CN112726208B - Wear-resistant waterproof composite carbon fiber cloth and preparation method thereof - Google Patents
Wear-resistant waterproof composite carbon fiber cloth and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/517—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond containing silicon-halogen bonds
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
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Abstract
The invention discloses a method for preparing wear-resistant waterproof composite carbon fiber cloth, which comprises the following steps: soaking the carbon fiber cloth in an epoxy resin acetone solution; then dipping the carbon fiber cloth in a modified single-layer zirconium phosphate nanosheet water suspension, washing and drying to obtain single-layer zirconium phosphate modified carbon fiber cloth; soaking the product in ethanol solution of octadecyl trichlorosilane, keeping the temperature for a certain time, washing and drying to obtain the product. In addition, a corresponding composite carbon fiber cloth is also disclosed. The composite carbon fiber cloth can provide both excellent wear resistance and excellent water resistance.
Description
Technical Field
The invention belongs to the technical field of fiber materials; relates to carbon fiber cloth and a preparation method thereof, in particular to wear-resistant waterproof composite carbon fiber cloth and a preparation method thereof.
Background
The carbon fiber mainly consists of carbon elements, is similar to common carbon materials, and has good electrical conductivity, thermal conductivity, high temperature resistance and corrosion resistance; and the carbon fiber shows good anisotropy and has higher mechanical strength in the fiber axial direction. Thus, carbon fibers are often composited with substrates such as metals, polymers, ceramics, and cements to produce composites with superior overall properties. Similarly, carbon fiber composites are increasingly used in military and civil applications such as aviation, aerospace, missiles, airplanes, transportation, construction, and engineering.
In practical application, carbon fibers are usually woven into a cloth shape, which is called a fibrous fabric material, also called carbon fiber cloth, carbon fiber tape, carbon fiber cloth and the like, and the carbon fiber fabric material has the characteristics of ultralight weight, softness and tensile resistance in the processing process besides the advantages of the carbon fibers, is suitable for the surfaces of various members in the current industrial application, can wrap the members with complex shapes, has flat fabric coverage and long storage life, and has the characteristics of creep resistance, good corrosion resistance and good seismic resistance under the action of permanent load, so that the carbon fiber fabric material is widely popularized in the aspects of seismic resistance, repair, reinforcement and the like of civil construction, bridges, tunnels and concrete structures; in addition, the chemical corrosion resistance of the fabric can be repeatedly utilized, so that the environment-friendly requirement is met.
However, the carbon fiber is subjected to high-temperature treatment in the graphitization process, so that the surface of the carbon fiber is inert, the interface bonding effect is large when the carbon fiber is compounded with other materials, the comprehensive performance of the carbon fiber resin matrix composite material is finally influenced, and the exertion of the excellent material performance of the carbon fiber is greatly inhibited. Among them, the outstanding contradiction is that the wear resistance and the water resistance of the carbon fiber cloth are difficult to be obtained at the same time.
Mianzhaolong chemical company Limited discloses a method for modifying the surface of carbon fiber cloth by using zirconium phosphate, wherein zirconium phosphate slurry is coated on the carbon fiber cloth, and then the carbon fiber cloth is punctured and heated for heat preservation; then dipping, crosslinking and curing. Finally, the fiber-reinforced zirconium phosphate high-temperature resistant composite material is obtained. The carbon fiber reinforced zirconium phosphate-based composite material obtained by the method has the advantages of high temperature resistance, friction resistance and the like. Although the composite material improves the wear resistance of the carbon fiber cloth, the composite material has poor waterproofness and is difficult to be applied to the field with high waterproofness.
Tankanning et al (Guangdong chemical engineering, 2017, volume 44, phase 2, page 24) studied the behavior of a mixed suspension of zirconium phosphate/silica microspheres in a dish form. The article uses a hydrothermal reaction method to prepare zirconium phosphate disk, and then uses an intercalation stripping method to obtain a single-layer zirconium phosphate disk. Studies have shown that the presence of silica microspheres in a ball-and-dish mixed suspension affects the phase behavior in zirconium phosphate suspension systems due to the creation of vacancy attraction between particles when particles of different shapes and sizes are present in the colloidal system. However, the above article does not focus on the further use of zirconium phosphate.
Therefore, there is an urgent need to develop a composite carbon fiber cloth that can provide both excellent wear resistance and excellent water resistance, and a method for preparing the same, in view of the above technical disadvantages of the carbon fiber cloth.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a wear-resistant waterproof carbon fiber cloth and a preparation method thereof.
In one aspect, the invention provides a method for preparing wear-resistant waterproof composite carbon fiber cloth, which comprises the following steps:
soaking the carbon fiber cloth in an epoxy resin acetone solution;
then dipping the carbon fiber cloth in a modified single-layer zirconium phosphate nanosheet water suspension, washing and drying to obtain single-layer zirconium phosphate modified carbon fiber cloth;
soaking the product in ethanol solution of octadecyl trichlorosilane, keeping the temperature for a certain time, washing and drying to obtain the product.
The method of the invention, wherein the carbon fiber cloth is selected from surface-etched carbon fiber cloth.
The method of the present invention, wherein the surface etching conditions are: heating in 5-15 wt% nitric acid solution at 80-100 deg.C for 10-60 min.
Preferably, the surface etching conditions are: heating in 6-14 wt% nitric acid solution at 82-98 deg.C for 15-55 min; more preferably, the surface etching conditions are: heating in 7-13 wt% nitric acid solution at 85-95 deg.C for 20-50 min; and, most preferably, the surface etching conditions are: heating in 8-12 wt% nitric acid solution at 88-92 deg.C for 25-45 min.
In a specific embodiment, the surface etching conditions are: heating at 90 deg.C for 30min in 10 wt% nitric acid solution.
In the present invention, the untreated raw carbon fiber cloth may be a commercially available two-way plain-woven carbon fiber cloth; or woven from commercially available carbon fibers into a two-way plain-woven carbon fiber cloth.
The method according to the invention, wherein the untreated raw carbon fiber cloth has a thickness of 1 to 5 mm.
In one specific embodiment, the untreated virgin carbon fiber cloth is from NJMKT300 carbon fiber cloth available from south China sea carbon fiber high tech., Inc. with a thickness of 3 mm.
The method according to the present invention, wherein the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol glycidyl ether type epoxy resin, aliphatic glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, epoxidized olefin compound type epoxy resin, and heterocyclic type and mixed type epoxy resin.
Preferably, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol glycidyl ether type epoxy resin, aliphatic glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine type epoxy resin; more preferably, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol glycidyl ether type epoxy resin, and aliphatic glycidyl ether type epoxy resin; and, most preferably, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin.
In a particular embodiment, the epoxy resin is selected from bisphenol a type epoxy resins.
The method according to the present invention, wherein the epoxy resin has an average epoxy value of 0.40 to 0.60.
Preferably, the epoxy resin has an average epoxy value of 0.42 to 0.58; more preferably, the epoxy resin has an average epoxy value of 0.45 to 0.55; and, most preferably, the epoxy resin has an average epoxy value of 0.48 to 0.53.
In a specific embodiment, the epoxy resin has an average epoxy value of 0.51.
In a more specific embodiment, the epoxy resin is selected from the group consisting of E51 epoxy resins.
The method of the invention, wherein the concentration of the epoxy resin acetone solution is 1-5 w/v%.
Preferably, the concentration of the epoxy resin acetone solution is 1.5-4.5 w/v%; more preferably, the concentration of the epoxy resin acetone solution is 2-4 w/v%; and, most preferably, the concentration of the epoxy resin acetone solution is 2.5-3.5 w/v%.
In a specific embodiment, the concentration of the epoxy resin acetone solution is 3 w/v%.
Advantageously, the carbon fiber cloth is soaked in an epoxy resin acetone solution for 15-60 min; preferably 20-40 min.
The method provided by the invention is characterized in that the single-layer zirconium phosphate nanosheets are obtained by subjecting zirconium phosphate nanosheets to tetrabutyl ammonium hydroxide intercalation and exfoliation.
In the invention, the zirconium phosphate nanosheet is obtained by a hydrothermal reaction method. Hydrothermal reaction and intercalation and exfoliation are well known to those skilled in the art, for example as described in the aforementioned references by Tan Corning et al. The surface of the finally obtained single-layer zirconium phosphate nano-sheet is provided with negative charge groups such as hydroxyl groups.
In a specific embodiment, the Zeta potential of the single-layer zirconium phosphate nanosheet is-38.4 mV, the average particle diameter of the nanosheet is 1.42 μm as determined by dynamic optical scattering, and the dispersity PDI is 0.034.
The method of the invention, wherein the modified monolayer zirconium phosphate nanosheets are obtained from reaction of the monolayer zirconium phosphate nanosheets with a hydrolysate of gamma-aminopropyltriethoxysilane.
Without wishing to be bound by any theory, the reaction principle of the two is mainly that negative charge groups such as hydroxyl groups on the surface of the single-layer zirconium phosphate nanosheet and three hydroxyl groups in the hydrolysate of the gamma-aminopropyltriethoxysilane form corresponding covalent bonds or ionic bonds through the bonding action of hydrogen bonds or electrostatic attraction action; on the other hand, the surface distal end of the modified monolayer zirconium phosphate nanosheet forms a propylamino group.
The method according to the invention, wherein the concentration of the aqueous suspension of modified single-layer zirconium phosphate nanoplates is between 0.2 and 0.8 wt%; preferably 0.3 to 0.7 wt%; more preferably 0.4 to 0.6 wt%.
In a particular embodiment, the aqueous suspension of modified monolayer zirconium phosphate nanoplates has a concentration of 0.5 wt%.
Advantageously, the epoxy resin impregnated carbon fiber cloth is then dipped in the aqueous suspension of the modified single-layer zirconium phosphate nanosheets for 30-120 min; preferably 45-90 min.
Without wishing to be bound by any theory, in this step, the propylamine groups on the surface of the modified monolayer zirconium phosphate nanosheets act as a curing agent, so that the epoxy resin of the carbon fiber cloth is cured, thereby forming a firm chemical bond and enhancing the anchoring effect between the zirconium phosphate and the carbon fiber cloth.
The method of the invention, wherein the volume percentage concentration of the octadecyl trichlorosilane ethanol solution is 0.5-4%; preferably 1-3 wt%.
In a specific embodiment, the ethanol solution of octadecyltrichlorosilane is prepared by mixing 100mL of absolute ethanol, 2mL of octadecyltrichlorosilane, 0.25mL of deionized water and 0.05mL of glacial acetic acid.
The method of the invention, wherein the incubation conditions are: keeping the temperature at 40-80 ℃ for 1-5 h; preferably, the temperature is kept at 50-70 ℃ for 1.5-3 h.
In one specific embodiment, the incubation conditions are: keeping the temperature at 60 ℃ for 2 h.
On the other hand, the invention also provides the wear-resistant waterproof composite carbon fiber cloth prepared by the method.
The inventors found that the resulting composite carbon fiber cloth can provide both excellent abrasion resistance and excellent water repellency by two impregnation steps and one hydrophobic modification step. Both of the above properties are simultaneously achieved mainly by the covalent bond or the ionic bond formed in the above step. In other words, the synergy between the reagents used in these steps and the steps themselves serves an unexpected technical effect.
The materials, compounds, compositions, and components described herein can be used in, or in combination with, the methods and compositions described herein, or can be used in the practice of the methods and in the preparation of the compositions, or as products from the methods. It is to be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each and every collective combination and permutation of these compounds may not be explicitly made, each is specifically contemplated and described herein. For example, if an extraction aid component is disclosed and discussed, and a number of alternative solid state forms of that component are discussed, each and every combination and permutation of the possible aid component and solid state forms are specifically contemplated unless specifically indicated to the contrary. This concept applies to all aspects of the invention including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a plurality of additional steps that can be performed it is understood that each of these additional steps can be performed by any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:
it must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include both one and more than one (i.e., two, including two) unless the context clearly dictates otherwise.
Unless otherwise indicated, the numerical ranges in this disclosure are approximate and thus may include values outside of the stated ranges. The numerical ranges may be stated herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the numerical ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
Reference in the specification and concluding claims to parts by weight of a particular element or component in a composition or article refers to the weight relationship between that element or component and any other elements or components in the composition or article, expressed as parts by weight.
Unless specifically indicated to the contrary, or implied by the context or customary practice in the art, all parts and percentages referred to herein are by weight and the weight percentages of a component are based on the total weight of the composition or product in which it is included.
References to "comprising," "including," "having," and similar terms in this specification are not intended to exclude the presence of any optional components, steps or procedures, whether or not any optional components, steps or procedures are specifically disclosed. In order to avoid any doubt, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials unless stated to the contrary. In contrast, the term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited. Unless otherwise specified, the term "or" refers to the listed members individually as well as in any combination.
Furthermore, the contents of any referenced patent or non-patent document in this application are incorporated by reference in their entirety, especially with respect to definitions disclosed in the art (where not inconsistent with any definitions specifically provided herein) and general knowledge.
Drawings
FIGS. 1a and 1b are SEM photographs and partial enlarged views of untreated carbon fiber cloth;
FIGS. 1c and 1d are SEM and partial enlarged views of the modified carbon fiber cloth of example 1;
FIGS. 2a and 2b are photomicrographs of the carbon fiber cloth of example 1 before and after the contact angle test, respectively.
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods described and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for.
Unless otherwise indicated, parts are parts by weight, temperatures are in degrees celsius or at ambient temperature, and pressures are at or near atmospheric. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Example 1
1.1 preparation of zirconium phosphate nanosheets
6g of ZrOCl 2 ·8H 2 And (3) placing the O powder into a hydrothermal reaction kettle, slowly dripping 30mL of 85 wt% concentrated phosphoric acid, uniformly stirring, sealing, and reacting at 200 ℃ for 24 hours. Cooling to room temperature, taking out the product, and washing the product with deionized water for multiple times until the pH value is more than or equal to 6; drying and crushing to obtain the zirconium phosphate nanosheet.
1.2 preparation of Single-layer zirconium phosphate nanosheets
Adding 4g of zirconium phosphate nanosheet into 30mL of deionized water, and ultrasonically dispersing uniformly; and then adding 20mL of 40 wt% tetrabutylammonium hydroxide solution, adding a proper amount of deionized water for dilution, performing ultrasonic treatment for 1h at room temperature, standing for 48h, and removing supernatant and a small amount of precipitate at the bottom to obtain a single-layer zirconium phosphate nanosheet suspension. The Zeta potential is-38.4 mV, the average grain diameter of the nano sheet is 1.42 μm measured by dynamic optical scattering method, and the dispersity PDI is 0.034. The single-layer zirconium phosphate nanosheet solid was isolated using a high speed centrifuge and dried to constant weight, weighing 2.6 g.
1.3 preparation of modified Single-layer zirconium phosphate nanosheets
Dispersing 2g of monolayer zirconium phosphate nanosheet solid powder into 50mL of anhydrous ethanol, and then dropwise adding a hydrolysate of gamma-aminopropyltriethoxysilane at 60 ℃, the latter being prepared according to the following method: 3mL of gamma-aminopropyltriethoxysilane was added to 20mL of a 4: 1 by volume ethanol solution and hydrolyzed for 1h with stirring at 1400rpm to give a hydrolyzate. And (3) continuing stirring for 6h after the dropwise addition is finished, then performing centrifugal separation and vacuum drying for 10h at the temperature of 60 ℃ to obtain the modified single-layer zirconium phosphate nanosheet.
1.4 etching surface of carbon fiber cloth
Removing impurities from carbon fiber cloth with the thickness of 3mm by using deionized water and absolute ethyl alcohol, and drying at 70 ℃; then soaked in 10 wt% nitric acid solution and heated at 90 deg.C for 30 min. And repeatedly washing with deionized water until the pH value is more than or equal to 6, and drying at 70 ℃ to obtain the carbon fiber cloth with the etched surface.
1.5 surface modification of carbon fiber cloth
Soaking the carbon fiber cloth of 1.4 in a 3% (w/v) E51 epoxy resin acetone solution for 30min, then soaking the carbon fiber cloth in a 0.5 wt% modified monolayer zirconium phosphate nanosheet water suspension for 1h, then repeatedly washing the carbon fiber cloth with deionized water until the pH value is more than or equal to 6, and drying the carbon fiber cloth at 70 ℃ for 12h to obtain the monolayer zirconium phosphate surface modified carbon fiber cloth. And then, soaking the single-layer zirconium phosphate surface-modified carbon fiber cloth in an octadecyl trichlorosilane ethanol solution, and keeping the temperature at 60 ℃ for 2 hours. And finally, removing excessive octadecyl trichlorosilane by using absolute ethyl alcohol, repeatedly washing by using deionized water, and drying in vacuum to obtain the hydrophobic surface modified carbon fiber cloth. The octadecyl trichlorosilane ethanol solution is prepared by mixing 100mL of absolute ethanol, 2mL of octadecyl trichlorosilane, 0.25mL of deionized water and 0.05mL of glacial acetic acid.
Comparative example 1
The same carbon fiber cloth as in example 1 was placed in a vacuum furnace, heated to 300 ℃ in an argon atmosphere, held at room temperature for 2 hours, and taken out to be used.
Firstly, the zirconium phosphate powder is prepared into slurry by water, and the concentration of the zirconium phosphate in the slurry is 35 wt%. Coating the slurry on carbon fiber cloth, wherein the thickness of the coating is 5 mu m), laminating the coated carbon fiber cloth, performing puncture operation, heating to 550 ℃, and preserving heat for 3 h; then sucking 20 wt% phosphoric acid solution in vacuum until the fabric is submerged, and soaking for 1 h; taking out, heating to 600 ℃, and preserving heat for 2h to crosslink and cure materials in the fabric; then placing the mixture into a high-temperature furnace, heating the mixture to 900 ℃ in a nitrogen atmosphere, preserving the heat for 2 hours, and cooling the mixture to room temperature to obtain the product.
Comparative example 2
The same as example 1, but omitting step 1.3, the monolayer zirconium phosphate nanoplates of the previous step 1.2 were used directly.
Comparative example 3
The same procedure as in example 1, except that step 1.4 was omitted, was followed by using untreated carbon fiber cloth.
The surface morphology of the carbon fiber cloth in different steps of example 1 was observed by using a Hitachi SU3500 scanning electron microscope.
The tribological properties of the carbon fiber cloths of example 1 and comparative examples 1 to 3 were measured at room temperature and without lubrication using a T2000 universal friction wear tester. The test conditions were: the applied load was 3MPa, and the sliding speed was 0.5 m/s. After 6 ten thousand rubs. The wear rate Wr is calculated according to the following formula:
wherein, the delta m is the weight loss of the sample; rho is the density of the carbon fiber cloth; f N To apply a load; and L is the pin sliding distance.
The initial contact angles of the surfaces of the carbon fiber cloths of example 1 and comparative examples 1 to 3 were first measured using a Biolin optical contact angle measuring instrument. The measurement was performed at room temperature, a water droplet was dropped on the surface of the carbon fiber cloth, contact angles were extracted from five different positions of the surface of the carbon fiber cloth, and an average value was taken. The final contact angles of the carbon fiber cloths of example 1 and comparative examples 1 to 3 were measured again after the tribological property test.
The results are shown in Table 1.
TABLE 1
The results show that the surface-modified carbon fiber cloths of examples of the present invention have not only excellent water repellency (contact angle greater than 150 °) but also excellent abrasion resistance (abrasion rate less than 1 × 10) as compared to comparative examples 1 to 3 -13 m 3 /N·m)。
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (8)
1. A method for preparing wear-resistant waterproof composite carbon fiber cloth, which comprises the following steps:
soaking the carbon fiber cloth in an epoxy resin acetone solution; wherein the epoxy resin has an average epoxy value of 0.40 to 0.60; the concentration of the epoxy resin acetone solution is 1-5 w/v%;
then soaking the carbon fiber cloth in the modified single-layer zirconium phosphate nanosheet water suspension, and washing and drying the carbon fiber cloth to obtain single-layer zirconium phosphate modified carbon fiber cloth; the modified single-layer zirconium phosphate nanosheet is obtained by reacting the single-layer zirconium phosphate nanosheet with a hydrolysis product of gamma-aminopropyltriethoxysilane; the concentration of the modified single-layer zirconium phosphate nanosheet aqueous suspension is 0.2-0.8 wt%;
soaking the product in an ethanol solution of octadecyl trichlorosilane, preserving heat for a certain time, washing and drying to obtain a product; wherein the volume percentage concentration of the octadecyl trichlorosilane ethanol solution is 0.5-4%; the heat preservation conditions are as follows: keeping the temperature at 40-80 ℃ for 1-5 h.
2. The method of claim 1, wherein the carbon fiber cloth is selected from surface etched carbon fiber cloth.
3. The method of claim 2, wherein the surface etching conditions are: heating in 5-15 wt% nitric acid solution at 80-100 deg.C for 10-60 min.
4. The method of claim 1, wherein the aqueous suspension of modified monolayer zirconium phosphate nanoplates has a concentration of 0.3-0.7 wt%.
5. The method of claim 4, wherein the aqueous suspension of modified monolayer zirconium phosphate nanoplates has a concentration of 0.4-0.6 wt%.
6. The method of claim 1, wherein the octadecyl trichlorosilane ethanol solution is at a concentration of 1-3% by volume.
7. The method of claim 1, wherein the incubation conditions are: keeping the temperature at 50-70 ℃ for 1.5-3 h.
8. A wear-resistant waterproof composite carbon fiber cloth, characterized by being prepared by the method according to any one of claims 1 to 7.
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| CN104212314A (en) * | 2014-09-26 | 2014-12-17 | 河南科技大学 | Abrasion-resisting epoxy resin/carbon fiber composite coating and preparation and coating method thereof |
| WO2016117422A1 (en) * | 2015-01-21 | 2016-07-28 | 東レ株式会社 | Sizing agent-coated carbon fiber bundle, method for manufacturing same, prepreg, and carbon fiber-reinforced composite material |
| CN107163245A (en) * | 2017-06-06 | 2017-09-15 | 湖南工业大学 | A kind of organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials and preparation method thereof |
| CN108485058A (en) * | 2018-03-02 | 2018-09-04 | 华南理工大学 | A kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212314A (en) * | 2014-09-26 | 2014-12-17 | 河南科技大学 | Abrasion-resisting epoxy resin/carbon fiber composite coating and preparation and coating method thereof |
| WO2016117422A1 (en) * | 2015-01-21 | 2016-07-28 | 東レ株式会社 | Sizing agent-coated carbon fiber bundle, method for manufacturing same, prepreg, and carbon fiber-reinforced composite material |
| CN107163245A (en) * | 2017-06-06 | 2017-09-15 | 湖南工业大学 | A kind of organically-modified basic zirconium phosphate of nanometer/MC nylon composite materials and preparation method thereof |
| CN108485058A (en) * | 2018-03-02 | 2018-09-04 | 华南理工大学 | A kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable |
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