CN105358275A - High performance thermoplastic composite laminates and composite structures made therefrom - Google Patents

Abstract

A fire resistant composite laminate includes a thermoplastic matrix material reinforced with fibers embedded in the matrix of the composite laminate, wherein the thermoplastic matrix material of the fire resistant composite laminate includes polyvinylidene fluoride (PVDF).

Description

The composite structure of High Performance Thermoplastic Composites laminate and manufacture thereof

Technical field

The composite structure that the present invention relates in general to composite layer rolled-up stock and manufactured by it, particularly relates to High Performance Thermoplastic Composites laminate, the composite structure manufactured by it, and its manufacture method.

Background technology

The application of composite is often only limitted to as bearing the low parts to medium structure load.But, in order to meet in Aero-Space and common transportation demand such as to the requirement of corrosion resistance, anti-flammability, anti-cigarette and/or resistance to poison, need light weight, low cost and high performance composite.In addition, the demand, especially relevant to flame-retardancy requirements demand, is also present in and the field generating electricity, build, extra large land transportation is relevant, and to such as the armor of vehicle or personnel or the relevant field of bullet resistant material.

Embodiment of the present invention can overcome the problems referred to above and solve the demand in above-mentioned field.

Summary of the invention

According to various aspects as herein described, provide a kind of refractory composite laminate, comprise by the thermoplastic matrix material being embedded in the intramatrical fiber of this composite layer rolled-up stock and strengthening.The thermoplastic matrix material of described refractory composite laminate comprises polyvinylidene fluoride (PVDF).

According to other aspects as herein described, also provide a kind of refractory composite laminate, comprise by the matrix material being embedded in the intramatrical fiber reinforcement of this composite layer rolled-up stock.The matrix material of described refractory composite laminate comprises at least one in polyvinylidene fluoride (PVDF), polyether-ether-ketone (PEEK), polyphenylene sulfide (PPS) and PEI (PEI).

According to other aspects as herein described, also provide a kind of flame resistant, ballistic resistant plate body comprising refractory composite laminate.Described composite layer rolled-up stock comprises by the fire resistant polymeric host material being embedded in the intramatrical fiber of this composite layer rolled-up stock and strengthening, wherein, described flame resistant, ballistic resistant plate body, when missile hits to this plate body, can reach at least one in the degree of protection of NIJ standard armor grade II-A, II, III-A, III and IV defined for this missile.

According to other aspects as herein described, a kind of flame resistant, ballistic resistant plate body with first surface and second is also provided, this plate body comprises striking face portion, this striking face portion comprises multiple first synusia, each described first synusia includes the fiber be placed in the first matrix material, and described first matrix material comprises the first flame-retarded resin.Described flame resistant, ballistic resistant plate body also comprises the support section adjacent with described striking face portion, this support section comprises multiple second synusia, each described second synusia includes the fiber being positioned at the second matrix material, described second matrix material comprises the second flame-retarded resin, wherein, each synusia is all bonding with adjacent lamina.

Accompanying drawing explanation

Fig. 1 is the high-performance composite materials structural upright schematic diagram according to embodiment comprising core body.

Figure 1A is the enlarged diagram of the structure of high-performance composite materials shown in Fig. 1.

Fig. 2 is the schematic perspective view according to the core body of embodiment shown in Fig. 1.

Fig. 3 is the non-limiting example schematic diagram of the layer body/synusia of the described composite structural laminate rolled-up stock that can be used as according to embodiment.

Fig. 4 is for the manufacture of such as according to the general illustration of the device of the composite layer rolled-up stock of the described composite structure of embodiment.

Fig. 5 is the refrigerated trailer rearview comprising composite structure according to embodiment and/or laminate.

Fig. 6 is the airfreight container stereo figure comprising composite structure according to embodiment and/or laminate.

Fig. 7 is the railway freight container stereo figure comprising composite structure according to embodiment and/or laminate.

Fig. 8 is the intermodal container stereogram comprising composite structure according to embodiment and/or laminate.

Figure 9 shows that the battery case of composite structure and/or the laminate comprised according to embodiment.

Figure 10 shows that the battery case of composite structure and/or the laminate comprised according to embodiment.

Figure 11 is the cut-away section schematic perspective view of the flame resistant, ballistic resistant plate body according to embodiment.

Detailed description of the invention

Herein, inventor describes High Performance Thermoplastic Composites laminate, the high-performance composite materials structure be made up of it and the method manufacturing this type of laminate and structure according to embodiment.The solution that this type of high strength laminate and structure can provide a demand degree high.Its reason is, inventor determines further, and some resin that can meet some needss in the application of such as space flight and aviation is very expensive and be difficult to process, and usually needs special process, but also need aftertreatment technology to obtain finished product in this production of resins.Such as, usually can cause performance loss after the flame-retardant additive that adulterates in commercially available olefin resin, the degree of this loss makes the mechanical performance of obtained final structure significantly reduce usually.In addition, this type of material cannot meet the flame-retardancy requirements of Aero-Space and other carriers usually.Therefore, according to embodiment of the present invention, inventor has determined how such as by the performance of high-performance refractory resin being combined with high strength fibre in thermoplastic matrix, thus be created on mechanical property aspect there is high performance composite, and the ability realizing corrosion resistance and do not produce fire, cigarette and toxicity (such as simultaneously, strong repellence/retardancy to fire, cigarette and noxious material), thus meet industrial requirement.

As discussed below in more detail, according to embodiment, the composite that a kind of thermoplastic strengthened by continuous fiber is formed is disclosed, this material is easy to manufacture, and provide high strength-weight ratio, high-impact, high fatigue durability, high resistance to chemicals corrosivity, high temperature tolerance, high flame retardant and/or low toxicity or nontoxicity, and provide other characteristic such as needed for commercial use.In addition, also as discussed below in more detail, the use to the such as high strength fibre such as E glass fibre and S glass fibre and polyvinylidene fluoride (PVDF) resin is preferably incorporated in embodiment of the present invention, to meet the requirement to forms such as such as high-performance wall scroll banding pattern laminate, the laminate of synusia type and/or battenboards, thus such as provide the unlikely fire that can meet such as aerospace field requirement, not raw cigarette, avirulent composite products.In addition, it has been determined that the materials such as such as carbon, acid amides, basalt and boron are also applicable to and are preferably applied to composite materials disclosed herein.

Inventor determines further, uses unidirectional tape can improve the mechanical performance of described composite in the structure of laminate disclosed herein, makes it be better than the mechanical performance of such as traditional Weaving type laminate.In addition, use the fibers such as such as glass fibre can realize replacing with lower cost materials the part high cost resin (as PVDF) that (as 50% to 85% mass percent) is intended to meet anti-cigarette, fire-resistant and resistance to poison requires and uses, and required mechanical performance can be realized.But need it is further noted that as mentioned below, described laminate disclosed herein, when the form such as strip-type laminate and the laminate of synusia type of employing, can realize providing intensity and reduction to cause the ability of bad temper.Generally speaking, according to embodiment, described high strength reinforced thermoplastic disclosed herein and structure comprise the combination of thermoplastic matrix material, high strength reinforcing fibre and other reinforcement material adoptable if desired.

Referring now to accompanying drawing, an aspect disclosed herein relates to a kind of composite structure 10 as shown in figs. 1 and ia, comprising: the first outer layer body/cortex 12; Second outer layer body/cortex 14; And the core body 16 be folded between the first outer layer body 12 and the second outer layer body 14.It should be noted that core body 16 might not need directly against the first outer layer body 12 and/or the second outer layer body 14.For example, as shown in figs. 1 and ia, also at least one intermediate layer body/cortex 17 can be set between the first outer layer body 12 and the second outer layer body 14.Therefore, according to embodiment, core body 16 can such as be folded between two intermediate layer bodies 17.In addition, according to demand, more or less intermediate layer body 17 can also be used.As another alternative scheme, also intermediate layer body 17 can not be used.

Although need first it is noted that structure 10 is shown for roughly in foursquare composite " battenboard " in Fig. 1 and Figure 1A, but the structure of composite structure 10 is not limited to this.According to final use goods, composite structure 10 can be made into any suitable shape, size, thickness etc.Therefore, comprise the laminate 12,14 and 17 in it of described layer body/such as, and the composite structure 10 of core body 16 can be made into any suitable shape, size, thickness, size etc., and can be made into any suitable goods/product structure.According to embodiment, after component information, hereafter provide more details and the example of this based article.

Core body 16 shown in Fig. 1 and Figure 1A comprises suitable material, is generally foam.According to a kind of embodiment, described foam comprises polyvinylidene fluoride (PVDF) foam, the PVDF foam of such as Zotek brand.It is to be noted, however, that according to embodiment, core body 16 can comprise any suitable material, comprises described herein such as material and any combination thereof of layer body 12,14 and 17.

With regard to the material for the first outer layer body 12, second outer layer body 14, at least one intermediate layer body 17 described and its assembly and tectosome, need it is mentioned that following non-limiting materials and process.Although be below referred to concrete thermoplastic, however, it is noted that, comprise the first and second outer layer bodies 12,14 and the embodiment of described composite structure 10 of intermediate layer body 17 can be made up of the reinforced thermoplastic resin of suitable fibers of the extra stiffener of any with or without, and any suitable thermoplastic skin layer/layer body can be comprised.

According to a kind of embodiment, " battenboard " 10 shown in Fig. 1 and Figure 1A can comprise and apply (such as bonding) to multiple layers of body of the opposite face of expanded thermoplastic foam piece (as core body 16) or laminated multi-layer product (as layer body 12 and/or 14 and/or 17) by proper adhesive.In one embodiment, be applied to the thermoplastic strip that each layer in the layer body of described opposite face or laminate can be strengthened by fiber and form, this band such as has the unidirectional and/or multiaxis fiber alignment set by finished product desirable characteristics.According to the embodiment that the present invention one is extremely suitable for, a kind of plate body is disclosed, described plate body comprises high strength layer body/cortex 12,14 and core body 16, described layer body/cortex such as comprises the PVDF resinous substrates strengthened by high strength continuous fiber (as glass fibre), and described core body comprises PVDF foam.Add in each structure disclosed herein PVDF material can make final structure and product have required fire-resistant/back-fire relief characteristic.

According to embodiment, at least one in first outer layer body 12, second outer layer body 14 and intermediate layer body 17 comprises multiple composite synusia, described multiple composite synusia at least comprises the first composite synusia and the second composite synusia, each in described first composite synusia and the second composite synusia includes the many fibers being positioned at thermoplastic matrix, described multiple synusia is bonded to each other, thus forms composite layer rolled-up stock.According to some embodiment, described first outer layer body 12, second outer layer body 14 and intermediate layer body 17 include above-mentioned component.According to embodiment, at least one in described layer body 12,14,17 and core body 16 comprises PVDF.

According to embodiment, the composite layer rolled-up stock of at least one in first outer layer body 12, second outer layer body 14 and intermediate layer body 17 can comprise one or more composite synusia of bonding mutually, and be usually at least two composite synusia, such as the first composite synusia and the second composite synusia.Each synusia includes many fibers.The described many fibers of each in described first composite synusia and the second composite synusia are all impregnated with thermoplastic matrix material.

According to embodiment, described thermoplastic matrix material can comprise any material or the combination of materials with the thermoplastic properties being applicable to described application, include but not limited to, final composite can be made to have the polyvinylidene fluoride (PVDF) of required fire-resistance property, polyamide (nylon), polyethylene, polypropylene, polyethylene terephthalate, polyphenylene sulfide, polyether-ether-ketone (PEEK), polyphenylene sulfide (PSS), PEI (PEI), generic fluoropolymers and Other Engineering resin, other thermoplastic polymer and/or its combination, such as there is the combination of desirable characteristics.

In one embodiment, the described many fibers in described first composite synusia are roughly parallel to each other, and the described many fibers in described second composite synusia are also roughly parallel to each other.Therefore, according to a kind of embodiment, the equal longitudinal arrangement of described fiber of each synusia (namely aliging each other) and overallly in synusia to extend continuously.According to embodiment, sometimes composite synusia is called synusia or sheet material herein, and according to machine-direction oriented being expressed as of described fiber, there is " unidirectional " feature.

According to other embodiments disclosed herein, many fiber crossovers in many fibers in described first composite synusia and described second composite synusia arrange (crosscut arranges).For example, the angle that many fiber crossovers in many fibers in the first composite synusia and described second composite synusia arrange, for being greater than about 0 ° to about 90 °, is specifically about 15 ° to about 75 °.Note also that, according to embodiment, above-mentioned angle can also be 0 ° to about 90 °.

In addition, according to embodiment, many fibers in many fibers in described first composite synusia and described second composite synusia both can be identical fibre, also can be different fiber.Therefore, according to embodiment, in composite synusia, various types of fiber can be used, comprise the fiber of varying strength.Such as, E glass fibre and S glass fibre can be used.E glass is low alkali borosilicate glass, and it has good electric and mechanical performance and good endurance.The high resistivity of E glass makes it be suitable for electric composite layer rolled-up stock, and " E " in its title namely refers to electrically.

For E glass, S glass is the material that a kind of intensity and cost are higher.S glass is a kind of magnesia/aluminium oxide/silicate glass, is generally used for needing high-tensile aerospace applications.At first, " S " represents high strength.E glass and S glass are the fiber be specially adapted in embodiment disclosed herein.

E glass fibre can add in thermoplastic polymer matrix's material with a wide fibre weight scope.According to embodiment, the weight range of E glass can be about 10 to about 40 ounces every square yard (oz./sq.yd.), is especially about 19 to about 30 ounces every square yard, more in particular is about 21.4 to about 28.4 ounces of every square yard of stiffeners.As non-limiting example, the minimum weight of chiasma type (X) synusia is about 18 ounces of every square yard of composites.When fiber weight percentage is 70%, the weight of described stiffener is 18 ounces 70%.

Alternatively, with thermoplastic matrix and total weight of fiber for benchmark, S glass fibre or the amount of E glass fibre in composite synusia can hold the thermoplastic matrix of about 40% to about 90% percentage by weight, are especially about 50% to about 85%, more in particular are the thermoplastic matrix of about 60% to about 80%.

In addition, also other fibers can be added, especially for together to add with E glass fibre and/or S glass fibre, or optional alternative E glass fibre and/or S glass fibre.Other fibers described comprise: ECR glass fibre, A glass fibre and C glass fibre, and other glass fibres, by quartz, Almasilate, non-alkaline aluminoborosilicate, sodium borosilicate, sodium silicate, sodium calcium aluminium silicate, lead silicate, non-alkaline boron lead aluminate, non-alkaline boron barium aluminate, non-alkaline boron zinc aluminate, non-alkaline manosil AS iron, cadmium borate, aluminum fiber, asbestos, boron, carborundum, by polyethylene, polyvinyl alcohol, saran, aramid fiber, polyamide, polybenzimidazoles, polyoxadiazoles, polyphenyl, PPR, oil and coal tar pitch (isotropism), mesophase pitch, the graphite that the carbonization of cellulose and polyacrylonitrile etc. are derivative and obtain and carbon, ceramic fibre, steel, the fiber that the metallic fibers such as aluminium alloy etc. are formed.

Requiring high-performance and in the rational situation of cost, the high strength organic polymer fiber formed by aramid fiber can used, such as Kevlar fiber or various carbon fiber.High-performance unidirectional fiber bundle has the tensile strength being greater than 7 grams of per dawn usually.This type of high-performance fiber bundle can be aramid fiber, chain extension ultra-high molecular weight polyethylene (UHMWPE), any one of poly-[to phenylene-2,6-benzo dioxazole] (PBO) and poly-[dihydroxy penylene the two imidazoles of pyridine] or combination.The use of this type of high tensile strength material has practical value for the composite plate body with additional strength characteristic.

Therefore, when in not departing from embodiment disclosed herein and being more extensive, fiber type well known to those skilled in the art can be used.For example, aramid fiber, such as, with the commercially available aramid fiber such as trade name Twaron, Technora; Basalt carbon fiber, such as, with the basalt carbon fiber that trade name Toray, Fortafil, Zoltek etc. are commercially available; Liquid crystal polymer (LCP), such as, but not limited to, with the commercially available LCP such as trade name Vectran.According to above description, embodiment of the present invention is also considered to use organic and inorganic and metallic fiber in mode alone or in combination.

According to embodiment, described composite synusia comprises continuous fiber, chopped strand, random composite fibre and/or braided fiber alternatively.In a specific embodiment, composite synusia described herein comprises longitudinal fiber, and does not substantially comprise non-longitudinal fiber.

In addition, according to embodiment, optional use such as foam, metal (such as aluminum steel and other black and/or non-ferrous metal etc.), plastics, epoxides, composite, chemicals and/or other materials, as stiffener, additive and/or inserts, such as have specific machinery, size or other physical propertys equably or in its specific region to make composite structure disclosed herein and/or laminate entire body.Therefore, it should be noted that, composite disclosed herein, laminate and structure can use the combination of any described fiber with any suitable amounts, optional other materials, stiffener etc., and can with above-mentioned optional other materials with any required combinationally using.

In addition, when using continuous reinforcing fibre in composite structure, can when being parallel to fiber orientation directions and measuring, realize larger intensity, wherein, described reinforcing fibre is such as the fiber that length is equal with described material or structure.If the arrangement such as making fiber be consistent and tensile property, and reinforcing fibre is thoroughly flooded by required host material, then the physical property of the composites such as the such as structure/layer rolled-up stock of acquisition can be made to obtain and strengthen.

According to embodiment, due to the fiber longitudinal arrangement in composite synusia, the fiber of certain the composite synusia therefore in composite layer rolled-up stock can be set to have particular kind of relationship with the fiber of other composite synusia one or more of this laminate.

In a kind of detailed description of the invention, fiber in a band or synusia is parallel to each other each other substantially, and described composite layer rolled-up stock comprises multiple synusia, fiber in a certain synusia and the fiber in adjacent lamina are arranged with interleaved mode, such as, the angle being less than about 90 ° with the processbearing astrocyte in this adjacent lamina is set to.According to embodiment, described fiber is uniformly distributed in synusia.Other embodiments comprise the band containing being located in thermoplastic matrix, cross strap or laminate.Such as, a certain material comprises two and has the synusia being located at fiber in thermoplastic matrix material, and wherein the fiber in a certain synusia and the fiber in another synusia are roughly in 90 °.

According to embodiment, composite layer rolled-up stock described herein is used as the material of at least one in described first outer layer body 12 and the second outer layer body 14, and the described thermoplastic matrix of one or more synusia of this composite layer rolled-up stock comprises the thermoplastic matrix such as containing PVDF.The non-limiting example of described thermoplastic includes, but are not limited to: polyamide (nylon), polyethylene, polypropylene, polyethylene terephthalate, polyphenylene sulfide, polyether-ketone and combination thereof etc.In addition, as discussed below in more detail, described matrix only can adopt Kynoar (PVDF) or adopt any combination of PVDF and other matrix components described herein, and the structure made can be made to have fire resistance adding of this PVDF material.

In addition; it has been determined that; compared with such as PP type composite layer rolled-up stock, in described thermoplastic matrix material, use the composite layer rolled-up stock obtained by polyethylene to have higher puncture resistance, and the weight generated needed for per unit puncture protection is less.In addition, compared with polypropylene, poly price is more stable.Polyacrylic price is extremely variable, and some reasons are that the manufacturing process of producing needed for propylene monomer is very complicated.As discussed below in more detail, because composite polyethylene material laminate is less than such as PP composite material laminate in weight, therefore to be made up of this material or the given container of liner just can load more goods, thus to improve fuel efficiency and the cost benefit of the truck, railcar, boats and ships etc. using this type of container.

According to embodiment, polyethylene and polyacrylic copolymer also can be used as described thermoplastic matrix.Such as, according to application and performance requirement, poly percentage by weight can be used to be greater than about 50% and polyacrylic percentage by weight lower than about 50% copolymer.

In other embodiments, the thermoplastic matrix of described one or more synusia comprises with the polyethylene of any suitable weight percentage combination coextrusion and polyethylene terephthalate (writing sometimes poly-(ethylene terephthalate)), is usually abbreviated as PET.Such as, comprise for the synthesis of fiber, the container of beverage, food and other liquid according to the pet polymer that embodiment adopts, thermoforming is applied, and the thermoplasticity pet polymer resin in the engineering resin shared with glass fibre.PET homopolymers can adopt the comonomer such as CHDM or M-phthalic acid to modify, and to reduce fusing point and the degree of crystallinity of PET, thus can at a lower temperature and/or use less active force to realize the plastic forming of described resin.Can optional additional release layer on this type of PET homopolymers and copolymer, with such as follow-up application etc.In addition, according to embodiment, this type of optional layer also can be laminated in described basic composite material structure.

Therefore, describedly polythene thermoplastic polymer is comprised for the matrix material in various embodiment disclosed herein.According to the physical characteristic requirement in the predetermined application target of product, the weight content of thermoplastic can change on a large scale.It should be noted that in most cases, polyethylene can be divided into different classes of according to its density and branch's situation, and poly mechanical performance depends on the parameter such as branch degree and type, crystal structure, molecular weight.Instantiation comprises low density polyethylene (LDPE) (LDPE), ultra-high molecular weight polyethylene (UHMWPE), ultra-low molecular weight northylen (ULMWPE or PE-WAX), High molecular weight polyethylene (HMWPE), high density polyethylene (HDPE) (HDPE), high density crosslinked polyethylene (HDXLPE), crosslinked polyethylene (PEX or XLPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) (LLDPE), very low density polyethylene (VLDPE) and combination thereof.Above, the Types of polyethylenes had use value especially comprises HDPE, LLDPE, LDPE and combination thereof, is especially LDPE.According to embodiment, about being specified in hereafter for all types of poly concrete property in thermoplastic matrix described herein.

The density range of LDPE is 0.910-0.940g/cm ³, and there is high long-chain and short chain degree of branching.Therefore, the strand of LDPE does not generally tightly fill in its crystal structure.Because the transient dipole induced dipole attraction of LDPE is more weak, it shows stronger molecular separating force, thus makes that its hot strength is more weak and ductility is better.LDPE is obtained by Raolical polymerizable.In addition, the high long chain branches degree of LDPE makes it have unique flow properties ideal in the molten state.

UHMWPE is the polyethylene that molecular weight is in 1,000,000 grades, and its molecular weight is between about 300 ten thousand to 600 ten thousand usually.Although the HMW of UHMWPE makes it become extremely tough and tensile material, as density lower than high density polyethylene (HDPE) (as 0.930-0.935g/cm ³) time situation about confirming the same, its HMW also may cause UHMWPE effectively to be inserted in crystal structure by strand.UHMWPE can be obtained by any catalyst technology, and normally used catalyst is Ziegler (Ziegler) catalyst.Due to the toughness of UHMWPE excellence, cutting, abrasiveness and endurance, this material has use value widely in various applications.

The density of HDPE is more than or equal to 0.941g/cm ³.Because the degree of branching of HDPE is lower, therefore it has stronger molecular separating force and hot strength.HDPE is by using chromium/SiO 2 catalyst, Z-N (Ziegler-Natta) catalyst and/or metalloscene catalyst obtained.In addition, the low degree of branching of HDPE realizes by selecting suitable catalyst (as chrome catalysts or Ziegler-Natta catalyst) and suitable reaction condition.

PEX (being also designated as XLPE) for introduce the Midst density of cross-bond to high density polyethylene (HDPE) in polymer architecture, the introducing of described cross-bond makes thermoplastic become elastomer, thus improve its high-temperature behavior, reduce mobility, and improve endurance.

The density range of MDPE is 0.926-0.940g/cm ³, MDPE is by using chromium/SiO 2 catalyst, Ziegler-Natta catalyst and/or metalloscene catalyst obtained.MDPE has good shock resistance and anti-dropping capability, and this material have lower than HDPE notch sensitivity and be better than the anti-stress cracking of HDPE.

The density range of LLDPE is 0.915-0.925g/cm ³.LLDPE is the essentially linear polymer that short-chain branch content is higher, is usually obtained by the copolymerization of ethene and short chain alpha-olefin (such as, 1-butylene, 1-hexene and 1-octene).Compared with LDPE, LLDPE has higher hot strength and higher shock resistance and puncture resistance.LDPE also has the characteristics such as toughness, flexibility and relative transparency.

The density range of VLDPE is 0.880-0.915g/cm ³.VLDPE its be the roughly linear polymer that short-chain branch content is higher, usually obtained by the copolymerization of ethene and short chain alpha-olefin (such as, 1-butylene, 1-hexene and 1-octene).There is due to metalloscene catalyst the reasons such as higher comonomer introducing ability, in the preparation process of VLDPE, usually use metalloscene catalyst.VLDPE also can with other polyblends, be used as impact modifier.

Except above-mentioned each concrete polymer, according to embodiment of the present invention disclosed herein, the copolymer/combination using above-mentioned any polymer also can be considered.As another non-limiting example, with on the basis of alpha-olefin copolymer, or as the replacement scheme with alpha-olefin copolymer, ethene (or polyethylene) also can with other monomer multiple and the ionic composition copolymerization that can generate ion radical, such as vinyl acetate and/or suitable acrylate, the product of described vinyl acetate and ethene is vinyl-vinyl acetate copolymer (EVA).In addition, described thermoplastic matrix can only include polyvinylidene fluoride (PVDF), or comprises polyvinylidene fluoride (PVDF) and any combination of other matrix components described herein, has fire resistance to make the structure made.

According to embodiment of the present invention disclosed herein, the described thermoplastic matrix of one or more synusia of composite layer rolled-up stock described herein only includes polyethylene, or comprises polyethylene and other polymer/copolymer/component, such as PVDF.For example, polyethylene/PVDF can be adopted as described host material, and adopt the thermoplastic polymer of HMW simultaneously, include but not limited to, polypropylene, nylon, PEI (PEI) and copolymer thereof, and any combination of above-mentioned substance.

According to embodiment, composite synusia comprises the polymer substrate of about 60% to about 10% percentage by weight, is especially about 50% to about 10% percentage by weight, more in particular is about 40% to about 15% percentage by weight.Other exemplary range comprise about 40% to about 20% percentage by weight and about 30% to about 25% percentage by weight.It should be noted that above-mentioned each percentage by weight is the percentage that in synusia, matrix material accounts for the gross weight of itself and fiber.

In one exemplary embodiment, the fiber content of described one or more synusia is greater than about 50% percentage by weight (total weight with polymer substrate in synusia and fiber), is especially up to about 85% percentage by weight.As mentioned above, although various types of fiber is all applicable, wherein glass fibre is particularly useful for realizing rigidity property.

In another illustrative embodiments, composite layer rolled-up stock described herein at least comprises the first synusia bonded to each other and the second synusia, and the crosscut and be different fiber each other of the fiber of the fiber of described first synusia and the second synusia.Wherein, the matrix of the one or both in described first synusia and the second synusia comprises polyethylene.Therefore, described composite layer rolled-up stock comprises at least two kinds of different fibers.In other words, the fiber at least the first composite synusia is set to become crosscut relation from the different fibers in adjacent second composite synusia, and is set in 90 ° from the different fibers in described adjacent second composite synusia alternatively.For the ease of expressing, herein, sometimes the first composite synusia arranged in a manner described and the second composite synusia are described as each other in crosscut relation (being chosen as in 90 ° each other), and without the need to describing especially the fiber in each synusia.

Above-mentioned phrase " different fiber " should be construed broadly as representing that described composite layer rolled-up stock comprises at least two composite synusia, and the fiber of these two composite synusia is made up of different materials, or is made up mutually of the different product of same material.Such as, as discussed below in more detail, with regard to the use of composite layer rolled-up stock described herein, the one side comprising the plate body of composite layer rolled-up stock can by Kevlar129 processbearing astrocyte, and the rear portion of this plate body or back can adopt high performance material to be formed.

Alternatively, composite layer rolled-up stock also can comprise the composite synusia be arranged in parallel with adjacent composites synusia, wherein, described adjacent lamina especially comprises the fiber identical with the first composite synusia, and the host material of at least one synusia, particularly the host material of all synusia comprises polyethylene.In addition, the host material of each synusia all can be different, and described host material can be different thermoplastic plastics, different polymer and combination thereof.Therefore, the some composite materials laminate comprising first kind fiber can partly by obtaining the mode that composite synusia stacks gradually with the relation be parallel to each other.

In a kind of embodiment practical especially, composite layer rolled-up stock comprises the composite synusia respectively containing E glass fibre and S glass fibre, and described multi-layer sheet structure is set to different synusia and arranges in mode about in 90 ° each other.

A kind of illustrative layers chip architecture with the composite layer rolled-up stock of at least one first synusia and the second synusia is that described second synusia and described first synusia are in 90 °.In order to obtain desirable characteristics, also can select other angle, being less than 90 ° to make the angle of described second synusia.Some embodiment adopts three-layer tablet structure, wherein, the direction of the first synusia is considered as reference direction (namely 0 °), second synusia is set to relative to described first synusia (such as, about 45 °) become the first angle (such as, positive acute angle), third layer sheet is set to become to be different from the second angle of described first angle (such as relative to described first synusia, negative acute angle, namely the acute angle (such as about-45 ° on opposite angles direction is in described second synusia, namely with on the same direction of relative described first synusia of described second synusia in the reflex angle of about 315 °)).Therefore, described second both can be mutually vertical with third layer sheet, also can not be mutually vertical.Described thermoplastic matrix can make, in the final molding step of the fiber in adjacent lamina in article manufacturing process, mutual movement to occur.

According to other embodiment, at least two composite synusia with about identical faces density are set to 0 to 90 ° of structure, or for being set to the angle into about 15 ° to 75 °.It should be noted that described term " surface density " (being typically expressed as pound per square foot (lbs./sq.ft.)) can be used to compare the relative intensity of different layers body structure.Higher surface density represents that this layer of body has higher punctured resistance.In addition, according to embodiment, second layer dignity density is also adopted to be greater than the composite synusia comprised to least two layers body of ground floor dignity density.According to embodiment, a non-limiting example of the applicable surface density of composite layer rolled-up stock is about 1 to about 10 pound per square foot.

Fig. 3 is the non-limiting example schematic diagram of composite layer rolled-up stock 200.According to embodiment, described composite layer rolled-up stock can be used as at least one in the first outer layer body 12, second outer layer body 14 shown in Fig. 1 and Figure 1A and intermediate layer body 17.In addition, described composite layer rolled-up stock also can be used as any required composite product of the structure further described hereafter by example.According to embodiment, composite layer rolled-up stock 200 at least comprises the first composite synusia 220 and the second composite synusia 240.But, composite layer rolled-up stock can comprise be set to intersect synusia, three-layer tablet, the isostructural any quantity synusia of four synusia.As mentioned above, according to embodiment, the thermoplastic matrix material of at least one synusia comprises PVDF, but also can comprise polyethylene etc.Composite synusia 220 and 240 in this non-limiting example is the unidirectional sheet material or synusia that comprise longitudinal arrangement fiber.Composite synusia 220 and 240 can be manufactured respectively by continuous processing, and can save as different materials volume respectively.Composite layer rolled-up stock described herein, such as Fig. 3 example shown composite layer rolled-up stock 200 comprises at least two composite synusia bonded to each other, and the fiber of different synusia is such as arranged in the mode of mutual crosscut each other.To it should be noted that in above-mentioned layer body one or more adopts any suitable thermoplastic.In addition, although Fig. 3 shows the non-limiting example of the concrete set-up mode of various layer body, but be understandable that, can also change its order and material as required.Therefore, the layer body of synusia 220 and 240 can be rendered as any required combination and order.

Note also that, structure shown in Fig. 3 also can adopt one or more other layer of body.Such as, one or more high strength fibre layer, such as heat of mixing Plasitc fibers, glass fibre etc. can be arranged at any position in described structure (as between layer body and/or as described in the extexine of structure), using such as a structure sheaf.In an embodiment of described structure sheaf, adopt mixed layer rolled-up stock product.A kind of commercially available prod being applicable to described layer body is wherein, for the registration mark of fiber glass industry company (FiberGlassIndustries).According to this manufacturer, for the thermoplastic glass's stiffener (rove) made by mixing E glass and polypropylene filament, it can be woven into the fabric of high conformal.Above-mentioned rove by be heated to its polypropylene-base fusing point (180 DEG C-230 DEG C) more than and before pressurization cooling, execute stressed mode consolidation.The weight percent of described glass is such as 53%, 60% or 70%.Described weaving method is such as plain weave or tiltedly knits.Size and the shape of described structure sheaf and shown other layer of body of Fig. 1 and Figure 1A can change according to the demand of required application.

Note also that, according to embodiment, the described thermoplastic matrix material of the first outer layer body 12, second outer layer body 14 and/or intermediate layer body 17 can also comprise thermosets or its combination.Such as, according to required application, above-mentioned fiber can also add in thermoplasticity/thermoset matrix material with above-mentioned addition.The non-limiting example of thermo set matrix material comprises phenolic resins, polyester, epoxides and combination thereof etc.

With regard to the manufacture method of composite disclosed herein and structure, multiple method is had to adopt.For example, host material described in accomplished in many ways can be adopted the dipping of fiber in synusia or optional coated, comprise and such as scrape the skill in using a kitchen knife in cookery, laminating, pultrusion processes, extrusion molding etc.It should be understood that according to embodiment, other composite synusia of composite layer rolled-up stock, and other composites described herein, composite layer rolled-up stock, plate body etc. also can be obtained by any appropriate method comprising methods described herein.

As a non-limiting example, single laminate, the laminate of synusia type and/or " battenboard " as composite structure 10 can such as be obtained by unidirectional tape, and described unidirectional tape is by using the such as various ways manufacture such as smelting process or power deposition method.Multi-ply layer rolled-up stock uses usually to be had heating and the hydraulic press of cooling capacity or aerostatic press and is obtained by one-shot forming.A kind of method be extremely suitable for is manufacture described material on the continuous band press using Teflon.In addition, also can use there is heating, pressurization and the steel belt pressing machine of cooling capacity.These class methods can manufacture the continuous laminating product of web form.

In addition, according to embodiment, composite material sheet disclosed herein is processed as complicated shape by compression molding method, such as Aero-Space trim panel.For example, this Aero-Space trim panel can be multi-layer sheet and/or be combined to form composite material structural slab with the core material that ZotekPVDF foam etc. is formed.Note also that, the various forms of laminates such as described intersection synusia, three-layer tablet, four synusia can manufacture for wrapping up tubing/being wound around or filament winding, thus improve its architectural characteristic, resistance to corrosion and/or fire resistance.Further, according to embodiment, the goods manufactured by the way, comprise structural slab disclosed herein and tubing can also be used for for the patience to burn into fire, cigarette and toxicity, light weight and/or high-strength structure have the oil of demand, in natural gas and mining industry.Therefore, it should be noted that composite disclosed herein is suitable for multiple industry and preferably has diversified purposes.Such as, as hereafter be described in further detail, the application/structure example of composite disclosed herein is as comprised: the application in aerospace industry, such as interior trim floor, cabin district and aircraft target ship (comprising outer wall), and other aircaft configurations; Application/structure in railcar and bus, comprises floor, wallboard and outer plaque; Application in oil-well rig; Application in carriage of special cargo, comprises fire prevention container; Fire-resistant/fire-retardant plate armour and armor application, such as fire-resistant/flame resistant, ballistic resistant composite plate body etc.

In addition, embodiment disclosed herein preferably can adopt by pultrusion or extrude pre-preg (preimpregnation) thermoplastic being processed into unidirectional tape form, and this material comprises the continuous reinforcing fibre flooded by thermoplastic matrix.In this regard, it should be noted that, in the situations such as composite plate body (such as composite plate body 10), the structure comprising the thermoplastic strip that the above-mentioned continuous fiber of multilayer is strengthened can combine with by having the expanded thermoplastic foam that the identical, similar of desirable characteristics or different materials make.

According to other embodiments, with regard to the manufacture method of composite disclosed herein and goods, be suitable for manufacturing the fiber-reinforced composites synusia such as comprising the many fibers being positioned at thermoplastic matrix described herein (as the first and second composite synusia 220,240) exemplary process equipment comprises the standard belt laminating system using coated tape, such as MaschinenfabrikHerbertMeyerGmbH laminating machine that company sells, the address of the said firm is: No. 1, German Herbert-Meyer street, D-92444Roetz.

Note also that, on above-mentioned basis or as above-mentioned replacement scheme, also can use other various method, with such as by bonded to each other for composite synusia, thus form composite layer rolled-up stock.These class methods comprise: superposed successively by composite synusia, make composite layer rolled-up stock; And by heat/pressure or by use liquid, PUR, reactive hot-melt or film, epoxy resin, methyl acrylate and urethane form adhesive form composite layer rolled-up stock plate.In addition, also acoustic vibration welding and solvent bonding can be used.Generally speaking, composite layer rolled-up stock by multiple synusia is stacked gradually and by this synusia is heated and pressurize (such as in press) make the mutual clinkering of adjacent lamina mode obtain.

The patent No. is 8,201,608 and authorize with herein identical patentee U.S. patents disclose the device and method being suitable for manufacturing composite material sheet, this patent content is incorporated to this paper by reference at this.Such device and method can be used for manufacturing composite layer rolled-up stock as herein described, material and structure.

Correspondingly, hereafter Reference numeral etc. is modified to consistent with composite layer rolled-up stock described herein and structure after, said apparatus and technique are quoted.

Fig. 4 is for can be used for the overall schematic block diagram of the suitable devices embodiment manufacturing composite layer rolled-up stock 200 shown in the Fig. 3 in all products of laminated composite as disclosed herein and structure, and wherein, this device is marked by Reference numeral 31.As shown in Figure 3, device 31 comprises unwind station 32.According to embodiment, in operation, the composite (such as composite synusia) comprising the many fibers be built in thermoplastic matrix by unwind station 32 from material webs charging or unwinding, to process further.Device 31 also comprises the laminating station 34 adjacent with unwind station 32, and wherein, other composite layer bodies can conform to the described composite that goes out from unwind station 32 unwinding.This type of other layer of body can be arranged so that fiber as other composite layer body parts described relative to the fiber alignment in the described composite gone out from unwind station 32 unwinding in different angles.But embodiment of the present invention is not limited to this, the fiber as other composite layer body parts described also can be arranged as the fiber the described composite being basically parallel to and going out from unwind station 32 unwinding.Alternatively, device 31 also comprises second unwind station 36 adjacent with described laminating station, and wherein, at least one other composite layer body can unwinding and going out from composite volume.These unwinding layer bodies can be covered to the described composite that goes out from unwind station 32 unwinding and on any other layer of body that laminating station 34 is additional.The downstream of laminating station 34 is provided with heating station 38, and wherein, each composite layer body is heated, thus realizes bonded to each other.In addition, the downstream of heating station 38 is also provided with process station 40.Process station 40 comprises at least one calendering wound module 41 as detailed below.The downstream of process station 40 is provided with packs up station 42, described in being wound in by composite layer rolled-up stock, pack up station.Herein, as shown in arrow each in Fig. 4, composite is called in " operation direction " from unwind station 32 to the whole process of packing up station 42.Sometimes the word " upstream " mentioned herein and " downstream " refer to direction relative to described operation direction or position.

It should be noted that according to embodiment, the concrete shape of composite layer rolled-up stock, size and composition can be adjusted as required by above-mentioned process equipment.Once for one of composite structure 10, the required composite layer rolled-up stock prepared of more than one or whole layers of body completed, composite structure 10 can be assembled into required shape and structure, and by its adhering components in together.

Such as can be used for multiple final use by the composite structure described herein 10 of said apparatus and manufacture technics and/or composite layer rolled-up stock to apply, especially in cargo handling container parts and cargo carrier application and Application in Building.In some embodiments, composite structure 10 disclosed herein and/or composite layer rolled-up stock are set to as the wall body in building and transport applications (as the cargo carrier such as aircraft and trailer), liner, plate body, floor, container and other structures.Such as, this type of material can be used for manufacturing the plate body of all size and intensity, liner, container, as the floors such as subfloor, door, top parts, wall, wall body exterior trim etc.Note also that, in the embodiment that the present invention is extremely suitable for, composite structure 10 disclosed herein and/or composite layer rolled-up stock are set to for needing the structure member of structure reactance and/or corrosion resistance and plate body, liner, delivery container, structural composite material, railcar, truck, bus and tubing in aerospace applications.

According to required application, different kind of material both can be used alone, and also can be combined with each other.This based article as herein described can provide robust structure etc.More specifically, it has been determined that composite structure 10 described herein and/or composite layer rolled-up stock can be set to obtained final use product, include but not limited to, wall body, door, plate body, liner, container, top parts etc.These goods such as have advantages characteristic in intensity, light weight, corrosion resistance, anti-flammability, anti-cigarette, resistance to poison etc.

In addition, the non-limiting example of the concrete final use product/application of composite structure 10 disclosed herein and/or composite layer rolled-up stock is hereinafter also described.With reference to figure 5, composite structure 10 disclosed herein and/or composite layer rolled-up stock such as can be used as the liner of land transportation trailer or other haulage vehicles, boats and ships, container etc.Figure 5 shows that the lining body 700 of the inside 702 of exemplary land transportation trailer 704.According to embodiment, lining body 700 availability can be better than the short composite plate body cutting thermoset articles of such as standard.For example, poly lining body 700 some PP type plate body comparable light weight, more easy to clean, more antifouling, more wear-resisting is more comprised.Lining body 700 can be set to interior wall liner body or inwall exterior trim and roof and serve as a contrast body.Therefore, the purposes serving as a contrast body 700 comprises the application of refrigerated container (refrigerator car), wall body exterior trim and other carriers.According to embodiment, lining body 700 can be set to the durable semirigid structure or the plate body that are used as specialized designs and prepare the thermal efficiency for improving refrigerated container.

According to other embodiments and final use application and as shown in Figure 5, composite structure 10 disclosed herein and/or composite layer rolled-up stock can be set to such as be used as the floor of trailer or other vehicles, boats and ships, container etc. or subfloor plate body 710.According to embodiment, plate body 710 can also add cover layer, such as the same durable pavement be made up of composite disclosed herein and/or composite layer rolled-up stock.

Note also that each embodiment disclosed herein can comprise composition in any combination of described each embodiment and structure.

Also need to recognize, composite layer rolled-up stock described herein can also be used for such as polytype cargo carrier such as trailer, van, goods transport vehicle, railcar, aircraft, boats and ships and delivery container etc. thereof usually.In addition, word used herein " trailer " is intended to comprise this type of all cargo carriers, and correspondingly, word " delivery container " is intended to comprise the delivery container in the inner of all use.

Therefore, apply according to other final uses, the composite structure 10 comprising composite layer rolled-up stock described herein is described as usually arranging the plate body be used as in the application of land transportation trailer truck according to embodiment of the present invention although above, but other application are also in the scope of embodiment described herein, such as, for liner/inner panel, the liner/inner panel of aircraft, the liner/inner panel, building structure, tubing etc. of container (such as intermodal container) of railcar.

In addition, composite disclosed herein, structure and laminate also can be used for the such as isostructural manufacture of above-mentioned container itself and/or renovation.As above-mentioned non-limiting example, Fig. 6 is the stereogram of airfreight container 970, and according to embodiment, the inside of described container 970 can comprise composite structure 10 described herein and/or composite layer rolled-up stock.As mentioned above, container 970 also can be manufactured by described composite and/or be renovated.

Apply according to other final uses, Fig. 7 is the stereogram of railcar 980, and according to embodiment, described railcar comprises the composite structure 10 and/or composite layer rolled-up stock that are used as lining body 982.Described lining body disclosed herein can be arranged at the various positions of container main body, the inside of such as railcar car wall and other positions.

In addition, Fig. 8 is the schematic perspective view of intermodal container 990, and according to embodiment, described intermodal container comprises the composite structure 10 as composite lining body 992.Intermodal container 990 comprises top 994, madial wall 996, base plate 998 and door portion 999.As described herein, the various positions of such as container or other structures can be arranged at according to the described lining body of embodiment of the present invention.For example, as shown in Figure 8, serve as a contrast body 992 to be located on base plate 998 with outer or one-body molded mode.Lining body 992 also can be positioned at going up at least partially of madial wall 996, and is positioned at the inside at top 994.Also have baffle plate 997 shown in Fig. 8, this baffle plate also can be made by lining body 992 described herein and/or be covered outward.Note also that, intermodal container 990 can be converted to another kind of Transportation Model by a kind of Transportation Model under the prerequisite without the need to resetting to its content or unload, such as, be converted to shipping, truck transport etc. from rail fortune.According to embodiment, the requirement of the size conforms iso standard of container 990.Such as, its length can be in 8 feet in 50 feet, and height can be in 8 feet within the scope of 9 feet 6 inches.

Figure 9 shows that the Another Application of composite structure 10 disclosed herein and/or composite layer rolled-up stock.Specifically, Figure 9 shows that the battery case of the composite structure 10 and/or laminate comprised according to embodiment.Figure 10 shows that Another Application, is specifically the battery case comprising composite structure 10 according to embodiment and/or laminate.

It is to be further understood that composite structure 10 disclosed herein and/or composite layer rolled-up stock can be attached in the structures such as such as internal backplane, sidewall, top, baffle plate and other con-tainer part.Similarly, composite structure 10 disclosed herein and/or composite layer rolled-up stock can be used for manufacturing all or part of of airfreight container, railway freight container, intermodal container, tubing etc.In addition, plate body as herein described, lining body and structure can also be used as such as trailer described herein, the isostructural part or all of outer surface of container.In such cases, described structure can comprise antiultraviolet and/or wear-resistant property.Embodiment of the present invention also comprises the described composite structure 10 of use and/or laminate (comprising the plate body manufactured by it, lining body etc.) is renovated.

In addition, as mentioned above, embodiment disclosed herein also can be used as such as vehicle and personnel's armor or bullet resistant material.For example, embodiment disclosed herein can be used as flame resistant, ballistic resistant composite and plate body.As non-limiting example, such as structure shown in Fig. 1, Fig. 3 and Figure 11 can be used as the shellproof plate body of flame-proof composite material.Described bullet resistant material and plate body can such as the manufacture of portable flame resistant, ballistic resistant shields; the shellproof clamping plate that such as police use; these shellproof clamping plate are used for providing flame resistant, ballistic resistant to protect for the such as fixation means such as control room or police service station, and provide flame resistant, ballistic resistant to protect for automotive occupant etc.In Figure 11 illustrated embodiment, plate body 20 comprises striking face portion 22, and this striking face portion comprises multiple first synusia 22a, 22b etc. and serves as the impact surface 23 of described plate body.Synusia in striking face portion 22 is composite synusia, is located at many first kind fibers 24 in the first host material 26 in this composite synusia comprises separately.As shown in synusia 22a and 22b, the fiber 24 in each synusia is parallel to each other substantially.Described each synusia is arranged so that the fiber in a certain synusia and the fiber in adjacent lamina intersect, and in the present embodiment, for intersecting with 90 ° each other.Such as, but be understandable that, according to embodiment, above-mentioned set-up mode can be other proper angle, is less than 90 °.Plate body 20 also comprises support section 28, and this support section comprises optional back layer 30 and interior section 33.Interior section 33 comprises multiple composite synusia, and each described composite synusia includes the many Equations of The Second Kind fibers 35 be located in the second host material 37.Back portion 30 such as comprises the non-composite material synusia be made up of substantially not fibrous host material.In other embodiments, synusia quantity and composition can change according to purposes.Plate body 20 obtains by such as under type: to the band cross-level of first kind fiber as described in comprising, comprise the band cross-level of described Equations of The Second Kind fiber, and described non-composite material synusia carries out stacking; By methods described herein by its pressing.Such as, by multiple synusia to be stacked gradually and by heat this synusia and pressurize (such as in press) makes the mode of the mutual clinkering of adjacent lamina obtain plate body by multiple synusia.

In one embodiment, shellproof plate body 20 has the main striking face portion containing the E glass fibre as low performance fiber, and the support section containing the S glass fibre as high-performance fiber.The thickness of the thickness of specific plate body and the E glass of this plate body and S glass part can change according to the performance standard of this plate body.Preferably, described S glass synusia and the percentage contribution of E glass synusia to described plate body weight approximately equal.

In a specific embodiment, E glass fibre can defer to the 4.2.2 partial content of ASTMD578-98, and can have the rove output of about 250-675 code/pound (yd/lb.), or the rove number of about 735-1985 gram/kilometer (g/km).S glass fibre can defer to ASTMC162-90 and/or ASM3832B, and can comprise the long filament that diameter is approximately 9 microns, and has the rove number of 675-1600 gram/kilometer or the rove output of 310-735 code/pound.

It is to be noted, however, that the fiber described herein in embodiment disclosed in any or all can be used as above-mentioned fiber 24 and 35 with any combination.Similarly, the composite described herein in the embodiment disclosed in any or all can be used as the described synusia of plate body 20 with any combination.

The content of composite synusia can be stated respectively by the output of used fiber and with the part by weight that the fiber that fiber and matrix material weight are benchmark accounts for this synusia.Such as, in one embodiment, composite synusia can comprise the E glass fibre being positioned at polypropylene matrix.Described fiber can have every pound of fiber and be about 56-1800 code and the output comprising every pound of fiber about 675 yards, and described fiber such as can comprise and comprises the synusia of about 60-80% with fiber and matrix material weight for the about 40-92% under benchmark.The scope of described filament diameter is such as about 0.005-0.025 micron.Note also that, described host material can comprise any or all host material described herein in various disclosed embodiment and any combination thereof, and preferably includes flame-retardant polymer host material described herein, such as, comprise PVDF.Therefore, the composite described herein in the embodiment disclosed in any or all can be used as described first host material 26 and the second host material 37 with any combination.

Note also that, can test the bullet resistant material comprising plate body according to standard, to evaluate the ability that it bears ballisticimpact.For example, country of Ministry of Justice judicial study wait and set up this class standard, name is called " NIJ anti-bullet protective materials standard " (" NIJ standard "), hereinafter simply describes this class standard.The ballistic threats caused due to bullet or other missiles depends on such as its composition, shape, bore, quality and impact velocity etc., and the degree of protection that different armor grade can provide is classified as follows by described NIJ standard: II-A class (low speed .357 Mai Genong and 9 millimeter); II class (high speed .357 Mai Genong and 9 millimeter); III-A class (.44 Mai Genong and 9 millimeter light machine gun); III class (high power rifle) and IV class (armour-piercing rifle).

More specifically, II-A class (low speed .357 Mai Genong and 9 millimeter): the standard testing bullet of the coated bullet form of .357 Mai Genong semimetal being 381 ± 15 meter per seconds can be defendd nominal weight to be 10.2 grams and be tested the speed to II-A class armor.II-A class bullet resistant material also can be defendd nominal weight to be 8 grams and test the speed to be 9 millimeters of coated bullets of all-metal of 332 ± 12 meter per seconds.

II class (high speed .357 Mai Genong; 9 millimeters): the missile of the coated bullet of similar .357 Mai Genong semimetal being 425 ± 15 meter per seconds can be defendd nominal weight to be 10.2 grams and be tested the speed to this type of armor.II class bullet resistant material also can be defendd nominal weight to be 8 grams and test the speed to be 9 millimeters of coated bullets of all-metal of 358 ± 12 meter per seconds.

III-A class (.44 Mai Genong, 9 millimeters of light machine guns): this type of armor can defend most of pistol to threaten, and nominal weight be 15.55 grams and test the speed be 426 ± 15 meter per seconds with band gas hood semi-piercing type .44 Mai Genong plumb, there is the missile of similar characteristics.III-A class bullet resistant material also can defend 9 millimeters of light machine gun bullets.This type of bullet is that nominal weight is 8 grams and tests the speed to be the coated bullet of all-metal of 426 ± 15 meter per seconds.

III class (high power rifle): this type of armor can defend 7.62 millimeter (308 ) ammunition and most of pistol threaten.

IV class (armour-piercing rifle): this type of armor can be defendd nominal weight to be 10.8 grams and test the speed to be 30 bore armor-piercing bullets of 868 ± 15 meter per seconds.

Outside above-mentioned, the test of other bullet resistant materials comprises " MIL-STD-622 – armor V ₅₀ballistic tests " V of defined ₅₀test.The patent No. is 7,598, and the United States Patent (USP) of 185 has further description to this test, and this patent content is incorporated to herein by reference at this.

Preferably, the embodiment disclosed herein comprising flame resistant, ballistic resistant plate body described herein hits at least one to reaching during described plate body in the degree of protection of above-mentioned NIJ standard armor grade II-A, II, III-A, III and IV defined at missile, and by above-mentioned V ₅₀test.

In addition, should be understood that, although the described composite of such as composite structure 10 and/or laminate are described as such as comprising one or two synusia in some embodiments, but embodiment of the present invention is not limited thereto, the synusia of any suitable quantity (such as intersect synusia, three-layer tablet, four synusia etc.) all can be used as any laminate of such as composite structure 10, and its composition can change according to predetermined final use application.So, for example, can realize comprising and be located at the synusia that forms containing the cheap low performance E glass fibre in polythene thermoplastic matrix and by being located at the such as plate body of the synusia formed containing polythene thermoplastic intramatrical high price high-performance S glass fibre, lining body, the isostructural manufacture of container in same by interior.

According to embodiment, comprise thermoplastic matrix material by using and substantially not containing the synusia of thermoset matrix material, can realize at low pressures and form plate body within the time needed for being shorter than thermoset matrix material and solidifying.In addition, without the need to degasification technique, and the VOC (VOC) of minute quantity can be produced or do not produce VOC by the plate body formed containing the synusia comprising poly thermoplastic matrix material.Alternatively, in composite panel described herein, can metal be added, or pottery, or other material.In addition, plate body described herein and other structures can cover it after the production as required, such as, use other composite, elastomer, metal shell etc. to cover, to prevent the impact of ultraviolet, moisture or other environmental factors.In addition, in described host material, can additive be added, to reach the objects such as fire prevention, Smoke prevention and resistance to poison, and reach aesthetic.

In addition, be understandable that, the final strength of finished product, rigidity and other desirable characteristics such as depend on used thermoplastic, and the type of the stiffener used and other material, size and orientation.In addition, the intensity of finished product and rigidity such as also depend on the overall 3D shape of this finished product, comprise length, width, thickness, sectional area etc.

The word of " first ", " second " herein and so on does not represent any order, quantity or importance, but for distinguishing different elements.In addition, indefinite article " a " herein and " an " do not represent logarithm quantitative limitation, but represent institute describe items number be at least one.When comprising word " about " in numeric type term, this term is intended to comprise, but not requirement, the exact numerical of stating in this term.Note also that, feature that is any and/or all embodiments described herein can combine in any combination with the feature that is any and/or all embodiments of other embodiments disclosed herein.

Although more than by detailed description of the invention, invention has been described, after above-mentioned disclosure being read and understanding is obtained to it, one skilled in the art can appreciate that the multiple change done for disclosed embodiment and change and all fall in the spirit and scope of the present invention and attached claims.

Should be understood that, the present invention is confined to concrete structure disclosed herein and/or shown in the drawings never in any form.On the contrary, the present invention also comprises and is in any modification within the scope of present disclosure or equivalent.

Claims (29)

1. a fire resistance composite layer rolled-up stock, is characterized in that, comprising:

The thermoplastic matrix material strengthened by the fiber be embedded in this composite layer rolled-up stock matrix, wherein, the thermoplastic matrix material of described refractory composite laminate comprises polyvinylidene fluoride (PVDF).

2. refractory composite laminate as claimed in claim 1, it is characterized in that, described fiber comprises glass fibre.

3. refractory composite laminate as claimed in claim 2, it is characterized in that, described glass fibre is selected from E glass fibre, S glass fibre and combination thereof.

4. refractory composite laminate as claimed in claim 3, it is characterized in that, described laminate comprises multi-layer sheet structure or ribbon structure.

5. refractory composite laminate as claimed in claim 3, it is characterized in that, described fiber is continuous fiber, and described laminate comprises ribbon structure.

6. refractory composite laminate as claimed in claim 4, is characterized in that, also comprise other reinforcement materials.

7. a composite structure (10), is characterized in that, comprising:

First outer layer body (12);

Second outer layer body (14); And

Core body (16), be folded between described first outer layer body (12) and the second outer layer body (14), wherein, described core body (16) comprises foam;

At least one in described first outer layer body (12) and the second outer layer body (14) comprises refractory composite laminate as claimed in claim 1.

8. composite structure (10) as claimed in claim 7, it is characterized in that, described refractory composite laminate comprises the multiple composite synusia at least comprising the first composite synusia and the second composite synusia, and each in described first composite synusia and the second composite synusia includes the described fiber be embedded in described thermoplastic matrix; Described multiple composite synusia bonds mutually, to form described refractory composite laminate.

9. composite structure (10) as claimed in claim 7, is characterized in that, at least one in described first outer layer body (12) and the second outer layer body (14) comprises the cover layer be located thereon.

10. composite structure (10) as claimed in claim 7, it is characterized in that, described fiber is parallel to each other each other substantially.

11. composite structures (10) as claimed in claim 8, it is characterized in that, described first composite synusia and the second composite synusia comprise the fiber of varying strength, described first composite synusia comprises E glass fibre, and described second composite synusia comprises S glass fibre.

12. 1 kinds of plate bodys comprising composite structure (10) as claimed in claim 7.

13. composite structures (10) as claimed in claim 7, is characterized in that, also comprise at least one the intermediate layer body (17) be positioned between described first outer layer body (12) and the second outer layer body (14).

14. composite structures (10) as claimed in claim 13, it is characterized in that, described core body comprises expansion polyvinylidene fluoride (PVDF) foam, and its thickness is greater than the thickness of described first outer layer body (12), described second outer layer body (14) and at least one intermediate layer body (17) described.

15. 1 kinds of tubing comprising refractory composite laminate as claimed in claim 1.

16. 1 kinds of tubing comprising composite structure as claimed in claim 7.

17. 1 kinds of battery cases comprising composite structure as claimed in claim 7.

18. 1 kinds of battery cases comprising composite structure as claimed in claim 7.

The manufacture method of 19. 1 kinds of refractory composite laminates as claimed in claim 1, is characterized in that, comprises, by smelting process, unidirectional tape is made in this laminate.

20. methods as claimed in claim 19, it is characterized in that, also comprise and be bonded on core body by described laminate, described core body comprises polyvinylidene fluoride (PVDF) foam.

21. 1 kinds of shellproof plate bodys comprising refractory composite laminate as claimed in claim 1.

22. 1 kinds of refractory composite laminates, is characterized in that, comprising:

The matrix material strengthened by the fiber be embedded in this composite layer rolled-up stock matrix, wherein, the matrix material of described refractory composite laminate comprises at least one in polyvinylidene fluoride (PVDF), polyether-ether-ketone (PEEK), polyphenylene sulfide (PPS) and PEI (PEI).

23. 1 kinds of flame resistant, ballistic resistant plate bodys comprising composite layer rolled-up stock as claimed in claim 22.

24. 1 kinds of flame resistant, ballistic resistant plate bodys, is characterized in that, comprising:

Refractory composite laminate, comprising:

The fire resistant polymeric host material strengthened by the fiber be embedded in this composite layer rolled-up stock matrix, wherein, described flame resistant, ballistic resistant plate body, when missile hits to this plate body, can reach at least one in the degree of protection of NIJ standard armor grade II-A, II, III-A, III and IV defined for this missile.

25. 1 kinds of flame resistant, ballistic resistant plate bodys, have first surface and second, it is characterized in that, comprising:

Striking face portion, comprises multiple first synusia, and each described first synusia includes the fiber be placed in the first matrix material, and this first matrix material comprises the first flame-retarded resin; And

The support section adjacent with described striking face portion, this support section comprises multiple second synusia, each described second synusia includes the fiber be placed in the second matrix material, this second matrix material comprises the second flame-retarded resin, wherein, each synusia is all bonding with adjacent lamina.

26. flame resistant, ballistic resistant plate bodys as claimed in claim 25, is characterized in that, at least one in described first matrix material and the second matrix material comprises polyvinylidene fluoride (PVDF).

27. flame resistant, ballistic resistant plate bodys as claimed in claim 26, it is characterized in that, described multiple first synusia comprises E glass fibre, described multiple second synusia comprises S glass fibre.

28. flame resistant, ballistic resistant plate bodys as claimed in claim 25, it is characterized in that, described plate body, when missile hits to this plate body, can reach at least one in the degree of protection of NIJ standard armor grade II-A, II, III-A, III and IV defined for this missile.

29. flame resistant, ballistic resistant plate bodys as claimed in claim 26, it is characterized in that, described fiber is all substantially parallel to each other each other in corresponding synusia, and described synusia is arranged so that the fiber of each synusia and the fiber of adjacent lamina intersect.