CN117363009A - Carbon fiber unidirectional cloth reinforced resin matrix composite material and preparation method thereof - Google Patents
Carbon fiber unidirectional cloth reinforced resin matrix composite material and preparation method thereof Download PDFInfo
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- CN117363009A CN117363009A CN202210778269.7A CN202210778269A CN117363009A CN 117363009 A CN117363009 A CN 117363009A CN 202210778269 A CN202210778269 A CN 202210778269A CN 117363009 A CN117363009 A CN 117363009A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 224
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 224
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 239000004744 fabric Substances 0.000 title claims abstract description 151
- 229920005989 resin Polymers 0.000 title claims abstract description 125
- 239000011347 resin Substances 0.000 title claims abstract description 125
- 239000002131 composite material Substances 0.000 title claims abstract description 98
- 239000011159 matrix material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003365 glass fiber Substances 0.000 claims abstract description 71
- 239000000835 fiber Substances 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000004513 sizing Methods 0.000 claims abstract description 27
- 238000000465 moulding Methods 0.000 claims abstract description 19
- 238000000748 compression moulding Methods 0.000 claims abstract description 9
- 239000012779 reinforcing material Substances 0.000 claims abstract description 8
- 238000001721 transfer moulding Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 32
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 25
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 25
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000005520 cutting process Methods 0.000 claims description 15
- 238000009941 weaving Methods 0.000 claims description 10
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 239000009719 polyimide resin Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 26
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 239000012943 hotmelt Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000805 composite resin Substances 0.000 description 5
- 238000009954 braiding Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
- D03D15/267—Glass
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
- D03D15/275—Carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/06—Glass
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
Abstract
The invention discloses a carbon fiber unidirectional cloth reinforced resin matrix composite material and a preparation method thereof, belonging to the technical field of composite material molding; solves the technical problems of low tensile modulus and poor high temperature resistance of the existing carbon fiber composite material. The carbon fiber unidirectional cloth reinforced resin matrix composite material comprises a resin matrix and a reinforcing material, wherein the heat resistance grade of the resin matrix is more than 200 ℃; the reinforcing material is carbon fiber unidirectional cloth, the carbon fiber unidirectional cloth comprises warp fibers and weft fibers, and the warp fibers are high-modulus carbon fibers; the weft fibers are glass fibers; the warp and weft fibers are secured together by a sizing agent. The preparation method of the invention comprises Resin Transfer Molding (RTM), compression molding or autoclave molding. The invention realizes the preparation of the high-modulus and high-temperature-resistant composite material.
Description
Technical Field
The invention relates to the technical field of composite material molding, in particular to a carbon fiber unidirectional cloth reinforced resin matrix composite material and a preparation method thereof.
Background
The carbon fiber fabric is woven from warp carbon fibers and weft fibers. Composite parts made of carbon fiber fabrics have very flat surfaces. The carbon fiber fabric has the advantages that the weft carbon fibers provide constraint force for fixing warp direction, and the carbon fibers are not easy to be dispersed by flowing resin during Resin Transfer Molding (RTM), so that the mechanical property of the composite material is maintained.
Generally, the carbon fiber braided fabric is woven by using T-series carbon fibers (T300, T700, T800 and the like), and the modulus of the fibers is not more than 350GPa because the composite material prepared by the braided fabric is made of the T-series carbon fibers, so that the tensile modulus of the corresponding composite material is also lower.
Some engineering application fields with complex structures and high modulus of materials require that the resin flowing through the RTM molding technology be injected into the high modulus carbon fiber to reach the designed modulus index. In order to ensure that the high-modulus carbon fiber is not scattered and deformed by resin, the existing high-modulus carbon fiber is prepared into a fabric and then is paved. The elongation at break of the adopted high-model carbon fiber is generally less than 1.2%, and due to poor toughness, if the high-model carbon fiber is used as weft woven fiber of a carbon fiber woven fabric to shuttle back and forth the warp high-modulus carbon fiber, the problem of breakage of the weft high-modulus carbon fiber is easily caused, so that the aim of weaving cannot be achieved.
In the prior art, some carbon fiber unidirectional braids for reinforcing reinforced concrete structures are formed by organic hot-melt wires, warp-wise carbon fibers are fixed after the weft is hot-melted, and the heat-resistant temperature of the weft is usually not more than 190 ℃, so that the composite material has a weak point when being applied at high temperature.
Some of the carbon fiber fabrics are formed by binding weft glass fibers and warp carbon fibers by using polyester binding wires, and the warp carbon fibers are not easily scattered by resin by the process of binding wires, but the problems of low braiding efficiency and weak points in high-temperature application of the composite material are brought (the highest use temperature of polyester is usually not more than 190 ℃), and the adopted carbon fibers such as C-L400 and C-L200 do not belong to high-modulus carbon fibers, so that the modulus of the obtained carbon fiber unidirectional fabric is not high.
How to prepare the high-modulus carbon fiber unidirectional cloth reinforced resin matrix composite material with the heat resistance grade exceeding 200 ℃ is a difficult point to be solved.
Disclosure of Invention
In view of the above analysis, the invention aims to provide a carbon fiber unidirectional cloth reinforced resin matrix composite material and a preparation method thereof, which are used for solving the technical problems of low tensile modulus and poor high temperature resistance of the existing carbon fiber composite material.
The aim of the invention is mainly realized by the following technical scheme:
the invention provides a carbon fiber unidirectional cloth reinforced resin matrix composite material, which comprises a resin matrix and a reinforcing material, wherein the heat resistance grade of the resin matrix is more than 200 ℃;
the reinforcing material is carbon fiber unidirectional cloth, the carbon fiber unidirectional cloth comprises warp fibers and weft fibers, and the warp fibers are high-modulus carbon fibers; the weft fibers are glass fibers;
the warp and weft fibers are secured together by a sizing agent.
Further, the tensile modulus of the high modulus carbon fiber is greater than 450GPa.
Further, the sizing agent is aqueous polymer polyurethane which can be cured at normal temperature so as to fix the warp fibers and the weft fibers together.
Further, the weight content of the sizing agent is 3-8% of the weight of the glass fiber.
Further, the weight of the glass fiber accounts for 1-3% of the weight of the carbon fiber unidirectional cloth.
Further, the resin matrix is a bismaleimide resin or a polyimide resin.
Further, the weight content of the carbon fiber unidirectional cloth accounts for 40-70% of the total weight of the carbon fiber unidirectional cloth reinforced resin matrix composite material.
On the other hand, the invention also provides a preparation method of the carbon fiber unidirectional cloth reinforced resin matrix composite material, which is used for preparing the carbon fiber unidirectional cloth reinforced resin matrix composite material, and the composite material is prepared by adopting Resin Transfer Molding (RTM), compression molding or autoclave molding.
Further, M55J is selected as the high-modulus carbon fiber;
the linear density of the glass fiber is 50-100 tex, and the surface density of the weft glass fiber in the carbon fiber unidirectional cloth is 1-5g/m 2 The surface density of the carbon fiber unidirectional cloth is 140-200g/m 2 。
Further, when the resin matrix is made of a bismaleimide resin and the Resin Transfer Molding (RTM) is adopted as a molding method, the preparation method comprises the following steps:
s1, preparing carbon fiber unidirectional cloth, which comprises the following substeps:
s11, taking the high-modulus carbon fiber as warp-wise carbon fiber after yarn feeding and fiber spreading;
s12, coating a sizing agent when the glass fiber is woven and then using the sizing agent as weft fiber;
s13, weaving the high-modulus carbon fiber and the glass fiber coated with the sizing agent in a plain weave mode;
s14, airing, solidifying and shaping the woven carbon fiber unidirectional cloth at room temperature;
s15, cutting, rolling, packaging and warehousing the carbon fiber unidirectional cloth;
s2, cutting the carbon fiber unidirectional cloth according to the size of a product, paving the cloth in a mould, preheating an injection charging barrel to 100-150 ℃, preheating the mould to 100-150 ℃, pouring a certain amount of bismaleimide resin into the mould to preheat the bismaleimide resin, and then finishing the injection of the bismaleimide resin, wherein the pressure is kept at 0.7-1.5MPa during the injection;
step 3, heating the die to 180-230 ℃ and curing at constant temperature for 1-3 hours, then heating to 240-260 ℃ and then treating for 3-6 hours, and then closing heating;
and step 4, demolding when the temperature of the mold is lower than 60 ℃, and obtaining the carbon fiber unidirectional cloth reinforced resin matrix composite material.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The carbon fiber unidirectional cloth of the invention takes high modulus carbon fiber as warp direction fiber, the tensile modulus of the high modulus carbon fiber is more than 450GPa, glass fiber is taken as weft direction fiber, the heat resistance grade of the two materials used by the carbon fiber unidirectional cloth is more than 500 ℃, and the carbon fiber unidirectional cloth is more suitable for serving in the high temperature field than the existing carbon fiber unidirectional cloth which uses an organic hot melt wire (the heat resistance grade is not more than 190 ℃) as weft. In addition, when an injection molding process of Resin Transfer Molding (RTM) is adopted, the carbon fiber unidirectional cloth is more suitable for being laid in a mold to be made into a preform than the existing high-modulus unidirectional fiber, and is less likely to be scattered by the resin.
(2) The carbon fiber unidirectional cloth reinforced resin matrix composite material adopts a resin matrix with the heat resistance grade of more than 200 ℃, and selects the carbon fiber unidirectional cloth with high modulus as the reinforced material, and the tensile modulus of the carbon fiber unidirectional cloth reinforced resin matrix composite material can be even more than 350GPa and is far more than that of a commonly used T800/resin matrix composite material (the tensile modulus is generally 150-170 GPa).
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the embodiments of the invention particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
Fig. 1 is a schematic flow chart of a plain weave method for the carbon fiber unidirectional cloth.
Fig. 2 is a schematic structural view of a high modulus carbon fiber cloth.
Reference numerals:
1-high modulus carbon fiber; 2-glass fiber.
Detailed Description
The following detailed description of preferred embodiments of the invention is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the invention, are used to explain the principles of the invention and are not intended to limit the scope of the invention.
In one aspect, the present invention provides a carbon fiber unidirectional cloth reinforced resin matrix composite, as shown in fig. 2, comprising a resin matrix and a reinforcing material; wherein the heat resistance grade of the resin matrix is more than 200 ℃; the reinforcing material adopts carbon fiber unidirectional cloth, the carbon fiber unidirectional cloth comprises warp fibers and weft fibers, wherein the warp fibers are high-modulus carbon fibers 1, and the weft fibers are glass fibers 2; the high modulus carbon fiber 1 and the glass fiber 2 both have heat resistance levels exceeding 500 ℃, and are fixed together through a sizing agent.
It should be noted that, the linear density of the glass fiber 2 is 50-100 tex, and when the linear density of the glass fiber 2 is greater than 100 tex, the weight reduction of the carbon fiber braid product structure is not facilitated, and when the linear density of the glass fiber 2 is too small (less than 50 tex), the strength of the glass fiber 2 is low, and the braiding process is easy to break.
In order to ensure the weight of the carbon fiber unidirectional cloth reinforced resin matrix composite and the strength of the glass fiber 2, the linear density of the glass fiber 2 adopted by the invention is 69 tex.
In the carbon fiber unidirectional cloth reinforced resin matrix composite, glass fibers 2 are uniformly arranged, and the surface density of the glass fibers 2 is 1-5g/m 2 The surface density of the glass fiber 2 is controlled within the range, so that the unit area quality of the carbon fiber unidirectional cloth is not affected, and the carbon fiber unidirectional cloth can be stabilized and the 90-degree direction reinforcement effect can be achieved. If the surface density of the glass fiber 2 is too large, the weight reduction of the carbon fiber unidirectional cloth product structure is not facilitated, and if the surface density is too small, the woven carbon fiber unidirectional cloth is easy to scatter.
The surface density of the carbon fiber unidirectional cloth is 140-200g/m 2 The reason why the areal density of the carbon fiber unidirectional cloth is controlled in the above range is that: the too large surface density of the carbon fiber unidirectional cloth can cause less gaps among the high-modulus carbon fibers 1, which is not beneficial to the injection inflow and impregnation of the RTM molding resin, while the too small surface density of the carbon fiber unidirectional cloth can cause the too large gaps among the high-modulus carbon fibers 1, and the injection inflow of the RTM molding resin can easily cause the scattering of the high-modulus carbon fibers 1, thereby causing the reduction of the mechanical property of the carbon fiber unidirectional cloth reinforced resin matrix composite material.
Compared with the prior art, the warp fiber adopted by the invention is the high-modulus carbon fiber 1, the tensile modulus of the high-modulus carbon fiber 1 is more than 450GPa, and the single tensile modulus of the composite material can be ensured to even reach more than 350 GPa; the heat-resistant grade of the resin matrix is higher than 200 ℃, so that the composite material can be ensured to have good high temperature resistance.
In addition, the weft glass fiber 2 and the warp carbon fiber are bound by using polyester binding wires to prepare the carbon fiber braided fabric in the prior art, so that the braiding efficiency is low, the high temperature resistance of the composite material is poor, and the modulus of the composite material is low. The glass fiber 2 is adopted as weft fiber, on one hand, because the thermal decomposition temperature of the glass fiber 2 is high, and on the other hand, the toughness of the glass fiber 2 is relatively suitable for being woven at high speed in a plain weave mode as weft fiber relative to the high modulus carbon fiber 1.
According to the invention, the sizing agent is coated on the weft glass fibers 2, and after the sizing agent is solidified, the high-modulus carbon fibers 1 and the glass fibers 2 can be fixed together, so that the braiding efficiency is improved, and the modulus of the composite material is also high.
The weft glass fibers 2 and the warp high modulus carbon fibers 1 are woven into the carbon fiber unidirectional cloth by a plain weave method in an alternating overlapping manner, and the weaving process is a conventional process and will not be described again.
It should be emphasized that the sizing agent used in the present invention is an aqueous polymer polyurethane which can be cured at normal temperature, thereby fixing the warp fibers and weft fibers together.
It should be noted that the weight content of the sizing agent of the present invention is 3-8% of the weight of the glass fiber 2, and the content of the sizing agent is controlled within this range because the heat resistance of the composite material is affected when the content of the sizing agent is more than 8%; and when the weight content of the sizing agent is less than 3%, the fixing effect of the high modulus carbon fibers 1 in the warp direction and the glass fibers 2 in the weft direction in the carbon fiber unidirectional cloth is affected.
In order to increase the constraint of weft fibers (i.e., glass fibers 2) on warp fibers (i.e., high modulus carbon fibers 1), the weight of glass fibers 2 of the present invention is 1-3% of the weight of the carbon fiber unidirectional cloth. It should be noted that when the content of the glass fiber 2 in the carbon fiber unidirectional cloth is less than 1%, the restraint effect of the glass fiber 2 on the high modulus carbon fiber 1 is reduced; when the weight content of the glass fiber 2 in the carbon fiber unidirectional cloth is more than 3%, the weight of the carbon fiber unidirectional cloth is increased, so that the weight reduction of the carbon fiber unidirectional cloth reinforced resin matrix composite material is not facilitated.
In order to improve the high temperature resistance of the composite material, the resin matrix adopts one of 8210 bismaleimide resin or polyimide resin, wherein the heat resistance grade of the 8210 bismaleimide resin or polyimide resin is more than 200 ℃.
In order to improve the tensile modulus of the composite material, the carbon fiber unidirectional cloth of the invention accounts for 40-70% of the total weight of the composite material. Compared with the prior art, the weight content of the carbon fiber unidirectional cloth is controlled in the range because: when the weight content of the carbon fiber unidirectional cloth is lower than 40%, the tensile modulus of the carbon fiber unidirectional cloth reinforced resin matrix composite material is lower; when the weight content of the carbon fiber unidirectional cloth is more than 70%, the interlaminar mechanical strength of the carbon fiber unidirectional cloth reinforced resin matrix composite material is reduced.
The carbon fiber unidirectional cloth reinforced resin matrix composite material is in the form of a flat sample or a product.
The carbon fiber unidirectional cloth reinforced resin matrix composite material with high temperature resistance and high modulus provided by the invention has the carbon fiber unidirectional cloth accounting for 40-70% of the weight of the composite material,
the tensile modulus of the high-modulus carbon fiber 1 is more than 450GPa, and one of 55J, M J or pitch carbon fiber is adopted.
On the other hand, the invention also provides a preparation method of the carbon fiber unidirectional cloth reinforced resin matrix composite material, which is used for preparing the carbon fiber unidirectional cloth reinforced resin matrix composite material, and the composite material is prepared by adopting RTM molding, compression molding or autoclave molding.
As shown in fig. 1, when the resin matrix is molded using a bismaleimide resin and the molding method is molded using RTM, the preparation method includes the steps of:
s1, preparing carbon fiber unidirectional cloth, which comprises the following substeps:
s11, high-modulus carbon fiber yarn and spread fiber are used as warp-wise carbon fibers;
s12, coating a sizing agent as weft fibers when the glass fibers 2 are woven;
s13, weaving high-modulus carbon fibers and glass fibers 2 coated with a sizing agent in a plain weave mode;
s14, airing, solidifying, shaping and weaving the carbon fiber unidirectional cloth at room temperature;
s15, cutting, rolling, packaging and warehousing the carbon fiber unidirectional cloth;
s2, cutting the carbon fiber unidirectional cloth according to the size of a product, paving in a mould, preheating an injection charging barrel to 100-150 ℃, wherein the resin is easy to solidify and crosslink viscosity is increased when the temperature of the charging barrel is too high, and the resin cannot be melted at too low temperature, so that the injection product is easy to laminate or loosen, preheating the mould to 100-150 ℃, pouring a certain amount of resin for preheating, finishing resin injection, and keeping the pressure at 0.7-1.5MPa;
step 3, heating the die to 180-230 ℃ and curing at constant temperature for 1-3 hours, then heating to 240-260 ℃ and then treating for 3-6 hours, and then closing heating;
and step 4, demolding the composite material when the temperature of the mold is lower than 60 ℃ to obtain the composite material.
The high modulus carbon fiber 1 is M55J, and the resin matrix is bismaleimide resin; the linear density of the glass fiber 2 is 50-100 tex, and the surface density of the weft glass fiber 2 in the carbon fiber unidirectional cloth is 1-5g/m 2 The surface density of the carbon fiber unidirectional cloth is 140-200g/m 2 。
The carbon fiber unidirectional cloth reinforced resin matrix composite material and the preparation method thereof of the invention are further described below with reference to specific examples and comparative examples, wherein glass fibers 2 are used as weft fibers in all of examples 1 to 4, and high-modulus carbon fibers 1 are used for preparing the composite material; while comparative example 1 is a composite material prepared by using organic hot-melt fibers as weft fibers, comparative example 2 is a T800 carbon fiber unidirectional cloth reinforced resin matrix composite material using glass fibers 2 as weft fibers, and comparative example 3 is a unidirectional resin board composite material of a high-modulus carbon fiber/epoxy resin system.
In comparative example 3, since the high modulus carbon fiber used was not woven into a cloth, it was impossible to perform RTM injection molding, and the obtained data was compression molding data. The carbon fiber cloths used in examples 1 to 4 and comparative examples 1 and 2 were each suitable for RTM injection molding, compression molding and autoclave molding.
Example 1
The embodiment provides a high-temperature-resistant high-modulus carbon fiber unidirectional cloth reinforced resin matrix composite material:
the high modulus carbon fiber 1 is M55J of WiHai extended fiber Co, and the high temperature resistant resin is 8210 bismaleimide resin of Beijing chemical university, and the linear density of the glass fiber 2 is 69 tex. The surface density of weft glass fiber 2 in the M55J carbon fiber unidirectional cloth is 2g/M 2 The unidirectional carbon fiber cloth surface density is 180g/m 2 . The test panel dimensions were 320 (mm) by 2 (mm).
S1, preparing carbon fiber unidirectional cloth, which comprises the following steps:
s11, taking the 500-axis high-modulus carbon fiber 1 as warp-direction carbon fiber after yarn feeding and fiber spreading;
s12, coating a sizing agent as weft-direction fibers when the glass fibers 2 with the linear density of 69 tex are woven;
s13, weaving high-modulus carbon fibers and glass fibers 2 coated with a sizing agent in a plain weave mode;
s14, airing for 3 hours at room temperature, curing, shaping and weaving the carbon fiber unidirectional cloth;
s15, cutting, rolling, packaging and warehousing the carbon fiber unidirectional cloth;
and 2, cutting the carbon fiber unidirectional cloth into 320 (mm) multiplied by 320 (mm) and unidirectional layering 10 layers in a mould, preheating the mould to 125 ℃, preheating an injection charging barrel to 120 ℃ to ensure that resin can flow in a melting way, pouring a certain amount of resin to preheat, finishing resin injection, and keeping the pressure at 1.2MPa.
In the step S2, the injection pressure is maintained for curing, so as to ensure that the composite material is compact, not layered and not loosened in the curing process, the product with too small pressure is not compact, and the capability of the equipment with too large pressure is not reached.
S3, heating the die to 200 ℃ and curing at constant temperature for 1-3 hours, then heating to 250 ℃ and then treating for 3-6 hours, and closing heating;
s4, demolding the composite material when the temperature of the mold is lower than 60 ℃.
Typical properties of the M55J high modulus carbon fiber unidirectional cloth reinforced 8210 bismaleimide resin composite in this example are shown in table 1.
The high modulus carbon fiber and the glass fiber are wound on the spool, when the carbon fiber unidirectional cloth is prepared, the high modulus carbon fiber in the 500-axis warp direction is simultaneously spun, and the spun number of the glass fiber in the weft direction is 1 axis.
Example 2
The high modulus carbon fiber 1 is selected from M55J of WiHai extended fiber Co., ltd, the high temperature resistant resin is selected from RTM-400 polyimide resin of the department of academy of sciences, and the linear density of the glass fiber 2 is 65 tex. The surface density of weft glass fiber 2 in the M55J carbon fiber unidirectional cloth is 3g/M 2 The M55J unidirectional cloth surface density is 170g/M 2 . The test panel dimensions were 320 (mm) by 2 (mm).
S1, preparing carbon fiber unidirectional cloth, which comprises the following steps:
s11, simultaneously feeding 500-axis high-modulus carbon fibers and spreading the fibers to serve as warp-direction carbon fibers;
s12, coating a sizing agent as weft fibers when the glass fibers 2 with the axial density of 65 tex are woven;
s13, weaving high-modulus carbon fibers and glass fibers 2 coated with a sizing agent in a plain weave mode;
s14, airing at room temperature for 3 hours, solidifying, shaping and weaving the carbon fiber unidirectional cloth;
s15, cutting, rolling, packaging and warehousing the carbon fiber unidirectional cloth;
s2, cutting the high-modulus carbon fiber unidirectional cloth into 320 (mm) multiplied by 320 (mm), unidirectional layering 10 layers in a mold, preheating the mold at 275 ℃, preheating an injection cylinder at 280 ℃, pouring a certain amount of resin for preheating, and then finishing resin injection, and keeping the pressure at 1.2MPa.
And 3, heating the die to 320 ℃ and keeping the temperature for 20minh, heating to 350 ℃ and keeping the temperature for 20min, and then heating to 380 ℃ and keeping the temperature for 2h, and closing heating.
And 4, demolding the composite material when the temperature of the mold is lower than 60 ℃.
Typical properties of the M55J high modulus carbon fiber unidirectional cloth reinforced RTM-400 polyimide composite material in this example are shown in Table 1.
Example 3
The high modulus carbon fiber 1 is M60J of Ningbo institute of Chinese sciences, the high temperature resistant resin is 8210 bismaleimide resin of Beijing university of chemical industry, and the linear density of the glass fiber 2 is 69 tex. The surface density of weft glass fiber 2 in the M55J carbon fiber unidirectional cloth is 2g/M 2 The surface density of the M60J carbon fiber unidirectional cloth is 180g/M 2 . The test panel dimensions were 320 (mm) by 2 (mm).
Step 1, preparing M55J carbon fiber unidirectional cloth/8210 bismaleimide resin prepreg with the width of 1000mm by adopting a hot melting method, cutting the prepreg into 320 (mm) multiplied by 320 (mm), and unidirectional layering 10 layers in a die;
step 2, heating the die by a press for 30min at the constant temperature of 125 ℃;
step 3, heating the die by a press, keeping the temperature at 160 ℃ for 30min, and pressurizing to 2.0MPa;
step 4, heating the die to 200 ℃ and curing for 2 hours at constant temperature, then carrying out high-temperature post-treatment for 4 hours at 250 ℃, and closing heating;
and 5, demolding the composite material when the temperature of the mold is lower than 60 ℃.
The properties of the M60J high modulus carbon fiber unidirectional cloth reinforced 8210 bismaleimide resin composite material in this example are shown in table 1.
Example 4
The high modulus carbon fiber 1 is M60J of Ningbo institute of Chinese sciences, the high temperature resistant resin is 5250-4 bismaleimide resin of Cyant company, and the linear density of the glass fiber 2 is 69 tex. The surface density of weft glass fiber 2 in the M60J carbon fiber unidirectional cloth is 2g/M 2 The surface density of the M60J carbon fiber unidirectional cloth is 180g/M 2 The method comprises the steps of carrying out a first treatment on the surface of the The test panel dimensions were 320 (mm) by 2 (mm).
Step 1, preparing M60J carbon fiber unidirectional cloth/5250-4 bismaleimide resin prepreg with the width of 1000mm by adopting a hot melting method, cutting the prepreg into 320 (mm) multiplied by 320 (mm), unidirectional layering 10 layers on a stainless steel flat plate, pumping a vacuum bag according to a conventional method, and sending the vacuum bag into an autoclave for curing;
and 2, heating the die for 30min at the constant temperature of 120 ℃.
And step 3, heating the die at 160 ℃ for 30min, and pressurizing to 0.6MPa.
And step 4, heating the die to 200 ℃ and curing for 2 hours at a constant temperature, and then performing high-temperature post-treatment at the temperature of 250 ℃ for 4 hours, and closing and heating.
And 5, demolding the composite material when the temperature of the mold is lower than 60 ℃.
Typical properties of the M60J high modulus carbon fiber unidirectional cloth reinforced 5250-4 bismaleimide resin composite in this example are shown in Table 1.
Comparative example 1
A high-modulus carbon fiber unidirectional cloth reinforced resin matrix composite material adopting organic hot melt fibers as weft fibers:
the high modulus carbon fiber is M55J of WiHai extended fiber Co., ltd, the high temperature resistant resin is 8210 double horse resin of Beijing university chemical industry, the organic hot melt fiber is polyester fiber yarn, and the M55J unidirectional cloth cover density is 180g/M 2 . The test panel dimensions were 320 (mm) by 2 (mm).
Step 1, cutting the high-modulus carbon fiber unidirectional cloth into 320 (mm) multiplied by 320 (mm) and unidirectional layering 10 layers in a mould,
and 2, preheating the die at 125 ℃, preheating the injection cylinder at 120 ℃, pouring a certain amount of resin to preheat, and then finishing resin injection, and keeping the pressure at 1.2MPa.
And step 3, heating the die to 200 ℃ and curing for 2 hours at constant temperature, and then performing high-temperature post-treatment at the temperature of 250 ℃ for 4 hours, and closing and heating.
And 4, demolding the composite material when the temperature of the mold is lower than 60 ℃.
Typical properties of the M55J high modulus carbon fiber unidirectional cloth/8210 bismaleimide resin composite material in this example using organic hot melt fibers as weft fibers are shown in Table 1.
Comparative example 2
The comparative example provides a T800 carbon fiber unidirectional cloth reinforced resin matrix composite material adopting glass fibers as weft fibers, which comprises the following preparation processes:
the high modulus carbon fiber is CCF800S of WiHai extended fiber Co., ltd, and the high temperature resistant resin is 8210 bismaleimide resin of Beijing university of chemical industry, glass fiberThe linear density is 69 tex, and the surface density of weft glass fiber in CCF800S carbon fiber unidirectional cloth is 2g/m 2 CCF800S unidirectional cloth cover density is 180g/m 2 . The test panel dimensions were 320 (mm) by 2 (mm).
Step 1, cutting the high-modulus carbon fiber unidirectional cloth into 320 (mm) multiplied by 320 (mm) and unidirectional layering 10 layers in a mould,
and 2, preheating the die at 125 ℃, preheating the injection cylinder at 120 ℃, pouring a certain amount of resin to preheat, and then finishing resin injection, and keeping the pressure at 1.2MPa.
And step 3, heating the die to 200 ℃ and curing for 2 hours at constant temperature, and then performing high-temperature post-treatment at the temperature of 250 ℃ for 4 hours, and closing and heating.
And 4, demolding the composite material when the temperature of the mold is lower than 60 ℃.
Typical properties of CCF800S carbon fiber unidirectional cloth/8210 bismaleimide resin composite materials in this example using glass fibers as weft fibers are shown in Table 1.
Comparative example 3
The comparative example provides a unidirectional resin board composite material of a high modulus carbon fiber/epoxy resin system, comprising the following preparation processes:
the high-modulus carbon fiber is selected from M55J of Ningbo institute of Chinese sciences, and the epoxy resin is selected from the epoxy resin of goods shelf commodity 8522 provided by aerospace 306. The fiber surface density of the unidirectional prepreg of the M55J/8522 epoxy resin is 135g/M 2 The epoxy resin content was 38%. The test panel dimensions were 320 (mm) by 2 (mm).
Step 1, preparing M55J/8522 epoxy resin unidirectional prepreg with the width of 1000mm by adopting a hot melting method, cutting the prepreg into 320 (mm) multiplied by 320 (mm) and unidirectional paving 8 layers in a die,
and 2, heating the die by a press for 30min at the constant temperature of 80 ℃.
And 3, heating the die by a press, keeping the temperature at 110 ℃ for 10min, and pressurizing to 2.0MPa.
And step 4, heating the die to 150 ℃, curing for 2 hours at constant temperature, and closing heating.
And 5, demolding the composite material when the temperature of the mold is lower than 60 ℃.
Typical properties of the M55J/8522 epoxy composite material in this example are shown in Table 1.
TABLE 1 Performance comparison Table of carbon fiber unidirectional cloth reinforced resin matrix composite prepared by the invention and composite prepared by comparative example
| Project | Tensile Strength/MPa (250 ℃ C.) | Tensile modulus/GPa (250 ℃ C.) |
| Example 1 | 1092 | 216 |
| Example 2 | 1449 | 282 |
| Example 3 | 1051 | 223 |
| Example 4 | 1052 | 204 |
| Comparative example 1 | 730 | 148 |
| Comparative example 2 | 1220 | 110 |
| Comparative example 3 | Failure of | Failure of |
Examples 1-4 in table 1 are carbon fiber unidirectional cloth reinforced resin matrix composites prepared by using glass fibers as weft fibers, while comparative example 1 is high modulus carbon fiber unidirectional cloth reinforced resin matrix composites prepared by using organic hot melt fibers as weft fibers, comparative example 2 is T800 carbon fiber unidirectional cloth reinforced resin matrix composites prepared by using glass fibers as weft fibers, and comparative example 3 is unidirectional resin board composites of high modulus carbon fiber/epoxy resin system.
In comparative example 3, since the high modulus carbon fiber used was not woven into a cloth, it was impossible to perform RTM injection molding, and the obtained data was compression molding data. The carbon fiber unidirectional cloths used in examples 1-4 and comparative examples 1 and 2 are suitable for RTM molding, compression molding and autoclave molding, and if the versatility of the molding process, the high temperature resistance of the composite material and the high modulus requirement are considered, the glass fiber of the present invention is preferably used as weft and the high modulus carbon fiber is used as warp unidirectional cloth material, i.e. examples 1-4.
As can be seen from table 1, the composite material in example 1 and comparative example 1 differs only in the weft direction fibers, and comparative example 1 is an organic hot-melt fiber, which has been softened at a high temperature of 250 ℃ when added to the composite material system, resulting in a decrease in the mechanical strength and modulus at high temperatures of the composite material used.
The difference between example 1 and comparative example 2 is only the warp fiber of example 1, and comparative example 2 is the use of the existing high strength carbon fiber unidirectional cloth CCF800S carbon fiber, so the tensile modulus of the composite of example 1 is 1.96 times that of comparative example 2. Comparative example 3 uses unidirectional resin sheet composite material of M55J high modulus carbon fiber/epoxy resin system, does not use weft glass fiber, is not suitable for RTM molding, and the obtained data is compression molding data, and the molding process is not applicable to the universality and the high temperature resistance as in examples 1-4.
From the above table 1, it can be seen that the tensile strength of the carbon fiber unidirectional cloth reinforced resin matrix composite material prepared by the invention is 1052-1449MPa under the condition of 250 ℃, the tensile modulus is 204-282GPa, and the tensile modulus data and the tensile strength data modulus are both data under the high temperature of 250 ℃, so that the carbon fiber unidirectional cloth reinforced resin matrix composite material of the invention has excellent heat resistance and high modulus property.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The carbon fiber unidirectional cloth reinforced resin matrix composite is characterized by comprising a resin matrix and a reinforcing material, wherein the heat resistance grade of the resin matrix is more than 200 ℃;
the reinforcing material is carbon fiber unidirectional cloth, the carbon fiber unidirectional cloth comprises warp fibers and weft fibers, and the warp fibers are high-modulus carbon fibers; the weft fibers are glass fibers;
the warp and weft fibers are secured together by a sizing agent.
2. The carbon fiber unidirectional cloth reinforced resin matrix composite of claim 1, wherein the high modulus carbon fibers have a tensile modulus greater than 450GPa.
3. The carbon fiber unidirectional cloth reinforced resin matrix composite of claim 1, wherein the sizing agent is an aqueous polymeric polyurethane that is curable at ambient temperature to secure the warp and weft fibers together.
4. The carbon fiber unidirectional cloth reinforced resin matrix composite of claim 1, wherein the weight content of the sizing agent is 3-8% of the weight of the glass fiber.
5. The carbon fiber unidirectional cloth reinforced resin matrix composite of claim 1, wherein the glass fibers comprise 1-3% by weight of the carbon fiber unidirectional cloth.
6. The carbon fiber unidirectional cloth reinforced resin matrix composite of claim 1, wherein the resin matrix is a bismaleimide resin or a polyimide resin.
7. The carbon fiber unidirectional cloth reinforced resin matrix composite of claim 1, wherein the weight of the carbon fiber unidirectional cloth is 40-70% of the total weight of the carbon fiber unidirectional cloth reinforced resin matrix composite.
8. The carbon fiber unidirectional cloth reinforced resin matrix composite according to claim 1, wherein the high modulus carbon fiber is M55J;
the linear density of the glass fiber is 50-100 tex, and the surface density of the weft glass fiber in the carbon fiber unidirectional cloth is 1-5g/m 2 The surface density of the carbon fiber unidirectional cloth is 140-200g/m 2 。
9. A method for preparing a carbon fiber unidirectional cloth reinforced resin matrix composite material, which is characterized in that the carbon fiber unidirectional cloth reinforced resin matrix composite material is prepared according to the claims 1 to 8, and the composite material is prepared by Resin Transfer Molding (RTM), compression molding or autoclave molding.
10. The method for preparing the carbon fiber unidirectional cloth reinforced resin matrix composite material according to claim 9, wherein when the resin matrix is made of a bismaleimide resin and the Resin Transfer Molding (RTM) is selected as a molding method, the preparation method comprises the following steps:
s1, preparing carbon fiber unidirectional cloth, which comprises the following substeps:
s11, taking the high-modulus carbon fiber as warp-direction fiber after yarn feeding and fiber spreading;
s12, coating a sizing agent when the glass fiber is woven and then using the sizing agent as weft fiber;
s13, weaving the high-modulus carbon fiber and the glass fiber coated with the sizing agent in a plain weave mode;
s14, airing, solidifying and shaping the woven carbon fiber unidirectional cloth at room temperature;
s15, cutting, rolling, packaging and warehousing the carbon fiber unidirectional cloth;
s2, cutting the carbon fiber unidirectional cloth according to the size of a product, paving the cloth in a mould, preheating an injection charging barrel to 100-150 ℃, preheating the mould to 100-150 ℃, pouring a certain amount of bismaleimide resin into the mould to preheat the bismaleimide resin, and then finishing the injection of the bismaleimide resin, wherein the pressure is kept at 0.7-1.5MPa during the injection;
step 3, heating the die to 180-230 ℃ and curing at constant temperature for 1-3 hours, then heating to 240-260 ℃ and then treating for 3-6 hours, and then closing heating;
and step 4, demolding when the temperature of the mold is lower than 60 ℃, and obtaining the carbon fiber unidirectional cloth reinforced resin matrix composite material.
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