US20060280938A1 - Thermoplastic long fiber composites, methods of manufacture thereof and articles derived thererom - Google Patents
Thermoplastic long fiber composites, methods of manufacture thereof and articles derived thererom Download PDFInfo
- Publication number
- US20060280938A1 US20060280938A1 US11/278,863 US27886306A US2006280938A1 US 20060280938 A1 US20060280938 A1 US 20060280938A1 US 27886306 A US27886306 A US 27886306A US 2006280938 A1 US2006280938 A1 US 2006280938A1
- Authority
- US
- United States
- Prior art keywords
- long fiber
- fiber composite
- fibers
- glass
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- the present invention is directed to thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom.
- Long fiber composites differ from other composites in that the fiber reinforcement has a substantially larger aspect ratio than the fiber reinforcement used in the other composites.
- the aspect ratio is defined as the ratio of the length to the diameter of the fiber.
- Long fiber composites generally employ glass long fibers disposed in a thermoplastic polymer.
- Long fiber composites can be manufactured in several ways, one of which is known as pultrusion. Pultruded long fiber composites are used to manufacture a variety of articles for automobiles, electronics, computers, or the like.
- Thermoplastic materials and glass fibers are generally electrically insulating in nature and hence are not useful in applications where electrostatic dissipation or electromagnetic shielding is required. Pultruded long fiber composites that use glass fibers therefore cannot be used in applications where electrical conductivity is desired. It is therefore desirable to manufacture long fiber composites that are electrically conducting and can be used in applications where electrostatic dissipation is desirable.
- an electrically conducting long fiber composite including a thermoplastic resin; carbon long fibers; and glass long fibers; wherein the carbon long fibers and the glass long fibers have a length of greater then or equal to about 2 millimeters and wherein the electrically conducting long fiber composite upon being molded into an article displays a surface resistivity of less than or equal to about 10 8 ohm per square centimeter and a notched Izod impact strength of greater than or equal to about 10 kilojoules per square meter.
- Also disclosed herein is a method of manufacturing an electrically conducting long fiber composite including the step of blending a carbon long fiber composite with a glass long fiber composite to produce an electrically conducting long fiber composite; wherein the carbon long fiber composite includes carbon long fibers having a length of greater than or equal to about 2 millimeters disposed in a first thermoplastic resin; and wherein the glass long fiber composite includes glass long fibers having a length of greater than or equal to about 2 millimeters disposed in a second thermoplastic resin.
- an electrically conducting long fiber including the steps of pultruding a first roving having carbon fibers through a first impregnation bath having a first molten thermoplastic polymer; impregnating the carbon fibers with the first molten thermoplastic polymer to produce a carbon long fiber composite; pultruding a second roving having glass fibers through a second impregnation bath having a second molten thermoplastic polymer; impregnating the glass fibers with the second molten thermoplastic polymer to produce a glass long fiber composite; and molding the carbon long fiber composite and the glass long fiber composite to form an electrically conducting long fiber composite.
- an electrically conducting composite including the steps of pultruding a roving having carbon fibers and glass fibers through an impregnation bath having a molten thermoplastic polymer; impregnating the carbon fibers and the glass fibers with the molten thermoplastic polymer to produce an electrically conducting long fiber composite; and molding the electrically conducting long fiber composite to form an article, wherein the article has a surface resistivity of less than or equal to about 10 8 ohm per square centimeter and a notched Izod impact strength of greater than or equal to about 15 kilojoules per square meter.
- approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not to be limited to the precise value specified, in some cases. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
- the electrically conducting long fiber composites include a thermoplastic polymer, glass fibers and carbon fibers. Both the glass fibers and the carbon fibers in the composite are long fibers, i.e., they have a length of about 2 to about 50 millimeters.
- a process involving pultrusion is generally used to manufacture the electrically conducting long fiber composites. The ability to electrostatically dissipate an electronic charge permits articles manufactured from these composites to be electrostatically painted.
- the thermoplastic polymer used in the long fiber composites is electrically insulating.
- the thermoplastic polymer may be any electrically insulating material including, but not limited to, an oligomer, a polymer, a copolymer, a block copolymer, a random copolymer, an alternating copolymer, an alternating block copolymer, a graft copolymer, a star block copolymer, an ionomer, a dendrimer, or the like, or a combination including at least one of the foregoing.
- thermoplastic polymers examples include polyarylene sulfides, polyalkyds, polystyrenes, polyesters, polyamides, polyaramides, polyamideimides, polyarylates, polyarylsulfones, polyethersulfones, polyphenylene sulfides, polysulfones, polyimides, polyetherimides, polytetrafluoroethylenes, polyetherketones, polyether etherketones, polyether ketone ketones, polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines, polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides, polyquinoxalines, polybenzimidazoles, polyoxindoles, polyoxoisoindolines, polydioxoisoindolines, polytriazines, polypyridazines, polypiperazines, polypyridines, polypiperidines, polytria
- the thermoplastic polymer is a polyamide.
- Exemplary polyamides are nylon 6, and nylon 6,6.
- the thermoplastic polymer is a blend of a polyamide with a polyarylene ether.
- An exemplary polyarylene ether is polyphenylene ether manufactured by General Electric Advanced Materials.
- the thermoplastic polymer is a compatibilized blend of a polyamide with a polyarylene ether.
- thermoplastic polymers employed in the process it is beneficial for the thermoplastic polymers employed in the process to have a melt viscosity of about 1 to about 50 Newton-seconds/square meter (Ns/m 2 ). In one embodiment, the melt viscosity of the thermoplastic polymer is less than or equal to about 30 Ns/m 2 . In another embodiment, the melt viscosity of the thermoplastic polymer is less than or equal to about 10 Ns/m 2 . The melt viscosity of the thermoplastic polymer is dictated by the molecular weight of the polymer.
- the thermoplastic polymer may be used in the long fiber composite in an amount of about 20 to about 90 weight percent (wt %), based on the weight of the electrically conducting long fiber composite. In one embodiment, the thermoplastic polymer may be used in the long fiber composite in an amount of about 30 to about 70 weight percent (wt %), based on the weight of the electrically conducting long fiber composite. In another embodiment, the thermoplastic polymer may be used in the long fiber composite in an amount of about 35 to about 65 weight percent (wt %), based on the weight of the electrically conducting long fiber composite. In yet another embodiment, the thermoplastic polymer may be used in the long fiber composite in an amount of about 40 to about 60 weight percent (wt %), based on the weight of the electrically conducting long fiber composite.
- the electrically conducting long fiber composite includes, in one embodiment, glass fibers and carbon fibers.
- the glass fibers may be continuous fibers.
- the glass fibers may also be referred to as a plurality of continuous filaments.
- continuous fibers or “plurality of continuous filaments” is meant a fibrous product in which the fibers are sufficiently long to give a roving or tow of sufficient strength, under the processing conditions used, to be hauled through the molten polymer without the frequency of breakage which would render the process unworkable.
- suitable fibers are glass fiber, carbon fiber, jute and high modulus synthetic polymer fibers.
- the majority of the continuous fibers of the fibrous product should lie in one direction so that the fibrous product can be drawn through molten polymer with the majority of the continuous fibers aligned.
- Fibrous products such as mats made up of randomly disposed continuous fibrous are suitable for the process if at least 40% by volume of the fibers are aligned in the direction of draw.
- the continuous fibers may be in any form having sufficient mechanical integrity to be pulled through the molten thermoplastic polymer.
- the continuous fibers generally include bundles of individual fibers or filaments, hereinafter termed “rovings” in which substantially all the fibers are aligned along the length of the bundles. Any number of such rovings may be employed. In the case of commercially available glass rovings each roving may include up to 8000 or more continuous glass filaments. Carbon fiber tapes containing up to 6000 or more carbon fibers may be used. Cloths woven from rovings are also suitable for use in the electrically conducting long fiber composites.
- the continuous fibers may be provided with a surface sizing. Surface sizings are generally designed to maximize bonding between the fiber and the matrix polymer. Exemplary sizings are ⁇ -aminopropyltriethoxysilane, aminosilane and/or epoxysilane.
- the surfaces of the individual filaments making up the fiber are beneficially wetted for optimum effect.
- the filament is treated with a sizing or anchoring agent, the polymer will not be in direct contact with the surface of the fiber or filament because the sizing is interposed between the fiber and the polymer.
- the product will have a high flexural modulus and the sizing will enhance the properties obtained.
- Useful glass fibers can be formed from any type of fiberizable glass composition and include those prepared from fiberizable glass compositions commonly known as “E-glass,” “A-glass,” “C-glass,” “D-glass,” “R-glass,” “S-glass,” as well as E-glass derivatives that are fluorine-free and/or boron-free.
- Most reinforcement mats have glass fibers formed from E-glass and are included in the conductive compositions of this invention. Such compositions and methods of making glass filaments therefrom are well known to those skilled in the art.
- Commercially produced glass fibers generally having nominal filament diameters of about 4 to about 35 micrometers may be used in the electrically conducting long fiber composites. In one embodiment, glass fibers generally having nominal filament diameters of about 9 to about 35 micrometers may be used in the electrically conducting long fiber composites.
- the glass fibers include glass strands that have been coated with a sizing agent. In another embodiment, the glass fibers are not coated with a sizing agent.
- the amount of sizing employed is generally the amount that is sufficient to bind the glass filaments into a continuous strand. When the fibers are coated with a sizing agent, it is generally beneficial for the glass fibers to have a sizing of about 0. 1 to about 5 wt %, based on the combined weight of the glass fibers and the sizing.
- the glass fibers are, in one embodiment, present in the electrically conducting long fiber composite in an amount of up to about 75 wt %, based on the total weight of the electrically conducting long fiber composite. In one embodiment, the glass fibers are present in the electrically conducting long fiber composite in an amount of about 5 about 60 wt %, based on the total weight of the electrically conducting long fiber composite. In another embodiment, the glass fibers are present in the electrically conducting long fiber composite in an amount of about 10 about 40 wt %, based on the total weight of the electrically conducting long fiber composite.
- Carbon fibers are generally classified according to their diameter, morphology, and degree of graphitization (morphology and degree of graphitization being interrelated). These characteristics are presently determined by the method used to synthesize the carbon fiber. For example, carbon fibers having diameters down to about 5 micrometers, and graphene ribbons parallel to the fiber axis (in radial, planar, or circumferential arrangements) are produced commercially by pyrolysis of organic precursors in fibrous form, including phenolics, polyacrylonitrile (PAN), or pitch. The carbon fibers may optionally be coated with a sizing agent if desired.
- PAN polyacrylonitrile
- the carbon fibers generally have a diameter of greater than or equal to about 1,000 nanometers (1 micrometer) to about 30 micrometers. In one embodiment, the fibers can have a diameter of about 2 to about 10 micrometers. In another embodiment, the fibers can have a diameter of about 3 to about 8 micrometers.
- Carbon fibers are, in one embodiment, used in amounts of up to about 60 wt % of the total weight of the electrically conducting long fiber composite. In one embodiment, carbon fibers are used in amounts of about 1 wt % to about 50 wt %, based on the weight of the electrically conducting long fiber composite. In another embodiment, carbon fibers are used in amounts of about 2 wt % to about 30 wt %, based on the weight of the electrically conducting long fiber composite. In yet another embodiment, carbon fibers are used in amounts of about 3 wt % to about 25 wt %, based on the weight of the electrically conducting long fiber composite.
- the glass and the carbon fibers in the long fiber composite can both have long fiber lengths.
- a long fiber length is about 2 millimeters to about 50 millimeters.
- a glass long fiber can be mixed with a short carbon fiber.
- a short fiber length is one that is less than or equal to about 2 millimeters.
- the use of short carbon fibers in combination with carbon long fibers will permit electrical conductivity to be developed in the long fiber composite at a loading of the carbon fiber that is different from the loading than when a carbon long fiber is employed.
- the carbon fiber is a long fiber.
- electrically conductive fillers may be added to the long fiber composite to enhance electrical conductivity in the composite.
- electrically conductive fillers are carbon black, carbon nanotubes, single wall carbon nanotubes, multiwall carbon nanotubes, vapor grown carbon fibers, metallic fillers, electrically conducting non-metallic fillers, or the like, or a combination including at least one of the foregoing electrically conductive fillers.
- the electrically conductive fillers may be used in loadings of about 0.01 to about 50 wt %, based on the weight of the electrically conducting long fiber composite. In one embodiment, the electrically conductive fillers may be used in amounts of about 0.25 wt % to about 30 wt %, based on the weight of the electrically conducting long fiber composite. In another embodiment, the electrically conductive fillers may be used in amounts of about 0.5 wt % to about 20 wt %, based on the weight of the electrically conducting long fiber composite. In yet another embodiment, the electrically conductive fillers may be used in amounts of about 1 wt % to about 10 wt %, based on the weight of the electrically conducting long fiber composite.
- a roving including glass and carbon fibers can be jointly and simultaneously pultruded using a thermoplastic resin as the binder.
- the thermoplastic resin may be in the form of a melt or in the form of a powder suspension.
- a single pellet manufactured in the pultrusion process will contain both glass long fibers and carbon long fibers.
- separate rovings including the glass fibers and the carbon fibers can be pultruded in separate steps.
- the composite formed after impregnation can be pelletized in a pelletizer.
- the respective pellets contain fibers of a length equal to the length of the pellet.
- the pellets generally have a length of about 2 mm to about 50 mm.
- An exemplary pellet length is 25 mm.
- the pellets containing either glass long fibers or carbon long fibers can then be combined in a molding machine to produce an article including the electrically conducting long fiber composite.
- first roving including carbon fibers is pultruded through a first impregnation bath including a first molten thermoplastic polymer.
- the carbon fibers are impregnated with the first molten thermoplastic polymer to produce a carbon long fiber composite.
- the carbon long fiber composite is pulled through a first die and then pelletized.
- a second roving including glass fibers is pultruded through a second impregnation bath including a second molten thermoplastic polymer.
- the glass fibers are impregnated with the second molten thermoplastic polymer to produce a glass long fiber composite.
- the carbon long fiber composite is pulled through a second die and then pelletized.
- the glass long fiber composite and the carbon long fiber composite are then molded into an electrically long fiber composite in a molding machine.
- An exemplary molding machine is an injection-molding machine.
- the first roving and the second roving can be the same or different.
- the carbon fibers and the glass fibers are contained in the same roving.
- the first impregnation bath and the second impregnation bath can be the same or different.
- strands of carbon fiber and glass fiber can be impregnated jointly and simultaneously in the same bath. After pelletization, the pellets may be molded in an injection-molding machine to form the electrically conducting long fiber composite.
- the first roving and the second roving can be impregnated in separate baths.
- the carbon long fiber composite and the glass long fiber composite are then pelletized and molded together in a injection-molding machine to form the electrically conducting long fiber composite.
- the glass fiber in another method of manufacturing the electrically conducting long fiber composite, can be pultruded separately in a single step to form glass long fiber composite pellets.
- the carbon fiber can be pultruded separately in a single step to form the carbon long fiber composite pellets.
- the molten thermoplastic resin that impregnates the glass long fiber composite and the carbon long fiber composite may contain an electrically conducting filler.
- the electrically conducting long fiber composite includes additional electrically conducting filler in addition to the carbon long fibers.
- the electrically conducting long fiber composite may be molded to have a smooth surface finish.
- the electrically conducting long fiber composite may have a Class A surface finish after molding.
- Articles molded from the electrically conducting long fiber composite may have an electrical specific volume resistivity (SVR) of less than of equal to about 10 12 ohm-cm.
- the molded articles may have an electrical volume resistivity of less than of equal to about 10 8 ohm-cm.
- the molded articles may have an electrical volume resistivity of less than of equal to about 10 5 ohm-cm.
- the molded articles may also have a surface resistivity of less than or equal to about 10 12 ohm per square centimeter (ohms/square).
- the molded articles may also have a surface resistivity of less than or equal to about 10 8 ohm per square centimeter. In another embodiment, the molded articles may also have a surface resistivity of less than or equal to about 10 4 ohm per square centimeter. In yet another embodiment, the molded articles may also have a surface resistivity of less than or equal to about 10 2 ohm per square centimeter.
- the electrically conducting long fiber composites also display mechanical properties that are favorable for a large number of high temperature, high strength applications.
- the electrically conducting long fiber composite has a notched Izod impact strength of greater than or equal to about 10 kilojoules per square meter (kJ/m 2 ).
- the electrically conducting long fiber composites also advantageously have a notched Izod impact strength of greater than or equal to about 15 kJ/m 2 .
- the electrically conducting long fiber composites also advantageously have a notched Izod impact strength of greater than or equal to about 20 kJ/m 2 .
- the electrically conducting long fiber composites also advantageously have a notched Izod impact strength of greater than or equal to about 30 kJ/m 2 .
- the electrically conducting long fiber composites advantageously display a flexural modulus of greater than or equal to about 8 gigapascals (GPa). In one embodiment, the electrically conducting long fiber composites display a flexural modulus of greater than or equal to about 10 GPa.
- thermoplastic composition described herein can be advantageously used in the manufacture of a variety of commercial articles.
- an exemplary article is a chip tray. They can also be used in other applications where dimensional stability and/or electrical conductivity are beneficial such as automobiles interiors, aircraft, lampshades, or the like.
- an exemplary article is an automotive exterior body panel that is to be electrostatically painted.
- This example was conducted to demonstrate the manufacture of a pultruded electrically conducting long fiber composite that contains both glass long fibers and carbon long fibers. Carbon long fibers and glass long fibers that were first pultruded through nylon 6,6 to create a pultruded composite.
- the pultruded composite contained 25 wt % carbon long fiber and 30 wt % glass long fiber.
- the pultruded composite was either blended with VERTON RF-7007 EM HS BK9001®, a nylon 6,6 containing only glass long fiber manufactured by General Electric Advanced Materials, or with STAT-KON R-1 HI®, a nylon 6,6 containing carbon black also manufactured by General Electric Advanced Materials to create the long fiber composite.
- the long fiber composites were in the form of rectangular molded plaques having dimensions of 10 centimeters ⁇ 12.5 centimeters.
- the samples were molded on a 220 Ton Milacron injection molding machine. Table 1 shows the molded compositions and the specific volume resistivity for these samples.
- Sample #s 1 through 7 from Table 1 are molded compositions that were derived by molding the pultruded composite with the VERTON RF-7007 EM HS BK9001®, while the Sample #s 8 through 15 in Table 1 were obtained by blending the pultruded composite with STAT-KON R-1HI®. Samples #s 1 through 15 contain from 3.5 to 11 wt % carbon fiber, based on the total weight of the electrically conducting long fiber composite.
- Table 1 shows the surface resistivity of the samples. Surface resistivity measurements were made by using a Keithley resistivity meter. The Table 1 below illustrates that a surprisingly low weight fraction of conductive additive can be used and still retain sufficient conductivity.
- the comparative sample (Sample #17) having carbon long fibers displays improved impact and flexural properties over the sample that has carbon short fibers.
- an electrically conducting long fiber composite including glass long fibers and carbon long fibers produces superior properties over a composite that includes glass long fibers and carbon short fibers.
- Table 4 shows two compositions, Sample #18 that includes nylon 6,6 and Sample #19 that includes a compatibilized blend of nylon 6,6 with polyphenylene ether.
- the compositions and the properties for the respective electrically conducting long fiber composites are shown in the Table 3 below.
- the electrically conducting long fiber composites can be manufactured with a wide range of carbon long fiber loadings.
- the amount of the carbon long fiber is varied from about 3.5 to about 10.5 wt %, based on the total weight of the electrically conducting long fiber composite.
- the amount of glass long fiber was varied from about 19 to about 48 wt %, based on the total weight of the electrically conducting long fiber composite.
- the results shown in the Table 5 demonstrate that the carbon long fibers produce advantageous mechanical and electrical properties in the electrically conducting long fiber composites. These synergistic properties cannot generally be achieved in other long fiber composites that contain only short carbon fibers, carbon powders such as carbon black, carbon nanotubes or the like.
- the electrically conducting long fiber composites can be advantageously used in automotive applications such as exterior body panels that are electrostatically painted. They may also be used in integrated circuit trays or the like.
Abstract
Description
- This application claims priority to U.S. Provisional Application No. 60/689,475, which was filed Jun. 10, 2005, which application is hereby incorporated by reference in its entirety.
- The present invention is directed to thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom.
- Long fiber composites differ from other composites in that the fiber reinforcement has a substantially larger aspect ratio than the fiber reinforcement used in the other composites. The aspect ratio is defined as the ratio of the length to the diameter of the fiber. Long fiber composites generally employ glass long fibers disposed in a thermoplastic polymer. Long fiber composites can be manufactured in several ways, one of which is known as pultrusion. Pultruded long fiber composites are used to manufacture a variety of articles for automobiles, electronics, computers, or the like.
- Thermoplastic materials and glass fibers are generally electrically insulating in nature and hence are not useful in applications where electrostatic dissipation or electromagnetic shielding is required. Pultruded long fiber composites that use glass fibers therefore cannot be used in applications where electrical conductivity is desired. It is therefore desirable to manufacture long fiber composites that are electrically conducting and can be used in applications where electrostatic dissipation is desirable.
- Disclosed herein is an electrically conducting long fiber composite including a thermoplastic resin; carbon long fibers; and glass long fibers; wherein the carbon long fibers and the glass long fibers have a length of greater then or equal to about 2 millimeters and wherein the electrically conducting long fiber composite upon being molded into an article displays a surface resistivity of less than or equal to about 108 ohm per square centimeter and a notched Izod impact strength of greater than or equal to about 10 kilojoules per square meter.
- Also disclosed herein is a method of manufacturing an electrically conducting long fiber composite including the step of blending a carbon long fiber composite with a glass long fiber composite to produce an electrically conducting long fiber composite; wherein the carbon long fiber composite includes carbon long fibers having a length of greater than or equal to about 2 millimeters disposed in a first thermoplastic resin; and wherein the glass long fiber composite includes glass long fibers having a length of greater than or equal to about 2 millimeters disposed in a second thermoplastic resin.
- Disclosed herein as well is a method of manufacturing an electrically conducting long fiber including the steps of pultruding a first roving having carbon fibers through a first impregnation bath having a first molten thermoplastic polymer; impregnating the carbon fibers with the first molten thermoplastic polymer to produce a carbon long fiber composite; pultruding a second roving having glass fibers through a second impregnation bath having a second molten thermoplastic polymer; impregnating the glass fibers with the second molten thermoplastic polymer to produce a glass long fiber composite; and molding the carbon long fiber composite and the glass long fiber composite to form an electrically conducting long fiber composite.
- Lastly, disclosed herein is a method of manufacturing an electrically conducting composite including the steps of pultruding a roving having carbon fibers and glass fibers through an impregnation bath having a molten thermoplastic polymer; impregnating the carbon fibers and the glass fibers with the molten thermoplastic polymer to produce an electrically conducting long fiber composite; and molding the electrically conducting long fiber composite to form an article, wherein the article has a surface resistivity of less than or equal to about 108 ohm per square centimeter and a notched Izod impact strength of greater than or equal to about 15 kilojoules per square meter.
- The present invention is more particularly described in the following description and examples that are intended to be illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. As used in the specification and in the claims, the singular form “a,” “an,” and “the” may include plural referents unless the context clearly dictates otherwise. Also, as used in the specification and in the claims, the term “comprising” may include the embodiments “consisting of” and “consisting essentially of.” Furthermore, all ranges disclosed herein are inclusive of the endpoints and are independently combinable.
- As used herein, approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not to be limited to the precise value specified, in some cases. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
- Disclosed herein are electrically conducting long fiber composites that may be used in applications where electrostatic dissipation and/or electromagnetic shielding are desirable. The electrically conducting long fiber composites include a thermoplastic polymer, glass fibers and carbon fibers. Both the glass fibers and the carbon fibers in the composite are long fibers, i.e., they have a length of about 2 to about 50 millimeters. A process involving pultrusion is generally used to manufacture the electrically conducting long fiber composites. The ability to electrostatically dissipate an electronic charge permits articles manufactured from these composites to be electrostatically painted.
- The thermoplastic polymer used in the long fiber composites is electrically insulating. The thermoplastic polymer may be any electrically insulating material including, but not limited to, an oligomer, a polymer, a copolymer, a block copolymer, a random copolymer, an alternating copolymer, an alternating block copolymer, a graft copolymer, a star block copolymer, an ionomer, a dendrimer, or the like, or a combination including at least one of the foregoing. Examples of suitable thermoplastic polymers are polyarylene sulfides, polyalkyds, polystyrenes, polyesters, polyamides, polyaramides, polyamideimides, polyarylates, polyarylsulfones, polyethersulfones, polyphenylene sulfides, polysulfones, polyimides, polyetherimides, polytetrafluoroethylenes, polyetherketones, polyether etherketones, polyether ketone ketones, polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines, polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides, polyquinoxalines, polybenzimidazoles, polyoxindoles, polyoxoisoindolines, polydioxoisoindolines, polytriazines, polypyridazines, polypiperazines, polypyridines, polypiperidines, polytriazoles, polypyrazoles, polycarboranes, polyoxabicyclononanes, polydibenzofurans, polyphthalides, polyacetals, polyanhydrides, polyvinyl ethers, polyvinyl thioethers, polyvinyl alcohols, polyvinyl ketones, polyvinyl halides, polyvinyl nitriles, polyvinyl esters, polysulfonates, polysulfides, polythioesters, polysulfones, polysulfonamides, polyureas, polyphosphazenes, polysilazanes, polyolefins, polysiloxanes, polybutadienes, polyisoprenes, or the like, or a combination including at least one of the foregoing thermoplastic polymers.
- In one exemplary embodiment, the thermoplastic polymer is a polyamide. Exemplary polyamides are nylon 6, and nylon 6,6. In another exemplary embodiment, the thermoplastic polymer is a blend of a polyamide with a polyarylene ether. An exemplary polyarylene ether is polyphenylene ether manufactured by General Electric Advanced Materials. In yet another exemplary embodiment, the thermoplastic polymer is a compatibilized blend of a polyamide with a polyarylene ether.
- It is beneficial for the thermoplastic polymers employed in the process to have a melt viscosity of about 1 to about 50 Newton-seconds/square meter (Ns/m2). In one embodiment, the melt viscosity of the thermoplastic polymer is less than or equal to about 30 Ns/m2. In another embodiment, the melt viscosity of the thermoplastic polymer is less than or equal to about 10 Ns/m2. The melt viscosity of the thermoplastic polymer is dictated by the molecular weight of the polymer.
- The thermoplastic polymer may be used in the long fiber composite in an amount of about 20 to about 90 weight percent (wt %), based on the weight of the electrically conducting long fiber composite. In one embodiment, the thermoplastic polymer may be used in the long fiber composite in an amount of about 30 to about 70 weight percent (wt %), based on the weight of the electrically conducting long fiber composite. In another embodiment, the thermoplastic polymer may be used in the long fiber composite in an amount of about 35 to about 65 weight percent (wt %), based on the weight of the electrically conducting long fiber composite. In yet another embodiment, the thermoplastic polymer may be used in the long fiber composite in an amount of about 40 to about 60 weight percent (wt %), based on the weight of the electrically conducting long fiber composite.
- The electrically conducting long fiber composite includes, in one embodiment, glass fibers and carbon fibers. The glass fibers may be continuous fibers. The glass fibers may also be referred to as a plurality of continuous filaments. By, the term “continuous fibers” or “plurality of continuous filaments” is meant a fibrous product in which the fibers are sufficiently long to give a roving or tow of sufficient strength, under the processing conditions used, to be hauled through the molten polymer without the frequency of breakage which would render the process unworkable. Examples of suitable fibers are glass fiber, carbon fiber, jute and high modulus synthetic polymer fibers.
- In order to have sufficient strength to be hauled through the molten polymer of the impregnation system without breakage, the majority of the continuous fibers of the fibrous product should lie in one direction so that the fibrous product can be drawn through molten polymer with the majority of the continuous fibers aligned. Fibrous products such as mats made up of randomly disposed continuous fibrous are suitable for the process if at least 40% by volume of the fibers are aligned in the direction of draw.
- The continuous fibers may be in any form having sufficient mechanical integrity to be pulled through the molten thermoplastic polymer. The continuous fibers generally include bundles of individual fibers or filaments, hereinafter termed “rovings” in which substantially all the fibers are aligned along the length of the bundles. Any number of such rovings may be employed. In the case of commercially available glass rovings each roving may include up to 8000 or more continuous glass filaments. Carbon fiber tapes containing up to 6000 or more carbon fibers may be used. Cloths woven from rovings are also suitable for use in the electrically conducting long fiber composites. The continuous fibers may be provided with a surface sizing. Surface sizings are generally designed to maximize bonding between the fiber and the matrix polymer. Exemplary sizings are γ-aminopropyltriethoxysilane, aminosilane and/or epoxysilane.
- It is generally desirable to wet as much of the surface of the fiber as possible with the molten polymer. Thus where a fiber includes a plurality of filaments, the surfaces of the individual filaments making up the fiber are beneficially wetted for optimum effect. Where the filament is treated with a sizing or anchoring agent, the polymer will not be in direct contact with the surface of the fiber or filament because the sizing is interposed between the fiber and the polymer. However, providing that good adhesion between the fiber and the sizing and between the sizing and the polymer are achieved, the product will have a high flexural modulus and the sizing will enhance the properties obtained.
- Useful glass fibers can be formed from any type of fiberizable glass composition and include those prepared from fiberizable glass compositions commonly known as “E-glass,” “A-glass,” “C-glass,” “D-glass,” “R-glass,” “S-glass,” as well as E-glass derivatives that are fluorine-free and/or boron-free. Most reinforcement mats have glass fibers formed from E-glass and are included in the conductive compositions of this invention. Such compositions and methods of making glass filaments therefrom are well known to those skilled in the art. Commercially produced glass fibers generally having nominal filament diameters of about 4 to about 35 micrometers may be used in the electrically conducting long fiber composites. In one embodiment, glass fibers generally having nominal filament diameters of about 9 to about 35 micrometers may be used in the electrically conducting long fiber composites.
- In one embodiment, the glass fibers include glass strands that have been coated with a sizing agent. In another embodiment, the glass fibers are not coated with a sizing agent. The amount of sizing employed is generally the amount that is sufficient to bind the glass filaments into a continuous strand. When the fibers are coated with a sizing agent, it is generally beneficial for the glass fibers to have a sizing of about 0. 1 to about 5 wt %, based on the combined weight of the glass fibers and the sizing.
- The glass fibers are, in one embodiment, present in the electrically conducting long fiber composite in an amount of up to about 75 wt %, based on the total weight of the electrically conducting long fiber composite. In one embodiment, the glass fibers are present in the electrically conducting long fiber composite in an amount of about 5 about 60 wt %, based on the total weight of the electrically conducting long fiber composite. In another embodiment, the glass fibers are present in the electrically conducting long fiber composite in an amount of about 10 about 40 wt %, based on the total weight of the electrically conducting long fiber composite.
- Various types of electrically conductive carbon fibers may also be used in the electrically conducting long fiber composite. Carbon fibers are generally classified according to their diameter, morphology, and degree of graphitization (morphology and degree of graphitization being interrelated). These characteristics are presently determined by the method used to synthesize the carbon fiber. For example, carbon fibers having diameters down to about 5 micrometers, and graphene ribbons parallel to the fiber axis (in radial, planar, or circumferential arrangements) are produced commercially by pyrolysis of organic precursors in fibrous form, including phenolics, polyacrylonitrile (PAN), or pitch. The carbon fibers may optionally be coated with a sizing agent if desired.
- The carbon fibers generally have a diameter of greater than or equal to about 1,000 nanometers (1 micrometer) to about 30 micrometers. In one embodiment, the fibers can have a diameter of about 2 to about 10 micrometers. In another embodiment, the fibers can have a diameter of about 3 to about 8 micrometers.
- Carbon fibers are, in one embodiment, used in amounts of up to about 60 wt % of the total weight of the electrically conducting long fiber composite. In one embodiment, carbon fibers are used in amounts of about 1 wt % to about 50 wt %, based on the weight of the electrically conducting long fiber composite. In another embodiment, carbon fibers are used in amounts of about 2 wt % to about 30 wt %, based on the weight of the electrically conducting long fiber composite. In yet another embodiment, carbon fibers are used in amounts of about 3 wt % to about 25 wt %, based on the weight of the electrically conducting long fiber composite.
- The glass and the carbon fibers in the long fiber composite can both have long fiber lengths. For purposes of this disclosure, a long fiber length is about 2 millimeters to about 50 millimeters. In one embodiment, a glass long fiber can be mixed with a short carbon fiber. A short fiber length is one that is less than or equal to about 2 millimeters. The use of short carbon fibers in combination with carbon long fibers will permit electrical conductivity to be developed in the long fiber composite at a loading of the carbon fiber that is different from the loading than when a carbon long fiber is employed. By using various combinations of carbon long fibers with short carbon fibers in the electrically conducting long fiber composite, a variety of physical properties can be achieved. In an exemplary embodiment, the carbon fiber is a long fiber.
- Other electrically conductive fillers may be added to the long fiber composite to enhance electrical conductivity in the composite. Examples of such electrically conductive fillers are carbon black, carbon nanotubes, single wall carbon nanotubes, multiwall carbon nanotubes, vapor grown carbon fibers, metallic fillers, electrically conducting non-metallic fillers, or the like, or a combination including at least one of the foregoing electrically conductive fillers.
- The electrically conductive fillers may be used in loadings of about 0.01 to about 50 wt %, based on the weight of the electrically conducting long fiber composite. In one embodiment, the electrically conductive fillers may be used in amounts of about 0.25 wt % to about 30 wt %, based on the weight of the electrically conducting long fiber composite. In another embodiment, the electrically conductive fillers may be used in amounts of about 0.5 wt % to about 20 wt %, based on the weight of the electrically conducting long fiber composite. In yet another embodiment, the electrically conductive fillers may be used in amounts of about 1 wt % to about 10 wt %, based on the weight of the electrically conducting long fiber composite.
- In one embodiment, in one method of manufacturing the electrically conducting long fiber composite, a roving including glass and carbon fibers can be jointly and simultaneously pultruded using a thermoplastic resin as the binder. The thermoplastic resin may be in the form of a melt or in the form of a powder suspension. Thus a single pellet manufactured in the pultrusion process will contain both glass long fibers and carbon long fibers. Alternatively, separate rovings including the glass fibers and the carbon fibers can be pultruded in separate steps. The composite formed after impregnation can be pelletized in a pelletizer.
- The respective pellets contain fibers of a length equal to the length of the pellet. The pellets generally have a length of about 2 mm to about 50 mm. An exemplary pellet length is 25 mm. The pellets containing either glass long fibers or carbon long fibers can then be combined in a molding machine to produce an article including the electrically conducting long fiber composite.
- In this embodiment, first roving including carbon fibers is pultruded through a first impregnation bath including a first molten thermoplastic polymer. The carbon fibers are impregnated with the first molten thermoplastic polymer to produce a carbon long fiber composite. The carbon long fiber composite is pulled through a first die and then pelletized. Additionally, a second roving including glass fibers is pultruded through a second impregnation bath including a second molten thermoplastic polymer. The glass fibers are impregnated with the second molten thermoplastic polymer to produce a glass long fiber composite. The carbon long fiber composite is pulled through a second die and then pelletized. The glass long fiber composite and the carbon long fiber composite are then molded into an electrically long fiber composite in a molding machine. An exemplary molding machine is an injection-molding machine.
- In one embodiment, the first roving and the second roving can be the same or different. When the first roving and the second roving are the same, the carbon fibers and the glass fibers are contained in the same roving. Similarly, the first impregnation bath and the second impregnation bath can be the same or different. In other words, strands of carbon fiber and glass fiber can be impregnated jointly and simultaneously in the same bath. After pelletization, the pellets may be molded in an injection-molding machine to form the electrically conducting long fiber composite.
- When the first roving is not the same as the second roving, the first roving and the second roving can be impregnated in separate baths. The carbon long fiber composite and the glass long fiber composite are then pelletized and molded together in a injection-molding machine to form the electrically conducting long fiber composite.
- In yet another embodiment, in another method of manufacturing the electrically conducting long fiber composite, the glass fiber can be pultruded separately in a single step to form glass long fiber composite pellets. Similarly, the carbon fiber can be pultruded separately in a single step to form the carbon long fiber composite pellets. However, the molten thermoplastic resin that impregnates the glass long fiber composite and the carbon long fiber composite may contain an electrically conducting filler. Thus the electrically conducting long fiber composite includes additional electrically conducting filler in addition to the carbon long fibers.
- The electrically conducting long fiber composite may be molded to have a smooth surface finish. In one embodiment, the electrically conducting long fiber composite may have a Class A surface finish after molding. Articles molded from the electrically conducting long fiber composite may have an electrical specific volume resistivity (SVR) of less than of equal to about 1012 ohm-cm. In one embodiment, the molded articles may have an electrical volume resistivity of less than of equal to about 108 ohm-cm. In another embodiment, the molded articles may have an electrical volume resistivity of less than of equal to about 105 ohm-cm. The molded articles may also have a surface resistivity of less than or equal to about 1012 ohm per square centimeter (ohms/square). In one embodiment, the molded articles may also have a surface resistivity of less than or equal to about 108 ohm per square centimeter. In another embodiment, the molded articles may also have a surface resistivity of less than or equal to about 104 ohm per square centimeter. In yet another embodiment, the molded articles may also have a surface resistivity of less than or equal to about 102 ohm per square centimeter.
- The electrically conducting long fiber composites also display mechanical properties that are favorable for a large number of high temperature, high strength applications. In one embodiment, the electrically conducting long fiber composite has a notched Izod impact strength of greater than or equal to about 10 kilojoules per square meter (kJ/m2). In another embodiment, the electrically conducting long fiber composites also advantageously have a notched Izod impact strength of greater than or equal to about 15 kJ/m2. In yet another embodiment, the electrically conducting long fiber composites also advantageously have a notched Izod impact strength of greater than or equal to about 20 kJ/m2. In still another embodiment, the electrically conducting long fiber composites also advantageously have a notched Izod impact strength of greater than or equal to about 30 kJ/m2.
- The electrically conducting long fiber composites advantageously display a flexural modulus of greater than or equal to about 8 gigapascals (GPa). In one embodiment, the electrically conducting long fiber composites display a flexural modulus of greater than or equal to about 10 GPa.
- As noted above, the thermoplastic composition described herein can be advantageously used in the manufacture of a variety of commercial articles. In one embodiment, an exemplary article is a chip tray. They can also be used in other applications where dimensional stability and/or electrical conductivity are beneficial such as automobiles interiors, aircraft, lampshades, or the like. In another embodiment, an exemplary article is an automotive exterior body panel that is to be electrostatically painted.
- The following examples, which are meant to be exemplary, not limiting, illustrate compositions and methods for manufacturing the electrically conducting long fiber composite described herein.
- This example was conducted to demonstrate the manufacture of a pultruded electrically conducting long fiber composite that contains both glass long fibers and carbon long fibers. Carbon long fibers and glass long fibers that were first pultruded through nylon 6,6 to create a pultruded composite. The pultruded composite contained 25 wt % carbon long fiber and 30 wt % glass long fiber. The pultruded composite was either blended with VERTON RF-7007 EM HS BK9001®, a nylon 6,6 containing only glass long fiber manufactured by General Electric Advanced Materials, or with STAT-KON R-1 HI®, a nylon 6,6 containing carbon black also manufactured by General Electric Advanced Materials to create the long fiber composite. The long fiber composites were in the form of rectangular molded plaques having dimensions of 10 centimeters×12.5 centimeters. The samples were molded on a 220 Ton Milacron injection molding machine. Table 1 shows the molded compositions and the specific volume resistivity for these samples.
- Sample #s 1 through 7 from Table 1 are molded compositions that were derived by molding the pultruded composite with the VERTON RF-7007 EM HS BK9001®, while the Sample #s 8 through 15 in Table 1 were obtained by blending the pultruded composite with STAT-KON R-1HI®. Samples #s 1 through 15 contain from 3.5 to 11 wt % carbon fiber, based on the total weight of the electrically conducting long fiber composite.
- Table 1 shows the surface resistivity of the samples. Surface resistivity measurements were made by using a Keithley resistivity meter. The Table 1 below illustrates that a surprisingly low weight fraction of conductive additive can be used and still retain sufficient conductivity.
TABLE 1 Carbon Carbon Surface Fiber Black Glass Resistivity Sample# (wt %) (wt %) (wt %) (Ohm/square) 1 3.5 0 34.2 3.10E+04 2 4.4 0 34 1.55E+04 3 5.3 0 33.8 7.76E+03 4 5.7 0 33.7 2.00E+03 5 7 0 33.4 2.90E+03 6 8.8 0 33 4.40E+02 7 11 0 32.5 2.50E+02 8 2.2 1.8 31 4.80E+05 9 2.75 2.25 30 2.80E+04 10 2.2 2.7 29.25 2.30E+04 11 3.3 2.7 29 5.50E+03 12 4.4 2.7 28.75 8.10E+02 13 3.3 3.6 27.25 4.40E+03 14 4.4 3.6 27 4.10E+02 15 5.5 4.5 25 4.40E+02 - The results from Table 1 show that the Samples #'s 1 to 7 that contain only the carbon long fiber and the glass long fiber have a surface resistivity that is generally equal to or better than Samples # 8-15 that contain carbon black in addition to the carbon long fiber and the glass long fiber.
- This example was undertaken to compare the properties of electrically conductive composites that contain carbon long fibers versus those that contain carbon short fibers. As noted above, carbon long fibers have lengths of greater than or equal to about 2 millimeters, while carbon short fibers have lengths of less than 2 millimeters. The plaques for testing were manufactured by injection molding a blend of a glass long fiber composite with either a carbon long fiber composite or a carbon short fiber composite. The air burnout indicates how much glass fiber is present; the nitrogen burnout indicates how much total fiber is present. Details of the test are shown in Table 2 below.
TABLE 2 Properties Sample # 16 Sample # 17 Carbon fiber form Long Short Air burnout, % 31.74 31.6 Nitrogen burnout, % 44.37 43.1 Specific gravity 1.45 1.46 Tensile strength, MPa 246.1 266 Tensile elongation, % 1.47 2.02 Tensile modulus, GPa 20 21.5 Flexural strength, MPa 381.1 372 Flexural modulus, GPa 17.64 16.6 Notch Izod, kJ/m2 35.3 28.4 - From the Table 2 it may be seen that the comparative sample (Sample #17) having carbon long fibers displays improved impact and flexural properties over the sample that has carbon short fibers. Thus an electrically conducting long fiber composite including glass long fibers and carbon long fibers produces superior properties over a composite that includes glass long fibers and carbon short fibers.
- This example was undertaken to demonstrate that electrically conducting long fiber composites can be manufactured with a variety of different resins. Table 4 shows two compositions, Sample #18 that includes nylon 6,6 and Sample #19 that includes a compatibilized blend of nylon 6,6 with polyphenylene ether. The compositions and the properties for the respective electrically conducting long fiber composites are shown in the Table 3 below.
TABLE 3 Sample # 18 Sample # 19 Composition (wt %) (wt %) Nylon 6,6 65 32.5 Polyphenylene ether 32.5 Carbon long fibers 10 10 Glass long fibers 25 25 Properties Specific gravity (g/cc) 1.35 1.32 Tensile strength, MPa 197.2 183.5 Tens elongation, % 1.52 1.41 Tens modulus, GPa 17.5 14.8 Notch Izod, kJ/m2 21.95 21.9 Surface resistivity, ohm/sq 2.50E+03 6.20E+02 - From the Table 3, it may be seen that electrically conducting long fiber composites can be advantageously manufactured with a variety of thermoplastic resins.
- This example demonstrates that the electrically conducting long fiber composites can be manufactured with a wide range of carbon long fiber loadings. The amount of the carbon long fiber is varied from about 3.5 to about 10.5 wt %, based on the total weight of the electrically conducting long fiber composite. The amount of glass long fiber was varied from about 19 to about 48 wt %, based on the total weight of the electrically conducting long fiber composite. These examples also show that the invention is not limited to a narrow range of overall fiber loading. These examples are shown in Table 4.
TABLE 4 Sample Sample Sample Sample Sample Sample Sample Sample Sample #20 #21 #22 #23 #24 #25 #26 #27 #28 Composition Nylon 6,6 wt % 70.1 70.2 70.15 58.6 61.8 59.6 50.05 49.2 50 Long Glass Fiber, wt % 19.34 26.28 22.81 34.36 34.68 29.84 42.91 47.28 39.44 Long Carbon Fiber, wt % 10.56 3.52 7.04 7.04 3.52 10.56 7.04 3.52 10.56 Total Long Fiber, wt % 29.9 29.8 29.85 41.4 38.2 40.4 49.95 50.8 50 Properties Nitrogen TGA burnout, % 30.4 30.8 32.3 44.2 41.7 40.2 52.8 52.4 52.3 Specific gravity 1.311 1.359 1.367 1.461 1.448 1.427 1.569 1.594 1.537 Tensile strength, MPa 196.57 185.13 180.11 233.75 225.87 233.34 231.56 261 226.57 Tensile elongation, % 1.14 1.56 1.38 1.46 1.7 1.3 1.18 1.46 0.96 Tensile modulus, GPa 20.4 12.9 14 17.9 15.1 20.6 22.5 21.8 27.7 Flexural strength, MPa 297.73 288.82 286.39 355.01 324.77 348.14 367.1 378.59 375.64 Flexural Modulus, GPa 12.8 11.6 11.4 15 12.7 15.9 18.5 16.4 19.4 Izod notched impact, kJ/m2 16.55 15.65 19.44 33.92 32 25.63 34.39 36.55 38.99 Surface Resistivity (ohm/sq) 0.9 1.1 1.7 0.7 4.6 1.1 1.1 5.1 0.9 - The results shown in the Table 5 demonstrate that the carbon long fibers produce advantageous mechanical and electrical properties in the electrically conducting long fiber composites. These synergistic properties cannot generally be achieved in other long fiber composites that contain only short carbon fibers, carbon powders such as carbon black, carbon nanotubes or the like. The electrically conducting long fiber composites can be advantageously used in automotive applications such as exterior body panels that are electrostatically painted. They may also be used in integrated circuit trays or the like.
- While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention.
Claims (32)
Priority Applications (15)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/278,863 US20060280938A1 (en) | 2005-06-10 | 2006-04-06 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived thererom |
AT06772129T ATE438183T1 (en) | 2005-06-10 | 2006-06-05 | THERMOPLASTIC LONG FIBER COMPOSITIONS, PRODUCTION PROCESSES THEREOF AND ARTICLES DEVELOPED THEREFROM |
PCT/US2006/021709 WO2006135597A1 (en) | 2005-06-10 | 2006-06-05 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom |
BRPI0606835-9A BRPI0606835A2 (en) | 2005-06-10 | 2006-06-05 | long fiber thermoplastic composites, their method of manufacture and articles derived therefrom |
CA002596045A CA2596045A1 (en) | 2005-06-10 | 2006-06-05 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom |
CN2006800206065A CN101194324B (en) | 2005-06-10 | 2006-06-05 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom |
KR1020077017904A KR20080015067A (en) | 2005-06-10 | 2006-06-05 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom |
KR1020137025506A KR20130124400A (en) | 2005-06-10 | 2006-06-05 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom |
MX2007009360A MX2007009360A (en) | 2005-06-10 | 2006-06-05 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom. |
EP06772129A EP1894210B1 (en) | 2005-06-10 | 2006-06-05 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom |
JP2008513845A JP4786711B2 (en) | 2005-06-10 | 2006-06-05 | Method for producing conductive long fiber composite material |
DE602006008142T DE602006008142D1 (en) | 2005-06-10 | 2006-06-05 | THERMOPLASTIC FIBER COMPOSITIONS, PRODUCTION METHOD AND PRODUCT DEVELOPED THEREFROM |
MYPI20062653A MY143389A (en) | 2005-06-10 | 2006-06-08 | Thermoplastic long fiber composites, methods of manufacture thereof and derived therefrom |
TW095120632A TW200703374A (en) | 2005-06-10 | 2006-06-09 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived thererom |
JP2011089049A JP2011174081A (en) | 2005-06-10 | 2011-04-13 | Thermoplastic long fiber composite and article obtained therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US68947505P | 2005-06-10 | 2005-06-10 | |
US11/278,863 US20060280938A1 (en) | 2005-06-10 | 2006-04-06 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived thererom |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060280938A1 true US20060280938A1 (en) | 2006-12-14 |
Family
ID=36889275
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/278,863 Abandoned US20060280938A1 (en) | 2005-06-10 | 2006-04-06 | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived thererom |
Country Status (13)
Country | Link |
---|---|
US (1) | US20060280938A1 (en) |
EP (1) | EP1894210B1 (en) |
JP (2) | JP4786711B2 (en) |
KR (2) | KR20080015067A (en) |
CN (1) | CN101194324B (en) |
AT (1) | ATE438183T1 (en) |
BR (1) | BRPI0606835A2 (en) |
CA (1) | CA2596045A1 (en) |
DE (1) | DE602006008142D1 (en) |
MX (1) | MX2007009360A (en) |
MY (1) | MY143389A (en) |
TW (1) | TW200703374A (en) |
WO (1) | WO2006135597A1 (en) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2055465A1 (en) | 2007-11-02 | 2009-05-06 | Exel Oyj | Method for manufacturing profiles, tubes and plates |
US20100143692A1 (en) * | 2008-12-10 | 2010-06-10 | Ryan James P | Carbon and Glass Fiber Reinforced Composition |
US20100310851A1 (en) * | 2009-05-18 | 2010-12-09 | Xiaoyun Lai | Conductive Fiber Glass Strands, Methods Of Making The Same, And Composites Comprising The Same |
WO2010148383A1 (en) * | 2009-06-19 | 2010-12-23 | Sabic Innovative Plastics Ip B.V | Single conductive pellets of long glass fiber reinforced thermoplastic resin and manufacturing method thereof |
CN102333910A (en) * | 2008-12-26 | 2012-01-25 | 阿克马法国公司 | Pekk composite fibre, method for manufacturing same and uses thereof |
EP2711938A1 (en) * | 2012-09-25 | 2014-03-26 | Nexans | Silicone multilayer insulation for electric cable |
US20140106166A1 (en) * | 2011-04-12 | 2014-04-17 | Ticona Llc | Continuous Fiber Reinforced Thermoplastic Rod and Pultrusion Method for Its Manufacture |
CN103881381A (en) * | 2014-04-03 | 2014-06-25 | 广州市聚赛龙工程塑料有限公司 | Polyether sulfone composite material with high dielectric constant and low dielectric loss and preparation method thereof |
US8859089B2 (en) | 2010-06-22 | 2014-10-14 | Ticona Llc | Reinforced hollow profiles |
US20150093562A1 (en) * | 2013-10-01 | 2015-04-02 | Samsung Sdi Co., Ltd. | Conductive Thermoplastic Resin Composition |
US9096000B2 (en) | 2010-06-22 | 2015-08-04 | Ticona Llc | Thermoplastic prepreg containing continuous and long fibers |
US9238347B2 (en) | 2010-06-11 | 2016-01-19 | Ticona Llc | Structural member formed from a solid lineal profile |
WO2016057735A1 (en) * | 2014-10-08 | 2016-04-14 | Ocv Intellectual Capital, Llc | Hybrid sheet molding compound material |
JP2016117840A (en) * | 2014-12-22 | 2016-06-30 | ダイキョーニシカワ株式会社 | Molten molding pellet mixture and molding manufactured using the same |
US9409347B2 (en) | 2010-06-22 | 2016-08-09 | Ticona Llc | Method for forming reinforced pultruded profiles |
US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
CN106283211A (en) * | 2015-06-08 | 2017-01-04 | 天津工业大学 | A kind of preparation method of PSA fiber nanofiber solution |
US9994371B2 (en) | 2014-07-22 | 2018-06-12 | Entegris, Inc. | Molded fluoropolymer breakseal with compliant material |
US10301468B2 (en) | 2014-06-19 | 2019-05-28 | Polyone Corporation | Thermally conductive and electrically conductive nylon compounds |
US10407552B2 (en) * | 2015-09-30 | 2019-09-10 | Teijin Limited | Press-molded product and composite material |
CN110248786A (en) * | 2017-02-03 | 2019-09-17 | 帝人株式会社 | Composite material comprising carbon fiber and thermoplastic resin, using the composite material formed body manufacturing method and formed body |
CN112937037A (en) * | 2019-11-26 | 2021-06-11 | 旭化成株式会社 | Continuous fiber reinforced resin composite material and method for producing same |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2918081B1 (en) * | 2007-06-27 | 2009-09-18 | Cabinet Hecke Sa | METHOD FOR IMPREGNATING FIBERS CONTINUOUS BY A COMPOSITE POLYMERIC MATRIX COMPRISING A THERMOPLASTIC POLYMER |
JP2010006856A (en) * | 2008-06-24 | 2010-01-14 | Nissei Plastics Ind Co | Carbon nanocomposite resin material |
JP5710502B2 (en) | 2009-02-05 | 2015-04-30 | アーケマ・インコーポレイテッド | Fiber sized with polyetherketoneketone |
CN102173005A (en) * | 2010-12-30 | 2011-09-07 | 金发科技股份有限公司 | Method for granulating polymer powder |
JP5749108B2 (en) * | 2011-07-26 | 2015-07-15 | ダイセルポリマー株式会社 | Seam member using fiber wound tape and method for manufacturing the same |
CN103073873B (en) * | 2011-10-25 | 2015-01-14 | 中国石油化工股份有限公司 | Novel material pressure-out ball used in staged fracturing pitching slide sleeve opening |
EP2703436B1 (en) * | 2012-08-28 | 2017-02-22 | Ems-Patent Ag | Polyamide moulding material and its application |
JP6777710B2 (en) * | 2013-05-30 | 2020-10-28 | ダイセルポリマー株式会社 | Radar transmit / receive antenna protection |
JP6467140B2 (en) * | 2013-05-30 | 2019-02-06 | ダイセルポリマー株式会社 | Thermoplastic resin composition for molded article having millimeter wave shielding performance |
US9598541B2 (en) * | 2013-06-04 | 2017-03-21 | Pbi Performance Products, Inc. | Method of making polybenzimidazole |
CN103474130B (en) * | 2013-09-30 | 2015-07-29 | 胡钧峰 | Preparation method of special nano grounding wire |
CN104292817A (en) * | 2014-01-08 | 2015-01-21 | 上海智高贸易有限公司 | Continuous fiber composite high thermal conductive material and processing technology thereof |
US20160160001A1 (en) * | 2014-11-06 | 2016-06-09 | Northrop Grumman Systems Corporation | Ultrahigh loading of carbon nanotubes in structural resins |
CN107474202A (en) * | 2017-07-06 | 2017-12-15 | 首都航天机械公司 | A kind of synthetic method of high temperature resistant phenolic resin containing carborane |
CN108467571B (en) * | 2018-03-14 | 2021-01-05 | 武汉理工大学 | Conductive composite material with wide resistivity distribution and preparation method thereof |
CN111584151B (en) * | 2020-05-26 | 2021-10-01 | 杭州幄肯新材料科技有限公司 | Carbon fiber/carbon/graphite composite carbon felt and method for enhancing heat conduction and electric conduction performance of polymer composite material |
CN111844524B (en) * | 2020-07-27 | 2021-08-10 | 西安交通大学 | Preparation method of hybrid fiber reinforced resin matrix composite material 3D printing wire |
CN111848930B (en) * | 2020-07-30 | 2021-07-13 | 清华大学 | Soluble polybenzfuran, preparation method thereof and application thereof in synthesizing 5-substituted benzofuran |
CN115298265B (en) * | 2022-07-06 | 2023-06-13 | 远东电缆有限公司 | Thermoplastic carbon fiber composite material and preparation method and application thereof |
Citations (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852113A (en) * | 1971-12-30 | 1974-12-03 | Osaka Soda Co Ltd | Positive electrode for high energy primary cells and cells using same |
US4565684A (en) * | 1984-08-20 | 1986-01-21 | General Motors Corporation | Regulation of pyrolysis methane concentration in the manufacture of graphite fibers |
US4749451A (en) * | 1986-02-05 | 1988-06-07 | Basf Aktiengesellschaft | Electrochemical coating of carbon fibers |
US4816289A (en) * | 1984-04-25 | 1989-03-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for production of a carbon filament |
US4950439A (en) * | 1987-07-10 | 1990-08-21 | C. H. Masland & Sons | Glossy finish fiber reinforced molded product |
US5019450A (en) * | 1981-01-21 | 1991-05-28 | Imperial Chemical Industries Plc | Fiber reinforced compositions and method of producing such compositions |
US5036580A (en) * | 1990-03-14 | 1991-08-06 | E. I. Du Pont De Nemours And Company | Process for manufacturing a polymeric encapsulated transformer |
US5248553A (en) * | 1989-03-16 | 1993-09-28 | Toyo Ink Manufacturing Co., Ltd. | Coated molded article |
US5256335A (en) * | 1992-11-09 | 1993-10-26 | Shell Oil Company | Conductive polyketone polymers |
US5300366A (en) * | 1990-05-09 | 1994-04-05 | Oiles Corporation | Fluororesin composition for a sliding member and a sliding member |
US5300553A (en) * | 1991-10-15 | 1994-04-05 | Yazaki Corporation | Method of producing electrically conductive composite |
US5354607A (en) * | 1990-04-16 | 1994-10-11 | Xerox Corporation | Fibrillated pultruded electronic components and static eliminator devices |
US5484838A (en) * | 1994-12-22 | 1996-01-16 | Ford Motor Company | Thermoplastic compositions with modified electrical conductivity |
US5643502A (en) * | 1993-03-31 | 1997-07-01 | Hyperion Catalysis International | High strength conductive polymers containing carbon fibrils |
US5718995A (en) * | 1996-06-12 | 1998-02-17 | Eastman Kodak Company | Composite support for an imaging element, and imaging element comprising such composite support |
US5830326A (en) * | 1991-10-31 | 1998-11-03 | Nec Corporation | Graphite filaments having tubular structure and method of forming the same |
US5844037A (en) * | 1996-07-24 | 1998-12-01 | The Dow Chemical Company | Thermoplastic polymer compositions with modified electrical conductivity |
US6153683A (en) * | 1996-11-14 | 2000-11-28 | Kawasaki Steel Corporation | Glass long fiber-reinforced thermoplastic resin form having conductivity and manufacturing method thereof |
US6183714B1 (en) * | 1995-09-08 | 2001-02-06 | Rice University | Method of making ropes of single-wall carbon nanotubes |
US6221283B1 (en) * | 1999-05-07 | 2001-04-24 | General Electric Company | Conductive compositions with compositionally controlled bulk resistivity |
US20010022356A1 (en) * | 2000-02-03 | 2001-09-20 | General Electric Co. | Carbon-reinforced thermoplastic resin composition and articles made from same |
US6344513B1 (en) * | 1999-02-26 | 2002-02-05 | Teijin Limited | Resin composition and jig for use in transportation |
US6384128B1 (en) * | 2000-07-19 | 2002-05-07 | Toray Industries, Inc. | Thermoplastic resin composition, molding material, and molded article thereof |
US6486255B2 (en) * | 1999-11-12 | 2002-11-26 | General Electric Company | Conductive polyphenylene ether-polyamide blend |
US20020183438A1 (en) * | 2001-04-27 | 2002-12-05 | Jayantha Amarasekera | Conductive plastic compositions and method of manufacture thereof |
US6528572B1 (en) * | 2001-09-14 | 2003-03-04 | General Electric Company | Conductive polymer compositions and methods of manufacture thereof |
US20030171877A1 (en) * | 2002-02-12 | 2003-09-11 | Adeyinka Adedeji | Method, system, storage medium, and data signal for supplying a multi-component composition |
US6673864B2 (en) * | 2000-11-30 | 2004-01-06 | General Electric Company | Conductive polyester/polycarbonate blends, methods for preparation thereof, and articles derived therefrom |
US20050074993A1 (en) * | 2000-08-09 | 2005-04-07 | Alam M Khairul | Polymer matrix composite |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0725988B2 (en) * | 1989-03-16 | 1995-03-22 | 東洋インキ製造株式会社 | Resin composition |
JPH04323225A (en) * | 1991-04-23 | 1992-11-12 | Mitsui Toatsu Chem Inc | Production of polyimide resin composition through kneading |
JP4160138B2 (en) * | 1996-11-14 | 2008-10-01 | ゼネラル・エレクトリック・カンパニイ | Thermoplastic resin molded product, material for molded product, and method for producing molded product |
JPH10158443A (en) * | 1996-12-05 | 1998-06-16 | Idemitsu N S G Kk | Stampable sheet excellent in conductivity and mechanical strength |
-
2006
- 2006-04-06 US US11/278,863 patent/US20060280938A1/en not_active Abandoned
- 2006-06-05 MX MX2007009360A patent/MX2007009360A/en active IP Right Grant
- 2006-06-05 AT AT06772129T patent/ATE438183T1/en not_active IP Right Cessation
- 2006-06-05 EP EP06772129A patent/EP1894210B1/en not_active Not-in-force
- 2006-06-05 JP JP2008513845A patent/JP4786711B2/en not_active Expired - Fee Related
- 2006-06-05 CN CN2006800206065A patent/CN101194324B/en not_active Expired - Fee Related
- 2006-06-05 KR KR1020077017904A patent/KR20080015067A/en active Application Filing
- 2006-06-05 BR BRPI0606835-9A patent/BRPI0606835A2/en not_active IP Right Cessation
- 2006-06-05 CA CA002596045A patent/CA2596045A1/en not_active Abandoned
- 2006-06-05 DE DE602006008142T patent/DE602006008142D1/en active Active
- 2006-06-05 KR KR1020137025506A patent/KR20130124400A/en active IP Right Grant
- 2006-06-05 WO PCT/US2006/021709 patent/WO2006135597A1/en active Application Filing
- 2006-06-08 MY MYPI20062653A patent/MY143389A/en unknown
- 2006-06-09 TW TW095120632A patent/TW200703374A/en unknown
-
2011
- 2011-04-13 JP JP2011089049A patent/JP2011174081A/en active Pending
Patent Citations (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852113A (en) * | 1971-12-30 | 1974-12-03 | Osaka Soda Co Ltd | Positive electrode for high energy primary cells and cells using same |
US5019450A (en) * | 1981-01-21 | 1991-05-28 | Imperial Chemical Industries Plc | Fiber reinforced compositions and method of producing such compositions |
US5019450B1 (en) * | 1981-01-21 | 1996-10-29 | Kawasaki Chem Holding | Fibre reinforced compositions and methods for producing such compositions |
US4816289A (en) * | 1984-04-25 | 1989-03-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for production of a carbon filament |
US4565684A (en) * | 1984-08-20 | 1986-01-21 | General Motors Corporation | Regulation of pyrolysis methane concentration in the manufacture of graphite fibers |
US4749451A (en) * | 1986-02-05 | 1988-06-07 | Basf Aktiengesellschaft | Electrochemical coating of carbon fibers |
US4950439A (en) * | 1987-07-10 | 1990-08-21 | C. H. Masland & Sons | Glossy finish fiber reinforced molded product |
US5248553A (en) * | 1989-03-16 | 1993-09-28 | Toyo Ink Manufacturing Co., Ltd. | Coated molded article |
US5036580A (en) * | 1990-03-14 | 1991-08-06 | E. I. Du Pont De Nemours And Company | Process for manufacturing a polymeric encapsulated transformer |
US5354607A (en) * | 1990-04-16 | 1994-10-11 | Xerox Corporation | Fibrillated pultruded electronic components and static eliminator devices |
US5300366A (en) * | 1990-05-09 | 1994-04-05 | Oiles Corporation | Fluororesin composition for a sliding member and a sliding member |
US5300553A (en) * | 1991-10-15 | 1994-04-05 | Yazaki Corporation | Method of producing electrically conductive composite |
US5830326A (en) * | 1991-10-31 | 1998-11-03 | Nec Corporation | Graphite filaments having tubular structure and method of forming the same |
US5256335A (en) * | 1992-11-09 | 1993-10-26 | Shell Oil Company | Conductive polyketone polymers |
US5643502A (en) * | 1993-03-31 | 1997-07-01 | Hyperion Catalysis International | High strength conductive polymers containing carbon fibrils |
US5484838A (en) * | 1994-12-22 | 1996-01-16 | Ford Motor Company | Thermoplastic compositions with modified electrical conductivity |
US6183714B1 (en) * | 1995-09-08 | 2001-02-06 | Rice University | Method of making ropes of single-wall carbon nanotubes |
US5718995A (en) * | 1996-06-12 | 1998-02-17 | Eastman Kodak Company | Composite support for an imaging element, and imaging element comprising such composite support |
US5844037A (en) * | 1996-07-24 | 1998-12-01 | The Dow Chemical Company | Thermoplastic polymer compositions with modified electrical conductivity |
US6153683A (en) * | 1996-11-14 | 2000-11-28 | Kawasaki Steel Corporation | Glass long fiber-reinforced thermoplastic resin form having conductivity and manufacturing method thereof |
US6344513B1 (en) * | 1999-02-26 | 2002-02-05 | Teijin Limited | Resin composition and jig for use in transportation |
US6221283B1 (en) * | 1999-05-07 | 2001-04-24 | General Electric Company | Conductive compositions with compositionally controlled bulk resistivity |
US6486255B2 (en) * | 1999-11-12 | 2002-11-26 | General Electric Company | Conductive polyphenylene ether-polyamide blend |
US20010022356A1 (en) * | 2000-02-03 | 2001-09-20 | General Electric Co. | Carbon-reinforced thermoplastic resin composition and articles made from same |
US6384128B1 (en) * | 2000-07-19 | 2002-05-07 | Toray Industries, Inc. | Thermoplastic resin composition, molding material, and molded article thereof |
US20050074993A1 (en) * | 2000-08-09 | 2005-04-07 | Alam M Khairul | Polymer matrix composite |
US6673864B2 (en) * | 2000-11-30 | 2004-01-06 | General Electric Company | Conductive polyester/polycarbonate blends, methods for preparation thereof, and articles derived therefrom |
US20020183438A1 (en) * | 2001-04-27 | 2002-12-05 | Jayantha Amarasekera | Conductive plastic compositions and method of manufacture thereof |
US20030181568A1 (en) * | 2001-04-27 | 2003-09-25 | Jayantha Amarasekera | Conductive plastic compositions and method of manufacture thereof |
US6689835B2 (en) * | 2001-04-27 | 2004-02-10 | General Electric Company | Conductive plastic compositions and method of manufacture thereof |
US6528572B1 (en) * | 2001-09-14 | 2003-03-04 | General Electric Company | Conductive polymer compositions and methods of manufacture thereof |
US20030171877A1 (en) * | 2002-02-12 | 2003-09-11 | Adeyinka Adedeji | Method, system, storage medium, and data signal for supplying a multi-component composition |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2055465A1 (en) | 2007-11-02 | 2009-05-06 | Exel Oyj | Method for manufacturing profiles, tubes and plates |
US20100143692A1 (en) * | 2008-12-10 | 2010-06-10 | Ryan James P | Carbon and Glass Fiber Reinforced Composition |
CN102333910A (en) * | 2008-12-26 | 2012-01-25 | 阿克马法国公司 | Pekk composite fibre, method for manufacturing same and uses thereof |
US9242897B2 (en) | 2009-05-18 | 2016-01-26 | Ppg Industries Ohio, Inc. | Aqueous dispersions and methods of making same |
US20100310851A1 (en) * | 2009-05-18 | 2010-12-09 | Xiaoyun Lai | Conductive Fiber Glass Strands, Methods Of Making The Same, And Composites Comprising The Same |
US20100311872A1 (en) * | 2009-05-18 | 2010-12-09 | Xiaoyun Lai | Aqueous Dispersions And Methods Of Making Same |
EP2443189B2 (en) † | 2009-06-19 | 2022-08-24 | SABIC Global Technologies B.V. | Single conductive pellets of long glass fiber reinforced thermoplastic resin and manufacturing method thereof |
WO2010148383A1 (en) * | 2009-06-19 | 2010-12-23 | Sabic Innovative Plastics Ip B.V | Single conductive pellets of long glass fiber reinforced thermoplastic resin and manufacturing method thereof |
US20100327235A1 (en) * | 2009-06-19 | 2010-12-30 | Sabic Innovative Plastics Ip B.V. | Single conductive pellets of long glass fiber reinforced thermoplastic resin and manufacturing method thereof |
US8524120B2 (en) * | 2009-06-19 | 2013-09-03 | Sabic Innovative Plastics Ip B.V. | Single conductive pellets of long glass fiber reinforced thermoplastic resin and manufacturing method thereof |
US9919481B2 (en) | 2010-06-11 | 2018-03-20 | Ticona Llc | Structural member formed from a solid lineal profile |
US9238347B2 (en) | 2010-06-11 | 2016-01-19 | Ticona Llc | Structural member formed from a solid lineal profile |
US9409347B2 (en) | 2010-06-22 | 2016-08-09 | Ticona Llc | Method for forming reinforced pultruded profiles |
US8859089B2 (en) | 2010-06-22 | 2014-10-14 | Ticona Llc | Reinforced hollow profiles |
US9096000B2 (en) | 2010-06-22 | 2015-08-04 | Ticona Llc | Thermoplastic prepreg containing continuous and long fibers |
US10676845B2 (en) * | 2011-04-12 | 2020-06-09 | Ticona Llc | Continuous fiber reinforced thermoplastic rod and pultrusion method for its manufacture |
US20140106166A1 (en) * | 2011-04-12 | 2014-04-17 | Ticona Llc | Continuous Fiber Reinforced Thermoplastic Rod and Pultrusion Method for Its Manufacture |
US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
US9196394B2 (en) | 2012-09-25 | 2015-11-24 | Nexans | Silicone multilayer insulation for electric cable |
KR102076671B1 (en) | 2012-09-25 | 2020-02-12 | 넥쌍 | Silicone multilayer insulation for electric cable |
KR20140040052A (en) * | 2012-09-25 | 2014-04-02 | 넥쌍 | Silicone multilayer insulation for electric cable |
EP2711938A1 (en) * | 2012-09-25 | 2014-03-26 | Nexans | Silicone multilayer insulation for electric cable |
US20150093562A1 (en) * | 2013-10-01 | 2015-04-02 | Samsung Sdi Co., Ltd. | Conductive Thermoplastic Resin Composition |
CN103881381A (en) * | 2014-04-03 | 2014-06-25 | 广州市聚赛龙工程塑料有限公司 | Polyether sulfone composite material with high dielectric constant and low dielectric loss and preparation method thereof |
US10301468B2 (en) | 2014-06-19 | 2019-05-28 | Polyone Corporation | Thermally conductive and electrically conductive nylon compounds |
US9994371B2 (en) | 2014-07-22 | 2018-06-12 | Entegris, Inc. | Molded fluoropolymer breakseal with compliant material |
WO2016057735A1 (en) * | 2014-10-08 | 2016-04-14 | Ocv Intellectual Capital, Llc | Hybrid sheet molding compound material |
US20170305075A1 (en) * | 2014-10-08 | 2017-10-26 | Ocv Intellectual Capital, Llc | Hybrid sheet molding compound material |
US20170297274A1 (en) * | 2014-10-08 | 2017-10-19 | Ocv Intellectual Capital, Llc | Hybrid long fiber thermoplastic composites |
US20170291375A1 (en) * | 2014-10-08 | 2017-10-12 | Ocv Intellectual Capital, Llc | Hybrid reinforcement assemblies |
WO2016057733A1 (en) * | 2014-10-08 | 2016-04-14 | Ocv Intellectual Capital, Llc | Hybrid reinforcement assemblies |
WO2016057734A1 (en) * | 2014-10-08 | 2016-04-14 | Ocv Intellectual Capital, Llc | Hybrid long fiber thermoplastic composites |
JP2016117840A (en) * | 2014-12-22 | 2016-06-30 | ダイキョーニシカワ株式会社 | Molten molding pellet mixture and molding manufactured using the same |
CN106283211A (en) * | 2015-06-08 | 2017-01-04 | 天津工业大学 | A kind of preparation method of PSA fiber nanofiber solution |
US10407552B2 (en) * | 2015-09-30 | 2019-09-10 | Teijin Limited | Press-molded product and composite material |
CN110248786A (en) * | 2017-02-03 | 2019-09-17 | 帝人株式会社 | Composite material comprising carbon fiber and thermoplastic resin, using the composite material formed body manufacturing method and formed body |
US11384209B2 (en) | 2017-02-03 | 2022-07-12 | Teijin Limited | Composite material including carbon fibers and thermoplastic resin, molded body production method using same, and molded body |
CN112937037A (en) * | 2019-11-26 | 2021-06-11 | 旭化成株式会社 | Continuous fiber reinforced resin composite material and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
ATE438183T1 (en) | 2009-08-15 |
KR20080015067A (en) | 2008-02-18 |
WO2006135597A1 (en) | 2006-12-21 |
BRPI0606835A2 (en) | 2009-07-21 |
DE602006008142D1 (en) | 2009-09-10 |
JP4786711B2 (en) | 2011-10-05 |
CN101194324B (en) | 2012-09-26 |
TW200703374A (en) | 2007-01-16 |
MY143389A (en) | 2011-05-13 |
CN101194324A (en) | 2008-06-04 |
EP1894210B1 (en) | 2009-07-29 |
EP1894210A1 (en) | 2008-03-05 |
JP2011174081A (en) | 2011-09-08 |
KR20130124400A (en) | 2013-11-13 |
CA2596045A1 (en) | 2006-12-21 |
MX2007009360A (en) | 2007-09-27 |
JP2008540818A (en) | 2008-11-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1894210B1 (en) | Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom | |
KR102347760B1 (en) | Thermoplastic resin composite composition for shielding electromagnetc wave | |
US5151322A (en) | Thermoplastic composite plate material and products molded from the same | |
CN110234481B (en) | Fiber-reinforced resin molding material | |
US10688734B2 (en) | Discontinuous fiber-reinforced composite material | |
WO2017110532A1 (en) | Structure | |
EP3421207B1 (en) | Discontinuous fibre-reinforced composite material | |
US20010023937A1 (en) | Carbon-reinforced PC-ABS composition and articles made from same | |
KR20170063703A (en) | Reinforcing fiber composite material | |
CN110869182A (en) | Integrated molded body and method for producing same | |
JP2001009860A (en) | Plastic housing reduced in strain | |
CN113710447B (en) | Glass yarn bundle cloth and glass fiber reinforced resin sheet | |
KR102463416B1 (en) | Polyamide complex composition reinforced with glass fiber and carbon fiber | |
JPH0560492B2 (en) | ||
JP3673293B2 (en) | Conductive molding | |
JP6890141B2 (en) | Carbon fiber sheet material, molded body, carbon fiber sheet material manufacturing method and molded body manufacturing method | |
JPWO2019131125A1 (en) | Fiber reinforced thermoplastic resin molding material | |
US11384209B2 (en) | Composite material including carbon fibers and thermoplastic resin, molded body production method using same, and molded body | |
KR102483485B1 (en) | Long fiber reinforced thermoplastics and molded article fabricated by the same | |
KR102358401B1 (en) | Coating agents for carbon fibers and carbon fiber reinforced composites using the same | |
EP3763773A1 (en) | Dry tape material for fiber placement use, method for producing same, and reinforcing fiber laminate and fiber-reinforced resin molded article each produced using same | |
JPH11255907A (en) | Discontinuous fiber-reinforced resin molding and molding material for discontinuous fiber-reinforced resin molding |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ATKINSON, PAUL M.;REEL/FRAME:017471/0493 Effective date: 20060328 |
|
AS | Assignment |
Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENERAL ELECTRIC COMPANY;REEL/FRAME:020985/0551 Effective date: 20070831 Owner name: SABIC INNOVATIVE PLASTICS IP B.V.,NETHERLANDS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENERAL ELECTRIC COMPANY;REEL/FRAME:020985/0551 Effective date: 20070831 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001 Effective date: 20080307 Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001 Effective date: 20080307 |
|
AS | Assignment |
Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:032459/0798 Effective date: 20140312 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION |