CN106626439A - Preparation method of low-cost and large-tow 48K carbon fiber preimpregnated cloth and composite material thereof - Google Patents
Preparation method of low-cost and large-tow 48K carbon fiber preimpregnated cloth and composite material thereof Download PDFInfo
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- CN106626439A CN106626439A CN201611222667.1A CN201611222667A CN106626439A CN 106626439 A CN106626439 A CN 106626439A CN 201611222667 A CN201611222667 A CN 201611222667A CN 106626439 A CN106626439 A CN 106626439A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- 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
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/30—Applications used for thermoforming
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Abstract
The invention discloses a preparation method of a low-cost and large-tow 48K carbon fiber preimpregnated cloth and a composite material thereof. According to the preparation method disclosed by the invention, a resin system compound formula and an impregnating-rolling dual-configuration method are adopted, so that the viscosity of a resins system is reduced, the infiltrating effect is improved, and the technical difficult problems that a fiber bundle is low in resin content, high in content of volatile components, uncontrollable in resin content and the like are solved. The invention also provides the preparation method of the 48K large-tow carbon fiber epoxy resin preimpregnated cloth; after forming, epoxy resin carbon fiber prepreg and a composite material thereof which are low in cost, high in performance and suitable for large-scale application in all industrial fields are obtained; the preparation cost of the composite material is greatly reduced, the application form and the application range of carbon fibers are widened, and the production efficiency and the stability of a process and a product are improved; large size, diversification and structural complication of the product can be realized; and the invention provides a low-cost carbon fiber raw material for application in the fields such as communication and transportation, engineering machinery, constructional engineering and energy.
Description
Technical field
The invention belongs to high performance composites manufacturing technology field, and in particular to a kind of inexpensive, big tow 48K
The manufacture method of polyacrylonitrile-based carbon fibre prepreg cloth and its composite.
Background technology
Carbon fiber (carbon fiber), belongs to high-performance novel fibrous material, and quality is lighter than metallic aluminium, and its proportion is not
To the 1/4 of steel, it is 7～9 times of steel all in more than 3500MPa that carbon fiber resin composite material tensile strength is general, tensile elastic
Modulus is also higher than steel for 23000～43000MPa.Carbon fiber has many premium properties, the axial strength and mould of carbon fiber simultaneously
Amount is high, and density is low, higher than performance, and without creep, superhigh temperature resistant under non-oxidizing atmosphere, fatigue durability is good, specific heat and electric conductivity between
It is nonmetallic and metal between, thermal coefficient of expansion is little and with anisotropy, and good corrosion resistance, X-ray transparent is good.Good leads
Conductance hot property, electromagnetic wave shielding are good etc..Carbon fiber is different according to the specification of product, carbon fiber be divided at present aerospace level and
The class of technical grade two, also known as little tow carbon fiber and large-tow carbon fiber.Generally more than 48K carbon fibers are called big tow carbon fine
Dimension, including 48K, 60K, 120K, 360K and 480K etc..The little tow carbon fiber initial stage develops into 12K based on 1K, 3K, 6K, gradually
And 24K.
Since 2011, worldwide carbon fiber consumption is concentrated mainly on Aero-Space, commercial Application and Leisure Sport product etc. three
Big field, accounts for respectively aggregate consumption 15%, 65% and 20%, and wherein commercial Application focuses primarily upon wind-power electricity generation, molding compound two
Big field.With increase of the fields such as communications and transportation, engineering machinery, architectural engineering and the energy to carbon fibre composite demand,
Industrial circle will continue to keep the status of its carbon fiber application biggest market.
Large-tow carbon fiber has the advantages such as low cost, performance height, is widely used in infrastructure, auto industry, the energy and opens
Send out and wait industry and civil area.At present the state such as America and Europe replaces little tow carbon fiber to succeed in industrial multiple fields, develops
Rapidly.However, domestic carbon fiber product is mainly the little tow of T300, T700 level, the large-tow carbon fiber demand and supply contraction is particularly
Protrusion, the large-tow carbon fiber whole dependence on import of building reinforcing field application, large-tow carbon fiber and prepreg cloth manufacturing technology
Even more need innovation badly, composite article production technology of the development with independent intellectual property right, the carbon fiber produced with China oneself is answered
Combination product is developed and is developed relatively low cost, steady quality, excellent performance, the world-class carbon fiber that forereaches and answers
Condensation material, to meet national defence, high-tech and product for civilian use market to carbon fibre composite increasing need.
At present both at home and abroad the production of thermosetting resin matrix carbon fiber prepreg is mainly two kinds of techniques：Solution dipping method and
Hot melt.The advantage of solution dipping method is that reinforcing material is easily impregnated with by resin matrix；Slim prepreg can be manufactured, also can be made
Make thicker prepreg；Equipment manufacturing cost is relatively low.Have the disadvantage to need drying oven to remove solvent or carry out solvent recovery.Deal with improperly
Burning can be caused or cause environmental pollution；Prepreg often remains a certain amount of solvent, and space is easily formed during shaping, affects compound
Material property.The advantage of hot melt infusion process is that technical process linear velocity is big, efficiency high；Resin content is easily controlled；Without solvent,
Prepreg volatile matter content is low, process safety；Do not need drying oven, reduce environmental pollution；Masking and dipping process can divide
Step is carried out, and reduces the loss that material is particularly expensive reinforcing material；And the presentation quality of this technique prepreg is also preferable.Lack
Point is that the big prepreg of thickness is particularly fabric and is difficult to be impregnated with, high-viscosity resin is difficult to impregnate, release liners and PE films consumption compared with
Greatly.Both processes cut both ways, and complement one another, and following both production technologies will exist simultaneously, to adapt to difference
Demand.
A kind of CNT disclosed in Chinese patent CN201110005086.3 and functionalized carbon fiber reinforced epoxy
The preparation method of composite.CNT is introduced after carboxylated functionalization, on the carbon nanotubes diamine for this invention
Or polyamine, obtain the CNT of surface amine groups；By aminated CNT and surface through carboxylated carbon fiber
Reaction, obtains aminated carbon fiber surface and is grafted with CNT, and in carbon fiber surface diamine or polyamine are introduced, and makes carbon
Fiber surface is not completely fully aminated with the carboxyl that aminated CNT reacts, by carbon fiber and epoxy resin prepolymerization
Reaction, the carbon fiber surface for obtaining functionalization is grafted with the reinforcement of epoxy resin；By aminated CNT and asphalt mixtures modified by epoxy resin
Fat reacts, and obtains the matrix of the epoxy resin of CNT Strengthening and Toughening；The functionalized carbon fiber surface grafting for obtaining there is into epoxy
The matrix of the reinforcement of resin and the epoxy resin of CNT Strengthening and Toughening is combined, and obtains required product.This invention reactions steps
Simply, using the intensity and toughness Strengthening and Toughening carbon fiber and matrix resin of CNT, carbon fiber is improved viscous with resin matrix
Knot performance, improves the interface binding intensity of composite, so as to improve the overall performance of composite.
Hollow carbon cloth epoxy resin composite material and its preparation side disclosed in Chinese patent CN201010184682.8
Method, it is related to carbon fiber epoxy resin composite material and preparation method thereof.Urea and ethylene glycol are put into graphite crucible by this invention
In, hollow carbon cloth is then made in atmosphere sintering furnace；Then hollow carbon cloth is immersed in by bisphenol type epoxy tree
In the epoxide-resin glue of fat, acetone and diethylenetriamine composition, after taking-up Jing after compacting and being vacuum dried, hollow carbon fiber is obtained
Cloth epoxy resin composite material.This invention addresses that existing carbon fiber epoxy resin composite material density is big and carbon fiber epoxy
The modified problem for first having to carry out carbon fiber complexity is needed during resin composite materials.
The content of the invention
In order to overcome the high cost problem for limiting Industry of Carbon Fiber field large-scale application, product quality stability and structure
Single-issue, it is an object of the invention to provide a kind of presoak 48K large-tow carbon fibers using epoxy resin, while using from main ring
Oxygen tree fat prepreg cloth formula is constituted, and overcomes many problems of volatile matter content, obtains low cost, high-performance, it is adaptable to each industry neck
The epoxy resin carbon fiber prepreg of domain large-scale application and its composite, the composite is using autoclave method and preforming
The realization of part vacuum assistant resin infused form, compares conventional moulded technique, and application form and the application of carbon fiber have been expanded significantly
Scope, improve production efficiency, good stability of the dimension greatly reduce composite manufacturing cost, realize the large scale of product
Change, variation and complex structure.
The method of the present invention is comprised the following steps：
Step one：Configuration is suitable for 48K large-tow carbon fiber vacuum assisted resin infusion epoxy-resin systems compositions, specifically
It is that composition epoxy resin includes component A and B component, formula is by following parts by weight：Component A epoxy resin 70-100phr,
Diluent 0-30phr, defoamer 0-5phr, coupling agent 0-3phr, antioxidant 0-5phr；B component curing agent 10-50phr.
Step 2：Fibre reinforced fabric be 48K large-tow carbon fiber continuous fiber felts, fiber cloth, non-crimped fabric,
Three-dimensional knitted fabric or three-dimensional braid；Because the presence of carbon fiber sizing agent can cause resin to be subject to serious with the interface of fiber
Affect, will cause to produce space and slight crack in product, affect the performance of composite, the method dried in the shade using normal temperature decompression is removed
Organic solvent in fabric so that solvent clearance is high, the generation in space and slight crack during weakening curing molding.
Step 3：Using dipping-rolling biconfiguration method, by 48K carbon fibre fabrics in T0And T90Direction applies 10～20N and leads
Stretch, is impregnated in the excellent combination composition glue liquid with epoxy-resin systems after 10min～15min, is placed in low-grade fever rolling on double elastomeric compound machines
Pressure, low-grade fever temperature is 35～50 DEG C, and repeatedly the high 48K carbon fiber/epoxy resins of the prepared infiltration degree of pad pasting are pre- after low-grade fever rolling
Leaching cloth；It is described it is excellent composition glue liquid is combined with epoxy-resin systems weight be 80 parts of E51 type epoxy resin, 14 part 1,4
Butanediol diglycidyl ether, 2 parts of 3- glycidol ether propoxyl group triethoxysilanes, 1 part of tributyl phosphite and 12 parts it is different
Diethylenetriamine is curing agent；
Step 4：Moulding process adopts autoclave molding, or directly to carry out vacuum using the 48K fabrics of step 2 manufacture auxiliary
Furtherance type, mold clean is clean, smear stand-by after hole sealing agent, releasing agent, prepreg cloth is cut into burr, it is cut into by die size
Fritter；Prepreg cloth is laid in mould by design, solidify afterwards are carried out after shaping, the demoulding is carried out to carbon fiber composite material article
Prune, target product is obtained.
Preferably, the step one epoxy resin composition component A formula is configured to epoxy resin 70
～100phr, 0～30phr of diluent, 0～5phr of defoamer, 0～3phr of coupling agent, 0～5phr of antioxidant；
Composition epoxy resin A：B component curing agent is 90～50phr by weight ratio：10～50phr.
Preferably, the epoxy resin of described step one be bisphenol-type epoxy resin, bisphenol f type epoxy resin, to ammonia
One or more of base phenol epoxy resin, orthoresol type epoxy resin, phenol aldehyde type epoxy resin and multiple functionality epoxide resin
Combination.
Preferably, described diluent is：Butyl glycidyl ether, tert-butyl phenol glycidol ether, 1,4 butanediols two
Glycidol ether, 1,6 ethylene glycol diglycidylethers, neopentyl glycol glycidol ether, ethylene glycol diglycidylether, dihydroxy first
Butylcyclohexane diglycidyl ether, poly- third dihydroxylic alcohols glycidol ether, dibromoneopentyl glycol diglycidyl ether, PPOX
Diglycidyl ether, resorcinolformaldehyde resin, cylohexanediol diglycidyl ether, polypropylene glycol diglycidyl ether,
Polyglycidyl ether, the glycidol ether of glycol one, n-octyl alcohol glycidol ether, 2- hexyl glycidyl ethers, expoxy propane
Allyl ether, phenyl glycidyl ether, adjacent expoxy propane iso-octyl ether, cresylglycidylether, benzyl glycidyl ether, aryl
One kind in glycidol ether, p-t-butyl phenol glycidol ether, logarithm carbonic acid glycidol ether and butyl glycidyl ether
Or it is several.
Preferably, the defoamer is the one kind in polyethers defoamer, alcohol defoaming agent and silicone defoamer
Or it is several.
Preferably, the coupling agent is silane coupling agent, by the emperor himself esters of gallic acid coupling agent, Borate Ester as Coupling and aluminic acid
One or more in esters coupling agent.
Preferably, the antioxidant is triethyl phosphite, tributyl phosphite or the monooctyl ester of phosphorous acid three.
Preferably, the curing agent is the one kind or several in straight-chain aliphatic amine, cycloaliphatic amines and aliphatic aromatic amine
Kind, curing agent is calculated with content of epoxy resin by formula below.
Preferably, in the step 2, carbon fiber is domestic 48K large-tow carbon fibers, except the organic solvent of sizing agent
Using acetone, the method for optimizing for removing acetone in fiber is that normal temperature decompression is dried in the shade method.
Preferably, in the step 3,48K carbon fibre fabric T0And T90It is 10～20N that direction applies drafting force, is impregnated
Time is 10min～15min, and double elastomeric compound machine roller temperatures are 35～50 DEG C.
Preferably, in the step 4, preferred releasing agent is the FLEX-Z 5.0 of ZYVAX, and hole sealing agent is ZYVAX's
FLEX-Z 5.0；Negative pressure in autoclave method or vacuum assisted resin infusion vacuum bag film is different according to resin system viscosity, 0.098
Set between～0.08MPa scopes.
Beneficial effects of the present invention
48K large-tow carbon fibers tow directly results in big tow carbon with respect to the thicker several times such as 3K, resin impregnation difficulties several times
Fiber is difficult to large-scale application, using above-mentioned technical proposal, has the beneficial effect that：Using resin system compound prescription and dipping-
Rolling biconfiguration method, reduces using resin system viscosity and improves effect of impregnation, solves that fibre bundle resin content is low, volatile matter
The technical barrier such as content is high, resin content is uncontrollable；Present invention simultaneously provides a kind of 48K large-tow carbon fibers epoxy resin preimpregnation
Cloth preparation method, Jing after shaping low cost, high-performance are obtained, it is adaptable to which the epoxy resin carbon of each industrial circle large-scale application is fine
Dimension prepreg and its composite, greatly reduce composite manufacturing cost, have expanded application form and the application of carbon fiber
Scope, improve production efficiency, technique and product stability are capable of achieving in large size, the diversified and complex structure of product, are
The application of the fields such as communications and transportation, engineering machinery, architectural engineering and the energy provides inexpensive carbon fiber material.
Specific embodiment
The method of the present invention is comprised the following steps：
Step one：Configuration is suitable for 48K large-tow carbon fiber vacuum assisted resin infusion epoxy-resin systems compositions, specifically
It is that composition epoxy resin includes component A and B component, formula is by following parts by weight：Component A epoxy resin 70-100phr,
Diluent 0-30phr, defoamer 0-5phr, coupling agent 0-3phr, antioxidant 0-5phr；B component curing agent 10-50phr.
Step 2：Fibre reinforced fabric be 48K large-tow carbon fiber continuous fiber felts, fiber cloth, non-crimped fabric,
Three-dimensional knitted fabric or three-dimensional braid；Because the presence of carbon fiber sizing agent can cause resin to be subject to serious with the interface of fiber
Affect, will cause to produce space and slight crack in product, affect the performance of composite, the method dried in the shade using normal temperature decompression is removed
Organic solvent in fabric so that solvent clearance is high, the generation in space and slight crack during weakening curing molding.
Step 3：Using dipping-rolling biconfiguration method, by 48K carbon fibre fabrics in T0And T90Direction applies 10～20N and leads
Stretch, is impregnated in the excellent combination composition glue liquid with epoxy-resin systems after 10min～15min, is placed in low-grade fever rolling on double elastomeric compound machines
Pressure, low-grade fever temperature is 35～50 DEG C, and repeatedly the high 48K carbon fiber/epoxy resins of the prepared infiltration degree of pad pasting are pre- after low-grade fever rolling
Leaching cloth；It is described it is excellent composition glue liquid is combined with epoxy-resin systems weight be 80 parts of E51 type epoxy resin, 14 part 1,4
Butanediol diglycidyl ether, 2 parts of 3- glycidol ether propoxyl group triethoxysilanes, 1 part of tributyl phosphite and 12 parts it is different
Diethylenetriamine is curing agent；
Step 4：Moulding process adopts autoclave molding, or directly to carry out vacuum using the 48K fabrics of step 2 manufacture auxiliary
Furtherance type, mold clean is clean, smear stand-by after hole sealing agent, releasing agent, prepreg cloth is cut into burr, it is cut into by die size
Fritter；Prepreg cloth is laid in mould by design, solidify afterwards are carried out after shaping, the demoulding is carried out to carbon fiber composite material article
Prune, target product is obtained.
According to the present invention, the carbon fiber of described carbon fibre initial rinse fabric adopts domestic 48K large-tow carbon fibers.
According to the present invention, the resin system of described carbon fibre initial rinse fabric is divided into the component of A, B two, component A by epoxy resin,
Diluent, defoamer, coupling agent and antioxidant composition.B component is made up of curing agent.
According to the present invention, described epoxy resin is preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, to amino
Phenol epoxy resin, orthoresol type epoxy resin, phenol aldehyde type epoxy resin, one or more group of multiple functionality epoxide resin
Close；
Diluent is butyl glycidyl ether, and tert-butyl phenol glycidol ether, poly- third dihydroxylic alcohols glycidol ether, phenyl contracts
Water glycerin ether, butyl glycidyl ether；
Defoamer be polyethers defoamer, alcohol defoaming agent, silicone defoamer；Coupling agent is silane coupling agent,
Esters of gallic acid coupling agent by the emperor himself, Borate Ester as Coupling and aluminate coupling agent；Antioxidant is triethyl phosphite, phosphorous acid three
Butyl ester, the monooctyl ester of phosphorous acid three.B component curing agent is ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, many ethene
Polyamines, diaminodiphenyl-methane, diamino diphenyl sulfone.
It is described except the organic solvent of sizing agent adopts acetone according to the present invention, remove the method for optimizing of acetone in fiber
It is that normal temperature decompression is dried in the shade method.
According to the present invention, described 48K carbon fibre fabric T0And T90Direction applies drafting force for 10～20N, dip time
For 10min～15min, double elastomeric compound machine roller temperatures are 35～50 DEG C.
According to the present invention, described releasing agent is the FLEX-Zs 5.0 of the FLEX-Z 5.0, hole sealing agent for ZYVAX of ZYVAX；
Negative pressure in autoclave method or vacuum assisted resin infusion vacuum bag film is different according to resin system viscosity, in 0.098～0.08MPa models
Set between enclosing.
Said method obtains 40～60Wt% of resin content that 48K large-tow carbon fibers epoxy resin presoaks cloth, fugitive constituent
(%)≤1.0,3 months below 0 DEG C of storage period.
48K large-tow carbon fibers after cured shaping/epoxy resin composite material bending strength ＞ 1100MPa, stretching
Intensity ＞ 980MPa.
Embodiment 1：
A kind of domestic 48K large-tow carbon fibers are epoxy resin base carbon fiber prepreg cloth and its composite wood prepared by raw material
Material, the prepreg cloth and its composite strengthen fabric and constitute by epoxy-resin systems composition and 48K large-tow carbon fibers, described
Epoxy-resin systems have epoxy resin group and curing agent group, and jointly configuration is formed, epoxy resin group include epoxy resin, diluent,
Coupling agent, defoamer and antioxidant.Take 80 parts of E51 type epoxy resin in parts by mass, 14 part of 1,4 butanediol two and shrink sweet
Oily ether, 2 parts of 3- glycidol ether propoxyl group triethoxysilanes, 1 part of tributyl phosphite is in 20 DEG C～30 DEG C temperature range bars
Under part, stirring 30min～40min is until be well mixed, 0.6 part of BYK-A530 defoamer keeping temperature of addition is constant, stirring
15min, finally stands 12h stand-by.Take by the weight measured with epoxy resin chemistry, take 12 parts of different diethylenetriamines for curing agent
Component.By the mixing of two components, the mixing and stirring under agitator effect, de-bubbled 10min is vacuumized under room temperature epoxy is obtained
Resin combination.
48K carbon cloths remove sizing agent after, using normal temperature decompression dry in the shade method remove fiber in acetone.Will be above-mentioned
48K carbon fibre fabric T0And T90Direction applies 15N drafting forces, and in being impregnated into resin pool, the time is 10min～15min, using double
Elastomeric compound machine low-grade fever roll-in, roller temperature is 45 DEG C, resin system is sufficiently impregnated with 48K large-tow carbon fiber cloth, pad pasting
Prepared 48K large-tow carbon fibers/epoxy resin preimpregnation cloth.The resin for obtaining 48K large-tow carbon fibers epoxy resin preimpregnation cloth contains
Amount 42Wt%, fugitive constituent (%)≤1.0,3 months below 0 DEG C of storage period.
Jing autoclaves method is distinguished again and directly applies 48K carbon cloths to be that preform is prepared using vacuum assistant resin injection
Composite, the negative pressure in two methods vacuum bag film is set as 0.098MPa, it is cured after obtain 48K large-tow carbon fibers and answer
Condensation material, bending strength 1426MPa, tensile strength 1180MPa (autoclave method)；Bending strength 1126MPa, tensile strength
983MPa (vacuum assistant resin injection).
Embodiment 2：
A kind of domestic 48K large-tow carbon fibers are epoxy resin base carbon fiber prepreg cloth and its composite wood prepared by raw material
Material, the prepreg cloth and its composite strengthen fabric and constitute by epoxy-resin systems composition and 48K large-tow carbon fibers, described
Epoxy-resin systems have epoxy resin group and curing agent group, and jointly configuration is formed, epoxy resin group include epoxy resin, diluent,
Coupling agent, defoamer and antioxidant.Take 80 parts of bisphenol f type epoxy resins (DER354), 14 parts of butyl contractings in parts by mass
Water glycerin ether, 2 parts of 3- glycidol ether propoxyl group triethoxysilanes, 1 part of tributyl phosphite is in 20 DEG C～30 DEG C temperature models
Under the conditions of enclosing, stirring 30min～40min is until be well mixed, 0.6 part of BYK-A530 defoamer keeping temperature of addition is constant, stirs
15min is mixed, 12h is finally stood stand-by.Take by the weight measured with epoxy resin chemistry, it is solid to take 27 parts of diamines diphenyl methanes
Agent component.By the mixing of two components, the mixing and stirring under agitator effect, de-bubbled 10min is vacuumized under room temperature and is obtained
Composition epoxy resin.
48K carbon cloths remove sizing agent after, using normal temperature decompression dry in the shade method remove fiber in acetone.Will be above-mentioned
48K carbon fibre fabric T0And T90Direction applies 15N drafting forces, and in being impregnated into resin pool, the time is 10min～15min, using double
Elastomeric compound machine low-grade fever roll-in, roller temperature is 45 DEG C, resin system is sufficiently impregnated with 48K large-tow carbon fiber cloth, pad pasting
Prepared 48K large-tow carbon fibers/epoxy resin preimpregnation cloth.The resin for obtaining 48K large-tow carbon fibers epoxy resin preimpregnation cloth contains
Amount 42Wt%, fugitive constituent (%)≤1.0,3 months below 0 DEG C of storage period.
Jing autoclaves method is distinguished again and directly applies 48K carbon cloths to be that preform is prepared using vacuum assistant resin injection
Composite, the negative pressure in two methods vacuum bag film is set as 0.098MPa, it is cured after obtain 48K large-tow carbon fibers and answer
Condensation material, bending strength 1552MPa, tensile strength 1210MPa (autoclave method)；Bending strength 1223MPa, tensile strength
1024MPa (vacuum assistant resin injection).
Claims (10)
1. a kind of manufacture method of inexpensive, big tow 48K carbon fibre initial rinse fabrics and its composite, the method includes following step
Suddenly：
Step one：Configuration is suitable for 48K large-tow carbon fiber vacuum assisted resin infusion epoxy-resin systems compositions, specially ring
Epoxy resin composition includes component A and B component, and formula presses following parts by weight：Component A epoxy resin 70-100phr, dilution
Agent 0-30phr, defoamer 0-5phr, coupling agent 0-3phr, antioxidant 0-5phr；B component curing agent 10-50phr.
Step 2：Fibre reinforced fabric is 48K large-tow carbon fiber continuous fiber felts, fiber cloth, non-crimped fabric, three-dimensional
Knitted fabric or three-dimensional braid；Because the presence of carbon fiber sizing agent can cause resin to be subject to serious shadow with the interface of fiber
Ring, will cause to produce space and slight crack in product, affect the performance of composite, the method dried in the shade using normal temperature decompression is removed knits
Organic solvent in thing so that solvent clearance is high, the generation in space and slight crack during weakening curing molding.
Step 3：Using dipping-rolling biconfiguration method, by 48K carbon fibre fabrics in T0And T90Direction applies 10～20N drawing-offs
Power, is impregnated in the excellent combination composition glue liquid with epoxy-resin systems after 10min～15min, is placed in low-grade fever rolling on double elastomeric compound machines,
Low-grade fever temperature is 35～50 DEG C, and repeatedly pad pasting is obtained the high 48K carbon fiber/epoxy resins preimpregnation of infiltration degree after low-grade fever rolling
Cloth；The described excellent weight that composition glue liquid is combined with epoxy-resin systems is 80 parts of E51 type epoxy resin, 14 part of 1,4 fourth
Hexanediol diglycidyl ether, 2 parts of 3- glycidol ether propoxyl group triethoxysilanes, 1 part of tributyl phosphite and 12 parts different two
Ethene triamine is curing agent；
Step 4：Moulding process adopts autoclave molding, or directly using the 48K fabrics of step 2 manufacture carry out vacuum aided into
Type, mold clean is clean, smear stand-by after hole sealing agent, releasing agent, prepreg cloth is cut into burr, it is cut into by die size little
Block；Prepreg cloth is laid in mould by design, solidify afterwards are carried out after shaping, the demoulding is repaiied to carbon fiber composite material article
Cut, target product is obtained.
2. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：In the step one, composition epoxy resin component A formula be configured to epoxy resin 70～
100phr, 0～30phr of diluent, 0～5phr of defoamer, 0～3phr of coupling agent, 0～5phr of antioxidant；
Composition epoxy resin A：B component curing agent is 90～50phr by weight ratio：10～50phr.
3. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：In described step one, epoxy resin be bisphenol-type epoxy resin, bisphenol f type epoxy resin, to amino
One or more group of phenol epoxy resin, orthoresol type epoxy resin, phenol aldehyde type epoxy resin and multiple functionality epoxide resin
Close.
4. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：Described diluent is butyl glycidyl ether, tert-butyl phenol glycidol ether, 1,4 butanediols two shrink
Glycerin ether, 1,6 ethylene glycol diglycidylethers, neopentyl glycol glycidol ether, ethylene glycol diglycidylether, dihydroxymethyl ring
Hexane diglycidyl ether, poly- third dihydroxylic alcohols glycidol ether, dibromoneopentyl glycol diglycidyl ether, PPOX two contract
Water glycerin ether, resorcinolformaldehyde resin, cylohexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, many contractings
Water glycerin ether, the glycidol ether of glycol one, n-octyl alcohol glycidol ether, 2- hexyl glycidyl ethers, expoxy propane allyl
Base ether, phenyl glycidyl ether, adjacent expoxy propane iso-octyl ether, cresylglycidylether, benzyl glycidyl ether, aryl shrink
One kind or several in glycerin ether, p-t-butyl phenol glycidol ether, logarithm carbonic acid glycidol ether and butyl glycidyl ether
Kind.
5. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：The defoamer is the one kind or several in polyethers defoamer, alcohol defoaming agent and silicone defoamer
Kind.
6. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：The coupling agent is silane coupling agent, admire esters of gallic acid coupling agent, Borate Ester as Coupling and Aluminate
One or more in class coupling agent.
7. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：The antioxidant is triethyl phosphite, tributyl phosphite or the monooctyl ester of phosphorous acid three.
8. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：The curing agent is one or more in straight-chain aliphatic amine, cycloaliphatic amines and aliphatic aromatic amine.
9. the manufacturer of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：In the step 2, carbon fiber is domestic 48K large-tow carbon fibers, except the organic solvent of sizing agent is adopted
Acetone, the method for optimizing for removing acetone in fiber is that normal temperature decompression is dried in the shade method.
10. the manufacture of a kind of inexpensive, big tow 48K carbon fibre initial rinse fabrics according to claim 1 and its composite
Method, it is characterised in that：In the step 4, preferred releasing agent is the FLEX-Z 5.0 of ZYVAX, and hole sealing agent is ZYVAX's
FLEX-Z 5.0；Negative pressure in autoclave method or vacuum assisted resin infusion vacuum bag film is different according to resin system viscosity, 0.098
Set between～0.08MPa scopes.
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| CN108314875A (en) * | 2018-01-27 | 2018-07-24 | 福星东联（北京）科技有限公司 | A kind of carbon fibre composite and preparation method thereof for collision prevention girders |
| CN109129984A (en) * | 2018-08-31 | 2019-01-04 | 湖北三江航天红阳机电有限公司 | A kind of preparation method of glass microballoon doping prepreg cloth |
| CN109265923A (en) * | 2018-08-29 | 2019-01-25 | 清华大学深圳研究生院 | A kind of continuous carbon fibre composite material and preparation method thereof |
| CN109679295A (en) * | 2019-01-15 | 2019-04-26 | 南通纺织丝绸产业技术研究院 | Method for enhancing the composite performance of carbon fiber and resin matrix |
| CN112358633A (en) * | 2020-10-23 | 2021-02-12 | 广州市聚欣盈复合材料科技有限公司 | Carbon cloth-epoxy resin composite material and preparation method and application thereof |
| CN112878055A (en) * | 2020-12-25 | 2021-06-01 | 中复神鹰碳纤维股份有限公司 | Preparation method of carbon fiber for building reinforcing carbon cloth |
| CN113492472A (en) * | 2020-07-31 | 2021-10-12 | 国际竹藤中心 | Thermosetting plant fiber prepreg and preparation method and application thereof |
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| CN108314875A (en) * | 2018-01-27 | 2018-07-24 | 福星东联（北京）科技有限公司 | A kind of carbon fibre composite and preparation method thereof for collision prevention girders |
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| CN109129984A (en) * | 2018-08-31 | 2019-01-04 | 湖北三江航天红阳机电有限公司 | A kind of preparation method of glass microballoon doping prepreg cloth |
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| CN109679295A (en) * | 2019-01-15 | 2019-04-26 | 南通纺织丝绸产业技术研究院 | Method for enhancing the composite performance of carbon fiber and resin matrix |
| CN113492472A (en) * | 2020-07-31 | 2021-10-12 | 国际竹藤中心 | Thermosetting plant fiber prepreg and preparation method and application thereof |
| CN112358633A (en) * | 2020-10-23 | 2021-02-12 | 广州市聚欣盈复合材料科技有限公司 | Carbon cloth-epoxy resin composite material and preparation method and application thereof |
| CN112358633B (en) * | 2020-10-23 | 2022-05-10 | 广州市聚欣盈复合材料科技股份有限公司 | Carbon cloth-epoxy resin composite material and preparation method and application thereof |
| CN112878055A (en) * | 2020-12-25 | 2021-06-01 | 中复神鹰碳纤维股份有限公司 | Preparation method of carbon fiber for building reinforcing carbon cloth |
| CN112878055B (en) * | 2020-12-25 | 2024-01-05 | 中复神鹰碳纤维股份有限公司 | Preparation method of carbon fiber for building reinforced carbon cloth |
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Application publication date: 20170510 |