CN115214201A - Carbon fiber/epoxy resin laminated plate and preparation method thereof - Google Patents
Carbon fiber/epoxy resin laminated plate and preparation method thereof Download PDFInfo
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/18—Handling of layers or the laminate
- B32B38/1858—Handling of layers or the laminate using vacuum
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B32B2250/00—Layers arrangement
- B32B2250/20—All layers being fibrous or filamentary
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/40—Weight reduction
Abstract
The invention provides a carbon fiber/epoxy resin laminated plate and a preparation method thereof, wherein the preparation method comprises the following steps: preparation of less-lamellar Ti by HCl/LiF etching method 3 C 2 T x A dispersion of a PVA solution and Ti of few-layered structure 3 C 2 T x Ti after mixing of dispersion 3 C 2 T x Soaking a CF layer by the PVA mixed solution, and then performing freeze-thaw circulation to obtain a self-interlocking TPA/CF layer; self-interlocking TPA/CF layers with epoxy resinsAnd after being layered, the carbon fiber/epoxy resin laminated plate is placed in a vulcanizing machine for hot pressing to obtain the carbon fiber/epoxy resin laminated plate. The CF/EP laminated plate toughened based on the self-interlocking MXene/PVA aerogel enables the three-dimensional skeleton of the aerogel to sew the laminated plate into a whole under the condition of not damaging the fiber arrangement and causing defects, and comprehensively and obviously enhances the interlaminar fracture toughness without sacrificing other properties.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a carbon fiber/epoxy resin laminated plate and a preparation method thereof.
Background
Carbon Fiber (CF) reinforced polymer Composites (CFRPs) are widely used in the fields of aerospace, automotive and sporting goods, etc. due to their excellent specific strength, elastic modulus, fatigue resistance and corrosion resistance. Although CFRPs are lighter in weight and have better in-plane properties than conventional metal and ceramic materials, their through-thickness properties are relatively poor due to the inherent brittleness of the epoxy matrix and poor interfacial interaction of the epoxy matrix with the carbon fibers, which limits the use of CFRPs in engineering equipment. Interlaminar delamination is the most common failure mode for carbon fiber reinforced epoxy (CF/EP) composites. Therefore, how to improve the interlayer fracture toughness and delamination resistance of the CF/EP composite material has important significance for developing CFRP with high performance. The currently common toughening methods are design of 3D fabric structure, transverse stitching, modification of CF, toughening of resin matrix and introduction of fiber insertion layer.
However, conventional toughening methods suffer from a number of deficiencies. For example, 3D fabric structures and cross-machine direction stitching, while enhancing the through-thickness mechanical properties of CFRP, result in a reduction in-plane mechanical properties due to the misalignment of the carbon fibers. By doping the nano phase, the polymer matrix can be strengthened, so that the through-thickness mechanical property of the CFRP is improved. However, the incorporation of nanoreinforcement phase reduces the fluidity of the polymer matrix, making it difficult for the CF to be completely wetted. The chemical modification of CF can significantly improve the interfacial properties of CF with the polymer matrix, but can cause damage to the CF structure, resulting in reduced strength of the CF itself. The fiber insertion layer largely avoids the disadvantages of the above-described methods. However, the interleaf layer does not form a tight interlocking effect with the CF, which makes the interfacial failure still dominated by adhesion failure. In addition, the preparation of the fibrous insert often requires the use of high cost and toxic organic solvents.
Disclosure of Invention
In order to solve the problems in the prior art, in view of the important practical requirements of the industries such as aerospace, automobiles and energy sources on carbon fiber reinforced epoxy resin composite materials and the problems existing in the method for improving the interlaminar fracture toughness at the present stage, the invention provides a carbon fiber/epoxy resin laminated plate and a preparation method thereof.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the first purpose of the invention is to provide a preparation method of a carbon fiber/epoxy resin laminated plate, which is characterized by comprising the following steps:
preparation of less-lamellar Ti by HCl/LiF etching method 3 C 2 T x A dispersion of a PVA solution and Ti of few-layered structure 3 C 2 T x Ti after mixing of dispersion 3 C 2 T x Soaking a CF layer by the PVA mixed solution, and then performing freeze-thaw circulation to obtain a self-interlocking TPA/CF layer; laying the self-interlocking TPA/CF layer and the epoxy resin layer by layer, and then placing the layer in a vulcanizing machine for hot pressing to obtain the carbon fiber/epoxy resin laminated plate.
Further, HCl/LiF etching method for preparing less-layered Ti 3 C 2 T x The process of the dispersion is as follows: mixing Ti 3 AlC 2 Slowly adding the powder into LiF/HCl solution for mixing, centrifugally washing, adding deionized water for ultrasonic treatment to obtain the few-layer Ti 3 C 2 T x And (3) dispersing the mixture.
Further, liF is dispersed and added into a 12M HCl solution, and the mixture is magnetically stirred to obtain a LiF/HCl solution, wherein the ratio of LiF to HCl solution is 2g:70 to 90ml.
Further, adding Ti 3 AlC 2 Slowly adding the powder into LiF/HCl solution to obtain sediment, repeatedly washing and centrifuging the sediment by using deionized water until the pH value is neutral to obtain multilayer Ti 3 C 2 T x And (4) depositing.
Further, a plurality of layers of Ti 3 C 2 T x The deposit is electromagnetically stirred in DMSO solution, washed by absolute ethyl alcohol, ultrasonically treated in deionized water and then centrifuged to obtain the few-layer Ti 3 C 2 T x And (3) dispersing the mixture.
Further, PVA is dissolved in deionized water under the condition of heating and stirring to obtain uniform and viscous PVA solution, and then the PVA solution and few-layer Ti are mixed 3 C 2 T x Mixing and stirring the dispersion to obtain Ti 3 C 2 T x PVA mixed solution.
Further, said Ti 3 C 2 T x The mass ratio of the PVA to the PVA is 4 to 12wt percent. Preferably, the Ti is 3 C 2 T x The mass ratio to PVA was 7.69wt%.
Furthermore, the concentration of the PVA solution is 60-100 mg/ml. Preferably, the concentration of the PVA solution is 60mg/ml.
Further, ti 3 C 2 T x After soaking the CF layer by the PVA mixed solution, placing the soaked CF layer in a vacuum drying box for degassing treatment, freezing, then unfreezing, and repeatedly carrying out freezing-unfreezing cycle for 4 times to obtain the self-interlocking TPA/CF layer. The self-interlocking TPA/CF layer is Ti 3 C 2 T x the/PVA aerogel coated CF layer, due to the porous structure of the aerogel, the self-interlocking TPA/CF layer was degassed by placing it in a vacuum environment at 60 ℃ prior to the lay-up process, thereby completely impregnating the TPA with epoxy.
Further, the freezing condition is-20 ℃,8 hours and the unfreezing time is 1 hour.
Furthermore, the self-interlocking TPA/CF layer and the epoxy resin are paved in a unidirectional layered manner, and the number of paving layers is 14-16.
Preferably, the self-interlocking TPA/CF layers are laid in layers with epoxy in a single direction, with 16 layers.
Further, the epoxy resin comprises E51 and MDA, and the mass ratio of the E51 to the MDA is 100.
Further, the laid product is placed in a vacuum bag before hot pressing, placed between heating templates of a vulcanizing machine, preheated at 60 ℃ and vacuumized for 1 hour.
Further, the hot pressing process comprises the following steps: hot-pressing at 120 ℃ for 17 hours and then postcuring at 180 ℃ for 2 hours.
The second purpose of the invention is to provide a carbon fiber/epoxy resin laminated plate prepared by the method.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention sews the CF/EP laminated board through the three-dimensional framework of the self-interlocking TPA, has good toughening effect on the laminated board, and comprehensively and effectively improves the G of the interlocking TPA/CF/EP laminated board IC Init 、G IC Prop And G IIC . In the preparation process, no toxic organic solvent is added, and water is used as the solvent, so that the preparation method has the advantages of low cost and environmental protection.
It should be noted that, in order to more conveniently and clearly express the materials, compositions and structures of the present invention, a plurality of letters are used in the present invention, and the expressions of the letters are described herein. Wherein CF means carbon fiber, CF/EP means carbon fiber-reinforced epoxy resin, ti 3 C 2 T x PVA means Ti 3 C 2 T x Mixed solution obtained by mixing with PVA, TPA/CF layer is Ti 3 C 2 T x PVA aerogel coated toughened CF layer, mxene refers to metal carbide with two-dimensional layered structure, G IC Init Indicates the initial fracture toughness between I-type layers, G IC Prop Indicates I type interlaminar expansion fracture toughness, G IIC Indicating fracture toughness of II-type layer.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
FIG. 1 shows a carbon fiber/epoxy resin laminate and a Ti layer formed by the preparation method thereof 3 C 2 T x The preparation flow chart of (1);
FIG. 2 is a flow chart of the preparation of TPA/CF in a carbon fiber/epoxy resin laminate and a method of preparing the same according to the present invention;
FIG. 3 is a schematic diagram of the preparation of a TPA/CF/EP laminate in a carbon fiber/epoxy laminate and a method of the invention;
FIG. 4 is a schematic diagram of a DCB test and an ENF test in a carbon fiber/epoxy resin laminated board and a preparation method thereof;
FIG. 5 is a comparison of toughening effect of a carbon fiber/epoxy resin laminate and a method of making the same according to the present invention, wherein (a) is CF/EP and has different Ti 3 C 2 T x G mass fraction of TPA/CF/EP composite IC Init And G IC Prop A histogram; (b) Is CF/EP and has a different Ti 3 C 2 T x G of TPA/CF/EP composite material IIC A histogram;
FIG. 6 is a comparison of toughening effect in a carbon fiber/epoxy resin laminate and a method of making the same according to the present invention, (a) is G for CF/EP and TPA/CF/EP composites with different TPA areal densities IC Init And G IC Prop A histogram; (b) G for CF/EP and TPA/CF/EP composites with different TPA areal densities IIC A histogram.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
In addition, unless otherwise specifically indicated, various starting materials, reagents, instruments and equipment used in the present invention may be commercially available or prepared by existing methods. The carbon fiber used in the present invention is a commercially available T300 unidirectional carbon fiber.
Example 1:
a preparation method of a carbon fiber/epoxy resin laminated plate comprises the following steps:
first step, referring to FIG. 1, the HCl/LiF etching method is used to prepare Ti with few layers 3 C 2 T x A dispersion liquid; the specific steps of the HCl/LiF etching method are as follows: dispersing 2g LiF into a polytetrafluoroethylene container filled with 80mL 12M hydrochloric acid solution, and magnetically stirring for 30 minutes to obtain LiF/HCl solution; subsequently, 2g of Ti 3 AlC 2 The powder was slowly added to the LiF/HCl solution and magnetic stirring (3500 rpm) was maintained at 40 ℃ for 36h; the resulting sediment was repeatedly washed with deionized water and centrifuged until the pH value became almost neutral (>6) Obtaining a multilayer Ti 3 C 2 T x And (4) depositing. A plurality of layers of Ti 3 C 2 T x Placing the sediment in a DMSO solution, electromagnetically stirring for 24h, then washing with absolute ethyl alcohol for 3 times, carrying out ultrasonic treatment for 6h in deionized water, and then centrifuging to obtain Ti with a small layer 3 C 2 T x And (3) dispersing the mixture. The obtained Ti 3 C 2 T x Freeze drying the dispersion to obtain dry Ti with few layers 3 C 2 T x And (5) preparing powder for later use.
In the second step, referring to FIG. 2, 6g of PVA was dissolved in 100mL of deionized water, heated to 90 ℃ and stirred for 3h to obtain a homogeneous viscous PVA solution. Respectively subjecting the Ti with few layers obtained in the first step to ultrasonic treatment for 1h, wherein the Ti with few layers has different masses (0.1 g, 0.3g, 0.5g, 0.7g and 0.9 g) 3 C 2 T x The powder was dispersed in 100mL of deionized water to obtain Ti 3 C 2 T x And (3) dispersing the mixture. Adding PVA solution to Ti 3 C 2 T x Stirring in the dispersion for 30min to obtain Ti 3 C 2 T x PVA mixed solution. The purpose of this step is to modify the initial Ti 3 C 2 T x Concentration of the dispersion to obtain different Ti 3 C 2 T x A TPA/CF layer in mass ratio to PVA;
third step, using Ti obtained in the second step 3 C 2 T x Soaking a CF fabric by using a PVA mixed solution, placing the soaked CF in a vacuum drying oven for degassing treatment, then placing the soaked CF in a refrigerator for freezing for 8 hours at the temperature of-20 ℃, then unfreezing for 1 hour at room temperature, and repeating the freezing-unfreezing process for 4 times to obtain a self-interlocking TPA/CF composite material;
in the fourth step, 16 unidirectional TPA/CF layers impregnated with epoxy were laid by hand. Due to the porous structure of the aerogel, the self-interlocking TPA/CF fabric is placed in a vacuum environment at 60 ℃ for degassing before the layering process, so that the TPA is completely soaked by the epoxy resin;
fifth, referring to FIG. 3, after the layup procedure, the stacked TPA/CF/EP composite is placed in a vacuum bag, which is sealed and connected to a vacuum pump. The vacuum bag was placed between heated platens of a curing press and preheated at 60 c while being evacuated for 1 hour. Subsequently, hot pressing was carried out at 120 ℃ for 17 hours, followed by postcuring at 180 ℃ for 2 hours. And obtaining the carbon fiber/epoxy resin laminated plate.
In this example, the first step is to reduce the Ti content 3 C 2 T x Freeze drying the dispersion to obtain Ti with few layers 3 C 2 T x After the powder is dispersed in deionized water in the second step to obtain dispersion, the method and the first step directly obtain Ti with few layers 3 C 2 T x The carbon fiber/epoxy laminate obtained by dispersing the dispersion and then directly mixing the dispersion with the PVA solution in the second step was identical. In this example, additional freeze-drying was added mainly to obtain precise Ti 3 C 2 T x The mass ratio of the Ti to the PVA is obtained, so that the Ti is accurately obtained 3 C 2 T x The influence of the mass ratio to PVA on the properties of the carbon fiber/epoxy resin laminate does not represent that the scope of the present invention must be such that the powder is obtained first and then redispersed to obtain a dispersion.
Referring to Table 1, various Ti are given 3 C 2 T x Nomenclature for fractional mass TPA/CF/EP samples, see FIG. 5, table 1 for various Ti 3 C 2 T x Histogram of GIC Init, GIC Prop and GIIC for TPA/CF/EP samples and CF/EP samples in mass fraction. It can be seen that the interlayer initial fracture toughness (G) of the I-type of the self-interlocking TPA/CF/EP laminate is comparable to that of the CF/EP laminate IC Init ) Type I interlaminar propagation fracture toughness (G) IC Prop ) And type II interlaminar fracture toughness (G) IIC ) Are all provided with more obviousEspecially when said Ti is 3 C 2 T x G when the mass ratio to PVA is 7.69wt% IC Init 、G IC Prop And G IIC The improvement is more obvious.
TABLE 1 different Ti 3 C 2 T x Nomenclature of TPA/CF/EP samples in terms of mass fraction
Example 2:
a preparation method of a carbon fiber/epoxy resin laminated plate comprises the following steps:
firstly, preparing less-lamellar Ti by adopting an HCl/LiF etching method 3 C 2 T x A dispersion liquid; the specific steps of the HCl/LiF etching method are as follows: dispersing 2g LiF into a polytetrafluoroethylene container filled with 80mL 12M hydrochloric acid solution, and magnetically stirring for 30 minutes to obtain LiF/HCl solution; subsequently, 2g of Ti 3 AlC 2 The powder was slowly added to the LiF/HCl solution and magnetic stirring (3500 rpm) was maintained at 40 ℃ for 36h; the resulting sediment was repeatedly washed with deionized water and centrifuged until the pH value became almost neutral (>6) Obtaining a multilayer Ti 3 C 2 T x And (4) depositing. A plurality of layers of Ti 3 C 2 T x Placing the sediment in a DMSO solution, electromagnetically stirring for 24h, then washing with absolute ethyl alcohol for 3 times, carrying out ultrasonic treatment for 6h in deionized water, and then centrifuging to obtain Ti with a small layer 3 C 2 T x And (3) dispersing the mixture. The obtained Ti 3 C 2 T x Freeze drying the dispersion to obtain dry Ti with few layers 3 C 2 T x And (5) preparing powder for later use.
In the second step, PVA of different masses (6 g, 8g, 10 g) was dissolved in 100mL of deionized water, heated to 90 ℃ and stirred for 3h to give a homogeneous and viscous PVA solution. By 1h ultrasonic treatment of less Ti layer 3 C 2 T x The powder was dispersed in 100mL of deionized water to obtain Ti 3 C 2 T x A dispersion of Ti 3 C 2 T x The mass ratio to PVA was kept at 7.69wt%. Adding PVA solution to Ti 3 C 2 T x Stirring in the dispersion for 30min to obtain Ti 3 C 2 T x PVA mixed solution. The purpose of this step is to modify the initial Ti 3 C 2 T x Concentration of the dispersion to obtain different Ti 3 C 2 T x TPA/CF layer in mass ratio to PVA;
third step, using Ti obtained in the second step 3 C 2 T x Soaking a CF fabric by using a PVA mixed solution, placing the soaked CF in a vacuum drying oven for degassing treatment, then placing the soaked CF in a refrigerator for freezing for 8 hours at the temperature of-20 ℃, then unfreezing for 1 hour at room temperature, and repeating the freezing-unfreezing process for 4 times to obtain a self-interlocking TPA/CF composite material;
in the fourth step, 16 unidirectional TPA/CF layers impregnated with epoxy were laid by hand. Due to the porous structure of the aerogel, the self-interlocking TPA/CF fabric was degassed by being placed in a vacuum environment at 60 ℃ prior to the layering process, so that the TPA was completely wetted by the epoxy resin;
in a fifth step, following the layup procedure, the stacked TPA/CF/EP composite is placed in a vacuum bag, which is sealed and in communication with a vacuum pump. The vacuum bag was placed between heated platens of a curing press and preheated at 60 c while being evacuated for 1 hour. Subsequently, hot pressing was carried out at 120 ℃ for 17 hours, followed by postcuring at 180 ℃ for 2 hours. And obtaining the carbon fiber/epoxy resin laminated plate.
In this example, the first step is to reduce the Ti content 3 C 2 T x Freeze drying the dispersion to obtain Ti with few layers 3 C 2 T x After the powder is dispersed in deionized water in the second step to obtain dispersion, the method and the first step directly obtain Ti with few layers 3 C 2 T x The carbon fiber/epoxy resin laminate obtained by dispersing and then directly mixing the dispersion with the PVA solution in the second step was identical. In this example, a further step of freeze-drying was added mainly to obtain precise Ti 3 C 2 T x With PVA (polyvinyl alcohol)The ratio of amounts in order to avoid affecting the various properties of the carbon fiber/epoxy resin laminate due to changes in the quality of the PVA does not represent the scope of the invention, which must be achieved by obtaining the powder and then redispersing it to obtain a dispersion.
Referring to Table 2, the designations of TPA/CF/EP samples of different TPA areal densities are given, referring to FIG. 6, GIC Init, G of TPA/CF/EP and CF/EP samples of different TPA areal densities in Table 2 IC Prop And G IIC Histogram contrast. It can be seen that in Ti 3 C 2 T x When the TPA areal density was different while the mass ratio to PVA was maintained at 7.69wt%, G of the sample was IC Ini t、G IC Prop And G IIC The influence is small when the area density of TPA is 27g/m 2 The sample had better G IC Ini t、G IC Prop And G IIC 。
TABLE 2 nomenclature of TPA/CF/EP samples of different TPA areal densities
Example 3:
referring to Table 3, ti was prepared by an electrospinning machine 3 C 2 T x A/PVA nanofiber (TPN) interleaf, control CF/EP and TPN/CF/EP laminate samples were prepared based on the hot pressing process of the present invention. With Ti in example 2 of the present application 3 C 2 T x The mass ratio to PVA was maintained at 7.69wt% and the areal density of TPA was 27g/m 2 Examples of (A) and (B) respectively for the initial fracture toughness (G) between type I layers IC Init ) Type I interlaminar propagation fracture toughness (G) IC Prop ) And type II interlaminar fracture toughness (G) IIC ) The detection results are shown in Table 3.
In the present invention, G of the laminate is measured based on the DCB test standard of ASTM D5528 IC Init And G IC Prop The laminate was cut into standard size DCB test specimens by a high speed rotating saw disc. Instron CMT5 equipped with 5KN weighing cellThe DCB test was performed on a 105 machine with the crosshead speed maintained at a constant 2mm/min. Referring to fig. 4, a schematic of the DCB test is shown. Five specimens were tested per set type of press fit. The calculation formula for GIC is:
where P is the breaking load (N), δ is the load point displacement (mm), b is the specimen width (mm), and a is the delamination length (mm), as derived from the formula a = (a 0+ Δ a), where Δ a is the crack propagation length.
ENF test standard based on ESIS protocol for measuring G of laminate IIC The laminate was cut into standard sized ENF test specimens by means of a high speed rotating saw disc. ENF tests were performed on an Instron CMT5105 machine equipped with a 5KN load cell, with the crosshead speed maintained at a constant 2mm/min. Fig. 4 shows a schematic diagram of the ENF test. Five specimens were tested per set type of press fit. G IIC The calculation formula of (c) is:
where P is the maximum load (N), δ is the load point displacement (mm), b is the average specimen width (mm), a is the crack length (mm), as given by the formula a = (a 0+ Δ a), where Δ a is the crack propagation length and L is the half span length (mm).
As can be seen from Table 3, the initial fracture toughness (G) between the I-type layers of the laminate after stitching the CF/EP laminate with the three-dimensional backbone of the self-interlocking TPA of the present invention is comparable to the CF/EP laminate IC Init ) Type I interlaminar propagation fracture toughness (G) IC Prop ) And type II interlaminar fracture toughness (G) IIC ) The improvement is 76%, 40% and 32% respectively. This indicates that CF/EP laminates can improve interlaminar fracture toughness globally and significantly by interlocking TPA; the traditional TPN insertion layer toughening mode only improves G IIC ，G IC Init 、G IC Prop But rather, the toughening effect is reducedThe fruit is incomplete. This is mainly due to: (1) cohesive failure by the TPA three-dimensional backbone interlocking mechanism; (2) deflection and distortion of the primary crack; (3) a competing mechanism between the secondary cracks and the primary cracks; (4) generating a plurality of microcracks; (5) TPA skeleton and Ti 3 C 2 T x And (4) pulling out. Interlocking TPA toughening is not only an overall effective improvement in G of interlocking TPA/CF/EP laminates compared to conventional interlayer toughening IC Init 、G IC Prop And G IIC And low-cost and green manufacturing is realized.
Table 3 comparative toughening of the present invention to conventional laminates
| Type of sample | G IC init (kJ/m 2 ) | G IC prop (kJ/m 2 ) | G IIC (kJ/m 2 ) |
| CF/EP | 0.24±0.01 | 0.47±0.02 | 1.74±0.43 |
| TPN/CF/EP | 0.24±0.01 | 0.41±0.02 | 2.03±0.18 |
| TPA/CF/EP | 0.43±0.02 | 0.66±0.03 | 2.29±0.13 |
In addition, referring to table 4, it is found that the toughening method and the organic solvent added during the preparation of the conventional nanofiber insert layer are studied, and that expensive and toxic organic solvents are often required to be used for preparing various conventional nanofiber insert layers, while the solvent used during the preparation of the TPA aerogel of the present invention is water, which is non-toxic and harmless, and has the advantages of low cost and environmental protection.
TABLE 4 comparison of solvent types for different preparation methods
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a carbon fiber/epoxy resin laminated plate is characterized by comprising the following steps:
preparation of less-lamellar Ti by HCl/LiF etching method 3 C 2 T x A dispersion of a PVA solution and Ti of few-layered structure 3 C 2 T x Ti after mixing of dispersion 3 C 2 T x Soaking a CF layer by the PVA mixed solution, and then performing freeze-thaw circulation to obtain a self-interlocking TPA/CF layer; laying the self-interlocking TPA/CF layer and the epoxy resin layer by layer, and then placing the layer in a vulcanizing machine for hot pressing to obtain the carbon fiber/epoxy resin laminated plate.
2. The method of claim 1, wherein the HCl/LiF etching process produces Ti with few layers 3 C 2 T x The process of the dispersion is as follows: mixing Ti 3 AlC 2 Slowly adding the powder into LiF/HCl solution for mixing, centrifugally washing, adding deionized water for ultrasonic treatment to obtain the few-layer Ti 3 C 2 T x And (3) dispersing the mixture.
3. The method of manufacturing a carbon fiber/epoxy laminate according to claim 1, wherein: dissolving PVA in deionized water under heating and stirring to obtain uniform viscous PVA solution, and mixing the PVA solution with less laminated Ti 3 C 2 T x Mixing and stirring the dispersion to obtain Ti 3 C 2 T x PVA mixed solution.
4. A method of producing a carbon fiber/epoxy resin laminate according to any one of claims 1 to 3, wherein: the Ti 3 C 2 T x The mass ratio of the PVA to the PVA is 4 to 12wt percent.
5. The method of manufacturing a carbon fiber/epoxy resin laminate according to claim 1, wherein: ti 3 C 2 T x After soaking the CF layer by the PVA mixed solution, placing the soaked CF layer in a vacuum drying box for degassing treatment, freezing, then unfreezing, and repeatedly carrying out freezing-unfreezing cycle for 4 times to obtain the self-interlocking TPA/CF layer.
6. The method of manufacturing a carbon fiber/epoxy resin laminate according to claim 5, wherein: the freezing condition is-20 ℃,8 hours, and the unfreezing time is 1 hour.
7. The method of manufacturing a carbon fiber/epoxy resin laminate according to claim 1, wherein: the self-interlocking TPA/CF layer and the epoxy resin are paved in a unidirectional layered manner, and the number of the paving layers is 14-16.
8. The method of manufacturing a carbon fiber/epoxy resin laminate according to claim 1, wherein: before hot pressing, the laid product is placed in a vacuum bag and placed between heating templates of a vulcanizing machine, and preheating is carried out at 60 ℃ and vacuumizing is carried out for 1 hour.
9. The method of manufacturing a carbon fiber/epoxy laminate according to claim 8, wherein: the hot pressing process comprises the following steps: hot-pressing at 120 ℃ for 17 hours and then postcuring at 180 ℃ for 2 hours.
10. A carbon fiber/epoxy resin laminate obtained by the production method according to any one of claims 1 to 9.
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