is in a closed position, a mold plate having at least one channel configured to convey a worlcing fluid theretllrough and a cavity mold section.
Iii one embodiment, the cavity mold section includes a molding surface that defines a portion of the mold space, a heat transfer inember and a body positioned, at least in part, between the molding surface and the heat transfer meinber. Iii another einbodinient, the heat transfer member at least partially extends within the chaiulel of the mold plate. In yet otlzer einbodiments, at least a portion of the cavity mold section comprises a high heat transfer material.
[0045] In one embodiment, the cavity mold section additionally includes a hardened material configured to reduce wear when the cavity mold section is moved between a first position and a second position. In anotlier einbodiment, the heat transfer nzember comprises an elongated member that extends at least partially into the channel, such that a working fluid conveyed within chamiel contacts a surface of the heat transfer member to transfer heat between the elongated member and a working fluid.
[0046] In one einbodiment, the heat transfer member comprises one or more heat transfer eifliancers that are configured to increase the ratio of surface area to voh.une of the heat transfer meinber. In anotller embodiment, the heat transfer eiAlancer coinprises one or more of the following: a fin, protrusion, slit, bore, chaiuiel, groove, opening, recess, indentation, mesh structure and combinations thereof.
[0047] hi some einbodiinents, a method of cooling a mold section includes placing a portion of the mold section in thennal coinmiulication vvith a channel configured to convey a fluid, delivering a fluid through the channel and transferrin.g heat between a molding surface of the mold section and the fluid. Iii other embodiments, placing a portion of the mold section in thermal coinrnunication with a chaiuiel includes positioning a heat transfer menzber of the mold section at least partially within the charuiel. In yet another einbodiment, transferring heat between the molding stuface and the fluid coinprises transferring heat through a high heat transfer material, said high heat transfer material forming at least a portion of the mold section. In other einbodiments, delivering a fluid through the chaiulel comprises. the use of pulse cooling tecluzology.

Brief Desc]jption of the Drawings [0048] FIGURE 1 is a prefonn as is used as a starting material for making a molded container;
[0049] FIGURE 2 is a cross-section of the monolayer prefonn of FIGURE 1;

[0050] FIGURE 3 is a cross-section of a multilayer preform;
[0051] FIGURE 4 is a cross-section of allother einbodiment of a inultilayer preforin;
[0052] FIGURE 5 is a three-layer einbodiment of a prefornl;
[0053] FIGURE 6 is a cross-section of a preforin in the cavity of a blow-molding apparatus of a type that may be used to make a container;
[0054] FIGURE 6A is a cross-section of another embodiment of a blow-molding apparatus;
[0055] FIGURE 7 is a side view of one embodiment of a container;
[0056] FIGURE 8 is a schematic illustration of a teinperattue control system;
[0057] FIGURES 9A-9L are schematic illustrations of temperatttre control systems;
[0058] FIGURE 10 is a cross-section of an injection mold of a type that may be used to malce a preferred multilayer preforin;
[0059] FIGURE 11 is a cross-section of the mold of FIGURE 10 talcen along lines 11-11;
[0060] FIGURE 12 is another embodiment of an injection mold of a type that may be used to make a multilayer preform;
[0061] FIGURE 13 is a cross-section of an injection mold of a type that may be used to make a monolayer preform;
[0062] FIGURES 13A-13F are side views of portions of neck finish molds;
[0063] FIGURE 14 is a cross-section of the inold of FIGUE 1.3 taken along lines 14-14;
[0064] FIGURE 15 is a cutaway close up view of the area of FIGURE 13 defined by line 15;
[0065] FIGURE 16 is a cross-section of an injection mold core having a double wall neclc finish portion;
[0066] FIGURE 17 is a cross-section of an enlianced injection mold core having a higll heat transfer base end portion;
[0067] FIGURE 18 is a cross-section of an injection mold utilizing a combination of hardened material components and high heat transfer material coinponents and fluid chamiels;
[0068] FIGURE 18A is a cross-section of another injection mold utilizing high heat transfer material;

[0069] FIGURES 19 and 20 are two halves of a molding inachine to make multilayer preforins;

[0070] FIGURES 21 and 22 are two halves of a nlolding nlachine to make forty-eight two layer prefonns;
[0071] FIGURE 23 is a perspective view of a scheniatic of a mold with cores partially located within the molding cavities;
[0072] FIGURE 24 is a perspective view of a mold wit11 cores fiilly withdrawn from the inolding cavities, prior to rotation;
[0073] FIGURE 25 is a top plan view of a compression molding systein for producing preforms;

[00741 FIGURE 25A is a top plan view of a compression molding system for producing multilayer prefonns;
[0075] FIGURE 26 is a cross-sectional view of the colnpression molding systein taken along lines 26-26 of FIGURE 25;
[0076] FIGLTRE 27 is a cross-section of a cavity section of FIGURE 26 containing a plug of material;

[0077] FIGURE 28 is a cross-sectional view of a core section and a cavity section in an open position;

[0078] FIGURE 29 is a cross-sectional view of the core section and the cavity section in a closed position;

[0079] FIGURE 29A is a cross-sectional view the core section and the cavity section of FIGURE 29 in a closed position, moldable material is disposed within a cavity defined by the core section and the cavity section;
[0080] FIGURE 30 is a cross-sectional view of a core section and a cavity section in a partially open position in accordance witli another einbodiment;
[0081] FIGURE 31 is a cross-sectional view of a core section and a cavity section in a closed position in accordance with another einbodiment;
[0082] FIGURE 32 is a top plan view of a coinpression molding system for producing preforms in accordance with another embodiment;
[0083] FIGURE 33 is a cross-sectional view of a core section and a cavity section of the system of FIGURE 32 in a closed position, the core section and the cavity section define a cavity for forming an outer layer of a prefoim;

[0084] FIGURE 34 is a cross-sectional view of another core section and the cavity section of the system of FIGURE 32 in a closed position, the core section and the cavity section define a space for forming an imler layer of a preforin;
[0085] FIGURE 35 is a cross-sectional view of a compression molding systein configured to make a closure;
[0086] FIGURE 36 is a sectional view of another cavity section and the core section of FIGURE 35, the core section and the cavity section define a space for forming an outer layer of a closure;
[0087] FIGURE 37 is a cross-sectional view of a portion of a mold for molding articles;
[0088] FIGU.RE 38 is a cross-sectional view of a heat transfer member of the mold of FIGURE 37 taken along a line 38-38;
[0089] FIGU.RE 39 is a cross-sectional view of a heat transfer meniber in accordance with another embodiment;
[0090] FIGURE 40 is a cross-sectional view of a heat transfer member in accordance witlz another embodiment;
[0091] FIGURE 41 is a side view of heat transfer member of FIGURE 40;
[0092] FIGURE 42 is a cross-sectional view of a portion of a mold for molding articles, wherein the mold has high wear material;
[0093] FIGURE 43 is a cross-sectional view of a portion of a mold for molding articles, the mold has a heat transfer member of a inulti-piece constn.iction;
[0094] FIGURE 44 is a cross-sectional view of the mold talcen along line 44-44 of Figure 43;
[0095] FIGURE 45 is a cross-sectional view of the mold taken along line 44-44 of Figure 43;
[0096] FIGURE 46 is a cross-sectional view of a portion of a mold for molding a prefoiln;
[0097] FIGURE 47 is a cross-sectional view of a portion of a mold for molding a preform in accordance wit11 another embodiment; and [0098] FIGURE 48 is a cross-sectional view of a portion of a mold for molding a preform in accordance with another einbodiment.
Detailed Description of the Preferred Embodiment [0099] All patents and publications mentioned herein are hereby incorporated by reference in their entireties. Except as further described herein, certain embodiments, features, systems, devices, materials, nlethods and teclmiques described herein may, in some embodiments, be similar to any one or more of the embodiinents, features, systems, devices, materials, inetllods and techniques described in U.S. Patents Nos.
6,109,006;
6,808,820; 6,528,546; 6,312,641; 6,391,408; 6,352,426; 6,676,883; 6,939,591;
U.S.
Patent Application Nos. 09/745,013 (Publication No. 2002-0100566); 10/168,496 (Publication No. 2003-0220036); 09/844,820 (2003-0031814); 10/395,899 (Publication No. 2004-0013833); 10/614,731 (Publication No. 2004-0071885), provisional application 60/563,02 1, filed April 16, 2004, provisional application 60/575,23 1, filed May 28, 2004, provisional application 60/586,399, filed July 7, 2004, provisional application 60/620,160, filed October 18, 2004, provisional application 60/621,511, filed October 22, 2004, and provisional application 60/643,008, filed January 11, 2005, U.S.
Patent Application Serial No. 11/108,342 en.titled MONO AND MULTI-LAYER ARTICLES
AND COMPRESSION METHODS OF MAKING THE SAME, filed on April 18, 2005 and published as Publication No. 2006-0065992, U.S. Patent Application Serial No.
11/108,345 entitled MONO AND MULTI-LAYER ARTICLES AND INJECTION
METHODS OF MAKING THE SAME, filed on April 18, 2005 and published as Publication No. 2006-0073294, U.S. Patent Application Serial No. 11/108,607 entitled MONO AND MULTI-LAYER ARTICLES AND EXTRUSION METHODS OF
MAICING THE SAME, filed on April 18, 2005 and published as Publication No.

0073298, which are hereby incorporated by reference in their entireties. In addition, the einbodiments, features, systems, devices, materials, methods and tecluliques described herein may, in certain embodiments, be applied to or used in connection with any one or more of the einbodiinents, features, systems, devices, materials, methods and tecluziques disclosed in the above-mentioned patents and applications.
A. Detailed Description of Some Preferred Materials 1. General Description of Preferred Materials [0100] The articles described herein may be described specifically in relation to a particular material, such as polyetliylene terephtllalate (PET) or polypropylene (PP), but prefeiTed methods are applicable to many other therinoplastics, including those of the of the polyester and polyolefin types. Otlier suitable inaterials include, but are not limited to, foain materials, various polymers and therinosets, tllennoplastic materials such as polyesters, polyolefins, including polypropylene and polyethylene, polycarbonate, polyamides, including nylons (e.g. Nylon 6, Nylon 66, MXD6), polystyrenes, epoxies, acrylics, copolyiners, blends, grafted polyiners, and/or modified polymers (nionomers or portion thereof having another group as a side group, e.g. olefin-modified polyesters).
These materials may be used alone or in conjunction witli each other. More specific material exaniples include, but are not limited to, ethylene vinyl alcohol copolymer ("EVOH"), etllylene vinyl acetate ("EVA"), etlzylene acrylic acid ("EAA"), linear low density polyetllylene ("LLDPE"), polyetliylene 2,6- and 1,5-naphthalate (PEN), polyethylene terephtlialate glycol (PETG), poly(cyclohexylenedimethylene terephthalate), polystryrene, cycloolefin, copolymer, poly-4-methylpentene-1, poly(inethyl methacrylate), acrylonitrile, polyvinyl chloride, polyvinylidine chloride, styrene acrylonitrile, acrylonitrile-butadiene-styrene, polyacetal, polybutylene terephthalate, ionomer, polysulfone, polytetra-fluoroetllylene, polytetrainethylene 1,2-dioxybenzoate and copolyiners of ethylene terephtlialate and etliylene isophthalate.
[0101] As used herein, the term "polyethylene tereplithalate glycol" (PETG) refers to a copolyiner of PET wherein an additional com.onomer, cyclohexane di-methanol (CHDM), is added in significant alnounts (e.g. approxiunately 40% or more by weigllt) to the PET mixture. In one einbodinlent, preferred PETG material is essentially ainorphous. Suitable PETG materials may be purchased from various sources. One suitable source is Voridian, a division of Eastman Chemical Coinpany. Other PET
copolyiners include CHDM at lower levels such that the resulting material remains crystallizable or semi-crystalliule. One example of PET copolyiner contaiuiing low levels of CHDM is Voridian 9921 resin.
[0102] In some embodiments polymers that have been grafted or modified inay be used. In one einbodiinent polypropylene or other polyiners may be grafted or modified witli polar groups including, but not limited to, inaleic aiAlydride, glycidyl metllacrylate, acryl methacrylate and/or similar compounds to iinprove adhesion. hi other einbodiments polypropylene also refers to clarified polypropylene. As used herein, the tenn "clarified polypropylene" is a broad tenn and is used in accordance with its ordinary meaning and may include, without limitation, a polypropylene that includes nucleation iiillibitors and/or clarifying additives. Clarified polypropylene is a generally transparent material as compared to the homopolyiner or block copolymer of polypropylene.
The inclusion of nucleation inhibitors helps prevent and/or reduce crystallinity, which contributes to the haziness of polypropylene, witlun the polypropylene.
Clarified polypropylene may be purchased from various sources such as Dow Chemical Co.
Alternatively, nucleation iiiliibitors may be added to polypropylene. One suitable source of nucleation inliibitor additives is Schuhnan.

[0103] Optionally, the inaterials may comprise microstiltctures such as microlayers, microspheres, and combinations thereof h1 certain embodiments preferred materials m.ay be virgin, pre-consunler, post-consuiner, regrind, recycled, and/or combinations thereof.
[0104] As used herein, "PET" includes, but is not liinited to, modified PET as well as PET bl.ended witli other inaterials. One example of a inodified PET is "high IPA
PET" or IPA-modified PET, which refer to PET in which the IPA content is preferably more than about 2% by weight, including about 2-10% IPA by weight, also including about 5-10% IPA by weiglit. PET can be virgin, pre or post-consumer, recycled, or regrind PET, PET copolyiners and combinations thereof.
[0105] In embodiments of preferred methods and processes one or more layers nlay comprise barrier layers, UV protection layers, oxygen scavenging layers, oxygen barrier layers, carbon dioxide scavenging layers, carbon dioxide bai7ier layers, and otller layers as needed for the particular application. As used hereiul, the ternzs "barrier material," "barrier resin," and the like are broad tenns and are used in their ordinary sense and refer, without linlitation, to materials which, when used in preferred inethods and processes, have a lower penneability to oxygen and carbon dioxide thari the one or more of the layers. As used herein, the tenns "UV protection" and the like are broad terms and are used in their ordinary sense and refer, without limitation, to materials which have a higher UV absorption rate than one or more layers of the article. As used herein, the teinzs "oxygen scavenging" and the like are. broad terms and are used in their ordinary sense and refer, without limitation, to materials which have a higher oxygen absorption rate than one or more layers of the article. As used herein, the tenns "oxygen ba.rrier" and the like are broad terms and are used in their ordinary sense and refer, without limitation, to materials which are passive or active in nature and slow the transmission of oxygen iulto and/or out of an article. As used herein, the terins "carbon dioxide scavengv.lg" and the like are broad tenns and are used in their ordinary sense and refer, without liinitation, to materials which have a higher carbon dioxide absorption rate than one or more layers of the article. As used herein, the terms "carbon dioxide barrier" and the like are broad tenns and are used in their ordinary sense and refer, without limitation, to materials which are passive or active in nature and slow the transmission of carbon dioxide into and/or out of an article. Without wishing to be bound to any theory, applicants believe that in applications wherein a carbonated product, e.g. a soft-drii-Ac beverage, contained in an article is over-carbonated, the inclusion of a carbon dioxide scavenger in one or more layers of the article allows the excess carbonation to saturate the layer which contains the carbon dioxide scavenger. Therefore, as carbon dioxide escapes to the atmosphere from the article it first leaves the article layer ratller than the product contained therein. As used herein, the ternis "crosslinlc," "crosslhiked," and the like are broad terms and are used in their ordinary sense and refer, witllout limitation, to materials and coatings wluch vary in degree from a very small degree of crosslinking up to and including fitlly cross linked materials such as a therinoset epoxy. The degree of crossliiilcing can be adjusted to provide the appropriate degree of chemical or mechaiucal abuse resistance for the particular circumstances. As used herein, the ternl "tie material" is a broad terin and is used in its ordinary sense and refers, without limitation, to a gas, liquid, or suspension coinprising a material that aids in binding two materials together physically and/or chemically, i,ncluding but not limited to adhesives, surface modification agents, reactive materials, and the like.
2. Preferred Materials [0106] In a preferred embodiment, materials coinprise thennoplastic materials. A furtller preferred enibodiment includes "Phenoxy-Type Thermoplastics."
Phenoxy-Type Thermoplastics, as that teiln is used herein, include a wide variety of materials including those discussed in WO 99/20462. In one embodiment, materials comprise thennoplastic epoxy resins (TPEs), a subset of Phenoxy-Type Thennoplastics.
A further subset of Phenoxy-Type Thennoplastics, and thermoplastic materials, are preferred hydroxy-phenoxyether polymers, of wliich polyhydroxyaminoether copolymers (PHAE) is a fiirther preferred material. See for exainple, U.S. Pat. Nos.
6,455,116;
6,180,715; 6,011,111; 5,834,078; 5,814,373; 5,464,924; and 5,275,853; see also PCT
Application Nos. WO 99/48962; WO 99/12995; WO 98/29491; and WO 98/14498. In some einbodiinents, PHAEs are TPEs.
[0107] Preferably, the Phenoxy-Type Thermoplastics used in preferred embodiments comprise one of the following types:
(1) hydroxy-fiinctional poly(amide ethers) having repeating units represented by any one of the Forinulae Ia, Ib or Ic:

4 OH II ~ II IH z Ia OCH2CCH2OAr-NHC-R -CNHAr-OCH2CCH2OAr I I tt O
~ lb 4 OCH I CH OAr-II -~_ II _ I OH
2 I 2NH R NHAr OCHz i CHZOAr R n or IH H
o ICH2C HzOArOCH2C CHzOAr' Ic R R

(2) poly(liydroxy ainide ethers) having repeating units represented independently by any one of the Foimulae IIa, Ilb or IIc:

OCH2ICCH2OAr-NHII-R1-IINHAr IIa R n OH
I Il ,-I1 IIv OCHzCI CH2OAr-CNH-R NHCAr R

or 4 1 OCH2CCH2OArIINHAr IIc I n R

(3) anlide- and hydroxyinetllyl-fiulctionalized polyethers having repeating i.uiits represented by Formula III:

H OH
(OCHIH2OAr1 OCHzCCH2OAr2 III
R X R -x (4) hydroxy-functional polyethers having repeating i.uiits represented by Formula IV:

I IV
OCHz i CHZOAr R

(5) hydroxy-functional poly(ether sulfonanlides) having repeating units represented by Fonnulae Va or Vb:

I ( 1I _II I I
OCH2ICCHZN-I-R~ II-NCH2i CHZOAr Va IH IH
OCHZCI CH2- i-CHZCI CH2OAr W
R 0=5=0 R
I n (6) poly(hydroxy ester ethers) having repeating units ~represented by Fonnula VI:

I II II I II II I VI
OCH2ICCH2OC-R~-CO (CH2cH2OR) OC-R'-CO i-CHZ
1-(x+y) R y R x (7) hydroxy-phenoxyether polyiners having repeating units represented by Formula VII:
iH OH

OCH2CI CH2-X-CH2CCH20-Ar3 VII
I
R n and (8) poly(hydroxyainino ethers) having repeating units represented by Fonnula VIII:

IH IO H
O
OCH2CCH2-A-CH2 ICCHaOAr VIII

R R n wherein each Ar individually represents a divalent aron7atic moiety, substituted divalent aromatic moiety or heteroaromatic moiety, or a combination of different divalent aromatic nioieties, substituted aromatic moieties or heteroaromatic moieties;
R is individually hydrogen or a monovalent hydrocarbyl moiety; each Arl is a divalent aromatic moiety or combination of divalent aromatic moieties bearing ainide or liydroxyinethyl groups; each Ar2 is the satne or different than Ar and is individually a divalent aromatic moiety, substituted aromatic moiety or heteroaromatic moiety or a coinbination of different divalent aromatic moieties, substituted aromatic moieties or heteroarom.atic moieties; Rl is individually a predominantly hydrocarbylene moiety, such as a divalent aromatic moiety, substituted divalent aromatic moiety, divalent heteroaromatic moiety, divalent allcylene moiety, divalent substituted alkylene moiety or divalent heteroalkylene moiety or a coinbination of such moieties; R2 is individually a monovalent hydrocarbyl moiety; A is an amine moiety or a combination of different amine moieties; X is an amine, an arylenedioxy, an arylenedisulfonanzido or an arylenedicarboxy moiety or combination of such moieties; and Ar3 is a "cardo"
moiety represented by any one of the Formulae:

\ Y ' \ Y

I I ( O
O

,~. Y

O
[0108] wherein Y is nil, a covalent bond, or a linleing group, wlierein suitable liiilcing groups include, for example, an oxygen atom, a sulfur atoin, a carbonyl atoln, a sulfonyl group, or a inetllylene group or similar lii-A,,age; n is an integer from about 10 to about 1000; x is 0.01 to 1.0; and y is 0 to 0.5.
[01091 The term "predonlinantly hydrocarbylene" means a divalent radical that is predominantly hydrocarbon, but which optionally contains a sinall quantity of a heteroatomic inoiety such as oxygen, sulfur, imino, sulfonyl, sulfoxyl, and the lilce.
[0110] The hydroxy-functional poly(anlide ethers) represented by Formula I
are preferably prepared by contacting an N,N'-bis(hydroxyphenylainido)allcane or arene with a diglycidyl ether as described in U.S. Patent Nos. 5,089,588 and 5,143,998.
[0111] The poly(hydroxy ainide ethers) represented by Forrnula II are prepared by contacting a bis(hydroxyphenylamido)alkane or arene, or a coinbination of 2 or more of these compounds, sucll as N,N'-bis(3-hydroxyphenyl) adipainide or N,N'-bis(3-hydroxyphenyl)glutararn.ide, with an epihalolzydrin as described in U.S. Patent No. 5,134,218.
[0112] The ainide- and hydroxymethyl-functionalized polyethers represented by Fonnula III can be prepared, for exainple, by reacting the diglycidyl ethers, such as the diglycidyl ether of bisphenol A, witli a dihydric phenol having pendant amido, N-substituted amido and/or hydroxyalkyl moieties, sucli as 2,2-bis(4-hydroxyphenyl)acetamide and 3,5-dihydroxybenzamide. These polyethers and their preparation are described in U.S. Patent Nos. 5,115,075 and 5,218,075.
[0113] The hydroxy-functional polyethers represented by Fonnula IV can be prepared, for example, by allowing a diglycidyl ether or coinbination of diglycidyl ethers to react witli a dihydric phenol or a coinbination of dilrydric phenols using the process described in U.S. Patent No. 5,164,472. Alternatively, the hydroxy-ft-Ictional polyethers are obtained by allowing a dihydric phenol or combination of dihydric phenols to react witli an epihalohydrin by the process described by Reuilcing, Barnabeo and Hale in the Joui7ial of Applied Polymer Science, Vol. 7, p. 2135 (1963).
[0114] The hydroxy-fiinctional poly(ether sulfonamides) represented by Foiinula V are prepared, for example, by polymerizing an N,N'-dialkyl or N,N'-diaryldisulfonamide with a diglycidyl ether as described in U.S. Patent No.
5,149,768.
[0115] The poly(hydroxy ester etllers) represented by Forinula VI are prepared by reacting diglycidyl ethers of aliphatic or aromatic diacids, such as diglycidyl terephthalate, or diglycidyl etllers of dihydric phenols with, aliphatic or aromatic diacids such as adipic acid or isoplzthalic acid. These polyesters are described in U.S. Patent No.
5,171,820.
[0116] The hydroxy-phenoxyether polymers represented by Foi7nula VII are prepared, for exainple, by contacting at least one dinucleophilic monomer with at least one diglycidyl ether of a cardo bisphenol, such as 9,9-bis(4-hydroxyphenyl)fluorene, phenolphthalein, or phenolphthalimidine or a substituted cardo bisphenol, such as a substituted bis(hydroxyphenyl)fluorene, a substituted phenolphthalein or a substituted phenolphthalimidine under conditions sufficient to cause the nucleophilic moieties of the dinucleophilic monomer to react with epoxy moieties to fonn a polyiner backbone containing pendant hydroxy moieties and ether, imino, ainino, sulfonamido or ester liiilcages. These hydroxy-phenoxyether polyiners are described in U.S. Patent No.
5,184,373.
[0117] The poly(hydroxyamino ethers) ("PHAE" or polyetherainines) represented by Fonnula VIII are prepared by contacting one or more of the diglycidyl ethers of a dihydric phenol with an amine having two ainine hydrogens under conditions sufficient to cause the amine moieties to react with epoxy moieties to forin a polyiner backbone having ainine linlcages, etller liiilcages and pendant hydroxyl moieties. These compounds are described in U.S. Patent No. 5,275,853. For example, polyhydroxyaminoether copolymers can be made from resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl etlier, or mixtures thereo~
[0118] The hydroxy-phenoxyether polymers are the condensation reaction products of a diliydric polynuclear phenol, such as bisphenol A, and an epihalohydrin and have the repeating units represented by Fonnula IV wherein Ar is an isopropylidene diphenylene moiety. The process for preparing these is described in U.S.
Patent No.
3,305,528, incorporated herein by reference in its entirety. One preferred non-liiniting hydroxy-phenoxyether polymer, PAPHEN 25068-38-6, is coininercially available from Phenoxy Associates, Inc. Other prefeiTed phenoxy resins are available from InCheinQ
(Rock Hill, South Carolina), these materials include, but are not limited to, the INCHEMREZt ' PEMH and PICHW product lines.
[0119] Generally, preferred phenoxy-type materials fonn stable aqueous based solutions or dispersions. Preferably, the properties of the solutions/dispersions are not adversely affected by contact with water. Preferred materials range froni about 10 %
solids to about 50 % solids, including about 15%, 20%, 25%, 30%, 35%, 40% and 45%, and ranges encornpassing such percentages. Preferably, the material used dissolves or disperses in polar solvents. These polar solvents include, but are not limited to, water, alcohols, and glycol ethers. See, for exainple, U.S. Pat. Nos. 6,455,116, 6,180,715, and 5,834,078 which describe some preferred phenoxy-type solutions and/or dispersions.
[0120] One preferred phenoxy-type material is a polyhydroxyaminoetlier copolyiner (PHAE), represented by Forinula VIII, dispersion or solution. The dispersion or solution, when applied to a container or preform, greatly reduces the penneation rate of a variety of gases through the container walls in a predictable and well known mamler.
One dispersion or latex made tllereof comprises 10-30 percent solids. A PHAE
solution/dispersion may be prepared by stiiTing or otherwise agitating the PHAE in a solution of water with an organic acid, preferably acetic or phosphoric acid, but also including lactic, malic, citric, or glycolic acid and/or mixtures thereof.
These PHAE
solution/dispersions also include organic acid salts produced by the reaction of the polyliydroxyaininoethers with these acids.
[0121] In other preferred embodiinents, phenoxy-type thermoplastics are inixed or blended witli otller materials using methods luzown to those of skill in the art. In some embodiments a compatibilizer may be added to the blend. When coinpatibilizers are used, preferably one or more properties of the blends are iinproved, such properties including, btit not limited to, color, haze, and adhesion between a layer comprising a blend and oth.er layers. One preferred blend comprises one or more phenoxy-type tliennoplastics and one or more polyolefins. A preferred polyolefin comprises polypropylene. Iil one einbodiment polypropylene or otller polyolefins may be grafted or modified with a polar molecule or monomer, including, but not lilnited to, maleic anhydride, glycidyl metllacrylate, acryl methacrylate and/or similar compoiulds to increase coinpatibility.

f 0122] The following PHAE soltttions or dispersions are exarnples of suitable phenoxy-type solutions or dispersions wliich inay be used if one or znore layers of resin are applied as a liquid such as by dip, flow, or spray coating, such as described in WO
04/004929 and U.S. Patent No. 6,676,883. One suitable material is BLOXQ
experiniental bairier resin, for exaYnple XU-19061.00 inade with phosphoric acid manufactured by Dow Chenlical Corporation. This particular PHAE dispersion is said to have the following typical characteristics: 30% percent solids, a speciftc gravity of 1.30, a pH of 4, a viscosity of 24 centipoise (Brookfield, 60 rprn, LVI, 22 C.), and a particle size ofbetween 1,400 aiid 1,800 aiigstroms. Other suitable materials include BLOXO

resins based on resorcinol have also provided superior results as a barrier material. This particular dispersion is said to have the following typical characteristics:
30 % percent solids, a specific gravity of 1.2, a pH of 4.0, a viscosity of 20 centipoise (Brookfield, 60 rpm, LVI, 22 C.), a.nd a particle size of between 1500 and 2000 angstroms.
Other variations of tlie polyhydroxyaininoether cheinistry may prove usefiil sucli as crystalline versions based on llydroquinone diglycidyletlzers. Other suitable materials include polyhydroxyaminoether solutions/dispersions by Iinperial Cheinical Iildustries ("ICI,"
Ohio, USA) available under the nanle OXYBLOK. In one enlbodiment, PHAE
solutions or dispersions can be crossliiiked partially (sezni-cross lifflced), fully, or to the exact desired degree as appropriate for the application by adding an appropriate cross liillcer material. The benefits of cross liiilcing include, but are n.ot limited to, one or more of the following: improved chemical resistance, inzproved abrasion resistance, low blusliing, low surface tension. Examples of cross 1iiAcer materials include, but are not limited to, fonnaldehyde, acetaldehyde or other nlembers - of the aldehyde family of materials. Suitable cross lii-Acers can also enable ch.anges to the Tg of the material, whicli can facilitate forination of specific containers. Other suitable inaterials include BLOXOO
5000 resin dispersion interinediate, BLOXOO XUR 588-29, BLOXOO 0000 and 4000 series resins. The solvents used to dissolve these materials include, but are not limited to, polar solvents such as alcohols, water, glycol ethers or blends thereof. Other suitable materials include, but are not limited to, BLOX R1.
[0123] In one einbodiment, preferred pheiioxy-type thermoplastics are soluble in aqueous acid. A polyiner solutioilldispersion niay be prepared by stirring or otherwise agitating the tlierinoplastic epoxy in a solution of water with an organic acid, preferably acetic or phosplioric acid, but also including lactic, inalic, citric, or glycolic acid and/or mixtures thereof. Iii a preferred embodiment, the acid concentration in the polyiner solution is preferably in the range of about 5% - 20%, including about 5% -10% by weight based on total weiglit. In other preferred embodiments, the acid concentration may be below about 5% or above about 20%; aud may vary depending on factors such as the type of polyiner and its molecular weight. Iii other preferred embodinzents, the acid concentration ranges from about 2.5 to about 5% by weight. The amount of dissolved polymer in a preferred einbodiment ranges from about 0.1% to about 40%. A
uniform and free flowing polyiner solution is preferred. In one embodiment a 10%
polyiner solution is prepared by dissolving the polymer in a 10% acetic acid solution at 90 C.
Then wllile still hot the solution is diluted with 20% distilled water to give an 8% polyiner solution. At higher concentrations of polyiner, the polyiner solution tends to be more viscous.
[0124] Exainples of preferred copolyester materials and a process for their preparation is described in U.S. Patent No. 4,578,295 to Jabarin. They are generally prepared by heating a mixture of at least one reactant selected from isophthalic acid, terephthalic acid and their C1 to C4 alkyl esters with 1,3 bis(2-hydroxyethoxy)benzene aiid ethylene glycol. Optionally, the mixture may fiirther coniprise one or more ester-fonning dihydroxy hydrocarbon and/or bis(4-(3-hydroxyethoxyphenyl)sulfone.
Especially preferred copolyester materials are available fiom Mitsui Petrochemical Ind.
Ltd. (Japan) as B-010, B-030 and others of this fainily.
[0125] Examples of preferred polyainide materials include MXD-6 from Mitsubishi Gas Chemical (Japan). Other preferred polyainide materials include Nylon 6, aiid Nylon 66. Other preferred polyamide materials are blends of polyainide and polyester, including those coinprising about 1-20% polyester by weigllt, more preferably about 1-10% polyester by weight, where the polyester is preferably PET or a modified PET. hi another embodiinent, preferred polyainide materials are blends of polyamide and polyester, including those comprising about 1-20% polyainide by weigllt, more preferably about 1-10% polyainide by weight, where the polyester is preferably PET or a modified PET. The blends may be ordinary blends or they may be coinpatibilized with an antioxidant or other material. Examples of such materials include those described in U.S.
Patent Publication No. 2004/0013833, filed March 21, 2003, which is hereby incoiporated by reference in its entirety. Other preferred polyesters include, but are not liinited to, PEN and PET/PEN copolyiners.

3. Preferred Foam Materials [0126] As used herein, the term "foam material" is a broad tenn and is used in accordance with its ordinary meaning and may include, without limitation, a foaming agent, a mixture of foaming agent and a binder or carrier material, an expandable cellular material, and/or a material having voids. The terms "foain material" and "expandable material" are used interchangeably herein. Preferred foaln materials may exhibit one or more physical characteristics that iinprove the thennal and/or structural characteristics of articles (e.g., containers) and may enable the preferred einbodiments to be able to withstand processing and physical stresses typically experienced by containers. In one einbodiment, the foam material provides stnictural support to the container.
In another einbodiment, the foam material forins a protective layer that can reduce damage to the container during processing. For exainple, the foam material can provide abrasion resistance wllich can reduce damage to the container during transport. Iii one embodiment, a protective layer of foam may increase the shock or iinpact resistance of the container and thus prevent or reduce brealcage of the container.
Furtherinore, in anotlier embodiment foam can provide a comfortable gripping surface and/or eilliance the aesthetics or appeal of the container.
[0127] hi one embodiment, foam material comprises a foaining or blowing agent and a cai.-rier material. Iil one prefelTed embodiment, the foaming agent comprises expandable sti-uctures (e.g., inicrospheres) that can be expanded and cooperate with the carrier material to produce foam. For example, the foaming agent can be thermoplastic inicrospheres, such as EXPANCELOO microspheres sold by Akzo Nobel. In one embodiment, microspheres can be thennoplastic hollow spheres conlprising thennoplastic shells that encapsulate gas. Preferably, when the microspheres are heated, the thennoplastic shell softens and the gas increases its pressure causing the expansion of the microspheres from an initial position to an expanded position. The expanded microspheres and at least a portion of the carrier material can form the foam portion of the articles described herein. The foam material can fonn a layer that comprises a single material (e.g., a generally hoinogenous mixture of the foaming agent and the can-ier material), a mix or blend of materials, a matrix formed of two or more materials, two or more layers, or a plurality of microlayers (lamellae) preferably including at least two different materials. Alternatively, the microspheres can be any other suitable controllably expandable material. For exainple, the microspheres can be structures comprising materials that can produce gas witliin or fiom the structures. In one embodiment, the inicrospheres are liollow stnictures containing chemicals wllich produce or contain gas wilerein an increase in gas pressure causes the sti-ttctures to expand aiid/or burst. In another einbodiment, the microspheres are structures made from and/or containing one or more materials which decoinpose or react to produce gas thereby expanding and/or bursting the microspheres. Optionally, the niicrosphere may be generally solid stilicttues.
Optionally, the microspheres can be shells filled witli solids, liquids, and/or gases. The inicrospheres can have a.ny configuration and shape suitable for forming foam.
For example, the microspheres can be generally spherical. Optionally, the inicrospheres can be elongated or oblique spheroids. Optionally, the microspheres caiz comprise any gas or blends of gases suitable for expanding the microspheres. In one einbodinlent, the gas can comprise an inert gas, such as nitrogen. In one embodiment, the gas is generally non-flainmable. However, in certain einbodiinents non-inert gas and/or flammable gas can fill the shells of the microspheres. In some einbodiinents, the foam material may comprise foaming or blowing agents as are lmown in the art. Additionally, the foain material may be mostly or entirely foaming agent.
[01281 Although some preferred einbodiments contain microspheres that generally do not break or burst, otlier embodiments comprise microspheres that may brealc, burst, fracture, and/or the like. Optionally, a portion of the microspheres may brealc while the reinaining portion of the microspheres does not break. hi some embodiments up to about 0.5%, 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30%, 40%, 50%, 60%
70%, 80%, 90% by weight of inicrospheres, and ranges encompassing these amounts, break. In one einbodiment, for example, a substantial portion of the microsplleres may burst and/or fracture wllen they are expanded. Additionally, various blends and mixtures of microspheres can be used to fonn foain material.
[0129] The microspheres can be fonned of any material suitable for causing expansion. In one embodiment, the microspheres can have a shell coinprising a polymer, resin, tllermoplastic, thermoset, or the like as described herein. The microsphere shell may comprise a single material or a blend of two or more different materials.
For exainple, the microspheres can have an outer shell comprising ethylene vinyl acetate ("EVA"), polyethylene terephtlialate ("PET"), polyainides (e.g. Nylon 6 and Nylon 66) polyethylene terephthalate glycol (PETG), PEN, PET copolymers, and coinbinations thereof. hi one embodiment a PET copolyiner comprises CHDM comonomer at a level between what is coininonly called PETG and PET. In another einbodiment, coinonomers such as DEG and IPA are added to PET to fonn miscrosphere shells. The appropriate conibination of material type, size, and inner gas can be selected to aclv.eve the desired expansion of the microspheres. In one einbodiment, the microspheres comprise shells fonned of a higli temperature material (e.g., PETG or similar material) that is capable of expanding when subject to high temperatures, preferably without causing the microspheres to burst. If the inicrospheres have a shell made of low temperature material (e.g., as EVA), the microspheres may break when subjected to higli temperatures that are suitable for processing certain carrier materials (e.g., PET or polypropylene having a high melt point). In some circumstances, for example, EXPANCELOO microspheres may be break when processed at relatively higli temperatures. Advantageously, mid or high temperature microspheres cail be used with a carrier material having a relatively high melt point to produce controllably, expandable foam material without breaking the microspheres. For example, microspheres can coinprise a inid teinperature material (e.g., PETG) or a high tenzperature material (e.g., acrylonitrile) and may be suitable for relatively higli teinperature applications. Thus, a blowing agent for foaniing polyiners can be selected based on the processing teinperatures einployed.
[0130] The foain material can be a matrix comprising a carrier material, preferably a material that can be mixed with a blowing agent (e.g., microspheres) to form an expandable material. The carrier material can be a thennoplastic, thennoset, or polyineric material, such as etliylene acrylic acid ("EAA"), ethylene vinyl acetate ("EVA"), linear low density polyethylene ("LLDPE"), polyetllylene terephthalate glycol (PETG), poly(hydroxyamino ethers) ("PHAE"), PET, polyethylene, polypropylene, polystyrene ("PS"), pulp (e.g., wood or paper pulp of fibers, or pulp nlixed with one or more polyiners), mixtures thereof, and the like. However, other materials suitable for carrying the foaming agent can be used to achieve one or more of the desired thermal, structural, optical, and/or other characteristics of the foam. In some embodinients, the cairier material has properties (e.g., a high melt index) for easier and rapid expansion of the microspheres, thus reducing cycle tiine thereby resulting in increased production.
[0131] hi preferred embodiments, the fonnable material may coinprise two or more coinponents including a plurality of components each having different processing windows and/or pllysical properties. The components can be combined such that the fonnable material has one or inore desired characteristics. The proportion of coinponents can be varied to produce a desired processing window and/or physical properties. For example, the first material may have a processing window that is similar to or different than the processing window of the second material. The processing win.dow may be based on, for example, pressure, temperature, viscosity, or the lilce. Thus, components of the fonnable material can be mixed to achieve a desired, for exainple, pressure or temperattire range for shaping the material.
[0132] In one einbodiment, the combination of a first material and a second nzaterial may result in a material having a processing window that is more desirable than the processing window of the second material. For example, the first material may be suitable for processing over a wide range of ten7peratures, and the second material may be suitable for processing over a narrow range of teinperatures. A material having a portion fonned of the first material and anotller portion forined of the second material may be suitable for processing over a range of temperatures that is wider than the narrow range of processing temperatures of the second material. Iii one embodiment, the processing window of a inulti-component material is similar to the processing window of the first material. In one einbodiment, the formable material coinprises a multilayer sheet or tube coinprising a layer coinprising PET and a layer coinprising polypropylene. The material formed from both PET and polypropylene can be processed (e.g., extruded) within a wide temperature range similar to the processing temperature range suitable for PET. The processing window may be for one or more paraineters, such as pressure, temperature, viscosity, and/or the like.
[0133] Optionally, the amount of each coinponent of the material can be varied to achieve the desired processing window. Optionally, the materials can be coinbined to produce a foi7mable material suitable for processing over a desired range of pressure, teinperature, viscosity, and/or the like. For example, the proportion of the material having a more desirable processing window can be increased and the proportion of material having a less undesirable processing window can be decreased to result in a material having a processing window that is very similar to or is substantially the saine as the processing window of the first material. Of course, if the more desired processin.g window is between a first processing window of a first material and the second processing window of a second material, the proportion of the first and the second material can be chosen to acllieve a desired processing window of the fonnable material.
[0134] Optionally, a plurality of materials each having similar or different processiuig windows can be combiuied to obtaui a desired processing window for the resultant material.
[0135] Iil one einbodiment, the rlleological characteristics of a formable material can be altered by varying one or more of its components having different rlieological characteristics. For example, a substrate (e.g., PP) may have a high melt strength and is amenable to extilision. PP can be combined with another material, such as PET wliich has a low melt strength malcing it difficult to extrude, to forin a material suitable for extrusion processes. For exainple, a layer of PP or otller strong material may support a layer of PET during co-extrusion (e.g., liorizontal or vei-tical co-extnision).
Thus, foiinable material formed of PET and polypropylene can be processed, e.g., extnided, in a temperature range generally suitable for PP and not generally suitable for PET.
[0136] hi some enibodiments, the composition of the forinable material may be selected to affect one or more properties of the ai-ticles. For exainple, the thennal properties, stnlctural properties, barrier properties, optical properties, rheology properties, favorable flavor properties, and/or otlier propei-ties or characteristics disclosed lierein can be obtained by using forinable materials described herein.
4. Additives to Enhance Materials [0137] An advantage of preferred metliods disclosed herein are their flexibility allowing for the use of multiple fi.inctional additives. Additives known by those of ordinary skill in the art for their ability to provide enllanced CO2 barriers, 02 balTiers, UV protection, scuff resistance, blush resistance, impact resistance and/or chemical resistance may be used.
[0138] Preferred additives may be prepared by methods known to those of skill in the art. For example, the additives may be mixed directly with a particular material, they may be dissolved/dispersed separately and then added to a particular material, or they may be combined witll a particular material to addition of the solvent that forms the inaterial solution/dispersion. Iil addition, in some einbodiments, preferred additives may be used alone as a single layer.
[0139] In preferred embodiments, the barrier properties of a layer inay be enhanced by the addition of different additives. Additives are preferably present in an alnount up to about 40% of the material, also including up to about 30%, 20%, 10%, 5%, 2% and 1% by weight of the material. In other enlbodiments, additives are preferably present in an ainount less than or equal to 1% by weight, preferred ranges of materials include, but are not liinited to, about 0.01% to about 1%, about 0.01% to about 0.1%, and about 0.1% to about 1% by weight. Further, in some einbodiments additives are preferably stable in aqueous conditions. For example, derivatives of resorcinol (m-dihydroxybenzene) may be used in conjunction with various preferred materials as blends or as additives or monomers in the fonnation of the material. The higher the resorcinol content the greater the baiTier properties of the material. For example, resorcinol diglycidyl etlier can be used in PHAE and hydroxyethyl ether resorcinol can be used in PET and other polyesters and Copolyester Barrier Materials.
[0140] Another additive(s) that may be used are "nanoparticles" or "nanoparticulate material." For convenience the terin nanoparticles will be used herein to refer to both nanoparticles and nanoparticulate material. These nanoparticles are tiny, micron or sub-micron size (diaineter), particles of materials which enllance the barrier properties of a material by creating a more tortuous path for migrating gas molecules, e.g.
oxygen or carbon dioxide, to take as they permeate a material. In prefelTed embodiments nanoparticulate material is present in ainounts ranging fiom 0.05 to 1% by weight, including 0.1%, 0.5% by weight and ranges encoinpassing these amotults.
[0141] One prefeiTed type of nanoparticulate material is a microparticular clay based product available from Southenl Clay Products. One preferred line of products available from Soutliern Clay products is Cloisite nanoparticles. h-1 one einbodiment preferred nanoparticles comprise momnorillonite modified with a quateniary ainmonium salt. lii other embodiments nanoparticles coinprise moiunorillonite modified with a ternary ammonium salt. In otlier embodiments nanoparticles comprise natural momnorillonite. In further einbodinients, nanoparticles coinprise organoclays as described in U.S. Pateiit No. 5,780,376, the entire disclosure of which is hereby incorporated by reference and forms pai-t of the disclosure of this application. Other suitable organic and inorganic microparticular clay based products may also be used.
Both man-made and natural products are also suitable.
[0142] Another type of preferred nanoparticulate material comprises a composite material of a metal. For exanzple, one suitable conlposite is a water based dispersion of aluminuin oxide in nanoparticulate fonn available from BYK
Chemie (Germany). It is believed that this type of nanoparticular material may provide one or more of the following advantages: increased abrasion resistance, increased scratch resistance, increased Tg, and tlzennal stability.
[0143] Another type of preferred nanoparticulate material comprises a polymer-silicate composite. hi preferred embodiments the silicate comprises montmorillonite. Suitable polyiner-silicate nanoparticulate material are available from Nanocor and RTP Company.

[0144] In prefeiled einbodiments, the UV protection properties of the material inay be eilllanced by the addition of different additives. hl a preferred embodiment, the W protection inaterial used provides UV protection up to about 350 iun or less, preferably about 370 iun or less, more preferably about 400 nm or less. The UV
protection material may be used as an additive with layers providing additional functionality or applied separately as a single layer. Preferably additives providing enhanced UV protection are present in the material from about 0.05 to 20% by weight, but also including about 0.1%, 0.5%, 1%, 2%, 3%, 5%, 10%, and 15% by weight, and ranges encompassing these ainotults. Preferably the UV protection material is added in a fonn that is coinpatible with the otlier materials. For example, a preferred UV protection material is Milliken UV390A C1earShieldOO. UV390A is an oily liquid for which mixing is aided by first blending the liquid with water, preferably in roughly equal parts by voluine. This blend is then added to the material solution, for example, BLOX
599-29, and agitated. The resultiiig solution contains about 10% UV390A and provides UV
protection up to 390 iun w11en applied to a PET prefonn. As previously described, in another embodiment the UV390A solution is applied as a single layer. hi other einbodiments, a preferred UV protection material comprises a polyiner grafted or modified with a UV absorber that is added as a concentrate. Otlzer preferred UV
protection materials include, but are not limited to, benzotriazoles, phenothiazines, and azaphenothiazines. UV protection materials may be added during the melt phase process prior to use, e.g. prior to injection molding or extrusion, or added directly to a coating material that is in the form of a solution or dispersion. Suitable UV
protection materials are available from Milliken, Ciba and Clariant.
[0145] In preferred embodiments, CO2 scavenging properties can be added to the materials. hi one preferred embodiment such properties are achieved by including an active amine which will react with CO2 forming a high gas barrier salt. This salt will then act as a passive COZ baiTier. The active ainine may be an additive or it may be one or more moieties in the tliermoplastic resin material of one or inore layers.
[0146] In preferred einbodiments, 02 scavenging properties can be added to preferred materials by including 02 scavengers sucll as anth.roquinone and otliers lalown in the art. In another ernbodiment, one suitable 02 scavenger is AMOSORB 02 scavenger available from BP Amoco Corporation and ColorMatrix Corporation which is disclosed in U.S. Patent No. 6,083,585 to Cahill et al., the disclosure of which is hereby incorporated in its entirety. In one einbodiment, 02 scavenging properties are added to prefeiTed phenoxy-type materials, or otller materials, by including 02 scavengers in the phenoxy-type material, with different activating inechanisms. Preferred 02 scavengers can act either spontaneously, gradually or with delayed action until initiated by a specific trigger. In some einbodiments the 02 scavengers are activated via exposure to either UV
or water (e.g., present in the contents of the container), or a coinbination of both. The 02 scavenger is preferably present in an ainount of from about 0.1 to about 20 percent by weight, more preferably in an anlount of from about 0.5 to about 10 percent by weight, and, most preferably, in an ainount of from about 1 to about 5 percent by weight, based on the total weight of the coating layer.
[0147] In another preferred embodiment, a top coat or layer is applied to provide chemical resistance to harsher chemicals than w11at is provided by the outer layer.
In certain embodiments, preferably these top coats or layers are aqueous based or non-aqueous based polyesters or acrylics which are optionally partially or ftilly cross linked.
A prefeiTed aqueous based polyester is polyethylene terephthalate, however other polyesters may also be used. In certain einbodiments, the process of applying the top coat or layer is that disclosed in U.S. Patent Pub. No. 2004/0071885, entitled Dip, Spray, and Flow Coating Process For Forming Coated Articles, the entire disclosure of which is hereby incorporated by reference in its entirety.
[0148] A prefeiTed aqueous based polyester resin is described in U.S. Pat. No.
4,977,191 (Salsman), incorporated herein by reference. More specifically, U.S.
Pat. No.
4,977,191 describes an aqueous based polyester resin, comprising a reaction product of 20-50% by weight of waste terephthalate polyiner, 10-40% by weight of at least one glycol and 5-25% by weight of at least one oxyalkylated polyol.
[0149] Another prefelTed aqueous based polyiner is a sulfonated aqueous based polyester resin composition as described in U.S. Pat. No. 5,281,630 (Salsman), herein incorporated by reference. Specifically, U.S. Pat. No. 5,281,630 describes an aqueous suspension of a sulfonated water-soluble or water dispersible polyester resin coinprising a reaction product of 20-50% by weight terephthalate polyiner, 10-40% by weiglit at least one glycol and 5-25% by weight of at least one oxyalkylated polyol to produce a prepolymer resin having hydroxyalkyl functionality where the prepolyiner resin is ftirther reacted with about 0.10 mole to about 0.50 mole of alpha, beta-etllylenically unsaturated dicarboxylic acid per 100 g of prepolymer resin and a thus produced resin, tenninated by a residue of an alpha, beta-ethylenically unsaturated dicarboxylic acid, is reacted with about 0.5 mole to about 1.5 mole of a sulfite per mole of alpha, beta-ethylenically unsaturated dicarboxylic acid residue to produce a sulfonated-terininated resin.
[0150] Yet another preferred aqueous based polyiner is the coating described in U.S. Pat. No. 5,726,277 (Salsnian), incorporated herein by reference.
Specifically, U.S. Pat. No. 5,726,277 describes coating coinpositions coniprising a reaction product of at least 50% by weight of waste terephthalate polymer and a mixture of glycols including an oxyalkylated polyol in the presence of a glycolysis catalyst wherein the reaction product is ftirther reacted with a difinlctional, organic acid and wherein the weight ratio of acid to glycols in is the range of 6:1 to 1:2.
[0151] While the above examples are provided as preferred aqueous based polymer coating coinpositions, other aqueous based polyiners are suitable for use in the products and methods describe herein. By way of example only, and not ineant to be limiting, fi,irther suitable aqueous based compositions are described in U.S.
Pat. No.
4,104,222 (Date, et al.), incorporated herein by reference. U.S. Pat. No.
4,104,222 describes a dispersion of a linear polyester resin obtained by mixing a linear polyester resin wit11 a higher alcohol/ethylene oxide addition type surface-active agent, melting the inixture and dispersing the resulting melt by pouring it into an aqueous solution of an alkali under stirring Specifically, this dispersion is obtained by mixing a linear polyester resin with a surface-active agent of the higlier alcohol/etllylene oxide addition type, melting the mixture, and dispersing the resulting melt by pouring it into an aqueous solution of an alkanolamine under stirring at a teinperature of 70-95 C, said alkanolainine being selected from the group consisting of monoethanolainine, diethanolamine, triethanolamine, monomethylethanolainine, monoethylethanolamine, diethyletlianolainine, propanolainine, butanolainine, pentanolamine, N-phenylethanolamine, and an alkanolamine of glycerin, said alkanolamine being present in the aqueous solution in an ainount of 0.2 to 5 weight percent, said surface-active agent of the higlier alcohol/ethylene oxide addition type being an ethylene oxide addition product of a higller alcohol having an alkyl group of at least 8 carbon atoms, an alkyl-substituted phenol or a sorbitan monoacylate and wlierein said surface-active agent has an HLB value of at least 12.

[0152] Likewise, by exainple, U.S. Pat. No. 4,528,321 (Allen) discloses a dispersion in a water iiruniscible liquid of water soluble or water swellable polyiner particles and which has been made by reverse phase polymerization in the water inuniscible liquid and wllich includes a non-ionic coinpound selected from C4_12 alkylene glycol monoethers, their CI_4 alkanoates, C6_12 polyalcylene glycol monoethers and their C1_4 alkanoates.
[0153] The materials of certain einbodiinents may be cross-linked to enhance therinal stability for various applications, for example hot fill applications. In one embodiment, inner layers may coinprise low-cross liiilcing materials while outer layers may coinprise higll crossliiiking materials or other suitable combinations.
For exainple, -ui iiuier coating on a PET surface may utilize non or low cross-linlced material, such as the BLOXOO 588-29, and the outer coat may utilize another material, such as EXP
12468-4b from ICI, capable of cross lii-Acing to ensure niaxiinum adhesion to the PET.
Suitable additives capable of cross linking may be added to one or more layers. Suitable cross linkers can be chosen depending upon the chemistry and functionality of the resin or material to which they are added. For example, amine cross linkers may be useful for crosslii-Acing resins comprising epoxide groups. Preferably cross liiAcing additives, if present, are present in an ainount of about 1% to 10% by weight of the coating solution/dispersion, preferably about 1% to 5%, more preferably about 0.01% to 0.1% by weight, also including 2%, 3%, 4%, 6%, 7%, 8%, and 9% by weight. Optionally, a thei7noplastic epoxy (TPE) can be used with one or more crosslinking agents.
In some embodiments, agents (e.g. carbon black) may also be coated onto or incorporated into the TPE material. The TPE material can fonn part of the articles disclosed herein.
It is contemplated that carbon black or similar additives can be employed in other polymers to eiillance material properties.
[0154] The materials of certain einbodiments may optionally coinprise a curing enhancer. As used herein, the term "curing enhancer" is a broad terin and is used in its ordinaiy meaning and includes, without limitation, chemical cross-liiAcing catalyst, thennal eillzancer, and the like. As used herein, the terin "therinal enhancer" is a broad tenn and is used in its ordinary meaning and includes, without limitation, transition metals, transition metal compounds, radiation absorbing additives (e.g., carbon blaclc).
Suitable transition metals include, but are not limited to, cobalt, rhodium, and copper.
Suitable transition metal compounds include, but are not limited to, metal carboxylates.
Preferred carboxylates include, but are not liinited to, neodecanoate, octoate, and acetate.
Thennal enliancers may be used alone or in combination with one or more other thermal eiAZancers.
[0155] The therinal enliancer can be added to a material and may significantly increase the teinperature of the material during a curing process, as compared to the material witliout the tllernlal enhancer. For exainple, in some embodinlents, the tllerinal ei-diancer (e.g., carbon blaclc) can be added to a polynler so that the temperature of the polyiner subjected to a curing process (e.g., IR radiation) is significantly greater than the polyiner without the thennal eilllan.cer subject to the same or similar curing process. The increased temperature of the polyiner caused by the therinal eiffiancer can increase the rate of curing and therefore increase production rates. In some enibodiments, the thennal ei-dlancer generally has a higller teinperature than at least one of the layers of an article when the tlierinal ei-dzancer and the article are heated with a heating device (e.g., infrared heating device).
[0156] hi some einbodinlents, the thermal enliancer is present in an amount of about 5 to 800 ppm, preferably about 20 to about 150 ppm, preferably about 50 to 125 ppm, preferably about 75 to 100 ppm, also including about 10, 20, 30, 40, 50, 75, 100, 125, 150, 175, 200, 300, 400, 500, 600, and 700 ppm and ranges encoinpassing these amounts. The ainount of thermal enliancer may be calculated based on the weigllt of layer which comprises the therinal effliancer or the total weigllt of all layers comprising the article.
[0157] In some embodiments, a preferred thermal enhancer comprises carbon black. In one embodiment, carbon black can be applied as a component of a coating material in order to enliance the curing of the coating material. Wlien used as a compoilent of a coating material, carbon black is added to one or more of the coating materials before, during, and/or after the coating material is applied (e.g., impregnated, coated, etc.) to the article. Preferably carbon black is added to the coating material and agitated to ensure thorough mixing. The thermal ei-ffiancer may coinprise additional materials to achieve the desired material properties of the article.
[0158] In another embodiment wherein carbon black is used in an injection molding process, the carbon black may be added to tl-ie polylner blend in the melt phase process.
[0159] In some embodiments, the polyiner coinprises about 5 to 800 ppm, preferably about 20 to about 150 ppm, preferably about 50 to 125 ppm, preferably about 75 to 100 ppm, also including about 10, 20, 30, 40, 50, 75, 100, 125, 150, 175, 200, 300, 400, 500, 600, and 700 ppm thermal ei~liancer and ranges encoinpassing these amounts.
In a further embodiment, the coating material is cured using radiation, such as infrared (IR) heating. In preferred embodiments, the IR heating provides a more effective coating than curing using other methods. Other thennal and cluing enhancers and methods of using same are disclosed in U.S. Patent Application Ser. No. 10/983,150, filed Noveniber 5, 2004 and published as Publication No. 2006-0099363, entitled "Catalyzed Process for Forming Coated Articles," the disclosure of which is hereby incorporated by reference it its entirety.
[0160] In some einbodiments the addition of anti-foani/bubble agents is desirable. In some embodiments utilizing solutions or dispersion the solutions or dispersions fonn foain and/or bubbles which can interfere with prefened processes. One way to avoid this interference, is to add anti-foam/bubble agents to the solution/dispersion. Suitable anti-foam agents include, but are not limited to, nonionic surfactants, alkylene oxide based materials, siloxane based materials, and ionic surfactants. Preferably anti-foam agents, if present, are present in an amount of about 0.01% to about 0.3% of the solution/dispersion, preferably about 0.01 % to about 0.2%, but also including about 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.25%, and ranges encompassing these amounts.
[0161] In another einbodiment foaming agents may be added to tlie coating materials in order to foam the coating layer. In a further embodiment a reaction product of a foaming agent is used. Useful foaming agents include, but are not limited to azobisformamide, azobisisobutyronitrile, diazoaminobenzene, N,N-dimethyl-N,N-dinitroso terephtllalamide, N,N-dinitrosopentamethylene-tetramine, benzenesulfonyl-hydrazide, benzene-1,3-disulfonyl hydrazide, diphenylsulfon-3-3, disulfonyl liydrazide, 4,4'-oxybis benzene sulfonyl hydrazide, p-toluene sulfonyl semicarbizide, barium azodicarboxylate, butylainine nitrile, nitroureas, trihydrazino triazine, phenyl-methyl-urethane, p-sulfoiiliydrazide, peroxides, aininoniuin bicarbonate, and sodium bicarbonate. As presently conteinplated, coininercially available foaming agents include, but are not limited to, EXPANCEL'~~', CELOGEN , HYDROCEROL , MIK'.ROFINE , CEL-SPAN , and PLASTRON FOAM.
[0162] The foaining agent is preferably present in the coating material in an ainount from about 1 up to about 20 percent by weight, more preferably from about 1 to about 10 percent by weight, and, most preferably, from about 1 to about 5 percent by weight, based on the weight of the coating layer. Newer foalning technologies known to those of skill in the art using compressed gas could also be used as an alternate means to generate foam in place of conventional blowing agents listed above.
[0163] The tie-layer is preferably a polyiner having functional groups, such as anllydrides and epoxies that react with the carboxyl and/or 1lydroxyl groups on the PET

polymer cllains. Usefitl tie-layer materials include, but are not limited to, DuPont BYNEL , Mitsui ADMER , Eastman's EPOLINE, Arlcema's LOTADER and ExxonMobil's EVELOY@.
B. Detailed Description of the Drawiiif4s [0164] Iii preferred enibodiments ai-ticles may comprise one or more fonnable materials. Ai-ticles described herein may be mono-layer or multi-layer (i.e., two or more layers). In some embodiments, the articles can be packaging, such as drinkware (including prefonns, containers, bottles, closures, etc.), boxes, cartons, tray, sheets, and the like.

[0165] The multi-layer articles may comprise an imier layer (e.g., the layer that is in contact with the contents of the container) of a material approved by a regulatory agency (e.g., the U.S. Food and Drug Association) or material having regulatory approval to be in contact with food (including beverages), di-u.gs, cosmetics, etc. hl other einbodiments, an imler layer comprises material(s) that are not approved by a regulatory scheine to be in contact with food. A second layer may coinprise a second material, which can be similar to or different t11an the material forming the inner layer. The articles can have as many layers as desired. It is contemplated that the articles may comprise one or more materials that form various portions that are not "layers."
[0166] Referring to FIGURE 1, a prefeiTed monolayer preforln 30 is illustrated. The preform is preferably made of an FDA approved material, such as virgin PET, and can be of any of a wide variety of shapes and sizes. The preform shown in FIGURE 1 is of the type which will forin a 16 oz. carbonated beverage bottle that ca.n have an oxygen and carbon dioxide barrier, but as will be understood by those skilled in the art, other preform configurations can be used depending upon the desired configuration, characteristics and use of the final article. The monolayer prefonn 30 may be made by methods disclosed herein.
[0167] Referring to FIGURE 2, a cross-section of the preform 30 of FIGURE
1 is illustrated. The preforin 30 has a neck portion 32 and a body portion 34, fonned monolithically (i.e., as a single, or unitary, stnicture). Advantageously, the monolithic arrangement of the preform, when blow-molded into a bottle, provides greater dimensional stability and iinproved physical properties in comparison to a prefonn constnicted of separate neck and body portions, which are bonded together.
However, the preforms can comprise a neck portion and body portion that are bonded together.

[0168] The neck portion 32 begins at the opening 36 to the interior of the preforni 30 and extends to and includes the support ring 38. The neclc portion 32 is ftirther characterized by the presence of the tlvreads 40, which provide a way to fasten a cap for the bottle produced froin the prefonn 30. Alternatively, the neck portion 32 can be configured to engage a closure or cap (e.g., a crown closure, cork (natural or artificial), snap cap, pLuictured seal, and/or the like). The body portion 34 is an elongated aiid cylindrically shaped stitiicture extending down froin the neck portion 32 and culminating in a rounded end cap 42. The prefonn thickiless 44 will depend upon the overall length of the prefonn 30 and the wall thiclmess and overall size of the resulting container.
[0169] Referring to FIGURE 3, a cross-section of one type of a multilayer prefonn 50 having features in accordance with a preferred embodiment is disclosed. The prefonn 50 has the neck portion 32 and the body portion 34 similar to the prefoim 30 in FIGURES 1 and 2. The layer 52 is disposed about the entire surface of the body portion 34, tenninating at the bottom of the support ring 38. The coating layer 52 in the embodiment shown in the figure does not extend to the neck portion 32, nor is it present on the interior surface 54 of the prefonn wliich is preferably made of an FDA
approved material, such as PET. The coating layer 52 may comprise either a single material or several microlayers of at least two materials. By way of exaanple, the wall of the bottom portion of the preform may have a thiclaiess of 3.2 millimeters; the wall of the neck, a cross-sectional dimension of about 3 millimeters; and the material applied to a thickness of about 0.3 inillimeters. The layer 52 may coinprise PET, RPET, barrier material, foam and/or other polymer materials suitable for fonning ari outer surface of a prefonn.
[0170] The overall thickness 56 of the prefonn is equal to the thicluiess of the iiiitial uncoated prefonn 39 plus the thiclazess 58 of the outer layer 52, and is dependent upon the overall size and desired coating thiclmess of the resulting container. However, the prefonn 50 inay have any thiclaless depending on the desired thermal, or structLlral properties of the container formed fiom the prefonn 50. The preforms and containers can have layers which have a wide variety of relative thiclc-lesses.
[0171] Referring to FIGURE 4, a preferred einbodiment of a multilayer preform 60 is shown in cross-section. The primary difference between the coated preform 60 and the coated prefonn 50 in FIGURE 3 is the relative thickiless of the two layers in the area of the end cap 42. The prefonn 50 of FIGURE 3 has an outer layer 52 that is generally thinner than the thiclfness of the imier layer of the prefonn throughout the entire body portion of the preform. The prefonn 60, however, has an outer layer 52 that is thicker at 62 near the end cap 42 than it is at 64 in the wall portion 66, aud conversely, the thiclaiess of the iiuier layer is greater at 68 in the wall portion 66 than it is at 70, in the region of the end cap 42. This prefornl design is especially useful when the outer layer which is applied to the initial preforin in an ovennolding process to make the coated prefonn, as described below, where it presents certain advantages including that relating to reducing molding cycle time. These advantages will be discussed in more detail below. The layer 52 may be homogeneous or it may comprise a plurality of microlayers.
[0172] The multilayer preforms and containers can have layers which have a wide variety of relative tliickn.esses. In view of the present disclosure the thickness of a given layer and of tlie overall preform or container, whether at a given point or over the entire container, can be chosen to fit a coating process or a particular end use for the container. Furtheimore, as discussed above in regard to the oLiter layer in FIGURE 3, the outer layer in the preforni and container embodiments disclosed herein may comprise a single material or several microlayers of two or more materials.
[0173] Referring to FIGURE 5 there is shown a preferred three-layer prefonn 72. This einbodiment of coated prefonn is preferably made by placing two coating layers 74 and 76 on a monolayer preform, such as prefonn 30 shown in FIGURE 1.
[0174] After a prefonn, such as that illustrated in FIGURE 3, is prepared by a inethod and apparatus such as those discussed in detail below, it is subjected to a stretch blow-molding process. Referring to FIGURE 6, in this process a niultilayer preforrin 50 is placed in a mold 80 having a cavity corresponding to the desired container shape. The prefonn is then heated and expanded by stretching and by air forced into the interior of the prefonn 50 to fill the cavity witliin the mold 80, creating a container 82 (FIGURE 7).
The blow molding operation normally is restricted to the body portion 34 of the preform witll the neck portion 32 including the threads, pilfer ring, and support ring retaining the original configuration as in the preform. Monolayer and multilayer containers can be fonned by stretch blow molding monolayer and multilayer prefonns, respectively.
[0175] FIGURE 6A illustrates a stretch blow mold designed to improve cycle times and thennal efficiency. The temperatlue of the walls of the mold 80A can be precisely controlled to achieve the desired temperature distribution tluough the blow molded container.
[0176] Refeiring to FIGURE 7, there is disclosed an embodiment of container 82 in accordance with a prefelTed einbodiment, such as that which might be made from blow molding the multilayer prefoi7n 50 of FIGURE 3. The container 82 has a neck portion 32 and a body portion 34 coiTesponding to the neck and body portions of the prefonn 50 of FIGURE 3. The neck portion 32 is ftirther characterized by the presence of the tlueads 40 which provide a way to fasten a cap onto the container.
[0177] The outer layer 84 covers the exterior of the entire body portion 34 of the container 82, stopping just below the support ring 38. The interior surface 86 of the container, which is made of an FDA-approved material, preferably PET, remains uncoated so that only the interior surface 86 is in contact witli beverages or foodstuffs. In one preferred enlbodiment that is used as a carbonated beverage container, the thiclaiess 87 of the layer is preferably 0.508 nnn - 1.524 nun (0.020-0.060 inch), more preferably 0.762 nnn - 1.016 inin (0.030-0.040 inch); the thi,cluless 88 of the PET layer is preferably 2.032 inin - 4.064 nuii (0.080-0.160 incli), more preferably 2.54 inin - 3.556 mm (0.100-0.140 incll); and the overall wall thicla-iess 90 of the barrier-coated container 82 is preferably 3.556 inm - 4,562 imil (0.140-0.180 inch), more preferably 3.82 inm - 4.3 18 inin (0.150-0.170 inc11). Preferably, on average, the overall wall thiclaiess 90 of the container 82 derives the majority of its thiclaiess from the imler PET layer.
Of course, the container 82 can be a monolayer container. For example, the container 82 can be made by stretch blow molding the prefonn 30 of FIGURE 1. Additional articles and associated inaterials are disclosed in U.S. Patent Application Serial No. 11/108,345 entitled MONO
AND MULTI-LAYER ARTICLES AND INJECTION METHODS OF MAKING THE
SAME, filed on April 18, 2005 that can be made by the systeins disclosed hereiul.
[0178] FIGURE 8 schematically illustrates a temperature control system 120 in accordance with a prefeiTed embodiment. The illustrated temperature control system 120 is an open loop system. The teinperature control system 120 can be used to control the temperature of a mold apparatus 122. The mold apparatus 122 can be configured to mold a single article or a plurality of articles. The mold apparatus 122 can be configured to fonn articles of any shape and configuration. For example, the mold apparatus 122 can be designed to produce prefoiins, containers, and other articles that are forined by molds.
In some embodiments, the mold apparatus 122 can be a stretch blow-molding apparatus, injection molding apparatus, compression molding apparatus, thermomolding or thernnofonning systein, vacuum fonning systein, and the like. The mold apparatus 122 may or may not coinprise high heat transfer material. Some exenlplary temperature control systems einploy a working fluid or other means for controlling the temperature of the mold apparatus during the molding process. The illustrated temperature control system 120 has a worlcing fluid passing througll the mold apparatus 122 to control the teinperature of the polymer in the mold apparatus 122. The working fluid can be at a wide range of teinperattires depending on the particular application.
[0179] The illustrated mold apparatus 122 comprises a plurality of mold sections that cooperate to define a molding cavity. In some embodiments, the mold apparatus 122 coinprises a mold section 122a and mold section 122b movable between an open position and a closed position. The mold section 122a and the mold section 122b can fonn a mold cavity or mold space sized and configured to inalce preforms, such as the prefonn 30 as illustrated. The mold apparatus 122 can also be designed to foi7n a layer of a inultilayer prefoimis or other articles. The temperature control system 120 can be used selectively control the teinperature of the mold apparatus 122 to reduce cycle time, produce a desired finish (e.g., an ainount of crystallinity), iinprove mold life, improve preform quality, etc.
[0180] In the illustrated embodiment, the temperature control systein 120 includes fluid lines 130, 140. The fluid line 130 coiuiects a fluid source 126 to the mold apparatus 122, and the fluid line 140 comlects the mold apparatus 122 to ali exhaust system 148. Fluid lines can define flow paths of the worlcing fluid passing tluough the systein 120.
[0181] As used herein, the tenn "fluid source" is a broad terin and is used in its ordinary sense and refers, without limitation, to a device which is stiitable for providing fluid that can be used to maintain the mold apparatus 122 at a suitable temperature. In various embodiments, the fluid source may comprise a bottle, canister, compressor system, or any other suitable fluid delivery device. The fluid source 126 might contain a quantity of liquid, preferably a refrigerant. For exainple, the fluid source 126 can comprise one or more refrigerants, such as Freon, Refrigerant 12, Refrigerant 22, Refrigerant 134a, and the like. The fluid source 126 can also comprise cryogenic fluids, such as liquid carbon dioxide (C02) or nitrogen (N2). In some embodiments, the working fluid can be conveniently stored at room temperature. For exanlple, COZ or nitrogen is liquid at typical room teinperatures when under sufficient pressure. hi some non-limiting embodiinents, the pressure of the stored fluid in the fluid source 126 will often be in the range of about 40 bars to about 80 bars. In some einbodiments, the fluid source 126 is a bottle and the pressure in the bottle will be reduced during the molding of preforms as fluid from the bottle is consuined. The fluid source 126 can contain a sufficient amount of fluid so that the mold apparatus 122 can be cooled for many cycles, as described below. The fluid source 126 may have a regulator to control the flow of fluid into the fluid line 130 and may conzprise a compressor that can provide pressure to the fluid in the fluid line 130. Optionally, the worlcing fluid of the temperature control system can coinprise a combination of two or more of the aforementioned fluids to achieve the desired thennal characteristics of the working fluid. Iii some enibodiments, the percentages of the components of the worlcing fluids can be selected based on the desired temperatures and pressures so that the components of the worlcing fluid do not solidify, for example. Otlier worlcing fluids, such as water, can also be employed to control the teinperature of molding apparatus. Of course, refrigerants can be used to more rapidly heat and/or cool the mold apparatus and associated molded articles as compared to non-refrigerants, such as water.
[0182] As used herein, the tenn "refrigerant" is a broad term and is used in its ordinary sense and refers, without limitation, to non-cryogenic refrigerants (e.g., Freon) and cryogenic refrigerants. As used herein, the terin "cryogenic refrigerant"
is a broad term and is used in its ordinary sense and refers, witllout limitation, to cryogenic fluids.
As used herein, the tenn "cryogenic fluid" means a fluid with a maximum boiling point of about -50 C at about 5 bar pressure when the fluid is in a liquid state. In some non-limiting einbodimelits, cryogenic fluids can comprise COZ, N2, Heliuin, combinations thereof, and the like. Iii some einbodimelits, the ciyogenic refrigerant is a higli temperature range cryogenic fluid having a boiling point higher than about -100 C at about 1.013 bars. In some einbodimelits, the cryogenic refrigerant is a mid temperature range cryogenic fluid having a boiling point between about -100 C and -200 C. In some einbodimelits, the cryogenic refrigerant is a low temperatLire range cryogenic fluid having a boiling point less than about -200 C at about 1.013 bars.
[0183] The heat load capabilities of a temperature control system using a non-cryogenic fluid may be nluch less than the heat load capabilities of a temperature control system using cryogenic fluid. Further, non-cryogenic refrigerants may lose its effective cooling ability before it reaches critical portions of the mold. For exainple, Freon refrigerant may be heated and completely vaporized after it passes tluough the expansion valve but before it reaches critical mold locations and, thus, may not effectively cool the mold surfaces. The temperature control systems using cryogenic fluid can provide rapid cooling and/or heating of the molding surface of the mold apparatus to reduce cycle times and increase mold output.

[0184] In one embodiment, a fluid source inlet 128 of the fluid line 130 is coiulected to the fluid source 126, and the fluid line 130 has an outlet 134 leading to mold apparatus 122. Fluid from the fluid sotuce 126 can pass tluough the fluid sotirce inlet 128 into the fluid line 130 and out of the outlet 134 to the mold apparatus 122.
The fluid line 130 is a conduit, such as a pipe or hose, in which pressurized fluid caii, pass. For example, in the illustrated embodiment of FIGURE 8, fluid in the fluid line 130 is a liquid refrigerant at a pressure of about 40 bars to about 80 bars.
[0185] Fluid from the fluid line 130 passes througli the mold apparatus 122 to control the temperature of the mold apparatus 122. In some einbodiments, the fluid passes tluougll one or more flow control devices (e.g., pressure reducing elements, valves, and the like) located upstreani of or within the mold apparatus 122.
The flow control devices receive the fluid (preferably a liquid) at a high presstue and output a low pressure and temperature fluid (e.g., gas or gas/liquid mixture) to one or more flow passageways in the mold apparatus 122. As shown in FIGURE 10, for example, the fluid can pass through a plurality of pressure reducing elements 212 in into a plurality of fluid passageways or chaiulels 204 to selectively control the temperature of the preforin. The fluid circulating through the mold apparattis of FIGURE 10 cools the warln melt to fonn a multilayer preform.
[0186] As used herein, the terin "pressure reducing element" is a broad term and is used in its ordinary sense and refers, without limitation, to a device configured to reduce the pressure of a working fluid. In some embodiments, the pressure reducing element can reduce the pressure of the working fluid to a pressure equal to or less than a vaporization pressure of the working fluid. The worlcing fluid can coinprise a refrigerant (e.g., a cryogenic refrigerant or a non-cryogenic refrigerant). In some embodiments, the pressure reducing elements are in the form of pressure reduction or expansion valves that cause vaporization at least a portion of the worlcing fluid passing theretluough. The pressure reducing eleinent can have a fixed orifice or variable orifice. In some embodiments, the pressure reducing element can be a nozzle valve, needle valve, Joule-Thomson expansion valve, or any other suitable valve for providing a desired pressure drop. For example, a Joule-Thomson expansion valve can recover work energy from the expansion of the fluid resulting in a lower downstreain temperature. In some embodiments, the pressure reducing element vaporizes an effective ainount of the working fluid (e.g., a cryogenic fluid) to reduce the temperature of the worlfing fluid such that the worlcing fluid can sufficiently cool an article within a mold to form a dimensionally stable outer surface of the article. h1 some einbodinients, the presstue reducing elements can be substituted with flow regulating elements (e.g., a valve systein) especially if the worlcing fluid is a non-refrigerant, such as water.
[0187] With reference again to FIGURE 8, after the worlcing fluid passes through the mold apparatus 122, the fluid passes tl-irougli the inlet 136 and tlirough the fluid line 140 and out of an outlet 144 to the exhaust system 148. The fluid line 140 is a conduit, such as pipe or hose, in wlzich pressurized fluid can pass. In some embodiments, the fluid in the fluid line 140 is at a pressure less than about 10 bars, 5 bars, 3 bars, 2 bars, and ranges encompassing such pressures. Of course, the pressure of working fluid may be different depending on the application.
[0188] The exhaust system 148 can receive and discharge the fluid froln the fluid line 140. The exhaust system 148 can include one or more valves that can control the pressure of the fluid in the fluid line 140 and the ainount of fluid emitted from the temperature control system 120. The exhaust systein 148 can include one or more fans and/or vents to fiirther ensure that the fluid properly passes througll the temperature control system 120. Preferably, the fluid is in the fonn of a gas that is discharged into the atmosphere by the exhaust systein 148. Tlius, fluid from the fluid soiuce 126 passes through the fluid line 130, the mold apparatus 122, the fluid line 140, and out of the exhaust system 148 into the atmosphere. Preferably, the working fluid of the teinperature control system 120 is a refrigerant, including cryogenic refrigerants like nitrogen, h.ydrogen, or combinations tll.ereo~ These fluids can be conveniently expelled into the atmosphere unlike some other refrigerants which may adversely affect the environment.
[0189] FIGURES 9A - 9L depict additional embodiments of temperature control systems for controlling the temperature of mold apparatuses. These teinperature control systems may be generally siinilar to the embodiment illustrated in FIGURE 8, except as furtlier detailed below. Where possible, similar or identical elements of FIGURES 8-9L are identified with identical reference nuinerals.
[0190] FIGURE 9A schematically illustrates a teinperature control systein 150, which is a closed loop system designed to control the temperature of the mold apparatus 122 during preform manufacturing. The temperattue control system 150 has a fluid source 152 in cominunication with the mold apparatus 122. The mold apparatus 122 is in commiulication witli a unit 156, which is in conununication with the fluid source 152. To cool the mold apparatus 122, the working fluid can flow clockwise as indicated by the arrow heads.

[0191] The fluid source 152 is colulected to an outlet 170 of a fluid line 166 and is coiulected to the source inlet 128 of the fluid line 130. The fluid source 152 receives fluid from the fluid line 166 and delivers fluid to the fluid line 130. The fluid source 152 can store the worlcing fluid before, during, and/or after a production cycle.
[0192] As illustrated in FIGURE 9A, the fluid line 130 is coiuiected to the fluid source 152 and the mold apparatus 122 in the manner described above. The fluid line 140 is in fluid commtuiication with the mold apparatus 122 and the unit 156. The mold inlet 136 of the line 140 is comlected to the mold apparatus 122, and the outlet 144 of the line 140 is comlected to the unit 156. Fluid passes from the mold apparatus 122 into the inlet 136 and through the fluid line 140 to the outlet 144. The fluid then passes through the outlet 144 and into the unit 156.
[0193] The unit 156 can recondition the fluid so that the fluid can be redelivered to the mold apparatus 122 for continuous flow througli the temperature control system 150. The unit 156 can include a coinpressor and/or heat exchanger. The fluid can flow tllrough a compressor which pressurizes the fluid and then flows through a heat exchanger (e.g., a condenser) that reduces the temperature of the pressurized fluid.
In some instances, the terms "heat exchanger" and "condenser" can be used interchangeably herein. Preferably, the unit 156 outputs a low temperature liquid to an inlet 168 of the fluid line 166. Fluid from the unit 156 can therefore pass through the fluid line 166 into the fluid source 152 by way of the outlet 170.
[0194] The unit 156 can change modes of operation to heat the mold apparatus 122, and the molded articles disposed therein. The working fluid can flow counter-clockwise tluougl-i the temperature control system 150 to heat the mold apparatus 122. In one embodiment, the unit 156 receives cool fluid (preferably a liquid) from the fluid line 166 and delivers a higli teiuperature gas or gas/liquid mixture, as compared to the cool liquid, to the fluid line 140. The high temperature fluid can heat the mold apparatus 122 and article disposed therein. The unit 156 can tllus include an evaporator and/or coinpressor for heating the working fluid. Thus, the Lu1it 156 can be used to change the mode of operation to heat or cool the mold apparatus 122 as desired.
[0195] With continued reference to FIGURE 9A, the temperature control system 150 can cool at least a portion of the mold apparatus 122, whicli in turn cools the plastic in the mold apparatus 122. hi one embodiment, the fluid source 152 delivers refiigerant, such as cryogenic fluid (preferably liquid carbon dioxide or nitrogen), to the fluid line 130 and the mold apparatus 122.' [0196] The liquid passes tlirough a portion of the mold apparatus 122 aaid is delivered to one or more pressure reducing elements 212 (see FIGURE 10). The pressure reducing elements 212 preferably receive tlie liquid at a high pressure and output fluid (e.g., gas or gas/liquid mixture) at a low temperature to the cllamZels in the mold apparatus 122. The pressure reducing element 212 can reduce the temperature of the worlcing fluid passing tllerethrough. The fluid passes tluough and cools portions of the mold apparatus 122, thereby cooling the polyiner in the mold apparatus.
[0197] As shown in FIGURE 9A, the mold apparatus 122 delivers the heated fluid to the fluid line 140, whicli, in tui7i, delivers the fluid to the unit 156 functioning as a compressor and condenser. The unit 156 outputs fluid in the forin of a low teinperatLire liquid to the fluid line 166 and the source 152. 1 [0198] In some einbodiinents, including the illustrated einbodiment of FIGURE 9A, the temperature control systein 150 can have an optional a feedback system 231 for delivering heated fluid from the mold apparatus 122 back into and through the mold apparatus 122. hi operation, fluid in the fluid line 140 passes through the feedback system 231 to mold apparatus 122 via a feedback line 232. Preferably, the tenlperature of the fluid in the feedback line 232 is at a temperature higher than the teinperature of the fluid in the fluid line 130. Different portions of the mold apparatus 122 can be maintained at different temperatures by utilizing both the fluid from the fluid line 130 and the feedback line 232. The fluid in the feedback line may or may not be at a temperature of the melt deposited into the mold apparatus. One or more valve systems can be disposed along the lines 130, 232 to regulate the flow of fluid through the mold apparatus 122. In some embodiments, the heating of the mold apparatus 122 by the utilizing the fluid from the feedback line 232 can be performed wlien the fluid flow from the source 152 to the mold apparatus 122 is reduced or stopped. In some embodiments, the heated fluid from the feedback line 232 can be used to reduce tl1e. rate of cooling of the melt in the mold apparatus 122 to, for exaniple, produce a high degree of crystallinity in the molded article. A variety of temperature distributions can be achieved in the mold by utilizing working fluids at different temperati.ues.
[0199] As discussed above, the teinperature control systein 150 can also heat at least a portion of the mold apparatus 122 by circulating the working fluid in the counter-clockwise direction. Iii one embodiment, the fluid source 152 delivers fluid to the fluid line 166, wllich delivers the fluid to the unit 156. The unit 156 can fiinction as a compressor and can increase the temperature of the working fluid. In some embodiments, the unit 156 can receive a fluid (e.g., a two-phase working fluid) from the line 162. The temperature of the two-phase working fluid can be increased by the unit 156 and then delivered to the line 140.
[0200] The unit 156 delivers heated fluid (e.g., a high temperature gas or gas/liquid mixture) to the fluid line 140. The fluid is then delivered to and passes througli the mold apparatus 122. The fluid passing througli the passageways in the mold apparatus 122 heats one or more portions of the mold, which in turn heats or reduces the rate of cooling of the polyiner in the mold apparatus 122. The fluid is cooled as it passes tluougli the mold apparatus 122 and is delivered to the fluid line 130, which delivers the cooled fluid to the fluid source 152. The fluid source 152 then delivers the fluid to the fluid line 166 as described above. Thus, fluid flows in one direction tl-uougli the temperature control systein 150 to cool the mold apparatus 122 and flows in the opposite direction througli the temperature control systein 150 to heat the mold apparatus 122.
Furtlzer, the flow of fluid can be reversed one or more times during preforin production to heat (e.g., reduce the rate of cooling of the melt) and cool the mold repeatedly as desired.
[0201] The temperature control systein 150 can have a device (not shown) for ensuring that the pressure in the mold apparatus 122 remains at a sufficiently low pressLUe. For example, the device can be a safety valve, blow off valve, or rupture disk that will prevent the pressure in the mold apparatus 122 fiom reaching critical limits, especially as the working fluid is heated within the mold apparatus 122 and iuldergoes a phase change (e.g., from liquid to gas).
[0202] If the working fluid passing through the mold apparatus 122 is a two-phase fluid, the two-phase fluid can reinain at a generally constant temperature. In some einbodiments, the two-phase liquid/gas mixture can be at a generally constant pressure, while absorbing heat and remaining at a relatively low teinperature so long as botlz liquid and gas phases of the working fluid are present. That is, the worlcing fluid in the mold (e.g., in the fluid chamiels) can remain at a somewhat constant temperature as long at least some of the working fluid is in a liquid state. Additionally, the size of the channel can increase in the downstream direction to limit or prevent a teinperature increase of the working fluid as the worlcing fluid is vaporized. If liquid (e.g., chilled water) is circulated through a mold, the temperature of the liquid may increase in the downstreain direction and, thus, may produce a declining cooling efficiency in the downstream direction.
Advantageously, the mold apparatus 122 can be cooled by the two-phase mixture that is at a generally constant telnperature througliout the mold apparatus 122 for eiAianced therinal efflciency and/or more unifoi7n cooling of the molded article.
[0203] In some embodiinents of operation the fluid source 152 stores a refrigerant, such as cryogenic fluid in the form of carbon dioxide, at a teinperature of about 20 C and at a pressure of about 57 bar. The teniperattue of the fluid within the fluid source 152 can be coijtrolled by increasiia.g or decreasing tlle pressure applied to the fluid. For example, the fluid source 152 can contain carbon dioxide at a pressure of 80 bar and a teinperature of about 25 C. If the pressure of tlie carbon dioxide is lowered to 20 bar, the licluid carbon dioxide niay vaporize and lower th.e teni.perature of the liquid/gas mixture to about - 20 C, so long as the cryogenic fluid cornprises liquid carbon dioxide. The carbon dioxide two-phase fluid can be passed, preferably at a relatively high flow rate, tl-irougli the mold apparatus 122. The high flow rate enhances wall contact, asid the vaporization causes a high degree of turbulen.ce resulting in effective heat transfer between the walls of the passageway and the worlcing fluid. Of course, other working fluids can be used to control the teznperature of the mold apparatus 150 in a similar inaini.er.
[0204] The proportion of liquid phase of the worlcing fluid can be increased to increase heat transfer to the working fluid. For example, a second fluid in the liquid phase can llave a freezing poiilt so low that the second fluid will be a stable liquid at most of all of the teinperatures and pressures experienced during the coolillg process. The second fluid can increase tlie rate of cooling of the polyn.zer in the mold apparatus 122.
The first fluid and the second fluid can be delivered together to the mold apparatus 122.
The first fluid can vaporize (at least partially) wliile the second fluid remains a liquid.
Additional fluids witl2 other freezing points can be used to control the temperature of the mold apparatus 122 for a desired application. In view of the present disclosure, a skilled artisan ean select the ntunber and types of worlcing fluids to achieve the desired thernnal characteristics of the worlcing fltiid. Iii some embodiments, a plurality of working fluids can be utilized, wherein the worlcing fluids can be selected to enhance znixing of the fluids. Iiz some einbodirnen.ts, the densities of two or inore of the worlcing fluids can be substantially siznilar to each other to promote even mixing and cooling.
However, in some elnbodinients, the densities of the working fluids can be substantially different from each other.
[02051 The fluid source of the temperature control systems can comprise a plurality of fluid sources. Each of the fluid sources can contain a differeilt working fluid.

For exainple, althougll not illustrated, the temperature control systeni 150 of FIGURE 9A
can have a second fluid source containing a second fluid. The second fluid can have a freezing point that is higher than the temperature of the vaporized fluid from the first fluid source 152, as discussed above. It is conteinplated that additional fluid sources can be added to a.ny of the fluid systeins described herein. Accordingly, any nuinber of fluid sources and working fluids can be used to control the temperature of the mold apparattis.
[0206] FIGURE 9B illustrates a modified tenlperature control system. The temperature control system 150 of FIGURE 9B can have a worlcing fluid (e.g., a refrigerant, cryogenic fluid, and the like) that circulates the closed loop system. The working fluid can flow in the clockwise direction through the systein 150 to provide chilled fluid to the mold apparatus 122. The fluid can flow in the counter-cloclcwise direction to provide a heated fluid to the mold apparatus 122.
[0207] Fluid can pass tllrougll the fluid line 130 to the pressure reducing element 212. The pressure reducing eleinent 212 can comprise one or more valves adapted to produce a change in temperature of the working fluid. The illustrated pressure reducing eleinents cause a pressure drop of the working fluid, thereby reducing the teinperature of the fluid. The pressure drop across the pressure reducing element 212 can be increased to increase the teinperature drop. In some einbodiinents, the pressure reducing eleinent 212 is configured to reduce the pressure of the refrigerant to a pressure equal to or less than a vaporization pressure of the worlcing fluid. When a fluid (e.g., a refrigerant) passes through a pressure reducing element 212, at least portion of the refrigerant is vaporized. The amount of fluid that is vaporized can be selected to achieve a desired teinperature change in the worlcing fluid. The fluid in the line 176 can thus comprise a two-phase fluid (e.g., a gas/vapor mixture), although the fluid in the line 176 can comprise mostly or entirely a gas phase fluid. The fluid line 176 can be insulated to miniinize temperature increases of the working fluid before the working fluid cools a material disposed in the mold apparatus 122.
[0208] With coiitinued reference to FIGURE 9B, the low pressure fluid outputted from the pressure reducing eleinent 212 then passes through a fluid line 176 and enters the mold apparatus 122. Preferably, the fluid enters the inold apparatus 122 as a low pressure and low temperature two-phase inixture coinprising liquid and gas. hi the mold apparatus 122, heat from the mold apparatus 122 is transferred to the two-phase mixttire such that some of the liquid component of the mixture is vaporized as a result of the heat transfer. The working fluid then passes through the fluid line 140 to the unit 156, wliich comprises a compressor 149a and condenser 149b. The coinpressor 149a compresses, preferably adiabatically, the fluid to produce a saturated vapor.
The saturated vapor is then passed to the condenser 149b. The condenser 149b can be a heat exchanger that condenses the fluid as heat is transfei7ed froin the worlcing fluid to the enviromnent. The fluid then passes througll the fluid line 130 and the pressure reducing element 212 to repeat the process for continuous mold cooling. The flow of the worlcing fluid can be continuous, intennittent, etc.
[0209] The teinperature control systein 150 can include an optional bypass system 178 that can be used to obtain the desired characteristics of the fluid delivered to the mold apparatus 1,22. In the illustrated einbodiment, the bypass system 178 can have a fluid line 180 that is comlected to the fluid line 130 and a fluid line 182 that is connected to the fluid line 176. The high pressure fluid in the fluid line 130 can pass tluough the fluid line 180 and the low pressure fluid in the fluid line 176 can pass through the fluid line 182. A valve system 188 can independently control the flow of fluid tluough the lines 180, 182 to adjust the pressure and temperature drop across the pressure reducing element 212. The fluid from the lines 180, 182 can be delivered along the line 230, thereby bypassing the mold apparatus 122. Altenlatively, the bypass system 178 can deliver heated downstrealn fluid in the line 140 to the inold apparatus 122.
Heated fluid can be drawn through the line 230 to the valve system 188. The valve system 188 can deliver the heated fluid directly to the mold or to the line 176 (as shown).
hi some embodiments, the valve system 188 comprises one or more flow regulating valves and one or more puinps or compressors. Thus, the bypass systein 178 can be used to vary the pressure, temperature, and/or flow rate of the fluid that is delivered to the mold apparatus 122.
[0210] The fluid line 182 can also deliver fluid directly to the mold apparatus 122. Althougli not illustrated, the fluid line 182 can be comiected to the mold apparatus 122. Heated fluid in the line 140 can flow through lines 230, 182 and into fluid chaimels in the mold apparatus 122. The heated fluid can be passed through the mold apparatus 122. The heated fluid can heat the mold apparatus 122 as the cool fluid from the line 130 is passed through the mold apparatus 122. Thus, portions of the mold apparatus .122 can be heated by a heated fluid while other portions of the mold apparatus 122 are heated with a cooled fluid. In some einbodiments, the flow of cooled fluid fiom the line 130 is reduce or stopped as the heated fluid from the line 182 flows through the mold apparatus. In operation, the cooled fluid can flow through the "mold apparatus 122 to cool melt disposed witllin the mold apparatus 122. The valve system 188 can stop the flow of heated fluid tluougll the line 182 and the mold apparatus 122. After the molded article is removed fTom the mold apparatus 122, heated fluid can be passed tluougli the valve systein 188, the line 182, and into mold apparatus 122. The heated fluid can limit the fonnation of condensation and/or heat the teinperature of the mold surfaces to facilitate the iujection of melt into the mold cavity or space of the mold apparatus 122.
[0211] Witli respect to FIGURE 9C, the temperature control systein 183 has a mold section 122b that coinprises one or more temperatLUe control elements 181. As used herein, the tenn "teinperature control element" is a broad tenn and is used in its ordinary sense and refers, without limitation, to a passageway, cliannel, temperature control rod (e.g., heating/cooling rods), heaters (e.g., resistance heaters), coinbinations thereof, and the like. Temperature control eleinents can be positioned within molds (including injection molds, coinpression molds, stretch blow inolds, and the lilce) to control the temperature of the mold. The temperature control elements can be strategically placed in the mold for a desired temperattue distribution. For exainple, to iizcrease thermally efficiency, the temperature control elements can be mold towards molding stirfaces of tlle molding apparatus 122.
[0212] The illustrated teinperature control elenlent 181 is in the foim of a fluid passageway. The fluid passageway 181 can conlprise a plurality of fluid chaiulels, such as the fluid chaiuzels 204 illustrated in FIGURE 10. The working fluid, preferably partially vaporized, in the passageway 181 absorbs heat delivered by the mold section 122b, which is heated by the hot polyiner within the mold apparatus 122. The working fluid can flow at a constant or variable flow rate depending on the application.
[0213] The mold section 122a can likewise have one or more teinperatlue control elements siinilar to or different than the teinperature control eleinent of the mold section 122b. In some einbodiments, at least a portion of the mold section 122b can be fonned of a high heat transfer material. The high heat transfer material can be at a location along the fluid passageway 181 where rapid cooling is especially desirable. The high heat transfer material can be proximate to or near the molding surfaces of the mold apparatus 122 to maximize heat transfer. The high heat transfer material can also form the molding surfaces that contact the melt aiid subsequently formed article, although other configurations can be used. The high heat transfer material and the teinperature control element 181 in combination can rapidly and efficiently control the temperature of the mold apparatus 122. However, the mold can also be formed partially or entirely of low heat transfer materials.
[0214] The temperature control system 183 can operate as cuz open loop system, closed loop systein, and combinations thereof. Iii one mode of operation, tlie system 183 operates as an open loop system. The worlcing fluid can flow througli the passageway 181 and into the lines 136, 140 and cali be vented off by the exhaust system 148. A valve system 179 can be used to selectively control the flow of fluid to the exhaust system 148. For example, the valve system 179 can be operated to maintain a target presstue in the fluid lines and/or mold apparatus 122. The target pressure can be equal to or above a predetermined pressure drop across the presslue reducing element 212. For exa.inple, if the working fluid is liquid carbon dioxide, a pressure drop across the pressure reducing device 212 that less than 5 bar could lead to the fonnation of solid carbon dioxide. The valve system 179 can be operated to ensure that the pressure of the working fluid maintains desirable operation of the systein.
[0215] In soine modes of operation, the system 183 can be operated as a closed-loop system. The system 183 can comprise a closed-loop portion 161 that feeds the working fluid back to the fluid source 152. The teinperature coiitrol system 183 cali thus be operated as a closed loop system or a closed loop systein depending on whether the working fluid is suitable for venting to atinosphere.
[0216] Witlz continued reference to FIGURE 9C, the closed-loop portion 161 can comprise a coznpressor 149a and a condenser 149b. The heated fluid in the line 136 can flow through the line 186 (shown in dashed line) to the coinpressor 149a.
The compressor 149a can be in series with the condenser 149b to reduce the teinperature of the fluid delivered to the source 152. The conlpressor 149a and the condenser 149b can cooperate to deliver fluid at a desired temperature and pressiue to the fluid source 152 tluough the line 189. Preferably, the worlcing fluid is delivered to the source 152 at the original pressure and temperature of the fluid in the source 152. In some einbodiinents, the fluid source(s) can be removed from the temperattire control system and the working fluid can be stored in the fluid lines.
[0217] The illustrated closed-loop system 161 can have an optional bypass systenl 163 that delivers heated fluid to some location upstream of the mold apparatus 122. The illustrated bypass system 163 has at least one valve system 163a (e.g., a flow control valve) positioned along the line 163b. The valve system 163a can be operated to let wai7n coinpressed fluid flow through the line 163b. The wartn fluid from the line 163b is mixed with the cool fluid outputted by the pressure reducing elenient 212. The ratio of the fluid from the line 163b and fluid fronl the pressure reducing element 212 can be selected to achieve a target fltiid temperature of the fluid circulating through the mold apparatus 122. Thus, the bypass systein 163 can be used to selectively control the temperature of the fluid delivered to the mold apparatus 122.
[0218] The pressure reducing element 212 can be disposed externlal to the mold apparatus 122 as shown in FIGURE 9C. However, the pressure reducing element 212 can be positioned within the mold apparatus 122. As shown in FIGURE 9D, for example, the pressure reducing eleinent 212 is disposed within the mold apparatus 122.
The pressure reducing eleinent 212 can be positioned aiiy suitable point along the passageway 181. For exainple, the pressure reducing element 212 can be positioned at the entrance of the passageway 181, inside the passageway 181. However, the pressure reducing elenlent 212 can be positioned inside a mold plate leading to the passageway 181, or any otlier suitable location.
[0219] FIGURE 9E illustrates a temperatLU=e control system 183 that has at least one flow separator 131. The line 136 delivers a fluid (e.g., a heated gas/liquid mixture) froin passageway 181 to the phase separator 131 which, in turn, delivers the gas phase fluids to the line 130a and liquid phase fluids to the line 130b. The flow separator 131 can be a membrane separation unit or other suitable device for separating liquid and gas flows.
[0220] The flow separator 131 can have a inembrane that allows certain substances to pass therethrough at a first flow rate aizd other substances to pass tlleretluougll at a second flow rate different tlian the first flow rate. For exainple, and more particularly, such ineinbrane separation unit can be provided with a menlbrane that allows liquids and gases to. pass therethrough at different rates. The effect is that the retentate liquid (e.g., liquid that do not permeate tluough the nleinbraiie) remains on one side of the membrane. The penneate gases pass through the membrane. In tliis marmer, the liquid and gas component of the working fluid are separated. The gas and fluid are then delivered to the lines 130a, 130b. It is contemplated that other types of flow separators can be einployed.

[0221] A compressor 124a and a heat exchanger 127a are positioned along the line 130a so as to deliver fluid to the source 152a at substantially the sanle pressure and temperature as the fluid contained in the source 152a. The flow separator 191 delivers the liquid component to the line 130b. The liquid is delivered to a compressor 124band a heat exchanger 127b, and is retui-lled to the fluid source 152b. Iil some embodiments, a single heat exchanger can be used to cool botll tlie gas phase component and liquid phase components from the flow separator 191.
[0222] Fluids from the fluid sources 152a, 152b flow along the lines 130a, 130b, respectively, and are preferably mixed at the junction 193. The fluid source 152a comprises a first fluid. The first fluid is preferably a cryogenic fluid that will at least partially vaporize as it passes through, the pressure reducing element 212.
The fluid source 152b preferably comprises a second fluid wllich remains a stable liquid as it passes tluougli the pressure reducing element 212. Thus, the passageway 181 can contain one or more different fluids. The first fluid can have a liquid coinponent that vaporizes as it absorbs heat from the mold apparatus 122. The second fluid from the source 152b can reinain a liquid, thus maintaining high therinal loading capabilities.
Alternatively, both fluids can vaporize as they circulate tlirough the mold apparatus 122.
[02231 FIGURE 9F shows the exainple of a temperature control system 183 that comprises a mold apparatus 122 having portions witli different thermal conductivities. The illustrated mold apparatus 122 coinprises a first section comprising a first material and a second section 310 comprising a second material. In some einbodiments, the second material preferably has a thermal conductivity greater than the first material. In some embodinlents, the second section 310 comprises a high heat transfer inaterial. The first section 199 can suiTotuld and thennally insulate the second section 310 to miniinize heat losses from the mold apparatus 122. For exanlple, the first section 199 can be in the forin of a mold plate that houses the second section 310.
The mold plate can comprise steel (e.g., stainless steel or other steel alloys) or other low therinally conductive material.
[0224] The passageway 181 can pass tluough the first section 199 and/or the second section 310. The position of the passageway 181 in the mold apparatus 122 can be selected based on the desired cooling rates and heat distribution of the polyiner in the mold apparatus 122. Additionally, the pressure reducing device 212 can be positioned external to the mold apparatus (shown), witllin the first section 199, within the second section 310, or anotller suitable location for reducing the pressure of the working fluid.
[0225] With respect to FIGURE 9G, the teinperature control systeln 183 comprises one or more sensors coupled to the nlold apparatus 122. In some embodiments, the sensors are configured to detect and send a signal indicative of the temperature of the mold apparatus 122. hl some embodiments, including the illustrated embodiment, a sensor 167 is positioned soniewhat between the passageway 181 and the polynler in the mold apparatus 122. hi some embodinients, the sensor 167 is inteiposed directly between the mold cavity and the passageway 181. hZ some einbodiments, the sensor 167 is positioned near the molding surface of the mold apparatus 122 for accurately measuring the teinperature of the molding surfaces.
[0226) The sensor 167 can send a signal directly or indirectly to a controller 165. The controller 165 can have a stored control program or map and can selectively control the valve 169 based on the signal from the sensor 167. The controller 165 can selectively control the valve 169 based on, for exaniple, absolute mold temperatures, rate of temperature changes, and/or the like to achieve the desired cycle and preforin finish.
Any number of sensors 167 can be positioned in the mold apparatus 122 to measure the temperature of the mold apparatus 122. A plurality of sensors can be positioned throughout the mold is measured the teinperature of the mold apparatus 122 at various locations.
[0227] The valve 169 can be any suitable flow regulator or valve for controlling the flow of fluid to the fluid line 184. The valve 169 can be a solenoid valve which inhibits flow of tlie fluid coming froin the fluid source 152 by way of the line 130.
In other embodiments, the valve 169 comprises a needle valve (preferably an adjustable needle valve). The valve 169 can provide a pressure drop so that a gas/liquid mixttue is delivered to the line 184, which leads to the passageway 181 of the mold section 122b.
[0228] In some einbodiments, at least a portion of the line 184 is disposed within the first section 199 in the fonn of a mold plate. The line 184 can be thennally insulated to inhibit the absorption of heat to the worlcing fluid from the mold apparatus or the surrounding enviroiunent. The line 184 can be insulated with stainless steel, phenolic, nomex, and/or otlier suitable low heat transfer material for enhancing thermal isolation of the fluid flowing th.rougll the line 184. In some embodiments, the line 184 is insulted by an insulating jacket. The insulating jacket can comprise a polymer, foam, or a metal (e.g., steel and its alloys, such as stainless steel). Advantageously, an insulator can limit or prevent the deposition of moisture (e.g., condensation) on fluid lines. The insulated line 184 reduces or limits temperature changes of the working fluid passing tl-irough tlie line 184 for increased thermal efficiency. As the fluid passes tluougll the passageway 181 it absorbs heat coming from the polymer, which causes additional vaporization of the fluid.
As described above, the heated fluid passes through the line 136 to the unit 156, which pressurizes the working fluid. The fluid can have a somewhat elevated temperature. The heat exchanger 197 receives and cools the fluid, which lead to final condensation. The condensed fluid is returned to the source 152. The valve 163a of the bypass system 163 is preferably closed when the worlcing fluid flows cloclcwise tlirougll the temperature control system 183 and cools the mold apparatus 122.
[0229] The tenlperature of the mold apparatus 122 can be raised for at least a portion of the production cycle. For exanlple, the temperature of the mold section 122 can be raised to prevent the formation of condensation on the mold surfaces.
The temperature of the mold surfaces can be raised before injection of the polyiner into the mold cavity in order to prevent fonnation of moisture on the Inold surfaces forming the mold cavity.
[0230] To wann the mold apparatus 122, the controller 165 can reduce or stop the flow of fluid tluough the valve 169 and can pernzit fluid flow through the valve 163a of the bypass system 163. The wann coinpressed fluid in the bypass line 163b is fed back into the passageway 181 to heat the molding surfaces, and preferably niiniinizing the formation of condensation.
[0231] When the mold surfaces of the mold apparatus 122 are exposed to atinospheric air, the temperature of the mold surfaces can be maintained at or above a dew point temperattire to limit the formation of condensation. The controller 165 can operate the valves 163a, 169 to maintain the temperature of the mold surfaces at a preset temperature preferably at or above the dew point. hi some enzbodiments, the mold surfaces can be preheated to aid the spreading of melt through the mold cavity. After the melt fills the mold cavity, the mold surfaces can be cooled at various rates to fonn articles with a particular finish.
[0232] The controller 165 can close the valve 163a and open the valve 169 to cool the mold surfaces before, during, and/or after the polymer has been injected into the mold cavity of the mold apparatus 122. The fluid in the line 184 can be at a relatively low pressure because the valve 163a is closed, thus introducing a fluid inixture with minimum teinperature and maxiinuin cooling efficiency to the chaiuiel 181.
[0233] High conductivity materials can be used for rapid teinperature changes of the mold apparatus 122. During the molding process, if the mold surfaces are relatively cool, the leading portions of the melt can travel the fiirtllest distance along the mold cavity and thus may be significantly cooler than the otlier portions of the melt (e.g., the polyiner in the vicinity of the gate). The non-unifonn cooling rates can lead to less than optimtun polymer properties. Tllus, during portions of the production cycle, certain sections of the mold apparatus 122 can be cool for portion(s) of the molding process and relatively wann for otller portion(s) of the injection process. To reduce production cycle times, the temperature cllanges in the mold can be relatively fast. The temperature and/or flow rate of the cooling fluid can vary considerably during the production cycle for different applications.
[0234] The materials fonning the mold apparatus 122 can be chosen to achieve the desired amount of crystallinity in the article. For example, the polyiner adjacent to the second section 310 can a can be rapidly cooled to fonn a polyiner with a low degree of crystallinity. Thus, the polymer near or contacting the second section 310 can coinprise mostly or entirely ainorphous material. The first portion 199 can coinprise a material with a lower thennal conductivity to reduce the rate cooling of the polyiner thereby increasing the degree of crystallinity of the polyiner. For example, the first portion 199 can be configured to form a crystalline neck finish of preforin.
[0235] With reference to FIGURE 9H, a temperature control system 183 is illustrated. The illustrated passageway 181 extends througll the first section 199 and the second section 310. As discussed above, first section 199 can be formed of a material having a higlier thermal conductivity than the second section 310 such that the first section 199 cools the polyiner at a lower rate than tlie second section 310.
In altenlative embodiments, the second section 310 and the first portion 199 can both be made of materials having similar conductivities. For example, the second section 310 aild the first section 199 can comprise materials having a high thennal conductivity. Low conductivity materials (e.g., inserts) can be positioned between the first section 199 and the second section 310 for thennal isolation. hi some einbodiments, the second section 310 and the first section 199 each comprises high heat transfer materials.
Each of the second section 310 and first section 199 can have one or more temperature sensors to measure the temperature of the mold apparatus 122.
[0236] With respect to FIGURE 91, the temperature control system 183 has a passageway 181 that may or may not pass through both sections 310, 199. Fluid from the fluid source 152 is delivered to a flow metering system 155. The flow metering system 155 can be a dosing system that includes a plurality of valves that cooperate to delivered doses of fluid to the mold apparatus 122. The illustrated flow metering system 155 can be used to deliver a precise amount of fluid witll desirable characteristics to the mold apparatus 122. The flow metering systein 155 can comprises a first valve 169a (e.g., a solenoid valve), a tank 157, and a second valve 169b (e.g., a solenoid valve).
The control lines 171a, 171b provide coininunication between the coii.trol unit 165 and the valves 169a, 169b, respectively. The controller 165 can operate the first valve 169a and the second valve 169b to accurately fill the tank 157 with a certain amount of fluid. The control unit 155 can be any suitable controller for selectively operating the valves 169a, 169b.
[0237] To cool the mold apparatus 122, the control unit 165 opens the valve 169a and fluid is delivered to the dosing tank 157. After the dosing tanlc 157 is filled witli a desired amount of fluid, the control i.uiit 165 opens the valve 169b and the fluid from the dosing tank 157 is delivered to the line 184. The capacity of the dosing tank 157 can be selected based on the desired amount of fluid delivered to the line 184. The tank 157 can be partially or completely filled depending on the desired ainount of fluid delivered to the mold apparatus 122. Thus, a precise amount of fluid can be delivered to the line 184 and ultimately to the mold apparatus 122.
[0238] The flow metering systein 155 is able to produce a rapid sequence of "inicro-pulses" of fluid that expands in the line 184 and the passageway 181 to cool the mold apparatus 122. The sensor 167 monitors the temperature of mold apparatus 122 and delivers a signal to control unit 165. The control unit 165 determines the number and timing of doses that are delivered to the line 184. The nuinber of doses of fluid delivered to the mold apparatus 122 can be increased or decreased to increased or decrease rate of cooling in the inold apparatus 122. When the molded article is demolded, the valve 169b can limit or prevent the circulation of working fluid through the mold apparatus 122 to minimize the fonnation of condensation on the mold surfaces.
[0239] Optionally, the mold apparatus 122 can coinprise one or *more temperature control elements for heating portions of the molds. The illustrated mold apparatus 122 colnprises a temperature control elenlents in the fonn of a heater 173 (FIGURE 91). The illustrated heater 173 is a resistance heater positioned within the mold apparatus 122. As such, the heater 173 can heat a desired portion of the polymer in the mold apparatus 122. hl some embodiments, the heater 173 can heat (including reducing the rate of cooling) a portion of mold apparatus 122 as the cooling fluid is delivered through the passageway 181. Tlius various portions of the mold apparatus 122 can be at any desired temperature. Otller suitable teinperature control devices can also be used to control the temperature of the mold apparatus 122.
[0240] A plurality of temperatLUe coiitrol systems can be comzected together.
As shown in FIGURE 9J, the teinperature control system 219 coinprises a plurality of ii2dependent flow circuits. The illustrated teinperature control system 219 comprises a first temperatttre control system 150' and a second temperature control system 150". The unit 156 can be a heat exclzanger configured to excliange heat between the working fluids of the first teniperature control system 150' and the second temperature control system 150". In some embodiments, the first teinperattire control system 150' can be configured to cool a first mold apparatus 122'.
[0241] A second temperature control system 150" can be used to cool the second mold apparatus 122" as the first temperature control system 150' heats the mold apparatus 122'. The heated fluid delivered from the line 140 to the tulit 156 can be cooled by the fluid passing tluough the tenzperature control systein 150'. The flows in the temperature control system 150', 150" can be reversed to change the mode of operation of the systems 150', 150".
[0242] The temperature control systems described herein can be combined and modified to acliieve the desired tllermal perfonnance. The fluid lines are schematically illustrated as a single line. However, the fluid lines can comprise a plurality of ltunen and/or a plurality of houses.
[0243] FIGURES 9K and 9L illustrate a plurality of mold apparatuses that are coiui.ected by a coiulecting line 213. Fluid wanned in one mold apparatus can be used to heat anotlier mold apparatus. For exainple, cool fluid can be used to cool a first mold apparatus. The fluid can be heated as it passes througli the first mold apparatus and then can be used to heat a second mold apparatus. For example, the second mold apparatus can be heated when the article is removed from the second mold apparatus.
During a second portion of the production cycle, fluid can be heated as it passes through the second mold apparatus and can then be used to heat a first mold apparatus.
[0244] Any number of mold apparatuses can be comzected together by any number of fluid lines depending on, e.g., the production cycles. The illustrated system comprises a first mold apparatus 122' and a second mold apparatus 122"
coiulected by a fluid line 213. In some embodiments, the line 217' and mold apparatus 122' can be part of a teinperature control system described above. Similarly, the line 217" and mold apparatus 122" can be a part of a temperature control system described above.
[0245] With continued reference to FIGURE 9K, during a first period of time, a working fluid is delivered through the line 217' to the mold apparatus 122' to cool at least one article therein. The working fluid is heated as it passes through the mold apparatus 122'. The heated fluid can flow through the coimecting line 213 to the mold apparatus 122". The heated fluid can then heat the mold apparatus 122". The mold apparatus 122" can be heated to limit or prevent the formation of condensation on the inold stirfaces, heat the surfaces of the mold to enhance the flow of melt tllrough a mold cavity, produce crystalline material, and the like.
[0246] During a second period of time, a working fluid is delivered through the line 217" to the mold apparatus 122" to cool at least one article therein, as shown in FIGURE 9L. The working fluid is heated as it passes through the mold apparatus 122".
The heated fluid can flow through the connecting line 213 to the mold apparatus 122'.
The heated fluid can then heat the mold apparatus 122'. The mold apparatus 122' can be heated to limit or prevent the fonnation of condensation on the mold surfaces, heat the surfaces of the mold to eil.ian.ce the flow of melt tlllougll a mold cavity, produce crystalline material, and the like.
[0247] The features, components, systeins, subsysteins, devices, materials, and methods of the temperature control systems in FIGURES 8-9L can be mixed and matched by one of ordinary slcill in this art in accordance witli. principles described herein. Additionally, one or more check valves, pressure sensors, flow regulators, fluid lines, temperature sensors, detectors, and the like can be added to the teinperature control systems as desired.

C. Methods and Auparatus for Iniection Moldin2 [0248] Monolayer and niultilayer articles (including packaging sucli as closures, prefonns, containers, bottles) can be fonned by an injection molding process.
One method of producing multi-layered articles is referred to herein generally as overmolding. Multilayer prefonns can be forined by ovennolding by, e.g., an inject-over-inject ("101") process. The name refers to a procedure wliich uses injection molding to inject one or more layers of a material over an existing prefonn or substrate, which preferably was itself made by inj ection molding. The tenns "overinj ecting"
and "overmolding" are ttsed herein to describe the molding process whereby a layer of material is injected over an existing preform. In an especially preferred einbodiment, the overinjecting process is perfonned wl2ile the underlying prefonn has not yet fully cooled.
Overinjecting may be used to place one or more additional layers of materials, such as those comprising bainier material, recycled PET, foam material, or other materials over a inonolayer or multilayer prefonn.

[0249] Molding may be used to place one or more layers of material(s) sucli as those comprising lamellar material, PP, foam material, PET (including recycled PET, virgin PET), barrier materials, phenoxy type th.ermoplastics, combinations tliereof, and/or otller materials described herein over a substrate (e.g., the underlying layer). In some non-limiting exeinplaiy einbodiments, the substrate is in the form of a preform, preferably having an interior stirface suitable for contacting foodstuff. The temperattue control systems can be utilized to control the temperature of prefonns fonned by these molding processes. The temperature control systenis can also be used when fonning a single monolayer preform, as described below in detail.
[0250] Articles made by a molding process may comprise one or more layers or portions having one or more of the following advantageous characteristics:
an insulating layer, a barrier layer, a foodstuff contacting layer, a non-flavor scalping layer, a high strength layer, a compliant layer, a tie layer, a gas scavenging layer, a layer or portion suitable for hot fill applications, a layer having a melt strengtli suitable for extrusion. hl one einbodiznent, the monolayer or multi-layer material comprises one or more of the following materials: PET (including recycled and/or virgin PET), PETG, foain, polypropylene, phenoxy type thennoplastics, polyolefins, phenoxy-polyolefin thennoplastic blends, and/or combinations thereof. For the sake of convenience, articles are described primarily with respect to prefonns, containers, and closures.
[0251] FIGURE 10 illustrates a prefeiTed type of mold apparatus 132 for use in methods wlz.ich utilize overmolding. The mold apparatus 132 can fonn a layer on the prefoim 30 to form a multilayer prefoinz, such as the pref6nn 50 of FIGURE 3.
The teinperature control systems described herein can be used to control the teinperature of the mold apparatus 132, and the other molds described below.
[0252] The mold apparatus 132 coinprises two halves, a cavity section 192 and a core section 194. The cavity section 192 conlprises a cavity in which the prefonn is placed. The core section 194 and the cavity section 192 are movable between a closed position and an open position. The preforin can be a monolayer preform (illustrated) or a nlultilayer preform. The preform 30 is held in place between the core section 194, which exerts pressure on the top of the prefonn and the ledge 196 of the cavity section 192 on which the support ring 38 rests. The neck portion 32 of the preform 30 is thus sealed off fxom the body portion of the prefonn 30. Iiiside the preforin 30 is the core 198. As the prefonn 30 sits in the mold apparatus 132, the body portion of the prefonn 30 is coinpletely surrounded by a void space 200. The space 200 is fonned by outer surface of the prefonn 30 and a cavity molding surface 203 of the cavity section 192. The preform, tlius positioned, acts as an interior die core in the subsequent injection procedure, in which the melt of the overmolding material is injected tllrougli the gate 202 into the void space 200 to fonn an outer layer of the prefonn.
[0253] The cavity section 192 and/or the core section 194 have one or inore temperature control elements 204. The teinperature control elements 204 are in the fonn of a plurality of passageways or cllaiuzels for controlling the temperature of the melt and the preforni 30. Fluids flowing tlhrough the chanriels 204 can, for exalnple, cool the mold apparatus 132, which in tum cools the injected melt. In the illustrated embodiment of FIGURE 10, the cavity section 192 has a plurality of channels 204 wliile the core section 194 also has a plurality of chaan~nlels 206. A plurality of pressure reducing elenients 212 are positioned upstrealn of the chaiuiels 204, 206. The pressure reducing elements 212 are positioned within the cavity section 192 and the core section 194.
However, the pressure reducing elements 212 can be positioned outside of the cavity section 192 and/or the core section 194. In the illustrated einbodiment, there is an tipper outlet 134 and a lower outlet 134 that deliver fluid to the charuiels 206, 204, respectively.
[02541 With continued reference to FIGURE 10, the mold outlets 134 can have) a flow regulator 214 in fluid cominLulication with the pressure reducing elements 212. The flow regulator 214 can be a valve system that selectively controls the flow of fluid to the channels 204. A plurality of conduits 216 can provide fluid flows between the flow regulator 214 and the presaure reducing elements 212. Each flow regulator 214 can selectively perinit or inhibit the flow of fluid fiom the outlet 134 into the coiiduits 216 and into the znold apparatus 132. Iii one embodiment, the flow regulator 214 can be solenoid valve, eitl-ier actuated electronically or pneumatically, to pennit or inhibit the flow into the mold apparatus 132. hi various other embodiments, the flow regulator 214 can be a gate valve, globe valve, or other suitable device that can control the flow of fluid.
A controller (e.g., the controller 218 of FIGURE 9A) can conunand the flow regulator 214 to permit or ii-Alibit the flow of fluid to the chaiulels (e.g., channels 204 and/or 206).
The flow regulator 214 can stop the flow of fluid tluough the mold apparatus 132 for intennittent fluid flow. Optionally, the flow regulator 214 can provide different fluid flow rates to each of the conduits 216.
[0255] Fluid from tlie conduits 216 passes tlirough pressure reducing eleinents 212 and into the channels 204 in the mold apparatus 132. Altliough not shown, the outlet 134 can feed fluid directly to the pressure reducing elements 212. As discussed above, there can be a temperature drop across tlie pressure reducing elements 212. In the illustrated einbodiment of FIGURE 10, there is a pressure drop across the pressttre reducing elements 212 so that the teinperature of the fluid in chaiuiels (e.g., channels 204) is at or near a desired temperatiire. The teinperature drop is preferably caused by a reduction in pressure across the pressure reducing elements 212.
[0256] Advantageously, during operation of the temperature control system, the pressure of the working fluid (e.g., a cryogenic fluid such as nitrogen) caxi be substantially less than'the pressure of non-cryogenic fluid (e.g., Freon).
Wllen the working fluid of the temperature control systems is a cryogenic fluid such as supercritical carbon dioxide (C02) or nitrogen (N2), the mold apparatus does not have to be able withstand the high pressures that are typical of non-cryogenic systeins. Thus, the low pressure molds cooled with cryogenic fluids may be less costly to produce than the high pressure molds that are cooled with non-cryogenic fluids. Additionally, because the cryogenic fluid in the mold apparatus is at such a low pressure, there may be less lealcage f-rom the mold apparatus and/or other sections of the teinperature control system. The non-cryogeni.c refrigerants based systezns may require expensive hennetic seals to ensure that the working fluid does not escape to the environinent.
[0257] With continued reference to FIGURE 10, the worlcing fluid can undergo a phase change as it passes througli the pressure reducing elements 212. A
portion of the fluid can change phases, i.e. vaporize to gas, as it passes through the pressure reducing elements 212 and the enthalpy of the gas can fiirther cool the cllannels in the mold. Iii one embodiment, at least a substantial portion of the liquid from the outlet 134 changes to gas as it passes through the pressure reducing eleinents 212.
In one embodiment, a controller 218 (FIGURE 9A) commands the pressure reducing elements 212 to increase or decrease the pressure change across the pressure reducing elements 212 in order to ensure the proper temperature of fluid in the chann.els of the mold apparatus 132.
[0258] In some einbodiments, for example, the fluid upstream of the pressure reducing elements 212 is liquid (e.g., liquid CO2 or N2) at about 40 bars to about 80 bars.
In some einbodiments, the fluid upstream of the pressure reducing elenlents 212 is at a pressure of about 60 bars to about 80 bars. In some embodiments, the fluid upstream of the pressure reducing eleinents 212 is at a pressure of 20 bars, 30 bars, 40 bars, 50 bars, 60 bars, 70 bars, 80 bars, and ranges encolnpassing such pressures. The pressure of the liquid is reduced across the pressure reducing eleinent 212 such that at least a portion, preferably a substantial portion, of the liquid vaporizes resulting in fluid coinprising gas downstream of the pressure reducing elements 212. The gas in the chaimels is preferably at 10 bars or less and will result in a reduced downstreain teinperature of the fluid. Iii some enibodiments, the pressure on the low side of the pressure reducing eleinent is 2 bars, 4 bars, 5 bars, 7 bars, 10 bars, 15 bars, and ranges encompassing such pressures.
For exainple, in some non-limiting einbodiments, the downstreain teinperature of the worlcing fluid inay less tlzan about 10 C, 0 C, - 5 C, -30 C, -60 C, -100 C, -150 C, -175 C, -200 C, and ra.nges encompassing such temperatures. Preferably, the temperature of t11e fluid can be maintained at a suitable teinperature by adjusting the pressure of the fluid in the chaiulels 204, 206. 'hl the illustrated embodiment, a valve 222 is disposed along the mold inlet 136 of the fluid line 140 aiid can selectively perinit or ii121ibit the flow of fluid such that the fluid in channels of the mold apparatus 132 is at the desired pressure aild temperature. A controller can therefore coimnand the pressure reducing elements 212, 222 so that the teinperature of the fluid in the chaiuiels 204 is at the desired temperature.
[0259] Witli continued reference to FIGU.RE 10, the pressure reducing elements 212 caii be proximate to the cavity molding surface 203 to ensure that the cavity rnolding surface 203 is maintained at a relatively low teinperature. As such, the teinperature of the fluid does not substantially change as it nioves through tlie mold apparatus 132 between the pressure reducing elements 212 and the channels 204.
In some einbodiments, the channels 204 are sized to perinit expansion and fiirther cooling of the working fluid. For exainple, the chaiulels 204 can be enlarged in the downstrearn direction to allow expansion of the worlcing fluid. It is conteinplated that the pressure reducing eleinents 212 can be positioned at other suitable locations for delivering fluid to the chamlels within the mold apparatus 132. For example, the pressure reducing eleinents 212 can be positioned outside of the mold apparatus 132 (e.g., see FIGURE 9B).
[0260] The chann.els 204, 206 are located in the mold apparatus 132 such that heat is transfei7ed to the fluid flowing through the charu-iels 204, 206 to cool the mold apparatus 132. As used herein, the term "chaa.ulel" is a broad teiin and is used in its ordinary sense and refers, witllout liinitation, to any structure or elongated passage tliat defines a fluid flow path for effectively controlling the teinperature of a mold. In some instances, the tenns "eharmels" and "passageways" are used interchangeably herein.
Liquids can flow along tlie length of the channels for high theimal loads. In some einbodiments, the chatulels can be a diffi.ision passage configured to produce a pressure drop. The diffi.tsion cliannels can be positioned downstream of the pressure reducing element. The chamiels can have varying cross sections along their lengths. For example, the chamlels can have a cross sectional area that increases in one direction.
hi some embodiments, if a two-phase fluid flows tlirougli a channel, the cross sectional area of the channel can increase in the downstream direction to accommodate an increase in the voluine of the fluid as some of the liquid coinponent vaporizes due to the absorption of lleat. Thus, the working fluid may not rise in pressure due to the absorption of heat. In some einbodiments, however, the fluid chaiulels can have a somewhat constant cross sectional area or otller suitable configuration.
[0261] Aii imler portion 220 of the cavity section 192 is disposed between one or more chamlels 204 and the cavity molding surface 203 and is designed to perinit efficient heating or cooling of the cavity molding surface 203. The terins "cavity molding surface" and "cavity surface" may be used interchangeably herein. In some einbodiments, the imier portion 220 of the mold comprises a high heat transfer material to cool rapidly the material engaging the cavity molding surface 203.
[0262] As used herein, the term "high heat transfer material" is a broad tenn and is used in accordance with its ordinary meaning and may include, without limitation, low range, mid range, and high range high heat transfer materials. Low range high heat transfer materials are materials that have a greater thermal conductivity than iron. For exainple, low range higli heat transfer materials may have a heat conductivity superior to iron and its alloys. High range high heat transfer materials have tlleiinal conductivity greater than the mid range materials. For example, a material that comprises mostly or entirely copper and its alloys can be a high range heat transfer material. Mid range high heat transfer materials have thermal conductivities greater than low range and less than the high range high heat transfer materials. For exainple, AMPCOLOYOO alloys, alloys coinprising copper and beryllium, and the like can be mid range high heat transfer inaterials. In some embodiments, the higli heat transfer m.aterials can be a pure material (e.g., pure copper) or an alloy (e.g., copper alloys). Advantageously, high heat transfer materials can result in rapid lieat transfer to reduce cycle times and increase production output. For example, the higli heat transfer material at room temperature can have a tlzermal conductivity more than about 100 W/(inK), 140 W/(mK), 160 W/(mK), 200 W/(inK), 250 W/(inK), 300 W/(inK), 350 W/(inK), and ranges encompassing such tllennal conductivities. In some embodiments, the higli heat transfer material has a theimal conductivity 1.5 times, 2 tiines, 3 times, 4 times, or 5 times greater than iron.
[0263] To enhance temperature control, the temperature control elements can be used in combination with high heat transfer material. For example, one or more teinperature control elements can be positioned near or within the high heat transfer material to maximize heat transfer between the mold surfaces and the teinperature control elernents. For exainple, the liigli heat transfer can foi7n at least a substantial portion mold niaterial interposed between the one or more temperature control elements and the molding surfaces.
[0264] The high heat transfer material may or may not form the molding surface that contact the melt. For example, a layer of material can be positioned between the high heat transfer material and the nzolding cavity. To protect the high heat transfer material, a thin layer of material (e.g., titanium nitride, hard chrome, and otlier materials harder than the high heat transfer material) may be deposited on the high heat transfer material and foiin a hard molding surface 203. Such a protective layer is preferably less tlian about 0.0254 min (0.001 inches), 0.127 inm (0.005 inches), 0.254 inin (0.01 inches), 1.27 inin (0.05 inches), 2.54 nun (0.1 inches), and ranges encoinpassing such thiclcllesses.
The protective layer can iinprove mold life while also providing rapid heat transfer from the melt to the high heat transfer material.
[0265] The high heat conductivity alloys can be used for rapid heating and cooling. The high heat conductivity alloys can achieve both high and low temperatures along the mold surfaces in contact with the polyiner. Additionally, the high heat conductivity alloys can produce a generally flat teinperature profile over most of the mold wall for efficient heat flow. This allows for increased flexibility of lnold design. For example, the temperature control elements can be moved away from the mold surfaces without substantially effecting the cooling/heating capacity of the temperature control elenients because heat can be rapidly conducted through the higll heat transfer material.
[0266] Time from injection to demolding, which may strongly influence cycle time, can be different for mold cooling and post-cooling operations. In the absence of post-cooling, the preforin has to remain in the mold until the bulk of the polyiner has cooled to a temperature profile which will not cause structural instability after deinolding.
After demolding, the periphery of the preforin is not actively cooled and is relZeated by the heat coming fiom the warm interior of the article. Because the bulk of the polymer has to cool down and polyiners can have low lleat conductivity, the time to demold, and thus cycle time, can largely depend on the prefonn diniensions (e.g., the prefonn's wall thiclu-iess). Thus, time to demold and cycle time can be increased as the preform's wall thiclcless is increased.

[0267] High conductivity mold materials caii be employed to reduce cycle times. For producing preforins with liigher wall thiclalesses, high conductivity mold materials may produce a negligible reduction of the cycle time, as heat flow is dominated by the largest heat resistor, which in this case is the bulk polyiner itself.
Nevertheless, molds comprising high heat conductive mold materials can be used for mold cooling processes.
[0268] If a post-cooling operation is utilized, demolding can be done at an earlier stage as structural stability of the molded article is primarily needed to withstand the inechanical forces dtuing demolding. The stnictural stability molded article can be quickly demolded from the mold. At the moment of demolding, due to the chilling effect of the mold wall the peripheral layers of the molded article have already fallen to lower temperatures while the interior of the article is a soft liquid. For example, there can be a steep temperature rise between the periphery of the prefonn and the interior of the prefonn. The peripheral low teinperature region of the polyiner mechanically stabilizes the preform at demolding. The mechanical strength of the preforin can therefore depend on the teinperature gradient dtuing the cooling process. For example, the cooled periphery of the preform (e.g., a cooled outer shell) depend on the peripheral temperature gradient. The peripheral temperature gradient is mainly a fiuiction of the mold surface temperature. A mold utilizing a high conductivity alloy and a cooling means, such as cold cooling fluid, can produce a low mold surface temperature, thus a steeper temperature gradient and tllerefore a mechanically stable "shell" faster than, e.g., a steel mold. Thus, the combination of high heat transfer material and a low temperature cooling fluid (e.g., refiigerants including cryogenic fluids) are especially useful for post-cooling processes.
[0269] Utilizing a low temperature cooling fluid in combination witli a steel mold will only bring moderate success. The poor heat conductivity of steel produces a steep temperature gradient in the mold, thereby leading to a high surface teinperature in the mold. Utilizing a higli conductivity mold alloy in combination with a non-refrigerant cooling fluid, such as water, will result in a generally flat teinperature gradient in the mold. Additionally, the teinperature of the mold surface can be warmer than mold surfaces cooled with refrigerants. Thus, if a mold utilizes steel or non-refrigerant cooling fluids, the formation of a rigid shell, which allows early deinoldiiig, will be delayed and th.erefore increase cycle time.

[0270] The cavity section 192 comprising the high heat transfer material can provide high heat transfer rates that may not be achieved with traditional molds.
Traditional molds are typically made of steel that is subjected to high therinal stresses upon rapid aiid large ten-iperature changes. The tliern7al stresses may cause strain hardening of the steel and may drainatically reduce mold life. For example, cyclic thei7nal loading can cause fatigue which eventual comproinises the structural integrity of the molds. Steel and some other typical mold materials may be unsuitable for the extreme teinperature loads and tliernial cycles. Thus, these materials may be unsuitable for use with refrigerants, such as cryogenic fluids. Copper has a high thei7nal conductivity and can undergo rapid teinperature cllanges. However, copper is a relatively soft material that has a relatively low nlechanical strength and hardness and, thus, lnay not be able to withstand high clanip forces experiericed during molding processes. Also, if copper forn.is the molding surfaces, the copper can become wonl and rougliened after extended use and can result in improperly fonned molded articles. However, some higll heat transfer materials are much more suitable for rapid and large temperature changes while also having improved mold life. The high heat transfer materials can withstand cyclic theiinal loading with limited ainounts of dainage due to fatigue. The high heat transfer materials can be hardened material for an iinproved life as compared to copper.
Advantageously, the high heat transfer material can transfer heat at a higher rate than steel and other traditional mold materials. Tlius, cycle times can be reduced due to the thennal properties of high heat transfer materials.
(0271] Additionally, because the fluid in the charuiels 204 is at such a low pressure, the channels can be located extremely close to the cavity molding surface 203.
For exainple, the distance between one or more of tlie channels 204 and the cavity molding surface 203 ean be less then about 5 cm, 3 cm, 2 cm, 1 cm, aiid ranges encoinpassing such distances. In one embodiment, the distance between one or more of the channels 204 and the cavity molding surface 203 can be less then about 1.5 cm. In yet another embodiment, the distance between one or more of the chaiinels 204 and the cavity molding surface 203 can be less then about 5 inm. In yet another embodiment, the distance between one or inore of the chaiuiels 204 and the cavity molding stirface 203 can be less then about 3 mm. The combination of the high heat transfer materials and the location of the channels 204 can provide extremely quick teinperature changes of the cavity molding surface 203. If high heat transfer material is einployed in the mold apparatus 132, the channels 204 can be moved away from the cavity molding sttrface 203 wllile still providing effective temperature control of the surface 203. Other types of temperature control eleinents than cllaiulels (e.g., heaters) can be similarly positioned in the mold apparatus 132.
[0272] As illustrated in FIGURE 10 and FIGURE 11 (an elevational partial cross-sectional view of the cavity section 192), the chaiulels 204 are generally aiulular channels, preferably substantially concentric witll the cavity molding surface 203 to ensure that the thicluless of the portion 220 between the cavity molding surface 203 and the channels 204 is substantially uniforin. The heat transfer between the melt and the fluid in the chamlels can be increased by decreasing the distance between the cllaiulels 204 and the cavity molding surface 203. Those slcilled in the art recognize that the charulels 204 can have various shapes and sizes depending on desired heat distributions in the mold apparatus 132. Tii the illustrated embodiinent, the chaimels 204 have a substantially circular cross-sectional profile. In other embodiments, the cliaiulels 204 can have a cross-sectional profile that is generally elliptical, polygonal (including rounded polygonal), or the like. hi one einbodiment, the cavity section 192 has less than about then about ten chaiuiels 204. In another eznbodiment, the cavity section 192 has less than about seven channels 204. Iii another embodiment, the cavity section 192 has less than about four chaiulels 204. The number and placement of chamlels 204 can be selected for efficient cooling of the mold apparatus 132.
[0273] With reference to FIGURE 11, fluid F flows from the conduit 216 through the pressure reducing element 212 and into the chaml.el 204. The fluid F
(preferably a two-phase flow) is split into two fluid flows and passes through the two semi-circular portions of the channel 204 towards the conduit 240. The fluid F
then passes through the conduit 240 to the mold inlet 136 and into the fluid line 140. Heat is transferred between the fluid F in the chamlels 204 and the mold cavity section 192 because of the temperature difference between the fluid F and the walls of the channels 204. If the working fluid F is a two-phase flow, the liquid component of the flow can undergo a phase change become a gas as the fluid absorbs heat. Advantageously, the temperature of the fluid F can remain generally constant along the chamiels 204, so long as the fluid F comprise liquid.
[0274] If the teinperature of the chaiuiels 204 is at a temperature higller than the teniperature of the fluid in the channels 204, there will be heat transferred to the fluid F. T11us, the mold apparatus 132 can be cooled as heat is transferred to the fluid F. If the temperature of the fluid F in the chaiulels 204 is higlier than the temperature of the cllamiels 204, heat will be transfeiTed to the chaiulels 204. The flow rate of the fluid F
can be increased to increase the heat transfer between the fluid F and the mold apparatus 132.
[0275] Witli reference again to FIGURE 10, the core section 194 has the core 198 that is hollow. The core 198 has a wall 244 having a generally uniform thiclGless proximate to the neck portion 32 of the preforin 30. The thiclazess of the wall 244 necks down to a distal portion having a generally uniform tliiclaiess. A temperature control arrangeinent 246 is disposed in the core 198 and comprises a core channel or tube 248 located centrally in the core 298 which preferably receives fluid F from the fluid line 130 and delivers fluid F directly to a base end 254 of the core 198. The fluid F
passes tlirough a pressure reducing element 260, preferably an expansion valve, and into a chamiel 208.
In the illustrated embodinlent, the charuze1208 is defined by the outer surface of the core chaiuiel 248 and an inner surface 210 of the wall 244 of the core. The fluid F
worlcs its way up the core 198 from the base end 254 though the channe1208 and exits tluough an output line 270. In one einbodiment, the fluid F in the core channe1248 is a liqttid that is vaporized as it passes through the presstire reducing eleinent 260. At least a substantial portion of the fluid in the channel 208 can be gas, preferably at a lower teinperature tlian the temperature of the fluid in the core charulel 248, to ensure that the core 198 is inaintained at a suitable temperature. - Ii1 some elnbodiments, the pressure reducing eleinent is positioned outside of the core 198. Tlnis, a gas or two-phase flow can be delivered to the core channe1208.
[0276] Different fluids can be used to control the teinperature of the cavity section 192 and the core section 194. In one embodiment, for example, the fluid line 130 caa.i comprise two tubes where one of the tubes delivers CO2 to the cavity section 192 and the other tube delivers N2 to the core section 194. Tllus, the teinperature control systems can use multiple fluids to maintain desirable temperatures in the mold apparatus 132. In other einbodinzents, similar fluids can be used in the cavity section 192 and the core section 194. For exainple, CO2 can be the working fluid in the cavity section 192 and the core section 194.
[0277] Pulse temperature control can be utilized to periodically heat or cool the mold apparatus 132. hl some embodiments, pulse temperature control coinprises pulse cooling. For pulse cooliulg, fluid can be pulsed through the mold apparatus 132 for periodic temperature changes. When the moldable material is disposed in the mold apparatus 132, chilled fluid can circulate tllrough the apparatus 132 to cool the polyiner material. During the reduced flow period of pulse cooling, the flow of chilled fluid is substantially reduced or stopped. In one embodiment, the flow regulator 214 is controlled to stop the flow of fluid tlirough the mold apparatus 132. The flow regulator 214 can independently stop or reduce the fluid flow into each of the conduits 216. In anotlzer einbodiment, the valve 222 can be operated to stop or reduce the flow of the fluid tlirough the mold apparatus 132.
[0278] The reduced flow period preferably corresponds to wlien the mold apparatus 132 is einpty and/or during non-use of the mold apparatus 132 (e.g., during repair periods). For example, after the preform is at a desired temperature, the core section 194 and the cavity section 192 can be separated, as shown in FIGURE
24, and the prefonn can be removed from the mold apparatus 132. While the core section 194 and cavity section 192 are separated, the flow rate of the fluid through the mold apparatus 132 is reduced to iiAlibit the foz7nation of eondensation on the surfaces of the mold. The flow of chilled fluid can be reduced before or after the core section 194 and the cavity section 192 are separated.
[0279] Advantageously, pulse cooling efficiently uses fluid fronl fluid source and can result in reduced cycle time aiZd properly foi7ned prefonns. The temperature control systeni may be an open loop with a fluid source having a limited supply of fluid.
The refrigerant is efficiently used during manufacturirlg periods that require heat transfer to the refrigerant, such as for cooling prefoi7ns. The freeluency of replacing the fluid source is reduced because fluid is used for cooling the prefonn and is not used wllen, for example, the mold apparatus 132 is empty.
[0280] As mentioned above, the pulse cooling can reduce condensation that foi7ns on the preforin molds during prefoi7i1 production. Condensation can foim on the molding surfaces when moisture in the air contacts the mold surfaces, which are at a low teznperature (i.e., the dew point or condensation fonnation tenZperature).
When the temperature of the air is lowered to its dew poin.t, condensation can forin on the mold surfaces. During the preform manufacturing process, the surfaces of the prefonn mold may be exposed to the air (e.g., after the preform has been removed from the inold but before the mold has been injected with melt). Conventional cooling systems may be continuously passing chilled water througli the mold causing the teniperature of the surfaces of the mold to reach the condensation forination temperature resulting in the fonnation of condensation. In otller words, while the surfaces of the mold are exposed to the air, the continuous cooling of conventional systeins may lower the surface teinperature of the mold such that inoisture froia.l tlie atmospllere condenses on the surfaces of the mold. This can interfere with the prefoiin nlanufacturing process. For exainple, condensation can contact the injected melt and inhibit the flow of the melt tluotigll the mold and tlierefore causes improperly foz7ned prefoi7ns.
[0281] Advantageously, pulse cooling is used to reniove heat from the melt while liiniting the fonnatioii of condensation on the surfaces of the mold.
The reduced flow period of the pulse cooling can co~.-respond to wlien the surfaces (e.g., the core surface 201 and the cavity molding surface 203) of the mold apparatus 132 are exposed to the air so that the surfaces are not at sufflciently low temperatures to cause the forination of condensation. Tllus, the prefonn can be rapidly cooled thereby redticing the cycle tiine without fonning condensation on the slufaces of the mold apparatus 132.
[0282] The mold apparatus 132 of FIGURE 10 can be used to produce prefornzs having thin walls with l'ow residual stresses. In one embodiment, the melt can be injected into the space 200 defined by the uncoated prefonn and the cavity molding surface 203, whicli are distanced to fol7n preforins witll thin walls. The temperatures of the surfaces 201, 203 are sufficiently high so that the melt injected into the space 200 remains in a liquid state as it passes along space 200. A reduced flow of the chilled fluid can ensure that the teinperature of the surfaces 201, 203 is sufficiently high for proper flow of the melt. In one embodiznent, to ensure that the melt passes easily tlirough the space 200, the surfaces 201, 203 cati be heated by a heated flow through the chaiu-iels 204. After the melt flows into the space 200, the flow of fluid can then be reversed to cool the inelt. Thus, the temperature coirtrol systezn can facilitate the flow of the melt into the inold and then can rapidly cool the melt resulting in reduced cycle times and prefoi7ns witli low residual stresses. Additionally, the melt can be injected into the mold at a lower injection pressure because of the high temperatu.res of the inold's surfaces facilitating spreading of the melt.

[0283] With continued reference to FIGURE 10, the core 198 can be very slender while providing rapid cooling of the melt. The teinperature control aiTangeinent 246 caii be utilized for substantial heat loads even though a low ainount of fluid flows tlirough the core 198. Advantageously, the low voluinetric flow rates allow asz increased thiclaless of the wall 244 to ensure that the core 198 is properly aligned with tlle cavity inolding surface 203 duri.ng the molding process. h-i some embodinzents, a portion of the core 198 for molding the preform has a length equal to or greater than about 7 cin, 8 em, 9 cm 10 cm, 11 cm, 12 cm, 13 cm and an average outer diameter equal to or less than about 1 cm, 1.5 cin, 2 cm, 2.5 cm. The length and diaineter can be selected based on the prefonn design. The length of the core corresponds to the portion of the core that molds the interior surface of the prefoini. T11tls, the length of the core generally corresponds to the distance from the opening of the preforin to the interior surface of the prefonn forming the end cap. The diaineter of the core is the average outer diameter of the portion of the core that fonns the prefozni. hi some embodunents, the core 198 has a length greater than about 11 cm and an ottter diameter of less than about 2 cm.
Preferably, the core 198 has a length to diameter (L/D) ratio equal to or greater than about 4, 4.5, 5, 5.5, 5.8, 6, 6.5, 7, 8, 9, 10, 11, 12, 13, and ranges enconlpassing such ratios. In some embodiinents, the core 198 has an L/D ratio greater than about 5. In yet another embodiinent, the core 198 has an L/D ratio greater than about 7. Tl1us, the core 198 can have a high L/D ratio because of tlie tenzperature control arrangement 246 having liigh heat transfer capabilities.
[0284] Due to the thermal capabilities of refiigerants, the channels in the core 198 can be smaller than water passages in conventional cores furtller allowing higher L/D
ratios. Conventional cores may not be rigid enough to fonn tllin walled prefoin7s because of their thin core walls. These conventional cores may inove during the molding process resulting in preforms that will likely have weak spots or other defects that could affect container performance. Additionally, the pressure reducing device 260 can be smaller than niany of the conventional valves used in typical cold-water bubblers.
[0285] The thickness of the wall 244 can be increased because of tlie reduced size of the chaiulels and valve within the core 198, tliereby increasing the rigidity of the core 198. The increased rigidity of the core 198 can ensure that the sttrface 201 of the core 198 is generally concentric with the surface 203 of the cavity section 192. The coneentric surfaces result in the production of prefoi7ns that have generally unifoim.i wall thiclalesses. Thus, the mold apparatus 132 can be used to produce the long, small diaineter articles wit11 thin wall sections that would not otherwise be manufactured by injection molding processes.
[0286] With continued reference to FIGURE 10, the core section 194 has channels 206 that are in fluid cominunication with the fluid lines 130, 140.
The core section 194 has chaiuiels and valves similar to the cavity section 192. The temperature of the core section 194 is maintained in a similar maiuZer as the cavity section 192 a.nd therefore will not be discussed in fitrther detail.

[0287] The melt, as well as the uncoated prefoim, is cooled or heated by fluid circulating in chaiuiels 204 and 206 in the two halves of the inold.
Preferably the clrculatzon in charmels 204 is completely separate fi-oni the circulatioil of fluid in the chainiels 206. Additionally, althougll not illustrated, cold water-bubblers can be used to cool the core 198 illustrated in FIGURE 10.
[0288] FIGURE 12 illustrates a niodiZed injection mold that can be used to znalce a multilayer preforms. To finther reduce condensation on the mold apparatus 132, the tenlperature control system can have the feedback line 232 (see FIGURE
9A), wliich is in fluid coinintulication witll the fluid line 140 and the mold apparatus.
The teniperattire of the fluid in the fluid line 140 is suf.ficiently high such that the fluid in the fluid line 140 caii be utilized to lleat portions of the nlold apparatus 132.
The channels 204 can be used to reduce the teinperature of portions of the znold apparatus 132 at different rates by passing fluid at different temperatures through different channels 204.
One or more of tlie channels can contain heated fluid while one or more of the chaim.els contain cooled fluid. Alternatively, heaters (sucli as resistance heaters) can be employed to heat portions of the prefoiin to, e.g., cause crystallization. Thus, the chaiua.els and the flow fluid can be used to obtain the desired temperattire distributions through the mold apparatus 132.
[0289] In the illustrated einbodiment, heated fluid frozn the fluid line 140 passes tlirough the feedback line 232 and througll the upper cliaiu-iel 204 while the cooling fluid from the fluid line 130 passes through the otlier channels 204. The teinperature of the upper portion of the preform body is higher than the teinperature of the lower portioii of the body portion of the preform. Similarly, altllough not illtistrated, heated fluid frozn the feedback line 232 can pass tllrough one or more of the cliamlels 206 while the cooling fluid from the fluid line 130 can pass tluough the other chaiuiels 206.
[0290] With reference to FIGURE 13, a preferred embodiment of the mold apparatLis 132 having a mold core 298 and associated mold cavity 300 are shown. The illustrated mold apparattts 132 is configured to produce a monolayer preform.
Channels 302 are formed just below the surface 304 of the mold cavity 300. The cliaiulels 302 can be formed in a spiral fashion or in any other configttration for pennitting flow through the inold apparatus 132. A gate area 306 of the cavity 300 is defined near a gate 308 and an insert 310 of a material with especially higll lleat trarlsfer propel-ties is disposed in the cavity at the gate area 306. Thus, the iiljected prefoltn's gate area/base end 314 is cooled especially quickly.

[0291] The core 298 is liollow and has a wall 320 of generally unifonn thiclaless. The outer surface of the wali 320 can define a core molding surface. A
teinperature control arrangement 330 is disposed in the hollow core 298 and comprises a core chaiulel or tube 3321ocated centrally in the core 298. The pressure reducing element 212 is located at the distal end of the chaiuiel 332. Fluid F passes tlu-ougll the pressure reducing elenlent 212 and is delivered to a base end 322 of the core 298.
Preferably, the pressure reducing element 212 provides a pressure reduction such that the fh.iid F in the cllannel 332 comprises liquid and the fluid is delivered by the pressure reducing element 212 to the base end 322 preferably comprises gas, or a liquid/gas mixture.
Since the base end 322 is the first point of the core 298 contacted by this fluid F, the fluid is coldest and most effective at this location. Thus, the gate area 314 of the injected preform is cooled at a faster rate than the rest of the prefonn. Fluid injected into the core at the base end 322 proceeds along the lengtli of the core 298 and exits througll an output line 334. A
plurality of ribs 336 are arranged in a spiral patteni around the core tube 332 to direct fluid F along the core wall. Fluid F works its way up the core from the base end 322 and exits through an output line 334. The core chamzel 332 is held in place by ribs 336 extending between the tube and the core wall 320.
[0292] To enliance the cooling effect of the core 298 on the imier surface of the prefornn and especially to enh.ance the cooling effect of the core 298 at the prefonn's gate area/base end 314, the core 298 is preferably substantially hollow, having a relatively thin unifonn wall 320. Preferably, this uniform thickn.ess is between 0.254 cm and 0.762 cm (0.1 inch and 0.3 inches) and is most preferably about 0.508 cm (0.2 inches). The wall 320 at the base end 322 of the core 298 may by thiiuier thari the rest of the core wall 320 because the tliin wall aids in rapidly communicating heat away from the molten gate area 314 of the injected prefonn.
[0293] In other embodiments wliere greater crystallinity and less crystalline gradient are desired, molds are paired witlz modified cores. In the modified cores, the fluid circulation in the cores is modified suclz that, for the portions to fonn the crystalline prefonn parts, the fluid circulation is iuidependent and at a relatively higher temperature, or the flow of chilled fluid is restricted or altered in these regions such that the teinperature of the surface of the core in the portion which fonns the crystalline portion of the prefonn is higher tlian that in the body regions. Alternatively, the relevant portions of the core may be heated by other means as described above. Use of cores having these characteristics allows for a greater degree of crystallization towards and/or at the iiuier surface of the preform in the neck, neck finish and/or neclc cylinder area and a lesser crystalline gradient between the irmer surface and the outer surface in these areas.
[0294] The cavity section 404 has several chaimels 302 through which a fluid, preferably a chilled gas or liquid/gas mixture, is circulated. The cavity section 404 can conlprise high heat transfer material to increase thennal communication between the melt and chaiuiels 302. The cavity section 404 cmi comprise a mold plate that comprises high heat transfer material.
[0295] The neclc finish mold 402 of FIGURE 13 is configured to foi7n at least a portion of the preforin. The neck finish mold 402 can coinprise high heat transfer material. For example, the neclc finish mold 402 can comprise more tlian about 5%, 20%, 50%, 70%, 80%, and 90% and ranges encompassing these amounts of high heat transfer material by weiglit. In some embodiments, the necic finish mold 402 coinprises mostly or entirely high heat transfer material, such as copper and its alloys (e.g., AMPCOLOYOO
alloy). The neck finish mold 402 can be formed of nzore than one material (e.g., bimetallic) or fonned of a single material. When high heat transfer material forins the neclc finish mold, the melt can be rapidly cooled so that a somewhat stable outer layer is forined on the preforin, so that the pr.eforin can be ejected from the mold.
This outer layer eggshell-lilce layer and may be relatively thin and suitable for pei7nitting demolding of the preform. Preferably, the preforin can be removed from the mold without damaging the preforin, even though the inner portions of the preforin may be very soft.
The preform can be removed from the mold when the iiuler and outer portions are both relatively cool. The eggshell-like layer pennits design flexibility. The outer layer functions as a protective layer tliat allows further cooling of the interior portions of the preforin subsequent to demolding. The prefoz7n can have thiclc and/or thin neck cylinders because of cooled outer layer and the ease of demolding. Even if the interior portion of the neck cylinder comprises a hot, soft polyiner, the prefomz can be demolded, thereby reducing cycle time.
[0296] The neck finish mold 402 can have one or more teinperature colztrol elements 403 for cooling and/or heating the molded material. The illustrated neck finish mold 402 comprises a plurality of teinperature control elements 403 in the fonn of chaiuzels in which a fluid circulates. A portion 411 the neck finish mold 402 is positioned between the chamiels 403. The portion 411 preferably forms at least a substantial portion of the neck finish mold interposed between the plurality of fluid chann.els 403 and the mold cavity or space 300. In some embodiments, the portion 411 preferably comprises high heat truisfer material for higli heat flow through the neck finish mold 402. The tenns "niold cavity" and "mold space" may be used interchangeably herein.
[0297] The fluid circulation in charulels 403, 302 are preferably separate and independent. The fluid F circulating tluough the core section 400 is also separate from both ch.aiulels 403, 302. However, a fluid source or single coolant source may provide the fluid for the core section 400, the channels 302, aald/or the cliannels 302.
[0298] Theniial isolation of the cavity section 404, neck finish mold 402 and core section 400 is achieved by utilizing inserts 406 having low thermal conductivity.
However, materials having low thennal conductivity should not be used on the molding surfaces which contact the preform. Examples of preferred low thermal conductivity materials include heat-treated tool steel (e.g. P-20, H-13, stainless steel, etc.), polyineric inserts of filled polyainides, nomex, air gaps and minimtun contact shut-off sLUfaces.
[0299] To produce prefonns with a crystalline neck finish, the fluid in the channels 402 can be warmer thaii the fluid in the portions of the mold used to forin non-crystalline portions of the prefoirn. To produce prefonns witll anlorphous neck finishes and body portions, all of the chamlels can contain relatively cool fluid. In some embodunents, the portions of the mold which fonn the crystalline portions of tlie prefonn, (corresponding to neck finish inold 402) contain a heating apparatus placed in the neck, neck finish, and/or neck cylinder portions of the mold so as to maintain the higher temperature (slower cooling) needed to promote ciystallinity of the material during cooling. Such a heating apparattis includes but is not liinited to heating coils, heating probes, and electric heaters. A feedback systeni can also deliver heated fluid used to heat portions of the inold to form crystalline material.
[0300] FIGURE 13A illustrates a neck finish mold 402a that comprises a first portion 401a and a second portion 419a. The first portion 401a aiid the second portion 419b can have different thermal conductivities. In some einbodiments, the first portion 401a has a thennal conductivity greater, preferably substantially greater, than the second portion 419a. The first portion 401 a preferably coinprises a high heat transfer material (e.g., a mid or higli range high heat transfer material). The second portion 419a can comprise a low thennally conductive material, such as tool steel. Such a neck finish mold can have one or more temperature control elements. The illustrated neck finish mold 402a has a plurality of temperature control elements in the form of fluid channels 405a.
Some exeinplary embodiments of neck finish molds may have temperature control systems 405a that include one or more of the following: chaiuiels, heat/cooling rods, bubblers, heaters (e.g., electric heaters) and combinations tllereof.
Preferably, the higli heat transfer material of the neck finish mold 402a is proximate to or forins the niolding surface which contacts the melt that is injected into a mold cavity. The illustrated neck finish mold 402a is configured to inold tlv-eads of a preform, although the neck nlolding surface can be configured to inold other types of neclc finishes.
[0301] Optionally, the neck finish mold 402a can have one or more portions 409 that can reduce heat transfer between the neck finish inold 402a and an adjacent cavity section and/or core section. Tlius, tllennal isolation of one or more portions of a prefonn can be achieved. During operation, the first portion 401a can be at a first ternperattue and the second portion 419a cati be at second temperature. The neck finish mold 402a may tllus selectively control the temperature of the neck of the prefonn to produce, e.g., crystalline neck finishes, necle finishes witll an egg-shell finish or layer, and the like.
[0302] In some embodiments, a portion 399 of the neclc finish mold 402a nearest the mold cavity has a length L and can conlprise more than about 5%, 20%, 50%, 70%, 80%, atid 90% of high heat transfer material by weiglit. That is, the portion 399 is the portion of the neck molding finish 402a within the distance L fiom tlie mold cavity.
The lengtl-i L of the portion 399 can be less than or equal to about 0.25 inch, 0.5 inch, 1 inch, 1.5 inches, and ranges encompassing such lengths. In some embodiinents, the length is greater than or equal to about 1.5 iilches, 2 inches, 2.5 inches, and ranges encoinpassing such lengths. In view of the present disclosure, a skilled artisan can select the length L suitable for foinling the neck finish mold 402a.
[0303] In some embodiments, the neck finish mold 402a comprises at least 5%, 20%, 30%, 50%, 60% 80%, 80%, 90% by weight of high heat transfer material.
A
substantial poi-tion of the neclc finish mold 402a extending between the teinperature control element(s) and the neck molding surface can coinprise high heat transfer material.
The higli heat transfer material preferably forms the neck molding surface for efficient therinal connnunication. The neck molding surface can be configured to fon.n one or more threads, flanges, recesses, or other structures for engaging a closure as mentioned above. The illustrated neck finish mold 402a is designed to mold threads of a prefoiin.
In some einbodiinents the neck finish mold 402a is configured to mold an outer stirface of a prefonn without any closure engaging structures. Threads or other structures can be ad.ded to the preforni in a subsequent process. Of course, the neck finish mold can be a split ring that is movable between a first position for inolding a portion of a prefoiin and a second position for deinolding the preform.
[0304] FIGURES 13B-13F illustrate embodiments of neclc finish inolds that are similar to the neck mold finish 402a, except as described below. FIGURE

illustrates a neclc finish mold 402b that has a first portion 401b that forms aii upper surface 413 and lower surface 415 of the neclc mold f nish 402b. The first poition 401b preferably comprises higll heat transfer material. A temperature control element 405b in the foi7n of a heating/cooling rod is positioned within the neclc finish mold 402b, preferably positioned within the first portion 401b. Additional temperature control eleinents (e.g., chan.nels, rods, heaters, etc.) can be positioned within the first portion 401b.
[0305] Witll reference to FIGURE 13C, a neclc finish mold 402c has a:Crst portion 401c that extends into the second portion 419c. A tenlperature control system 405c can be positioned within the first portion 401c to cool effectively the melt, eveii though the tenlperature control systen2 405c may not be proxiinate to the molding surface 407c.
[0306] With reference to FIGURE 13D, the neck finish mold 402d coinprises a phirality of portions 401d, 410d' comprising high heat tran.sfer material that have different or similar thermal conductivities. Each of the portions 401d, 401d' can have one or inore temperature control elements 405d. A portion 409d is positioned between the portions 401d, 401d' for thermal isolation of the portions 401d, 401 d' .
T11us, the portions 401d, 401d' can be at the same or different temperatures to precisely control the teniperature of the prefornn.
[0307] FIGURES 13E aiid 13F illustrated additional einbodiments of neck fmish niolds having a plurality of teinperature control elements. The illustrated neck finish mold 402e has a temperature control element 405e in the forin of a heating/cooling rod and a channel 405e' positioned within the portion 401e. FIGURE 13F
illustrates a neck finish mold 402f comprising a plurality of a heating/cooling rods 405f and a plurality of channels 405f. As such, the temperature control elements may or may not be positioned within high heat transfer material. It is contemplated that the neclc finish molds of FIGURES 13A-13F can be used with the molding systenls (e.g., the injection and coinpression molding systems) described herein. Neck finish molds can thus be bimetallic or formed of a single material. The type and location of materials can be selected to achieve the desired heat flow through the neck finish mold.
Various types of temperature control eleinents can be used to control the temperature of the neclc finish molds.
[0308] Referring to FIGURES 13, 14, and 15, an air insertion system 340 is shown fonned at a joint 342 between meznbers of the mold cavity 300. A notch 344 is forined circumferentially around the cavity 300. The notch 344 is sufficiently small that substantially no nlolten plastic will enter during melt injection. Aii air line 350 coiuiects the notch 344 to a source of air pressure and a valve regulates the supply of air to the notch 344. During melt injection, the valve is closed. When injection is coinplete, the valve is opened and pressurized air A is supplied to the notch 344 in order to defeat a vacuunl that may forin between an injected prefonn and the cavity wall 304.
Additionally, similar air insertion systems 340 may be utilized in otller portions of the mold, such as the thread area, for example but without limitation.
[0309] FIGURE 16 is a cross-section of an injection mold core having a double wall neck finish portion. The mold is configured to produce a monolayer preform that may or may not be ovei=inolded. In some einbodiments, the core 299 is configured to achieve greater crystallinity of the neclc portion of an injected prefoiln.
The mold of FIGURE 16 is similar in constitiiction to the mold described above wit11 reference to FIGURE 13 and includes a core section 400, the cavity section or body mold 404, and the neck finish poi-tion 402. The channel or tubes 302, 403 spiral around the core 299. The mold cooling system can be optimized for the niold cavities by arrailging channels 302 in a spiral arrangement around the mold cavity 300 and just below the surface 304.
[0310] The core 299 of FIGUR.E 16 includes a double wall portion 408 generally adjacent to the neck finish portion 402 of the mold. An iiuler wall substantially inhibits circulating fluid F from coming into contact with the outer wal1412 of the core 299 in the region proximate to the neck finish portion 402 of the mold. In addition, an insulating space 414 is defined between the imler wall and the outer wall 412.
Accordingly, the insulating space 414 reduces the cooling effect of the circulating fluid F
on the neclc portion of a prefonn within the mold cavity 300, thereby increasing the crystallinity of the resulting prefonn and reducing the crystallinity gradient between the outer surface and the ii 7.er surface of the resulting preform.
[0311] The irmer wall 410 of the modified core 299 may optionally include one or more openings 416. These openings 416 pennit circulating fluid F to enter the insulating space 414. Preferably, the size of the openings 416 are configtired sucli that a liinited ainount of circulating fluid F enters the insulating space 414. Such a constrLiction provides a greater cooling effect on the neck portion of the resulting preforin than when no fluid is permitted within the insulating space 414, but less cooling than unrestricted contact of the circulating fluid F witli the outer wall 412 of the core 299.
Advantageously, adjustinent of the size and placement of the openings 416 allows adjustinent of the cooling on the neclc portion of the injected prefonn, thereby allowing adjustment of the crystallinity and crystallinity gradient in the neclc portion.
[0312] FIGURE 17 is a schematic representation of another enlbodiment of a core 301, including a modified base end 417 or tip. The mold core 301 of FIGURE 17 is siniilar in construction to the mold described above with reference to FIGURB
13.
[0313] As described above, the end cap portion of the injection molded prefonn adjacent the base end 417, receives the last portion of the melt streazn to be injected into the mold cavity 300. Thus, this portion is the last to begin cooling. If the PET layer has not sufficiently cooled before the overinolding process talces place, tlie force of the barrier material melt entering the mold may wash away some of the PET near the base end 417 of the core 301. To speed cooling in the base end 417 of the core in order to decrease cycle tiine, the modified core 301 includes a base end 442 portion constru.cted of an especially high heat transfer material, preferably a high heat transfer material, such as AMPCOLOY or other copper alloy. Advantageously, the AMPCOLOY
base end 442 allows the circulating fluid F to withdraw heat frozn the injected preform at a higller rate than the renlainder of the core 301. Such a construction allows the end cap portion of the prefonn to cool quiclcly, in order to decrease the necessary cooling time and, thus, reduce the cycle time of the initial prefoinl injection.
[0314] The modified core 301 illustrated in FIGURE 17 generally coinprises an upper core portio7.i 418, substantially as illustrated in FIGURE 13, and a base end portion 442-constructed of a high heat transfer material, including, but not limited to, a beryllium-free copper alloy, such as AMPCOLOY. A pressure reducing eleinent 430 is at the distal end of the core channel 332, as described above. That is, the pressure reducing eleinent 430 can provide a fluid pressure drop. As in FIGURE 13, the present core channe1332 is operable for delivering circulating cooling fluid F to the base end 442 of the core 301.
[0315] The core 301 is substantially hollow and defines an iiuler diaineter D
and wall thicluless T. The upper core portion 418 includes a recessed step 420 having a diaineter Ds which is greater than the imler diaineter D of the core 301. The upper core portion 418 can be for molding a neclc portion of a preform. The base end portion 442 includes a flange 422 having a diaineter DF wllich is smaller than the diaineter Ds of the step 420. The difference between the diameters Ds and DF of the step 420 and flange 422, respectively, is preferably between about 0.0254 mm and 0.635 nun (0.001 and 0.025 inches). More preferably, the difference is between about 0.254 nun and 0.381 nnn (0.010 and 0.015 inches). When the base end portion. 442 is placed concentrically within the upper core portion 418, the difference in the diameters Ds, DF results in a gap G being formed between the base end and upper core portions 442, 418. The width W of the gap G is approximately equal to one-half the difference between the diaineters Ds, Dr.
Additionally, the base end portion 442 is preferably about 1.905 cm and 3.175 cm (0.750-1.250 inches) in lengtli.
[0316] Preferably, the modified core 301 is constnicted by starting witli an umnodified core 298 made from a single material, substantially as illustrated in FIGURE
13. The end portion, or tip, of the umnodified core 298 is cut off approximately at the point where the lligh heat transfer base end 442 is desired to begin. A
drilling, or boring, tool may then be inserted from the end portion of the core 301 to ensure that the imler diameter D is coiTectly sized aild concentric with a center axis of the core 301. This also ensures that the wall thiclaless T is consistent tluougllout the portion of the core 301 which is in contact with the inj ected preform, thus ensuring that the cooling of the preforin is consistent as well. Such a method of construction presents a distinct advantage over conventionally fonned cores. In a conventional core, because the length to diameter ratio is large, the drilling tool used to create the hollow inner portion of the core often tends to wander, that is, tends to deflect from the center axis of the core. The wandering of the drilling tool results in a core having an inconsistent wall thiclciless and, thus, inconsistent heat transfer properties. With the above-described method of sizing the iiuier diameter D from the base end of the core 301, the problem of tool wandering is substantially reduced or elinzinated. Therefore, a consistent wall thiclaiess T and, as a result, consistent heat transfer properties are acllieved.
[0317] The upper core portion 418 and base end portion 442 are preferably joined by a silver solder process. AMPCOLOY is a preferred material for the base end portion 442 in part because it contains some silver. This allows the silver solder process to provide a joint of sufficient strength to be useful in injection molding applications.
Preferably,'the soldering process results in a ftill contact joint. That is, solder material is disposed on all of the mating surfaces (424, 426 and gap G) between the upper core portion 418 and base end portion 442. Advantageously, the provision of the gap G

enhances the flow of solder material such that a strong joint is acllieved. In addition, the fitll contact joint is advantageous because it provides for eonsistent heat transfer properties and high strengtll. If the soldered joint was not a full contact joint, any air present in the gap G would result in inconsistent heat transfer tluough the gap G portion of the core 301. Although it is preferred to join the upper core portion 418 and base end portion 442 witli a silver solder process, other suitable joining processes may also be used.
[0318] As illustrated in FIGURE 17, the base end portion 442 of the modified core 301 is preferably of a larger size tlian the final dimension desired (illustrated by the dashed line 428) when it is joined to the upper core portion 418.
Advantageously, this allows for the base end portion 442 to be machined to its desired dimension after assembly to the upper core portion 418 in order to ensure a proper final dianieter and a smootli surface at the transfer from the upper core poition 418 to the base end portion 442.
[0319] Another way to eiihance cooling of the preform's gate area was discussed above and involves forming the mold cavity so that the iruier polyiner layer (e.g., a PET layer) is thiiuier at the gate area than at the rest of the injected preforin as shown in FIGURE 4. The thin gate area thus cools quichly to a substantially solid state and caii be quickly renioved from the first mold cavity, inserted into the second mold cavity, and have a layer of barrier material injected thereover without causing washing of the PET.
[0320] In the continuing effort to reduce cycle time, inj ected preforins are reinoved from mold. cavities as quiclely as possible. However, it may be appreciated that the newly injected material is not necessarily fiilly solidified wllen the injected prefonn is reinoved froin the mold cavity. This results in possible probleins renioving the preforin from the cavity 300. Friction or even a vacutun between the hot, malleable plastic and the mold cavity surface 304 can cause resistance resulting in dainage to the injected preform when an atteinpt is made to remove it from the mold cavity 300 as shown in FIGURE 13:
[0321] Typically, mold surfaces are polished and extremely smooth in order to obtain a smooth surface of the injected part. However, polished surfaces tend to create surface tension along those surfaces. Tlus surface tension may create friction between the mold and the iiijected prefonn whicli may result in possible damage to the injected prefonn during removal from the mold. To reduce sttrface tension, the inold surfaces are preferably treated with a very fine sanding device to slightly roughen tlie surface of the mold. Preferably the sandpaper has a grit rating between about 400 and 700.
More preferably a 600 grit rating sandpaper is used. Also, the mold is preferably sanded in only a longitudinal direction, further facilitating removal of the injected preform from the mold.
[0322] While some of the above-described iinproveinents to mold perfoi7nance are specific to the method and apparatus described herein, those of skill in the art will appreciate that these improvenients may also be applied in many different types of plastic injection molding applications arid associated apparatus. For instance, use of high heat transfer material in a mold may quiclcen heat removal and drainatically decrease cycle times for a variety of mold types and melt nlaterials. Pulse cooling can be used to cool the cores, neck finish portion, and/or the cavity section of the mold. Also, roughening of the inolding surfaces and provides air pressure supply systems inay ease part removal for a variety of mold types and melt materials.
[0323] FIGURE 18 illustrates an injection mold apparatus, similar to those described above, and referred to generally by the reference nuineral 500. The injection mold assembly 500 is configured to produce a monolayer preforin. In the illustrated anangement, the mold 500 utilizes one or more haidened materials to define contact surfaces between various components of the mold 500. As used herein, the tez7n "hardened material" is a broad terln and is used in its ordinary sense and refers, witllout limitation, to any material which is suitable for preventing wear, such as, for example, tool steel. In various embodhnents, the hardened or wear resistant material inay coinprise a heat-treated material, alloyed rnaterial, chemically treated material, or any other suitable material. The mold 500 also uses one or more materials having high heat transfer properties to define at least a portion of the mold cavity surfaces. The mold 500 inay also utilizes the hardened materials (having generally slower heat transfer properties) to produce a preform having regions witli varyiizg degrees of crystallinity, similar to the injection molds described above. Iii some embodiinents, the molds described herein can comprise a hardened high heat transfer material to reduce wear. For example, hardened copper and its alloys can have a hardness and/or strengtli properties (e.g., yield strength, ultimate tensile strength, and the lilce) greater than unhardened pure copper.
[0324] As in the mold arrangenlents described above, the mold assembly 500 coinprises a core section 502 and a cavity section 504. The core section 502 and the cavity section 504 define a parting line P, indicated generally by the dashed line of FIGURE 18, between thein. The core section 502 and the cavity section 504 cooperate to fonn a mold cavity 506, which is generally shaped in the desired final shape of the prefonn. In the illustrated eznbodiment, at least a portion of the mold cavity 506 is defined by a core molding stuface 507 and a cavity molding stuface 509. The cavity section 504 of the mold 500 can define a passage, or gate 508, which communicates with the cavity 506. Aii injection nozzle 510 delivers a molten polyiner to the cavity 506 tlirough the gate 508.
[0325] Preferably, the core section 502 of the mold 500 includes a core member 512 an.d a core holder 514. The core holder 514 is sized and shaped to be concentric about, and support a proximal end of, the core men-iber 512. The core menlber 512 extends from an open end 516 of the core holder 514 and extends into the cavity section 504 of the mold to define an internal surface of the cavity 506 and thus, ari intenlal surface of the final prefonn. The core member 512 and the core holder include cooperating tapered portions 518, 520, respectively, which locate tlie core ineinber 512 relative to the core holder 514.
[0326] Preferably, the core meinber 512 is stibstantially hollow, tllus defining an elongated cavity 522 therein. A core chamlel or tube 524 extends toward a distal end of the core cavity 522 to deliver a fluid, preferably a cooling fluid, to the distal end of the cavity 522. As in the previous arrangements, cooling fluid passes tlirouglZ
the core 524 aild through a pressure reducing element 561, which can be similar to pressure reducing eleinent 212, and is delivered to the end of the core menlber 512, and progresses througli the cavity 522 toward the base of the core ineznber 512. The pressure reducing eleinent 561 can provide a pressure drop in the working fluid similar to pressure reducing element 212 for vaporizing at least a portion of the working fluid. A plurality of tangs 526 extend radially outward from the body of the tube 524 and contact the iiuler surface of the cavity 522 to maintain the tube 524 in a coaxial relationship wit11 the core member 512. Such a construction iill.iibits vibration of a distal end of the tube 524, t11us irnproving the diinensional stability of the prefonns produced by the mold 500.
[0327] The cavity section 504 of the mold 500 includes a neck finish mold 528, a main cavity section 530 and a gate portion 532. All of these portions 528, 530, 532 cooperate to define an outer surface of the cavity 506, and thus an outer surface of the finished prefonn produced by the mold 500. The distal end of the core member coiTelates to the distal end of the cavity 506. The neclc finish mold 528 is positioned adjacent the core section 502 of the mold 500 and cooperates with the core section 502 to define the parting line P. The neclc finish mold 528 defines the threads 534 and neck ring 536 portions of the cavity 506, and thus of the final preforin. Preferably, the neclc finisli mold 528 comprises two semicircular portions, which cooperate to define the neck finish mold of the cavity 506 so that the neclc finish mold 528 may be split apart from one another, in a plane perpendicular to the plazle of separation between the core section 502 and cavity section 504, to permit removal of the finished prefonn froin the cavity 506, as is laiown in the art.
[0328] The niain cavity section 530 defines the main body portion of the cavity 506. Desirably, the main cavity section 530 also defines a plurality of temperature control elements in the foi7n of chaiulels 538, which direct fluid around the main body portion 530 to maintain the ternperattue the prefonn within the cavity 506.
Several conduits 554 receive fluid from the fluid line (e.g., the fluid line 130 shown in FIGURE 8 and FIGURE 9A), and deliver the fluid to the pressure reducing device 558.
[0329] The pressure reducing devices are proximate to the high heat transfer material portion 530b. The fluid passes through the pressure reducing devices 558 and is delivered to the channels 538. As described above, there can be a pressure drop across the pressure redticing devices 558 resulting in low teinperature fluid, preferably a gas or liquid/gas mixture, in the channels 538. The fluid passes through the charulels 538 and removes heat from the mold 500 and passes through the conduits 560 and into the fltiid line 140. Ii-i the illustrated embodiment, narrow passages 562 coiuiect the chaiulels 538.
Fluid can pass between the chaiuiels 538 by passing tlzrough the passages 562.
The cliaimels in the mold 500 can be diffusion passages that cause a pressure drop downstream of the pressure reducing elements 558. The diffizsion passages can lower the tenlperature of the worlcing fluid. Although not illustrated, the channels 538 can spiral around the cavity molding surface 509.

[0330] The gate portion 532 of the mold 500 is interposed between the main cavity section 530 and the injection nozzle 510, and defines at least a portion of the gate 508. The gate portion 532 defines one large chamlel 540, but any nttmber of smaller chaiulels may alternatively be provided. Fluid can flow tluough the channel 540 of the gate portion 532 to maintain the proper tenlperature of the gate portion 532.
In the illustrated embodiment, the conduit 554 delivers pressurized fluid to the pressure reducing eleznent 558. The temperatLtre and pressure of the fluid is reduced as it passes througli the pressure reducing element 558 and into the charmel 540. The fluid passes tluough the chaimel 540 and heat can be transferred to the fluid. The heated fluid passes out of the chamiel 540 and into the conduit 560, wllicll can be connected to the fluid line 140.
[0331] A controller can be coiuiected to the valves which feed fluid into the cllaiuiels. In one einbodiment, a controller 564 is coiuiected to the pressure reducing elements 558 to command one of more of the pressure reducing elements to stop or vary the flow of fluid. The valves 558, for exainple, can be controlled to produce pulse cooling for rapid cooling of the cavity 506 with mininial forination of condensation on the core surface 507 and the cavity molding surface 509. Iii the illustrated enibodilnent, portions of surfaces 507, 509 forined by high heat transfer materials ca.n be rapidly cooled, especially after the prefonn has been removed from the cavity 506.
[0332] The mold 500 defines a ntunber of contact surfaces defined between the various coinponents that make up the mold 500. For exainple, in the illustrated arrangenient, the core section 502, and specifically the core holder 514, defines a contact stuface 542 that cooperates with a contact surface 544 of the cavity section 504 and, more specifically, the neck finish mold 528 of the mold 500. Similarly, the opposing side of the neclc finish mold 528 defines a contact surface 546 that cooperates with a contact surface 548 of the main cavity section 530.
[0333] The corresponding contact surfaces 542, 544 and 546, 548 intersect the mold cavity 506 and, therefore, it is desirable to maintain a sufficient seal between the contact surfaces 542, 544 and 546, 548 to inliibit molten polyiner witliin the cavity 506 fiom entering between the respective contact surfaces. Preferably, the corresponding contact surfaces 542, 544 and 546, 548 include mating tapered surfaces, generally referred to as taper locks. Due to the high pressure at whicli molten polyiner is introduced into the cavity 506, a large clanip force is utilized to maintain the core section 502 and the cavity section 504 of the mold in contact with one anotlier and maintain a good seal between the contact surfaces 542, 544 and 546, 548. As a result of such a high clainp force, it is desirable that the components of the mold 500 defining the contact surfaces are forined from a hardened inaterial, such as tool steel, for example, to prevent excessive wear to these areas a.nd increase the life of the mold.
[0334] Ftuthermore, as described in detail throughout the present application, it is also desirable that at least a portion of the mold 500 that defines the cavity 506 be made of a higll heat transfer material, such as AMPCOLOY. Such ari arrangement pernnits rapid heat withdrawal froin the znolten polyiner within the cavity 506, which cools the preforin to a solid state so that the cavity sections 502 and 504 may be separated and the preform reinoved from the mold 500. As described above, the rate of cooling of the prefonn is related to the cycle time that may be achieved without resulting in dainage to tlie preform ouce it is removed from the mold 500.
[0335] A decrease in cycle time means that more parts may be produced in a given ainount of time, therefore reducing the overall cost of each preforin.
However, high heat transfer materials that are preferred. for at least portions of the inolding surface of the cavity 506 are generally too soft to withstand the repeated higll clamping pressures that exist at the contact surfaces 542, 544 and 546, 548, for exainple.
Accordingly, if an entire mold were to be fonned from a high heat transfer material, the relatively short life of such a mold may not justify the decrease in cycle time that may be achieved by using such materials. The illustrated mold 500 of FIGURE 18, however, is made up of individual components strategically positioned such that the contact sttrfaces 542, 544 and 546, 548 comprise a hardened material, such as tool steel, while at least a portion of the mold 500 defining the cavity 506 comprises a high heat transfer material to reduce cycle tinle.
[0336] In the illustrated embodiment, the core holder 514 is desirably constructed of a hardened material while the core member 512 is constructed from a high heat transfer material. Furtherinore, the neck finish mold 528 of the mold desirably is constructed of a hardened material. The main cavity section 530 preferably inclttdes a liardened material portion 530a and a high heat transfer material portion 530b. The hardened material portion 530a could be inade fronl the sanie material the neck finisli mold 528. The hardened material portion 530a could be made from a different material than the neck finish mold 528. Preferably, the hardened material portion 530a defines the contact surface 548 while the high heat transfer material portion 530b defines a significant portion of the inold surface of the cavity 506. The higli heat transfer material portion 530b and the gate portion 532 may be made from the saine or different inaterial.
The hardened material portion 530a and the higli heat transfer inaterial poi-tion 530b of the inain cavity section 530 may be coupled in any suitable inaluzer, such as a silver soldering process as described above, for example. Furthennore, the gate portion 532 of the inold 500 is also desirably formed from a high heat transfer material, similar to the inolds described above.
[0337] Iii some embodiments, the neclc finish inold 528 may or lnay not comprise higli heat transfer material. The illustrated neck finish mold 528 comprises a contact portion 802 coupled to an optional insert 801 (preferably a tlueaded insert configured to mold tlueads of a prefonn), wliich preferably conlprises high heat transfer material. The contact portion 802 is positioned adjacent the core section 502 of the mold 500 and cooperates with the core section 502 to define the parting line P.
Preferably, the contact porfion 802 is made from a hardened material, such as tool steel. The threaded insert 801 can define the threads 534 and the neck ring 536 portion of the cavity 506. The tlireaded insei-ts 801 can be coupled to the contact portion 802 and can be formed from a high heat transfer material. Of course, the threaded insert 801 and the contact portion 802 can forzn a portion of the tlueads 534 and/or neck ring 536 and the proximal end of the cavity 506.
[0338] With a construction as described above, advantageously the inold 500 includes hardened materials at the contact surfaces 542, 544 and 546, 548 to provide a long life to the mold 500. hl addition, the niold 500 also includes high heat transfer materials defining at least a poi-tion of the nlolding surfaces of the cavity 506 such that cycle times may be reduced and, therefore, through-put of the mold 500 is increased.
Such an arrangement is especially advantageous in molds designed to fonn prefornns, which are later blow inolded into a desired final shape.
[0339] Anotlier benefit of the mold 500 is that the hardened niaterial neclc finish mold 528 has a lower rate of heat transfer than the high heat traiisfer portions of the mold 500. Accordingly, the neck finish of the prefonn may become semi-crystalline or crystalline, which allows the neck finish to retain its fonned dimensions during a hot-fill process. Furthermo-re, the portion of tlie core meznber 512 adjacent the neck finish mold 528 is preferably high heat transfer material, which rapidly cools the imier surface of the thread finish of the prefonn, thereby allowing the preforin to maintain its fonned dimensions when reinoved from the mold in a less than ftilly cooled state. The cycle time may be reduced by 15%-30% utilizing a tnold construction such as mold 500 in coinparison with a mold made from conventional materials and consti-uction tecluliques.
In addition, certain portions of tlie mold 500 may be replaced, without necessitating replacement of the entire mold section. For example, the core mem.ber 512 and core holder 514 may be replaced independently of one another. In the illustrated embodiment, the valves 558 can be easily replaced by removing the portions of the mold 500. After portions of the mold 500 are removed, the valves 558 are exposed for convenient valve replacement. For exainple, the portion 530b can be removed from the mold apparatus 132 so that the pressure reducing eleinent 558 is exposed for rapid replacement.
Preferably, the pressure reducing eleinents 558 are expansion valves that can be inserted into the mold 500. Valves wit11 different diaineter orifices can be easily and rapidly replaced to produce various prefonns comprising different materials. However, in otller einbodiments the pressure reducing elenients 558 are built in the mold 500.
[0340] The mold 500 can be thermally insulated to reduce heat losses. The illustrated mold 500 can include a portion 577 conzprising a low tliennally conductivity material (e.g., tool steel) that surroi.ulds the cliaiulels 538. The portion 577 can be a therinal barrier that reduces heat transfer between the mold 500 and the surrounding enviromnent. The portion 577 can be a mold plate that llolds various components of the mold. The portion 579 of the core section 502 can likewise coinprise low tlieimally conductivity material to reduce thermal inefficiencies.
[0341] FIGURE 18A illustrates a modified niold siinilar to the mold 500 of FIGURE 18. The neck finish mold 528a of FIGURE 18A coinprises one or more teniperature control elements. The illustrated neck finish mold 528a comprises a pair of teinperature control elements 578 in tlie forin of heating/cooling rods. The teinperature control elements 578 can be spaced from the molding surface 580 by a distance of about 2 cm, 5 em, 10 cm, 15 cm, 20 em, 25 cin, 30 cm, 50 cm, and ranges enconlpassing such distances. The temperature control elements 578 can be in the fonn of cliaiulels, bubblers, and/or other devices to control the temperatLtre of the neck finish mold 528a.
Airy number of teinperatti.re control elements can be spaced about the cavity 506. Of course, cooliiig chamiels or other temperature control elements, such as resistance heaters, can also be disposed in the neck finish mold 528a.
[0342] FIGURES 19 and 20 are a scheinatic of a portion of tlie preferred type of apparatus to make coated preforms in accordance with a preferred embodiment. The apparatus is an injection molding system desigiled to malce one or more uncoated prefonns and subsequently coat the newly-made preforins by over-injection of a material.
FIGU.RES 19 and 20 illustrate the two halves of the mold portion of the apparatus which will be in opposition in the molding machine. The aligiunent pegs 610 in FIGURE 19 fit into their corresponding receptacles 612 in the other half of the mold.
[0343] The mold half depicted in FIGURE 20 has several pairs of mold cavities, each cavity being siinilar to tlie inold cavity depicted in FIGURE
13. The mold cavities are of two types: first injection preform molding cavities 614 and second injection prefonn coating cavities 620. The two types of cavities are equal in number and are preferably arranged so that all cavities of one type are on tlie saine side of the injection bloclc 624 as bisected by the line between the aligninent peg receptacles 612.

This way, every prefonn molding cavity 614 is 180 away from a prefonn coating cavity 620.
[0344] The mold half depicted in FIGURE 19 has several cores, such as core 198, one for each mold cavity (614 and 620). When the two halves wliich are FIGURES
19 and 20 are put together, a core 198 (which can be siniilar to the core 298 of FIGURE
13) fits inside each cavity and seives as the mold for the interior of the prefoi7n for the prefonn molding cavities 614 and as a centering device for the uncoated preforms in preforin coating cavities 620. The cores 198 are mounted on a turntable 630 which rotates 180 about its center so that a core 198 originally aligned with a preforin inolding cavity 614 will, after rotation, be aligned witll a prefonn coating cavity 620, and vice-versa. As described in greater detail below, tlzis type of setup allows a preforzn to be molded and then coated in a two-step process using the sanze piece of equipment.
[0345] It should be noted that the drawings in FIGURES 19 and 20 are merely illustrative. For instance, the drawings depict an apparatus having three inolding cavities 614 and three coating cavities 620 (a 3/3 cavity machine). However, the machines may have any number of cavities, as long as there are equal numbers of molding and coating cavities, for example 12/12, 24/24, 48/48 and the like. The cavities may be arranged in any suitable manner. These and other ininor alterations are contemplated as part of this disclosure.
[0346] The two mold halves depicted in FIGURES 21 and 22 illustrate an embodiment of a mold of a 48/48 cavity maclline as discussed for FIGURES 19 and 20.
Referring to FIGURE 23 there is shown a perspective view of a mold of the type for an oveimolding (inject-over-inject) process in which the cores, sucli as cores 198, are partially located within the davities 614 and 620. The ai7ow shows the moveinent of the niovable mold half 642, on which the cores 198 lie, as the mold closes.
[0347] FIGURE 24 shows a perspective view of a mold of the type used in an overinolding process, wherein the cores 198 are fi.illy witlidrawn from the cavities 614 and 620. When the cores 198 are fully withdrawn from the cavities 614, 620, the inoisture in tlie air may form condensation on each cavity if the teniperature of the surface of the cavity is sufficiently low. The arrow indicates that the ttuntable 630 rotates 180 to move the cores 198 from one cavity to the next. In the illustrated embodiment, the flnid lines 130 and 140 rotate witll the tunltable 630. On the stationary half 644, the cooling for the preform molding cavity 614 is separate from the cooling for the preform coating cavity 620. The fluid line 130 coiuiected to the tunltable 630 and the fluid li.ne 130 connected to the stationary half 644 can be coiulected to the saine fluid source or different fluid sottrces. Tlius, the stationary half 644 and the turntable 630 can have independent teniperature control systeins, stich as the temperature control system 120.
The cooling of the cavities of the stationary half 644 is separate from the cooling for the cores 198 in the movable half.
[0348] The preferred nlethod and apparatus for inalcing multilayer prefonns is discussed in more detail below. Because the methods and apparatus are especially preferred for use in foi7ning nlultilayer bottles comprising certain preferred materials, the physical characteristics, identification, preparation and ei-Aiancement of ttle preferred materials is discussed prior to the preferred methods and apparatus for working with tlie materials.
1. Preferred Overmolding (Inject-over-Inject) Processes [0349] The overmolding is preferably cat7ied out by using an injection molding process using equipment similar to that used to foim the uncoated preform itself.
A preferred mold for overmolding, witll an uncoated preform in place is shown in FIGURE 10. The mold coinprises two halves, a cavity section 192 and a core section 194, and is shown in FIGURE 10 in the closed position prior to overinj ecting.
The cavity section 192 comprises a cavity in whiclz the uncoated prefonn is placed. The support ring 38 of the preform rests on a ledge 196 and is held in place by the core section 194, which exerts pressure on the support ring 38, tlius sealing the neck portion off from the body portion of the prefonn. The cavity section 192 has a plurality of tubes or channels 204 therein whicli carry a fluid as discussed above. Preferably the fluid in the chaiuiels circulates in a path in which the fluid passes into the cavity section 192, through the chaiuzels 204, and out of the cavity section 192. In a closed loop systenl, the fluid is passed back into the cavity section 192 after the fluid reaches a desired teinperature. The circulating fluid serves to cool the mold, wliich in turn cools the plastic melt which is injected into the mold to fonn coated or uncoated preforins. Of course, the fluid can flow through an open loop system, as described above.
[0350] The core section 194 of the mold comprises the core 198. The core 198, sometimes called a mandrel, protrudes from the core section 194 of the mold and occupies the central cavity of the preforin. In addition to helping to center the prefonn in the mold, the core 198 cools the interior of the preforin. The cooling is done by fluid circulating tln-ough chamlels in the core section 194 of the mold, most iznportantly tlv-ougll the length of the core 198 itself. The channels 206 of the core section 194 work in a mainler similar to the chamiels 204 in the cavity section 192, in that they create the portion of the patli tlhrough which the cooling fluid travels which lies in the interior of the mold half.
[0351] As the preforin sits in the inold cavity, the body portion of the preforin is centered witlZin the cavity and is completely surrounded by a void space 200. The preforni, tllus positioned, acts as an interior die core in the subsequent injection procedure. The melt of the ovennolding material, which in a preferred embodiment coniprises a barrier material, is then introduced into the mold cavity from the injector via gate 202 and flows around the preform, preferably surrounding at least the body portion 34 of the preform. Following overinj ection, the overmolded layer will take the approximate size and shape of the void space 200.
[0352] To carry out the overinolding procedure, one preferably heats the initial prefonn which is to be coated preferably to a teinperature above its Tg. In the case of PET, that temperature is preferably about 60 to 175'C, more preferably about 80-110~C. If a temperature at or above the ininiinum teinperature of crystallization for PET
is used, which is about 120 C, care sliould be talcen when cooling the PET in the preforin.
The cooling should be sufficient to minimize crystallization of the PET in the preform so that the PET is in the preferred semi-crystalline state. Advantageously, the neck portion of the prefonn is not in contact witll the melt of overriding material, and thus retains its crystalline stiLicture. Alternatively, the initial preform used may be one which has been very recently injection molded and not fully cooled, as to be at an elevated temperature as is preferred for the overmolding process.
[0353] The coating material is heated to form a melt of a viscosity coznpatible with use in an injection molding apparatus. The temperature for this, the inject temperature, will differ among materials, as melting ranges in polyiners and viscosities of melts may vary due to the history, cheinical character, molecular weight, degree of branching and other characteristics of a material. For the preferred barrier materials disclosed above, the inject temperature is preferably in the range of about 160-325'C, more preferably 200 to 275~C. For example, for the Copolyester Barrier Material B-010, the preferred temperature is around 210 C, whereas for the PHAE XU-19040.OOL, BLOX
0005 or BLOX 0003 the preferred temperature is in the range of 160-260 C, and is more preferably about 175-240~C. Most preferably, the PHAE inject teinperature is about 175-200C. If recycled PET is used, the inject teinperature is preferably 250-320 C. The coating material is then injected into the mold in a volume sufficient to fill the void space 200.
[0354] The coated preforin is preferably cooled at least to the point wllere it can be displaced from the mold or handled witliout being dainaged, and removed from the nzold wliere fiirther cooling may talce place. If PET is used, and the preform has been heated to a teniperattire near or above the teinperature of crystallization for PET, the cooling should be fairly rapid and sufficient to ensure that the PET is prilnarily in the seini-crystalline state when the prefonn is ftilly cooled. As a result of this process, a strong and effective bonding takes place between the initial prefonn and the subsequently applied coating material.
[0355] Overinolding can be also used to create coated prefoiziis with three or more layers. In FIGURE 5, there is shown a three-layer einbodiment of a prefonn 72 in accordance with one preferred embodiment. The preforin shown therein has two coating layers, a middle layer 74 and an outer layer 76. The relative thickness of the layers shown in Figure 5 may be vatied to suit a particular coznbination of layer nlaterials or to allow for the inalcing of different sized bottles. As will be understood by one skilled in the art, a procedure analogous to that disclosed above would be followed, except that the initial preforin would be one which had already been coated, as by one of the metliods for making coated prefonns described herein, including overmolding.
a. A Preferred Method and Apparatus for Overmolding [0356] A prefelTed apparatus for performing the oveirnolding process is based upon the use of a 330-330-200 machine by Engel (Austria). The preferred mold portion the machine is shown schematically in FIGURES 19-24 and comprises a movable half 642 and a stationary half 644. In one preferred embodiment, both halves are preferably made from hard metal. The stationary half 644 comprises at least two mold sections 146, 148, wherein each mold section comprises N(N>0) identical mold cavities 614, 620, an input and output for cooling fluid, channels allowing for circulation of cooling fluid within the inold section, injection apparatus, and hot rumiers chaiuleling the molten material fioin the injection apparatus to the gate of each mold cavity.
Because each mold section fonns a distinct preform layer, and each preform layer is preferably made of a different material, each mold section is separately controlled to accoirunodate the potentially different conditions required for each material and layer. The injector associated with a particular mold section injects a inolten inaterial, at a teinperature suitable for that particular material, through that mold section's hot ruiuiers and gates and iiito the mold cavities. The mold section's own input and output for cooling fluid allow for changing tlie teinperature of the mold section to acconmlodate the characteristics of the particular material injected into a mold section. Different cooling fluids can be used in different chamiels wIt11In the mold for proper temperature distributions.
Further, although not illustrated, the distance between the cavity mold surface and the each of the chamlels can be different. Similarly, the distance between the cavity mold surface and the valves (e.g., pressure reducing elements) can be different. Consequently, each mold section may have a different injection temperattue, mold temperature, pressure, injection volume, cooling fluid teniperature, etc. to accointnodate the material and operational requirements of a particular prefonn layer.
[0357] The movable half 642 of the mold coznprises a turntable 630 and a plurality of cores 198. The aligiunent pins guide the movable half 642 to slidably move in a preferably horizontal direction towards or away from the stationary half 644. The tLU-ntable 630 may rotate in either a cloclcwise or counterclockwise direction, and is motulted onto the movable half 642. The plurality of cores 198 are affixed onto the tLU7ltable 630. These cores 198 serve as the mold fonn for the interior of the preforin, as well as serving as a calTier an.d cooling device for the prefoim during the molding operation. The cooling systein in the cores is separate from the cooling systeln in the mold sections.
[0358] The mold temperature or coolizig for the mold is controlled by circulating fluid. The flow rate of fluid can be varied depending on the stage of the preforni production. There is separate cooling fluid circulation for the movable half 642 and for the overinolding section 648 of the stationary half 644. Additionally, the initial prefonn mold section 646 of the stationary half 644 coinprises two separate cooling fluid circulation systems; one for the non-crystalline regions and one for the crystalline regions. Each cooling fluid circulation set up worlcs in a sisnilar maiu-ier.
The fluid enters the mold, flows through a network of chaiuzels or tubes inside as discussed above, and theii exits through an output (e.g., mold inlet 136). From the output, the fluid travels tluough a temperature control system before going back Into the mold. In another eznbodiment, the fluid exits out the temperature control systein by passing out of an exhaust system.
[0359] In a preferred embodiment, the cores and cavities are constnicted of a high heat transfer material, such a beryllium, which is coated with a hard metal, such as tin or chrome. The hard coating keeps the berylliuin from direct contact with the preforln, as well as acting as a release for ejection and providing a hard surface for long life. The IZigh heat transfer material allows for lnore efficient cooling, and thus assists in achieving lower cycle times. The liigh heat transfer material may be disposed over the entire area of each core andlor cavity, or it may be only on portions tllereof. Preferably, at least the tips of the cores comprise high heat transfer material. In some enlbodiments, the high heat transfer material is AMPCOLOY, wlaicli is colnmercially available from Uudenholm, I11c. The temperature control system can employ pulse cooling to cool the cavity and/or core while limiting the forlnation of condensation on the surfaces of the hig11 heat transfer material.
[0360] The nulnber of cores is equal to the total number of cavities, and the arrangenient of the core 198 on the movable half 642 mirrors the arrangement of the cavities 614, 620 on the stationary half 644. To close the lnold, the movable half 642 moves towards the stationary half 644, mating the core 198 wit11 the cavities 614, 620.
To open the mold, the lnovable half 642 moves away fronl the stationary half 644 such that the cores 198 are well clear of the block on the stationary half 644.
After the cores are fully withdrawn froln the mold sections 646, 648, the turntable 630 of the movable half 642 rotates the cores 198 into alignment with a different mold section.
Thus, the movable half rotates 360 /(nuinber of mold sectioiis in the stationaly half) degrees after each withdrawal of the cores from the stationary half. When the macliine is in operation, during the withdrawal and rotation steps, there will be preforlns present on some or all of the cores.
[0361] The size of the cavities in a given mold section 646, 648 will be identical; however the size of the cavities will differ ainong the mold sections. The cavities in which the uncoated preforms are first molded, the preforln molding cavities 614, are smallest in size. The size of the cavities 620 in the mold sectioi2 648 in which the first coating step is performed are larger than the prefonn molding cavities 614, in order to accolnmodate the i.uicoated prefol7n and still provide space for the coating material to be injected to form the overlnolded coating. The cavities in each subsequent mold section wherein additional overmolding steps are perforined will be increasingly larger in size to accommodate the prefonn as it gets larger witll each coating step.
[0362] After a set of preforms has been molded and overmolded to completion, a series of ejectors eject the finished preforms off of the cores 198. The ejectors for the cores operate independently, or at least there is a single ejector for a set of cores equal in number and configuration to a single mold section, so that only the completed prefoi7ns are ejected. Uncoated or incompletely-coated prefornls remain on the cores so that they may continue in the cycle to the next mold section. The ejection may cause the preforins to coznpletely separate fiom the cores and fall into a bin or onto a conveyor. Altei7iatively, the preforms may renlain on the cores after ejection, after which a robotic arm or other such apparatus grasps a preforin or group of prefornzs for ren7oval to a bin, conveyor, or other desired location.
[0363] FIGURES 19 and 20 illustrate a schematic for an einbodiinent of the apparatus described above. FIGURE 20 is the stationary half 644 of the mold.
Iiz this embodiment, the block 624 has two mold sections, one section 646 comprising a set of three prefonn molding cavities 614 and the otlier section 648 coiiiprising a set of three prefornn coating cavities 620. Each of the preform coating cavities 620 is preferably lilce that shown in FIGURE 10, discussed above. Each of the prefonn inolding cavities 614 is preferably similar to that shown in FIGURE 13, in that the material is injected into a space defined by the core 198 (albeit without a preforin already thereon) and the wall of the mold which is cooled by fluid circulating through channels inside the mold block.
Consequently, one full production cycle of this apparatus will yield tliree two-layer prefonns. If more than three preforms per cycle is desired, the stationary half can be reconfigured to accommodate more cavities in each of the mold sections. An exainple of this is seen in FIGURE 22, wherein there is shown a stationary half of a mold coniprising two mold sectioiis, one 646 comprising forty-eight prefonn molding cavities 614 and the other 648 comprising forty-eight prefonn coating cavities 620. If a tliree or more layer preforln is desired, the stationary half 644 can be reconfigured to accommodate additional mold sections, one for each preforin layer [0364] FIGURE 19 illustrates the movable half 642 of the mold. The movable half coinprises six identical cores 198 mounted oli the tui7ltable 630. Each core 198 corresponds to a cavity on the stationary half 644 of the mold. The movable half also comprises align.inent pegs 610, which correspond to the receptacles 612 on the stationary lialf 644. When the movable half 642 of the mold moves to close the mold, the aligiunent pegs 610 are mated with their corresponding receptacles 612 sucll that the molding cavities 614 and the coating cavities 620 align with the cores 198. After aligrunent and closure, half of the cores 198 are centered within prefonn molding cavities 614 and the otlier half of the cores 198 are centered within preform coating cavities 620.
[0365] The configuration of the cavities, cores, and alignm.ent pegs and receptacles must all have sufficient syrnrnetry such that after the mold is separated and rotated the proper nuinber of degrees, all of the cores line up witll cavities and all aligiunent pegs Iine up with receptacles. Moreover, each core niust be in a cavity in a different mold section tlzan it was in prior to rotation in order to achieve the orderly process of molding and ovei7iiolding in an identical fashion for each preforin made in the machine.
[0366] Two views of the two mold halves together are shown in FIGURES 23 and 24. Iii FIGURE 23, the movable half 642 is moving towards the stationary half 644, as indicated by the arrow. Two cores 198, mounted on the tLu7ltable 630, are beginning to enter cavities, one enters a molding cavity 614 and the other is entering a coating cavity 620 mounted in the block 624. In FIGURE 24, the cores 198 are fillly withdrawn from the cavities on the stationary side. The preforn2 molding cavity 614 has two cooling circulation systems which are separate from the cooling circulation for the prefonn coating cavity 620, which coniprises the other mold section 648. The two cores 198 are cooled by a single system that linlcs all the cores together. The arrow in shows the rotation of the turntable 630. The turntable 630 could also rotate clockwise.
Not shown are coated and uncoated prefonns which would be on the cores if the inachine were in operation. The align.inent pegs and receptacles have also been left out for the salce of clarity.
[0367] The operation of the overl~nolding apparatus will be discussed in terms of the preferred two mold section apparatus for making a two-layer preform.
The mold is closed by moving the movable half 642 towards the stationary half 644 until they are in contact. A first injection apparatus injects a melt of first inaterial into the first mold section 146, through the hot nuzners and into the prefonn molding cavities 614 via their respective gates to fotm the uncoated preforins each of which become the iiuler layer of a coated preform. The first material fills the void between the preforin molding cavities 614 and the cores 198. Simultaaleously, a second injection apparatus injects a melt of second material into the second mold section 648 of the stationary half 644, tlirough the liot rum.lers and into each prefonn coating cavity 620 via their respective gates, such tliat the second material fills the void (200 in Figure 20) between the wall of the coating cavity 620 and the uncoated preform mounted on the core 198 therein.
[0368] During this entire process, cooling fluid is circulating through the four separate areas, cozTesponding to the non-crystalline regions of mold section 646 of the prefonn molding cavities 614, the crystalline regions of mold section 646 of the preform molding cavities 614, mold section 648 of the preform coating cavities 620, and the movable half 642 of the mold, respectively. Thus, the melts and preforms are being cooled in the center by the cireulation in the movable half that goes tluough the interior of the cores, as well as on the outside by the circulation in each of the cavities.
[0369] The movable half 642 then slides back to separate the two mold halves and open the mold until all of the cores 198 having prefonns thereon are completely withdrawn from the preforin molding cavities 614 and preforin coating cavities 620. The ejectors eject the coated, finished preforins off of the cores 198 which were just reinoved from the prefoi7n coating cavities. As discussed above, the ejection may cause the preforins to completely separate from the cores and fall into a bin or onto a conveyor, or if the prefonns reinain on the cores after ejection, a robotic ann or other apparatus may grasp a preforln or group of preforins for removal to a bin, conveyor, or other desired location. The turntable 630 then rotates 180 so that eacli core 198 having an tu.~icoated prefonn thereon is positioned over a preform coating cavity 620, and each core from which a coated prefonn was just ejected is positioned over a prefonn molding cavity 614.
Rotation of the turntable 630 may occur as quickly as 0.5-0.9 seconds. Using the aligiunent pegs 610, the mold halves again align and close, and the first injector injects the first material into the prefoZ nl molding cavity 614 while the second inj ector inj ects a second material into the prefonn coating cavity 620.
[0370] A production cycle of closing the mold, injecting the melts, opening the mold, ejecting finished n-iultilayer preforms, rotating the turntable, and closing the mold is repeated, so that preforms are continuously being molded and ovennolded.
[0371] When the apparatus first begins ruiuiing, during the initial cycle, no prefonns are yet in the prefonn coating cavities 620. Therefore, the operator should either prevent the second injector from injecting the second material into the second mold section during the first injection, or allow the second material to be injected and eject and then discard the resulting single layer preform comprised solely of the second material.
After this start-up step, the operator may either manually control the operations or prograin the desired paraineters such that the process is automatically controlled.
[0372] Two layer preforms may be made using the first preferred ovei7nolding apparatus described above. Ili one preferred embodiment, the two layer preform coinprises an imler layer coinprising polyester and an outer layer coinprising a baiTier material, foasn, polyester, and other materials disclosed herein. In especially preferred eznbodiments, the inner layer coznprises virgin PET. The description hereunder is directed toward the especially preferred einbodiments of two layer prefoi7ns coinprising an iiuier layer of virgin PET, in which the neck portion is generally crystalline and the body portion is generally non-crystalline. The description is directed toward describing the formation of a single set of coated prefoinls 60 of the type seen in FIGURE 4, that is, following a set of preforins througli the process of molding, overmolding and ejection, rather tllan describing the operation of the apparatus as a whole. The process described is directed toward prefonns having a total thiclaless in the wall portion 66 of about 3 nun, coinprising about 2mm of virgin PET and about 1 tnin of barrier material. The thiclcness of the two layers will vary in other portions of the prefoiin 60, as shown in FIGURE 4.
[0373] It will be apparent to one skilled in the art that some of the parameters detailed below will differ if other enlbodiments of preforms are used. For exainple, the amount of tinie whicll the mold stays closed will vary depending upon the wall thiclcizess of the preforlns. However, given the disclostue below for this preferred einbodilnent and the remainder of the disclosure herein, one skilled in the art would be able to detei7nine appropriate paraineters for other prefoi7n embodiments. ' [0374] The apparatus described above is set up so that the injector supplying the inold section 646 containing the preforin molding cavities 614 is fed with virgin PET
and that the injector supplying the mold section 648 containing the preforin coating cavities 620 is fed with a barrier material.
[0375] The movable half 642 of the mold is moved so that the mold is closed.
A melt of virgin PET is injected through the back of the block 624 and into each prefonn molding cavity 614 to forln an iulcoated prefoi-ln 30 wliich becomes the irmer layer of the coated preform. The injection teinperature of the PET melt is preferably 250 to 320 C, more preferably 255 to 280 C. The mold is kept closed for preferably 1 to 10 seconds, inore preferably 2 to 6 seconds wliile the PET melt streani is injected and then cooled by the coolant circulating in the mold.
[0376] Iii the first step, the PET stibstrate is injection molded by injecting molten PET into the cavities forined by the molds and cores in the mold stack.
When the cavity is filled, the resin in the body portion will come into contact with cooling surfaces an.d the resin in the neclc finish will come into contact witli the heated tliread mold. As the PET in the neck finish cools, it will begin to crystallize as a result of this contact with the relatively hot mold. Once in contact, the crystallization will stal-t and continue at a rate deteiinined by time and temperature. When the neck finish portions of the molds are kept above the minimum teinperature of crystallization of the PET used, crystallization will begin on contact. Higher temperatures will increase the rate of crystallization and decrease the time required to reach the optiinum level of crystallization wllile maintaining post mold dimensional stability of the neck finish of the preform. At the same time the r=esin in the neclc finish portion is cooling into a crystallized state, the resin in the body portion or lower body poi-tion of the preform will be in contact witlz the chilled portions of the mold and thus cooled into an atnorphous or semi-crystalline state.
[0377] The movable half 642 of the mold is then moved so that the two halves of the mold are separated at or past the point where the newly molded preforms, which renzain on the cores 198, are clear of the stationary side 644 of the mold.
When the cores 198 are clear of the stationary side 644 of the mold, the turntable 630 t11en rotates 1800 so that each core 198 having a lnolded prefonn thereon is positioned over a prefonn coating cavity 620. Tlzus positioned, each of the otller core 198 which do not have molded prefonns thereon, are each positioned over a prefonn inolding cavity 614. The inold is again closed. Preferably the time between reinoval from the preforin molding cavity 614 to insertion into the prefonn coating cavity 620 is 1 to 10 seconds, and more preferably 1 to 3 seconds.
[0378] When the molded prefonns are first placed into prefonn coating cavities 620, the exterior surfaces of the body portions of the prefonns are not in contact with a mold surface. Thus, the exterior skin of the body portion is still softened and hot as described above because the contact cooling is only from the core inside.
The high teinperature of the exterior surface of the lmcoated prefonn (which fonns the inner layer of the coated prefonn) aids in promoting adliesion between the PET and barrier layers in the finished coated prefonn. It is postulated that the surfaces of the materials are more reactive when hot, and thus chemical interactions between the barrier material and the virgin PET will be enlianced by the high temperatures. Barrier material will coat and adhere to a prefonn with a cold surface, and thus the operation may be perfornied using a cold initial uncoated prefonn, but the adhesion is marlcedly better when the overmolding piocess is done at an elevated temperature, as occurs iininediately following the molding of the uncoated prefonn. As discussed earlier, the neck portion of the prefonn has desirably crystallized from the "separated, thennally isolated cooling fluid systenzs in the preform molding cavity. Since the coating operation does not place material on the neck portion, its crystalline structure is substantially undisturbed. However, the neck portion of the prefonn can also be amorphous or partially crystalline as desired. Iii some embodiments, the prefonn may have a hardened or egg-shell outer layer that surrounds a soft interior of the prefonn. The overniolding material can be selected to achieve the desired interaction between substrate and the overinolded layer.
[0379] A second injection operation then follows in whiclz a melt of a material (e.g., a barrier melt, recycled melt, polypropylene melt, foam melt, etc.) is injected into each prefonn coating cavity 620 to coat the prefonns. The teinperature of the melt of polyiner material is preferably 160 to 325'C. The exact temperature range for any individual barrier material is dependent upon the specific characteristics of that material, but it is well within the abilities of one skilled in the art to detennine a suitable range by routine experimentation given the disclosure herein. For example, if BLOX 0005 or BLOX 0003 is used, the teinperature of the melt (inject teinperature) is preferably 160 to 260 C, more preferably 200 to 240 C, aiid most preferably 175 to 200'C. If the Copolyester BaiTier Material B-010 is used, the injection temperature is preferably 160 to 260 C, more preferably 190 to 250 C. Dtuing the same time that this set of prefonns are being ovennolded witli polymer material in the preform coating cavities 620, another set of uncoated prefonns is being molded in the prefonn molding cavities 614 as described above.
[0380] The two halves of the mold are again separated preferably 3 to 10 seconds, more preferably 4 to 6 seconds following the initiation of the injection step. The prefonns which have just been coated in the prefonn coating cavities 620, are ejected from the cores 198. The uncoated prefonns wliich were just molded in prefonn molding cavities 614 reinain on their cores 198. The turntable 630 is then rotated 180 so that each core having an uncoated preform thereon is positioned over a coating cavity 620 and each core 98 from which a coated prefonn was just removed is positioned over a molding cavity 614.
[0381] The cycle of closing the mold, injecting the materials, opening the mold, ejecting finished prefonns, rotating the turntable, and closiuig the mold is repeated, so that prefonns are continuously being molded and overinolded. Those of skill in the al-t will appreciate that dry cycle time of the apparatus may increase the overall production cycle time for molding a complete prefonn.
[0382] The process using modified molds and chilled cores will produce a unique combination of ainorpllous/crystalline properties. As the core is chilled and the thread mold is heated, the thennal transfer properties of the PET act as a barrier to heat exchange. The heated tliread molds crystallize the PET at the surface of the thread finisll, and the PET material transitions into an amorphous fonn near the core as the temperattire of the PET reduces closer to the core. This variation of the material from the izuier (core) portion to the outer (thread) portion is also referred to herein as the crystallinity gradient.
[0383] The core temperature and the rate of crystallization of the resin play a part in deterinining the deptli of crystallized resin. In addition, the amorphous iiuzer surface of the neclc finish stabilizes the post mold dimensions allowing closer inolding tolerances t11an other crystallizing processes. On the other side, the crystallized outer surface supports the amorphous structure during high teniperature filling of the container.
Physical properties are also eiilZanced (e.g. brittleness, iinpact etc.) as a result of this unique crystalline/amorplious structure.
[0384] The optunuln teinperature for crystallization inay vary depending upon factors including resin grade, resiil crystallization temperature, intrinsic viscosity, wall tllicla-iess, exposure time, mold temperature. Preferred resins include PET
homopolymer and copolymers (including but not limited to high-IPA PET, Copolyester Barrier Materials, and copolyiners of PET and polyatnides) and PEN. Such resins preferably have low intrinsic viscosities aild moderate melt temperatures, preferably IVs of about 74 is 86, and melt temperatures of about 220-300 C. The preferred mold temperature range for PET is froin about 240-280 C, with t11e maximum ciystallization rate occurring at about 180 C, depending upon the above factors, the prefeiTed exposure time range is from about 20 to 60 seconds overall, whicll includes both injeetion steps in inject-over-inject embodiments, and the preferred injection cavity pressure range is about 5000 to 22000 PSI. Thicker finish wall thickn.ess will require more time to achieve a particular degree of crystallinity as compared to that needed for a thiiuler wall thiclnless. Ilicreases in exposure time (time in mold) will increase the deptli of crystallinity and the overall percentage of crystallinity in the area, and clianges in the mold teinperature in the region for which crystallinity is desired will affect the crystallinity rate and dimensional stability.
[0385] One of the many advantages of using the process disclosed herein is that the cycle times for the process are similar to those for the standard process to produce iuicoated prefoilns; that is tlie molding and coating of preforms by this process is done in a period of tilne similar to that required to malce uncoated PET preforms of similar size by standard metliods currently used in prefoi7n production. Therefore, one can malce barrier coated PET preforms instead of uncoated PET prefonns without a significant change in production output and capacity.
[0386] If a PET melt cools slowly, the PET will talce on a crystalline fonn.
Because crystalline polyiners do not blow mold as well as ainorphous polyiners, a preforin coinprised of a bocty portion of crystalline PET would not be expected to perfonn as well in fonning containers as one having a body portion formed of PET
having a generally non-crystalline fonn. If, however, the body portion is cooled at a rate faster than the crystal fonnation rate, as is described herein, crystallization of the PET will be minimized and the PET will talce on an amorphous or semi-crystalline form.
Thus, sufficient cooling of the PET in the body poi-tion of the prefonn is crucial to forining prefonns wllich will perfonn as needed wl7en processed.
[0387] The rate at which a layer of PET cools in a mold such as described hereiil is proportional to the thickness of the layer of PET, as well as the tem.perature of the cooling surfaces with wlzich it is in contact. If the mold teniperature factor is held constant, a thick layer of PET cools more slowly -tlian a tllin layer. This is because it takes a longer period of time for heat to transfer from the iiuier portion of a tliick PET
layer to the outer surface of the PET which is in contact with the cooling surfaces of the mold tlian it would for a thiiiner layer of PET because of the greater distance the heat must travel in the thicker layer. Thus, a prefoini having a thiclcer layer of PET needs to be in contact witli the cooling surfaces of the mold for a longer time than does a prefonn having a thimler layer of PET. Iti other words, with all things being equal, it talces longer to mold a preforni having a tllick wall of PET than it takes to mold a preforzn having a thin wall of PET. The temperature control system witll the valves proximate to the prefoiiii can rapidly cool tlie preforin to miniinize the cooling time for tliiclc wall or thin wall PET.
[0388] The uncoated preforms, including those made by the first injection in the above-described apparatus, are preferably tliiiuler than a conventional PET prefon.n for a given container size. This is because in malcin.g the baiTier coated prefoi7ns, a quantity of the PET which would be in a conventional PET prefoim can be displaced by a similar quantity of one of the preferred barrier materials. This can be done because the preferred barrier materials have physical properties siinilar to PET, as described above.
Thus, when the barrier materials displace an approximately equal quantity of PET in the walls of a prefonn or container, ther.e will not be a significant difference in the pllysical perfonnance of the container. Because the prefeiTed uncoated prefonns whieh forln the iiuler layer of the barrier coated preforms are thin-walled, they can be removed from the inold sooner tlian their thicker-walled conventional cotulteiparts. For example, the tulcoated preform can be removed from the mold preferably after about 4-6 seconds witliout the body portion crystallizing, as conlpared to about 12-24 seconds for a conventional PET prefoim having a total wall thiclu-iess of about 3 imn. All in all, the tizne to malce a barrier coated prefonn is equal to or sliglltly greater (up to about 30%) than the time required to malce a monolayer PET prefonil of this same total thiclffiess.
[0389] Additionally, because the preferred barrier materials are ainorphous, they will not require the saine type of treatment as the PET. Thus, the cycle time for a molding-overmolding process as described above is generally dictated by tlie cooling time required by the PET. In the above-described method, barrier coated preforms can be made in about the saine time it takes to produce an uncoated conventional prefonn.
[0390] The advantage gained by a tliimler prefonn can be talcen a step farther if a preforin made in the process is of the type in FIGURE 4. Ii1 this embodiment of a coated prefornl, the PET wall tliicla-iess at 70 in the center of the area of the end cap 42 is reduced to preferably about 1/3 of the total wall thicla-iess. Moving from the center of the end cap out to the end' of the radius of the end cap, the tliiclciless gradually increases to preferably about 2/3 of the total wall thiclcless, as at reference nuinber 68 in the wall portion 66. The wall thiclmess may reinain constant or it may, as depicted in FIGURE 4, transition to a lower thickness prior to the support ring 38. The thiclaless of the various portions of the prefolTn may be varied, but in all cases, the PET and barrier layer wall thiclalesses must remain above critical melt flow tb.ickness for any given prefonn design.
[0391] Using preforms 60 of the design in FIGURE 4 allows for even faster cycle times than that used to produce prefoinls 50 of the type in FIGURE 3. As mentioned above, one of the biggest barriers to short cycle time is the length of time that the PET needs to be cooled in the mold following injection. If the body portion of a preform comprising PET has not sufficiently cooled before it is ejected from the core, it will become substantially crystalline and potentially cause difficulties during blow molding. Furthennore, if the PET layer has not cooled enough before the ovennolding process tal:es place, the force of the barrier material entering the mold will wash away some of tlie PET near the gate area. The prefonn design in FIGURE 4 talces care of both problems by making tlie PET layer thiiulest in the center of the end cap region 42, which is where the gate is in the mold. The thin gate section allows the gate area to cool more rapidly, so that the iulcoated PET layer may be renzoved from the mold in a relatively sh.ort period of time while still avoiding crystallization of the gate area and washing of the PET during the second injection or overmolding phase.
[0392] The physical characteristics of the prefeiTed barrier materials help to make this type of prefonn design workable. Because of the similarity in plzysical properties, containers having wall portions whicll are primarily barrier material can be made without sacrificing the perforniance of the container. If the barrier material used were not similar to PET, a container having a variable wall coinposition as in would likely have wealc spots or other defects that could affect container performance.
D. Formation of Preferred Containers by Blow Moldinq~
[0393] The containers are preferably produced by blow-mol.ding prefonns, the creation of wliicli is disclosed above. The mold 80 of FIGURE 6 can comprise one or more temperature control systeins 710. The illustrated mold 80 coinprises a blow mold neck portion 706 and a blow mold body portion 708. The temperature control systein 710 can comprise a single or multi circuit system. The illustrated teinperature control system 710 coinprises a plurality of temperature control eleineilts in the foz7n of channels 712, 714, althougli other temperature control eleinents can be used. The fluid circulation in the chaiuiels 712 is preferably independent from the fluid circulation in the channels 714.
The channels 712 pass through the blow mold neclc portion 706, and the chamlels 714 pass through the blow mold body portion 708. However, the channels can be at any suitable location for controlling the temperature of the blow inolded container. The blow mold temperature control systein can also comprise heating/cooling rods, electric heaters, az-id the like.
[0394] The inold 80 can coinprise high heat transfer material to cool rapidly the nlolded container, thus reducing the ainount of chilled air (e.g., food grade air) used to reduce the temperature of the container, altlzough cllilled air can be blown into the container to further reduce the teinperature of the container. For exaanple, at least a portion of the blow molding interior surface 718 can comprise high heat transfer material.
In some etnbodiments, high heat transfer material fonn at least about 10%, 40%, 60%, 80%, 90% and ranges encompassing these amounts of the interior surface. In some eznbodiments, the entire interior surface 718 comprises higlz heat transfer material. The high heat transfer material can rapidly change the temperature of the blow molded container when the container contacts the interior surface 718.
[0395] The blow niold 80 can be substituted witli the molding apparatuses of the temperature control systems described above. As such, various configl.uations of fluid systems and working fluids can be employed with blow molds. Additionally, one or more pressure reducing elements can be in fluid in coininunication with the fluid channels 712, 714. The pressure reducing elements ca.n vaporizes an effective amount of refrigerant (e.g., cryogenic fluids) to reduce the temperature of the cryogenic fluid such that the cryogenic fluid can sufficiently cool the blow molded container within the mold cavity.
Once the container contacts the interior surface 718, the wall of the blown container cazl be quiclcly cooled to fornl a dimensionally stable wall of the container.
[0396] In other prefelTed embodinlents in wliich it is desired for the entire container to be heat-set, it is preferred that the containers be blow-molded in accordance with processes generally lalown for heat set blow-molding, 111chldlllg, but not limited to, those which involve orienting and heating in the mold, and those which involve steps of blowing, relaxing and reblowing. The mold 80 can quickly cool the container during this process, especially with higli heat transfer material absorbing heat fiom the container at a higll rate.

[0397] In some embodiments, the mold 80 can be used to produce crystalline neck f nishes. For example, the blow mold neck portion 706 and the blow mold body portion 708 can selectively control the temperature of the preforin/container to achieve a desired amount of crystallization. Tlius, the neck portion of the preform/container can be heated and gradually reduced in telnperature to produce a desired amount of crystalline material. To enhance thermal isolation, inserts 750 may be used to reduce heat transfer between portions of the mold 80. The illustrated insel-ts 750 are positioned between the blow mold neck portion 706 and the blow mold body portion 708 and can be forined of an insulator.

[0398] In some einbodiments for prefornns in which the neck finish is formed primarily of PET, the preform is heated to a temperature of preferably 80 C to 120 C, with higher telnperatures being preferred for the heat-set embodiments, and given a brief period of time to equilibrate. After equilibration, it is stretched to a length approximating the length of the final container. Following the stretching, pressurized air, such as chilled food grade air, is forced into the prefoi7n which acts to expand the walls of the prefonn to fit the mold in whicli it rests, thus creating the container. Worlcing fluid is circulated tlirough the channels 712, 714 and rapidly cools the container contacting the interior surface 718. The temperature of the chilled air for stretching the preforin and the temperature of the working fluid cooling the interior surface 718 can be selected based on the desired container finish, production time, and the like.

[0399] FIGIJRE 6A illustrates another embodiment of the mold for stretch blow molding preforms. The blow mold body portion 708a colnprises an inner portion 740 and an outer portion 742. The inner portion 740 and the outer portion 742 can colnprise materials with different tllermal conductivities. The imler portion 740 defines blow niolding interior surface 718a and preferably comprises a high heat transfer material. A chilled fluid, such as a refrigerant, can be passed tluough the channels 710a to cool quiclcly the blow molded container. The outer portion 742 can fornl a thennal baiTier to reduce heat trallsfer to the surrounding enviroinnent. The outer portion 742 surrounds the imler portion 740 to therinally isolate the iiuler portion 740.
The outer poi-tion 742 can comprise steel or other tllennally insulating material in coinparison to the material fonning the imier portion 740.
[0400] The mold neck portion 706a can coniprise a neclc portion 746 and an upper neck portion 748. The neck portion 746 preferably coinprises higli heat transfer material. The upper neck portion 748 can comprise an insulating material to thennally isolate the intenlal portions of the mold 80a similar to the body portion 708a.
[0401) The teinperature of the interior surfaces of the blow molds 80, 80a can be selected based on the preform design. For exainple, the teinperatures of the interior inold surfaces can be different for blow molding prefonns comprising an outer layer of foain material and for blow molding prefonns coinprising an outer layer of PET.
Although the blow mold 80 is discussed primarily with respect to stretch blow molding a prefonn, the mold 80 can be an extrusion blow mold. Thus, it is conteniplated that the mold 80 can be used for an extrusion blow molding process. Additionally, the einbodiments, features, systenls, devices, materials, methods and tecluliques described herein may, in some embodiments, be similar to any one or more of the embodiments, features, systems, devices, materials, methods and tecluliques described in U.S. Patent Application Serial No. 11/108,607 entitled MONO AND MULTI-LAYER ARTICLES
AND EXTRUSION METHODS OF MAICNG THE SAME, filed on April 18, 2005 which is incorporated herein by reference in its entirety.
E. Compression Methods and Apparatuses for Makin2 Preferred Articles [0402] Monolayer and multilayer articles (including packaging such as closures, prefonns, containers, bottles) can be formed by a coinpression molding process.
As discussed above, one metllod of producing inulti-layered articles is referred to herein generally as ovennolding. The name also refers to a procedure which uses compression molding to mold one or more layers of material over an existing layer, which preferably was itself made by a molding process, such as compression molding.
[0403] One overmolding method for makulg articles involves using a melt source in conjunction with a mold comprising one or more cores (e.g., mandrels) and one or more cavity sections. The melt source delivers a first amount of moldable material (e.g., a molten polymer (i.e., polyiner melt)) to the cavity section. A first portion of an article is molded between the core and the cavity section. The first portion (e.g., a substrate layer) reniains in the cavity section when the core is pulled out of the cavity section. A second ainount of material is then deposited onto the interior of the first portion of the article. A second core is used to mold the second ainount of material into a second portion of the article, thus fonning a niulti-layer article. This process may be referred to as "conlpress-over-compress."
[0404] In one einbodiment of compress-over-compress a melt source deposits a first moldable material into a cavity section. A first portion (e.g., a substrate layer) of articles is molded between a core and the first cavity section. The first layer reinains on the core when the core is pulled out of the first cavity section. A second moldable material is then deposited into a second cavity section in order to make an exterior portion of the article. The core and the corresponding first portion are then inserted into the second cavity section. As the core and the first layer are moved into the second cavity section, the second material is molded into a second portion of the article.
The core and the accompanying article are then removed from the second cavity section and the article is removed from the core.
[0405] Thus, the ovennolding method and apparattis can be used to mold imzer layers and/or outer layers of articles as desired. The multilayer articles can be containers, preforms, closures, and the like. Additionally, one or more compression systeins can be employed to form multilayer articles. Eacli compression system can be a coinpression mold having cavity sections and cores that are used to mold a portion of an article. A transport systein can transport articles between each pair compression molding systeins. Thus, a plurality of compression molding systems can be used for an overmolding process.
[0406] In an especially preferred embodiment, the compress-over-coinpress process is performed while the first portion, e.g. a substrate layer, has not yet fully cooled.
The underlying layer may have retained inherent heat from a molding process that fonned the underlying layer. hi some einbodiments, the underlying layer can be at room temperature or any other temperature suitable for ovennolding. For example, articles at room temperature can be overmolded with one or more layers of material. These articles may have been stored for an extended period of time before being oveiinolded.
[0407] Molding may be used to place one or more layers of material(s) such as those coinprising lamellar material, PP, foain material, PET (including recycled PET, virgin PET), barrier materials, phenoxy type thermoplastics, combinations thereof, and/or otller materials described herein over a substrate (e.g., the underlying layer). In some non-limiting exemplary embodiments, the substrate is in the fonn of a preform, preferably having an interior surface for contacting foodstuff.
[0408] Articles made by compression molding may comprise one or more layers or portions having one or more of the following advantageous characteristics: an insulating layer, a barrier layer, a foodstuff contacting layer, a non-flavor scalping layer, a higli strength layer, a coinpliant layer, a tie layer, a gas scavenging layer, a layer or portion suitable for hot fill applications, a layer having a melt strength suitable for extrusion. In one embodiment, the monolayer or inulti-layer material comprises one or more of the following materials: PET (including recycled and/or virgin PET), PETG, foam, polypropylene, phenoxy type thermoplastics, polyolefins, phenoxy-polyolefin thennoplastic blends, and/or combinations th.ereo~ For the sake of convenience, articles are described primarily with respect to prefonns, containers, and closures.
[0409] The temperature control systems described above can coinprise a molding apparatus configured to mold articles (e.g., monolayer and multilayer articles) by a compression molding process. FIGURE 25 illustrates a inolding system 1500 designed to make preforms that comprise one or more layers. hi the illustrated embodiment, the inold'uig systein 1500 is a coinpression molding systein and coinprises a melt source 1502 configured to deliver moldable material to a turntable 1504 that has cavity portions 1508 with one or more mold cavity sections 1506 (FIGURE 26).
[0410] The core section 1510 can cooperate with a coiTesponding cavity section 1506 to mold the moldable material. The illustrated core section 1510 (FIGUR.E
26) has a core 1512 sized and adapted to be inserted into a corresponding cavity section 1506. The core 1512 can be inoved between an open position and a closed position. The illustrated core section 1512a is in a closed position.
[0411] The source 1502 can feed melt material into the mold cavity section 1506 from above or through an injection point along the mold 6avity section 1506. The term "melt material" is a broad tenn and may comprise one or more of the materials disclosed herein. hi some embodiments, melt material may be at a temperattire (e.g., an elevated temperature) suitable for coinpression molding. As shown in FIGURE
27, the source 1502 can produce and/or deliver melt material to the mold cavity sections 1506 of the turntable 1504. The turntable 1504 can rotate about a central axis to move the mold cavity sections 1506 into position such that the source 1502 can fill a portion of a mold cavity section 1506 with inelt for subsequent compression nzolding. The turntable 1504 and the mold core section 1510 can continuously or inerementally rotate about the center of the turntable 1504. Preferably, the core section 1510 and the tLUntable 1504 move in unison for a portion of the molding process as discussed below.
[0412] As shown in FIGURE 26, the mold core 1510 has a core 1512 that is configured to cooperate wit11 the tunltable 1504 to mold the melt material.
The core 1512 is configured and sized so that the core 1512 can be advanced into and out of a corresponding mold cavity section 1506. The core 1512 is designed to form the interior of a preforni. The illustrated core 1512 is an elongated body that has a base end 1548 (FIGURE 28). The core 1512 has a generally cylindrical body that tapers and fonns the rounded based end 1548. The core 1512 can have a core molding surface 1513 for moldiulg melt. The core section 1510 can be colulected to a tuilltable or other suitable structure for moving the core section 1510.
[0413] The mold cavity sections 1506 can be evenly or unevenly spaced along the turntable 1504. The illustrated cavity sections 1506 are designed to mold the exterior of a prefonn. The molding systeni 1500 can have one or more circular arrangements of mold cavity sections 1506 that are preferably disposed near the periphery of the turntable 1504. In the illustrated embodiment of FIGURE 25, the tliintable 1504 has one circular arra.ngement of mold cavity sections 1506.
[0414] The source 1502 is adapted to produce a melt streain suitable for inolding. The source 1502 can output foain material, PET, lamellar material, PP, or other moldable materials. In the illustrated einbodiment, the melt from the source 1502 can be deposited into one or more of the mold cavity sections 1506 and then molded by compression molding.
[0415] With reference to FIGURE 27, the mold cavity section 1506 can have a movable neck finish mold for molding the neck finish of a prefonn. Iii one embodiment, the mold cavity section 1506 coinprises a movable neclc finish mold 1520 that has a neclc molding surface 1522 configured to fonn the neck portion of a prefoim and a body molding surface 1524 coiifigured to fonn the body portion of the prefonn.
The neck finish mold 1520 comprises a plurality of temperature control eleinents 1521 in the fonn of channels. The neclc finish mold 1520 can be siinilar or identical to the neck fmish molds described above. The neck finish mold 1520 can be used to produce non-crystalline and crystalline neclc finishes. In some embodiments, the neclc finish mold 1520 coinprises liigh heat transfer material to increase through-put of the molding system.

Of course, a worlcing fluid (e.g., a refrigerant) can flow tlirougll the cllannels 1521 of the neck finish mold 1520 for rapid teinperature changes.
[0416] The neclc finish mold 1520 is movable between one or more positions.
In the illustrated einbodiment, the neck finish mold 1520 is located in a molding position so that the neclc molding stuface 1522 cooperates witll the body molding surface 1524 of the molding body 1529 to fonn a molding surface 1525. The neck finish mold 1520 can be moved outward to a second position, in which the outer surface 1324 of the neck finish mold is proximate to or contacts the stop 1527. When the neck finish mold 1520 is in the second position, a preform fonned witliin the inold cavity section 1506 can be ejected therefrom. After the preform has been removed from the mold cavity section 1506, the neck finish mold 1520 can then be moved back to the illustrated first position so that another prefonn can be fonned.
[0417] The mold body 1529 can have one or more teinperature control elements for controlling the temperature of the polyiner. The illustrate mold body 1529 coinprises a plurality of temperature control eleinents 1541 in the forin of channels for circulating fluid througli the mold body 1529. A working fluid can be passed through the chaimels 1541 to control the temperature of the material positioned within the mold.
[0418] FIGURE 28 illustrates the core section 1510 positioned above a corresponding cavity section 1508 defining the mold cavity section 1506. The core section 1510 can be moved along a line of action 1532 in the direction indicated by the arrows 1534 until the core section 1510 mates with the cavity section 1508. As shown in FIGURES 29 and 29A, the core section 1510 and the cavity section 1508 cooperate to form a space or cavity 1536 having the desired shape of a prefornz. After material has been deposited into the mold cavity section 1506, the core section 1510 can be moved from the open position of FIGURE 28 to the closed position of FIGURE 29 in order to compress the melt such that the melt substantially fills the space or cavity 1536 (FIGURE
29A). To cool the polymer, a worleing fluid (e.g., a refrigerant) can be passed through pressure reducing elements 1356 and through the charmels 1541 to cool the material in the mold.
[0419] hi operation, the turntable 1504 can be positioned so that one of the mold cavity sections 1506 is located below the output 1530 of the source 1502 as shown in FIGURES 25 and 27. A plug or shot of melt is delivered out of the opening 1538 of the output 1530 such that the plug falls into the mold cavity section 1506.
Preferably, the plug drops to the end cap area 1539 (FIGURE 27) of the mold cavity section 1506.

[0420] The plug 1544 may comprise a ph.uality of layers. The plug 1544 may coinprise lainellar material in any desirable orientation for subsequent compression molding. For example, one or more of the layers of the plug 1544 can be horizontally oriented, vertically oriented, or in any other orientation such that resulting prefonn nlade fiom the plug 1544 has a desired microstructure. In the illustrated embodiment of FIGURES 27 and 28, ma.ny or most of the layers of the plug 1544 are generally perpendicular to the line of action 1532. In some enibodiments, the plug 1544 comprises material without any orientation. For example, the plug 1544 may coinprise a substantially isotropic material.
[0421] The plug 1544 can be at any suitable temperature for inolding. In some einbodiinents, the teinperature of the plug 1544 is generally above the glass transition temperature (Tg) of at least one of the materials ~'foinling the plug 1544, especially if the plug 1544 comprises lamellar material. Preferably, a substantial portion of the material forming the plug 1544 is at a teinperature that is generally above its glass transition temperature (Tg). In other embodiments, the temperature of the plug 1544 is in the range of about the Tg to the melt temperature (T,,,) of a substantial portion of the material forining the plug. In other embodiments, the temperature of the plug 1544 is in the range of about Tg to about T,,, of most of the material forining the plug.
In some embodiinents, the temperature of the plug 1544 is generally above the T,,, of at least one of the materials fonning the plug 1544. Preferably, the teinperature of the plug 1544 is generally above the T,,, of a substantial portion of the materials forming the plug 1544. A
slcilled artisan can determine the appropriate teinperature of the plug 1544 delivered fioni the source 1502 for coinpression molding.
[0422] The turntable 1504 can be rotated about its center such that the filled mold cavity sections 1506 are moved about the center of the turntable 1504 and the core section 1510 can be moved downwardly along the line of action 1532.
[0423) After the core section 1510 has moved downward a certain distance, it will contact the upper surface 1546 of the plug 1544. As the base end, 1548 of the core 1512 advances into the plug 1544, the plug 1544 spreads to generally fill the entire cavity section 1536. The plug 1544 preferably coinprises sufficient material to generally fill the entire cavity section 1536 as shown in FIGURE 29A. The mold may or may not be preheated to facilitate the flow of the polylner material between the core section 1510 a.nd the cavity section 1536.

[0424] With reference to FIGURES 29 and 29A, the core section 1510 is in the closed position so that the lower surface 1550 of the core section 1510 engages or contacts the upper surface 1551 of the cavity section 1506. The core section 1510 and the cavity section 1506 can have cliaiuzels 1541 that can remove heat froin the material fonning the prefonn 30 disposed within the cavity section 1536. To reduce cycle times, a refrigerant can flow through the chamiels 1541 to cool rapidly the melt. The refrigerant can be a two-phase mixture for increased therinal load capabilities. The core section 1510 a11d/or the cavity section 1506 may or may not comprise high heat transfer that may worlc in combination witll the worlcing fluid to achieve rapid temperature changes.
[0425] After the preform has been sufficiently cooled, the core section 1510 can be inoved upwardly along the line of action 1532 to the open position so that the preform can be removed from the mold cavity section 1506. Ejector pisis or other suitable devices can be used to eject the prefonn from the mold cavity section 1506.
Preferably, before the preform is ejected from the mold cavity section 1506, the neck finish mold 1520 is moved radially away from the prefonn to the second position, such that the preform can be conveniently and easily moved vertically out of the mold cavity section 1506. hi some embodiments, pulse cooling can be employed to limit the forination of condensation on the molding surfaces.
[0426] The preform is forined within the cavity section 1536 at some point after the source 1502 deposits material iiito the mold cavity section 1506 and before the mold cavity section 1506 is rotated around and located once again beneath the output 1530 of tlie source 1502. Of course, the core section 1510 aiid tunltable 1504 preferably rotate in unison about the center of the turiztable 1504 during the compression molding process. The core section 1510 can be attached to a complementary tui-ntable similar to the turntable 1504. The two turntables can rotate together during the molding process.
[0427] Moldable material can also be disposed by other suitable meaiis.
FIGURE 30 illustrates a moldable inaterial that can be delivered directly by a.n injection nzolding process into a modified cavity section 1558. The components of the illustrated embodiment are identified with the same reference numerals as those used to identify the corresponding components of the cavity section 1510 and tw-iltable 1504 discussed above.
[0428] - The turntable 1504 comprises a feed systeni 1552 configured to deliver moldable material (e.g., foain, lamellar material, PP, PET, etc.) directly into the cavity section 1558. The feed system 1552 delivers moldable material (e.g., melt) at any point along the cavity section 1558 and preferably coinprises the output 1530 of a source and a means for pushing material from the outptit 1530 into the cavity section 1558.
[0429] In one embodiment, the feed systein 1552 comprises a push assenlbly 1560 (e.g., a piston asseinbly) that is configured to push melt into the cavity section 1558.
The push asseinbly 1560 can reciprocate between a first position and a second position and has a plunger or piston 1562 illustrated in a first position so that the upper surface 1564 of the pltuiger 1562 fonns a portion of the cavity section 1558.
Preferably, the upper surface 1564 forms the lower portion or end cap region of the cavity section 1558.
The plunger 1562 can be moved from the illustrated first position to a second position 1563 (shown in phantom) for receiving material from the output 1530. When the plunger 1562 is in the second position, the output 1530 feeds melt into a cylindrical chainber defined by the tube 1566 and the upper surface 1564 of the plunger 1562. The plunger 1562 can be moved from the second position to the first position, thereby moving the material to the illustrated position. In this mamier, material can be repeatedly outputted from the output 1530 and into the cllamber defined by the tube 1566 and then advanced into the cavity section 1558 for compression molding.
[0430] After the plug 1544 is positioned in the cavity section 1558, the core 1512 can be advanced into the cavity section 1558 to compress and spread the material of the plug 1544 through the cavity 1536 in the manner described above.
Preferably, the plug 1544 is molten plastic (e.g., lainellar, PET, PP, foam, phenoxy type thermoplastic) that can be spread easily throughout the cavity 1536.
[0431] With reference to FIGURE 31, the turntable 1604 can have a mold cavity section 1568 that is generally similar to the mold cavities section discussed above.
However, u.1 the illustrated einbodiunent, the turntable 1604 can have an injection systein 1570 for injecting material into the cavity section 1568. The injection system 1570 can be configured to inject material at a desired location and/or with a desired orientation. In some embodiments, the injection systein 1570 can be adjusted to inject material at desired locations and/or with desired orientations.
[0432] In the illustrated einbodiment, the turntable 1604 has an injection system 1570 that is configured to inject a lamellar melt stream into the cavity section 1568 at a suitable points along the cavity section surface. One or more injection systems 1570 can be used to inject a lamellar melt stream at one or more locations along the mold cavity section 1568. The iiijection system 1570 can inject a lamellar melt stream into a lower portion or end cap region of the mold cavity section 1568.
Alternatively, the injection system 1570 can znject a lainellar melt into the upper portion of the mold cavity section 1568.
[0433] The injection system 1570 can comprise a gate 1572 at the downstreain end of the otttptit of the lainellar macliine. The gate 1572 may selectively control the flow of the lamellar melt streain from the output 1530 into a space or cavity section 1574 defined by the core 1580 and the cavity section stuface 1578 of the cavity section. The gate 1572 may coinprise a valve systein 1573 that selectively inllibits or pennits the melt streain into the cavity section 1568. In one einbodiment, the injection system 1570 injects material to fonn a plug (illustrated as a lamellar plug) at the bottom of the cavity section 1568, similar to the plug shown in FIGURE 30. The plug can then be coinpressed by the core 1580 to fornn a prefornn within the cavity 1574.
[0434] One metllod of lainellar molding is carried out using modular systeins similar to those disclosed in U.S. Patent No. 6,352,426 B1 and U.S.
Application No.
10/705,748 filed on Noveinber 10, 2003, the disclosures of which are hereby incorporated by reference in their entireties and form part of this disclosure. h.l view of the present disclosure, a skilled artisann can inodify the methods and apparatus of the incorporated disclosures for compression molding. For exainple, the injection-over-injection ("101") systems of the U.S. Patent No. 6,352,426 B1 can be modified for compression moldixng.
For example, the melt of those systems can be injected into a mold cavity section and then the core can be used to compress the melt to fornn a prefornz. Those systems can be modified into compress-over-compress systeins used to make nzultilayer prefonns formed by coinpression molding. Additionally, one or more coinponents, subassemblies, or systems, of these apparatuses can be employed in the mold described herein.
For exainple, the cavity sections and/or core sections of the molds disclosed herein may comprise high heat transfer material for enhancing tliermal transfer with heating/cooling systems.
[0435] The compression molding system 1500 can be used to produce preforms that coinprise non-lamellar inaterials (e.g., foain material, PET, PP, barrier material, combinations thereof, and otlzer materials disclosed herein).
Compression molding systems for malcing prefoiins coinprising laznellar material, and prefonns comprising foain, can be similar to eacll otlier, except as fiirther detailed below. That is, in some elnbodiments a foam melt can be molded in a similar manner as the lamellar material described herein. The teniperature control elements of the mold caii be used to precisely control the temperature and expansion of the foam material.

[0436] FIGURE 25A illustrates a system 1591 coinprising a plurality of subsystems and is arranged to produce multilayer articles. Each of the subsystems can have a temperature control systeni for controlling the teinperature of molds.
Generally, the system 1591 includes one or more systems (e.g., conipression systenls, closure lining systeins, etc.) and is configured to produce multilayer articles, such as prefonns, closures, trays, and other articles described herein. Iil some embodiments, the system comprises a first systein 1500a comlected to a second system 1500b. The first system 1500a can be a coinpression inolding systein that molds a first portion of an article, and the second systeni 1500b can be configured to fonn a second portion of the article. The illustrated systems 1500a, 1500b have turntables that rotate in the counter-clockwise direction during a production process. A tralsport system 1599 can transport a substrate article from the first molding system 1500a to the second system 1500b. Of course, additional subsystem(s) can be added to the system 1591. For exainple, the one or more coinpression molding system similar to the compression molding system 1500 can be connected to the system 1591. Thus, systems (similar to or different than the systems 1500, 1500a, 1500b, etc.) can be added to the systein 1591 to produce articles having more than two layers, to place liners in multilayer closures, and the like.
[0437] The illustrated systein 1591 coinprises a first molding systein 1500a that can be similar to or different than the molding systeins described herein, suc11 as the molding systein 1500 of FIGURE 25. - The first molding system 1500a can have a plurality of cavity sections 1506a configured to mold substrate articles. The cavity sections 1506a, 1506b are arranged in a substantially circular pattern. The first molding system 1500a can deliver the substrate articles to the transport system 1599.
[0438] The illustrated transport system 1599 can carry substrates produced by the first compression molding system 1500a to the second system 1500b. The transport systein 1599 carries and delivers the substrates to the second system 1500b, which can be a compression molding system. The transport systein 1599 can coinprise one or more of the following: handoff mechanisms, conveyor systems, starwheel systems, tLUrets, and the like. The illustrated transport system 1599 is positioned between the systeins 1500a, 1500b.
[0439] The second system 1500b in some embodiments can fonn an outer layer over the substrate delivered by the transport system 1599. For example, the transport systein 1599 can deliver substrate prefonns to a core (not shown) of the molding system 1500b. The source 1519b can deposit melt into the cavity section 1506b, and the core holding the substrate can be advanced into the cavity section 1506b to mold the inelt therein. The cores and the cavity sections 1506b can rotate continuously during the prodtiction process. The cavities of the cavity section 1506b can be larger than the cavities of the cavity sections 1506a in order to form an outer layer on the article. For exainple, the systein 1591 can be configured to mold the prefonn 50 of FIGURE
3. The first systein 1500a can fonn the inner layer 54 of the prefoi7n 50. The transport systeni 599 can remove the iiuier layerl4 and deliver the iiuler layer 54 to the second systein 1500b. The second systein 1500b can have a holder (e.g., a core) that holds the iiuler layer 54. The cavity sections 1506b can be rotated and moved under the source 1519b to receive melt. After melt has be delivered into a cavity section 1506b, the core and the irmer layer 54 can be advanced into the cavity section 1506b,'wliich can be similar to the cavity sections 1568 of FIGURE 33, to form the outer layer 52 of the prefonn 50. The outer surface of the layer 54 and the cavity section 1506b cooperate to mold the ni.elt. Of course, the systein 1591 can be modified to fonn tlie otller preforms described herein.
[0440] In some embodiments, the tran.sport system 1599 can place the substrate prefoixn in the cavity section 1506b. Melt can be deposited by the source 1519b into the interior of the substrate preform. A core (not sllown) of the second systein 1500b can be advanced into substrate located within the cavity section 1506b to mold the melt.
Thus, the second system 1500b can mold a layer over the substrate produced by the first lnolding system 1500a. The system 1591 can tlierefore be a compress-over-coinpress systein for producing multilayer articles.
[0441] The system 1591 can be configured to produce other articles such as iiiultilayer closures. The first systeni 1500a can mold at least a portion of a closure (e.g., a closure comprising lamellar material, foam, and/or other materials described hereiui).
The transport system 1599 can receive the at least a portion of a closure and deliver the at least a portion of the closure to the second system 1599. The second system 1599 can be a spxaying systein that sprays material onto the closure, lirling system (e.g., a spray lining system, a spin lu2ing system, insertion system, etc.), compression molding systein, and the lilce. For example, the second molding system 1500b can coinprise systems or einploy techniques siunilar to those disclosed in U.S. Patents Nos. 5,259,745 to Murayama and 5,542,557 to ICoyama et al., which are ulcorporated by reference in their entireties.
[0442] FIGURE 32 shows a compression moldiulg system 1590 configured to mold multi-layer articles in the form of preforms. The compression molding system 1590 can be a compress-over-compress processing machine. Generally, the system 1590 can comprise one or more material sources configured to deliver inaterial to the mold cavity sections 1508 of the turntable 1569. hi the illustrated embodiment, the molding system 1590 comprises a pair of material sources configured to output melt streains into the mold cavity sections 1506. For exaniple, in the illustrated einbodiment, the system 1590 can coinprise a pair of melt machines tliat can be similar or different from each otller. The molding system 1590 can also coinprise one or more ejector systems 1580 configured to reniove the coinpletely fonned prefoims from the tunltable 1569.
[0443] As sllown in FIGURE 33, the core section 1568 has a core 1582 that is configured to be disposed within a corresponding mold cavity section 1568 and can have various sizes depending on the desired article formed through the compression inolding process. For example, a plurality of coinpression molding steps can be perfozmed, wherein each step fonns a different layer of a prefonn. As the turntable 1569 rotates about its center, various cores can be inserted into the tunitable 1569 at different times to form various portions of the preforms as described below.
[0444] With reference to FIGURE 33, the core sectiori 1568 aiid the cavity section 1568 are in the closed position. The core 1582 and the mold cavity section 1568 are configured to fonn a portion of a prefonn. The core 1582 and znold cavity section 1568 cooperate to define a cavity 1585 in the shape of the outer layer 52 of tlie prefonn 50 of FIGLT.RE 3. Melt material can be placed in the mold cavity 1585 when the core section 1568 is in the open position. The core 1582 and mold cavity section 1568 can cooperate to coinpress the melt material to fill the cavity 1585 to form the outer layer 52 in the maiuier described above. A skilled artisan can detennine the appropriate amount of material to deposit into the mold cavity section 1568 to fill the cavity 1585 defined by the core section 1568 and the mold cavity section 1568. A temperature control systein can deliver cooling fluid tlirough the chamlel 1530 to cool the prefonn.
[0445] After the outer layer 52 is fonned, the core 1582 can be reinoved from the cavity 1584 wllile the layer 52 is retained in the cavity 1584. Another core can be used to mold another layer of material, which is preferably molded over the layer 52. As shown in FIGURE 34, another core (i.e., core 1612) can be used to mold melt over the layer 52.
[04461 The cavity section 1602 can be formed between the outer surface 1601 of the layer 52 and the outer surface 1213 of the core 1613. The core 1612 may have a shape that is generally similar to the shape of the core 1582. Preferably, however, the core 1612 is smaller than the core 1582 so that the surface 1613 of the core 1612 is spaced froln the layer 52 when the core section 1610 is in the illustrated closed position.
The size and configuration of the core 1512 cail be determined by one of ordinary slcill in the art to achieve the desired size and shape of the cavity 1602 which is to be filled witli material to form a portion of the preforni.
[0447] hi operation, the system 1590 can have a source 1502 that outputs melt and drops it into the mold cavity section 1568 disposed beneatlz the output 1530. Afl;er the mold cavity section 1506 witli the plug rotates in the direction indicated by the arrow 1593, the core 1582 can be advanced downwardly and into the mold cavity section 1568.
As the base end 1534 of the core 1512 compresses the plug, the material spreads and proceeds upwardly along the cavity 1587 uiitil the material substantially fills the entire cavity 1587. A cooling fluid can be run tluough a teinperature system 1530 within the core section 1568 and the turntable 1569 to cool quickly the material forming the outer layer 52. After the material has sufficiently cooled, the core section 1568 is moved upwardly so that the core 1582 moves out of the mold cavity section 1568.
[0448] Witll continued reference to FIGURE 32, after the core section 1568 has been moved to the open position, the turntable 1569 can be rotated in the direction indicated by the aiTow 1593 until the mold cavity section 1506 is located under tlle second material source 1502a. The source 1502a can output a melt streain from the output 1595 onto the interior surface 1601 (FIGURE 34) of tlhe outer layer 52.
The turntable 1509 can then rotate in the direction indicated by the arrow 1597 and the core section 1610 can be inserted into the turntable 1509 to compresses and spread the melt throughout the cavity 1602. In this manner, this second compression process can form the inner layer 53 of the preform 50. Once again, the temperature control systein 1530 can rapidly and efficiently cool the preform 50 for subsequent reinoval. After the core section 1610 has moved to the open position and the neclc finish mold 1520 is moved apart, the preform 50 can be conveniently lifted vertically out of the tzu7ltable 1509 by the ejector system 1580. The process can then be repeated to produce additional inultilayer preforms.
[0449] It is contemplated that any nuinber of core sections, cavity sections, azld sources of materials can be used in various combinations to form prefonns of different configurations alid sizes. The preforms may have more than two layers of material. Although not illustrated, there can be additional cores that are used to fonn additional layers through compression molding. Additionally, the above coinpression process can be used to produce coatings or layers on conventional preforms.

[0450] Those of ordinary skill in the art will recognize that the mold cavity sections can be located in any structure suitable for molding. For exainple, the mold cavity sections 1506 can be located in a stationary table. One or more extillders or melt sources and the cores can be znovable witli respect to the mold cavity sections. Thus, an extruder can move to each mold cavity sections and deposit melt within the cavity section. The core section can then move into the corresponding core to mold the prefonn.
[0451] The molding systein 1590 can be configured to malce inulti-layer prefonns by the compress-over-compress process. In some embodiments, the molding system 1590 can have a core 1582 that is configured to mate witli the inold cavity 1568 to form an iiuler portion of a prefonn, such as the izuler layer 54 of the preforln 50 of FIGURE 3. Iii other words, the cavity 1585 can be in the shape of the inner layer 54 of the prefonn 50. Melt can be deposited into the cavity section 1568 and can then be conipressed between the core 1582 and the cavity section 1568 to form the iiuler layer 54.
After the im-ier layer 54 has been formed, the core section 1568 can be moved upwardly out of the cavity section 1568. When the cavity section 1568 is moved out of the cavity section 1568, the outer layer 54 is preferably retained on the core 1582. The outer layer 54 and the core 1582 can then be inserted into a second cavity, preferably configured to mate with the outer surface of the outer layer 54 to define a cavity in the shape of the outer layer 52 of the prefonn 50. Melt can be deposited into the second cavity section and then compressed as the core section 1568 and layer 54 are inoved into the second cavity. Tl1us, the second material can be coinpressed into the shape of the outer layer 52 of the preform 50. After the prefonn 50 has been formed, the cavity section 1568 can be moved upwardly out of the second cavity so that the prefonn 50 can be reinoved. Thus, one or more layers of a prefonn can be positioned on a core and used to mold inultiple layers of a prefonn in one or more cavities section. In view of the present disclosure, a skilled artisan can select and modify the molds disclosed herein to make various prefonns and otlier articles disclosed herein.
[0452] It is conteinplated that articles of other shapes and configurations caii be molded tluough similar compression inolding process. For example, FIGURE 35 illustrates a molding system 1630 that is configured to mold a mono or multilayer closures. The molding system 1630 is_defined by a core section 1632 having a core 1634 and a mold cavity section 1636. Iil one embodiment, material is passed through the line 1639 and through the gate 1640 and into the cavity 1642 defined between the core 1634 and the cavity section 1636. The core half 1632 can be in the open position wlien tlie material is passed tlirough the gate 1640. The core half 1632 can then be moved to the closed position to mold the melt into the desired shape of the closure. hi the illustrated enibodinient, the cavity 1642 also optionally includes a portion 1644 for forining a band and connectors between the body and the band of tlie closure. The mold 1630 can optionally include neck finish molds 1644, 1646 (e.g., split rings) that can be moved apart allowing the core half 1632 to move out of the cavity section 1636.
[0453] Additional layers can be added to the closure by additional conzpression molding processes. For example, the substrate 1650 (FIGTJRE 36) fonned in the cavity 1642 can be retained on the core 1634 and inserted into a second cavity section 1652. The delivery system of the second cavity section 1652 can deposit material ottt of a gate 1654 and into the cavity section 1652, preferably when the core section 1632 and cavity section 1652 are in the open position. The core half 1632 can be moved from the open position to a closed position, while the substrate 1650 is positioned on the core 1634, the outer surface of the substrate 1650 acts as a molding surface to coinpress the melt between the substrate 1650 and the surface 1655 of the cavity section 1652. The melt can be spread throughout the space 1657 defined between the substrate 1650 and the surface* 1655. After the closure has sufficiently cooled, the core half 1632 can be removed from the cavity section 1652. Optionally, additional layers of material can be nlolded onto the closure by a similar compress-over-coinpress process. In view of the present disclosure, a skilled artisan can design the desired shape of the systems and molds disclosed herein to make various types of articles and paclcaging described herein.
Multiple layer closures can also be formed by the compress-over-compress processes as described above. For example, the inner layer of the closure can be molded witllin the outer layer.
[0454] The system 1591 of FIGURE 25A can be configured to produce multilayer closures. The first system 1500A of FIGURE 25A of the system 1591 can mold a first layer of the closures in a similar manner as described with respect to FIGURE
35. The second systein 1500B of FIGURE 25A can mold an outer layer of the closure in a similar manner as described with respect to FIGURE 36.
[0455] Ot11er types of inolding systeins can be employed to forin mono and inulti-layer articles. As described below, there are various systems that can be employed to deliver material to a compression molding systein. Altliough the exemplary exnbodiinents are disclosed primarily with respect to stationnary mold cavities section, these systeins can be used in rotary systems, such as the turntable system described above. Additionally, described herein, certain embodiments, features, systenas, devices, materials, methods and tecluiiques described herein may, in some embodiments, be similar to any one or more of the embodiments, features, systems, devices, materials, metliods and tecluliques described in U.S. Patent Application Serial No.

11/108,342 entitled MONO AND MULTI-LAYER ARTICLES AND COMPRESSION METHODS
OF MAKING THE SAME, filed on April 18, 2005 and published as Publication No.
2006-0065992, wh.ich is hereby incorporated by reference in its entirety. The temperature control systems can be used to control the temperature of these coinpression molding systems.
1. Method and Apparatus of Makinlz Crystalline Material [0456] Molds (including coinpression and injection molds) can be used to produce prefoiins having a crystalline material. While a non-crystalline prefonzi is preferred for blow-molding, a bottle having greater crystalline character is preferred for its dimensional stability during a hot-fill process. Accordingly, a preform constiLicted according to preferred einbodiments has a generally non-crystalline body portion and a generally crystalline neclc portion. To create generally crystalline and generally non-crystalline portions in the saine preform, one needs to achieve different levels of heating and/or cooling in the mold in the regions from which crystalline portions will be fonned as compared to those in which generally non-crystalline portions will be foiined. The different levels of heating and/or cooling are preferably maintained by thennal isolation of the regions having different temperatures. In some einbodiments, this tliennal isolation between the thread split, core and/or cavity interface can be accomplished utilizing a combination of low and high thermal conduct materials as inserts or separate coinponents at the mating surfaces of these portions.
[0457] The cooling of the mold in regions which fonn preform surfaces for which it is preferred that the material be generally aznorphous or semi-crystalline, can be accomplished by chilled fluid circulating tlhrough the mold cavity and core.
Iii preferred embodiments, a mold set-up similar to conventional injection molding applications is used, except that there is an independent fluid circuit or electric lieating system for the portions of the znold from which crystalline portions of the preform will be formed.
[0458] The molding systems of FIGURES 25-36 can be configured to produce prefonns having crystalline material. In the illustrated the cavity section 1508 includes the body mold 1529 coinprising several chaiuiels 1541 through which a fluid, preferably chilled water or a refrigerant, is circulated. The neck finisll mold 1520 has one or more chaiuiels 1521 in which a fluid circulates. The fluid mid circulation of cliatulels 1541 and chaiuiels 1521 are preferably separate and independent.
[0459] The thennal isolation of the body mold 1529, neclc finish mold 1520 and core section is achieved by use of inserts or having low tliennal conductivity.
Exainples of preferred low tliennal conductivity materials include heat-treated tool steel (e.g. P-20, H-13, Stainless etc.), polyineric inserts of filled polyainides, nomex, air gaps and minimuin contact shut-off surfaces.
[0460] In this independent fluid circuit tllrougll chaiulels 1521, the fluid preferably is warnner tllan that used in the portions of the mold used to fonn non-crystalline portions of the preform. Preferred fluids include water, silicones, and oils. In another einbodiment, the portions of the mold whicli fonns the crystalline portions of the prefonn, (corresponding to neck finish inold 1520) contain a heating apparatus placed in the neck, neck finish, and/or neck cylinder portions of the nlold so as to maintain the higher temperature (slower cooling) to promote crystallinity of the material during cooling. Such a lieating apparatus ean include, but is not liinited to, heating coils, heating probes, and electric heaters. Additional features, systeins, devices, materials, methods and techniques are described in Patent Application No. 09/844,820 (U.S.
Publication No.
2003-0031814) wliich is incorporated by reference in its entirety and made a part of this specification. Additionally, the cliann.els 1521 can be used to heat the molds and cause expansion of foaan material.
F. Improved Molding System [0461] FIGURE 37 is a cross-sectional view of a portion of a mold configiired to mold a preform 2000. The mold 1999 coinprises a neck finish mold 2002 and a component 2003 of a mold cavity section. Alteniatively, the component 2003 may be intricately formed within the saine structure as the neck finish mold or be part of another meinber. The preform 2000 has a neck finish 2005 that is molded, at least in part, by the neck finish mold 2002. The neck finish mold 2002 and component 2003 are in therinal cotlununication with each other. A cooling system 1191 is disposed witliin the coinponent 2003. To cool the preform 2000, a chilled working fluid can flow tluough the cooling system 1191 and across at least a portion of the neck finish mold 2002. The cooling systein 1191 can have at least one chaiulel 2004, which is defined by an interior wa112031. Fluid flowing through the channe12004 can flow around a portion of the neclc finish mold 2002 positioned within the chaiu-iel 2004, and can absorb heat from the neck finish mold 2002. As used herein, the term "chilled working fluid" is a broad term and is used in its ordinary sense and refers, witllout limitation, to non-cryogenic reffigerants (e.g., Freon) and cryogenic refrigera.nts. As used herein, the tenn "cryogenic refrigerant"
is a broad tertn and is used in its ordinary sense and refers, without liinitation, to cryogenic fluids. As used herein, the tenn "cryogenic fluid" means a fluid with a maximi.un boiling point of about -50 C at about 5 bar pressure when the fluid is in a liquid state. hi some non-limiting einbodiments, cryogenic fluids can coinprise C02, N2, Helium, combinations thereof, and the like. In some einbodiinents, the cryogenic refrigerant is a high teinperature range cryogenic fluid having a boiling point higher than about -100 C at about 1.013 bars. h1 some enlbodiinents, the cryogenic refrigerant is a mid temperature range ciyogenic flttid having a boiling point between about -100 C and -200 C. hi some embodiments, the cryogenic refrigerant is a low temperature range cryogenic fluid having a boiling point less thaii about -200 C at about 1.013 bars. The tenns "chilled working fluid," "chilled fluid," "chilling fluid," and "cooling fluid" may be used interchangeably herein.
[0462] Heat from the warm molded prefonn 2000 can flow tlirough the neck finish mold 2002 to the worlcing fluid flowing througli the cooling system 1191. As such, the neck finish mold 2002 and the component 2003 cooperate to transfer part of the heat away from the preform 2000 for a reduced cycle time. The mold 1999 can be included in a machine used for and/or in processes for injection molding, compression molding, extrusion blow molding or any otller type of plastics molding.
[0463] In some embodiments, including the illustrated einbodiinent of FIGURE 37, the neclc finish mold 2002 is in the fonn of a thread split that has a molding surface 2007 configured to mold tlueads on the neck portion 2005 of the preform 2000.
The molding surface 2007 at least partially defines a mold cavity or mold space in which a moldable material is received and molded. The terms "mold cavity" and "mold space"
may be used interchangeably herein. The neck finish mold 2002 can, however, have otlier configurations depending on tlie desired article to be formed. For example, the illustrated neck finish mold 2002 also comprises a body 2009 and a heat transfer mernber 2023 in thennal coininunication with each other. Furthermore, although a screw top type fmish mold is sliown, other types of finishes may be molded, such as press fit, snap-on and the lilce.

[0464] At least a portion of the heat traiisfer member 2023 can be positioned, at least partially, witliin the channel 2004. hi other einbodiments, an exteiision (not shown) of the heat transfer member in thennal communication with the heat transfer meinber 2023 caai be positioned within the channel 2004. Working fluid can flow through the chaimel 2004 and absorb heat from the heat transfer menlber 2023.
Altenlatively, the heat transfer member 2023 can be used to provide lleat to the prefonza.
2000 or other product being molded, by absorbing heat from the chazulel 2004 and delivering it to the molding surface 2007. As used herein, the terin "heat transfer meinber" is a broad term and is used in its ordinary meaning and includes, witliout limitation, a protrusion, an extension, an elongated member, and/or a heat transfer element. The heat transfer member can have a hollow or solid constzliction.
Heat ca.n be transferred from the heat transfer meinber to a fluid surrounding all or part of the heat transfer member. Heat transfer members can have a one-piece or niulti-piece construction. The illustrated heat transfer mernber 2023 of FIGURE 37 has a one-piece constiliction and is monolitliically formed with the body 2009. The heat transfer member 2023 protrudes from the body 2009 and extends, at least partially, through the cliamzel 2004. In otller embodiments, the heat transfer member 2023 inay extend across the entire channel 2004 or a substantial distance across the chaiulel 2004.
[04651 The body 2009 of the neck finish mold 2002 comprises a fiontal portion 2021 that defines a surface 2011 configured to engage a lower component of the cavity section of the mold 1999, and the molding surface 2007. Ti-i the illustrated einbodiznent, the frontal portion 2021 includes a slight taper towards the body portion of the prefonn 2000. A central section 2022 of the body 2009 is coiuzected to the frontal portion 2021 aild the heat transfer member 2023. The frontal portion 2021, the central section 2022, and/or tlie heat transfer meinber 2023 may be separate items or a unitaiy member. Regardless, heat can be tra.nsferred along a flow path 2051 througli the frontal portion 2021, the central portion 2022, and the heat trailsfer member 2023, and then ultimately to a fluid passing through the channe12004. The fluid ca.n flow adjacent to any portion of the heat transfer member 2023 and/or across any other portion of the neck finish mold 2002.
[0466] The neclc finish mold 2002 may coinprise a higli heat transfer material.
In some embodiments, including the illustrated embodixnent of FIGURE 37, the neck finish mold 2002 can comprise mostly a high heat transfer material, although other materials can be employed to reduce wear, provide thermal insulation, and the like. For example, the neck finish mold 2002 can comprise more than about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99%, or ranges enconipassing such percentages of high heat transfer material by weight and/or volume. In another embodiinent, the entire neck finish mold 2002 is comprised of one or more higll heat transfer materials. Iii yet other einbodiments, the neck fin.ish mold 2002 may coinprise less than about 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2%, 1%, or ranges encoinpassing suc11 percentages. In yet other arrangements, the neck finish mold 2002 may not coinprise any high heat transfer materials. Thus, in some embodiments, heat transfer froin the molding surface to the charmel 2004 may involve both the use of a higli heat transfer material in the mold and the use of a cryogenic refrigerant and/or other fluid.
[0467] In some non-liniiting embodinlents the neclc i'iilish mold 2002 coinprises one or more higli heat transfer materials that define a heat flow path 2051. As illustrated in FIGURE 37, the heat flow path 2051 may be oriented along a middle portion of the mold body 2009. However, in other einbodiments, a heat flow path 2051 may be different than shown in FIGURE 37. For example, the flow patll 2051 may be oriented along one or more outer portions of the mold body 2009. Ii1 other einbodiments, a mold body 2009 may comprise two or more different heat flow paths 2051. Further, if the heat transfer member 2023 is used to deliver heat to the molding surface 2007, the general direction of the flow patli may be opposite or substantially opposite of that depicted in FIGURE 37.
[0468] With continued reference to FIGURE 37, heat from the preform 2000 is transferred to a working fluid in the chaiulel 2004 through the body 2009 along a flow path 2051. The configuration of the neclc finish mold 2002 can be varied to achieve the desired heat flow path(s) depending on the particular application. Arrows 2052, 2053, 2054 indicate heat flowing from the neck finish mold 2002 to the worlcing fluid flowing through the chamiel 2004. In the depicted einbodunent, lateral heat flows, indicated by the arrows 2052, 2053, and the axial heat flow, indicated by the arrow 2054, illustrate the possible directions which heat can talce to move towards the heat transfer element 2023.
The axial heat flow 2054 can be traiisferred through the face 2232 to the worlcing fluid.
Likewise, the lateral heat flows 2052, 2053 can flow through the surface 2231 to the working fluid. In this maimer, there can be multi-dimensional heat flow from the heat transfer meinber 2023 to enhance the heat transfer efficiency to the worleing fluid passing thereby.
[0469] Heat from the preform 2000, at any point during_the molding cycle, can be transferred througll the surface 2007 and along the path 2051 through the frontal portion 2021. The heat can then flow along the central portion 2022 tmtil it reaches the heat transfer meniber 2023. The heat then is dissipated (sucli as indicated by the arrows 2052, 2053, 2054) and delivered to the fluid witllin the clianne12004. The worlcing fluid can flow continuously (at one or more rates) or interniittently througli the chainiel 2004.
In some enlbodiments, pulse cooling can be used as described below. Furtller, the teinperature of the fluid flowing witliin the chaiulel 2004 may be varied to provide additional control of the cooling of the molded material and/or heat dissipation across the neck finish mold. For example, a fluid (e.g., C02) nzay be vaporized to lower the teniperature of the fluid conveyed within the channel 2004. In some embodiments, one or more temperature elements and/or regulators may be used to regulate the flow and/or temperature of the fluid conveyed thought the chaiulel 2004 to accurately control the cooling rate of the preforin or other molded material. In this inaiu-ier, heat can be transferred to the worlcing fluid at any time in the molding cycle, which can reduce cycle time and increase output of the mold 1999. A cuived outer surface (not shown) of the heat transfer member promotes high flow rates through the channel 2004. For exanlple, the outer surface of the heat transfer member 2023 can be configi.ued to promote any desired flow characteristic (e.g., laminar flow, turbulent flow, etc.).
However, as nzentioned above, it will be appreciated that the transfer of heat across the mold body 2009 may be different than illustrated in FIGURE 37.
[0470] The component 2003 can be any part of the mold 1999 suitable for containing the channel 2004. In some embodiments, including the illustrated einbodiinent of FIGURE 37, the component 2003 is in the form of a section or portion of a mold plate that receives a portion of the neck finish mold 2002. h1 some embodiments, the component and/or the chamiel may be disposed within the saine mold section or structure as the neck finish mold. The heat transfer meinber 2023 extends, at least partially, into the component 2003 and preferably contacts the worlcing fluid during operation. In a preferred embodiinent, the heat transfer member 2023 may be partially and/or coznpletely inunersed in the working fluid during operation to provide enhanced heat transfer from the mold to the working fluid.
[0471] In some einbodiments, the chamlel 2004 is included within the mold body 2009. For instance, a single mold structure can coinprise a cooling system 1191, including one or more channels 2031 configured to acconunodate a working fluid. The channels- 2031 may be fonned from the mold body 2009, or they may be separate nlembers that are incorporated or otherwise attached to the body 2009. In addition, two or more channels 2031 configured to cairy a working fluid may be included in a single mold 1999. In such an arrangement, the heat tran.sfer meinbers 2023 positioned within the channels 2031 can be in thei7nal coinmunication with one another. For exainple, if a mold comprises two chaiulels 2031 the heat transfer nlembers 2023 may be oriented along the sanie general heat flow path 2051. Thus, depending on the desired heat transfer from or to a molding surface 2007, working fluid may be routed through one or both of the chaiuiels 2031. hi suc11 embodiments that coniprise two or more chaiuiels 2031, the cllaiuiels 2031 may or may not be in fluid communication with one another.
[0472] Ii1 the einbodiment illustrated in FIGURE 37, the heat transfer menzber 2023 extends approximately half-way across the width of the chaiuiel 2004. It will be appreciated that the distance wllich the heat transfer inember 2023 extends into the chaiulel 2004 may be greater or smaller tlian shown. Lz one embodiinent, the heat transfer ineinber 2023 can extend through substantially the entire chaiulel 2004. In other etnbodiments, the heat transfer member 2023 can extend less than half-way through the chaiuzel 2023. For example, the heat transfer inember 2023 can extend about 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.9%, or ranges enconlpassing sucli percentages across the widtli or diazneter of the channel 2004. In other embodiments, the heat transfer member 2023 inay be flush with the imler wall 2031 of the channel 2004. hi yet other embodinients, the heat transfer inember 2023 may be recessed with respect to the iiuler wall 2031 defining the chainlel 2004, such that even if it does not extend ilito the chalulel 2031 it is still in thennal coinrnunication with it.
[0473] Advantageously, the component 2003 can have one or more chainlels 2031 of any size and configuration to transfer heat away from the neck finish znold 2002.
The chaiulel 2004 can be generally larger than a traditional internal chaiulel of a thread split. However, the channels 2031 can be the same size as or sinaller than a traditional internal channel of a thread split. The cross-sectional area of the channel 2004, as defuled by its interior wall 2031, is preferably greater than the cross-sectional area of a traditional internal chainiel of a thread split. The channel 2004 can provide a higlier voluinetric flow rate as coinpared to an internal channel in a thread split. Thus, the channel 2004 may provide increased thennal loading capacity. hi some non-limiting embodiments, the channel 2004 can have a cross-sectional area that is at least about 0.1 cm2, 0.25 cin2, 0.5 cm2, 1 cin2, 2 cm2, 3 cmZ, 4 czna, 5 cm2, 6 cin"', 7 cn~, 8 cm2, 9 cinZ, 10 cm2, 15 cznz, and ranges encoinpassing such cross-sectional areas. In some embodiments, the channe12004 has a cross-sectional area that is greater than about 2 cm2, 4 cm2, 5 e1n2, and ranges encoinpassing such cross-sectional areas. In other embodiments, the cross-sectional area of the channel 2004 may be smaller than 2 cm2. Iii yet other einbodiments, the cross-sectional area of the cham1e12004 may be larger than 5 cm2, 10 cm2, or 15 cm2.
It will be appreciated that the cross-sectional area of the cllaiulel 2004 may be higher and/or lower than indicated herein. As such, the working fluid can flow at a high flow rate tlirough the cllamie12004 to rapidly cool the heat transfer meinber 2023.
[0474] Althougli not illustrated, the neck finish mold 2002 can have temperature control elements that can be used in coinbination with the cooling systein 2011. Cooling chaiulels, bubblers, heating/cooling rods and/or the like can be used to control the temperature of the neck finish mold 2002. Thus, various structures and devices can be einployed, eitlier in addition to or in lieu of structures and devices discussed herein, to control the temperature of the neck finish mold 2002.
[0475] The charn1e12004 can have a generally circular cross-section, elliptical cross-section, polygonal cross-section, or any other type of cross-section capable of conveying a working fluid. In the illustrated einbodiment FIGURE 37, the channel 2004 is generally circular, and the heat transfer member 2023 extends partially therethrough.
The illustrated heat transfer member 2023 extends laterally through a portion of the channel 2004. In some embodiments, the heat transfer meniber 2023 extends at least halfway through the channel 2004. As indicated above, the extent to which the heat transfer meinber 2023 may protrude into the channel may be greater or lesser than depicted in the FIGURE 37.
[0476] A sealing system 2032 of FIGURE 37 can be used to limit or prevent fluid from escaping from the channel 2004. The sealing system 2032 can be positioned between the neck finish mold 2002 and the coxnponent 2003 and preferably comprises one or more of the following: sealing members, gaskets, 0-rings, mechanical seals, packing, and combinations thereof. The illustrated sealing system 2032 coinprises an 0-ring that is disposed in a recess of the component 2003 and surrounds the base of the heat transfer member 2032. Altenlatively, the 0-ring and/or otller meinber comprising the sealing system 2032 may be positioned within a recess of the body 2009. In anotlier einbodiment, the sealing system 2032 need not be positioned within a recess of the component 2003 or body 2009. For exainple, the sealirig system 2032 can coinprise a gasket that is positioned between adjacent surfaces of the component 2003 and the body 2009. Aiiy 0-ring, gasket and/or other member of the sealing system 2032 may coinprise rubber, silicone, neoprene, polyurethane, otlier elastomeric materials and/or other at least partially compliant materials adapted to form a seal.

[0477] hi some preferred einbodiments, pulse cooling or similar tecluiology can be incorporated into one or more mold sections. If a cooling fluid is conveyed tluough the chaiuze12004 when the mold space does not incltide a preform or other object or when the mold space or cavity is otherwise exposed to ainbient air, moisture from the surrounding air can condense on a molding surface. The condensation may interfere with the molding operation by reducing prefonn production, decreasing molding quality, increasing cycle times and the like. Therefore, it may be desirable in certain embodiinents to eliminate cooling of one or more mold sections (e.g., core, cavity, etc.) wlzen molding surfaces are exposed to moist air or other conditions wllere condensation can form on a molding surface.
[0478] In one embodiment, pulse cooling includes directing a cooling fluid tluough a mold once every molding cycle. The cooling fluid can be conveyed within a cllannel, sucll as the chamiels 2004 in tlie enibodiments illustrated in FIGURES 37 48.
Furtlzer, pulse cooling can include directing a cooling fluid througll one or more cooling channels, such as, for example, the cooling chaiulels in the einbodiments illustrated in FIGURES 6 36, eitller in lieu of or in addition to chaiulels 2004 illustrated and discussed in relation to the einbodiments of FIGURES 37 48. The flow rate, tenlperature, pressure uid/or other properties of the cooling fluid are preferably capable of acllieving the desired heat removal from the preform (or other object being foimed) and/or the mold itself. It will be appreciated that pulse cooling can comprise directing a cooling fluid once, twice or more times through a cooling chamlel during a single molding cycle.
[0479] hi some embodiments, one or more of the mold sections (e.g., core, cavity) may include temperature sensors to facilitate control of the heat dissipation caused by a particular pulse of cooling fluid. As used herein, the tenn. "pulse" is a broad term and is used in accordance with its ordinary ineaning and may include, without limitation, one or more surges of fluid througll a channel or a system of channels. Pulse can include one of a plurality of surges occurring during a particular molding cycle.
Alternatively, pulse may refer to two or more surges that together regulate the temperature of the mold and/or moldable object during a molding cycle. The temperature sensors can be included on a molding surface, within a cooling channel, within the body of a mold and/or any other suitable location. In some preferred embodiments, a molding apparatus may include inultiple temperature sensors to provide more accurate control of the cooling process.

[0480] In addition, the molding apparatus can include one or more controllers that regulate the rate of flow and presstue of the cooling fluid tlirough the chazuzels of the inold. For exainple, in soine enibodilnents, the controllers nlay conlprise a valve.
Furtller, such controllers can regulate the temperature of the cooling fluid being conveyed tluough a chamzel. Ilz one einbodiment, a valve or other controller can control the fluid teinperature by regulating its discharge pressure, such as, for exainple, the extent to which the cooling fluid is vaporized. Tllus, during pulse cooling, controllers can assist in the control of inold and/or preform temperature by regulating the tenlperature, pressure and/or flow rate of the cooling fluid.
[0481] Pulse cooling teclmiques may be used in a mold comprising one or more high heat transfer materials. For exainple, pulse control principles can be used to deliver cooling fluid tluough the charnlel 2004 illustrated in the embodinzents of FIGURES 37 48. Tlius, the cooling fluid can more efficiently reinove heat from the mold and/or the prefonn.

[0482] In operation, one or more pulses of cooling fluid are delivered tlzrougli a chalulel, such as, for example, the chan.nel 2004 illustrated in FIGURE 37.
The pulses are preferably delivered when the mold cavity or space has been filled, either partially or fully, with a moldable material (e.g., a polylneric material for the formation of a prefonn).
The type, temperature, flow rate, pressure and/or otlier characteristics of the cooling fluid are preferably selected to adequately control the temperature of the mold 1-999 and/or- to adequately deliver heat from the molding surface 2007 to the cllann.el 2004 during a single molding cycle. In one einbodiment, after completion of a molding cycle, the teinperature of the molding surface 2007 will be sufficiently high to prevent unwanted condensation from forming thereon. The surge of cooling fluid is preferably configured to quickly reduce the temperature of the molding surface. Therefore, the use of pulse cooling can result in higher quality molding and reduction of cycle times.
[0483] FIGURE 38 illustrates the heat transfer meinber 2023 and the coinponent 2003 talcen along the line 38-38 of FIGURE 37. During the molding cycle, working fluid, such as, for exainple chilled working fluid (e.g., non-cryogenic refrigerant, cryogenic refrigerant, water, etc.) can flow through the chaime12004 and around the heat transfer member 2023. In some non-limiting embodiments, tlie working fluid comprises water. The water is heated as it absorbs heat from the heat transfer member 2023. The working fluid can be chilled, 11ot, or at any other temperature to heat or cool the neck finish mold 2002 as desired.

[0484] In one embodiment, the worlcing fluid is preferably at a temperature less than the temperature of the stirfaces of the heat transfer member 2023, such that heat may be transferred from the heat transfer meinber 2023 to the working fltiid.
The difference in temperatures and the heat capacities of the materials are two factors in detennining the cooling rate. The cham1e12004 can be completely or partially filled with the worlcing fluid. The heat transfer nieniber 2023 can be completely immersed in the worlcing fluid to ei-Aiance dissipation of heat to the worlcing fluid.
Alternatively, only a relatively small portion of the heat transfer member 2023 may contact the worlcing fluid.
The worlcing fluid may be configured to flow eitlier co11t1n1loUsly or intennittently tlirough the one or more chanliels 2031 of the cooling system 1191.
[0485] The heat transfer member 2023 may have a generally circular cross-section, as shown in FIGURE 38. However, the heat transfer niember 2023 can have one or more other configurations. For example, a heat transfer meinber 2023a of has a generally ellipsoidal sliape. The heat transfer meniber can have a generally circular profile, ellipsoidal profile, polygonal profile (including rounded polygonal), ovoid, coinbination of the foregoing, or a.ny other suitable profile.
[0486] With continued reference to FIGURE 39, the heat tra.nsfer meinber 2023a can be at any suitable orientation. The illustrated ellipsoidal heat transfer meinber 2023a has a lnajor axis that is generally aligned witlz the flow of the worlcing fluid, as indicated by the arrow 2041. As such, tla.e lateral area 2231 of the heat transfer ineinber 2023a may be effectively increased to maximize heat transfer to the working fluid. It is contemplated that the heat transfer member 2023a can also have otlier elongate shapes to increase the heat transfer melnber's surface area that contacts the working fluid.
[0487] In other embodiments, heat trausfer enliancers can be utilized to facilitate heat dissipating from the heat transfer member to the worlcing fluid. Witli respect to FIGURE 40, the heat transfer member 2023b has heat transfer enhancers which increase the effective surface area for heat transfer. The heat transfer enhancers 2231b, 2232b, 2233b are configured to increase the ratio of surface area to volume of the heat transfer member 2023b.
[0488] As shown in FIGURES 40 and 41, the heat transfer member 2023b has a plurality of heat transfer enhancers 2231b, 2232b, 2233b that are spaced from each other. In the illustrated embodiment, each of the heat transfer eiillancers 2231b, 2232b, 2233b is in the fonn of a fin. Each of the fins has a pair of longitudinally extending lateral surfaces to iinprove the transfer of heat to the worlcing fluid. It is conteinplated that aiiy ntunber of fins can be employed. Although the illustrated heat transfer ei-dlancers are longitudinally extending fins (e.g., fins extending generally parallel the longitudinal axis of the heat transfer member), the heat transfer members and/or the fins (or other heat transfer ei-d-lancers) can be arranged in other orientations. The heat trailsfer inember 2023b can have loilgitudinally extending fins, laterally extending fins, obliquely extending fins, combinations thereof, or any otlier suitably oriented fins for the desired heat transfer. The terins "heat transfer ei-Jlancer" and "fin" are used interchangeably herein.
[0489] Other types and combinations of heat transfer eifllancers can also be utilized. Heat transfer enhancers can comprise one or more of the following:
fins, protntsions, slits, bores, chaiulels, grooves, openings, recesses, indentations, mesh structures, and coinbinations thereof. The heat transfer enhancers can be selected based on the properties of the worlcing fluid, desired flow characteristics, heat transfer efficiency, and the like. In view of the present di'sclostue, a skilled artisan can select the type, configuration, and position of the heat transfer eiAiancers of the neck fiilish mold 2002 for a particular application. The heat transfer eilliancers may or inay not comprise a high heat transfer inaterial. In some non-limiting einbodinzents, the heat transfer ei-d-iancers comprise a high heat transfer inaterial, such as copper and its alloys, for efficient heat transfer.
[0490] It will appreciated by those of skill in the art that the heat transfer devices and methods described hereiii are not limited to neclc fixnish molds.
For exainple, cooling systeins comprising one or more channels may be included in other portions of the cavity mold section, such as for exainple, the body of the mold cavity section tliat surrounds the main portion of a prefonn or other itein being molded. hi addition, as discussed in greater detail below, suc11 cooling systems may be included in the mold core section of a molding apparatus. In some enibodiments, suc11 heat transfer devices may be included in botli a inold cavity section and a mold core section of a mold apparatus.
Thus, the transfer of heat to and/or from a inolding surface using a heat transfer ineinber which is, at least partially, disposed within a chaiuiel may be used in any part of a mold, mold section or molding apparatus, either in lieu of or in addition to otller temperature control methods. For example, such cooling systems may be used to eiAiance cooling in the gate region of either or both parts of the mold (e.g., cavity, core).
[0491] FIGURES 42-48 depict additional embodiments of molds, which are generally siinilar to the enibodiments illustrated in FIGURES 37-41, except as further.

detailed below. Where possible, sinlilar elements are identified witli identical reference nuinerals in the depiction of the einbodinlents of FIGURES 37-48.
[0492] Witli respect to FIGURE 42, the mold 2081 comprises a neclc finish mold 2002 that includes at least one wear resistant portion. The wear resistant portion is configured to reduce wear attribtttable to interaction between the neclc finish mold 2002 and adjacent components of the mold 2081. For example, when the neck finish mold 2002 moves between a first position for molding the prefonn 2000 and a second position for reinoval of the prefonn 2000, the wear resistant material can reduce wear of the neck finish mold 2002 so as to extend the life of the mold. In some einbodinlents, the wear resistant material can be a hardened material. h1 a preferred embodiment, the wear resistant material is a hardened, high wear material such as steel (e.g., including tool steel, higli strengtli steels, nitride steels, etc.). The wear resistant material can also coinprise cerainics (e.g., engineering ceramics), polymers, and the like. The wear resistant material preferably fonns one or more of the surfaces of the mold 2081 that bear against one or more adjacent surfaces.
[0493] In the illustrated embodiinent of FIGURE 42, high wear portions 2211a, 2221a form portions of the neck mold finish 2002. The high wear portion 2211a reduces wear of the frontal portion 2021, while the high wear portion 2221a reduces wear of the body 2009. Therefore, such high wear portions can be utilized to protect one or more surfaces of the neck finish mold 2002 whicll are in sliding contact with other parts of the mold or other surface, or subjected to other potentially dainaging contact and/or exposure to elements that may cause wear on the neck finish mold. One or more other portions of the neclc finish mold 2002 can coinprise high heat transfer materials. For exainple, in some embodiments the liigh wear portions 2211 a, 2221a conlprise steel and the body 2009 comprises one or more higli heat transfer materials. h-i other embodiments, the entire or substantial poi-tion of the neck finish mold 2002 may include a high heat transfer material.
[0494] FIGURE 43 illustrates a neck finish mold 2082 that has a inulti-piece construction. The illustrated neck finish mold 2082 comprises a multi-piece heat transfer ineinber 2090 positioned within a mold component 2003. In the depicted einbodiment, the heat transfer member 2090 comprises a first portion 2060 coupled to a second portion 2024. It will be appreciated that in other embodiments, the heat transfer lneinber can coinprise more or fewer pieces than illustrated in FIGURB 43.

[0495] As illustrated in FIGURE 43, the first portion 2060 is iiitegrally foi7ned with the body 2009 of the neclc finish mold 2002. However, in other embodiinents, the first portion 2060 and the body 2009 can have a nzulti-piece constr ction. The first portion 2060 is an elongated protiusion that extends from the body 2009 and is received within chaniber of the second portion 2024. The chaniber of the second portion 2024 asid the first portion 2060 have a modified frusto-conical shape. The chainber of the second portion 2024 and the first portion 2060 can have any other shape, such as, for example, conical, frusto-spherical and the like.
[0496] The second portion 2024 is configured to maximize heat transfer to a working fluid wltllil the channel 2004. The second portion 2024 in FIGURE 43 comprises a plurality of heat transfer enliancers 2242 configured to increase the ratio of surface area to volume of the second portion 2024. The heat transfer enliancers 2242 are illustrated as fins, although other types of heat transfer eiihancers and/or different configurations of heat transfer enha.ncers can be utilized. As illustrated, the heat transfer enhancers 2242 are outwardly extending fins which are spaced from each other along the chainiel 2004. Between adjacent heat transfer eiiIlancers 2242 is a corresponding recess 2241 througll wlllch worlcing fluid can flow. Althougll the illustrated heat transfer enhaiices 2242 have a generally straiglit shape, they may have any other configuration, such as, for example, curved, tapered, arcuate, circular, conical, helical and/or the like.
[0497] Aiiy suitable coupling means can be einployed to couple the second portion 2024 to the first portion 2060. One or more fasteners 2025 (e.g., a threaded member such as a bolt, pressure or snap fit coupling systezn, etc.) can be used to couple the second portion 2024 to the first portion 2060. The fastener 2025 is disposed tl-lrougli a tlirougl-fliole in the second portion 2024 and a bore in the first portion 2060. In one embodiment, tlie fastener 2025 threadably couples to the second portion 2024 and, preferably, securely holds the first portion 2060 to the second portion 2024.
In other einbodiments, welding, adhesives, threads, mechanical fasteners (e.g., nut and bolt asselnblies), pins, press fitting, and combinations thereof can be employed to couple the components of the heat transfer meinber 2090 together. Such multi-piece heat transfer ineinbers may iinprove heat transfer, facilitate replacement and maintenance of the heat transfer meinbers and the lilce.

[0498] The tlleimal conductivities of the first portion 2060 and the second portion 2024 can be generally similar to each other. For example, both the first portion 2060 and the second portion 2024 can coinprise a higli heat transfer material.
Heat can flow rapidly through the first portion 2060, the second portion 2024, and then to the fluid flowing across the heat transfer meinber 2090. Iii alternative enlbodiments, the first portion 2060 and the second portion 2024 comprise materials having different or substantially different therinal conductivities.
[0499] The component 2003 can be configured to ii-Aiibit or prevent fluid in the chamiel 2004 from escaping between the component 2003 and the neck finish mold 2002. A plate 2253 may comprise grooves 2251, 2252 that are in.terposed between the mold plate 2261 and the neclc finish mold 2082. In the illustrated embodixnent of FIGURE 43, the recess 2252 is positioned between the plate 2253 and the mold plate 2261 and contains a sealing meinber (e.g., a rubber O-ring). The recess 2251 is positioned between the neclc finish mold 2082 and the plate 2253, and preferably holds a sealing member. The sealing meinbers act to seal fluid within the chazulel 2004. Aiiy number of sealing meinbers can be employed at various locations in the mold to ensure that fluid is retained in the chatule12004.
[0500] With continued reference to FIGURE 43, the heat transfer member 2090 can have an overall lateral dimension that may be greater than a size (e.g., diameter) of a tluoughhole 2270 of the mold component 2003. The second portioii 2024 can have varioi,is configurations depending on the application. As shown in FIGURE 44, the second poi-tion 2024 has a generally circular profile as viewed along the longittidinal axis of the heat transfer member 2090. It will be appreciated, however, that the second portion 2024 can have any other configuration. For example, as shown in FIGURE 45, the secoild portion 2024 has a generally polygonal profile, illustrated as a rectangle. Non-lizniting embodiments of the second portions of the heat transfer inember can have a shape that is generally elliptical, circular, polygonal, ovoid, or combinations thereof. The second portion 2024 of FIGURE 45 extends along the chaiuiel 2004 and can have a greater effective surface area for heat transfer than the second portion 2024 illustrated in FIGURE 44.
[0501] FIGURE 46 illustrates a mold 2101 that has a cooling system 2003 configured to cool the preforin 2000 disposed on a core 2300 that does not have any cooling channels therein. The cooling system 2003 can have one or more cliaiulels for directly or indirectly cooling the core 2300 and the associated prefoi7n 2000.
In other einbodiments, the core section may include one or more other heating or cooling members, such as, for exainple, other heating/cooling charm.els. Generally, fluid can flow tlrrougli a mold plate and/or over a portion of a core 2300 to control the temperature of the core.

[0502] The core 2300 can extend upwardly and be held by a core holder 2007.
The core holder 2007 and the core 2300 cooperate to deflne the fluid chaiulel suitable for holding a worlcing fluid. The fluid flows around the core 2300 to absorb heat from the adjacent core 2300.
[0503] In FIGURE 46, the rear portion 2062 of the core 2300 can be positioned within a mold plate 2008. The rear portion 2062 has one or more heat transfer ei-diancers for increased heat transfer. In the illustrated embodiment, the rear portion 2062 has a plurality of heat transfer eiiliancers 2622 (e.g., fins) that are in fluid coinmunication with the worlcing fluid flowing through a chamiel 2004. Heat can be conducted away from the prefol7n 2000 along the pat112051 through the core 2300 to the rear portion 2062. hi some einbodiments, depending on the materials of constrtitction, dimensions, shape, teinperature gradient, *and/or other characteristics of the mold and its surroundings, heat can flow somewhat laterally, as indicated by the arrows 2052, to the thermal enhancers 2622, and ultimately to the worlcing fluid in the chaiu-ie12004. hi otlier einbodiinents, the core 2300 may have more or fewer heat transfer enhancers 2622 than indicated in FIGURE 46. In yet another embodiinent, the core 2300 may not have any heat transfer enhancers at all.

[0504] FurtlZer, the systein may be configured with two or more chaiulels 2004 that are configured to be in thermal coininunication with the core 2300, either directly or tl-irough one or more heat transfer ei-Aiancers 2622. If two or more chaiulels 2004 are included in a single design, the cha.iulels 2004 can be configured so that they are in fluid conununication with one another. In a preferred einbodiment, the chaiulels 2004 can comprise a valve or other inember to optionally control whether or not the chamaels 2004 are in fluid communication with each other. h2 otlier einbodiments, chaa.nlels 2004 need not be in fluid coininunication with one anotller. The channels 2004 may be positioned anywhere along the mold plate 2008 and/or elsewliere in a mold apparatus. It will be appreciated that tlie shape, size, orientation, distance from the core 2300, and other characteristics of the clia.nn.els 2004 can be different than illustrated in FIGURE 46.
[0505] As discussed above in relation to FIGURES 37-45 for neck finish molds, heat transfer members and/or heat transfer enhancers may have any sliape, size, dimensions, or general conflguration. For example, the extent to which heat transfer members and/or heat transfer enhancers are disposed within a chamlel may vary.
In addition, the total surface area of the heat transfer members and/or heat transfer ei-dlancers that may contact the worlcing fluid conveyed within a chaimel can also vary.
[0506] The core 2300 can comprise a high heat transfer material for ei-diaa.lced tlZermal efficiency. For exainple, the core 2300 can coinprise copper and/or its alloys. To reduce wear between the core 2300 and the core liolder 2007 or other mold area, portions of the core 2300 and the core holder 2007 that engage each other can comprise a high wear material. For example, the core holder 2007 can coinprise a high wear material, such as steel. To reduce wearing of the core 2300, the core 2300 can have an externally hardened layer that engages the core holder 2007. However, the core 2300 can comprise a low wear material that can bear against the core holder 2007.
[0507] In operation, working fluid 2041 can flow through the chaiulel 2004 and around the core 2300, preferably absorbing heat from the core 2300. The working fluid flows generally orthogonal to the longitudinal axis of the core 2300.
Altein.atively, the working fluid can flow in any otller direction with respect to the core 2300. The working fluid may be a cryogenic or a non-cryogenic fluid. For example, the working fluid may be cooling/heating water, refrigerant, carbon dioxide, nitrogen, and/or any other liquid or gas.

[0508] Although not illustrated, the split ring 2002 can have a heat transfer member also in fluid communication with the working fluid 2041. Alternatively, the split ring 2002 can be cooled by worlcing fluid in a separate cooling system. The split ring 2002 and the core 2300 can therefore be cooled by the saine system or different cooling systems.

[0509] In some einbodiments, the mold 2101 can include a means for controlling the temperature of the core 2300. The core 2300 can include, but is not limited to, bubblers, channels, resistors, insulating materials, heating/cooling rods, or other means for controlling the temperature of the core. In FIGURE 46, the illustrated core 2300 is a generally solid piece of material extending from the core holder 2007 thougli the split ring 2002 when the mold is in the illustrated closed position. However, in other embodiments, the core 2300 may include areas having non-solid features, such as, for exainple, other heating/cooling channels and the like.

[0510] With respect to FIGURE 47, the core 2500 can be configured for thermal isolation of one or more of its portions. Thus, a portion of the core 2500 can be thermally isolated from another portion of the core 2500 so as to cool and/or heat one or more portions of the prefonn 2000 at different rates. The core 2500 can be utilized to fonn prefonns with a particular finish or stnicture, sucll as a crystalline neclc finish, seini-crystalline structure, amorphous structure or the like. Alternatively, the therinally isolated portions of the core 2500 can be used to maintain a prefonn at a generally unifonn temperature. For example, having increased cooling at tliicker portions of the preform may maintain a relatively unifonn overall tenlperature. Various sections of the core 2500 can be tllermally isolated and maintained at any desired teinperature, as detailed below.
[0511] In some einbodiments, including the illustrated embodiment of FIGURE 47, the core 2500 has a body portion 2061b and a neck portion 2006b that are generally tliermally isolated from one anotlier. For example, in such a configuration, the body portion 2061b can cool the body of the prefonn 2000 at a first rate, while the neclc portion 2006b cools the neck of the prefonn 2000 at a second rate. The first rate can be the same or different from the second rate. For example, to fonn generally ainorphous prefonns, the first rate of cooling and the second rate of cooling can be relatively high.
To form preforms with a crystalline neck fiiiish, the second rate can be less than the first rate so that the polymer of the neck portion can undergo crystallization.
[0512] The body portion 2061b can be a generally cylindrical, elongated member that extends from the rear portion 2062a to the end cap of the prefolin 2000.
One or more insulators 2006c or thermal insulating materials can be positioned between the body portion 2061b and the neck portion 2006b. The insulator 2006c can be a sleeve or tubular member that extends along the rearward portioil of the body portion 2061b.
The illustrated insulator 2006c is interposed between the neck portion 2006b and a portion of the body portion 2061b. However, the ntunber, material(s) of construction, size, shape, position, orientation, and/or otlier characteristics of the insulators 2006c or thermal insulating materials may be different than illustrated in FIGURE 47.
For example, in some embodiments, the insulators 2006c can be manufactured froln a rubber, polyiner, foain, metal, carbon, ceranlic and/or any other material. In other embodiments, the insulators 2006c can coinprise an air gap or any otller ineinber or cavity that will prevent or reduce the heat transfer between adjacent surfaces. The tenns "insulator" and "thennal insulating material" are used interchangeably herein.
[0513] With continued reference to FIGURE 47, the neck portion 2006b extends from the rearward portion 2062a and terminates just below the neck portion of the prefonn 2000. hi the depicted einbodiinent, the neck portion 2006b fonns the iiuler surface of the neck portion of the prefonn 2000, while the body portion 2061b fonns the inner surface of the body portion of the prefolin 2000. Thus, the insulator 2006c may impair heat exchange between the neck portion 2006b alid the body portion 2061b. The extent to whicli such heat excliange inlpainnent is accoinplished generally depends on one or more variables, including the types of materials used, tl-ie operating teniperattire range of the molding apparatus, the size, shape, orientation, spacing and otller cllaracteristics of the various mold coinponents (e.g., the core 2005, insulators 2006c, mold cavity, etc.), the characteristics of the prefoiln 2000 and/or the like.
[0514] T.he insulator 2006c can comprise low heat transfer materials. As used herein, tl-ie terin "low heat transfer material" is a broad tenn and is used in accordance with its ordinary meaning and may include, without limitation, rubbers, polyiners, plastics, carbon, eeramics, air, or other suitable insulating material for limiting heat transfer between the neck portion 2006b and the body portion 2061b. Low heat transfer materials have a tliennal conductivity that is less than the therinal conductivity of higli heat transfer materials. The thicln-iess of the insulator 2006c can be increased or decreased to decrease or increase heat transfer through tl-ie insulator 2006c.
[05151 If the core 2500 is a solid single piece, heat fiom tl-ie prefonn body passes through the core 2500. This thermal energy can heat or limit cooling of the upper portion of the core 2500 adjacent to the thread or neclc finish of the prefonn 2000, thus reducing cooling efficiency in the upper portion of the core 2500. That is, heat from the body portion of preform 2000 can heat or increase the temperature of the core adjacent to the neck portion of the prefonn. However, in the embodiment illustrated in FIGURE 47, the core 2500 has separate regions that are not appreciably heated by the heat traveling through otlier portions of the core 2500. Heat traveling up the core 2500 along the body portion 2061b does not substantially inhibit cooling of the neck portion 2006b. Thus, each thennally isolated portion of the core 2500 can cool a portion of the prefonn at a precise rate without impairment froin the heat traveling along otlier portions of the core 2500. The core 2500 and/or mold cavity sections of a mold may strategically include insulators to create one or more other thermally isolated portions, either in lieu of or in addition to those illustrated in FIGURE 47.

10516] FIGURE 48 illustrates a core 2600 that has a plurality of sections, each in fluid communication with a cooling systein 2062. One or more cooling systems can be used to cool the core 2600. Insulation, such as one or more insulators or theimal insulating materials, can be positioned between each of the sections to enliance thermal isolation of these sections.

[0517] The core 2600 coinprises a first portion 2608 configured to mold a portion of preform 2000. Aii adjacent portion 2610 of the core 2600 is configured to niold another portion of the prefoiin 2000. A-iiother portion 2612 of the core 2600 is configured to form a different portion of the prefonn 2000. The central portion 2614 of the core 2600 is configured to form a portion of the preforin 2000. In the illustrated einbodiinent, the central portion 2614 is configured to mold the end cap of the prefonn 2000. The central portion 2614 extends upwardly through the central portion of the core 2600 and is preferably in tlzermal cominiulication with the temperature control systein 2602. One or more of the portions 2608, 2610, 2612, 2614 can coinprise an insulating material. As such, each of the portions can define an isolated heat flow pat11 frozn the preform 2000 to the cooling systein 2602.
[05181 A1t11ough this disclosure is in the context of certain prefeiTed embodiments and exa.inples, it will be understood by those skilled in the art that the inventions extend beyond the specifically disclosed embodiznents to other alternative embodiments and/or uses of the inventions and obvious inodifications and equivalents tliereof. In addition, while several variations have been shown and described in detail, other modifications, which are within the scope hereof, will be readily apparent to those of skill in the art based upon this disclosLUe. It is also contenlplated that various combination or sub-coinbinations of the specific features and aspects of the embodiinents may be made and still fall within the_scope of the inventions. It should be understood that various features and aspects of the disclosed embodiments can be combined witli or substituted for one another in order to foim varying modes. For exalnple, the channels, heat tra.nsfer meinbers, heat transfer eliliancers, insulators, high wear portions and/or other portions of molds disclosed in the einbodiments illustrated in FIGURES 37-48, may be combined with one another in any combination to achieve a device (e.g., a mold plate, core portion, cavity section, neck finish lnold and/or any other device), a systein or a related method for controlling mold teinperatures. Thus, it is intended that the scope should not be limited by the particular disclosed einbodiments described above.

Claims (36)

1. A mold defining a mold space configured to receive a moldable material, said mold comprising:
a mold plate having a channel configured to convey a fluid; and a neck finish mold comprising:
a mold body that includes a molding surface, the molding surface at least partially defining the mold space; and a heat transfer member at least partially disposed within the channel;
wherein a portion of the heat transfer member is in thermal communication with a fluid when a fluid is being conveyed within the channel.

2. The mold of Claim 1, wherein at least a portion of the neck finish mold comprises a high heat transfer material.

3. The mold of Claim 2, wherein the high heat transfer material has a thermal conductivity higher than the thermal conductivity of iron.

4. The mold of Claim 2 or 3, wherein the high heat transfer material has a thermal conductivity higher than 100 W/(mK).

5. The mold of any of the preceding claims, wherein at least a portion of the heat transfer member comprises a high heat transfer material.

6. The mold of any of the preceding claims, wherein a substantial portion of the neck finish mold comprises a high heat transfer material.

7. The mold of any of the preceding claims, wherein the neck finish mold further comprises at least one hardened material configured to reduce wear when the neck finish mold is moved relative to an adjacent surface.

8. The mold of any of the preceding claims, wherein the neck finish mold further comprises a thermal insulating material configured to form a thermal barrier.

9. The mold of any of the preceding claims, wherein the neck finish mold comprises a thread split movable between a closed position and an open position.

10. The mold of any of the preceding claims, wherein the heat transfer member comprises at least one heat transfer enhancer configured to increase the ratio of surface area to volume of the heat transfer member.

11. A mold defining a mold space configured to receive a moldable material, said mold comprising:

a first mold portion comprising at least one channel, said channel configured to convey a fluid; and a second mold portion comprising:
a molding surface that at least partially defines the mold space;
a heat transfer member, said heat transfer member at least partially extending into the channel of the first portion; and a mold body extending between the molding surface and the heat transfer member;
wherein the heat transfer member is configured to transfer heat between the molding surface and a fluid being conveyed within the channel.

12. The mold of Claim 11, wherein the second mold portion is part of a mold cavity section.

13. The mold of Claim 11, wherein the second mold portion is part of a neck finish mold.

14. The mold of Claim 13, wherein the neck finish mold comprises a thread split movable between a closed position and an open position.

15. The mold of Claim 13 or 14, wherein the first mold portion forms part of a mold plate which is configured to receive a section of the neck finish mold.

16. The mold of any of Claims 11 through 15, wherein at least a portion of the second mold portion comprises a high heat transfer material.

17. The mold of Claim 16, wherein the high heat transfer material has a thermal conductivity higher than the thermal conductivity of iron.

18. The mold of Claim 16 or 17, wherein the high heat transfer material has a thermal conductivity higher than 100 W/(mK).

19. The mold of any of Claims 11 through 18, wherein at least a portion of the heat transfer member comprises a high heat transfer material.

20. The mold of any of Claims 11 through 19, wherein a substantial portion of the mold body of the second mold portion and the heat transfer member comprise a high heat transfer material.

21. The mold of any of Claims 11 through 20, wherein at least 50% of the mold body is a high heat transfer material.

22. The mold of any of Claims 11 through 21, wherein the second mold portion further comprises at least one hardened material configured to reduce wear when the second mold portion is moved relative to an adjacent surface.

23. The mold of any of Claims 11 through 22, wherein the second mold portion further comprises a thermal insulating material configured to form a thermal barrier.

24. The mold of any of Claims 11 through 23, wherein the second mold portion forms an area of a mold core section.

25. The mold of any of Claims 11 through 24, wherein the heat transfer member comprises an elongated member that extends at least partially into the channel.

26. The mold of any of Claims 11 through 25, wherein the heat transfer member comprises at least one heat transfer enhancer, said enhancer configured to increase the ratio of surface area to volume of the heat transfer member.

27. The mold of Claim 26, wherein the heat transfer enhancer comprises at least one selected from the following: a fin, protrusion, slit, bore, channel, groove, opening, recess, indentation, mesh structure and combinations thereof..

28. The mold of any of Claims 11 through 27, wherein the first mold portion and the second mold portion are part of single unitary member.

29. A mold moveable between an open position and a closed position, the mold comprising:
a mold space configured to receive moldable material when the mold is in a closed position;
a mold plate having at least one channel configured to convey a working fluid therethrough; and a cavity mold section comprising:
a molding surface that defines a portion of the mold space;
a heat transfer member, said heat transfer member at least partially extending within the channel of the mold plate; and a body positioned, at least in part, between the molding surface and the heat transfer member;
wherein at least a portion of the cavity mold section comprises a high heat transfer material.

30. The mold of Claim 29, wherein the cavity mold section further comprises a hardened material configured to reduce wear when the cavity mold section is moved between a first position and a second position.

31. The mold of Claim 29 or 30, wherein the heat transfer member comprises an elongated member that extends at least partially into the channel, such that a working fluid conveyed within channel contacts a surface of the heat transfer member to transfer heat between the elongated member and a working fluid.

32. The mold of any of Claims 29 through 31, wherein the heat transfer member comprises at least one heat transfer enhancer, said heat transfer enhancer configured to increase the ratio of surface area to volume of the heat transfer member.

33. The mold of Claim 32, wherein the heat transfer enhancer comprises at least one selected from the following: a fin, protrusion, slit, bore, channel, groove, opening, recess, indentation, mesh structure and combinations thereof.

34. A method of cooling a mold section, the method comprising:
placing a portion of the mold section in thermal communication with a channel configured to convey a fluid;
delivering a fluid through the channel; and transferring heat between a molding surface of the mold section and the fluid;
wherein said placing a portion of the mold section in thermal communication with a channel comprises positioning a heat transfer member of the mold section at least partially within the channel.

35. The method of Claim 34, wherein transferring heat between the molding surface and the fluid comprises transferring heat through a high heat transfer material, said high heat transfer material forming at least a portion of the mold section.

36. The method of Claim 34 or 35, wherein delivering a fluid through the channel comprises the use of pulse cooling technology.