CN110218901B - Bicrystal tungsten carbide synergistically enhanced copper-based composite material and preparation method thereof - Google Patents
Bicrystal tungsten carbide synergistically enhanced copper-based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a bicrystal tungsten carbide synergistically enhanced copper-based composite material and a preparation method thereof, wherein the method comprises the following steps: preparing twinned tungsten carbide-copper reinforcing particles having a core-shell structure, the twinned tungsten carbide including a first tungsten carbide having a larger grain size and a second tungsten carbide having a smaller grain size; mixing the bicrystal tungsten carbide-copper reinforced particles with pure copper powder, and sintering by discharge plasma to obtain a bicrystal tungsten carbide synergistically reinforced copper-based composite material; wherein the bicrystal tungsten carbide accounts for 0.5-10% of the total mass of the copper-based composite material. The copper-based composite material with remarkably improved mechanical properties is obtained by utilizing the particle size synergistic effect of tungsten carbide powder with different grain sizes; the bicrystal tungsten carbide-copper reinforced particles with the core-shell structure are adopted, so that the segregation of tungsten carbide is avoided; the spark plasma sintering is adopted, so that the growth of copper crystal grains is effectively inhibited.
Description
Technical Field
The invention relates to a copper-based composite material and a preparation method thereof; more particularly, the invention relates to a tungsten carbide reinforced copper-based composite material and a preparation method thereof.
Background
The pure copper material has the comprehensive properties of high conductivity, high thermal conductivity, good ductility and the like, and is widely applied to the fields of electronic information, power and electricity, transportation and the like. However, copper also has the disadvantages of low strength, low hardness, poor wear resistance, etc., which limits its expanded application in industry. With the rapid development of electronic information and other technologies, higher and higher requirements are also put forward on the comprehensive performance of copper materials, and in order to solve the problem, a second-phase strengthening method is usually adopted so as to maintain the conductivity of the copper-based composite material unchanged or reduce the conductivity of the copper-based composite material as much as possible while enhancing the mechanical property of the copper-based composite material. In recent years, the reaction interface formed in the compounding process of the in-situ compounding technology enhances the bonding capability between the matrix and the reinforcement, and is also applied to the field of copper-based reinforced composite materials.
For example, chinese patent document CN106435237A discloses a method for preparing a nano titanium dioxide reinforced copper-based composite material, which uses powder metallurgy to synthesize TiO in situ2a/Cu composite material of TiO2Has good particle size distribution. Specifically, firstly, the concentrated ammonia water, the absolute ethyl alcohol, the tetrabutyl titanate and the copper nitrate trihydrate are used as raw materials to prepare composite powder of the titanium oxide polymer and the copper nitrate with different contents, and the composite powder is calcined and reduced to obtain TiO2the/Cu powder is sintered by a vacuum hot-pressing sintering furnace to prepare the nano TiO2A reinforced copper-based composite material.
Chinese patent document CN101613816A discloses an in-situ generated multi-element dispersion strengthened copper-based composite material and a preparation method thereof. Wherein the reinforcing phase used comprises at least three of the following: zirconium carbide is more than or equal to 0.3 percent and less than or equal to 5 percent, titanium carbide is more than or equal to 0.3 percent and less than or equal to 5 percent, aluminum carbide is more than or equal to 0.1 percent and less than or equal to 5 percent, aluminum oxide is more than or equal to 0.3 percent and less than or equal to 5 percent, titanium boride is more than or equal to 0.3 percent and less than or equal to 5 percent, chromium oxide is more than or equal to 0.3 percent and less than or equal to 5 percent, zirconium oxide is more than or equal to 0.3 percent; the balance being copper. The particle size of the reinforcing phase material is in the range of 10nm-10 μm. The preparation method adopts ball milling mixing, compression molding, sintering and subsequent extrusion to prepare the multi-element dispersion reinforced copper-based composite material.
Chinese patent document CN108384979A discloses a hybrid reinforced copper-based composite material, which contains three reinforcements: CNTs, TiB2And TiC, CNTs are layered, TiB2And TiC are dispersed in the copper matrix to form a composite structure with three reinforcements reinforced in a synergetic mode. The CNTs are in laminated distribution with consistent orientation, which is beneficial to giving play to the effect that the CNTs share the load of the matrix and improveThe function of high composite material toughness; by introducing small-sized and uniformly distributed TiB into the copper matrix between the CNTs stacks2And TiC particles increase the resistance of dislocation movement in the deformation process of the material, and the TiC particles are mutually supplemented with the strengthening effect of the CNTs, so that the strength of the material is improved.
Chinese patent document CN102978434A discloses a copper-based composite material reinforced by short fibers and particles. Short fiber and particles are used as reinforcing phase, the content of the short fiber is 0.1-2 wt%, and the content of the reinforcing body particles is 0.1-10 wt%. The short fiber can be carbon nano tube, nano carbon fiber, ceramic short fiber, etc., and the reinforcing phase particle can be alumina, zirconia, magnesia, titania, silicon carbide, titanium carbide, tungsten carbide, silicon nitride, aluminum nitride, titanium diboride, Ti3SiC2, etc.
Factors such as the selection of the reinforcing phase of the copper-based composite material, the distribution of the reinforcing phase in the copper matrix, the interface bonding strength between the reinforcing phase and copper and the like all have important influence on the mechanical property of the copper-based composite material, and the production cost and the manufacturing difficulty are also factors to be considered.
Disclosure of Invention
The main object of the present invention is to provide a method for producing a copper-based composite material having excellent and stable mechanical properties at low cost.
It is another object of the present invention to provide a copper-based composite material having excellent and stable mechanical properties at low cost.
In order to achieve the above-mentioned primary object, a first aspect of the present invention provides a method for preparing a bicrystal tungsten carbide synergistically reinforced copper-based composite material, comprising the steps of:
preparing double-crystal tungsten carbide-copper reinforced particles with a core-shell structure; the double-crystal tungsten carbide comprises a first tungsten carbide with a first crystal grain size and a second tungsten carbide with a second crystal grain size, wherein the first crystal grain size is larger than the second crystal grain size, and the mass ratio of the first tungsten carbide to the second tungsten carbide is 5: 1-1: 5; preferably, the mass ratio of the first tungsten carbide to the second tungsten carbide in the double-crystal tungsten carbide is 2: 1-1: 1;
mixing the bicrystal tungsten carbide-copper reinforced particles with pure copper powder, and sintering by discharge plasma to obtain a bicrystal tungsten carbide synergistically reinforced copper-based composite material; wherein the bicrystal tungsten carbide accounts for 0.5-10% of the total mass of the copper-based composite material; preferably, the bicrystal tungsten carbide accounts for 1.0-5.0% of the total mass of the copper-based composite material, and more preferably 1.0-2.0%.
In the technical scheme, two tungsten carbides with different grain sizes are selected as reinforcing phases, wherein the first tungsten carbide with larger grain size has higher obdurability, and provides high obdurability and plasticity for the copper-based composite material; the second tungsten carbide with smaller grain size provides the copper material with high hardness and high wear resistance. The proportion of the two tungsten carbide powders is controlled to generate a good synergistic enhancement effect, and the copper-based composite material can achieve a synergistic enhancement effect on the comprehensive performance. In addition, compared with reinforced phases such as Carbon Nanotubes (CNTs), the cost of the tungsten carbide is much lower, and the production cost of the copper-based composite material can be obviously reduced.
In the technical scheme, the twinned tungsten carbide-copper reinforced particles with a core-shell structure (tungsten carbide is taken as a core and copper is taken as a shell) are prepared by coating copper on the surfaces of two kinds of tungsten carbide, so that the subsequent uniform mixing of the twinned tungsten carbide-copper reinforced particles and pure copper powder is facilitated (preferably, the twinned tungsten carbide-copper reinforced particles and the pure copper powder are mixed by ball milling), and the partial aggregation of the tungsten carbide is effectively inhibited; in addition, the reinforcing particles taking copper as the shell can be more tightly combined with pure copper, which is beneficial to improving the combination strength between the reinforcing particles and the copper matrix. The tungsten carbide particles are uniformly dispersed in the copper matrix, and dislocation migration generated by deformation and creep of the copper-based composite material under the action of external force needs to bypass the tungsten carbide, so that extra energy is needed, and the strength of the composite material is improved. In addition, the chemical property of the tungsten carbide is stable, and the growth of particles or composite reaction hardly occurs in the preparation and deformation processes of the copper-based composite material, so that the stability of the material performance is ensured.
In the technical scheme, the sintering is carried out by adopting a spark plasma sintering process, the sintering process can be finished at local high temperature in a short time, and copper crystal grains in the sintering process are effectively inhibited from growing, so that the material performance of the copper-based composite material is improved. In addition, the diffusion amount of the tungsten carbide serving as the reinforcing phase into the copper matrix in the short-time sintering process is small, and the tungsten carbide is mainly distributed at the interface of the copper crystal grains, so that the electric conductivity of the copper matrix is reduced to a small extent after the tungsten carbide serving as the reinforcing phase is added, and the copper matrix composite material still has high electric conductivity.
Preferably, the mass ratio of the first tungsten carbide to the second tungsten carbide in the double-crystal tungsten carbide is 2: 1-1: 1; and preferably, the double-crystal tungsten carbide accounts for 1.0-5.0% of the total mass of the copper-based composite material, and more preferably 1.0-2.0%.
In the invention, a solid copper precursor can be coated on the surface of tungsten carbide particles, for example, tungsten carbide powder is added into a copper salt aqueous solution, and after being uniformly stirred, an alkaline solution is added to generate copper hydroxide serving as a copper precursor, so as to obtain tungsten carbide particles coated with copper hydroxide; then, a gas-phase reduction method or a liquid-phase reduction method is adopted, or a two-step reduction method of firstly liquid-phase reduction and then gas-phase reduction is adopted, the copper precursor is reduced into copper, and copper is coated on the surface of the tungsten carbide, so that the tungsten carbide-copper reinforced particles with the core-shell structure are formed.
As a preferred embodiment of the present invention, firstly, copper hydroxide is grown in situ on tungsten carbide particles by using an aqueous solution blending method, so that the tungsten carbide particles are coated with the copper hydroxide to obtain tungsten carbide-copper hydroxide particles with a core-shell structure, then the copper hydroxide is reduced to cuprous oxide particles through a liquid phase, and the cuprous oxide is reduced to elemental copper through heating vapor phase reduction, so as to form tungsten carbide-copper reinforced particles with a core-shell structure. Specifically, the step of preparing the bicrystal tungsten carbide-copper reinforced particle having a core-shell structure includes the following sub-steps:
preparing a precursor suspension: adding first tungsten carbide powder with a first grain size and second tungsten carbide powder with a second grain size into a copper salt aqueous solution, uniformly stirring, and adding an alkaline solution to generate copper hydroxide to obtain a precursor suspension;
liquid-phase reduction: heating the precursor suspension to 55-95 ℃, continuously stirring, adding a reducing agent into the precursor suspension, and reducing copper hydroxide in the precursor suspension into cuprous oxide;
gas-phase reduction: and filtering, cleaning and drying a product obtained by liquid phase reduction, placing the product in a reduction furnace, heating, introducing a reducing gas to reduce cuprous oxide into copper, and obtaining the double-crystal tungsten carbide-copper reinforced particles with the core-shell structure.
Compared with the method of only coating copper on the surfaces of the tungsten carbide particles by a liquid phase reduction method or a gas phase reduction method, the method adopts a two-step reduction process of firstly liquid phase reduction and then gas phase reduction to ensure that the copper can more uniformly coat the tungsten carbide particles and more effectively inhibit the contact growth and segregation among the tungsten carbide particles. In addition, the two-step reduction process of liquid phase reduction first and gas phase reduction later can enhance the wettability between the tungsten carbide and the copper-clad layer on the surface of the tungsten carbide, improve the bonding strength between the copper and the tungsten carbide and is beneficial to further improving the comprehensive performance of the copper-based composite material.
According to a specific embodiment of the invention, the copper salt is any one or more of copper acetate, copper nitrate, copper sulfate and copper chloride, and the copper ion concentration of the copper salt aqueous solution is 3.2-32 g/L.
According to a specific embodiment of the present invention, the reducing agent is any one or more of glucose, fructose, lactose, and citric acid.
According to an embodiment of the present invention, the reducing gas is hydrogen or carbon monoxide, or a mixture of at least one of nitrogen, argon and helium with hydrogen or carbon monoxide.
According to a specific embodiment of the invention, in the gas-phase reduction substep, the heating rate of the reduction furnace is 5-15 ℃/min, and the temperature is kept at 250-350 ℃ for 1-3 h; the obtained bicrystal tungsten carbide-copper reinforced particles are cooled along with the furnace.
According to a specific embodiment of the present invention, the discharge plasma sintering process parameters are as follows: the heating rate is 50-150 ℃/min, the sintering temperature is 600-900 ℃, the sintering pressure is 40-60 MPa, and the heat preservation time is 5-30 min.
Preferably, the process parameters of spark plasma sintering are as follows: the heating rate is 80-100 ℃/min, the sintering temperature is 700-800 ℃, the sintering pressure is 40-50 MPa, and the heat preservation time is 5-15 min.
In a preferred embodiment of the present invention, the first crystal grain size is 0.3 to 0.6 μm, and the second crystal grain size is 0.05 to 0.2 μm.
In order to achieve another object, another aspect of the present invention provides a twin-crystal tungsten carbide synergistically reinforced copper-based composite material comprising 0.5 to 10% by mass of the total mass of the copper-based composite material, the twin-crystal tungsten carbide comprising a first tungsten carbide having a first crystal size and a second tungsten carbide having a second crystal size, the first crystal size being larger than the second crystal size, and the mass ratio of the first tungsten carbide to the second tungsten carbide being 5:1 to 1: 5.
The copper-based composite material comprises a copper matrix and twinned tungsten carbide particles uniformly dispersed in the copper matrix, and the dislocation migration generated by deformation and creep of the copper-based composite material under the action of external force needs to bypass the tungsten carbide, so that extra energy is needed, and the strength of the composite material is improved. Two tungsten carbides with different grain sizes are used as reinforcing phases, wherein the first tungsten carbide with larger grain size has higher obdurability, and provides high obdurability and plasticity for the copper-based composite material; the second tungsten carbide with smaller grain size provides the copper material with high hardness and high wear resistance. The proportion of the two tungsten carbide powders is controlled to generate a good synergistic enhancement effect, and the copper-based composite material can achieve a synergistic enhancement effect on the comprehensive performance.
The solid solubility of the tungsten carbide reinforced phase in copper is low, the diffusion quantity of the tungsten carbide reinforced phase into the copper matrix is relatively small during spark plasma sintering, and the tungsten carbide reinforced phase is mainly distributed at the interface of copper crystal grains, so that the electric conductivity reduction range of the copper matrix is smaller after the tungsten carbide is added as the reinforced phase, and the copper-based composite material still has high electric conductivity.
Because the chemical property of the tungsten carbide is stable, the particle growth or the composite reaction hardly occurs in the preparation and deformation processes of the copper-based composite material, thereby ensuring the stability of the performance of the composite material. In addition, compared with reinforced phases such as Carbon Nanotubes (CNTs), the cost of the tungsten carbide is much lower, and the production cost of the copper-based composite material can be obviously reduced.
Preferably, the mass ratio of the first tungsten carbide to the second tungsten carbide in the double-crystal tungsten carbide is 2: 1-1: 1; and preferably, the double-crystal tungsten carbide accounts for 1.0-5.0% of the total mass of the copper-based composite material, and more preferably 1.0-2.0%.
Preferably, the first crystal size is 0.3 μm to 0.6 μm and the second crystal size is 0.05 μm to 0.2 μm.
In view of the characteristics, the twin-crystal tungsten carbide synergistically reinforced copper-based composite material can be used for copper contact materials, high-speed rail pulley guide rails, wear-resistant electrical connectors, aircraft structural parts and the like.
In order to more clearly illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following detailed description.
Drawings
FIG. 1 is a TEM image of a twinned tungsten carbide-copper reinforced particle having a core-shell structure prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of a copper-based composite material prepared in example 1 of the present invention.
Detailed Description
Example 1
The twinned tungsten carbide synergistically reinforced copper-based composite material of example 1, comprising a twinned tungsten carbide reinforcing phase in an amount of about 6.25% by mass of the total mass, the twinned tungsten carbide comprising first tungsten carbide particles having a grain size of about 0.5 μm and second tungsten carbide particles having a grain size of about 0.1 μm, and the mass ratio of the first tungsten carbide particles to the second tungsten carbide particles being 5: 1.
Example 1 a method for preparing a bicrystal tungsten carbide synergistically reinforced copper-based composite material includes: step S1, preparing bicrystal tungsten carbide-copper reinforced particles having a core-shell structure; and step S2, mixing the double-crystal tungsten carbide-copper reinforced particles with pure copper powder and then performing discharge plasma sintering. Wherein, step S1 includes the following sub-steps:
preparing a precursor suspension: adding 10 g of tungsten carbide with the grain size of about 0.5 mu m and 2g of tungsten carbide with the grain size of about 0.1 mu m into 2L of copper acetate aqueous solution with the copper ion concentration of 10.0g/L, stirring at the rotating speed of 100r/min for 10min, and adding 0.5L of NaOH solution with the hydroxide ion concentration of 1.26mol/L to generate copper hydroxide to obtain copper hydroxide coated tungsten carbide precursor suspension;
liquid-phase reduction: heating the precursor suspension to 60 ℃, continuously stirring, adding 60 g of glucose into the precursor suspension, and reducing copper hydroxide into cuprous oxide;
gas-phase reduction: filtering, cleaning and drying a product obtained by liquid phase reduction to obtain composite powder with twin-crystal tungsten carbide as a core and cuprous oxide as a shell; placing the composite powder in a reduction furnace, introducing hydrogen, controlling the heating rate of the reduction furnace to be 10 ℃/min, and keeping the temperature at 260 ℃ for 1 h; the cuprous oxide is reduced to copper to obtain double-crystal tungsten carbide-copper reinforced particles/powder with tungsten carbide as a core and copper as a shell, and the double-crystal tungsten carbide-copper reinforced particles/powder is cooled along with the furnace.
Fig. 1 is a TEM image of the twinned tungsten carbide-copper reinforcing particles prepared in step S1 of example 1. As can be seen in fig. 1, the tungsten carbide surface is well coated with copper, forming a copper-coated tungsten carbide core-shell structure.
In step S2, 1 part by mass of the twinned tungsten carbide-copper reinforced particles prepared in step 1 and 5 parts by mass of pure copper powder are uniformly mixed, and spark plasma sintering is performed with the following process parameters: the heating rate is 50 ℃/min, the sintering temperature is 700 ℃, the sintering pressure is 45MPa, and the heat preservation time is 8 min.
FIG. 2 is an SEM image of a twin crystal tungsten carbide synergistically reinforced copper-based composite material prepared in example 1. As can be seen from fig. 2, in the copper-based composite material, tungsten carbide is mainly distributed at the interface of the copper crystal grains, and the copper-based composite material has fewer sintering holes and good sintering compactness.
Example 2
The twinned tungsten carbide synergistically reinforced copper-based composite material of example 2, comprising a twinned tungsten carbide reinforcing phase in an amount of about 3.4% by mass of the total mass, the twinned tungsten carbide comprising first tungsten carbide particles having a grain size of about 0.4 μm and second tungsten carbide particles having a grain size of about 0.1 μm, and the mass ratio of the first tungsten carbide particles to the second tungsten carbide particles being 1: 5.
Embodiment 2 a method for preparing a bicrystal tungsten carbide synergistically reinforced copper-based composite material includes: step S1, preparing bicrystal tungsten carbide-copper reinforced particles having a core-shell structure; and step S2, mixing the double-crystal tungsten carbide-copper reinforced particles with pure copper powder and then performing discharge plasma sintering. Wherein, step S1 includes the following sub-steps:
preparing a precursor suspension: adding 2g of tungsten carbide with the grain size of about 0.4 mu m and 10 g of tungsten carbide with the grain size of about 0.1 mu m into 1L of copper acetate aqueous solution with the copper ion concentration of 20.0g/L, stirring at the rotating speed of 150r/min for 20min, and adding 0.5L of NaOH solution with the hydroxide ion concentration of 1.26mol/L to generate copper hydroxide so as to obtain copper hydroxide coated tungsten carbide precursor suspension;
liquid-phase reduction: heating the precursor suspension to 65 ℃, continuously stirring, adding 60 g of glucose into the precursor suspension, and reducing copper hydroxide into cuprous oxide;
gas-phase reduction: filtering, cleaning and drying a product obtained by liquid phase reduction to obtain composite powder with twin-crystal tungsten carbide as a core and cuprous oxide as a shell; placing the composite powder in a reduction furnace, introducing hydrogen, controlling the heating rate of the reduction furnace to be 15 ℃/min, and keeping the temperature at 350 ℃ for 1 h; the cuprous oxide is reduced to copper to obtain double-crystal tungsten carbide-copper reinforced particles/powder with tungsten carbide as a core and copper as a shell, and the double-crystal tungsten carbide-copper reinforced particles/powder is cooled along with the furnace.
In step S2, 1 part by mass of the twinned tungsten carbide-copper reinforced particles prepared in step 1 is uniformly mixed with 10 parts by mass of pure copper powder, and spark plasma sintering is performed with the following process parameters: the heating rate is 130 ℃/min, the sintering temperature is 800 ℃, the sintering pressure is 50MPa, and the heat preservation time is 15 min.
Example 3
The twinned tungsten carbide synergistically reinforced copper-based composite material of example 3, comprising a twinned tungsten carbide reinforcing phase in an amount of about 1.5% by mass of the total mass, the twinned tungsten carbide comprising first tungsten carbide particles having a grain size of about 0.3 μm and second tungsten carbide particles having a grain size of about 0.06 μm, and the mass ratio of the first tungsten carbide particles to the second tungsten carbide particles being 2: 1.
Embodiment 3 a method for preparing a bicrystal tungsten carbide synergistically reinforced copper-based composite material includes: step S1, preparing bicrystal tungsten carbide-copper reinforced particles having a core-shell structure; and step S2, mixing the double-crystal tungsten carbide-copper reinforced particles with pure copper powder and then performing discharge plasma sintering. Wherein, step S1 includes the following sub-steps:
preparing a precursor suspension: adding 8 g of tungsten carbide with the grain size of about 0.3 mu m and 4 g of tungsten carbide with the grain size of about 0.06 mu m into 1L of copper acetate aqueous solution with the copper ion concentration of 15.0g/L, stirring at the rotating speed of 200r/min for 10min, and adding 0.38L of NaOH solution with the hydroxide ion concentration of 1.26mol/L to generate copper hydroxide so as to obtain a precursor suspension of the tungsten carbide coated by the copper hydroxide;
liquid-phase reduction: heating the precursor suspension to 80 ℃, continuously stirring, adding 45 g of glucose into the precursor suspension, and reducing copper hydroxide into cuprous oxide;
gas-phase reduction: filtering, cleaning and drying a product obtained by liquid phase reduction to obtain composite powder with twin-crystal tungsten carbide as a core and cuprous oxide as a shell; placing the composite powder in a reduction furnace, introducing hydrogen, controlling the heating rate of the reduction furnace to be 8 ℃/min, and preserving heat for 2.5h at 310 ℃; the cuprous oxide is reduced to copper to obtain double-crystal tungsten carbide-copper reinforced particles/powder with tungsten carbide as a core and copper as a shell, and the double-crystal tungsten carbide-copper reinforced particles/powder is cooled along with the furnace.
In step S2, 1 part by mass of the twinned tungsten carbide-copper reinforced particles prepared in step 1 and 28 parts by mass of pure copper powder are uniformly mixed, and spark plasma sintering is performed with the following process parameters: the heating rate is 90 ℃/min, the sintering temperature is 800 ℃, the sintering pressure is 50MPa, and the heat preservation time is 10 min.
Example 4
The twinned tungsten carbide synergistically reinforced copper-based composite material of example 4, comprising a twinned tungsten carbide reinforcing phase in an amount of about 5.3% by mass of the total mass, the twinned tungsten carbide comprising first tungsten carbide particles having a grain size of about 0.5 μm and second tungsten carbide particles having a grain size of about 0.2 μm, and the mass ratio of the first tungsten carbide particles to the second tungsten carbide particles being 1: 2.5.
Example 4a method for preparing a bicrystal tungsten carbide synergistically reinforced copper-based composite material includes: step S1, preparing bicrystal tungsten carbide-copper reinforced particles having a core-shell structure; and step S2, mixing the double-crystal tungsten carbide-copper reinforced particles with pure copper powder and then performing discharge plasma sintering. Wherein, step S1 includes the following sub-steps:
preparing a precursor suspension: adding 4 g of tungsten carbide with the grain size of about 0.5 mu m and 10 g of tungsten carbide with the grain size of about 0.2 mu m into 1L of copper acetate aqueous solution with the copper ion concentration of 30.0g/L, stirring at the rotating speed of 200r/min for 10min, and adding 0.75L of NaOH solution with the hydroxide ion concentration of 1.26mol/L to generate copper hydroxide so as to obtain copper hydroxide coated tungsten carbide precursor suspension;
liquid-phase reduction: heating the precursor suspension to 85 ℃, continuously stirring, adding 90 g of glucose into the precursor suspension, and reducing copper hydroxide into cuprous oxide;
gas-phase reduction: filtering, cleaning and drying a product obtained by liquid phase reduction to obtain composite powder with twin-crystal tungsten carbide as a core and cuprous oxide as a shell; placing the composite powder in a reduction furnace, introducing hydrogen, controlling the heating rate of the reduction furnace to be 6 ℃/min, and keeping the temperature at 280 ℃ for 2 h; the cuprous oxide is reduced to copper to obtain double-crystal tungsten carbide-copper reinforced particles/powder with tungsten carbide as a core and copper as a shell, and the double-crystal tungsten carbide-copper reinforced particles/powder is cooled along with the furnace.
In step S2, 1 part by mass of the twinned tungsten carbide-copper reinforced particles prepared in step 1 and 5 parts by mass of pure copper powder are uniformly mixed, and spark plasma sintering is performed with the following process parameters: the heating rate is 70 ℃/min, the sintering temperature is 650 ℃, the sintering pressure is 60MPa, and the heat preservation time is 5 min.
Example 5
The twinned tungsten carbide synergistically reinforced copper-based composite material of example 5, comprising a twinned tungsten carbide reinforcing phase in an amount of about 1.1% by mass of the total mass, the twinned tungsten carbide comprising first tungsten carbide particles having a grain size of about 0.4 μm and second tungsten carbide particles having a grain size of about 0.1 μm, and the first tungsten carbide particles and the second tungsten carbide particles being in a mass ratio of 1: 1.
Example 5 a method of preparing a bicrystal tungsten carbide synergistically reinforced copper-based composite material includes: step S1, preparing bicrystal tungsten carbide-copper reinforced particles having a core-shell structure; and step S2, mixing the double-crystal tungsten carbide-copper reinforced particles with pure copper powder and then performing discharge plasma sintering. Wherein, step S1 includes the following sub-steps:
preparing a precursor suspension: adding 5 g of tungsten carbide with the grain size of about 0.4 mu m and 5 g of tungsten carbide with the grain size of about 0.1 mu m into 1L of copper acetate aqueous solution with the copper ion concentration of 17.0g/L, stirring at the rotating speed of 150r/min for 20min, and adding 0.5L of NaOH solution with the hydroxide ion concentration of 1.07mol/L to generate copper hydroxide so as to obtain a precursor suspension of the tungsten carbide coated by the copper hydroxide;
liquid-phase reduction: heating the precursor suspension to 70 ℃, continuously stirring, adding 55 g of glucose into the precursor suspension, and reducing copper hydroxide into cuprous oxide;
gas-phase reduction: filtering, cleaning and drying a product obtained by liquid phase reduction to obtain composite powder with twin-crystal tungsten carbide as a core and cuprous oxide as a shell; placing the composite powder in a reduction furnace, introducing hydrogen, controlling the heating rate of the reduction furnace to be 5 ℃/min, and keeping the temperature at 300 ℃ for 2 h; the cuprous oxide is reduced to copper to obtain double-crystal tungsten carbide-copper reinforced particles/powder with tungsten carbide as a core and copper as a shell, and the double-crystal tungsten carbide-copper reinforced particles/powder is cooled along with the furnace.
In step S2, 1 part by mass of the twinned tungsten carbide-copper reinforced particles prepared in step 1 is uniformly mixed with 32 parts by mass of pure copper powder, and spark plasma sintering is performed with the following process parameters: the heating rate is 100 ℃/min, the sintering temperature is 750 ℃, the sintering pressure is 60MPa, and the heat preservation time is 10 min.
Comparative example 1
Comparative example 1 differs from example 5 only in the tungsten carbide reinforcing phase, and in comparative example 1 only a single grain size of tungsten carbide is used as the reinforcing phase. Specifically, the tungsten carbide reinforced copper-based composite material of comparative example 1 includes a tungsten carbide reinforcing phase in an amount of about 1.1% by mass of the total mass thereof, and the grain size of the tungsten carbide reinforcing phase is about 0.4 μm.
Comparative example 1 a method of preparing a tungsten carbide reinforced copper-based composite material includes: step S1, preparing tungsten carbide-copper reinforcing particles having a core-shell structure; and step S2, mixing the tungsten carbide-copper reinforced particles with pure copper powder and then sintering the mixture by discharge plasma. Wherein, step S1 includes the following sub-steps:
preparing a precursor suspension: adding 10 g of tungsten carbide with the grain size of about 0.4 mu m into 1L of copper acetate aqueous solution with the copper ion concentration of 17.0g/L, stirring at the rotating speed of 150r/min for 20min, and adding 0.5L of NaOH solution with the hydroxide ion concentration of 1.07mol/L to generate copper hydroxide, thereby obtaining a precursor suspension of tungsten carbide coated by the copper hydroxide;
liquid-phase reduction: heating the precursor suspension to 70 ℃, continuously stirring, adding 55 g of glucose into the precursor suspension, and reducing copper hydroxide into cuprous oxide;
gas-phase reduction: filtering, cleaning and drying a product obtained by liquid phase reduction to obtain composite powder with tungsten carbide as a core and cuprous oxide as a shell; placing the composite powder in a reduction furnace, introducing hydrogen, controlling the heating rate of the reduction furnace to be 5 ℃/min, and keeping the temperature at 300 ℃ for 2 h; the cuprous oxide is reduced to copper to obtain tungsten carbide-copper reinforced particles/powder with tungsten carbide as a core and copper as a shell, and the particles/powder is cooled along with the furnace.
In step S2, 1 part by mass of the tungsten carbide-copper reinforced particles prepared in step 1 is uniformly mixed with 32 parts by mass of pure copper powder, and spark plasma sintering is performed with the following process parameters: the heating rate is 100 ℃/min, the sintering temperature is 750 ℃, the sintering pressure is 60MPa, and the heat preservation time is 10 min.
Comparative example 2
Comparative example 2 differs from example 5 only in the tungsten carbide reinforcing phase, and comparative example 2 employs only tungsten carbide of a single grain size as the reinforcing phase. Specifically, the tungsten carbide reinforced copper-based composite material of comparative example 2 includes a tungsten carbide reinforcing phase in an amount of about 1.1% by mass of the total mass thereof, and the grain size of the tungsten carbide reinforcing phase is about 0.1 μm.
Comparative example 1 a method of preparing a tungsten carbide reinforced copper-based composite material includes: step S1, preparing tungsten carbide-copper reinforcing particles having a core-shell structure; and step S2, mixing the tungsten carbide-copper reinforced particles with pure copper powder and then sintering the mixture by discharge plasma. Wherein, step S1 includes the following sub-steps:
preparing a precursor suspension: adding 10 g of tungsten carbide with the grain size of about 0.1 mu m into 1L of copper acetate aqueous solution with the copper ion concentration of 17.0g/L, stirring at the rotating speed of 150r/min for 20min, and adding 0.5L of NaOH solution with the hydroxide ion concentration of 1.07mol/L to generate copper hydroxide, thereby obtaining a precursor suspension of tungsten carbide coated by the copper hydroxide;
liquid-phase reduction: heating the precursor suspension to 70 ℃, continuously stirring, adding 55 g of glucose into the precursor suspension, and reducing copper hydroxide into cuprous oxide;
gas-phase reduction: filtering, cleaning and drying a product obtained by liquid phase reduction to obtain composite powder with tungsten carbide as a core and cuprous oxide as a shell; placing the composite powder in a reduction furnace, introducing hydrogen, controlling the heating rate of the reduction furnace to be 5 ℃/min, and keeping the temperature at 300 ℃ for 2 h; the cuprous oxide is reduced to copper to obtain tungsten carbide-copper reinforced particles/powder with tungsten carbide as a core and copper as a shell, and the particles/powder is cooled along with the furnace.
In step S2, 1 part by mass of the tungsten carbide-copper reinforced particles prepared in step 1 is uniformly mixed with 32 parts by mass of pure copper powder, and spark plasma sintering is performed with the following process parameters: the heating rate is 100 ℃/min, the sintering temperature is 750 ℃, the sintering pressure is 60MPa, and the heat preservation time is 10 min.
The electrical conductivity and tensile strength of the copper-based composite materials obtained in the above examples and comparative examples were measured, and the measurement results are shown in table 1:
table 1: performance test results of copper-based composite materials obtained in examples and comparative examples
As can be seen from Table 1, the strength of the copper-based composites in examples 1 to 5 was 330MPa or more, and particularly, the strength of the copper-based composites prepared in examples 3 and 5 was 370MPa or more, which is much higher than 240MPa of pure copper. In addition, as can be seen from the comparison between example 5 and comparative examples 1 and 2, an obvious synergistic effect is generated between the tungsten carbides with two grain sizes, and the mechanical properties of the copper-based composite material are remarkably improved.
In various embodiments of the present invention, before adding the tungsten carbide into the aqueous copper salt solution, the tungsten carbide may be dispersed in deionized water (preferably, a dispersant is added to deionized water), and mechanically or ultrasonically stirred until the tungsten carbide is sufficiently dispersed, and then added into the aqueous copper salt solution.
While the invention has been described with reference to specific embodiments, it should be understood that the description is not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that changes may be made without departing from the scope of the invention, and it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. Therefore, the protection scope of the present invention is defined by the claims.
Claims (7)
1. A method for preparing a bicrystal tungsten carbide synergistically reinforced copper-based composite material is characterized by comprising the following steps:
preparing core-shell structure bicrystal tungsten carbide-copper reinforced particles with tungsten carbide as a core and copper as a shell; the double-crystal tungsten carbide comprises a first tungsten carbide with a first grain size and a second tungsten carbide with a second grain size, wherein the first grain size is larger than the second grain size, and the mass ratio of the first tungsten carbide to the second tungsten carbide is 5: 1-1: 5;
mixing the bicrystal tungsten carbide-copper reinforced particles with pure copper powder, and sintering by discharge plasma to obtain a bicrystal tungsten carbide synergistically reinforced copper-based composite material; wherein the double-crystal tungsten carbide accounts for 0.5-10% of the total mass of the copper-based composite material;
the technological parameters of the spark plasma sintering are as follows: the heating rate is 50-150 ℃/min, the sintering temperature is 600-900 ℃, the sintering pressure is 40-60 MPa, and the heat preservation time is 5-30 min.
2. The method for preparing a bicrystal tungsten carbide co-reinforced copper-based composite material according to claim 1, wherein the step of preparing the bicrystal tungsten carbide-copper reinforced particle having a core-shell structure comprises the sub-steps of:
preparing a precursor suspension: adding first tungsten carbide powder with a first grain size and second tungsten carbide powder with a second grain size into a copper salt aqueous solution, uniformly stirring, and adding an alkaline solution to generate copper hydroxide to obtain a precursor suspension;
liquid-phase reduction: heating the precursor suspension to 55-95 ℃, continuously stirring, adding a reducing agent into the precursor suspension, and reducing copper hydroxide in the precursor suspension into cuprous oxide;
gas-phase reduction: and filtering, cleaning and drying a product obtained by liquid phase reduction, placing the product in a reduction furnace, heating, introducing a reducing gas to reduce cuprous oxide into copper, and obtaining the double-crystal tungsten carbide-copper reinforced particles with the core-shell structure.
3. The method of preparing a twin crystal tungsten carbide synergistically reinforced copper based composite according to claim 2, wherein: the copper salt is any one or more of copper acetate, copper nitrate, copper sulfate and copper chloride, and the copper ion concentration of the copper salt aqueous solution is 3.2-32 g/L.
4. The method of preparing a twin crystal tungsten carbide synergistically reinforced copper based composite according to claim 2, wherein: the reducing agent is any one or more of glucose, fructose, lactose and citric acid.
5. The method of preparing a twin crystal tungsten carbide synergistically reinforced copper based composite according to claim 2, wherein: the reducing gas is hydrogen or carbon monoxide, or a mixed gas of at least one of nitrogen, argon and helium and hydrogen or carbon monoxide.
6. The method of preparing a twin crystal tungsten carbide synergistically reinforced copper based composite according to claim 2, wherein: in the gas-phase reduction step, the heating rate of the reduction furnace is 5-15 ℃/min, and the temperature is kept at 250-350 ℃ for 1-3 h; the obtained bicrystal tungsten carbide-copper reinforced particles are cooled along with the furnace.
7. The method of preparing a twin crystal tungsten carbide synergistically reinforced copper based composite according to claim 1, wherein: the first crystal grain size is 0.3-0.6 μm, and the second crystal grain size is 0.05-0.2 μm.
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