CN115214201B - 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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- 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
- 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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- 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
- 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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- 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
- 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
- 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
- B32B38/08—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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- 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
- 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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- 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
- B32B2250/00—Layers arrangement
- B32B2250/20—All layers being fibrous or filamentary
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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
- 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
- B32—LAYERED PRODUCTS
- 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 application provides a carbon fiber/epoxy resin laminated board and a preparation method thereof, comprising the following steps: preparation of less layered Ti by HCl/LiF etching method 3 C 2 T x Dispersion of PVA solution and less lamellar Ti 3 C 2 T x Ti after mixing of the dispersion 3 C 2 T x Soaking the CF layer by the PVA mixed solution, and then carrying out freeze-thawing cycle to obtain a self-interlocking TPA/CF layer; and laying the self-interlocking TPA/CF layer and epoxy resin layer, and then placing the layered TPA/CF layer and the layered epoxy resin layer in a vulcanizing machine for hot pressing to obtain the carbon fiber/epoxy resin laminated board. Based on the self-interlocking MXene/PVA aerogel toughened CF/EP laminated plate, the three-dimensional framework of the aerogel is enabled to stitch the laminated plate into a whole under the condition of not damaging fiber arrangement and causing defects, and interlayer fracture toughness is comprehensively and remarkably enhanced without sacrificing other performances.
Description
Technical Field
The application 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, automobiles, sports goods, and the like due to their excellent specific strength, elastic modulus, fatigue resistance, and corrosion resistance. Although CFRPs are lighter weight and have better in-plane performance than conventional metal and ceramic materials, their relatively poor through-thickness performance is limited to CFRPs in engineering equipment due to the inherent brittleness of the epoxy matrix and poor interfacial interactions of the epoxy matrix with the carbon fibers. Interlayer 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 is of great importance for developing CFRP with high performance. The toughening methods commonly used at present are the design of 3D fabric structures, transverse stitching, modification of CF, toughening of resin matrix and the introduction of fiber insertion layers.
However, the conventional toughening method has a number of disadvantages. For example, 3D fabric structures and transverse stitching, while enhancing the through-thickness mechanical properties of CFRP, result in a decrease in the in-plane mechanical properties due to dislocation of the carbon fibers. By doping the nanophase, the polymer matrix can be reinforced, so that the thickness penetrating mechanical property of the CFRP is improved. However, incorporation of the nanoreinforcement phase reduces the flowability of the polymer matrix, making it difficult for CF to be fully infiltrated. Chemically modified CF can significantly improve the interfacial properties of CF with the polymer matrix, but can cause structural damage to CF resulting in reduced strength itself. The fibrous insert layer largely avoids the disadvantages of the above-described methods. However, the intercalation layer does not form a tight interlocking effect with the CF, which allows the interface failure to remain dominated by adhesion failure. In addition, the preparation of fibrous intercalation often requires the use of costly and toxic organic solvents.
Disclosure of Invention
In order to solve the problems in the prior art, in view of the great practical demands of 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 interlayer fracture toughness in the prior art, the application provides a novel preparation process.
The application solves the technical problems by adopting the following technical scheme:
the first object of the present application is to provide a method for preparing a carbon fiber/epoxy resin laminate, characterized by comprising the steps of:
preparation of less layered Ti by HCl/LiF etching method 3 C 2 T x Dispersion of PVA solution and less lamellar Ti 3 C 2 T x Ti after mixing of the dispersion 3 C 2 T x Soaking the CF layer by the PVA mixed solution, and then carrying out freeze-thawing cycle to obtain a self-interlocking TPA/CF layer; and laying the self-interlocking TPA/CF layer and epoxy resin layer, and then placing the layered TPA/CF layer and the layered epoxy resin layer in a vulcanizing machine for hot pressing to obtain the carbon fiber/epoxy resin laminated board.
Further, HCl/LiF etching method for preparing less layered Ti 3 C 2 T x The process of the dispersion liquid is as follows: ti is mixed with 3 AlC 2 Slowly adding the powder into LiF/HCl solution, mixing, centrifugally washing, adding deionized water, and performing ultrasonic treatment to obtain the few-layer Ti 3 C 2 T x And (3) a dispersion.
Further, liF was added to 12M HCl solution and magnetically stirred to obtain LiF/HCl solution, wherein the ratio of LiF to HCl solution is 2g: 70-90 ml.
Further, ti is as follows 3 AlC 2 Slowly adding the powder into LiF/HCl solution to obtain sediment, repeatedly washing with deionized water, centrifuging to neutral pH value to obtain multilayer Ti 3 C 2 T x And (3) depositing.
Further, multi-layer Ti 3 C 2 T x Washing sediment with absolute ethyl alcohol after electromagnetic stirring in DMSO solution, performing ultrasonic treatment in deionized water, and centrifuging to obtain the few-layer Ti 3 C 2 T x And (3) a dispersion.
Further, PVA is dissolved in deionized water under heating and stirring to obtain a uniformly viscous PVA solution, and then the PVA solution and less lamellar Ti are mixed 3 C 2 T x Mixing and stirring the dispersion liquid to obtain Ti 3 C 2 T x Mixed solution of PVA.
Further, the Ti is 3 C 2 T x The mass ratio of the modified polyvinyl alcohol to PVA is 4-12 wt%. Preferably, the Ti is 3 C 2 T x The mass ratio to PVA was 7.69wt%.
Further, the concentration of the PVA solution is 60 to 100mg/ml. Preferably, the PVA solution has a concentration of 60mg/ml.
Further, ti 3 C 2 T x After the CF layer is infiltrated by the PVA mixed solution, the infiltrated CF layer is placed in a vacuum drying oven for degassing treatment, then frozen, then thawed, and the TPA/CF layer with self-interlocking is obtained after repeated freezing-thawing cycle for 4 times. The self-interlocking TPA/CF layer is Ti 3 C 2 T x PVA aerogel coated CF layer due to the porous structure of the aerogel, the self-interlocking TPA/CF layer was subjected to a degassing treatment at 60 ℃ under vacuum prior to the laying process, thereby allowing the TPA to be completely impregnated with epoxy resin.
Further, the freezing condition is-20 ℃,8 hours, and the thawing time is 1 hour.
Further, the TPA/CF layer and the epoxy resin which are self-interlocking are laid in a one-way layered manner, and the laying layer number is 14-16.
Preferably, the TPA/CF layer which is self-interlocking and epoxy resin are laid in a one-way layer manner, and the laying layer number is 16.
Further, the epoxy resin comprises E51 and MDA, and the mass ratio of the E51 to the MDA is 100:13.6-26.7.
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 is as follows: hot-pressed at 120 ℃ for 17 hours and then post-cured at 180 ℃ for 2 hours.
The second object of the present application is to provide a carbon fiber/epoxy resin laminate prepared by the above method.
Compared with the prior art, the application has the beneficial technical effects that:
the application uses the three-dimensional framework of the self-interlocking TPA to stitch the CF/EP laminated board, 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 . No toxic organic solvent is added in the preparation process, and water is used as a solvent, so that the preparation method has the advantages of low cost and environmental protection.
In order to more conveniently and clearly describe the substance, composition and structure of the present application, a plurality of letters are used in the present application, and the expression of the letters is described herein. Wherein CF refers to carbon fiber, CF/EP refers to carbon fiber reinforced epoxy resin, ti 3 C 2 T x PVA means Ti 3 C 2 T x The TPA/CF layer is prepared by mixing with PVA to obtain a mixed solution, and the TPA/CF layer is prepared by passing through Ti 3 C 2 T x PVA aerogel coated and toughened CF layer, mxene refers to metal carbide with two-dimensional lamellar structure, G IC Init Refers to the initial fracture toughness between I-type layers, G IC Prop Refers to type I interlayer expansion fracture toughness, G IIC Refers to type II interlaminar fracture toughness.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
FIG. 1 shows a carbon fiber/epoxy resin laminate and Ti in the method of preparing the same 3 C 2 T x Is a preparation flow chart of (2);
FIG. 2 is a flow chart of the TPA/CF process in the carbon fiber/epoxy laminate and process for making the same according to the present application;
FIG. 3 is a schematic illustration of the preparation of a TPA/CF/EP laminate in a carbon fiber/epoxy resin laminate and a method of making the same in accordance with the present application;
FIG. 4 is a schematic diagram showing DCB test and ENF test in a carbon fiber/epoxy resin laminate and a method for manufacturing the same according to the present application;
FIG. 5 is a graph showing the comparison of toughening effects in a carbon fiber/epoxy resin laminate and a method for preparing the same according to the present application, (a) is CF/EP and has different Ti 3 C 2 T x G of TPA/CF/EP composite material IC Init And G IC Prop A histogram; (b) For CF/EP and with different Ti 3 C 2 T x Mass fraction G of TPA/CF/EP composite IIC A histogram;
FIG. 6 is a graph showing the comparison of toughening effects in a carbon fiber/epoxy resin laminate and a method for preparing the same according to the present application, (a) is CF/EP and G is a TPA/CF/EP composite material having 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 scheme of the application is further described in detail below with reference to the attached drawings and specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
In addition, unless otherwise specifically indicated, the various raw materials, reagents, instruments and equipment used in the present application may be obtained commercially or prepared by existing methods. The carbon fibers used in the present application are commercially available T300 unidirectional carbon fibers.
Example 1:
a preparation method of a carbon fiber/epoxy resin laminated board comprises the following steps:
first, referring to FIG. 1, a HCl/LiF etching process is used to prepare less layered Ti 3 C 2 T x A dispersion; the specific steps of the HCl/LiF etching method are as follows: 2g of LiF is dispersed and added into a polytetrafluoroethylene container filled with 80mL of 12M hydrochloric acid solution, and magnetic stirring is carried out for 30 minutes to obtain LiF/HCl solution; subsequently, 2g of Ti 3 AlC 2 The powder was slowly added to the LiF/HCl solutionAnd kept under magnetic stirring (3500 rpm) at 40℃for 36h; the sediment is repeatedly washed by deionized water and centrifuged until the PH value becomes neutral>6) Obtaining multi-layer Ti 3 C 2 T x And (3) depositing. Multilayer Ti 3 C 2 T x Placing the sediment in DMSO solution, electromagnetic stirring for 24h, washing with absolute ethanol for 3 times, performing ultrasonic treatment in deionized water for 6h, and centrifuging to obtain a few-layer Ti 3 C 2 T x And (3) a dispersion. The obtained Ti 3 C 2 T x Freeze-drying the dispersion to obtain dry Ti with few layers 3 C 2 T x The powder is ready for 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 3 hours to give a uniformly viscous PVA solution. The different masses (0.1 g, 0.3g, 0.5g, 0.7g, 0.9 g) of the reduced Ti fraction obtained in the first step were each treated by 1h of ultrasound 3 C 2 T x Dispersing the powder in 100mL deionized water to obtain Ti 3 C 2 T x And (3) a dispersion. Adding PVA solution to Ti 3 C 2 T x Stirring the dispersion for 30min to obtain Ti 3 C 2 T x Mixed solution of PVA. The purpose of this step is to change the initial Ti 3 C 2 T x The concentration of the dispersion to obtain different Ti 3 C 2 T x A TPA/CF layer in mass ratio to PVA;
third step, ti obtained in the second step is used 3 C 2 T x Impregnating CF fabric with PVA mixed solution, placing the impregnated CF in a vacuum drying oven for degassing treatment, then placing the impregnated CF in a refrigerator for freezing at the temperature of-20 ℃ for 8 hours, and then thawing at the room temperature for 1 hour, and repeating the freezing-thawing process for 4 times to obtain the self-interlocking TPA/CF composite material;
fourth, 16 unidirectional TPA/CF layers impregnated with epoxy resin were laid by hand. Due to the porous structure of the aerogel, the self-interlocking TPA/CF fabric is subjected to degassing in a vacuum environment at 60 ℃ before the layering process, so that the TPA is completely infiltrated by the epoxy resin;
fifth, referring to fig. 3, after the lay-up 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℃ while evacuated for 1 hour. Subsequently, the mixture was hot-pressed at 120℃for 17 hours and then post-cured at 180℃for 2 hours. A carbon fiber/epoxy resin laminate was obtained.
In the present embodiment, the first step is to reduce the amount of Ti 3 C 2 T x Lyophilizing the dispersion to obtain a small layer of Ti 3 C 2 T x After the powder, the powder is dispersed in deionized water to obtain a dispersion liquid in the second step, and the method directly obtains the Ti with a small layer in the first step 3 C 2 T x The carbon fiber/epoxy resin laminate obtained by directly mixing the dispersion with the PVA solution in the second step is identical. In this example, a further freeze-drying step was added to obtain accurate Ti 3 C 2 T x To PVA mass ratio, thereby accurately obtaining Ti 3 C 2 T x The effect of mass ratio to PVA on various properties of the carbon fiber/epoxy resin laminate does not represent the scope of the present application in which the powder must be obtained first and then dispersed to obtain a dispersion.
Referring to Table 1, different Ti are given 3 C 2 T x Naming of TPA/CF/EP samples in mass fraction, see FIG. 5, different Ti in Table 1 3 C 2 T x GIC Init, GIC Prop, and GIIC bar graphs of TPA/CF/EP samples and CF/EP samples. It can be seen that the type I interlayer initiation fracture toughness (G) of the self-interlocking TPA/CF/EP laminate compared to the CF/EP laminate IC Init ) Type I interlayer expansion fracture toughness (G) IC Prop ) And type II interlaminar fracture toughness (G) IIC ) Are all significantly improved, especially when the Ti is 3 C 2 T x At a mass ratio of 7.69wt% to PVA, G IC Init 、G IC Prop And G IIC The improvement of (2) is more obvious.
TABLE 1 different Ti 3 C 2 T x Naming of TPA/CF/EP samples in mass fraction
Example 2:
a preparation method of a carbon fiber/epoxy resin laminated board comprises the following steps:
first, HCl/LiF etching method is adopted to prepare less-layered Ti 3 C 2 T x A dispersion; the specific steps of the HCl/LiF etching method are as follows: 2g of LiF is dispersed and added into a polytetrafluoroethylene container filled with 80mL of 12M hydrochloric acid solution, and magnetic stirring is carried out 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 kept magnetically stirred (3500 rpm) at 40℃for 36h; the sediment is repeatedly washed by deionized water and centrifuged until the PH value becomes neutral>6) Obtaining multi-layer Ti 3 C 2 T x And (3) depositing. Multilayer Ti 3 C 2 T x Placing the sediment in DMSO solution, electromagnetic stirring for 24h, washing with absolute ethanol for 3 times, performing ultrasonic treatment in deionized water for 6h, and centrifuging to obtain a few-layer Ti 3 C 2 T x And (3) a dispersion. The obtained Ti 3 C 2 T x Freeze-drying the dispersion to obtain dry Ti with few layers 3 C 2 T x The powder is ready for use.
In the second step, PVA of different masses (6 g, 8g, 10 g) was dissolved in 100mL deionized water, heated to 90℃and stirred for 3h to give a homogeneous viscous PVA solution. Treatment of few-layer Ti by 1h ultrasound 3 C 2 T x Dispersing the powder in 100mL deionized water to obtain Ti 3 C 2 T x 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 the dispersion for 30min to obtain Ti 3 C 2 T x Mixed solution of PVA. The purpose of this step is to change the initial Ti 3 C 2 T x Of dispersionsConcentration of different Ti 3 C 2 T x A TPA/CF layer in mass ratio to PVA;
third step, ti obtained in the second step is used 3 C 2 T x Impregnating CF fabric with PVA mixed solution, placing the impregnated CF in a vacuum drying oven for degassing treatment, then placing the impregnated CF in a refrigerator for freezing at the temperature of-20 ℃ for 8 hours, and then thawing at the room temperature for 1 hour, and repeating the freezing-thawing process for 4 times to obtain the self-interlocking TPA/CF composite material;
fourth, 16 unidirectional TPA/CF layers impregnated with epoxy resin were laid by hand. Due to the porous structure of the aerogel, the self-interlocking TPA/CF fabric is subjected to degassing in a vacuum environment at 60 ℃ before the layering process, so that the TPA is completely infiltrated by the epoxy resin;
fifth, after the lay-up 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℃ while evacuated for 1 hour. Subsequently, the mixture was hot-pressed at 120℃for 17 hours and then post-cured at 180℃for 2 hours. A carbon fiber/epoxy resin laminate was obtained.
In the present embodiment, the first step is to reduce the amount of Ti 3 C 2 T x Lyophilizing the dispersion to obtain a small layer of Ti 3 C 2 T x After the powder, the powder is dispersed in deionized water to obtain a dispersion liquid in the second step, and the method directly obtains the Ti with a small layer in the first step 3 C 2 T x The carbon fiber/epoxy resin laminate obtained by directly mixing the dispersion with the PVA solution in the second step is identical. In this example, a further freeze-drying step was added to obtain accurate Ti 3 C 2 T x And PVA mass ratio, thereby avoiding influencing the influence of PVA mass change on various performances of the carbon fiber/epoxy resin laminated board, and not representing the protection scope of the application, the powder is obtained firstly and then dispersed to obtain the dispersion liquid.
Referring to Table 2, TPA +.Naming of CF/EP samples, see FIG. 6, GIC Init, G for TPA/CF/EP samples and CF/EP samples of different TPA areal densities in Table 2 IC Prop And G IIC Bar graph. It can be seen that in Ti 3 C 2 T x G of sample when TPA areal density was different while the mass ratio to PVA was kept at 7.69wt% IC Ini t、G IC Prop And G IIC Less impact when the area density of TPA is 27g/m 2 The sample has better G IC Ini t、G IC Prop And G IIC 。
TABLE 2 naming of TPA/CF/EP samples for different areal densities of TPA
Example 3:
referring to Table 3, ti was prepared by an electrospinning machine 3 C 2 T x PVA Nanofiber (TPN) intercalation based on the hot-pressing process of the present application, control CF/EP and TPN/CF/EP laminate samples were prepared. With Ti in inventive example 2 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 herein refer to type I interlayer initiation fracture toughness (G IC Init ) Type I interlayer expansion fracture toughness (G) IC Prop ) And type II interlaminar fracture toughness (G) IIC ) The detection results are shown in Table 3.
In the present application, the 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 samples by a high speed rotating serrated disc. DCB testing was performed on an Instron CMT5105 machine equipped with a 5KN load cell, with the crosshead speed kept at a constant 2mm/min. Referring to fig. 4, a schematic diagram of the DCB test is shown. Five specimens were tested for each group type of press fit. The calculation formula of GIC is:
where P is the breaking load (N), δ is the load point displacement (mm), b is the specimen width (mm), a is the delamination length (mm), and is derived from the formula a= (a0+Δa), where Δa is the crack propagation length.
ENF test standard measurement laminate G based on ESIS protocol IIC The laminate was cut into standard size ENF specimens by a high speed rotating saw tooth disc. The ENF test was performed on an Instron CMT5105 machine equipped with a 5KN load cell, with the crosshead speed kept at a constant 2mm/min. Fig. 4 shows a schematic diagram of the ENF test. Five specimens were tested for each group type of press fit. G IIC The calculation formula of (2) is as follows:
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), and is derived from the formula a= (a0+Δa), where Δa is the crack propagation length, and L is the half-span length (mm).
As can be seen from Table 3, the present application provides a laminate having type I interlayer initiation fracture toughness (G IC Init ) Type I interlayer expansion fracture toughness (G) IC Prop ) And type II interlaminar fracture toughness (G) IIC ) The improvement is 76%, 40% and 32%, respectively. This suggests that CF/EP laminates can fully and significantly improve interlaminar fracture toughness by interlocking TPA; the traditional TPN insertion layer toughening mode only improves G IIC ，G IC Init 、G IC Prop Instead, the toughening effect is incomplete due to the decrease. This is mainly due to: (1) cohesive failure by a TPA three-dimensional backbone interlocking mechanism; (2) deflection and distortion of the main crack; (3) a competing mechanism between the secondary crack and the primary crack; (4) generating a plurality of microcracks; (5) TPA framework and Ti 3 C 2 T x Is pulled out.The interlocking TPA toughening not only improves overall effectiveness of the G of the interlocking TPA/CF/EP laminate compared to conventional interleaf toughening IC Init 、G IC Prop And G IIC But also realizes low cost and green manufacturing.
TABLE 3 toughening comparison of the application with conventional laminates
| Sample type | 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, the toughening manner of the conventional nanofiber intercalating layer and the organic solvent added in the preparation are studied, and it is found that the preparation of various conventional nanofiber intercalating layers often requires expensive and toxic organic solvents, while the solvent adopted in the preparation process of the TPA aerogel of the present application 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 foregoing embodiment numbers of the present application are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
The embodiments of the present application have been described above with reference to the accompanying drawings, but the present application is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those having ordinary skill in the art without departing from the spirit of the present application and the scope of the claims, which are to be protected by the present application.
Claims (10)
1. The preparation method of the carbon fiber/epoxy resin laminated plate is characterized by comprising the following steps of:
preparation of less layered Ti by HCl/LiF etching method 3 C 2 T x Dispersion of PVA solution and less lamellar Ti 3 C 2 T x Ti after mixing of the dispersion 3 C 2 T x Soaking the CF layer by the PVA mixed solution, and then carrying out freeze-thawing cycle to obtain a self-interlocking TPA/CF layer; and laying the self-interlocking TPA/CF layer and epoxy resin layer, and then placing the layered TPA/CF layer and the layered epoxy resin layer in a vulcanizing machine for hot pressing to obtain the carbon fiber/epoxy resin laminated board.
2. The method for producing a carbon fiber/epoxy resin laminate as claimed in claim 1, wherein the HCl/LiF etching method is used for producing less layered Ti 3 C 2 T x The process of the dispersion liquid is as follows: ti is mixed with 3 AlC 2 Slowly adding the powder into LiF/HCl solution, mixing, centrifugally washing, adding deionized water, and performing ultrasonic treatment to obtain the less lamellar Ti 3 C 2 T x And (3) a dispersion.
3. The method for manufacturing a carbon fiber/epoxy resin laminate according to claim 1, wherein: dissolving PVA in deionized water under heating and stirring to obtain uniformly viscous PVA solution, and mixing PVA solution with less-lamellar Ti 3 C 2 T x Mixing and stirring the dispersion liquid to obtain Ti 3 C 2 T x Mixed solution of PVA.
4. A method for producing a carbon fiber/epoxy resin laminate as claimed in any one of claims 1 to 3, characterized in that: the Ti is 3 C 2 T x The mass ratio of the modified polyvinyl alcohol to PVA is 4-12 wt%.
5. The method for manufacturing a carbon fiber/epoxy resin laminate according to claim 1, wherein: ti (Ti) 3 C 2 T x After the CF layer is infiltrated by the PVA mixed solution, the infiltrated CF layer is placed in a vacuum drying oven for degassing treatment, then frozen, then thawed, and the TPA/CF layer with self-interlocking is obtained after repeated freezing-thawing cycle for 4 times.
6. The method for manufacturing a carbon fiber/epoxy resin laminate according to claim 5, wherein: the freezing condition is-20 ℃, the thawing time is 8 hours, and the thawing time is 1 hour.
7. The method for manufacturing a carbon fiber/epoxy resin laminate according to claim 1, wherein: the TPA/CF layer and the epoxy resin are laid in a unidirectional layered manner, and the laying layer number is 14-16.
8. The method for manufacturing a carbon fiber/epoxy resin laminate according to claim 1, wherein: and placing the paved product in a vacuum bag before hot pressing, placing the vacuum bag between heating templates of a vulcanizing machine, preheating at 60 ℃, and vacuumizing for 1 hour.
9. The method for manufacturing a carbon fiber/epoxy resin laminate according to claim 8, wherein: the hot pressing process comprises the following steps: hot-pressed at 120 ℃ for 17 hours and then post-cured 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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