CN114959333B - Tungsten-copper alloy and preparation method thereof - Google Patents
Tungsten-copper alloy and preparation method thereof Download PDFInfo
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- CN114959333B CN114959333B CN202210611479.7A CN202210611479A CN114959333B CN 114959333 B CN114959333 B CN 114959333B CN 202210611479 A CN202210611479 A CN 202210611479A CN 114959333 B CN114959333 B CN 114959333B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a tungsten-copper alloy and a preparation method thereof, belonging to the technical field of tungsten-copper alloys; the preparation method comprises the following steps: s1, preparing porous hollow tungsten oxide nano microspheres; s2, preparing tungsten-copper nano microspheres; s3, preparing a composite activating element; s4, modifying the carbon nano tube; and S5, forming and sintering. The tungsten-copper alloy prepared by the invention has better comprehensive properties such as mechanical property, ablation resistance, thermal shock resistance and the like, and is different from the traditional method for preparing the tungsten-copper alloy.
Description
Technical Field
The invention relates to the technical field of tungsten-copper alloy, in particular to a tungsten-copper alloy and a preparation method thereof.
Background
Tungsten-copper alloy is a composite material consisting of body-centered cubic tungsten particles and face-centered cubic copper binder phase that neither mutually dissolves nor forms intermetallics, and is commonly referred to as a pseudoalloy or pseudoalloy. It combines the characteristics of tungsten and copper, such as high-temperature strength, high electric and thermal conductivity, good electric corrosion resistance, higher hardness, low thermal expansion coefficient and certain plasticity, and can control and adjust the corresponding mechanical and physical properties through changing the composition ratio. In addition, the tungsten-copper composite material has the advantages of tungsten and copper, and can meet the use requirements of materials in many fields. Such as: the tungsten has good fusion welding resistance and erosion resistance, and the copper has good conductivity, and the tungsten and the copper are combined to be used for the vacuum circuit breaker, so that the high-capacity on-off requirement of the vacuum circuit breaker can be met; the tungsten-copper composite material is used as a radiating element in large-scale integrated circuits and microwave devices, can effectively reduce the stress problem caused by insufficient radiation and linear expansion coefficient difference, and prolongs the service life of electronic elements. Therefore, it can be widely applied to various industrial departments of spaceflight, electronics, machinery, electrical appliances and the like, in particular to high-technology fields. Tungsten-copper alloys cannot be produced by the conventional fusion casting method, and therefore are mostly produced by the powder metallurgy method.
In the method for preparing the tungsten-copper alloy at present, mixing, die pressing and high-temperature sintering are commonly used preparation processes, but the method has the following defects: (1) The metal powder is directly mixed in a rolling ball mill according to the proportion, but the mixing uniformity is poor due to the specific gravity difference of the powder, and the performance of the prepared alloy is unstable; (2) The density of the initial pressed compact is poor, defects are easy to generate, and the effective densification of the initial pressed compact influences the density and quality of a final sintered part; (3) The sintering temperature is high, a large amount of energy is consumed, the resource cost is wasted, the cost and the resource are not favorably saved, and the unfavorable material defects of overlarge grain size and the like are caused due to higher temperature; (4) The vacuum sintering atmosphere has high requirements on a sintering furnace, and the process difficulty and the investment cost are increased.
Disclosure of Invention
The invention aims to provide a tungsten-copper alloy and a preparation method thereof, which have better comprehensive properties such as mechanical property, ablation resistance, thermal shock resistance and the like, and are different from the traditional method for preparing the tungsten-copper alloy.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a tungsten-copper alloy, which comprises the following steps:
s1, preparing porous hollow tungsten oxide nano microspheres: dissolving sodium tungstate in water, and adding ammonium chloride and a pore-forming agent into the water to obtain a water phase; adding an oil-soluble surfactant into an organic solvent, and uniformly mixing to obtain an oil phase; adding the oil phase into the water phase, emulsifying at a high speed, dropwise adding concentrated hydrochloric acid, stirring, filtering, centrifuging, and drying to obtain porous hollow tungsten oxide nano microspheres;
s2, preparing tungsten-copper nano microspheres: adding the porous hollow tungsten oxide nano-microspheres prepared in the step S1 into a solution containing copper salt, uniformly dispersing, dropwise adding a complexing agent, and heating to evaporate the solvent to obtain sol; then raising the temperature, reducing the vacuum degree to obtain dry gel, taking out the dry gel, igniting the dry gel, carrying out ball milling, and carrying out low-temperature hydrogen reduction to obtain tungsten-copper nano microspheres;
s3, preparing a composite activating element: weighing high-purity iron powder and high-purity chromium powder, mixing, and performing ball milling to obtain a composite activated element;
s4, modification of the carbon nano tube: mixing the carbon nano tube with a No. 92 gasoline medium, and performing ball milling to obtain a modified carbon nano tube;
s5, forming and sintering: and (3) mixing the tungsten-copper nano microspheres prepared in the step (S2), the composite activating elements prepared in the step (S3) and the modified carbon nano tubes prepared in the step (S4), then performing ball milling to obtain mixed powder, performing cold pressing, and then performing vacuum pressure sintering and inert gas protection high-temperature pressureless sintering to obtain the tungsten-copper alloy.
As a further improvement of the present invention, in the aqueous phase in step S1, the mass ratio of sodium tungstate, ammonium chloride and the pore-forming agent is 10:5-8:0.5 to 1; the pore-foaming agent is a compound mixture of a macroporous pore-foaming agent and a mesoporous pore-foaming agent, the mass ratio is 5-10; the mesoporous pore-foaming agent is selected from at least one of Cetyl Trimethyl Ammonium Bromide (CTAB), oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO 106; the oil-soluble surfactant is selected from at least one of fatty acid soap, lauryl sodium sulfate, lauryl polyoxyethylene ether sodium sulfate, cetyl polyoxyethylene ether sodium phosphate, lecithin, octadecyl trimethyl ammonium chloride, C12-14 alkyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl sodium chloride, sorbitan monocinnamate, ethylene oxide addition product, lauryl polyoxyethylene ether, coco diethanolamide, oleic acid monoglyceride, polyoxyethylene castor oil, polyoxyethylene lanolin, coco amido propyl betaine, span-20, span-80 and span-85; the organic solvent is at least one selected from ethyl acetate, methyl formate, petroleum ether, dichloromethane, trichloromethane, tetrachloromethane, toluene, xylene, cyclohexane and normal hexane; the content of the oil-soluble surfactant in the oil phase is 2-5wt%; the concentration of the concentrated hydrochloric acid is 35-37wt%, the rotating speed of the high-speed emulsification is 17000-20000r/min, and the time is 3-5min.
As a further improvement of the invention, in step S2, the copper salt is at least one of copper nitrate, copper sulfate and copper chloride; the mass ratio of the porous hollow tungsten oxide nano-microspheres to the copper salt is 10:3-20 parts of; the complexing agent is citric acid or sodium citrate; the mass ratio of the copper salt to the complexing agent is 1:2-5; the heating temperature is 50-70 ℃, the temperature is increased to 120-150 ℃, and the vacuum degree is reduced to 0.01-0.1MPa; the ball milling time is 5-12h; the low-temperature hydrogen reduction adopts a strong-drainage breathable tubular furnace to introduce hydrogen at the temperature of 600-750 ℃ for reduction for 3-5h, and the ventilation quantity of the hydrogen is 15-20L/min.
As a further improvement of the invention, the ball milling conditions are that materials are put into a ball milling tank, the material of the milling ball is natural agate, the ball-material ratio is 3-7, absolute ethyl alcohol is used as a ball milling medium, the rotating speed of a main shaft of the ball mill is 200-300r/min, and the reversing is performed once every 5-10min of operation.
As a further improvement of the invention, the mass ratio of the high-purity iron powder to the high-purity chromium powder in the step S3 is 1:2-3; the ball milling time is 5-7h.
As a further improvement of the invention, the mass ratio of the carbon nano tubes to the No. 92 gasoline medium in the step S4 is 1:0.5-1.2; the ball milling time is 2-4h.
As a further improvement of the invention, the mass ratio of the tungsten-copper nano microspheres, the composite activating elements and the modified carbon nano tubes in the step S5 is 96.5-97.8: 0.2-0.5; the ball milling time is 5-10h; the cold pressing condition is that the pressing is carried out for 1 to 3 hours under the pressure of 50 to 70 MPa.
As a further improvement of the present invention, the vacuum pressure sintering conditions in step S5 are: sintering at room temperature of-650 deg.C for 50-70min under 25-30MPa at 650-900 deg.C for 40-60min and 900-1000 deg.C for 60-70min; the inert gas protection high-temperature non-pressure condition is as follows: the temperature is between room temperature and 920 ℃, the sintering time is between 100 and 140min, the sintering time is between 920 and 1350 ℃, the sintering time is between 120 and 160min, the sintering time is between 1350 and 1450 ℃, and the sintering time is between 300 and 400min; introducing hydrogen in the whole sintering process, wherein the ventilation amount of the hydrogen is 5-12L/min; during the whole sintering process, the temperature is increased to 50-80 ℃/min.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, preparing porous hollow tungsten oxide nano microspheres: dissolving 10 parts by weight of sodium tungstate in water, and adding 5-8 parts by weight of ammonium chloride and 0.5-1 part by weight of pore-foaming agent into the water to obtain a water phase; adding an oil-soluble surfactant into an organic solvent, and uniformly mixing to obtain an oil phase, wherein the content of the oil-soluble surfactant is 2-5wt%; adding the oil phase into the water phase, emulsifying for 3-5min at the rotating speed of 17000-20000r/min, dropwise adding 7-12 parts by weight of 35-37wt% concentrated hydrochloric acid, stirring, filtering, centrifuging, and drying to obtain porous hollow tungsten oxide nano microspheres;
the pore-foaming agent is a compound mixture of a macroporous pore-foaming agent and a mesoporous pore-foaming agent, and the mass ratio is 5-10;
s2, preparing tungsten-copper nano microspheres: adding 10 parts by weight of the porous hollow tungsten oxide nano-microspheres prepared in the step S1 into a solution containing 3-20 parts by weight of copper salt, uniformly dispersing, dropwise adding 20-50 parts by weight of complexing agent, and heating to 50-70 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 120-150 ℃, reducing the vacuum degree to 0.01-0.1MPa to obtain dry gel, taking out, igniting the dry gel, carrying out ball milling for 5-12h, introducing hydrogen into a strong drainage breathable tubular furnace at 600-750 ℃ for reduction for 3-5h, wherein the ventilation capacity of the hydrogen is 15-20L/min, and obtaining tungsten-copper nano microspheres;
s3, preparing a composite activating element: weighing 1 part by weight of high-purity iron powder and 2-3 parts by weight of high-purity chromium powder, mixing, and performing ball milling for 5-7 hours to obtain a composite activated element;
s4, modification of the carbon nano tube: mixing 1 part by weight of carbon nano tube with 0.5-1.2 parts by weight of No. 92 gasoline medium, and carrying out ball milling for 2-4h to obtain a modified carbon nano tube;
s5, forming and sintering: mixing 96.5-97.8 parts by weight of tungsten-copper nano microspheres prepared in the step S2, 0.2-0.5 part by weight of composite activating elements prepared in the step S3 and 2-3 parts by weight of modified carbon nano tubes prepared in the step S4, performing ball milling for 5-10 hours to obtain mixed powder, pressing for 1-3 hours under the pressure of 50-70MPa, and performing vacuum pressure sintering and inert gas protection high-temperature pressureless sintering two-step molding to obtain tungsten-copper alloy;
the vacuum pressure sintering conditions are as follows: sintering at room temperature of-650 deg.C for 50-70min under 25-30MPa at 650-900 deg.C for 40-60min and 900-1000 deg.C for 60-70min; the inert gas protection high-temperature non-pressure condition is as follows: sintering at room temperature of-920 deg.C for 100-140min, at 920-1350 deg.C for 120-160min, at 1350-1450 deg.C for 300-400min; introducing hydrogen in the whole sintering process, wherein the ventilation amount of the hydrogen is 5-12L/min; in the whole sintering process, the temperature is increased to 50-80 ℃/min;
the ball milling conditions are that the materials are put into a ball milling tank, the material of the milling ball is natural agate, the ball material ratio is 3-7, the absolute ethyl alcohol is used as a ball milling medium, the rotating speed of a main shaft of the ball milling machine is 200-300r/min, and the reversing is performed once every 5-10min of operation.
The invention further protects the tungsten-copper alloy prepared by the preparation method.
The invention has the following beneficial effects:
the invention prepares a porous hollow tungsten oxide nano microsphere by a sol-gel method, and concretely comprises the steps of dissolving sodium tungstate in water, and adding ammonium chloride and a pore-forming agent into the water to obtain a water phase; in addition, the oil phase contains a surfactant, the surfactant and the oil phase are mixed and emulsified to form oil-in-water microsphere emulsion droplets, concentrated hydrochloric acid is dripped to obtain porous hollow oxide nano microspheres in the presence of a pore-forming agent and the surfactant, and the oil phase in the microspheres is removed by centrifugation, wherein the specific chemical equation is as follows:
12Na 2 WO 4 +14HCl＝5Na 2 O·12WO 3 +14NaCl+7H 2 O
Na 2 O·12WO 3 +10NH 4 Cl＝5(NH 4 ) 2 O·12WO 3 +10NaCl
5(NH 4 ) 2 O·12WO 3 +10HCl+7H 2 O＝12H 2 WO 4 +10NH 4 Cl
H 2 WO 4 ＝WO 3 +H 2 O
further, the obtained porous hollow tungsten oxide nano-microspheres are added into a solution containing copper nitrate, citric acid is added to form a citric acid-copper complex inside and outside the porous hollow tungsten oxide nano-microspheres, xerogel is obtained by heating, the xerogel is ignited to obtain the tungsten oxide nano-microspheres with copper oxide inside and on the surface, and the tungsten-copper nano-microspheres are further obtained by a reduction method.
According to the invention, by additionally adding the composite activating element, the sintering activation energy is reduced, the material structure is improved, the compactness and the performance of the material are improved, and the sintering material has the advantages of low sintering temperature, short sintering time, higher structure performance and the like. The added composite activating elements comprise Fe and Cr, and when the Fe and the Cr are added, the density of the activated liquid phase sintering can be obviously improved. The addition of Fe improves the wettability and the adhesiveness between copper and tungsten, the addition of Cr element improves the interface strength of tungsten and copper, and makes the alloy structure more uniform, and the W-W connectivity is reduced, thereby reducing the particle debonding of tungsten particles and the debonding of a tungsten-copper interface during fracture, increasing the cleavage fracture of tungsten particles, improving the mechanical property of the alloy, and in addition, obviously reducing the negative influence of an activating element on the heat conductivity and the electric conductivity of the tungsten-copper alloy, thereby obviously influencing the microstructure of the tungsten-copper alloy, improving the density and the mechanical property, not influencing the heat conductivity and the electric conductivity of the alloy, and preparing the tungsten-copper alloy with good performance. Meanwhile, the added composite activating elements are Fe and Cr, so that the use of noble metal activating elements such as Pd, ag and the like is avoided, a good modification effect can be achieved, the cost is lower, and the method is more suitable for industrial application;
because of poor wettability of the phase interface, tungsten and copper have slow diffusion of atoms in the sintering process and are difficult to sinter compactly. According to the invention, the tungsten nanosphere framework is prepared, copper is dissolved in the microsphere framework, the dispersion of the tungsten nanosphere framework is limited, the particle size of the tungsten nanosphere framework is extremely small, the compatibility is improved through fine grain strengthening at the nanometer level, and the wettability and the adhesiveness of a tungsten-copper interface in a microsphere are further activated through an activating element, so that the tungsten-copper alloy can be fully mixed, and a compact alloy material is obtained.
The addition of the carbon nano tube can improve the high-temperature strength of the tungsten-copper alloy material in an extreme environment, has high heat conduction and high electric conductivity, and can also improve the heat conduction and the electric conductivity of the alloy material, so that the high-performance tungsten-copper alloy material is prepared, but the carbon nano tube is directly added, and is easy to agglomerate and cannot be uniformly dispersed in the alloy material.
The mixture is subjected to ball milling, and the impact and the grinding of the milling balls further reduce the grain size of the powder, increase the activity and intensify the diffusion of copper into a tungsten phase to form an unsaturated solid solution. The tungsten-copper composite microsphere generates violent plastic deformation in the process, the particles generate great stress and strain, and a large amount of microscopic defects such as dislocation, distortion and the like are formed in the crystal grains. The atomic activity and the energy storage in the system are increased, so that solid solution is formed, the formation of cellular substructure is promoted, the grain size is reduced, and the obtained alloy material is more compact after the subsequent cold pressing and sintering.
The invention adopts two-step sintering, when sintering is carried out at the temperature slightly higher than the melting point of copper, the copper is melted to be a solid-liquid phase, tungsten particles are rearranged and contacted with each other due to the action of viscous flow and capillary force, the copper phase is redistributed and filled, and the activation elements can be fully diffused with the tungsten phase and the copper phase by the slow heating rate and proper heat preservation time in the sintering process, so that the wettability of the tungsten and copper interface is improved, the sintering performance is further improved, the loss of the copper phase is reduced, and the defect of a large number of holes in a sintered body is avoided, thereby ensuring the performance of the alloy material;
the tungsten-copper alloy prepared by the invention has better comprehensive properties such as mechanical property, ablation resistance, thermal shock resistance and the like, and is different from the traditional method for preparing the tungsten-copper alloy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of porous hollow tungsten oxide nanospheres prepared in example 1 of the present invention;
FIG. 2 is a TEM image of porous hollow tungsten oxide nanospheres prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional view of the tungsten-copper alloy obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
High-purity iron powder with the fineness of 1250 meshes and the iron content of more than 99.95 percent is purchased from Nangong Cuiteng alloy materials Co., ltd; high-purity chromium powder with the fineness of 500 meshes and the chromium content of more than 99.95 percent is purchased from Tianjin Hexokes alloy welding materials Co. The carbon nanotube is a single-walled carbon nanotube with a length of 1-5 μm and a diameter of 2-10nm, and is available from Nanjing Xiancheng nanomaterial science and technology Co.
Example 1
The embodiment provides a preparation method of a tungsten-copper alloy, which specifically comprises the following steps:
s1, preparing porous hollow tungsten oxide nano microspheres: dissolving 10 parts by weight of sodium tungstate in 100 parts by weight of water, and adding 5 parts by weight of ammonium chloride and 0.5 part by weight of pore-foaming agent into the water to obtain a water phase; adding lauryl alcohol polyoxyethylene ether sodium sulfate into ethyl acetate, and uniformly mixing to obtain an oil phase, wherein the content of the lauryl alcohol polyoxyethylene ether sodium sulfate is 2wt%; adding 50 parts by weight of oil phase into 70 parts by weight of water phase, emulsifying for 3min at the rotating speed of 17000r/min, dropwise adding 7 parts by weight of 35wt% concentrated hydrochloric acid, stirring, filtering, centrifuging at 3000r/min for 10min, and drying at 75 ℃ for 2h to obtain porous hollow tungsten oxide nano microspheres; FIG. 1 is an SEM image of the prepared porous hollow tungsten oxide nanospheres, which shows that a large number of pores are formed on the surface of the nanospheres to facilitate the subsequent entry of copper-containing solution; fig. 2 is a TEM image of the prepared porous hollow tungsten oxide nano-microsphere, which shows that the microsphere is a hollow structure and can contain a copper-citric acid composite.
The pore-foaming agent is a compound mixture of polyoxyethylene sorbitan fatty acid ester and hexadecyl trimethyl ammonium bromide, and the mass ratio is 5;
s2, preparing tungsten-copper nano microspheres: adding 10 parts by weight of the porous hollow tungsten oxide nano microspheres prepared in the step S1 into 100 parts by weight of a solution containing 3 parts by weight of copper chloride, ultrasonically dispersing for 30min at 1000W, dropwise adding 20 parts by weight of citric acid, and heating to 50 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 120 ℃, reducing the vacuum degree to 0.01MPa to obtain dry gel, taking out, igniting the dry gel, carrying out ball milling for 5 hours, introducing hydrogen into a strong drainage breathable tubular furnace at 600 ℃ for reduction for 3 hours, wherein the ventilation capacity of the hydrogen is 15L/min, and obtaining tungsten-copper nano microspheres;
s3, preparing a composite activating element: weighing 1 part by weight of high-purity iron powder and 2 parts by weight of high-purity chromium powder, mixing, and performing ball milling for 5 hours to obtain a composite activated element;
s4, modification of the carbon nano tube: mixing 1 part by weight of carbon nano tube with 0.5 part by weight of No. 92 gasoline medium, and carrying out ball milling for 2 hours to obtain a modified carbon nano tube;
s5, forming and sintering: mixing 96.5 parts by weight of tungsten-copper nano microspheres prepared in the step S2, 0.2 part by weight of composite activating elements prepared in the step S3 and 2 parts by weight of modified carbon nanotubes prepared in the step S4, performing ball milling for 5 hours to obtain mixed powder, pressing for 1 hour under the pressure of 50MPa, and then performing vacuum pressure sintering and inert gas protection high-temperature pressureless sintering two-step molding to obtain tungsten-copper alloy; FIG. 3 is a sectional view of the obtained W-Cu alloy, which shows that the alloy has a compact structure and almost no hole defects, i.e., no Cu phase loss.
The vacuum pressure sintering conditions are as follows: the temperature is between 650 ℃ and 650 ℃, the sintering time is 50min, the pressure is 25MPa, the temperature is 650-900 ℃, the sintering time is 40min, the temperature is 900-1000 ℃, and the sintering time is 60min; the argon protection high-temperature non-pressure condition is as follows: at room temperature of-920 ℃, the sintering time is 100min,920-1350 ℃, the sintering time is 120min,1350-1450 ℃, and the sintering time is 300min; introducing hydrogen in the whole sintering process, wherein the ventilation amount of the hydrogen is 5L/min; in the whole sintering process, the temperature is raised to 50 ℃/min; the sintering time includes a temperature rise time.
The ball milling conditions are that materials are put into a ball milling tank, the materials of the milling balls are natural agates, the ball material ratio is 3.
Example 2
The embodiment provides a preparation method of a tungsten-copper alloy, which specifically comprises the following steps:
s1, preparing porous hollow tungsten oxide nano microspheres: dissolving 10 parts by weight of sodium tungstate in 100 parts by weight of water, and adding 8 parts by weight of ammonium chloride and 1 part by weight of pore-foaming agent into the water to obtain a water phase; adding span-20 into petroleum ether, and uniformly mixing to obtain an oil phase, wherein the content of span-20 is 5wt%; adding 50 parts by weight of oil phase into 70 parts by weight of water phase, emulsifying for 5min at the rotating speed of 20000r/min, dropwise adding 12 parts by weight of 37wt% concentrated hydrochloric acid, stirring, filtering, centrifuging at 3000r/min for 10min, and drying at 75 ℃ for 2h to obtain porous hollow tungsten oxide nano microspheres;
the pore-foaming agent is a compound mixture of polyoxyethylene sorbitan fatty acid ester and hexadecyl trimethyl ammonium bromide, and the mass ratio is 10;
s2, preparing tungsten-copper nano microspheres: adding 10 parts by weight of the porous hollow tungsten oxide nano-microspheres prepared in the step S1 into 100 parts by weight of solution containing 20 parts by weight of copper sulfate, performing ultrasonic dispersion at 1000W for 30min, dropwise adding 50 parts by weight of citric acid, and heating to 70 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 150 ℃, reducing the vacuum degree to 0.1MPa to obtain dry gel, taking out, igniting the dry gel, carrying out ball milling for 12 hours, introducing hydrogen into a strong drainage breathable tubular furnace at 750 ℃ for reduction for 5 hours, wherein the ventilation capacity of the hydrogen is 20L/min, and obtaining tungsten-copper nano microspheres;
s3, preparing a composite activating element: weighing 1 part by weight of high-purity iron powder and 3 parts by weight of high-purity chromium powder, mixing, and performing ball milling for 7 hours to obtain a composite activated element;
s4, modification of the carbon nano tube: mixing 1 part by weight of carbon nano tube with 1.2 parts by weight of No. 92 gasoline medium, and performing ball milling for 4 hours to obtain a modified carbon nano tube;
s5, forming and sintering: mixing 97.8 parts by weight of tungsten-copper nano microspheres prepared in the step S2, 0.5 part by weight of composite activating elements prepared in the step S3 and 3 parts by weight of modified carbon nano tubes prepared in the step S4, performing ball milling for 10 hours to obtain mixed powder, pressing for 3 hours under the pressure of 70MPa, and then performing vacuum pressure sintering and inert gas protection high-temperature pressureless sintering two-step molding to obtain tungsten-copper alloy;
the vacuum pressure sintering conditions are as follows: sintering at room temperature-650 deg.C for 70min, 30MPa at 650-900 deg.C for 60min at 900-1000 deg.C for 70min; the argon protection high-temperature non-pressure condition is as follows: sintering at room temperature of-920 deg.C for 140min,920-1350 deg.C for 160min,1350-1450 deg.C for 400min; introducing hydrogen in the whole sintering process, wherein the ventilation amount of the hydrogen is 12L/min; in the whole sintering process, the temperature is increased to 80 ℃/min; the sintering time comprises a temperature rise time;
the ball milling conditions are that materials are put into a ball milling tank, the material of a milling ball is natural agate, the ball material ratio is 7.
Example 3
The embodiment provides a preparation method of a tungsten-copper alloy, which specifically comprises the following steps:
s1, preparing porous hollow tungsten oxide nano microspheres: dissolving 10 parts by weight of sodium tungstate in 100 parts by weight of water, and adding 6.5 parts by weight of ammonium chloride and 0.7 part by weight of pore-foaming agent into the water to obtain a water phase; adding span-80 into methyl acetate, and uniformly mixing to obtain an oil phase, wherein the content of span-80 is 3.5wt%; adding 50 parts by weight of oil phase into 70 parts by weight of water phase, emulsifying for 4min at the rotating speed of 18500r/min, dropwise adding 10 parts by weight of 36wt% concentrated hydrochloric acid, stirring, filtering, centrifuging at 3000r/min for 10min, and drying for 2h at 75 ℃ to obtain porous hollow tungsten oxide nano-microspheres;
the pore-foaming agent is a compound mixture of polyethylene glycol octyl phenyl ether and an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20, and the mass ratio is 7;
s2, preparing tungsten-copper nano microspheres: adding 10 parts by weight of the porous hollow tungsten oxide nano microspheres prepared in the step S1 into 100 parts by weight of a solution containing 12 parts by weight of copper nitrate, ultrasonically dispersing for 30min at 1000W, dropwise adding 35 parts by weight of sodium citrate, and heating to 60 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 135 ℃, reducing the vacuum degree to 0.05MPa to obtain dry gel, taking out, igniting the dry gel, carrying out ball milling for 8 hours, introducing hydrogen into a strong drainage breathable tubular furnace at 670 ℃ for reduction for 4 hours, wherein the ventilation capacity of the hydrogen is 17L/min, and obtaining tungsten-copper nano microspheres;
s3, preparing a composite activating element: weighing 1 part by weight of high-purity iron powder and 2.5 parts by weight of high-purity chromium powder, mixing, and performing ball milling for 6 hours to obtain a composite activated element;
s4, modification of the carbon nano tube: mixing 1 part by weight of carbon nano tube with 0.7 part by weight of No. 92 gasoline medium, and carrying out ball milling for 3 hours to obtain a modified carbon nano tube;
s5, forming and sintering: mixing 97.15 parts by weight of tungsten-copper nano microspheres prepared in the step S2, 0.35 part by weight of composite activating elements prepared in the step S3 and 2.5 parts by weight of modified carbon nano tubes prepared in the step S4, performing ball milling for 7 hours to obtain mixed powder, pressing for 2 hours under the pressure of 60MPa, and then performing vacuum pressure sintering and inert gas protection high-temperature pressureless sintering two-step molding to obtain tungsten-copper alloy;
the vacuum pressure sintering conditions are as follows: the temperature is between room temperature and 650 ℃, the sintering time is 60min, the pressure is 27MPa, the sintering time is 50min, the sintering time is 900-1000 ℃, and the sintering time is 65min; the argon protection high-temperature non-pressure condition is as follows: sintering at room temperature of-920 deg.C for 120min,920-1350 deg.C for 140min,1350-1450 deg.C, and 350min; introducing hydrogen in the whole sintering process, wherein the ventilation amount of the hydrogen is 9L/min; in the whole sintering process, the temperature is raised to 70 ℃/min; the sintering time comprises a temperature rise time;
the ball milling conditions are that materials are put into a ball milling tank, the material of the milling ball is natural agate, the ball material ratio is 5, absolute ethyl alcohol is used as a ball milling medium, the rotating speed of a main shaft of the ball milling machine is 250r/min, and the reversing is performed once every 7min of operation.
Example 4
Compared with the embodiment 3, the pore-foaming agent is single polyethylene glycol octyl phenyl ether, and other conditions are not changed.
Comparative example 5
Compared with example 3, the pore-foaming agent is a single oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20, and other conditions are not changed.
Comparative example 1
Compared with the example 3, the composite activating element is single high-purity iron powder, and other conditions are not changed.
Comparative example 2
Compared with the embodiment 3, the composite activating element is single high-purity chromium powder, and other conditions are not changed.
Comparative example 3
Compared with example 3, the composite activating element is added, and other conditions are not changed.
Comparative example 4
Compared with example 3, the carbon nanotubes without modification were not changed in other conditions.
Comparative example 5
Compared with example 3, the ball milling was not performed in step S5, and other conditions were not changed.
Comparative example 6
Compared with the embodiment 3, the inert gas protection high-temperature pressureless sintering is not carried out in the step S5, and other conditions are not changed.
Comparative example 7
In step S5, vacuum pressure sintering was not performed, and other conditions were not changed, as compared with example 3.
Test example 1
The tungsten copper alloy samples obtained in examples 1 to 5 and comparative examples 1 to 7 were tested for porosity using an AutoPore model IV 9510 mercury porosimeter, and the density of the samples was measured by the Archimedes drainage method. The results are shown in Table 1.
TABLE 1
| Group of | Relative density (%) | Porosity (%) |
| Example 1 | 98.87 | 0.212 |
| Example 2 | 99.12 | 0.207 |
| Example 3 | 99.37 | 0.201 |
| Example 4 | 96.56 | 0.721 |
| Example 5 | 96.22 | 0.522 |
| Comparative example 1 | 95.15 | 1.241 |
| Comparative example 2 | 94.75 | 1.172 |
| Comparative example 3 | 92.28 | 3.213 |
| Comparative example 4 | 96.82 | 0.352 |
| Comparative example 5 | 93.45 | 2.582 |
| Comparative example 6 | 95.21 | 1.982 |
| Comparative example 7 | 94.48 | 2.261 |
As can be seen from the above table, the tungsten-copper alloy prepared in the embodiments 1 to 3 of the present invention has a small porosity, a high relative density, and a high density, and thus, a large number of void defects in the sintered body are avoided, and the performance of the alloy material is ensured.
Test example 2
The tungsten copper alloy samples obtained in examples 1 to 5 of the present invention and comparative examples 1 to 7 were subjected to the performance test, and the results are shown in Table 2.
The conductivity of the alloy samples was measured at room temperature with a D60K digital metal conductivity meter.
The hardness of the alloy sample was measured with an HBRV-187.5 electric Brookfield hardness tester under conditions of an indenter diameter of 5mm, a test load of 750kg, and a dwell time of 30 s.
The thermal conductivity of the alloy sample is measured by a TCT416 type thermal conductivity measuring instrument, and the size of the used alloy sample is phi 10mm multiplied by 3mm.
The tensile strength of the alloy sample is tested by a JWL50KN type electronic universal tester, the tensile rate is 1mm/min, and the test is carried out at room temperature.
TABLE 2
As can be seen from the above table, the tungsten-copper alloy prepared in the embodiments 1 to 3 of the present invention has good mechanical properties, good thermal conductivity and electrical conductivity, and high hardness.
Compared with the embodiment 3, the embodiments 4 and 5 have the advantages that the pore-forming agent is single polyethylene glycol octyl phenyl ether or an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20, the relative density is reduced, the porosity is improved, and the mechanical property is reduced. Because of poor wettability of the phase interface, tungsten and copper have slow diffusion of atoms in the sintering process and are difficult to sinter compactly. According to the invention, the tungsten nanosphere framework is prepared, copper is dissolved in the microsphere framework, the dispersion of the tungsten nanosphere framework is limited, the particle size of the copper nanosphere framework is extremely small and is nano-scale, the compatibility is improved through fine grain strengthening, and the wettability and the adhesiveness of a tungsten-copper interface in a microsphere are further activated through an activating element, so that tungsten-copper alloy can be fully mixed, and a compact alloy material is obtained.
Compared with the embodiment 3, the compound activating elements of the comparative examples 1 and 2 are single high-purity iron powder or high-purity chromium powder. Comparative example 3 in comparison with example 3, a composite activating element was added. The invention reduces the relative density, improves the porosity, reduces the mechanical property, reduces the electrical conductivity and the thermal conductivity, reduces the sintering activation energy, improves the material structure and improves the density and the performance thereof by adding the composite activation element additionally, and has the advantages of low sintering temperature, short sintering time, higher structure performance and the like. The added composite activating elements comprise Fe and Cr, and when the Fe and the Cr are added, the density of the activated liquid phase sintering can be obviously improved. The addition of Fe improves the wettability and the adhesiveness between copper and tungsten, the addition of Cr element improves the interface strength of tungsten and copper, and makes the alloy structure more uniform, and the W-W connectivity is reduced, thereby reducing the particle debonding of tungsten particles and the debonding of a tungsten-copper interface during fracture, increasing the cleavage fracture of tungsten particles, and improving the mechanical property of the alloy. Meanwhile, the added composite activating elements are Fe and Cr, so that the use of noble metal activating elements such as Pd and Ag is avoided, a good modification effect can be achieved, the cost is lower, and the method is more suitable for industrial application.
Compared with the example 3, the mechanical property, the electric conductivity and the thermal conductivity of the comparative example 4 are obviously reduced without adding the modified carbon nano tube. The addition of the carbon nano tube can improve the high-temperature strength of the tungsten-copper alloy material in an extreme environment, has high heat conduction and high electric conductivity, and can also improve the heat conduction and the electric conductivity of the alloy material, so that the high-performance tungsten-copper alloy material is prepared, but the carbon nano tube is directly added, and is easy to agglomerate and cannot be uniformly dispersed in the alloy material.
Comparative example 5 compared to example 3, no ball milling was performed in step S5. The relative density is reduced, the porosity is improved, the mechanical property is reduced, and the electric conductivity and the thermal conductivity are reduced. The mixture is subjected to ball milling, and the impact and the grinding of the grinding balls further reduce the grain size of the powder, increase the activity and intensify the diffusion of copper into a tungsten phase to form an unsaturated solid solution. The tungsten-copper composite microsphere generates violent plastic deformation in the process, the particles generate great stress and strain, and a large amount of microscopic defects such as dislocation, distortion and the like are formed in the crystal grains. The atomic activity and the energy storage in the system are increased, so that solid solution is formed, the formation of cellular substructure is promoted, the grain size is reduced, and the obtained alloy material is more compact after the subsequent cold pressing and sintering.
Compared with the embodiment 3, the comparative examples 6 and 7 have the advantages that the inert gas protection high-temperature pressureless sintering or vacuum pressure sintering is not carried out in the step S5, the relative density is reduced, the porosity is improved, and the mechanical property is reduced. The invention adopts two-step sintering, when the sintering temperature is slightly higher than the melting point of copper, the copper is melted to be a solid-liquid phase, tungsten particles are rearranged and contacted with each other due to the viscous flow and the action of capillary force, the copper phase is redistributed and filled, and the activation elements can be fully diffused with the tungsten phase and the copper phase by the slow temperature rise rate and the proper heat preservation time in the sintering process, so that the wettability of the tungsten and copper interface is improved, the sintering performance is further improved, the copper phase loss caused by the loss of the copper phase is reduced, and a large amount of hole defects in a sintered body are avoided, thereby ensuring the performance of the alloy material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. The preparation method of the tungsten-copper alloy is characterized by comprising the following steps of:
s1, preparing porous hollow tungsten oxide nano microspheres: dissolving sodium tungstate in water, and adding ammonium chloride and a pore-foaming agent into the water to obtain a water phase; adding an oil-soluble surfactant into an organic solvent, and uniformly mixing to obtain an oil phase; adding the oil phase into the water phase, emulsifying at a high speed, dropwise adding concentrated hydrochloric acid, stirring, filtering, centrifuging, and drying to obtain porous hollow tungsten oxide nano microspheres; in the water phase, the mass ratio of sodium tungstate to ammonium chloride to the pore-foaming agent is 10:5-8:0.5 to 1; the pore-foaming agent is a compound mixture of a macroporous pore-foaming agent and a mesoporous pore-foaming agent, and the mass ratio is 5-10; the content of oil-soluble surfactant in the oil phase is 2-5wt%; the concentration of the concentrated hydrochloric acid is 35-37wt%, the rotating speed of the high-speed emulsification is 17000-20000r/min, and the time is 3-5min;
s2, preparing tungsten-copper nano microspheres: adding the porous hollow tungsten oxide nano-microspheres prepared in the step S1 into a solution containing copper salt, uniformly dispersing, dropwise adding a complexing agent, and heating to evaporate the solvent to obtain sol; then raising the temperature, reducing the vacuum degree to obtain dry gel, taking out the dry gel, igniting the dry gel, carrying out ball milling, and carrying out low-temperature hydrogen reduction to obtain tungsten-copper nano microspheres; the mass ratio of the porous hollow tungsten oxide nano-microspheres to the copper salt is 10:3-20 parts of; the complexing agent is citric acid or sodium citrate; the mass ratio of the copper salt to the complexing agent is 1:2-5; the heating temperature is 50-70 ℃, the temperature is increased to 120-150 ℃, and the vacuum degree is reduced to 0.01-0.1MPa; the ball milling time is 5-12h; introducing hydrogen into the low-temperature hydrogen reduction furnace at 600-750 ℃ by adopting a strong-drainage breathable tubular furnace for reduction for 3-5h, wherein the ventilation capacity of the hydrogen is 15-20L/min;
s3, preparing a composite activating element: weighing high-purity iron powder and high-purity chromium powder, mixing, and performing ball milling to obtain a composite activated element; the mass ratio of the high-purity iron powder to the high-purity chromium powder is 1:2-3; the ball milling time is 5-7h;
s4, modification of the carbon nano tube: mixing the carbon nano tube with a No. 92 gasoline medium, and performing ball milling to obtain a modified carbon nano tube; the mass ratio of the carbon nano tube to the 92# gasoline medium is 1:0.5-1.2; the ball milling time is 2-4h;
s5, forming and sintering: mixing the tungsten-copper nano microspheres prepared in the step S2, the composite activating element prepared in the step S3 and the modified carbon nano tubes prepared in the step S4, then carrying out ball milling to obtain mixed powder, carrying out cold pressing, and then carrying out vacuum pressure sintering and inert gas protection high-temperature pressureless sintering to obtain tungsten-copper alloy; the mass ratio of the tungsten-copper nano-microspheres to the composite activating elements to the modified carbon nano-tubes is 96.5-97.8: 0.2-0.5; the ball milling time is 5-10h; the cold pressing condition is that the pressure is kept at 50-70MPa for 1-3h; the vacuum pressure sintering conditions are as follows: sintering at room temperature of-650 deg.C for 50-70min under 25-30MPa at 650-900 deg.C for 40-60min and 900-1000 deg.C for 60-70min; the inert gas protection high-temperature non-pressure condition is as follows: sintering at room temperature of-920 deg.C for 100-140min, at 920-1350 deg.C for 120-160min, at 1350-1450 deg.C for 300-400min; introducing hydrogen in the whole sintering process, wherein the ventilation amount of the hydrogen is 5-12L/min; during the whole sintering process, the temperature is increased to 50-80 ℃/min.
2. The preparation method of the tungsten-copper alloy according to claim 1, wherein the macroporous pore-forming agent in step S1 is at least one selected from polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether; the mesoporous pore-foaming agent is selected from at least one of Cetyl Trimethyl Ammonium Bromide (CTAB), oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO 106; the oil-soluble surfactant is selected from at least one of fatty acid soap, lauryl sodium sulfate, lauryl polyoxyethylene ether sodium sulfate, cetyl polyoxyethylene ether sodium phosphate, lecithin, octadecyl trimethyl ammonium chloride, C12-14 alkyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl sodium chloride, sorbitan monocinnamate, ethylene oxide addition product, lauryl polyoxyethylene ether, coco diethanolamide, oleic acid monoglyceride, polyoxyethylene castor oil, polyoxyethylene lanolin, coco amido propyl betaine, span-20, span-80 and span-85; the organic solvent is at least one selected from ethyl acetate, methyl formate, petroleum ether, dichloromethane, trichloromethane, tetrachloromethane, toluene, xylene, cyclohexane and n-hexane.
3. The method of claim 1, wherein the copper salt in step S2 is at least one of copper nitrate, copper sulfate, and copper chloride.
4. The preparation method of the tungsten-copper alloy according to claim 1, wherein the ball milling conditions are that materials are put into a ball milling tank, the material of a milling ball is natural agate, the ball material ratio is 3-7.
5. The preparation method of the tungsten-copper alloy according to claim 1, which specifically comprises the following steps:
s1, preparing porous hollow tungsten oxide nano microspheres: dissolving 10 parts by weight of sodium tungstate in water, and adding 5-8 parts by weight of ammonium chloride and 0.5-1 part by weight of pore-foaming agent into the water to obtain a water phase; adding an oil-soluble surfactant into an organic solvent, and uniformly mixing to obtain an oil phase, wherein the content of the oil-soluble surfactant is 2-5wt%; adding the oil phase into the water phase, emulsifying for 3-5min at the rotating speed of 17000-20000r/min, dropwise adding 7-12 parts by weight of 35-37wt% concentrated hydrochloric acid, stirring, filtering, centrifuging, and drying to obtain porous hollow tungsten oxide nano microspheres;
the pore-foaming agent is a compound mixture of a macroporous pore-foaming agent and a mesoporous pore-foaming agent, and the mass ratio is 5-10;
s2, preparing tungsten-copper nano microspheres: adding 10 parts by weight of the porous hollow tungsten oxide nano-microspheres prepared in the step S1 into a solution containing 3-20 parts by weight of copper salt, uniformly dispersing, dropwise adding 20-50 parts by weight of complexing agent, and heating to 50-70 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 120-150 ℃, reducing the vacuum degree to 0.01-0.1MPa to obtain dry gel, taking out, igniting the dry gel, carrying out ball milling for 5-12h, introducing hydrogen into a strong drainage breathable tubular furnace at 600-750 ℃ for reduction for 3-5h, wherein the ventilation capacity of the hydrogen is 15-20L/min, and obtaining tungsten-copper nano microspheres;
s3, preparing a composite activating element: weighing 1 part by weight of high-purity iron powder and 2-3 parts by weight of high-purity chromium powder, mixing, and performing ball milling for 5-7 hours to obtain a composite activated element;
s4, modification of the carbon nano tube: mixing 1 part by weight of carbon nano tube with 0.5-1.2 parts by weight of No. 92 gasoline medium, and carrying out ball milling for 2-4h to obtain a modified carbon nano tube;
s5, forming and sintering: mixing 96.5-97.8 parts by weight of tungsten-copper nano microspheres prepared in the step S2, 0.2-0.5 part by weight of composite activating elements prepared in the step S3 and 2-3 parts by weight of modified carbon nano tubes prepared in the step S4, performing ball milling for 5-10 hours to obtain mixed powder, pressing for 1-3 hours under the pressure of 50-70MPa, and performing vacuum pressure sintering and inert gas protection high-temperature pressureless sintering for two-step molding to obtain tungsten-copper alloy;
the vacuum pressure sintering conditions are as follows: sintering at room temperature of-650 deg.C for 50-70min under 25-30MPa at 650-900 deg.C for 40-60min and 900-1000 deg.C for 60-70min; the inert gas protection high-temperature non-pressure condition is as follows: sintering at room temperature of-920 deg.C for 100-140min, at 920-1350 deg.C for 120-160min, at 1350-1450 deg.C for 300-400min; introducing hydrogen in the whole sintering process, wherein the ventilation amount of the hydrogen is 5-12L/min; in the whole sintering process, the temperature is increased to 50-80 ℃/min;
the ball milling conditions are that materials are put into a ball milling tank, the material of the milling ball is natural agate, the ball material ratio is 3-7, absolute ethyl alcohol is used as a ball milling medium, the rotating speed of a main shaft of the ball milling machine is 200-300r/min, and the reversing is performed once every 5-10min of operation.
6. A tungsten-copper alloy produced by the production method according to any one of claims 1 to 5.
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