CN114411011A - Preparation method of aluminum oxide and tungsten particle synergistically enhanced copper alloy - Google Patents
Preparation method of aluminum oxide and tungsten particle synergistically enhanced copper alloy Download PDFInfo
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Abstract
The invention relates to a preparation method of an aluminum oxide and tungsten particle synergistically enhanced copper alloy, and belongs to the technical field of copper-based composite materials. The preparation method comprises the following steps: firstly, mixing ammonium metatungstate, soluble copper salt, soluble aluminum salt and water,adjusting the pH value to 0.5-2.0 to obtain a mixed solution; ② carrying out hydrothermal reaction on the mixed solution at 120-200 ℃, drying and calcining the product of the hydrothermal reaction to obtain CuO-WO3‑Al2O3Compounding powder; ③ mixing CuO-WO3‑Al2O3Reducing the composite powder to obtain Cu-W-Al2O3Compounding powder; fourthly, mixing Cu-W-Al2O3Pressing the composite powder into a blank, and then sintering and hot extruding. According to the preparation method of the aluminum oxide and tungsten particle synergistically enhanced copper alloy, the prepared copper alloy has the advantages of uniform distribution of alloy tissues, excellent tensile strength and hardness and easiness in extrusion forming.
Description
Technical Field
The invention belongs to the technical field of copper-based composite materials, and particularly relates to a preparation method of an aluminum oxide and tungsten particle synergistically enhanced copper alloy.
Background
The copper alloy has the characteristics of excellent electrical conductivity, high thermal conductivity and the like, and is widely applied to the engineering fields of military industry, electronics, aerospace, machinery and the like. The pure copper has low melting point and low hardness, and is gradually difficult to meet the service requirements of extreme working conditions. In order to improve the mechanical properties of pure copper, in recent years, metal tungsten is added into a copper matrix for reinforcement to form a Cu — W composite material.
The Cu-W alloy has the characteristics of high melting point, high density, high strength, ablation resistance of metal W, high conductivity and high thermal conductivity of metal copper and the like, has the advantages of good arc erosion resistance, fusion welding resistance, high strength, high hardness and the like, is widely used as an electrical contact material, resistance welding, electric spark machining and plasma electrode material, an electrothermal alloy, a high-density alloy, a military material with special purposes (such as a rocket nozzle, a flying throat liner) and the like, and particularly in the military aspect, for example, the Cu-W alloy is used as a medicine cover of an aerospace vehicle, a tank armour piercing bomb, a tail nozzle of an extended-range gun, a material of an electromagnetic gun orbit and the like due to the wider application range. The requirements for the properties of Cu-W alloys in these fields far exceed the requirements for general contact materials. Therefore, the physical properties and the forming properties of the tungsten-copper composite material are improved, and high-performance products are manufactured, which is always a hot point for researches of scholars at home and abroad.
At present, the research on the high-performance Cu-W alloy is slow, and mainly has the following four reasons: (1) in the prior art, the Cu-W alloy mainly adopts direct mechanical powder mixing of Cu powder and W powder and then sintering densification, and the mechanical mixing causes non-uniformity due to large density difference of Cu and W, so that the mechanical property of the alloy is reduced; (2) w and Cu atoms are not in solid solution, the bonding force is poor, the melting point difference is large, and high-performance Cu-W alloy is difficult to prepare due to the fact that Cu has low melting point and is easy to grow grains in the sintering and compacting process; (3) because W is a typical room temperature brittle metal, the ductility of the copper alloy can be greatly reduced by adding W, the plasticity of the Cu-W alloy is poor, and the Cu-W alloy is difficult to extrude and form, especially a conical thin-walled part; (4) the existing method for preparing tungsten-copper alloy is mainly an infiltration method, namely, a porous tungsten skeleton with certain density and strength is prepared, and then molten copper is infiltrated into the tungsten skeleton. For example, chinese patent No. CN110313233B discloses a manufacturing process of a new pseudo alloy WCu liner material with two elements of tungsten and copper being incompatible with each other, specifically, a powder metallurgy injection molding process is adopted to manufacture a porous tungsten skeleton material of a tungsten-copper liner, and then the tungsten skeleton material is made into a tungsten-copper alloy liner by processes of degumming, pre-sintering, solution infiltration sintering copper, and the like.
In the infiltration method, the porosity of the tungsten skeleton is difficult to control, and secondly, the tungsten skeleton is difficult to ensure to be completely filled with copper liquid, even if the tungsten skeleton can be filled in place, the final Cu-W alloy structure is extremely uneven due to the fact that the pore distribution is difficult to control, and the service requirement of high-precision parts is difficult to meet.
Disclosure of Invention
The invention aims to provide a preparation method of an aluminum oxide and tungsten particle synergistically enhanced copper alloy, which is uniform in alloy structure distribution and excellent in tensile strength and hardness.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an aluminum oxide and tungsten particle synergistically enhanced copper alloy comprises the following steps:
(1) mixing ammonium metatungstate, soluble copper salt, soluble aluminum salt and water, and adjusting the pH to 0.5-2.0 to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution at 120-200 ℃, drying and calcining a product of the hydrothermal reaction to obtain CuO-WO3-Al2O3Compounding powder;
(3) mixing CuO-WO3-Al2O3Reducing the composite powder to obtain Cu-W-Al2O3Compounding powder;
(4) adding Cu-W-Al2O3Pressing the composite powder into a blank, and then sintering and hot extruding.
The preparation method of the aluminum oxide and tungsten particle synergistically enhanced copper alloy adopts a wet chemical method, utilizes hydrothermal reaction to enable ammonium metatungstate, soluble copper salt and soluble aluminum salt to react and precipitate together in water, avoids segregation of tungsten atomic nucleus, aluminum atomic nucleus and copper atomic nucleus in the precipitation process due to large mass difference, and greatly improves CuO and WO3And Al2O3The uniformity of each component in the composite powder fundamentally solves the problem of uneven direct mechanical powder mixing of Cu powder and W powder in the traditional method.
CuO-WO of the present invention3-Al2O3In the reduction process of the composite powder, tungsten oxide volatilizes in the atmosphere and is transferred into a gas phase, and the tungsten oxide is reduced in a steam form and is precipitated on the surface of low-valence tungsten oxide, aluminum oxide or copper oxide, so that uniform composite powder is formed, tungsten and aluminum oxide can be adsorbed on the surface of copper in situ and self-generated, and the problems that W and Cu atoms are not solid-dissolved and the binding force is poor are solved; reduced Cu-W-Al2O3The composite powder is very uniform, copper infiltration in subsequent procedures is not needed, and the problem of nonuniform texture of tungsten-copper alloy prepared by the traditional infiltration method is solved.
The invention introduces Al which is finely dispersed and distributed into Cu-W composite powder2O3Particles of Al2O3Has excellent high-temperature strength and good chemical stability, and is an ideal reinforcement. During the sintering process of the copper alloy, Al is used2O3The pinning effect of the particles on the grain boundary can play a fine grain strengthening role. The fine grain strengthening can simultaneously improve the strength and the plasticity of the material and solve the problem of grain growth caused by low melting point of Cu in the sintering and compacting process.
Further, the total concentration of the raw materials of ammonium metatungstate, soluble copper salt and soluble aluminum salt in water is 0.5-0.7 g/mL. Preferably, the total concentration of the raw materials of ammonium metatungstate, soluble copper salt and soluble aluminum salt in water is 0.5-0.6 g/mL.
Further, the aluminum oxide accounts for 0.1-0.8 wt% of the copper alloy synergistically enhanced by the aluminum oxide and tungsten particles. The tungsten particles account for 10 wt% -25 wt% of the aluminum oxide and tungsten particles synergistically enhanced copper alloy. Preferably, the aluminum oxide accounts for 0.1-0.2 wt% of the copper alloy synergistically enhanced by the aluminum oxide and tungsten particles. The tungsten particles account for 10 wt% -20 wt% of the aluminum oxide and tungsten particles synergistically enhanced copper alloy.
In the step (1), the hydrothermal reaction is to perform heat preservation treatment on ammonium metatungstate, soluble copper salt, soluble aluminum salt and water in a closed container. Furthermore, the time of the hydrothermal reaction is 8-25 h. Preferably, the temperature of the hydrothermal reaction is 120-150 ℃, and the time of the hydrothermal reaction is 20-25 h.
Further, the drying temperature is 80-100 ℃.
Further, in the step (4), a mold is designed according to the shape of the copper alloy product cooperatively enhanced by the aluminum oxide and the tungsten particles, then the copper alloy product is preformed after being pressed into a blank in the mold, and the blank is sintered, densified and strengthened and finally formed by extrusion. The invention adopts a near-net forming preparation method of cold extrusion preforming, sintering compact strengthening and hot extrusion, has simple process and short flow, has good powder extrusion forming, ensures the yield, and fundamentally solves the problems of poor plasticity and difficult extrusion forming of the Cu-W alloy.
Further, the aluminum oxide and tungsten particles cooperatively reinforce the copper alloy to be a multi-taper or taper thin-wall part. The multi-taper thin-wall part means that the inner circumferential surface and the outer circumferential surface of the taper thin-wall part are formed by sequentially connecting a plurality of conical surfaces with different tapers.
In the step (4), the die is designed according to the multi-taper or taper thin-wall part. And (3) performing the pressing in a die to obtain a multi-taper or conical thin-wall part blank. And sintering and hot extruding the multi-taper or conical thin-wall part blank to obtain a multi-taper or conical thin-wall part finished product. The multi-taper or taper thin-wall part has a taper structure, belongs to a thin-wall part, and can be used as a military device such as a shaped charge liner, and the like, but the conventional Cu-W alloy has poor deformability, so that the finished product rate of the products is low, and the performance of the products cannot reach the military standard easily.
Further, the pH value is adjusted to 0.5-2.0 by oxalic acid in the step (1). The hydrogen ions and the tungstate ions react to generate tungstic acid precipitate, the oxalate ions and the copper ions react to generate copper oxalate precipitate, and the oxalate ions and the aluminum ions react to generate aluminum oxalate precipitate. Tungstic acid, aluminum oxalate and copper oxalate can be co-reacted in water to co-precipitate. Preferably, the pH value is adjusted to 0.5-1.0 by oxalic acid in the step (1).
Further, the soluble copper salt is one or any combination of copper nitrate, copper sulfate and copper halide. The soluble aluminum salt is one or any combination of aluminum nitrate, aluminum sulfate and aluminum halide.
Further, in the step (2), the calcining temperature is 400-550 ℃. The calcination time is 30-120 min. The calcination is carried out in a muffle furnace. Preferably, the calcining temperature is 510-550 ℃ and the calcining time is 30-60 min.
Further, in the step (3), the reduction is carried out twice, wherein the temperature of the first reduction is 580-630 ℃, and the temperature of the second reduction is 880-920 ℃. Furthermore, the time for the first reduction is 4-7 h, and the time for the second reduction is 8-12 h. Preferably, the temperature of the first reduction is 620-630 ℃, the temperature of the second reduction is 920 ℃, and the time of the second reduction is 8-10 h.
Further, hydrogen is adopted to react CuO-WO3-Al2O3And (5) reducing the composite powder.
Further, the pressing pressure is 10-30 MPa. Furthermore, the pressure maintaining time for pressing is 2-5 min. Preferably, the pressing pressure is 10-20 MPa, and the pressure maintaining time is 4-5 min.
Further, in the step (4), the Cu-W-Al is processed by a hydraulic press2O3Pressing the composite powder into a blank.
Furthermore, graphite is adopted to lubricate the surface of the die before pressing, so that subsequent demoulding is facilitated.
Further, the sintering is vacuum sintering. The sintering temperature is 900-1050 ℃. Preferably, the sintering temperature is 1000-1050 ℃.
Further, the sintering time is 1-3 h. Preferably, the sintering time is 1 h.
Further, the sintering is performed in a vacuum sintering furnace. In the sintering process, a solid ceramic part is required to be used for propping against a multi-taper or conical thin-wall part blank. And sintering the multi-taper or taper thin-wall part blank to obtain a sintered part.
Further, the temperature of the hot extrusion is 1000-1050 ℃, and the pressure is 20-30 MPa. Preferably, the pressure of the hot extrusion is 20-25 MPa.
Further, the sintered part is preheated before hot extrusion. Furthermore, the preheating temperature of the sintered part is 1000-1050 ℃. The preheating time of the sintered piece is 20-40 min. The preheating of the sintered parts is carried out in a resistance furnace.
Further, the die is preheated before hot extrusion. Furthermore, the preheating temperature of the die is 200-250 ℃, and the heat preservation time is 1-3 h.
According to the preparation method of the aluminum oxide and tungsten particle synergistically enhanced copper alloy, the utilization rate of the raw materials is 98%, and the raw materials are saved, so that the preparation method is suitable for large-scale industrial production; the structure uniformity is stable, the density can reach up to 100%, the energy-gathered jet form of a multi-taper or conical thin-wall part product can be stable, the penetration capability is improved by more than 40% compared with that of a pure copper product, the tensile strength can reach up to 536MPa, and the hardness can reach up to 220 HV.
Drawings
FIG. 1 is a diagram showing the reaction and forming states of the synergistic enhancement of copper alloy by alumina and tungsten particles in example 1 of the present invention;
FIG. 2 is a diagram of a mold designed for preparing a copper alloy with synergistically enhanced particles of aluminum oxide and tungsten in example 1 of the present invention;
FIG. 3 is an EBSD structural morphology of the copper alloy synergistically enhanced by the aluminum oxide and tungsten particles in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation method of the copper alloy synergistically enhanced by the alumina and the tungsten particles in the embodiment is shown in fig. 1, and comprises the following steps:
(1) with W, Cu, Al2O3The mass ratio of ammonium metatungstate to copper nitrate to aluminum nitrate is 9.99:89.91:0.1, the using amounts of the raw materials of ammonium metatungstate, copper nitrate and aluminum nitrate are calculated, the raw materials are added into distilled water, the total concentration of the raw materials is 0.5g/mL, then oxalic acid is added while stirring, the raw materials are mixed uniformly, and the pH value of the solution is adjusted to be 0.5, so that a mixed solution is obtained;
(2) pouring the mixed solution obtained in the step (1) into a high-pressure reaction kettle for hydrothermal reactionCarrying out suction filtration on suspension after reaction at the reaction temperature of 120 ℃ for 25h, drying substances after suction filtration at the temperature of 80 ℃ to thoroughly remove moisture, then carrying out calcination treatment in a muffle furnace at the temperature of 550 ℃ for 30min to obtain CuO-WO3-Al2O3Compounding powder;
(3) reacting CuO-WO with flowing hydrogen3-Al2O3Reducing the composite powder, wherein the temperature of the first reduction is 630 ℃ and the time is 4h, the temperature of the second reduction is 920 ℃ and the time is 8h, and obtaining Cu-W-Al2O3Compounding powder;
(4) 30g of Cu-W-Al are weighed2O3Placing the composite powder into a die, carrying out extrusion forming on a hydraulic press, wherein the extrusion die is shown in figure 2 to obtain a blank, the pressing pressure is 10MPa, the pressure maintaining time is 5min, and graphite is required to lubricate the surface of the die before pressing, so that the subsequent demoulding is convenient; in fig. 2, the extrusion die comprises an upper die 1 and a lower die 2, and a die cavity for forming the tapered thin-walled workpiece 3 is formed when the upper die 1 and the lower die 2 are closed;
(5) putting the blank into a vacuum sintering furnace for sintering densification to obtain a sintered part, wherein the sintering temperature is 1050 ℃, the heat preservation time is 1h, a solid ceramic part is required to be used for propping against the copper alloy conical thin-wall part in the sintering process, the sintered part is put into a resistance furnace to be heated to 1000 ℃, the heat preservation time is 40min, meanwhile, a designed mold is preheated, the preheating temperature is 250 ℃, the heat preservation time is 3h, then the sintered part heated by the resistance furnace is put into the mold for hot extrusion molding, the hot extrusion molding temperature is 1000 ℃, the pressure is 20MPa, finally, the aluminum oxide and tungsten particles synergistically enhanced copper alloy conical thin-wall part is prepared, and the thin-wall part is analyzed by EBSD (electron back scattering detector), and the result is shown in figure 3.
Example 2
The preparation method of the aluminum oxide and tungsten particle synergistically enhanced copper alloy comprises the following steps:
(1) with W, Cu, Al2O3The mass ratio of (A) to (B) is 19.96:79.84:0.2,Adding the raw materials of copper nitrate and aluminum nitrate into distilled water, wherein the total concentration of the raw materials is 0.6g/mL, then adding oxalic acid while stirring, uniformly mixing, and adjusting the pH value of the solution to 1.0 to obtain a mixed solution;
(2) pouring the solution obtained in the step (1) into a high-pressure reaction kettle for hydrothermal reaction at the reaction temperature of 150 ℃ for 20 hours, carrying out suction filtration on the suspension after reaction, drying the substance after suction filtration at the temperature of 100 ℃ to thoroughly remove moisture, then carrying out calcination treatment in a muffle furnace at the temperature of 510 ℃ for 60 minutes to obtain CuO-WO3-Al2O3Compounding powder;
(3) reacting CuO-WO with flowing hydrogen3-Al2O3Reducing the composite powder, wherein the temperature of the first reduction is 620 ℃, the time is 7h, the temperature of the second reduction is 920 ℃, the time is 10h, and obtaining Cu-W-Al2O3Compounding powder;
(4) 30g of Cu-W-Al are weighed2O3Filling the composite powder into a die, carrying out extrusion forming on the composite powder on a hydraulic press to obtain a blank, wherein the pressing pressure is 20MPa, the pressure maintaining time is 4min, and the surface of the die is lubricated by graphite before pressing so as to facilitate subsequent demoulding;
(5) and putting the blank into a vacuum sintering furnace for sintering densification to obtain a sintered piece, wherein the sintering temperature is 1000 ℃, the heat preservation time is 1h, a solid ceramic piece is required to prop against the copper alloy multi-taper thin-wall piece in the sintering process, the sintered piece is put into a resistance furnace to be heated to 1050 ℃, the heat preservation time is 20min, meanwhile, a designed mold is preheated, the preheating temperature is 250 ℃, the heat preservation time is 3h, then the sintered piece heated by the resistance furnace is put into the mold to be subjected to hot extrusion molding, the temperature of the hot extrusion molding is 1050 ℃, the pressure is 25MPa, and finally the aluminum oxide and tungsten particle synergistically enhanced copper alloy multi-taper thin-wall piece is prepared.
Examples of the experiments
The properties of the aluminum oxide and tungsten particles synergistically enhanced copper alloy of examples 1 and 2 and commercial pure copper were tested and the results are shown in table 1. The test method comprises the following steps: the tensile strength test is carried out according to GB/T228-.
Table 1 performance test results for the alumina and tungsten particles of examples 1, 2 synergistically enhanced copper alloys and commercial pure copper
As can be seen from Table 1, the aluminum oxide and tungsten particles synergistically enhanced copper alloy prepared in the embodiment of the invention has excellent comprehensive performance, the highest compactness is 100%, the utilization rate of raw materials is 98%, the highest tensile strength is 536MPa, the highest hardness is 220HV, the performance indexes are far higher than corresponding performance indexes reported in the prior art publications, the penetration depth of a test is improved by 50% compared with that of commercial pure copper under the same condition, and the copper alloy has very wide application prospect and popularization value.
Claims (10)
1. A preparation method of an aluminum oxide and tungsten particle synergistically enhanced copper alloy is characterized by comprising the following steps:
(1) mixing ammonium metatungstate, soluble copper salt, soluble aluminum salt and water, and adjusting the pH to 0.5-2.0 to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution at 120-200 ℃, drying and calcining a product of the hydrothermal reaction to obtain CuO-WO3-Al2O3Compounding powder;
(3) mixing CuO-WO3-Al2O3Reducing the composite powder to obtain Cu-W-Al2O3Compounding powder;
(4) adding Cu-W-Al2O3Pressing the composite powder into a blank, and then sintering and hot extruding.
2. The method for preparing the aluminum oxide and tungsten particle synergistically enhanced copper alloy according to claim 1, wherein the aluminum oxide accounts for 0.1 to 0.8 wt% of the aluminum oxide and tungsten particle synergistically enhanced copper alloy; the tungsten particles account for 10 wt% -25 wt% of the aluminum oxide and tungsten particles synergistically enhanced copper alloy.
3. The method for preparing the aluminum oxide and tungsten particle synergistically enhanced copper alloy according to claim 1, wherein in the step (4), a mold is designed according to the shape of the aluminum oxide and tungsten particle synergistically enhanced copper alloy product, then the aluminum oxide and tungsten particle synergistically enhanced copper alloy product is pressed into a blank in the mold to realize preforming, densification and strengthening through sintering, and then the blank is finally formed through extrusion.
4. The method for preparing the aluminum oxide and tungsten particle synergistically enhanced copper alloy according to claim 3, wherein the aluminum oxide and tungsten particle synergistically enhanced copper alloy is a multi-taper or tapered thin-walled part; in the step (4), a mould is designed according to the multi-taper or taper thin-wall part; performing the pressing in a die to obtain a multi-taper or conical thin-wall part blank; and sintering and hot extruding the multi-taper or conical thin-wall part blank to obtain a multi-taper or conical thin-wall part finished product.
5. The method for preparing the copper alloy with the synergistically enhanced aluminum oxide and tungsten particles as claimed in claim 1, wherein in the step (1), the pH is adjusted to 0.5 to 2.0 by oxalic acid; the soluble copper salt is one or any combination of copper nitrate, copper sulfate and copper halide; the soluble aluminum salt is one or any combination of aluminum nitrate, aluminum sulfate and aluminum halide.
6. The method for preparing the copper alloy reinforced by the aluminum oxide and the tungsten particles synergistically according to claim 1, wherein in the step (2), the calcining temperature is 400-550 ℃.
7. The method for preparing the copper alloy synergistically enhanced by the aluminum oxide and tungsten particles according to claim 1, 5 or 6, wherein in the step (3), the reduction is carried out twice, the temperature of the first reduction is 580-630 ℃, and the temperature of the second reduction is 880-920 ℃.
8. The method for preparing the copper alloy reinforced synergistically with the particles of aluminum oxide and tungsten according to claim 1, 3 or 4, wherein the pressure for the pressing is 10 to 30 MPa.
9. The method for preparing the aluminum oxide and tungsten particle synergistically enhanced copper alloy according to claim 1, wherein the sintering is vacuum sintering, and the sintering temperature is 900-1050 ℃.
10. The method for preparing the aluminum oxide and tungsten particle synergistically reinforced copper alloy according to claim 1, wherein the temperature of the hot extrusion is 1000 to 1050 ℃ and the pressure is 20 to 30 MPa.
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| CN202210080324.5A CN114411011A (en) | 2022-01-24 | 2022-01-24 | Preparation method of aluminum oxide and tungsten particle synergistically enhanced copper alloy |
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| CN115094265A (en) * | 2022-07-22 | 2022-09-23 | 合肥工业大学 | Tungsten/metal oxide particle complex phase reinforced copper-based composite material and preparation method thereof |
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