CN105082690A - Fiber-reinforced thermoplastic composite material member containing foam core layer and preparation method thereof - Google Patents
Fiber-reinforced thermoplastic composite material member containing foam core layer and preparation method thereof Download PDFInfo
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- CN105082690A CN105082690A CN201410175827.6A CN201410175827A CN105082690A CN 105082690 A CN105082690 A CN 105082690A CN 201410175827 A CN201410175827 A CN 201410175827A CN 105082690 A CN105082690 A CN 105082690A
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Abstract
A disclosed composite material comprises a core layer and at least one outer layer, the core layer contains polymethacrylimide foam, the outer layer contains a thermoplastic composite material, the thermoplastic composite material contains a fiber-reinforced thermoplastic matrix, the core layer and the outer layer are in connection via a welding manner, and the welding area is formed through cooling solidification after the matrix fused on the thermoplastic composite material surface enters into holes on the foam surface. The composite material member possesses high mechanical strength, and possesses lower density compared with metal members with equal strength, and therefore the composite material member is extremely applicable as a member of a spacecraft, an aircraft, a ship and a land traffic tool, and other members such as an external shell.
Description
Technical field
The present invention relates to composite processing field.Specifically, the present invention relates to the composite element containing poly-(methyl) acrylimide foamed core and fibre-reinforced thermoplastic outer, with and preparation method thereof.
Background technology
Containing poly-(methyl) acrylimide foamed core and fibre-reinforced outer field composite element usually by being connected foamed core with adhesive and skin is produced.Produce in the mode of adhesive-free that these composite elements are not too many in file in the prior art to be described.
WO02/098637 describes a kind of method, and wherein thermoplastic cladding material is applied to the surface of foamed core material with the form of fused mass, then shaping in doubling plate technique, hardens in a mold after thermoplastic cooling.
EP0272359 describes a kind of method, wherein the preform of foam core is first cut into certain shape, and is placed in mould, and then the fused mass of thermoplastic is injected into its surface, heat up to make the preform of foam core expand, thus be pressed into the surface of cladding material.
WO2012/013393 describes a kind of method, and wherein the combination of cladding material and foam core is realized by the raw-material foaming of foam core.
PolymerComposites, 1998,19 (3), 275-9 page describes a kind of method, wherein the prepreg of fibre-reinforced cladding material and foam core heat lamination, form fibre-reinforced skin simultaneously and skin and foamed core linked together in a step.
Summary of the invention
Summary of the invention
The invention provides a kind of composite element, it contains a sandwich layer and at least one is outer, and described sandwich layer contains poly-(methyl) acrylimide foam, and described skin contains thermoplastic composite, described thermoplastic composite contains fibre-reinforced thermoplastic matrix, wherein:
Described sandwich layer and skin are linked together by the mode of welding, and described welding region be enter into foam surface by the matrix of described thermoplastic composite melt surface abscess in afterwards cooled and solidified formed.
The present invention also provides the preparation method of described composite element, and it comprises the steps:
A) provide the sandwich layer containing poly-(methyl) acrylimide foam and the skin containing thermoplastic composite, described thermoplastic composite contains fibre-reinforced thermoplastic matrix,
B) heat each layer of described composite element, thus make outer field contact surface melt but not destroy, and the contact surface of sandwich layer softens but does not destroy,
C) each layer of composite element described in hot pressing, thus make the matrix that outer layer face is melted enter in the abscess of sandwich layer contact surface foam,
D) cool, thus contact surface is solidified and welded together.
Composite element of the present invention has excellent peel strength, and it is at least 10N/mm, measures according to DIN53295.
Composite element of the present invention, has lower density compared with the hardware suitable with intensity, thus is suitable as very much the component of spacecraft, airborne vehicle, ship and land craft, and other structural member, such as external shell.
The advantage of the inventive method is, sandwich layer and skin are fused together rapidly, and are linked together securely fast by cooled and solidified.
Detailed Description Of The Invention
Main points of the present invention are, contact surface that is outer and sandwich layer is fused together, thus additive is optional for the present invention, such as adhesive, welding adjuvant or solvent.The hot processing temperature of poly-(methyl) acrylimide foam is generally 165-240 DEG C, and the matrix of therefore desirable thermoplastic composite also should can carry out hot-working at the temperature disclosed above.
Sandwich layer of the present invention contains poly-(methyl) acrylimide foam.
Poly-(methyl) acrylimide foam for sandwich layer of the present invention has the repetitive that can be represented by formula (I),
Wherein
R
1and R
2hydrogen or methyl identical or differently, R
3hydrogen or the alkyl or aryl containing 20 carbon atoms at the most.
The unit of preferred structure (I) form described poly-(methyl) acrylimide foam more than 30 % by weight, especially more than 50 % by weight, very especially more than 80 % by weight.
The production of poly-(methyl) acrylimide rigid foam is that itself is known, and is described in such as GB patent 1078425, GB patent 1045229, DE patent 1817156 (=US patent 3627711) or DE patent 2726259 (=US patent 4139685) or DE19917987.
Such as, the unit of structural formula (I) can especially be formed (see DE-C1817156, DE-C2726259, EP-B146892) via cyclisation isomerization reaction by the unit of adjacent (methyl) acrylic acid and (methyl) acrylonitrile when being heated to 150-250 DEG C.Usually, first in the presence of a free-radical initiator, at low temperature (at such as 30-60 DEG C), via monomer polymerization, being heated to 60-120 DEG C and prepare precursor subsequently, then being undertaken foam (see EP-B356714) by the blowing agent existed by being heated to about 180-250 DEG C.
For this reason, such as, first can form copolymer, this copolymer comprises (methyl) acrylic acid and (methyl) acrylonitrile by the mol ratio of preferred 1:3-3:1.
Described copolymer can comprise other monomeric unit in addition, it such as derives from the ester of acrylic or methacrylic acid, especially with the ester of the lower alcohol containing 1-4 carbon atom, derive from styrene, maleic acid or its acid anhydrides, itaconic acid or its acid anhydrides, vinyl pyrrolidone, vinyl chloride or vinylidene chloride.Can not cyclisation the or only ratio of the very difficulty comonomer of cyclisation can should not exceed following value, the weight based on described monomer: 30 % by weight, preferably 20 % by weight, especially preferably 10 % by weight.
Other monomer that advantageously can use by mode known is equally a small amount of crosslinking agent, such as allyl acrylate, allyl methacrylate, glycol diacrylate or ethylene glycol dimethacrylate, or the multivalent metal salt of acrylic or methacrylic acid, as magnesinm methacrylate.In the quantitative proportion of the described crosslinking agent scope through being everlasting 0.005 % by weight-5 % by weight, based on the total amount of polymerisable monomer.
In addition can use slaine additive, they are commonly used to the amount reducing smog.They especially comprise acrylates or the methacrylate of alkali metal or alkaline-earth metal or zinc, zirconium or lead.(methyl) acrylates of preferred Na, K, Zn and Ca.Consumption is that the monomer of 2-5 weight portion is reducing smoke density significantly according in the combustion testing of FAR25.853a.
The polymerization initiator used is those of the polymerization itself being usually used in (methyl) acrylate; example is azo-compound, such as azodiisobutyronitrile, and peroxide; such as dibenzoyl peroxide or dilauroyl peroxide; or other peroxide, such as cross octanoic acid ter-butyl ester, or cross ketal; and optionally; redox initiator is (in this respect, see such as H.Rauch-Puntigam, Th.
acryl-undMethacrylverbindungen [acrylic compounds and methacrylic compounds], Springer, Heidelberg, 1967, or Kirk-Othmer, EncyclopediaofChemicalTechnology [chemical technology is complete works of], 1st volume, the 286th page and continued page, JohnWiley & Sons, NewYork, 1978).The amount of the polymerization initiator of preferred use is 0.01-0.3 % by weight, based on parent material.
Also the polymerization initiator that time and temperature aspect have different decomposition performance can be advantageously combined in.Fit closely is such as used the neopentanoic acid tert-butyl ester, t-butyl perbenzoate simultaneously and crossed the 2 ethyl hexanoic acid tert-butyl ester, or use t-butyl perbenzoate, 2 simultaneously, iso-2, the 4-methyl pentane nitriles of 2-azo two, 2,2-azodiisobutyronitriles and di-t-butyl peroxide.
The molecular weight of described copolymer by regulating via the polymerization of monomer mixture under the existence of molecular weight regulator, described molecular weight regulator is especially such as this known mercaptan, such as butyl mercaptan, n-dodecyl mercaptan, 2 mercapto ethanol or 2-ethylhexyl mercaptoacetate, or quinone or terpenes; The consumption of wherein said molecular weight regulator normally counts 0.01 % by weight-5 % by weight based on monomer mixture, be preferably based on monomer mixture and count 0.1 % by weight-2 % by weight, especially preferably 0.2 % by weight-1 % by weight (see such as H.Rauch-Puntigam, Th.
acryl-undMethacrylverbindungen [acrylic compounds and methacrylic compounds], Springer, Heidelberg, 1967; Houben-Weyl, MethodenderorganischenChemie [organic chemistry procedures], XIV/1 rolls up, 66th page, GeorgThieme, Heidelberg, 1961 or Kirk-Othmer, EncyclopediaofChemicalTechnology [chemical technology is complete works of], 1st volume, the 296th page and continued page, J.Wiley, NewYork, 1978).
Polymerization is preferably via the modification of polymerisation in bulk, and such as so-called separate slot method is carried out, but is not limited thereto.
The weight average molecular weight of polymer
be preferably greater than 10
6g/mol, is particularly greater than 3 × 10
6g/mol, but do not wish to cause restriction thus.
Blowing agent is in the known manner for the foaming of described copolymer during changing into containing the polymer of imide, and described blowing agent forms gas phase via decomposition or evaporation at 150-250 DEG C.Blowing agent containing amide structure, as urea, monomethyl urea or N, N'-dimethyl urea, formamide or monomethyl formamide discharge ammonia or amine when decomposing, and it can contribute to additional formation imide group.But, also can use without nitrogen blowing agent, as formic acid, water or the unitary aliphatic alcohol containing 3-8 carbon atom, as 1-propyl alcohol, 2-propyl alcohol, positive fourth-1-alcohol, positive fourth-2-alcohol, isobutyl-1-alcohol, isobutyl-2-alcohol, amylalcohol and/or hexanol.
The use amount of blowing agent depends on required foam density, is typically about 0.5 % by weight-15 % by weight, based on used monomer in this blowing agent amount in the reactive mixture.
Precursor can comprise conventional additives in addition.They especially comprise antistatic additive, antioxidant, releasing agent, lubricant, dyestuff, fire retardant, flow improving agent, filler, light stabilizer and organic phosphorus compound as phosphite ester or phosphonate ester, pigment, Weather-stable agent and plasticizer.
Conductive particle is another kind of preferred additive, and described particle prevents the static electrification of foam.They especially comprise metallic particles and carbon black pellet, and they also can exist, as described in EP0356714A1 as having the fiber being of a size of 10nm-10mm.
In addition, can obtain poly-(methyl) acrylimide with high resistance to heat distorsion via making to gather (methyl) methyl acrylate or its copolymer and primary amine reaction, they equally can be used according to the invention.Representative as the lot of examples of the imidizate of described polymeranaloguous can be mentioned: US4246374, EP216505A2, EP860821.High resistance to heat distorsion can be reached via use arylamine (JP05222119A2) or via the specific comonomer of use (EP561230A2, EP577002A1) at this.But all described reactions do not obtain foam, but obtain solid polymer, it must foam to obtain foam in independent second step.Equally, to this, technology is known in the art.
The density of copolymerization (methyl) acrylimide foam is preferably 20kg/m
3-320kg/m
3, be especially preferably 50kg/m
3-110kg/m
3.
Do not wish to cause any restriction thus, before hot pressing, the thickness of sandwich layer is at least 0.05mm, and preferably 0.1-100mm, more preferably 0.1-20mm, depend on final application.
In a specific embodiment of the present invention, described sandwich layer contains polymethacrylimide foam.
Sandwich layer can additionally have other layer in inside.
As the skin that the present invention is used, it contains fibre-reinforced thermoplastic composite.
In a specific embodiment of the present invention, described thermoplastic composite has the matrix of semi-crystalline, preferably its T
mwithin the scope of 165-240 DEG C, more preferably in the scope of 170-220 DEG C.
In a specific embodiment of the present invention, described thermoplastic composite has the matrix of amorphous state, preferably its T
g-T
dtemperature range and 165-240 DEG C have common factor.
T
mand T
gbe fusing point and the glass transition temperature of described matrix respectively, it is determined according to ISO11357 by the method for DSC.
T
dbe the decomposition temperature of described matrix, it is determined according to ISO11358 by the method for TGA.
In a specific embodiment of the present invention, the matrix of described thermoplastic composite is selected from polyamide, polypropylene, polyalkylene terephthalates and polyether-ether-ketone, preferred fat polyamide, more preferably PA6, PA11, PA12, PA46, PA66, PA10, PA610, PA612, PA1010, PA1012 and blend thereof.
The reinforcing material that can be used for described thermoplastic composite is conventional those of plastic industry, and example comprises:
-glass fibre, such as, in short fiber, long fibre, continuous fiber, fleece, fiber textile, knitted fabric, supatex fabric or felt pan form
-carbon fiber, such as, in short fiber, long fibre, continuous fiber, fleece, fiber textile, knitted fabric, supatex fabric or felt pan form
-aramid fibre, such as, in short fiber, long fibre, continuous fiber, fleece, fiber textile, knitted fabric, supatex fabric or felt pan form
-natural fiber is such as wood fibre, flax fiber, hemp, sisal fiber
-synthetic fibers are such as polyester fiber, nylon fiber, polyethylene fibre, Plexiglas fiber
-bead, example is the polyamide (such as PA6GK30) that bead strengthens.
In a specific embodiment of the present invention, described thermoplastic composite is strengthened by carbon fiber, glass fibre, natural fiber or aramid fibre.
Described fibre-reinforced thermoplastic composite can by preparing with matrix resin impregnation of fibers.Preferably, by pressure sintering matrix resin impregnated fiber material.In hot pressing, fibrous material, matrix resin are subject to the effect of heat and pressure, thus make resin melting and penetrate into fibrous material, thus flood described fibrous material.Usually, pressure sintering is carried out under the following conditions: pressure is between 2 and 100 bar, and more preferably between 10 and 40 bar, and temperature is higher than the fusing point of matrix resin, preferably higher than fusing point at least about 20 DEG C, thus can suitably to flood.
Apply impregnation pressure by static method or continuation method (also referred to as dynamic approach), for speed reason, continuation method is preferred.The example of dipping method includes but not limited to vacuum mo(u)lding, in-mould coating, horizontal mould is extruded, pultrusion, wire rod application type method, lamination, thermoprint, diaphragm forming or compression moulding, lamination is preferred.In lamination process, by pressure roller or band by relative in the thermal treatment zone heat and pressure be applied on fibrous material and matrix resin, then apply pressure preferably by pressue device continuously in cooling zone, to complete consolidation and the fibrous material that will flood cools.The example of lamination includes but not limited to calendering, platform lamination and biobelt press lamination.When lamination is used as dipping method, biobelt press is preferably used to carry out lamination.
Conventional method can be adopted to be administered on fibrous material by matrix resin, and these methods such as have the combination of powder coated, film lamination, Extrusion Coating or wherein two or more methods.
In powder coating process, the polymer powder obtained by conventional method for grinding is administered on fibrous material.By disseminating, spraying, spray, powder is administered on fibrous material by thermal spraying or flame-spraying or fluidized bed coating methods.Optionally, powder coating method also can comprise the step of the powder on fibrous material being carried out to rear sintering.Matrix resin is administered on fibrous material, subsequently, the fibrous material of powder coated carries out hot pressing, and optionally outside pressor areas, preheating is carried out to the fibrous material of powder coated.
In film lamination process, one or more film be made up of matrix resin is administered on fibrous material by stacked, these films are obtained by conventional extrusion process known in the art in advance, and such as blow moulding film extruding, cast film are extruded and extruded with cast-sheet.Subsequently, carry out hot press operation to sub-assembly, described sub-assembly comprises one or more film be made up of matrix resin and one or more fibrous materials.In the composite construction of gained, film melts also infiltrates whole fibrous material, forms continuous print polymer entity around fibrous material.
In Extrusion Coating process, the pellet be made up and/or particle are extruded by one or more flat-die melting, to form one or more molten curtain, by molten curtain one or more described in lay, molten curtain is administered on fibrous material subsequently of matrix resin.Subsequently, the assembly comprising matrix resin and one or more fibrous materials carries out hot pressing.
Preferably, in described fibre-reinforced thermoplastic composite, the volume content of fiber is 30-70%, preferred 40-60%.
Preferably, described outer field thickness is 0.1-20mm, more preferably 0.5-10mm, and this depends on final application.
In a specific embodiment of the present invention, described composite element has sandwich structure, containing two skins and a sandwich layer.
In a specific embodiment of the present invention, described skin and/or sandwich layer contain one or more impact modifiers, one or more heat stabilizers, one or more oxidation stabilizers, one or more ultra-violet stabilizers, one or more fire retardants or its mixture.
In a specific embodiment of the present invention, described poly-(methyl) acrylimide is selected from commodity and is called
polymethacrylimide, it can be commercially available from EvonikIndustries.
In a specific embodiment of the present invention, the matrix of described thermoplastic composite is selected from commodity and is called
polyamide, it can be commercially available from EvonikIndustries.
Composite element of the present invention can be prepared by aforesaid method.
In a detailed description of the invention of method of the present invention, in step c) in, sandwich layer is pressed into less than 90% of original thickness, and preferably less than 80%.
In a detailed description of the invention of method of the present invention, in step c) in, the thickness of sandwich layer is reduced by least 0.05mm, preferably at least 0.15mm.
In a detailed description of the invention of method of the present invention, in step c) in, each layer of described composite element is being no more than 0.5MPa, preferably more than the laminated under pressure of 0.3MPa.
In a detailed description of the invention of method of the present invention, in step b) in, described contact surface is heated to 165-240 DEG C, preferred 170-220 DEG C.
In a detailed description of the invention of method of the present invention, in step b) in, heating completes by various ways, comprises contact heating, radiating gas heating, infrared heating, convection current or Forced Convection Air heating, eddy-current heating, heating using microwave or their combination.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of each layer of sandwich composite component raw material of embodiment 1;
Fig. 2 is the structural representation of the sandwich composite component of embodiment 1;
Fig. 3 is the sandwich composite element cross-section microphotograph of embodiment 1;
Fig. 4 is the microphotograph of sandwich composite component release surface after disbonded test of embodiment 1.
Detailed description of the invention
Embodiment
Embodiment 1 sandwich composite component
Preparation
As depicted in figs. 1 and 2, described sandwich composite component contains two skins 1 and a foamed core 2.Described two skins 1 are all carbon fiber reinforced PA1010, and thickness is 0.6mm, and fiber volume fraction is 45-55%, its by the mode of hot pressing with matrix PA1010 (
evonikIndustries, T
m200 DEG C) impregnation of carbon fibers obtain.Described foamed core 2 be Polymethacrylimide (
evonikIndustries), thickness is 1.5mm.
Heat two skins 1 and foamed core 2 until its surface temperature reaches 210 DEG C with metallic plate, at such a temperature the surface melting of outer 1, the surface of sandwich layer 2 is softened.Under the pressure of 0.2MPa, each layer of hot pressing, was then cooled to 60 DEG C in 10 minutes, thus made contact surface 3 welded together.The final thickness of sandwich composite component is 2.4mm, and the final thickness of its center core layer is 1.2mm.
This sandwich composite element cross-section photo is taken under microscope (optics digit microscope, manufacturer: KEYENCE (Keyemce), model: VHX-100K).As shown in Figure 3, connect the interface of each layer and not obvious, this represent outer 1 and the connection of adjacently situated surfaces of sandwich layer 2 be very uniform.
Disbonded test
For detecting the bonding strength of each interlayer, from prepared sandwich composite component with the mode strip off of craft skin and sandwich layer.Surprisingly, stripping occurs in the inside of foamed core instead of the intersection at each layer.As shown in the microphotograph of Fig. 4, the both sides after strip off are all observed sandwich layer and are known and uniform abscess, and this represents that stripping only occurs in foamed core, and also further illustrate, the bonding strength of each interlayer is at least higher than the cohesive force of foamed core simultaneously.And such intensity is for the application of component, enough.
Claims (15)
1. a composite element, it contains a sandwich layer and at least one is outer, described sandwich layer contains poly-(methyl) acrylimide foam, described skin contains thermoplastic composite, described thermoplastic composite contains fibre-reinforced thermoplastic matrix, wherein said sandwich layer and skin are linked together by the mode of welding, and described welding region be enter into foam surface by the matrix of described thermoplastic composite melt surface abscess in afterwards cooled and solidified formed.
2. composite element as claimed in claim 1, wherein said thermoplastic composite has
(1) matrix of semi-crystalline, preferably its T
mwithin the scope of 165-240 DEG C, or
(2) matrix of amorphous state, preferably its T
g-T
dtemperature range and 165-240 DEG C have common factor,
Wherein,
T
mand T
gbe fusing point and the glass transition temperature of described matrix respectively, it is determined according to ISO11357 by the method for DSC, and
T
dbe the decomposition temperature of described matrix, it is determined according to ISO11358 by the method for TGA.
3. composite element as claimed in claim 1 or 2, wherein said composite element has sandwich structure, containing two skins and a sandwich layer.
4. the composite element according to any one of claim 1-3, wherein said thermoplastic composite has the matrix of semi-crystalline, its T
mwithin the scope of 170-220 DEG C, wherein T
mbe the fusing point of described matrix, it is determined according to ISO11357 by the method for DSC.
5. the composite element according to any one of claim 1-4, the matrix of wherein said thermoplastic composite is selected from polyamide, polypropylene, polyalkylene terephthalates and polyether-ether-ketone, preferred fat polyamide, more preferably PA6, PA11, PA12, PA46, PA66, PA10, PA610, PA612, PA1010, PA1012 and blend thereof.
6. the composite element according to any one of claim 1-5, wherein said thermoplastic composite is strengthened by carbon fiber, glass fibre, natural fiber or aramid fibre.
7. the composite element according to any one of claim 1-6, wherein said sandwich layer contains polymethacrylimide foam.
8. the composite element according to any one of claim 1-7, wherein said thermoplastic composite is by preparing, preferably by the mode of hot pressing with matrix resin impregnated fiber material.
9. the composite element according to any one of claim 1-8, in wherein said thermoplastic composite, the volume content of fiber is 30-70%, preferred 40-60%.
10. prepare the method for composite element as claimed in any one of claims 1-9 wherein, comprise the steps:
A) provide the sandwich layer containing poly-(methyl) acrylimide foam and the skin containing thermoplastic composite, described thermoplastic composite contains fibre-reinforced thermoplastic matrix,
B) heat each layer of described composite element, thus make outer field contact surface melt but not destroy, and the contact surface of sandwich layer softens but does not destroy,
C) each layer of composite element described in hot pressing, thus make the matrix that outer layer face is melted enter in the abscess of sandwich layer contact surface foam,
D) cool, thus contact surface is solidified and welded together.
11. methods as claimed in claim 10, wherein in step c) in, sandwich layer is pressed into less than 90% of original thickness, and preferably less than 80%.
12. methods as described in claim 10 or 11, wherein in step c) in, the thickness of sandwich layer is reduced by least 0.05mm, preferably at least 0.15mm.
13. methods as described in any one of claim 10-12, wherein in step c) in, each layer of described composite element is being no more than 0.5MPa, preferably more than the laminated under pressure of 0.3MPa.
14. methods as described in any one of claim 10-13, wherein in step b) in, described contact surface is heated to 165-240 DEG C, preferred 170-220 DEG C.
15. methods as described in any one of claim 10-14, wherein in steps d) in, described contact surface welded together is cooled to and is no more than 80 DEG C, preferably more than 60 DEG C.
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| CN201410175827.6A CN105082690A (en) | 2014-04-29 | 2014-04-29 | Fiber-reinforced thermoplastic composite material member containing foam core layer and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113710472A (en) * | 2019-04-17 | 2021-11-26 | 塞特工业公司 | Lightweight sandwich structure with flame retardant properties and method of making same |
| WO2022041358A1 (en) * | 2020-08-24 | 2022-03-03 | 上海骏赐投资管理中心(有限合伙) | Novel composite panel and production method therefor |
| CN114466766A (en) * | 2019-10-07 | 2022-05-10 | 科思创知识产权两合公司 | Vehicle seat comprising a fibrous composite and an expanded thermoplastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113710472A (en) * | 2019-04-17 | 2021-11-26 | 塞特工业公司 | Lightweight sandwich structure with flame retardant properties and method of making same |
| CN114466766A (en) * | 2019-10-07 | 2022-05-10 | 科思创知识产权两合公司 | Vehicle seat comprising a fibrous composite and an expanded thermoplastic |
| WO2022041358A1 (en) * | 2020-08-24 | 2022-03-03 | 上海骏赐投资管理中心(有限合伙) | Novel composite panel and production method therefor |
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Application publication date: 20151125 |