CN108439457B - Method for preparing zinc oxide nanorod/carbon cloth friction material by hydrothermal electrophoresis method - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000004744 fabric Substances 0.000 title claims abstract description 146
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 144
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 53
- 238000001962 electrophoresis Methods 0.000 title claims abstract description 49
- 239000002073 nanorod Substances 0.000 title claims abstract description 40
- 239000002783 friction material Substances 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000013078 crystal Substances 0.000 claims abstract description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001993 dienes Chemical class 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 35
- 239000011701 zinc Substances 0.000 claims description 35
- 229910052725 zinc Inorganic materials 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 abstract description 8
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 238000004513 sizing Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 125
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 238000007731 hot pressing Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 14
- 238000010790 dilution Methods 0.000 description 14
- 239000012895 dilution Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 229920000049 Carbon (fiber) Polymers 0.000 description 12
- 239000004917 carbon fiber Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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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
- 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
- D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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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
- 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
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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- 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
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
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Abstract
The invention discloses a method for preparing a zinc oxide nanorod/carbon cloth friction material by a hydrothermal electrophoresis method, which comprises the steps of firstly ultrasonically treating carbon cloth by ethanol to remove impurities on the surface of the carbon cloth, then cleaning the carbon cloth by acetone by a Soxhlet extraction method to remove organic matters and sizing agents on the surface of the carbon cloth, further synthesizing diene to graft oxygen-containing functional groups on the surface of the carbon cloth without damage, then inoculating a layer of zinc oxide seed crystal layer on the surface of the carbon cloth, uniformly growing ZnO nanorods on the surface of the carbon cloth by the hydrothermal electrophoresis method, carrying out vacuum impregnation on the treated carbon cloth by a modified phenolic resin solution, and finally carrying out hot press molding. The invention adopts a hydrothermal electrophoresis method to quickly grow the zinc oxide nano-rod on the carbon cloth and construct a multi-scale reinforcement to improve the performance of the friction material.
Description
Technical Field
The invention belongs to the field of friction materials, and particularly relates to a method for preparing a zinc oxide nanorod/carbon cloth friction material by a hydrothermal electrophoresis method.
Background
With the development of high-speed and heavy-load directions of high-technology equipment, rail transit and vehicles, strict requirements are put forward on the safety and stability of a wet-type transmission/braking system. As an important component of a wet type transmission/braking system, a wet type friction material mainly plays a role of generating torque and transmitting load, and directly determines the safety and stability of the transmission/braking system. The carbon cloth reinforced resin-based friction material is widely applied to engineering friction materials due to the excellent performances of low density, high specific strength, fatigue resistance, strong designability and the like. However, the carbon fiber and resin have poor wettability, and the friction stability and the service life of the material are severely limited by resin debonding at the interface. Based on the method, the surface of the carbon cloth fiber is modified, so that the interface bonding strength between the carbon cloth fiber and the resin matrix is enhanced, and the application of the carbon cloth fiber in the friction field is further expanded.
The invention adopts hydrothermal electrophoresis technology to grow ZnO nano-rods on the surface of the carbon cloth, forms rich network branch structures and improves the performance vertical to the axial direction of the fiber. The process integrates the advantages of a hydrothermal growth method and an electrochemical deposition method, has low growth temperature, is quick and efficient, can obtain ZnO nanorods with uniform appearance and moderate length-diameter ratio, and provides a new idea for constructing multi-scale reinforcements.
Disclosure of Invention
The invention aims to provide a method for preparing a zinc oxide nanorod/carbon cloth friction material by a hydrothermal electrophoresis method, which overcomes the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a zinc oxide nanorod/carbon cloth friction material by a hydrothermal electrophoresis method comprises the following steps:
the method comprises the following steps: after the carbon cloth is treated by ethanol ultrasound, the carbon cloth is cleaned;
step two: methacrylic acid is used as a grafting monomer, and diene synthesis is adopted to graft oxygen-containing functional groups on the surface of the cleaned carbon cloth without damage;
step three: respectively dissolving zinc acetate dihydrate and sodium hydroxide in ethanol solution, uniformly stirring to respectively obtain zinc acetate dihydrate solution and sodium hydroxide solution, respectively marking as solution B and solution C, adding ethanol solution into solution B to dilute to obtain solution D, adding ethanol solution into solution C to dilute to obtain solution E, dropwise adding solution E into solution D, stirring and standing to obtain zinc source seed crystal layer sol;
step four: dipping the carbon cloth obtained in the step two in the zinc source crystal seed layer sol, then drying, and repeating dipping and drying for a plurality of times to obtain the carbon cloth with the crystal seed layer on the surface;
step five: mixing a zinc source and an alkali source in a ratio of 1: 1, mixing and adding the mixture into ultrapure water to obtain a growth solution;
step six: placing the carbon cloth with the surface containing the seed crystal layer in a growth solution, and growing a ZnO nano rod on the surface of the carbon cloth by adopting a hydrothermal electrophoresis method;
step seven: and (3) dipping the surface of the carbon cloth obtained in the step six with modified phenolic resin by adopting a vacuum pressure dipping method, drying, and finally performing hot press molding to obtain the zinc oxide nanorod/carbon cloth friction material.
Further, the cleaning in the step one is specifically as follows: washing the carbon cloth after ultrasonic treatment with deionized water for 3-5 times, extracting the washed carbon cloth with acetone solution at 60-80 deg.C for 2-3 hr by Soxhlet extraction method, and washing with deionized water for 10 min.
Further, in the third step, zinc acetate dihydrate and sodium hydroxide are respectively dissolved in ethanol solution, the zinc acetate dihydrate solution with the molar concentration of 0.0125mol/L and the sodium hydroxide solution with the molar concentration of 0.025mol/L are respectively obtained by stirring uniformly, the solution B and the solution C are respectively marked as solution B, the ethanol solution is added into the solution B for dilution to obtain solution D with the concentration of 0.0014mol/L, and the ethanol solution is added into the solution C for dilution to obtain solution E with the concentration of 0.0071 mol/L.
Further, in the fourth step, the dipping time is 15-30min, the drying temperature is 100-150 ℃, and the dipping and the drying are repeated for 3-5 times.
Further, in the fifth step, the zinc source is zinc nitrate hexahydrate; the alkali source is hexamethylenetetramine, ammonium fluoride or ammonium chloride.
Furthermore, the molar concentration of the zinc source in the growth solution obtained in the fifth step is 0.025 mol/L.
Further, in the step six, the hydrothermal electrophoresis method uses a graphite plate as an anode and carbon cloth as a cathode, the electrophoresis time is 15-60min, the electrophoresis current is 0.15-0.2A, and the voltage is 0.3-0.35V.
And furthermore, the mass fraction of the modified phenolic resin after impregnation in the seventh step is 30-40%.
Further, in the seventh step, the drying temperature is room temperature, and the drying time is 24 hours.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a hydrothermal electrophoresis method to quickly grow the zinc oxide nano-rod on the carbon cloth and construct a multi-scale reinforcement to improve the performance of the friction material. Firstly, methacrylic acid is adopted to activate the carbon cloth, so that active functional groups are added on the surface of the carbon cloth under the condition of not damaging the fiber strength, the process is simple, the requirement on equipment is low and the like, secondly, a zinc oxide crystal seed layer is inoculated on the surface of the carbon cloth, a buffer transition layer is provided for growing zinc oxide nano rods on the surface of the carbon cloth, the foundation is laid for growing zinc oxide on the surface of the carbon cloth in the later period, the interface adhesion between the carbon cloth and resin is enhanced, then the zinc oxide nano rods are grown on the surface of the carbon cloth, a nano pinning layer is formed, all the layers are fully exerted, the gradient transition of composition and structure is formed between the two layers, the high-strength bonding of the pinning layer and the buffer layer is ensured, the synergistic effect of chemical bonding and mechanical meshing of all the layers is fully exerted, and the strength, toughness and friction stability.
Drawings
FIG. 1 is a schematic diagram of a hydrothermal electrophoresis method for growing zinc oxide nanorods on the surface of carbon cloth;
FIG. 2 is a SEM photograph of unmodified carbon fiber and hydrothermal electrophoresis grown zinc oxide nano rod/carbon cloth, wherein (a) shows the micro morphology of the surface of the carbon fiber without treatment, and (b) shows the micro morphology of the grown zinc oxide nano rod/carbon cloth;
FIG. 3 is a graph showing the kinetic friction coefficient of an untreated carbon cloth and a carbon cloth after hydrothermal electrophoretic growth, in which CP-1 represents the untreated carbon cloth and CP-2 represents the carbon cloth after hydrothermal electrophoretic growth.
Detailed Description
Embodiments of the invention are described in further detail below:
a method for preparing a zinc oxide nanorod/carbon cloth friction material by a hydrothermal electrophoresis method comprises the following steps:
1) firstly cutting a carbon cloth into a 5 multiplied by 8 rectangle, locking edges at the periphery, ultrasonically treating the carbon cloth locked edges in ethanol for 24 hours, taking out the carbon cloth, washing the carbon cloth with deionized water for 3 to 5 times, then extracting the cleaned carbon cloth with acetone solution by a Soxhlet extraction method at 60 to 80 ℃ for 2 to 3 hours, and washing with the deionized water for 10 minutes;
2) methacrylic acid is used as a grafting monomer, and diene is adopted to synthesize the oxygen-containing functional group on the surface of the carbon cloth without damage.
3) Respectively dissolving zinc acetate dihydrate and sodium hydroxide in an ethanol solution, uniformly stirring to obtain a zinc acetate dihydrate solution (marked as solution B) with the molar concentration of 0.0125mol/L and a sodium hydroxide solution (marked as solution C) with the molar concentration of 0.025mol/L, adding the ethanol solution into the solution B for dilution to obtain a solution D with the concentration of 0.0014mol/L, adding the ethanol solution into the solution C for dilution to obtain a solution E with the concentration of 0.0071mol/L, slowly dropwise adding the solution E into the solution D, stirring and standing to obtain a zinc source seed crystal layer sol;
4) soaking the carbon cloth in the zinc source seed crystal layer sol for 15-30min, drying at 100-150 ℃, and repeating for 3-5 times to obtain the carbon cloth with the seed crystal layer on the surface;
5) mixing a zinc source and an alkali source in a ratio of 1: 1, mixing and adding the mixture into ultrapure water to obtain a growth solution, wherein a zinc source is zinc nitrate hexahydrate; the alkali source is hexamethylenetetramine, ammonium fluoride or ammonium chloride, and the molar concentration of the zinc source in the growth liquid is 0.025 mol/L.
6) And (3) placing the carbon cloth with the surface containing the seed crystal layer in a growth solution, and growing a ZnO nanorod on the surface of the carbon cloth by adopting a hydrothermal electrophoresis method, wherein the graphite plate is used as an anode, and the carbon cloth is used as a cathode. The electrophoresis time is 15-60min, the electrophoresis current is 0.15-0.2A, and the voltage is 0.3-0.35V.
7) And (3) impregnating the surface of the carbon cloth obtained in the step 6) with modified phenolic resin by adopting a vacuum pressure impregnation method, so that the resin accounts for 30-40% of the weight of the composite material, drying the carbon cloth at room temperature for 24 hours, and then carrying out hot pressing on the carbon cloth in a vulcanizing machine to obtain the zinc oxide nanorod/carbon cloth friction material.
According to the invention, a hydrothermal electrophoresis method is adopted to grow the zinc oxide nano rod on the surface of the carbon fiber, a hydrothermal synthesis technology is taken as a basis, an electrophoresis deposition technology is coupled, the characteristics of hydrothermal supercritical high-pressure environment and high efficiency of an electric field are fully utilized, crystal nuclei with charged surfaces are directionally deposited on the surface of the carbon fiber, then zinc oxide is efficiently and uniformly grown in situ on the surface, the zinc oxide is used as bridging between the fiber and resin, the chemical bonding and mechanical meshing effects of the zinc oxide effectively enhance the interface bonding between the fiber and a resin matrix, the microscopic wear behaviors such as three-dimensional carbon fiber wear, matrix stripping, third body abrasive particles and the like in the touch process are further improved, and the tribological performance and the mechanical performance are greatly improved. The hydrothermal electrophoresis method has the advantages of high growth speed, simple process and low cost, is suitable for industrial batch production, and has wide application prospect.
The present invention is described in further detail below with reference to examples:
example 1
1) Cutting the carbon cloth into a rectangle of 5cm multiplied by 8cm, locking edges at the periphery by using lines, carrying out ultrasonic treatment on the carbon cloth with the locked edges in an ethanol solution for 24 hours, taking out the carbon cloth, washing the carbon cloth with deionized water for 3 times, and drying the carbon cloth in an oven at the temperature of 60 ℃. Cleaning the carbon cloth with acetone solution at 80 deg.C for 2 hr by Soxhlet extraction, washing with deionized water for 10min, and oven drying at 60 deg.C for 24 hr;
2) methacrylic acid is taken as a grafting monomer, and diene is synthesized on the surface of the carbon cloth under the condition of oil bath (80 ℃, 3h) to obtain the lossless grafting oxygen-containing functional group.
3) Respectively dissolving zinc acetate dihydrate and sodium hydroxide in an ethanol solution under stirring at 60 ℃ to obtain a zinc acetate dihydrate solution with the molar concentration of 0.0125mol/L as a solution B and a sodium hydroxide solution with the molar concentration of 0.025mol/L as a solution C, adding the ethanol solution into the solution B for dilution to obtain a solution D with the concentration of 0.0014mol/L, adding the ethanol solution into the solution C for dilution to obtain a solution E with the concentration of 0.0071mol/L, slowly dropwise adding the solution E into the solution D at 60 ℃, stirring and standing to obtain a zinc source seed crystal layer sol;
4) soaking the carbon cloth in the zinc source seed crystal layer sol for 15min, drying at 150 ℃, and repeating for 4 times to obtain the carbon cloth with the seed crystal layer on the surface;
5) zinc nitrate hexahydrate and hexamethylenetetramine were mixed in a ratio of 1: 1, mixing and adding the mixture into deionized water to obtain zinc source growth solution with the zinc source molar concentration of 0.025 mol/L;
6) and (3) placing the carbon cloth with the seed crystal layer on the surface in a hydrothermal electrophoresis device, heating the hydrothermal electrophoresis device to the growth temperature of 90 ℃, taking the graphite plate as an anode and the carbon cloth as a cathode, keeping the current at 0.2A and the voltage at 0.35V, and growing the zinc oxide by hydrothermal electrophoresis for 30 min.
7) And (3) soaking the carbon cloth into the phenolic resin by adopting a vacuum pressure impregnation method, ensuring that the content of the resin accounts for 35% of the mass of the composite material, and drying the composite material for 24 hours at room temperature. And then hot-pressing at the hot-pressing temperature of 150 ℃ and the hot-pressing pressure of 10MPa for 10min to obtain the zinc oxide nanorod/carbon cloth reinforced resin friction material.
Example 2
1) Cutting a carbon cloth into a rectangle of 5cm multiplied by 8cm, locking the periphery with lines, ultrasonically treating the carbon cloth with an ethanol solution for 24 hours, taking out the carbon cloth, using deionized water for 4 times, and drying in an oven at 60 ℃. Cleaning the carbon cloth with acetone solution at 70 deg.C for 1 hr by Soxhlet extraction, washing with deionized water for 5min, and oven drying at 60 deg.C for 24 hr;
2) methacrylic acid is taken as a grafting monomer, and diene is synthesized on the surface of the carbon cloth under the condition of oil bath (80 ℃, 3h) to obtain the lossless grafting oxygen-containing functional group.
3) Respectively dissolving zinc acetate dihydrate and sodium hydroxide in an ethanol solution under stirring at 60 ℃ to obtain a zinc acetate dihydrate solution with the molar concentration of 0.0125mol/L as a solution B and a sodium hydroxide solution with the molar concentration of 0.025mol/L as a solution C, adding the ethanol solution into the solution B for dilution to obtain a solution D with the concentration of 0.0014mol/L, adding the ethanol solution into the solution C for dilution to obtain a solution E with the concentration of 0.0071mol/L, slowly dropwise adding the solution E into the solution D at 60 ℃, stirring and standing to obtain a zinc source seed crystal layer sol;
4) soaking the carbon cloth in the zinc source seed crystal layer sol for 30min, drying at 100 ℃, and repeating for 3 times to obtain the carbon cloth with the seed crystal layer on the surface;
5) zinc nitrate hexahydrate and ammonium fluoride were mixed in a ratio of 1: 1, mixing and adding the mixture into deionized water to obtain zinc source growth solution with the zinc source molar concentration of 0.025 mol/L;
6) and (3) placing the carbon cloth with the seed crystal layer on the surface in a hydrothermal electrophoresis device, heating the hydrothermal electrophoresis device to the growth temperature of 90 ℃, taking the graphite plate as an anode and the carbon cloth as a cathode, keeping the current at 0.15A and the voltage at 0.3V, and growing the zinc oxide by hydrothermal electrophoresis for 45 min.
7) And (3) soaking the carbon cloth into the phenolic resin by adopting a vacuum pressure impregnation method, ensuring that the content of the resin accounts for 30% of the mass of the composite material, and drying the composite material for 24 hours at room temperature. And then hot-pressing at the hot-pressing temperature of 170 ℃ and the hot-pressing pressure of 10MPa for 15min to obtain the zinc oxide nanorod/carbon cloth reinforced resin friction material.
Example 3
1) Cutting a carbon cloth into a rectangle of 5cm multiplied by 8cm, locking edges at the periphery by using lines, carrying out ultrasonic treatment on the carbon cloth with the locked edges in an ethanol solution for 24 hours, taking out the carbon cloth, using deionized water for 4 times, and drying in an oven at 60 ℃. Cleaning the carbon cloth with acetone solution at 60 deg.C for 3 hr by Soxhlet extraction, washing with deionized water for 15min, and oven drying at 60 deg.C for 24 hr;
2) methacrylic acid is taken as a grafting monomer, and diene is synthesized on the surface of the carbon cloth under the condition of oil bath (80 ℃, 3h) to obtain the lossless grafting oxygen-containing functional group.
3) Respectively dissolving zinc acetate dihydrate and sodium hydroxide in an ethanol solution under stirring at 60 ℃ to obtain a zinc acetate dihydrate solution with the molar concentration of 0.0125mol/L as a solution B and a sodium hydroxide solution with the molar concentration of 0.025mol/L as a solution C, adding the ethanol solution into the solution B for dilution to obtain a solution D with the concentration of 0.0014mol/L, adding the ethanol solution into the solution C for dilution to obtain a solution E with the concentration of 0.0071mol/L, slowly dropwise adding the solution E into the solution D at 60 ℃, stirring and standing to obtain a zinc source seed crystal layer sol;
4) soaking the carbon cloth in the zinc source seed crystal layer sol for 120min, drying at 120 ℃, and repeating for 5 times to obtain the carbon cloth with the seed crystal layer on the surface;
5) mixing zinc nitrate hexahydrate and ammonium chloride according to the proportion of 1: 1, mixing and adding the mixture into deionized water to obtain zinc source growth solution with the zinc source molar concentration of 0.025 mol/L;
6) and (3) placing the carbon cloth with the seed crystal layer on the surface in a hydrothermal electrophoresis device, heating the hydrothermal electrophoresis device to the growth temperature of 90 ℃, taking the graphite plate as an anode and the carbon cloth as a cathode, keeping the current at 0.18A and the voltage at 0.3V, and growing the zinc oxide by hydrothermal electrophoresis for 60 min.
7) And (3) soaking the carbon cloth into the phenolic resin by adopting a vacuum pressure impregnation method, ensuring that the mass of the resin accounts for 40% of the mass of the composite material, and drying the composite material for 24 hours at room temperature. And then hot-pressing at the hot-pressing temperature of 170 ℃ and the hot-pressing pressure of 10MPa for 10min to obtain the zinc oxide nanorod/carbon cloth reinforced resin friction material.
Example 4
1) Cutting a carbon cloth into a rectangle of 5cm multiplied by 8cm, locking edges at the periphery by using lines, carrying out ultrasonic treatment on the carbon cloth with the locked edges in an ethanol solution for 24 hours, taking out the carbon cloth, using deionized water for 3 times, and drying in an oven at 60 ℃. Cleaning the carbon cloth with acetone solution at 80 deg.C for 2 hr by Soxhlet extraction, washing with deionized water for 10min, and oven drying at 60 deg.C for 24 hr;
2) methacrylic acid is taken as a grafting monomer, and diene is synthesized on the surface of the carbon cloth under the condition of oil bath (80 ℃, 3h) to obtain the lossless grafting oxygen-containing functional group.
3) Respectively dissolving zinc acetate dihydrate and sodium hydroxide in an ethanol solution under stirring at 60 ℃ to obtain a zinc acetate dihydrate solution with the molar concentration of 0.0125mol/L as a solution B and a sodium hydroxide solution with the molar concentration of 0.025mol/L as a solution C, adding the ethanol solution into the solution B for dilution to obtain a solution D with the concentration of 0.0014mol/L, adding the ethanol solution into the solution C for dilution to obtain a solution E with the concentration of 0.0071mol/L, slowly dropwise adding the solution E into the solution D at 60 ℃, stirring and standing to obtain a zinc source seed crystal layer sol;
4) soaking the carbon cloth in the zinc source seed crystal layer sol for 25min, drying at 100 ℃, and repeating for 3 times to obtain the carbon cloth with the seed crystal layer on the surface;
5) mixing zinc nitrate hexahydrate and ammonium fluoride according to the proportion of 1: 1, mixing and adding the mixture into deionized water to obtain zinc source growth solution with the zinc source molar concentration of 0.025 mol/L;
6) and (3) placing the carbon cloth with the seed crystal layer on the surface in a hydrothermal electrophoresis device, heating the hydrothermal electrophoresis device to the growth temperature of 90 ℃, taking the graphite plate as an anode and the carbon cloth as a cathode, keeping the current at 0.2A and the voltage at 0.3V, and growing the zinc oxide by hydrothermal electrophoresis for 15 min.
7) And (3) soaking the carbon cloth into the phenolic resin by adopting a vacuum pressure impregnation method, ensuring that the content of the resin accounts for 30% of the mass of the composite material, and drying the composite material for 24 hours at room temperature. And then hot-pressing at the hot-pressing temperature of 150 ℃ and the hot-pressing pressure of 10MPa for 15min to obtain the zinc oxide nanorod/carbon cloth reinforced resin friction material.
Example 5
1) Cutting a carbon cloth into a rectangle of 5cm multiplied by 8cm, locking edges at the periphery by using lines, carrying out ultrasonic treatment on the carbon cloth with the locked edges in an ethanol solution for 24 hours, taking out the carbon cloth, using deionized water for 5 times, and drying in an oven at 60 ℃. Cleaning the carbon cloth with acetone solution at 70 deg.C for 2 hr by Soxhlet extraction, washing with deionized water for 15min, and oven drying at 60 deg.C for 24 hr;
2) methacrylic acid is taken as a grafting monomer, and diene is synthesized on the surface of the carbon cloth under the condition of oil bath (80 ℃, 3h) to obtain the lossless grafting oxygen-containing functional group.
3) Respectively dissolving zinc acetate dihydrate and sodium hydroxide in an ethanol solution under stirring at 60 ℃ to obtain a zinc acetate dihydrate solution with the molar concentration of 0.0125mol/L as a solution B and a sodium hydroxide solution with the molar concentration of 0.025mol/L as a solution C, adding the ethanol solution into the solution B for dilution to obtain a solution D with the concentration of 0.0014mol/L, adding the ethanol solution into the solution C for dilution to obtain a solution E with the concentration of 0.0071mol/L, slowly dropwise adding the solution E into the solution D at 60 ℃, stirring and standing to obtain a zinc source seed crystal layer sol;
4) soaking the carbon cloth in the zinc source seed crystal layer sol for 200min, drying at 100 ℃, and repeating for 4 times to obtain the carbon cloth with the seed crystal layer on the surface;
5) mixing zinc nitrate hexahydrate and ammonium chloride according to the proportion of 1: 1, mixing and adding the mixture into deionized water to obtain zinc source growth solution with the zinc source molar concentration of 0.025 mol/L;
6) and (3) placing the carbon cloth with the seed crystal layer on the surface in a hydrothermal electrophoresis device, heating the hydrothermal electrophoresis device to the growth temperature of 90 ℃, taking the graphite plate as an anode and the carbon cloth as a cathode, keeping the current at 0.15A and the voltage at 0.3V, and growing the zinc oxide by hydrothermal electrophoresis for 30 min.
7) And (3) soaking the carbon cloth into the phenolic resin by adopting a vacuum pressure impregnation method, ensuring that the content of the resin accounts for 30% of the mass of the composite material, and drying the composite material for 24 hours at room temperature. And then hot-pressing at the hot-pressing temperature of 150 ℃ and the hot-pressing pressure of 10MPa for 10min to obtain the zinc oxide nanorod/carbon cloth reinforced resin friction material.
FIG. 1 is a schematic diagram of in-situ growth of ZnO nanorods on the surface of carbon cloth by hydrothermal electrophoresis, which makes full use of the characteristics of hydrothermal supercritical high-pressure environment and high efficiency of electric field to make surface-charged crystal nuclei directionally deposit on the surface of carbon fiber, and then grow in situ efficiently and uniformly on the surface. The nano oxide is used as a bridge between the fiber and the resin, the chemical bonding and mechanical meshing effect of the nano oxide effectively enhances the interface bonding between the fiber and the resin matrix, fig. 2 is a result graph of example 1, and the comparison between the original carbon fiber and the fiber after hydrothermal electrophoresis growth shows that the zinc oxide nano rod can be successfully grown on the surface of the carbon fiber by adopting the preparation method of the invention, fig. 3 is a result graph of example 1, and the comparison observation shows that the continuous friction coefficient of the carbon cloth composite material treated by the method is more stable, and the dynamic friction coefficient of the carbon cloth composite material is higher than that of the original untreated carbon cloth composite material, thus the friction performance is stable and the friction performance is good.
Claims (6)
1. A method for preparing a zinc oxide nanorod/carbon cloth friction material by a hydrothermal electrophoresis method is characterized by comprising the following steps:
the method comprises the following steps: after the carbon cloth is treated by ethanol ultrasound, the carbon cloth is cleaned;
step two: methacrylic acid is used as a grafting monomer, and diene synthesis is adopted to graft oxygen-containing functional groups on the surface of the cleaned carbon cloth without damage;
step three: respectively dissolving zinc acetate dihydrate and sodium hydroxide in ethanol solution, uniformly stirring to respectively obtain zinc acetate dihydrate solution and sodium hydroxide solution, respectively marking as solution B and solution C, adding ethanol solution into solution B to dilute to obtain solution D, adding ethanol solution into solution C to dilute to obtain solution E, dropwise adding solution E into solution D, stirring and standing to obtain zinc source seed crystal layer sol;
step four: dipping the carbon cloth obtained in the step two in the zinc source seed crystal layer sol for 15-30min, then drying at the temperature of 100-150 ℃, and repeating dipping and drying for 3-5 times to obtain the carbon cloth with the seed crystal layer on the surface;
step five: mixing a zinc source and an alkali source in a ratio of 1: 1, mixing and adding the mixture into ultrapure water to obtain a growth solution, wherein the molar concentration of a zinc source in the growth solution is 0.025mol/L, and the zinc source is zinc nitrate hexahydrate; the alkali source is hexamethylenetetramine, ammonium fluoride or ammonium chloride;
step six: placing the carbon cloth with the surface containing the seed crystal layer in a growth solution, and growing a ZnO nano rod on the surface of the carbon cloth by adopting a hydrothermal electrophoresis method;
step seven: and (3) dipping the surface of the carbon cloth obtained in the step six with modified phenolic resin by adopting a vacuum pressure dipping method, drying, and finally performing hot press molding to obtain the zinc oxide nanorod/carbon cloth friction material.
2. The method for preparing the zinc oxide nanorod/carbon cloth friction material by the hydrothermal electrophoresis method according to claim 1, wherein the cleaning in the first step is specifically as follows: washing the carbon cloth after ultrasonic treatment with deionized water for 3-5 times, extracting the washed carbon cloth with acetone solution at 60-80 deg.C for 2-3 hr by Soxhlet extraction method, and washing with deionized water for 10 min.
3. The method for preparing the zinc oxide nanorod/carbon cloth friction material by the hydrothermal electrophoresis method according to claim 1, wherein zinc acetate dihydrate and sodium hydroxide are respectively dissolved in ethanol solutions in the third step, the zinc acetate dihydrate and the sodium hydroxide are uniformly stirred to respectively obtain a zinc acetate dihydrate solution with a molar concentration of 0.0125mol/L and a sodium hydroxide solution with a molar concentration of 0.025mol/L, the zinc acetate dihydrate solution and the sodium hydroxide solution are respectively marked as a solution B and a solution C, the ethanol solution is added into the solution B to dilute the solution B to obtain a solution D with a concentration of 0.0014mol/L, and the ethanol solution is added into the solution C to dilute the solution C to obtain a solution E with a concentration of 0.0071 mol/L.
4. The method for preparing zinc oxide nanorod/carbon cloth friction material according to claim 1, wherein in the sixth step, a graphite plate is used as an anode and carbon cloth is used as a cathode, the electrophoresis time is 15-60min, the electrophoresis current is 0.15-0.2A, and the voltage is 0.3-0.35V.
5. The method for preparing the zinc oxide nanorod/carbon cloth friction material by the hydrothermal electrophoresis method according to claim 1, wherein the mass fraction of the modified phenolic resin after dipping in the seventh step is 30-40%.
6. The method for preparing the zinc oxide nanorod/carbon cloth friction material by the hydrothermal electrophoresis method according to claim 1, wherein in the seventh step, the drying temperature is room temperature, and the drying time is 24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951921A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method of Y4Si3O12 whisker toughened Y2SiO5 composite coating |
| CN104415401A (en) * | 2013-08-26 | 2015-03-18 | 惠州比亚迪电子有限公司 | Preparation method of hard tissue substitute material |
| CN106898663A (en) * | 2017-02-23 | 2017-06-27 | 京东方科技集团股份有限公司 | The preparation method and electrical equipment of a kind of solar cell, solar cell |
| CN107778502A (en) * | 2017-10-26 | 2018-03-09 | 陕西科技大学 | A kind of preparation method of zinc oxide nano rod/carbon cloth reinforced resin friction material |
-
2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951921A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method of Y4Si3O12 whisker toughened Y2SiO5 composite coating |
| CN104415401A (en) * | 2013-08-26 | 2015-03-18 | 惠州比亚迪电子有限公司 | Preparation method of hard tissue substitute material |
| CN106898663A (en) * | 2017-02-23 | 2017-06-27 | 京东方科技集团股份有限公司 | The preparation method and electrical equipment of a kind of solar cell, solar cell |
| CN107778502A (en) * | 2017-10-26 | 2018-03-09 | 陕西科技大学 | A kind of preparation method of zinc oxide nano rod/carbon cloth reinforced resin friction material |
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