CN117070051B - Epoxy resin system suitable for T800 carbon fiber and preparation method of composite material thereof - Google Patents
Epoxy resin system suitable for T800 carbon fiber and preparation method of composite material thereof Download PDFInfo
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- CN117070051B CN117070051B CN202311329110.8A CN202311329110A CN117070051B CN 117070051 B CN117070051 B CN 117070051B CN 202311329110 A CN202311329110 A CN 202311329110A CN 117070051 B CN117070051 B CN 117070051B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 175
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 175
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 97
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 29
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims abstract description 20
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 230000002787 reinforcement Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000007790 scraping Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 17
- 239000006082 mold release agent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
- C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
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- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a method for manufacturing an epoxy resin system suitable for T800 carbon fibers and a composite material thereof, which is suitable for the technical field of manufacturing high-performance carbon fiber/epoxy resin composite materials for aviation, and comprises the following components in parts by mass: 80-120 parts of 4,4' -diaminodiphenyl methane epoxy resin, 2.5-12.5 parts of 1, 4-butanediol diglycidyl ether, 5-30 parts of carboxyl-terminated nitrile rubber and 60-100 parts of methyl tetrahydrophthalic anhydride, wherein the composite material takes an epoxy resin system as a matrix, and T800 carbon fiber as a reinforcement body and is prepared by a manual pasting method.
Description
Technical Field
The invention relates to the technical field of manufacturing of high-performance carbon fiber/epoxy resin composite materials for aviation, in particular to an epoxy resin system suitable for T800 carbon fibers and a manufacturing method of the composite material.
Background
The carbon fiber/epoxy resin composite material takes carbon fiber as a reinforcement and epoxy resin as a matrix. The density of the material is lighter than that of aluminum, and the strength of the material is close to that of steel; the elastic modulus is larger than that of aluminum alloy, the fatigue strength is high, and the impact toughness is high; meanwhile, the composite material also has the advantages of good wet heat stability, high chemical stability, good thermal conductivity, unchanged strength and modulus when being irradiated by X rays, and the like, and is widely applied to the fields of aerospace and the like.
The overall performance of the carbon fiber reinforced resin matrix composite is determined by the reinforcement carbon fibers, the matrix resin and the interfacial properties. For high-performance carbon fibers, the surface is smooth and lacks active functional groups, which affects the effective bonding with matrix resins; meanwhile, a three-dimensional network structure with high crosslinking density is formed after a matrix prepared from the traditional epoxy resin system is cured, and the defects of large internal stress, poor toughness and the like exist, so that the application of the traditional epoxy resin composite material in some high-end fields is limited finally.
At present, many researches on high-performance carbon fiber/epoxy composite materials are developed at home and abroad, and researchers mainly adopt the following two measures to prepare the composite material with excellent performance: surface modification is carried out on the carbon fiber, and the toughness of a matrix made of an epoxy resin system is improved. The traditional carbon fiber surface modification includes air oxidation, chemical grafting, physical deposition, radiation irradiation, liquid phase oxidation, surface coating and the like. The toughening of epoxy resins is largely divided into two types: firstly, the toughness of the epoxy resin system is improved by adding a plurality of substances with high second phase toughness, such as elastomer (rubber and the like), thermoplastic resin or rigid particles and the like; secondly, the toughness of the epoxy resin is improved in the curing process by changing the chemical structure of a crosslinked network (such as adding a flexible molecular chain segment into an epoxy resin curing agent), so that the activity of network chain molecules is improved for toughening. Patent CN104988736a discloses a method for improving the interfacial toughness of an epoxy resin-based carbon fiber composite material, which improves the interfacial toughness of the composite material by adding carboxyl-terminated nitrile rubber at the interface of the composite material. However, the method is characterized in that firstly, carboxyl-terminated nitrile rubber serving as a toughening substance is dissolved in a large amount of organic solvent, the carboxyl-terminated nitrile rubber is difficult to remove in the later period, the harmful effect on the environment is generated, and the preparation process of the method is complex. Patent CN104774431a discloses an "epoxy resin/carbon fiber composite material and a method for preparing the same", which reduces the interfacial stress of the composite material and improves the impact strength thereof by immersing carbon fiber cloth in an organic silicone rubber solution. However, the method also uses a large amount of organic solvent when removing impurities from the carbon fiber; meanwhile, the elastomer silicon rubber is easy to crack and oxidize at high temperature, and the performance of the composite material is greatly reduced.
Disclosure of Invention
In order to solve the defects and the shortcomings of the prior art, the epoxy resin system suitable for the T800 carbon fiber and the preparation method of the composite material thereof provided by the invention do not use an organic solvent to dissolve a toughening substance, have a simple preparation process, can effectively improve the mechanical properties of the high-performance carbon fiber/epoxy resin composite material, and have important significance in the field of manufacturing of aviation composite materials.
The invention provides an epoxy resin system suitable for T800 carbon fibers, which comprises the following components in parts by weight: 80-120 parts of 4,4' -diaminodiphenyl methane epoxy resin, 2.5-12.5 parts of 1, 4-butanediol diglycidyl ether, 5-30 parts of carboxyl-terminated nitrile rubber and 60-100 parts of methyl tetrahydrophthalic anhydride.
The preparation method of the epoxy resin system suitable for the T800 carbon fiber comprises the following steps:
step 1, weighing 1, 4-butanediol diglycidyl ether serving as a diluent, heating the 1, 4-butanediol diglycidyl ether to 30-100 ℃ in an oil bath while stirring, adding 4,4' -diaminodiphenylmethane epoxy resin at the moment, and continuously stirring at the temperature for 5-20min at a stirring speed of 100-800rpm to obtain a mixed solution A; if the fluidity of the mixed solution A is good, the amount of the 1, 4-butanediol diglycidyl ether can be used as the experimental amount; on the premise of ensuring the fluidity of the liquid, the proportion of the 4,4' -diaminodiphenyl methane epoxy resin in the mixed solution A is increased as much as possible.
4,4' -diaminodiphenylmethane epoxy resin (trade name AG-80, structure formula: the following figure):
step 2, adding carboxyl-terminated nitrile rubber serving as a toughening agent into the mixed solution A, and stirring for 10-30min at 30-100 ℃ to obtain a mixed solution B;
step 3, when the temperature of the mixed solution B is stabilized at 50-60 ℃, methyl tetrahydrophthalic anhydride is added to prevent the occurrence of a curing reaction, the mixed solution is stirred for 5-30min, and then the defoaming treatment is carried out under the conditions of vacuum and drying, so as to obtain an epoxy resin system; specifically, the time of the defoaming treatment is 10-120min.
Methyl tetrahydrophthalic anhydride (as curing agent, chemical formula C 9 H 10 O 3 Molecular weight 166.17, structural formula is shown in the figure):
and 4, slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, and curing to obtain the epoxy resin. Specifically, the conditions of the curing treatment are: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
The composite material is prepared by using an epoxy resin system as a matrix and T800 carbon fibers as reinforcements through a manual pasting method, and belongs to an aviation high-performance carbon fiber composite material, wherein the volume fraction of the T800 carbon fibers in the composite material is 3.77% -15.08%.
The composite material is prepared by adopting a manual pasting method, and the specific operation is as follows:
pouring an epoxy resin system into a mold, taking and straightening T800 carbon fibers in parallel, putting the T800 carbon fibers into the mold, scraping the excessive epoxy resin system exceeding the mold by adopting a scraping plate after the epoxy resin system is immersed in the T800 carbon fibers, putting a flat plate sprayed with a release agent on the mold, pressing 0.5-2kg of dumbbell pieces on the flat plate, and then curing to obtain the composite material. Wherein, the conditions of the curing treatment are as follows: 120 ℃/2h+140 ℃/2h, and after curing, turning off the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, taking out the carbon fiber epoxy resin composite material obtained after curing.
Optimally, the T800 carbon fiber is set as T800SC carbon fiber. The performance parameters of the T800SC carbon fiber are as follows: high-strength untwisted Dongli T800 carbon fibers, each bundle of which contains 24000 monofilaments; the sizing agent on the surface of the fiber is epoxy resin, and the surface sizing amount is 0.5%.
Optimally, the T800 carbon fiber is set as T800HB carbon fiber. The performance parameters of the T800HB carbon fiber are as follows: high-strength untwisted Dongli T800 carbon fibers, wherein each bundle of carbon fibers comprises 12000 monofilaments; the sizing agent on the surface of the fiber is epoxy resin, and the surface sizing amount is 1.0%.
Specifically, the fluidity of the mixed solution a was observed by the following method: a small amount of mixed solution A is sucked by a disposable dropper, if the mixed solution A can be smoothly extruded, the residual liquid on the wall of the dropper is less, or the liquid close to a pipe orifice can smoothly flow out, the mixed solution A is poured into a mould to observe the fluidity of the mixed solution A, and if the mixed solution A can be smoothly poured out and can automatically fill the gap of a groove of the mould, the fluidity of the mixed solution A is good, and the subsequent experiment can be carried out.
The beneficial effects of the invention are as follows:
compared with the prior art, the epoxy resin system suitable for the T800 carbon fiber and the preparation method of the composite material thereof provided by the invention have the advantages that the organic solvent is not used for dissolving the toughening substance, the preparation process is simple, the mechanical property of the high-performance carbon fiber/epoxy resin composite material can be effectively improved, and the method has important significance in the field of manufacturing of aviation composite materials.
The carboxyl-terminated nitrile rubber used as a toughening substance participates in the curing reaction to form a sea-island phase system, so that the comprehensive mechanical properties, particularly impact toughness, of the epoxy resin obtained by curing the epoxy resin system can be obviously improved.
The composite material prepared by the method has good compatibility between the T800 carbon fiber and the matrix interface of the epoxy resin system, is tightly combined, has good interface combination capacity, and can effectively improve the transfer efficiency between the load reinforcing carbon fiber and the matrix epoxy resin system when loaded, thereby improving the bearing capacity.
Drawings
The invention is described in further detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a drawing of the tensile fracture morphology of example 1 of a T800HB carbon fiber epoxy resin composite;
FIG. 2 is a drawing of the tensile fracture morphology of example 2 of a T800HB carbon fiber epoxy resin composite;
FIG. 3 is a drawing of the tensile fracture morphology of example 3 of a T800HB carbon fiber epoxy resin composite;
FIG. 4 is a drawing of the tensile fracture morphology of example 4 of a T800HB carbon fiber epoxy resin composite;
FIG. 5 is a drawing of the tensile fracture morphology of example 5 of a T800HB carbon fiber epoxy resin composite;
FIG. 6 is a drawing of the tensile fracture morphology of example 6 of a T800HB carbon fiber epoxy resin composite;
FIG. 7 is a drawing of the tensile fracture morphology of example 1 of a T800SC carbon fiber epoxy composite;
FIG. 8 is a drawing of the tensile fracture morphology of example 2 of a T800SC carbon fiber epoxy resin composite;
FIG. 9 is a drawing of the tensile fracture morphology of example 3 of a T800SC carbon fiber epoxy composite;
FIG. 10 is a graph of the tensile fracture morphology of example 4 of a T800SC carbon fiber epoxy composite;
FIG. 11 is a drawing of the tensile fracture morphology of example 5 of a T800SC carbon fiber epoxy composite;
FIG. 12 is a graph of the tensile fracture morphology of example 6 of a T800SC carbon fiber epoxy composite;
the Chinese meaning corresponding to each English parameter in the drawing is as follows:
print Mag: magnification; WD: working distance; BC: a current; det: a detector; SE: secondary electrons; foV: a field of view; energy: electron beam energy; scan Mode: a scanning mode; RESOLUTION: resolution ratio; 2.00 kx:2000 times.
Detailed Description
The invention provides a method for manufacturing an epoxy resin system suitable for T800 carbon fibers and a composite material thereof, which concretely comprises the following steps:
example 1
The epoxy resin system is prepared from the following raw materials in parts by weight: 80 parts of 4,4' -diaminodiphenyl methane epoxy resin, 2.5 parts of 1, 4-butanediol diglycidyl ether, 5 parts of carboxyl-terminated nitrile rubber and 80 parts of methyl tetrahydrophthalic anhydride. The preparation process comprises the following steps: weighing 2.5 parts of 1, 4-butanediol diglycidyl ether, controlling the temperature of the system to 100 ℃, adding 80 parts of 4,4' -diaminodiphenylmethane epoxy resin, and stirring for 5min at a stirring speed of 100rpm; then adding 5 parts of carboxyl-terminated nitrile rubber, and stirring for 10min at 100 ℃ at a stirring speed of 100rpm; after that, 80 parts of methyltetrahydrophthalic anhydride was added thereto after the temperature of the system was lowered to 50℃and stirring was continued for 5 minutes. And (5) putting the epoxy resin into a vacuum drying oven for defoaming treatment for 10min to obtain the epoxy resin system. Slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, wherein the curing conditions are as follows: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
The matrix made of the epoxy resin system is prepared as shown in the example 1, a small amount of the prepared epoxy resin system is poured into a mold, the T800 carbon fibers are arranged in parallel and are straightened and placed into the mold, the content of the T800 carbon fibers is adjusted to 3.77%, the epoxy resin system is immersed in the T800 carbon fibers, then the excessive epoxy resin system exceeding the mold is scraped by a scraping plate, and then the mold is placed into an oven. When the mold release agent was put into the oven, a flat plate sprayed with the mold release agent was placed on the mold, and 0.5kg of dumbbell sheet was pressed on the flat plate. The curing parameters of the composite material are consistent with those of the epoxy resin system. And after curing is finished, closing a power supply of the baking oven, and opening a door of the baking oven to take out the composite material after the temperature of the baking oven is reduced to about 50 ℃.
Example 2
The epoxy resin system is prepared from the following raw materials in parts by weight: 120 parts of 4,4' -diaminodiphenyl methane epoxy resin, 12.5 parts of 1, 4-butanediol diglycidyl ether, 30 parts of carboxyl-terminated nitrile rubber and 100 parts of methyl tetrahydrophthalic anhydride. The preparation process comprises the following steps: weighing 12.5 parts of 1, 4-butanediol diglycidyl ether, controlling the system temperature to 80 ℃, adding 120 parts of 4,4' -diaminodiphenylmethane epoxy resin, and stirring for 20min at a stirring speed of 400rpm; then adding 30 parts of carboxyl-terminated nitrile rubber, and stirring for 30min at 80 ℃ at a stirring speed of 400rpm; after that, 100 parts of methyltetrahydrophthalic anhydride was added thereto after the temperature of the system was lowered to 50℃and stirring was continued for 30 minutes. And (5) putting the epoxy resin into a vacuum drying oven for defoaming treatment for 120min to obtain an epoxy resin system. Slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, wherein the curing conditions are as follows: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
The high-performance carbon fiber epoxy resin composite material is characterized in that a matrix made of an epoxy resin system is made as shown in the embodiment 2, a small amount of the prepared epoxy resin system is poured into a mold, T800 carbon fibers are arranged in parallel and are straightened and placed into the mold, the content of the T800 carbon fibers is adjusted to be 15.08%, after the T800 carbon fibers are immersed in the epoxy resin system, a scraping plate is used for scraping out the excessive epoxy resin system exceeding the mold, and then the mold is placed into an oven. When the mold release agent was put into the oven, a flat plate sprayed with the mold release agent was placed on the mold, and 0.5kg of dumbbell sheet was pressed on the flat plate. The curing parameters of the composite material are consistent with those of the epoxy resin system. And after curing is finished, closing a power supply of the baking oven, and opening a door of the baking oven to take out the composite material after the temperature of the baking oven is reduced to about 50 ℃.
Example 3
The epoxy resin system is prepared from the following raw materials in parts by weight: 90 parts of 4,4' -diaminodiphenyl methane epoxy resin, 10 parts of 1, 4-butanediol diglycidyl ether, 10 parts of carboxyl-terminated nitrile rubber and 60 parts of methyl tetrahydrophthalic anhydride. The preparation process comprises the following steps: weighing 10 parts of 1, 4-butanediol diglycidyl ether, controlling the system temperature to 50 ℃, adding 90 parts of 4,4' -diaminodiphenylmethane epoxy resin, and stirring for 15min at a stirring speed of 300rpm; then adding 10 parts of carboxyl-terminated nitrile rubber, and stirring for 15min at 50 ℃ at a stirring speed of 300rpm; after that, 60 parts of methyltetrahydrophthalic anhydride was added thereto after the temperature of the system was lowered to 50℃and stirring was continued for 10 minutes. And (5) putting the epoxy resin into a vacuum drying oven for defoaming treatment for 80 minutes to obtain the epoxy resin system. Slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, wherein the curing conditions are as follows: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
The matrix made of the epoxy resin system is prepared as shown in the example 3, a small amount of the prepared epoxy resin system is poured into a mold, the T800 carbon fibers are arranged in parallel and are straightened and placed into the mold, the content of the T800 carbon fibers is adjusted to 11.31%, the epoxy resin system is immersed in the T800 carbon fibers, then the excessive epoxy resin system exceeding the mold is scraped by a scraping plate, and then the mold is placed into an oven. When the mold release agent was put into the oven, a flat plate sprayed with the mold release agent was placed on the mold, and 1.0kg of dumbbell sheet was pressed on the upper surface. The curing parameters of the composite material are consistent with those of the epoxy resin system. And after curing is finished, closing a power supply of the baking oven, and opening a door of the baking oven to take out the composite material after the temperature of the baking oven is reduced to about 50 ℃.
Example 4
The epoxy resin system is prepared from the following raw materials in parts by weight: 100 parts of 4,4' -diaminodiphenyl methane epoxy resin, 12.5 parts of 1, 4-butanediol diglycidyl ether, 15 parts of carboxyl-terminated nitrile rubber and 70 parts of methyl tetrahydrophthalic anhydride. The preparation process comprises the following steps: weighing 12.5 parts of 1, 4-butanediol diglycidyl ether, controlling the system temperature to 90 ℃, adding 100 parts of 4,4' -diaminodiphenylmethane epoxy resin, and stirring for 10min at a stirring speed of 800rpm; then adding 15 parts of carboxyl-terminated nitrile rubber, and stirring for 10min at 90 ℃ at a stirring speed of 800rpm; after that, 70 parts of methyltetrahydrophthalic anhydride was added thereto after the temperature of the system was lowered to 60℃and stirring was continued for 5 minutes. And (5) putting the epoxy resin into a vacuum drying oven for defoaming treatment for 50min to obtain the epoxy resin system. Slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, wherein the curing conditions are as follows: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
The matrix made of the epoxy resin system is prepared as shown in the example 4, a small amount of the prepared epoxy resin system is poured into a mold, the T800 carbon fibers are arranged in parallel and are straightened and placed into the mold, the content of the T800 carbon fibers is adjusted to be 15.08%, the epoxy resin system is immersed in the T800 carbon fibers, then the excessive epoxy resin system exceeding the mold is scraped by a scraping plate, and then the mold is placed into an oven. When the mold release agent was put into the oven, a flat plate sprayed with the mold release agent was placed on the mold, and 1.0kg of dumbbell sheet was pressed on the upper surface. The curing parameters of the composite material are consistent with those of the epoxy resin system. And after curing is finished, closing a power supply of the baking oven, and opening a door of the baking oven to take out the composite material after the temperature of the baking oven is reduced to about 50 ℃.
Example 5
The epoxy resin system is prepared from the following raw materials in parts by weight: 110 parts of 4,4' -diaminodiphenyl methane epoxy resin, 10 parts of 1, 4-butanediol diglycidyl ether, 20 parts of carboxyl-terminated nitrile rubber and 90 parts of methyl tetrahydrophthalic anhydride. The preparation process comprises the following steps: weighing 10 parts of 1, 4-butanediol diglycidyl ether, controlling the system temperature to be 60 ℃, adding 110 parts of 4,4' -diaminodiphenylmethane epoxy resin, and stirring for 20min at a stirring speed of 600rpm; then adding 20 parts of carboxyl-terminated nitrile rubber, and stirring for 20min at 60 ℃ at a stirring speed of 600rpm; after that, 90 parts of methyltetrahydrophthalic anhydride was added thereto after the temperature of the system was lowered to 60℃and stirring was continued for 30 minutes. And (5) putting the epoxy resin into a vacuum drying oven for defoaming treatment for 40min to obtain the epoxy resin system. Slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, wherein the curing conditions are as follows: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
The matrix made of the epoxy resin system is prepared as shown in the example 5, a small amount of the prepared epoxy resin system is poured into a mold, the T800 carbon fibers are arranged in parallel and are straightened and placed into the mold, the content of the T800 carbon fibers is adjusted to 7.54%, the epoxy resin system is immersed in the T800 carbon fibers, then the excessive epoxy resin system exceeding the mold is scraped by a scraping plate, and then the mold is placed into an oven. When the mold release agent was put into the oven, a flat plate sprayed with the mold release agent was placed on the mold, and 2.0kg of dumbbell pieces were pressed on the flat plate. The curing parameters of the composite material are consistent with those of the epoxy resin system. And after curing is finished, closing a power supply of the baking oven, and opening a door of the baking oven to take out the composite material after the temperature of the baking oven is reduced to about 50 ℃.
Example 6
The epoxy resin system is prepared from the following raw materials in parts by weight: 100 parts of 4,4' -diaminodiphenyl methane epoxy resin, 7.5 parts of 1, 4-butanediol diglycidyl ether, 25 parts of carboxyl-terminated nitrile rubber and 70 parts of methyl tetrahydrophthalic anhydride. The preparation process comprises the following steps: 7.5 parts of 1, 4-butanediol diglycidyl ether is weighed, 100 parts of 4,4' -diaminodiphenyl methane epoxy resin is added after the system temperature reaches 30 ℃, and stirring is carried out for 15min at the stirring speed of 200rpm; then adding 25 parts of carboxyl-terminated nitrile rubber, and stirring for 15min at 30 ℃ at a stirring speed of 200rpm; after that, 70 parts of methyltetrahydrophthalic anhydride was added thereto after the temperature of the system was lowered to 55℃and stirring was continued for 10 minutes. And (5) putting the epoxy resin into a vacuum drying oven for defoaming treatment for 110min to obtain the epoxy resin system. Slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, wherein the curing conditions are as follows: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
The matrix made of the epoxy resin system is prepared as shown in the example 6, a small amount of the prepared epoxy resin system is poured into a mold, the T800 carbon fibers are arranged in parallel and are straightened and placed into the mold, the content of the T800 carbon fibers is adjusted to 11.31%, the epoxy resin system is immersed in the T800 carbon fibers, then the excessive epoxy resin system exceeding the mold is scraped by a scraping plate, and then the mold is placed into an oven. When the mold release agent was put into the oven, a flat plate sprayed with the mold release agent was placed on the mold, and 2.0kg of dumbbell pieces were pressed on the flat plate. The curing parameters of the composite material are consistent with those of the epoxy resin system. And after curing is finished, closing a power supply of the baking oven, and opening a door of the baking oven to take out the composite material after the temperature of the baking oven is reduced to about 50 ℃.
To verify the effectiveness of the present invention, the following tests were performed:
test 1: three-point bending test of epoxy resin obtained by curing epoxy resin system
According to the test standard GB/T2567-2021, the bending strength of the epoxy resin obtained by curing different epoxy resin systems in examples 1-6 is tested, and the span L is 64mm, the test speed is 10mm/min and the stop end point is 6mm. The dimensions of the epoxy resin system test pieces were 80 mm. Times.10 mm. Times.4 mm. And respectively carrying out bending strength test on epoxy resin obtained by curing an epoxy resin system (the mass parts of other components are the same as those of the corresponding examples) without adding the carboxyl-terminated nitrile rubber. The test results are shown in Table 1. Compared with an epoxy resin system without adding carboxyl-terminated nitrile rubber, the bending strength of the epoxy resin system can be improved by 21.08-86.63% by adding the carboxyl-terminated nitrile rubber. It is shown that the flexible mosaic copolymer generated by the reaction of the carboxyl-terminated nitrile rubber and the epoxy resin system can improve the bending performance of the epoxy resin.
Test 2: impact test of epoxy resins obtained by curing epoxy resin systems
Impact tests are carried out on epoxy resins obtained by curing different epoxy resin systems in examples 1-6 according to test standard GB/T1843-2008, wherein the sizes of the epoxy resin system samples are 80mm multiplied by 10mm multiplied by 4mm, and the epoxy resin system samples are notched. And respectively carrying out impact test on epoxy resin obtained by curing an epoxy resin system (the mass parts of other components are the same as those of the corresponding examples) without adding the carboxyl-terminated nitrile rubber. The test results are shown in Table 2. Compared with an epoxy resin system without adding carboxyl-terminated nitrile rubber, the impact toughness of the epoxy resin can be greatly improved by adding the carboxyl-terminated nitrile rubber, and the highest improvement range can reach 210.06%. It also proves that the carboxyl groups on the molecular ends of the carboxyl-terminated nitrile rubber react with the epoxy groups of the resin in a ring-opening manner during the curing process to form flexible copolymer molecular chains which can play a role in macroscopically resisting impact when being subjected to impact load.
Test 3: 0 degree tensile test is carried out on the high-performance carbon fiber epoxy resin composite material
The different composite systems of examples 1-6 were tested for 0 ° stretch with reference to national standard GB/T3354-2014. Before the test, the size and the gauge length of the sample are measured, the aluminum alloy plate is selected by the reinforcing sheet, the reinforcing sheet is cut into standard sizes, the aluminum alloy plate and the standard sizes are firmly adhered by using 502 glue, and the reinforcing sheet is placed for a period of time to cure the glue for tensile test, wherein the test speed is 1mm/min. The test results are shown in Table 3. It can be seen that as the fiber content increases, the tensile strength of the composite increases significantly. Meanwhile, the tensile properties of the composite materials corresponding to the two T800 carbon fibers are also different to a certain extent.
Test 4: tensile fracture morphology characterization of high-performance carbon fiber epoxy resin composite material
The tensile fracture morphology of the two high performance carbon fiber/toughened epoxy composites was characterized by Scanning Electron Microscopy (SEM), as shown in figures 1-12. From the figure, the two T800 carbon fibers (T800 SC carbon fibers and T800HB carbon fibers) have better interface bonding effect with the toughened and modified epoxy resin system.
The conclusion obtained by the test can lead the T800 carbon fiber composite material to be better applied to the fields of aerospace and the like.
TABLE 1 flexural Strength of epoxy resins
TABLE 2 impact Strength of epoxy resins
TABLE 3 tensile Strength of high Performance carbon fiber epoxy composites
The above embodiments are not limited to the technical solution of the embodiments, and the embodiments may be combined with each other to form a new embodiment. The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and any modifications or equivalent substitutions without departing from the spirit and scope of the present invention should be covered in the scope of the technical solution of the present invention.
Claims (4)
- The preparation method of the T800 carbon fiber/epoxy resin composite material is characterized in that the composite material takes an epoxy resin system as a matrix, T800 carbon fibers as reinforcements, and the volume fraction of the T800 carbon fibers in the composite material is 3.77-15.08% by a manual pasting method;the epoxy resin system comprises the following components in parts by mass: 80-120 parts of 4,4' -diaminodiphenyl methane epoxy resin, 2.5-12.5 parts of 1, 4-butanediol diglycidyl ether, 5-30 parts of carboxyl-terminated nitrile rubber and 60-100 parts of methyl tetrahydrophthalic anhydride, and the preparation method of the epoxy resin system comprises the following steps:step 1, weighing 1, 4-butanediol diglycidyl ether, heating the 1, 4-butanediol diglycidyl ether to 30-100 ℃ in an oil bath while stirring, adding 4,4' -diaminodiphenylmethane epoxy resin at the moment, and continuously stirring at the temperature for 5-20min at a stirring speed of 100-800rpm to obtain a mixed solution A;step 2, adding carboxyl-terminated nitrile rubber into the mixed solution A, and stirring for 10-30min at 30-100 ℃ to obtain a mixed solution B;step 3, when the temperature of the mixed solution B is stabilized at 50-60 ℃, adding methyl tetrahydrophthalic anhydride, stirring for 5-30min, and then carrying out defoaming treatment under the conditions of vacuum and drying to obtain an epoxy resin system, wherein the defoaming treatment time in the step 3 is 10-120min;step 4, slowly and uniformly pouring the epoxy resin system into a mould sprayed with a release agent, and performing curing treatment to obtain the epoxy resin, wherein the curing treatment conditions in the step 4 are as follows: 120 ℃/2h+140 ℃/2h, and after curing, closing the power supply of the oven, and after the temperature of the oven is reduced to about 50 ℃, opening the oven door to take out the epoxy resin obtained by curing the epoxy resin system.
- 2. The preparation method of the T800 carbon fiber/epoxy resin composite material according to claim 1, wherein the composite material is prepared by a manual pasting method, and comprises the following specific operations:pouring an epoxy resin system into a mold, taking and straightening T800 carbon fibers in parallel, putting the T800 carbon fibers into the mold, scraping the excessive epoxy resin system exceeding the mold by adopting a scraping plate after the epoxy resin system is immersed in the T800 carbon fibers, putting a flat plate sprayed with a release agent on the mold, pressing 0.5-2kg of dumbbell pieces on the flat plate, and then curing to obtain the composite material.
- 3. The method for preparing a T800 carbon fiber/epoxy resin composite material according to claim 2, wherein the T800 carbon fiber is a T800SC carbon fiber.
- 4. The method for preparing a T800 carbon fiber/epoxy resin composite material according to claim 2, wherein the T800 carbon fiber is a T800HB carbon fiber.
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