阅读说明：本技术 一种金属粒子协同改性碳纤维织物及其制备方法 (Metal particle synergistic modified carbon fiber fabric and preparation method thereof ) 是由 赵普 王齐华 李宋 徐明坤 陶立明 张耀明 张新瑞 王廷梅 于 2021-01-04 设计创作，主要内容包括：本发明提供了一种金属粒子协同改性碳纤维织物的制备方法,属于摩擦材料技术领域。本发明以银粉和镍粉作为改性填料,其中银粉具有易流动性和良好的延展性,镍粉具有好的耐腐蚀性、硬度和延展性,能够提高碳纤维织物的界面承载能力,镍粉和银粉共同作用,二者具有协同改性效果,能够在碳纤维织物表面形成“滚珠效应”,增加碳纤维织物的自润滑效果,降低碳纤维织物的摩擦系数；同时,银粉和镍粉具有良好的导热性能,解决摩擦热的散热问题。实施例结果表明,本发明制备得到的金属粒子协同改性碳纤维织物摩擦系数在0.121～0.135之间,磨痕宽度在232～312μm之间。(The invention provides a preparation method of a metal particle synergistic modified carbon fiber fabric, and belongs to the technical field of friction materials. According to the invention, silver powder and nickel powder are used as modified fillers, wherein the silver powder has easy flowability and good ductility, the nickel powder has good corrosion resistance, hardness and ductility, the interface bearing capacity of the carbon fiber fabric can be improved, the nickel powder and the silver powder act together, the nickel powder and the silver powder have a synergistic modification effect, a ball effect can be formed on the surface of the carbon fiber fabric, the self-lubricating effect of the carbon fiber fabric is increased, and the friction coefficient of the carbon fiber fabric is reduced; meanwhile, the silver powder and the nickel powder have good heat conductivity, and the problem of heat dissipation of friction heat is solved. The embodiment result shows that the friction coefficient of the metal particle synergistic modified carbon fiber fabric prepared by the invention is between 0.121 and 0.135, and the width of a grinding crack is between 232 and 312 mu m.)

1. A preparation method of a metal particle synergistically modified carbon fiber fabric comprises the following steps:

(1) ultrasonically mixing silver powder, nickel powder, phenolic resin, lubricating filler and a polar organic solvent to obtain coating liquid;

(2) and (3) soaking the carbon fiber fabric in the coating liquid, and drying the obtained soaked carbon fiber fabric to obtain the metal particle synergistic modified carbon fiber fabric.

2. The production method according to claim 1, wherein the silver powder has a particle size of 30 to 50nm, and the nickel powder has a particle size of 400 to 600 nm.

3. The preparation method according to claim 1, wherein the lubricating filler is one or more of polytetrafluoroethylene, graphite, graphene and molybdenum disulfide; the particle size of the lubricating filler is 400-500 nm;

the polar organic solvent is one or more of ethanol, acetone and ethyl acetate.

4. The method according to any one of claims 1 to 3, wherein the mass ratio of the lubricant filler, the silver powder, the nickel powder, the phenolic resin and the polar organic solvent is (0.14 to 0.2): (0.01 to 0.03): (2 to 4): (4 to 8).

5. The preparation method of claim 1, wherein the power of the ultrasonic mixing is 450-550W, and the time is 25-35 min.

6. The preparation method of claim 1, wherein the carbon fiber fabric has a fiber specification of 1K, a warp density of 10 pieces/10 mm, a weft density of 10 pieces/10 mm, and a mass per unit area of 120-130 g/m²(ii) a The thickness of the carbon fiber fabric is 0.2-0.22 mm.

7. The preparation method according to claim 1, wherein the time for the immersion is 10 to 20 min; the drying temperature is 70-80 ℃, and the drying time is 30-60 min.

8. The metal particle synergistic modified carbon fiber fabric prepared by the preparation method of any one of claims 1 to 7, which comprises a carbon fiber fabric, and silver powder, nickel powder, a lubricating filler and phenolic resin loaded on the surface of carbon fibers of the carbon fiber fabric.

9. The metal particle synergistically modified carbon fiber fabric according to claim 8, wherein the mass of the silver powder in the metal particle synergistically modified carbon fiber fabric is 0.2 to 0.6% of the mass of the carbon fiber fabric, and the mass of the nickel powder is 0.2 to 0.6% of the mass of the carbon fiber fabric.

10. The metal particle synergistically modified carbon fiber fabric according to claim 8, wherein the mass of the lubricating material is 29-38% of the mass of the carbon fiber fabric, and the mass of the phenolic resin is 10-22% of the mass of the carbon fiber fabric.

Technical Field

The invention relates to the technical field of friction materials, in particular to a metal particle synergistic modified carbon fiber fabric and a preparation method thereof.

Background

The carbon fiber fabric composite material is widely applied to friction parts such as bearings, sealing rings and the like due to the unique self-lubricating property. However, as the use conditions become more complicated and more severe, the frictional heat generated at the frictional interface has a higher and higher influence on the material performance. The accumulation of frictional heat accelerates the performance decay of the resin, reducing the overall performance of the material. Currently, the improvement of tribological properties of fiber fabric composites by the addition of functional fillers is one of the most effective means of modification and is widely accepted.

At present, polytetrafluoroethylene and the like are mostly used as lubricating fillers to reduce the wear rate of carbon fiber fabrics in the prior art, but the polytetrafluoroethylene cannot effectively solve the heat dissipation problem of friction heat; the existing heat-conducting fillers comprise aluminum oxide, magnesium oxide, silicon carbide and the like, but the self-lubricating property of the carbon fiber fabric is reduced after the fillers are added.

Disclosure of Invention

In view of the above, the present invention aims to provide a metal particle synergistically modified carbon fiber fabric and a preparation method thereof. The metal particle synergistic modified carbon fiber fabric has good heat conductivity and friction performance.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of a metal particle synergistic modified carbon fiber fabric, which comprises the following steps:

(1) ultrasonically mixing silver powder, nickel powder, phenolic resin, lubricating filler and a polar organic solvent to obtain coating liquid;

(2) and (3) soaking the carbon fiber fabric in the coating liquid, and drying the obtained soaked carbon fiber fabric to obtain the metal particle synergistic modified carbon fiber fabric.

Preferably, the particle size of the silver powder is 30-50 nm, and the particle size of the nickel powder is 400-600 nm.

Preferably, the lubricating filler is one or more of polytetrafluoroethylene, graphite, graphene and molybdenum disulfide; the particle size of the lubricating filler is 400-500 nm;

the polar organic solvent is one or more of ethanol, acetone and ethyl acetate.

Preferably, the mass ratio of the lubricating filler, the silver powder, the nickel powder, the phenolic resin and the polar organic solvent is (0.14-0.2): (0.01-0.03): (2-4): (4-8).

Preferably, the power of ultrasonic mixing is 450-550W, and the time is 25-35 min.

Preferably, the specification of the carbon fiber fabric is 1K, the warp density is 10 pieces/10 mm, the weft density is 10 pieces/10 mm, and the mass per unit area is 120-130 g/m²(ii) a The thickness of the carbon fiber fabric is 0.2-0.22 mm.

Preferably, the dipping time is 10-20 min; the drying temperature is 70-80 ℃, and the drying time is 30-60 min.

The invention provides a metal particle synergistic modified carbon fiber fabric prepared by the preparation method, which comprises a carbon fiber fabric, and silver powder, nickel powder, lubricating filler and phenolic resin loaded on the surface of carbon fibers of the carbon fiber fabric.

Preferably, the mass of the silver powder in the metal particle synergistically modified carbon fiber fabric is 0.2-0.6% of the mass of the carbon fiber fabric, and the mass of the nickel powder is 0.2-0.6% of the mass of the carbon fiber fabric.

Preferably, the mass of the lubricating material is 29-38% of the mass of the carbon fiber fabric, and the mass of the phenolic resin is 10-22% of the mass of the carbon fiber fabric.

The invention provides a preparation method of a metal particle synergistic modified carbon fiber fabric, which comprises the following steps: (1) ultrasonically mixing silver powder, nickel powder, phenolic resin, lubricating filler and a polar organic solvent to obtain coating liquid; (2) and (3) soaking the carbon fiber fabric in the coating liquid, and drying the obtained soaked carbon fiber fabric to obtain the metal particle synergistic modified carbon fiber fabric. The silver powder and the nickel powder are used as modified fillers, wherein the silver powder has easy flowability and good ductility, and can improve the wear resistance of the carbon fiber fabric; the nickel powder has good corrosion resistance, hardness and ductility, and can improve the interface bearing capacity of the carbon fiber fabric; the nickel powder and the silver powder act together to form a ball effect on the surface of the carbon fiber fabric, so that a synergistic modification effect is achieved, the self-lubricating effect of the carbon fiber fabric is improved, and the friction coefficient of the carbon fiber fabric is reduced; meanwhile, the silver powder and the nickel powder have good heat conductivity, and the problem of heat dissipation of frictional heat can be solved. The embodiment result shows that the friction coefficient of the carbon fiber fabric synergistically modified by the metal particles prepared by the invention is between 0.121 and 0.135, and the width of a grinding crack is between 232 and 312 mu m.

Drawings

FIG. 1 is an SEM photograph of silver powder in example 1;

FIG. 2 is an SEM photograph of nickel powder in example 1;

fig. 3 is an SEM image of the carbon fiber fabric of example 1.

Detailed Description

The invention provides a preparation method of a metal particle synergistic modified carbon fiber fabric, which comprises the following steps:

(1) ultrasonically mixing silver powder, nickel powder, phenolic resin, lubricating filler and a polar organic solvent to obtain coating liquid;

(2) and (3) soaking the carbon fiber fabric in the coating liquid, and drying the obtained soaked carbon fiber fabric to obtain the metal particle synergistic modified carbon fiber fabric.

The coating liquid is prepared by ultrasonically mixing silver powder, nickel powder, phenolic resin, lubricating filler and a polar organic solvent. In the present invention, the particle size of the silver powder is preferably 30 to 50nm, and more preferably 35 to 45 nm. The source of the silver powder is not particularly required in the invention, and the silver powder which is conventionally sold on the market in the field can be used. As one embodiment of the present invention, the silver powder is silver powder produced by dacomi gold. In the invention, the particle size of the nickel powder is preferably 400-600 nm, and more preferably 450-550 nm; the nickel powder source of the invention has no special requirement, and the nickel powder which is conventional and commercially available in the field can be used. As a specific example of the present invention, the nickel powder is nickel powder produced by Dakojima corporation.

In the invention, the silver powder has easy flowability and good ductility, the nickel powder has good corrosion resistance, hardness and ductility, the interface bearing capacity of the carbon fiber fabric can be improved, the nickel powder and the silver powder have a synergistic modification effect under the combined action of the nickel powder and the silver powder, a ball effect can be formed on the surface of the carbon fiber fabric, the self-lubricating effect of the carbon fiber fabric is improved, and the friction coefficient of the carbon fiber fabric is reduced; meanwhile, the silver powder and the nickel powder have good heat conductivity, and the problem of heat dissipation of friction heat is solved.

The phenolic resin is not particularly required in the present invention, and a phenolic resin well known to those skilled in the art may be used. As a specific embodiment of the invention, the phenolic resin is the phenol-formaldehyde resin of the iron Anchor brand 204 produced by Shanghai New photo chemical industry Co. According to the invention, the silver powder and the nickel powder can be firmly adhered to the surface of the carbon fiber through the phenolic resin.

In the invention, the lubricating filler is preferably one or more of polytetrafluoroethylene, graphite, graphene and molybdenum disulfide; the particle size of the lubricating filler is preferably 400-500 nm, and more preferably 420-480 nm. In the invention, the lubricating filler can prolong the service life of the composite material.

In the present invention, the polar organic solvent is preferably one or more of ethanol, acetone and ethyl acetate, and more preferably ethyl acetate.

In the present invention, the mass ratio of the lubricant filler, the silver powder, the nickel powder, the phenolic resin, and the polar organic solvent is preferably (0.14 to 0.2): (0.01-0.03): (0.01-0.03): (2-4): (4-8), more preferably (0.16-0.18): (0.015 to 0.025): (0.015 to 0.025): (2.5-3.5): (5-7), and more preferably 0.017:0.02:0.02:3: 6.

In the invention, the power of the ultrasonic mixing is preferably 450-550W, more preferably 500W, and the time is preferably 25-35 min, more preferably 30 min.

After the coating liquid is obtained, the carbon fiber fabric is soaked in the coating liquid, and the obtained soaked carbon fiber fabric is dried to obtain the metal particle synergistic modified carbon fiber fabric. In the invention, the fiber specification of the carbon fiber fabric is preferably 1K, the warp density is preferably 10 pieces/10 mm, the weft density is preferably 10 pieces/10 mm, and the mass per unit area is preferably 120-130 g/m²More preferably 150g/m²(ii) a The thickness of the carbon fiber fabric is preferably 0.2-0.22 mm, and more preferably 0.21 mm. The invention has no special requirement on the source of the carbon fiber fabric, and the carbon fiber fabric which is generally sold in the field can be used.

In the invention, the soaking time is preferably 10-20 min, more preferably 12-18 min, and further preferably 15 min; the temperature of the impregnation is preferably room temperature. In the invention, the drying temperature is preferably 70-80 ℃, and more preferably 75 ℃; the drying time is preferably 30-60 min, and more preferably 40-50 min.

In the invention, compared with the carbon fiber fabric, the weight of the metal particle synergistic modified carbon fiber fabric is increased by 40-60%, more preferably 45-55%, and further preferably 50%. When the weight of the composite material cannot reach 40-60%, the impregnation and drying operations are preferably repeated until the weight is increased to meet the requirement.

The invention provides a metal particle synergistic modified carbon fiber fabric prepared by the preparation method, which comprises a carbon fiber fabric, and silver powder, nickel powder, a lubricating material and phenolic resin loaded on the surface of the carbon fiber. In the invention, the mass of the silver powder in the metal particle synergistically modified carbon fiber fabric is preferably 0.2-0.6% of the mass of the carbon fiber fabric, and more preferably 0.3-0.5%; the mass of the nickel powder is preferably 0.2-0.6%, and more preferably 0.3-0.5% of the mass of the carbon fiber fabric. The mass of the lubricating material is preferably 29-38% of that of the carbon fiber fabric, and more preferably 30-35%; the mass of the phenolic resin is preferably 10-22% of that of the carbon fiber fabric, and more preferably 15-20%.

In the present invention, the method for using the metal particle synergistically modified carbon fiber fabric preferably comprises the following steps:

and (3) adhering the metal particle synergistic modified carbon fiber fabric to the surface of the metal piece by using an adhesive, and curing under the condition of applying pressure.

In the invention, the adhesive is preferably one or more of phenolic resin, epoxy resin, polyimide resin and polyether ether ketone resin. The amount of the binder used in the present invention is not particularly limited, and may be those known to those skilled in the art. In the present invention, the metal member is preferably made of titanium alloy, 304 steel, aluminum alloy, or bearing steel.

In the present invention, the pressure to be applied is preferably 0.1 to 0.3MPa, and more preferably 0.2 MPa. In the invention, the curing temperature is preferably 120-150 ℃, and more preferably 130-140 ℃; the heating rate for heating to the curing temperature is preferably 5-10 ℃/min, and more preferably 6-8 ℃/min. In the invention, the curing time is preferably 2-5 h, and more preferably 3-4 h; the present invention calculates the curing time from the temperature rise to the curing temperature.

In the invention, in the curing process, the phenolic resin in the metal particle synergistic modified carbon fiber fabric is crosslinked with the adhesive, so that the adhesive strength of the metal particle synergistic modified carbon fiber fabric on the surface of the metal piece can be improved.

The metal particle synergistically modified carbon fiber fabric and the method for producing the same according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.

Example 1

(1) Mixing molybdenum disulfide with the particle size of 400nm, silver powder with the particle size of 30nm, nickel powder with the particle size of 400nm, phenolic resin, ethyl acetate, ethanol and other organic solvents in a mass ratio of 18g, 0.3g, 40g and 80g, and dispersing for 35min under the ultrasonic condition of 450W to obtain coating liquid;

(2) the specification is 1K, the warp density is 10 pieces/10 mm, the weft density is 10 pieces/10 mm, and the mass per unit area is 125g/m²The carbon fiber fabric is soaked in the coating liquid for 10min, then the carbon fiber fabric is moved to a blast oven at 80 ℃ for drying for 60min, the soaking process is repeated until the weight of the blended fiber fabric is increased by 60%, and the metal particle synergistic modified carbon fiber fabric is obtained, wherein the loading capacity of silver is 0.6% of the mass of the fiber fabric, and the loading capacity of nickel is 0.6% of the mass of the fiber fabric;

(3) and (3) attaching the dried modified carbon fiber fabric to the surface of the titanium alloy by using phenolic resin, applying a pressure of 0.2MPa, raising the temperature from room temperature to 150 ℃ at a speed of 10 ℃/min, curing for 5h, and then forming, wherein the sample is marked as a # 1 sample.

Wherein the SEM image of silver powder is shown in FIG. 1, the SEM image of nickel powder is shown in FIG. 2, and the SEM image of carbon fiber fabric without supported filler is shown in FIG. 3.

Example 2

(1) Mixing lubricating filler formed by mixing molybdenum disulfide with the particle size of 500nm, graphene and the like in mass, silver powder with the particle size of 40nm, nickel powder with the particle size of 500nm, phenolic resin and acetone according to the mass of 14g, 0.1g, 20g and 40g, and dispersing for 30min under the ultrasonic condition of 550W to obtain coating liquid;

(2) the specification is 1K, the warp density is 10 pieces/10 mm, the weft density is 10 pieces/10 mm, and the mass per unit area is 120g/m²The carbon fiber fabric is soaked in the coating liquid for 15min, then the carbon fiber fabric is moved to a 70 ℃ blast oven to be dried for 30min, the soaking process is repeated until the weight of the blended fiber fabric is increased by 40%, and the metal particle synergistic modified carbon fiber fabric is obtained, wherein the loading capacity of silver is 0.2% of the mass of the fiber fabric, and the loading capacity of nickel is 0.2% of the mass of the fiber fabric;

(3) and (3) pasting the dried modified carbon fiber fabric on the surface of 304 steel by using phenolic resin, applying a pressure of 0.1MPa, raising the temperature from room temperature to 140 ℃ at a speed of 5 ℃/min, curing for 2h, and then forming, wherein the sample is marked as a No. 2 sample.

Example 3

(1) Mixing lubricating filler formed by mixing graphite with the particle size of 450nm and graphene in equal mass, silver powder with the particle size of 50nm, nickel powder with the particle size of 600nm, phenolic resin and ethanol according to the mass of 20g, 0.2g, 40g and 60g, and dispersing for 28min under the ultrasonic condition of 500W to obtain coating liquid;

(2) the specification is 1K, the warp density is 10 pieces/10 mm, the weft density is 10 pieces/10 mm, and the mass per unit area is 130g/m²The carbon fiber fabric is soaked in the coating liquid for 12min, then the carbon fiber fabric is moved to a blast oven at 75 ℃ for drying for 40min, the soaking process is repeated until the weight of the blended fiber fabric is increased by 50%, and the metal particle synergistic modified carbon fiber fabric is obtained, wherein the loading capacity of silver is 0.3% of the mass of the fiber fabric, and the loading capacity of nickel is 0.3% of the mass of the fiber fabric;

(3) and (3) pasting the dried modified carbon fiber fabric on the surface of the aluminum alloy by using phenolic resin, applying a pressure of 0.2MPa, raising the temperature from room temperature to 130 ℃ at a speed of 7 ℃/min, curing for 4h, and then forming, wherein the mark is a sample No. 3.

Example 4

(1) Mixing polytetrafluoroethylene with the particle size of 500nm, lubricating filler mixed by graphite, graphene and the like, silver powder with the particle size of 50nm, nickel powder with the particle size of 400nm, phenolic resin, organic solvent mixed by ethyl acetate, acetone and the like according to the mass of 16g, 0.1g, 0.2g, 30g and 50g, and dispersing for 32min under the ultrasonic condition of 450W to obtain coating liquid;

(2) the specification is 1K, the warp density is 10 pieces/10 mm, the weft density is 10 pieces/10 mm, and the mass per unit area is 125g/m²The carbon fiber fabric is soaked in the coating liquid for 18min, then the carbon fiber fabric is moved to a 70 ℃ blast oven to be dried for 50min, the soaking process is repeated until the weight of the blended fiber fabric is increased by 50%, and the metal particle synergistic modified carbon fiber fabric is obtained, wherein the loading capacity of silver is 0.2% of the mass of the fiber fabric, and the loading capacity of nickel is 0.4% of the mass of the fiber fabric;

(3) and (3) pasting the dried modified carbon fiber fabric on the surface of bearing steel by using phenolic resin, applying a pressure of 0.3MPa, raising the temperature from room temperature to 120 ℃ at a speed of 8 ℃/min, curing for 3h, and then forming, wherein the sample is marked as a No. 4 sample.

Comparative example 1

Mixing phenolic resin and ethanol according to a mass ratio of 60.4 g: 60g of the coating solution is dispersed for 28min under 500W of ultrasonic wave to obtain the coating solution. The rest of the operation was exactly the same as in example 3, and a sample No. 5 was obtained.

Comparative example 2

Mixing the lubricating filler mixed by graphite with the particle size of 450nm and graphene in mass, phenolic resin and ethanol according to the mass of 20.4g, 40g and 60g, and dispersing for 28min under the ultrasonic condition of 500W to obtain the coating liquid. The rest of the operation was exactly the same as in example 3, and sample No. 6 was obtained.

Comparative example 3

Mixing the lubricating filler formed by mixing graphite with the particle size of 450nm and graphene in mass, silver powder with the particle size of 50nm, phenolic resin and ethanol according to the mass of 20.2g, 0.2g, 40g and 60g, and dispersing for 28min under the ultrasonic condition of 500W to obtain the coating liquid. The rest of the operation was exactly the same as in example 3, and a 7# sample was obtained.

Comparative example 4

Mixing graphite with the particle size of 450nm, graphene and the like by mass to obtain a lubricating filler, mixing nickel powder with the particle size of 600nm, phenolic resin and ethanol according to the mass of 20.2g, 0.2g, 40g and 60g, and dispersing for 28min under the ultrasonic condition of 500W to obtain the coating liquid. The rest of the operation was exactly the same as in example 3, and sample No. 8 was obtained.

Performance testing

The samples obtained in examples 1 to 4 and comparative examples 1 to 4 were tested for the friction coefficient and the wear scar width, respectively, and the results are shown in table 1. Wherein the coefficient of friction is measured by a CSM friction machine according to the formula μ ═ F/N, where μ is the coefficient of friction, F is the friction force, and N is the positive pressure. The width of the grinding crack was measured by a scanning electron microscope.

And (3) oppositely grinding the side, adhered with the modified carbon fiber fabric, of the sample obtained in the examples 1-4 and the comparative examples 1-4 with a steel ball with the diameter of 3mm, wherein the test loading force is 5N, the rotating speed is 5cm/s, the running time is 1h, and the friction coefficient and the grinding crack width are the average values of 5 tests.

TABLE 1 Friction and thermal conductivity of samples obtained in examples 1 to 4 and comparative examples 1 to 4

As can be seen from the examples and comparative examples, silver powder and nickel powder have synergistic effect, and can improve the tribological performance of the carbon fiber fabric.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.