Tungsten carbide copper and preparation method thereof

Abstract

The invention belongs to the technical field of alloy, and particularly discloses tungsten carbide copper and a preparation method thereof.The tungsten carbide copper comprises, by weight, 70-80 parts of tungsten carbide, 24-35 parts of copper powder, 0.1-0.25 part of modified carbon fiber powder and 0.1-0.25 part of additives; the additive is Ti3C2 modified by polydopamine; the modified carbon fiber powder and the polydopamine modified Ti3C2 are added into the tungsten-copper carbide, the compactness of the tungsten-copper carbide is effectively improved, the modified carbon fiber powder and the polydopamine modified Ti3C2 can be uniformly dispersed in a system, cannot be locally dispersed too much or too little and are uniformly filled in pores of the tungsten-copper carbide, and the compactness of the tungsten-copper carbide is improved. And meanwhile, grains can be effectively refined, so that copper is fully infiltrated into a tungsten carbide framework to form firm combination, and the conductivity and the mechanical property are effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of alloy materials, and in particular to tungsten carbide copper and a preparation method thereof. Background Art

[0002] Tungsten carbide copper is an alloy material mainly composed of tungsten carbide and copper. Based on its composition characteristics, its organization is uniform and dense. It has the advantages of high melting point, high boiling point, high strength and high hardness of tungsten carbide, and has the advantages of copper's strong electrical and thermal conductivity and low contact resistance. Composite materials with excellent mechanical properties, electrical conductivity and wear resistance are widely used in electrical, electronic and mechanical industries.

[0003] However, the wear resistance, thermal conductivity and electrical conductivity of traditional tungsten carbide copper alloys still need to be improved, which limits their application in some occasions that require high wear resistance and high electrical conductivity. Therefore, it is of great significance to develop a tungsten carbide copper with high wear resistance, good thermal conductivity and high electrical conductivity and its preparation method. Summary of the invention

[0004] The invention provides tungsten carbide copper and a preparation method thereof. The tungsten carbide copper has excellent electrical conductivity and mechanical properties.

[0005] The present invention solves the technical problem by adopting the following technical solutions: A tungsten carbide copper comprises the following raw materials in parts by weight: 70-80 parts of tungsten carbide, 24-35 parts of copper powder, 0.1-0.25 parts of modified carbon fiber powder, and 0.1-0.25 parts of an additive; the additive is polydopamine-modified Ti3C2; The preparation method of the modified carbon fiber powder is: (1) Dispersing hexamethyldisiloxane and a silane coupling agent containing a carbon-carbon double bond in water, adding carbon fiber powder, and stirring evenly to obtain a precursor solution; (2) Add coconut oil, paraffin wax and mercapto silicone oil into water and stir evenly to obtain a modified liquid; (3) Add the catalyst and the modified liquid to the precursor solution, heat to 65-80°C, stir evenly, ultrasonically treat, filter, and dry to obtain modified carbon fiber powder.

[0006] The present invention creatively adds modified carbon fiber powder and polydopamine modified Ti3C2 to tungsten carbide copper, which effectively improves the density of tungsten carbide copper. The modified carbon fiber powder and polydopamine modified Ti3C2 can be evenly dispersed in the system without being dispersed too much or too little locally, and are evenly filled in the pores of tungsten carbide copper. At the same time, they can effectively refine the grains, so that copper can be fully infiltrated into the tungsten carbide skeleton to form a firm bond, effectively improving the electrical conductivity and mechanical properties.

[0007] In the modification process of the modified carbon fiber powder described in the present invention, the mercapto group and the silane coupling agent containing a carbon-carbon double bond are firmly combined to promote the uniform dispersion of the modified carbon fiber powder. Coconut oil and paraffin wax form a microfilm covering the surface, which plays the role of a binder, lubricant, adhesive, and interface activation, effectively activates the interface, and combines with the polydopamine-modified Ti3C2 interface. During the sintering process, a complex phase structure (such as WC phase, CuC phase, and TiC phase) is formed, which effectively improves the electrical conductivity and mechanical properties.

[0008] As a preferred embodiment of the present invention, the following components are included in parts by weight: 69.65 parts of tungsten carbide, 30 parts of copper powder, 0.2 parts of modified carbon fiber powder, and 0.15 parts of additives.

[0009] As a preferred embodiment of the present invention, the silane coupling agent containing carbon-carbon double bonds includes at least one of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(2-methoxyethoxy)silane and vinyl triisopropoxysilane.

[0010] As a preferred embodiment of the present invention, the weight ratio of hexamethyldisiloxane, the silane coupling agent containing carbon-carbon double bonds, the carbon fiber powder and water is (0.01-0.03): (0.02-0.05): 1: (4-10).

[0011] As a preferred embodiment of the present invention, the weight ratio of the coconut oil, paraffin, mercapto silicone oil and water is 1: (0.5-2): (0.02-0.05): (4-10).

[0012] As a preferred embodiment of the present invention, the mass ratio of the catalyst, the modifying liquid and the precursor liquid is (0.005-0.02): (0.2-0.5): 1.

[0013] As a preferred embodiment of the present invention, the viscosity of the mercapto silicone oil at 25°C is 200-300 mPa·s; The catalyst includes at least one of dibutyltin dilaurate and stannous octoate.

[0014] As a preferred embodiment of the present invention, the preparation method of the polydopamine modified Ti3C2 is: disperse dopamine hydrochloride and Ti3C2 in water, stir evenly, adjust the pH to 7.8-8.2 with tris(hydroxymethyl)aminomethane hydrochloride, stir evenly at 60-80°C, filter, and dry to obtain modified Ti3C2.

[0015] As a preferred embodiment of the present invention, the mass ratio of dopamine hydrochloride, Ti3C2 and water is (0.5~0.8):1:(4~10).

[0016] The present invention also provides a method for preparing tungsten copper carbide, comprising the following steps: The carbide, copper powder, modified carbon fiber powder and additives are mixed evenly, the mixture is isostatically pressed and sintered to obtain tungsten carbide copper; The isostatic pressing pressure is 200-300 MPa and the time is 4-10 min; The sintering temperature is 1160-1180° C. and the sintering time is 2-5 hours.

[0017] Beneficial effects of the present invention: The present invention adds modified carbon fiber powder and polydopamine modified Ti3C2 to tungsten carbide copper, which effectively improves the density of tungsten carbide copper. It can be evenly dispersed in the system without excessive or insufficient local dispersion, and evenly fills the pores of tungsten carbide copper. At the same time, it can effectively refine the grains, so that copper can fully penetrate into the tungsten carbide skeleton to form a strong bond, effectively improving the electrical conductivity and mechanical properties. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0020] In the present invention, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0021] In the present invention, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0022] The reagents or instruments used in the present invention without indicating the manufacturer are all conventional products that can be obtained commercially. The raw materials used in the comparative examples and the raw materials used in the parallel experiments of the embodiments are the same commercially available products unless otherwise specified.

[0023] Example 1 A tungsten carbide copper comprises the following components in parts by weight: 70 parts of tungsten carbide, 30 parts of copper powder, 0.2 parts of modified carbon fiber powder, and 0.15 parts of additives.

[0024] The additive is polydopamine-modified Ti3C2.

[0025] The preparation method of the modified carbon fiber powder is: (1) Dispersing hexamethyldisiloxane and vinyltriethoxysilane in water, adding carbon fiber powder, and stirring at a speed of 500 rpm to obtain a precursor solution; the weight ratio of the hexamethyldisiloxane, vinyltriethoxysilane, carbon fiber powder, and water is 0.02:0.04:1:6.

[0026] (2) Add coconut oil, paraffin wax, and mercapto silicone oil (KF-2001) into water, stir evenly at a speed of 500 rpm to obtain a modified liquid; the weight ratio of the coconut oil, paraffin wax, mercapto silicone oil, and water is 1:1:0.04:6.

[0027] (3) Add dibutyltin dilaurate and modifying liquid to the precursor solution, heat to 70°C, stir evenly at 500 rpm, ultrasonically treat at 500 W for 25 min, filter, and dry to obtain modified carbon fiber powder. The mass ratio of dibutyltin dilaurate, modifying liquid, and precursor solution is 0.01:0.4:1.

[0028] The preparation method of polydopamine modified Ti3C2 is as follows: dopamine hydrochloride and Ti3C2 are dispersed in water, stirred evenly, and tris(hydroxymethylaminomethane) hydrochloride (C4H 11 NO3·HCl) to a pH of 8.1, stirred at 70°C at a speed of 500 rpm, filtered, and dried to obtain modified Ti3C2. The mass ratio of dopamine hydrochloride, Ti3C2, and water is 0.6:1:6.

[0029] The preparation method of tungsten copper carbide comprises the following steps: The carbide, copper powder, modified carbon fiber powder and additives are mixed evenly, and the mixture is isostatically pressed and sintered to obtain tungsten carbide copper; the isostatic pressing pressure is 280MPa and the time is 8min; the sintering temperature is 1170°C and the time is 4h.

[0030] Example 2 A tungsten carbide copper comprises the following components in parts by weight: 75 parts of tungsten carbide, 34.65 parts of copper powder, 0.1 parts of modified carbon fiber powder, and 0.25 parts of additives.

[0031] The additive is polydopamine-modified Ti3C2.

[0032] The preparation method of the modified carbon fiber powder is: (1) Dispersing hexamethyldisiloxane and vinyltriethoxysilane in water, adding carbon fiber powder, and stirring at a speed of 500 rpm to obtain a precursor solution; the weight ratio of the hexamethyldisiloxane, vinyltriethoxysilane, carbon fiber powder, and water is 0.02:0.04:1:6.

[0033] (2) Add coconut oil, paraffin wax, and mercapto silicone oil (KF-2001) into water, stir evenly at a speed of 500 rpm to obtain a modified liquid; the weight ratio of the coconut oil, paraffin wax, mercapto silicone oil, and water is 1:1:0.04:6.

[0034] (3) Add dibutyltin dilaurate and modifying liquid to the precursor solution, heat to 70°C, stir evenly at 500 rpm, ultrasonically treat at 500 W for 25 min, filter, and dry to obtain modified carbon fiber powder. The mass ratio of dibutyltin dilaurate, modifying liquid, and precursor solution is 0.01:0.4:1.

[0035] The preparation method of polydopamine modified Ti3C2 is as follows: dopamine hydrochloride and Ti3C2 are dispersed in water, stirred evenly, and tris(hydroxymethylaminomethane) hydrochloride (C4H 11 NO3·HCl) to a pH of 8.1, stirred at 70°C at a speed of 500 rpm, filtered, and dried to obtain modified Ti3C2. The mass ratio of dopamine hydrochloride, Ti3C2, and water is 0.6:1:6.

[0036] The preparation method of tungsten copper carbide comprises the following steps: The carbide, copper powder, modified carbon fiber powder and additives are mixed evenly, and the mixture is isostatically pressed and sintered to obtain tungsten carbide copper; the isostatic pressing pressure is 280MPa and the time is 8min; the sintering temperature is 1170°C and the time is 4h.

[0037] Example 3 A tungsten carbide copper comprises the following components in parts by weight: 80 parts of tungsten carbide, 24.65 parts of copper powder, 0.25 parts of modified carbon fiber powder, and 0.1 parts of additives.

[0038] The additive is polydopamine-modified Ti3C2.

[0039] The preparation method of the modified carbon fiber powder is: (1) Dispersing hexamethyldisiloxane and vinyltriethoxysilane in water, adding carbon fiber powder, and stirring at a speed of 500 rpm to obtain a precursor solution; the weight ratio of the hexamethyldisiloxane, vinyltriethoxysilane, carbon fiber powder, and water is 0.02:0.04:1:6.

[0040] (2) Add coconut oil, paraffin wax, and mercapto silicone oil (KF-2001) into water, stir evenly at a speed of 500 rpm to obtain a modified liquid; the weight ratio of the coconut oil, paraffin wax, mercapto silicone oil, and water is 1:1:0.04:6.

[0041] (3) Add dibutyltin dilaurate and modifying liquid to the precursor solution, heat to 70°C, stir evenly at 500 rpm, ultrasonically treat at 500 W for 25 min, filter, and dry to obtain modified carbon fiber powder. The mass ratio of dibutyltin dilaurate, modifying liquid, and precursor solution is 0.01:0.4:1.

[0042] The preparation method of polydopamine modified Ti3C2 is as follows: dopamine hydrochloride and Ti3C2 are dispersed in water, stirred evenly, and tris(hydroxymethylaminomethane) hydrochloride (C4H 11 NO3·HCl) to a pH of 8.1, stirred at 70°C at a speed of 500 rpm, filtered, and dried to obtain modified Ti3C2. The mass ratio of dopamine hydrochloride, Ti3C2, and water is 0.6:1:6.

[0043] The preparation method of tungsten copper carbide comprises the following steps: The carbide, copper powder, modified carbon fiber powder and additives are mixed evenly, and the mixture is isostatically pressed and sintered to obtain tungsten carbide copper; the isostatic pressing pressure is 280MPa and the time is 8min; the sintering temperature is 1170°C and the time is 4h.

[0044] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not contain modified carbon fiber powder, and Comparative Example 1 uses an equal amount of additives to replace the modified carbon fiber powder, and the rest are the same.

[0045] A tungsten carbide copper comprises the following components in parts by weight: 70 parts of tungsten carbide, 30 parts of copper powder, and 0.35 parts of additives.

[0046] The additive is polydopamine-modified Ti3C2.

[0047] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 does not contain additives, and Comparative Example 2 uses an equal amount of modified carbon fiber powder to replace the additives, and the rest are the same.

[0048] A tungsten carbide copper comprises the following components in parts by weight: 75 parts of tungsten carbide, 30 parts of copper powder, and 0.35 parts of modified carbon fiber powder.

[0049] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the modified carbon fiber powder is replaced by carbon fiber powder in Comparative Example 3, and the other contents are the same.

[0050] A tungsten carbide copper comprises the following components in parts by weight: 70 parts of tungsten carbide, 30 parts of copper powder, 0.2 parts of carbon fiber powder, and 0.15 parts of additives.

[0051] The additive is polydopamine-modified Ti3C2.

[0052] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the preparation method of the modified carbon fiber powder is different, and the other aspects are the same.

[0053] The preparation method of the modified carbon fiber powder is: (1) Dispersing hexamethyldisiloxane and vinyltriethoxysilane in water, adding carbon fiber powder, and stirring at a speed of 500 rpm to obtain a precursor solution; the weight ratio of the hexamethyldisiloxane, vinyltriethoxysilane, carbon fiber powder, and water is 0.02:0.04:1:6.

[0054] (2) Add mercapto silicone oil (KF-2001) into water and stir evenly at a speed of 500 rpm to obtain a modified liquid; the weight ratio of the mercapto silicone oil to water is 0.04:6.

[0055] (3) Add dibutyltin dilaurate and modifying liquid to the precursor solution, heat to 70°C, stir evenly at 500 rpm, ultrasonically treat at 500 W for 25 min, filter, and dry to obtain modified carbon fiber powder. The mass ratio of dibutyltin dilaurate, modifying liquid, and precursor solution is 0.01:0.4:1.

[0056] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the preparation method of the modified carbon fiber powder is different, and the other aspects are the same.

[0057] The preparation method of the modified carbon fiber powder is: (1) Dispersing hexamethyldisiloxane in water, adding carbon fiber powder, and stirring at a speed of 500 rpm to obtain a precursor solution; the weight ratio of the hexamethyldisiloxane, carbon fiber powder, and water is 0.02:0.04:1:6.

[0058] (2) Add coconut oil and paraffin into water, stir evenly at a speed of 500 rpm to obtain a modified liquid; the weight ratio of the coconut oil, paraffin and water is 1:1:0.04:6.

[0059] (3) Add dibutyltin dilaurate and modifying liquid to the precursor solution, heat to 70°C, stir evenly at 500 rpm, ultrasonically treat at 500 W for 25 min, filter, and dry to obtain modified carbon fiber powder. The mass ratio of dibutyltin dilaurate, modifying liquid, and precursor solution is 0.01:0.4:1.

[0060] Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that the additive in Comparative Example 6 is Ti3C2, and the other contents are the same.

[0061] A tungsten carbide copper comprises the following components in parts by weight: 69.65 parts of tungsten carbide, 30 parts of copper powder, 0.2 parts of modified carbon fiber powder, and 0.15 parts of additives.

[0062] The additive is Ti3C2.

[0063] Performance Testing The properties of the embodiments and comparative examples are shown in Table 1.

[0064] Table 1

[0065] It can be seen from Table 1 that the tungsten carbide copper of the present invention has excellent electrical conductivity and mechanical properties.

[0066] By comparing Example 1 with Comparative Examples 1-2, it can be seen that the modified carbon fiber powder and the additives described in the present invention are indispensable, and the excellent electrical conductivity and mechanical properties of the present invention are achieved under the synergistic effect of the two.

[0067] By comparing Example 1 with Comparative Examples 3 to 5, it can be seen that the modified carbon fiber powder of the present invention can significantly improve the electrical conductivity and mechanical properties, and the modified carbon fiber powder prepared by the preparation method of the present invention can significantly improve the electrical conductivity and mechanical properties.

[0068] Finally, it should be noted that the above embodiments are intended to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A tungsten carbide copper, characterized in that: The preparation method comprises the following raw materials in parts by weight: 70-80 parts of tungsten carbide, 24-35 parts of copper powder, 0.1-0.25 parts of modified carbon fiber powder, and 0.1-0.25 parts of additives; the additive is polydopamine-modified Ti3C2; The preparation method of the modified carbon fiber powder is: (1) Dispersing hexamethyldisiloxane and a silane coupling agent containing a carbon-carbon double bond in water, adding carbon fiber powder, and stirring evenly to obtain a precursor solution; (2) Add coconut oil, paraffin wax and mercapto silicone oil into water and stir evenly to obtain a modified liquid; (3) Add the catalyst and the modified liquid to the precursor solution, heat to 65-80°C, stir evenly, ultrasonically treat, filter, and dry to obtain modified carbon fiber powder.

2. The tungsten carbide copper according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 69.65 parts of tungsten carbide, 30 parts of copper powder, 0.2 parts of modified carbon fiber powder and 0.15 parts of additives.

3. The tungsten carbide copper according to claim 1, characterized in that: The silane coupling agent containing carbon-carbon double bonds includes at least one of vinyl triethoxy silane, vinyl trimethoxy silane, vinyl tri(2-methoxyethoxy) silane and vinyl triisopropoxy silane.

4. The tungsten carbide copper according to claim 1, characterized in that: The weight ratio of the hexamethyldisiloxane, the silane coupling agent containing carbon-carbon double bonds, the carbon fiber powder and water is (0.01-0.03): (0.02-0.05): 1: (4-10).

5. The tungsten carbide copper according to claim 1, characterized in that: The weight ratio of the coconut oil, paraffin, mercapto silicone oil and water is 1: (0.5-2): (0.02-0.05): (4-10).

6. The tungsten carbide copper according to claim 1, characterized in that: The mass ratio of the catalyst, the modifying liquid and the precursor liquid is (0.005-0.02): (0.2-0.5):

1.

7. The tungsten carbide copper according to claim 1, characterized in that: The viscosity of the mercapto silicone oil at 25° C. is 200-300 mPa·s; The catalyst includes at least one of dibutyltin dilaurate and stannous octoate.

8. The tungsten carbide copper according to claim 1, characterized in that: The preparation method of the polydopamine modified Ti3C2 is as follows: dopamine hydrochloride and Ti3C2 are dispersed in water, stirred evenly, adjusted to a pH of 7.8-8.2 with tris(hydroxymethyl)aminomethane hydrochloride, stirred evenly at 60-80° C., filtered, and dried to obtain modified Ti3C2.

9. The tungsten carbide copper according to claim 8, characterized in that: The mass ratio of dopamine hydrochloride, Ti3C2 and water is (0.5-0.8):1:(4-10).

10. The method for preparing tungsten copper carbide according to any one of claims 1 to 9, characterized in that: The following steps are involved: The carbide, copper powder, modified carbon fiber powder and additives are mixed evenly, the mixture is isostatically pressed and sintered to obtain tungsten carbide copper; The isostatic pressing pressure is 200-300 MPa and the time is 4-10 min; The sintering temperature is 1160-1180° C. and the sintering time is 2-5 hours.

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