CN112974814A - Method for preparing regenerated copper-tungsten alloy powder - Google Patents
Method for preparing regenerated copper-tungsten alloy powder Download PDFInfo
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention discloses a method for preparing regenerated copper-tungsten alloy powder, which relates to the technical field of copper-tungsten alloy regeneration and comprises the following steps of S1: cleaning the waste copper-tungsten alloy material and removing surface dirt; s2, oxidation: oxidizing the cleaned waste copper-tungsten alloy material in an air atmosphere to obtain a mixture of tungsten, tungsten oxide, copper oxide and copper, wherein the oxidation temperature is 500-700 ℃; s3, ball milling: performing ball milling treatment on the mixture obtained in the step S2; s4, reduction: reducing the mixed powder A in a hydrogen atmosphere; s5, mechanical alloying: pouring the mixed powder B into a planetary high-energy ball mill for high-energy ball milling to mechanically alloy the mixed powder B to obtain regenerated copper-tungsten alloy powder; the regenerated copper-tungsten alloy prepared by the method has high utilization rate of waste copper-tungsten alloy materials, does not generate any waste water, waste gas and the like, and does not pollute the environment.
Description
Technical Field
The invention relates to the technical field of copper-tungsten alloy regeneration, in particular to a method for preparing regenerated copper-tungsten alloy powder.
Background
Tungsten belongs to rare metal and is strategic material, and tungsten alloy is widely applied to the fields of aviation, aerospace, weapon industry, nuclear industry and the like. In China, the reserves, the yields and the export of foreign trade of tungsten are the first in the world at present, but after the exploitation for many years, particularly the rapid increase of the exploitation for people since the 20 th century and the 80 th era, the tungsten resources are seriously damaged, and the tungsten resources available for exploitation are sharply reduced. Under the condition, all countries take the waste tungsten alloy as a precious second resource, and the waste tungsten alloy is taken as an important means for solving the problem of resource shortage, improving the utilization rate of raw materials and reducing the cost of the tungsten alloy.
The copper-tungsten alloy has both good electric conduction and heat conduction performance of copper and high temperature resistance, arc ablation resistance and fusion welding resistance of tungsten, so that the copper-tungsten alloy can be widely used as an electric contact, an electric spark electrode, a resistance welding electrode and the like.
The copper-tungsten alloy contains l0% -40% of copper, the traditional copper-tungsten alloy waste recovery method comprises a saltpeter method, a zinc melting method and a chemical method, the saltpeter method and the zinc melting method ignore the recovery of the copper, the chemical method adopts a method of leaching the copper by inorganic acid to separate the tungsten and the copper, the used inorganic acid mainly comprises nitric acid, dilute sulfuric acid and concentrated sulfuric acid, the chemical method has complex process, and can generate a large amount of NO2、SO2And the waste gas and the waste liquid can generate a large amount of waste liquid, and meanwhile, the equipment is corroded, so that serious environmental pollution is easily caused.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for preparing regenerated copper-tungsten alloy powder.
The technical scheme of the invention is as follows: a method for preparing regenerated copper-tungsten alloy powder comprises the following steps:
s1: cleaning of
Cleaning the waste copper-tungsten alloy material, and cleaning surface dirt to obtain a cleaned waste copper-tungsten alloy material;
s2: oxidation by oxygen
Oxidizing the cleaned waste copper-tungsten alloy material in an air atmosphere to obtain a mixture of tungsten, tungsten oxide, copper oxide and copper, wherein the oxidation temperature is 500-700 ℃;
s3: ball mill
Performing ball milling on the mixture obtained in the step S2 to obtain mixed powder containing tungsten, tungsten oxide and copper oxide, wherein tungsten alloy balls are adopted for ball milling, the ball-to-material ratio is 1:1-10:1, and mixed powder A is obtained after ball milling;
s4: reduction of
Reducing the mixed powder A in a hydrogen atmosphere to obtain mixed powder B of tungsten powder and copper powder, wherein the reduction temperature is 620 ℃ and 1000 ℃;
s5: mechanical alloying
Pouring the mixed powder B into a planetary high-energy ball mill for high-energy ball milling, and mechanically alloying the mixed powder B to obtain regenerated copper-tungsten alloy powder, wherein argon is used as protective gas in the mechanical alloying process, and the parameters of the high-energy ball milling are as follows: the ball-material ratio is 20:1-50:1, the ball-milling speed is 600-.
Further, the step S1 cleaning includes the following steps:
s1-1: rinsing
Washing the waste copper-tungsten alloy material on an 8-mesh filter screen at high pressure for 1-2min at 15-30 ℃ to obtain a washed copper-tungsten alloy material, and washing off easily-removed stains on the surface of the copper-tungsten alloy material by washing pressure;
s1-2: decontamination
Putting the copper-tungsten alloy material washed in the step S1-1 into an ozone cleaning device with ultraviolet rays, cleaning for 50-60S at 30-40 ℃ to obtain the copper-tungsten alloy material after decontamination treatment, and removing stubborn stains through ethanol dissolution and ozone oxidation;
s1-3: drying
And (4) rinsing the copper-tungsten alloy material subjected to decontamination treatment in the step S1-2 in clear water at the temperature of 80-90 ℃ for 7-10 times, taking out the copper-tungsten alloy material after rinsing, and air-drying at the air-drying temperature of 80-100 ℃ at the air speed of 8-10 m/S.
Further, the cleaning liquid adopted in the high-pressure washing in the step S1-1 comprises the following components in parts by weight: 13-16 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 15-20 parts of soap base, 3-5 parts of amino acid humectant, 5-8 parts of absolute ethyl alcohol, 8-10 parts of coconut diethanolamide and 500-600 parts of water.
Further, the ultraviolet ray of the ozone cleaning device in the step S1-2 adopts a low-pressure mercury lamp, the wavelength of the ultraviolet ray is 254nm, and the cleaning agent is prepared from deionized water and industrial ethanol with the mass percentage concentration of 95% according to the mass ratio of 5: 1.
Further, the oxidation time of the step S2 is 1-6h, the copper-tungsten alloy will expand after oxidation, and is easy to grind, and the particle size of the grinded powder will be smaller.
Further, the ball milling processing in step S3 specifically includes: firstly, carrying out high-speed dry grinding at the dry grinding speed of 500-600r/min for 5-8h, then adding a grinding aid accounting for 0.7-0.9% of the mass of the copper-tungsten alloy material into the ball mill for carrying out low-speed wet grinding for 3-5h, and carrying out vacuum drying after the wet grinding is finished; wherein the parameters of vacuum drying are as follows: the vacuum drying temperature is 80 deg.C, the vacuum degree is 0.1MPa, and the vacuum drying time is 2-3 h.
Further, the grinding aid consists of the following components in parts by weight: 8-10 parts of ethanol, 3-5 parts of isopropanol and 5-7 parts of stearic acid, and the grinding aid is beneficial to improving the ball milling efficiency.
Further, the volume of the waste copper-tungsten alloy material monomer in the step S1 is 0.5-2cm3And is convenient for cleaning and oxidation.
Further, in the step S4, the reduction time is 1-2h, stirring is carried out along with the reduction process, the stirring speed is 80r/min, hydrogen is fully contacted with the mixed powder A, and the reduction efficiency is improved.
Further, in the step S3, the obtained mixed powder a is sieved with a 325-mesh sieve, and the undersize product is taken as the mixed powder a for reduction in the step S4, thereby improving the consistency of the finally obtained copper-tungsten alloy powder.
The invention has the beneficial effects that:
(1) the method has the advantages of simple process, high economy, high reliability and wide application range, and is suitable for preparing the regenerated copper-tungsten alloy powder and also suitable for preparing the regenerated tungsten-nickel-copper, tungsten-nickel-iron and copper-tungsten carbide alloy powder.
(2) The invention can not only obtain the regenerated copper-tungsten alloy powder, if the tungsten carbide powder or the nickel powder with a certain proportion is added into the mixed powder obtained in the step S4, the step S5 is carried out, and the copper-tungsten-carbide alloy powder and the tungsten-nickel-copper alloy powder can be prepared.
(3) The regenerated copper-tungsten alloy prepared by the method has high utilization rate of waste copper-tungsten alloy materials, does not generate any waste water, waste gas and the like, and does not pollute the environment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1:
as shown in fig. 1, a method for preparing a recycled copper-tungsten alloy powder includes the following steps:
s1: cleaning of
Cleaning the waste copper-tungsten alloy material, and removing dirt on the surface to obtain the cleaned waste copper-tungsten alloy material, wherein the volume of the waste copper-tungsten alloy material monomer is 0.5-1cm3And the cleaning and the oxidation are convenient, and the cleaning comprises the following steps:
s1-1: rinsing
Carrying out high-pressure washing on the waste copper-tungsten alloy material on an 8-mesh filter screen, wherein the high-pressure washing time is 1min, the washing temperature is 15 ℃, obtaining the washed copper-tungsten alloy material, washing off easily-fallen stains on the surface of the copper-tungsten alloy material through the washing pressure, and adopting a washing liquid consisting of the following components in parts by weight: 13 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 15 parts of soap base, 3 parts of amino acid humectant, 5 parts of absolute ethyl alcohol, 8 parts of coconut diethanolamide and 500 parts of water;
s1-2: decontamination
Putting the copper-tungsten alloy material washed in the step S1-1 into ozone cleaning equipment with ultraviolet rays, wherein the cleaning time is 50S, the cleaning temperature is 30 ℃, so that the copper-tungsten alloy material after decontamination treatment is obtained, dissolving the copper-tungsten alloy material with ethanol and oxidizing ozone to remove stubborn stains, the ultraviolet rays of the ozone cleaning equipment adopt a low-pressure mercury lamp, the wavelength of the ultraviolet rays is 254nm, and the cleaning agent is prepared from deionized water and industrial ethanol with the mass percentage concentration of 95% according to the mass ratio of 5: 1;
s1-3: drying
Rinsing the copper-tungsten alloy material subjected to decontamination treatment in the step S1-2 in clear water at 80 ℃ for 7 times, taking out the copper-tungsten alloy material after rinsing, and air-drying at the air-drying temperature of 80 ℃ at the air speed of 8 m/S;
s2: oxidation by oxygen
Oxidizing the cleaned waste copper-tungsten alloy material in the air atmosphere to obtain a mixture of tungsten, tungsten oxide, copper oxide and copper, wherein the oxidation temperature is 500 ℃, the oxidation time is 1h, the oxidized copper-tungsten alloy can expand and is easy to grind, and the granularity of the ground powder is smaller;
s3: ball mill
Performing ball milling treatment on the mixture obtained in the step S2 to obtain mixed powder containing tungsten, tungsten oxide and copper oxide, wherein tungsten alloy balls are adopted for ball milling, the ball-to-material ratio is 1:1, and the ball milling treatment specifically comprises the following steps: firstly, carrying out high-speed dry grinding at a dry grinding speed of 500r/min for 5h, and then adding a grinding aid accounting for 0.7 percent of the mass of the copper-tungsten alloy material into a ball mill for carrying out low-speed wet grinding, wherein the grinding aid consists of the following components in parts by weight: 8 parts of ethanol, 3 parts of isopropanol and 5 parts of stearic acid, wherein the grinding aid is beneficial to improving the ball milling efficiency, the wet milling time is 3 hours, and vacuum drying is carried out after the wet milling is finished; wherein the parameters of vacuum drying are as follows: the vacuum drying temperature is 80 ℃, the vacuum degree is 0.1MPa, the vacuum drying time is 2 hours, the mixed powder A is obtained after ball milling, the obtained mixed powder A is screened by a 325-mesh screen, and undersize products are taken as the mixed powder A for reduction in the step S4, so that the consistency of the finally obtained copper-tungsten alloy powder is improved;
s4: reduction of
Reducing the mixed powder A in a hydrogen atmosphere to obtain mixed powder B of tungsten powder and copper powder, wherein the reduction temperature is 620 ℃, the reduction time is 1h, stirring is carried out along with the reduction process, the stirring speed is 80r/min, so that hydrogen is fully contacted with the mixed powder A, and the reduction efficiency is improved;
s5: mechanical alloying
Pouring the mixed powder B into a planetary high-energy ball mill for high-energy ball milling, and mechanically alloying the mixed powder B to obtain regenerated copper-tungsten alloy powder, wherein argon is used as protective gas in the mechanical alloying process, and the parameters of the high-energy ball milling are as follows: the ball-material ratio is 20:1, the ball milling speed is 600r/min, and the ball milling time is 12 h.
Example 2:
as shown in fig. 1, a method for preparing a recycled copper-tungsten alloy powder includes the following steps:
s1: cleaning of
Cleaning the waste copper-tungsten alloy material, and removing dirt on the surface to obtain the cleaned waste copper-tungsten alloy material, wherein the volume of the waste copper-tungsten alloy material monomer is 1-2cm3And the cleaning and the oxidation are convenient, and the cleaning comprises the following steps:
s1-1: rinsing
Carrying out high-pressure washing on the waste copper-tungsten alloy material on an 8-mesh filter screen, wherein the high-pressure washing time is 1.5min, the washing temperature is 20 ℃, obtaining the washed copper-tungsten alloy material, washing off easily-fallen stains on the surface of the copper-tungsten alloy material through the washing pressure, and adopting a washing liquid consisting of the following components in parts by weight: 14 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 16 parts of soap base, 4 parts of amino acid humectant, 6 parts of absolute ethyl alcohol, 9 parts of coconut diethanolamide and 550 parts of water;
s1-2: decontamination
Putting the copper-tungsten alloy material washed in the step S1-1 into ozone cleaning equipment with ultraviolet rays, wherein the cleaning time is 55S, the cleaning temperature is 35 ℃, so that the copper-tungsten alloy material after decontamination treatment is obtained, dissolving the copper-tungsten alloy material with ethanol and oxidizing ozone to remove stubborn stains, the ultraviolet rays of the ozone cleaning equipment adopt a low-pressure mercury lamp, the wavelength of the ultraviolet rays is 254nm, and the cleaning agent is prepared from deionized water and industrial ethanol with the mass percentage concentration of 95% according to the mass ratio of 5: 1;
s1-3: drying
Rinsing the copper-tungsten alloy material subjected to decontamination treatment in the step S1-2 in clean water at 85 ℃ for 8 times, taking out the copper-tungsten alloy material after rinsing, and air-drying at the air-drying temperature of 85 ℃ at the air speed of 9 m/S;
s2: oxidation by oxygen
Oxidizing the cleaned waste copper-tungsten alloy material in the air atmosphere to obtain a mixture of tungsten, tungsten oxide, copper oxide and copper, wherein the oxidizing temperature is 600 ℃, the oxidizing time is 3 hours, the oxidized copper-tungsten alloy can expand and is easy to grind, and the granularity of the ground powder is smaller;
s3: ball mill
Performing ball milling treatment on the mixture obtained in the step S2 to obtain mixed powder containing tungsten, tungsten oxide and copper oxide, wherein tungsten alloy balls are adopted for ball milling, the ball-to-material ratio is 5:1, and the ball milling treatment specifically comprises the following steps: firstly, carrying out high-speed dry grinding at a dry grinding speed of 550r/min for 6h, and then adding a grinding aid accounting for 0.8 percent of the mass of the copper-tungsten alloy material into a ball mill for carrying out low-speed wet grinding, wherein the grinding aid consists of the following components in parts by weight: 9 parts of ethanol, 4 parts of isopropanol and 6 parts of stearic acid, wherein the grinding aid is beneficial to improving the ball milling efficiency, the wet milling time is 4 hours, and vacuum drying is carried out after the wet milling is finished; wherein the parameters of vacuum drying are as follows: the vacuum drying temperature is 80 ℃, the vacuum degree is 0.1MPa, the vacuum drying time is 2.5 hours, the mixed powder A is obtained after ball milling, the obtained mixed powder A is screened by a 325-mesh screen, and undersize products are taken as the mixed powder A for reduction in the step S4, so that the consistency of the finally obtained copper-tungsten alloy powder is improved;
s4: reduction of
Reducing the mixed powder A in a hydrogen atmosphere to obtain mixed powder B of tungsten powder and copper powder, wherein the reduction temperature is 800 ℃, the reduction time is 1.5h, stirring is carried out along with the reduction process, the stirring speed is 80r/min, so that hydrogen is fully contacted with the mixed powder A, and the reduction efficiency is improved;
s5: mechanical alloying
Pouring the mixed powder B into a planetary high-energy ball mill for high-energy ball milling, and mechanically alloying the mixed powder B to obtain regenerated copper-tungsten alloy powder, wherein argon is used as protective gas in the mechanical alloying process, and the parameters of the high-energy ball milling are as follows: the ball-material ratio is 30:1, the ball milling speed is 800r/min, and the ball milling time is 18 h.
Example 3:
as shown in fig. 1, a method for preparing a recycled copper-tungsten alloy powder includes the following steps:
s1: cleaning of
Cleaning the waste copper-tungsten alloy material, and removing dirt on the surface to obtain the cleaned waste copper-tungsten alloy material, wherein the volume of the waste copper-tungsten alloy material monomer is 0.5-2cm3And the cleaning and the oxidation are convenient, and the cleaning comprises the following steps:
s1-1: rinsing
Carrying out high-pressure washing on the waste copper-tungsten alloy material on an 8-mesh filter screen, wherein the high-pressure washing time is 1.5min, the washing temperature is 25 ℃, obtaining the washed copper-tungsten alloy material, washing off easily-fallen stains on the surface of the copper-tungsten alloy material through the washing pressure, and adopting a washing liquid consisting of the following components in parts by weight: 15 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 18 parts of soap base, 4 parts of amino acid humectant, 7 parts of absolute ethyl alcohol, 9 parts of coconut diethanolamide and 580 parts of water;
s1-2: decontamination
Putting the copper-tungsten alloy material washed in the step S1-1 into ozone cleaning equipment with ultraviolet rays, wherein the cleaning time is 58S, the cleaning temperature is 38 ℃, so that the copper-tungsten alloy material subjected to decontamination treatment is obtained, dissolving the copper-tungsten alloy material with the ultraviolet rays and oxidizing the copper-tungsten alloy material with the ozone to remove stubborn stains, the ultraviolet rays of the ozone cleaning equipment adopt a low-pressure mercury lamp, the wavelength of the ultraviolet rays is 254nm, and the cleaning agent is prepared from deionized water and industrial ethanol with the mass percentage concentration of 95% according to the mass ratio of 5: 1;
s1-3: drying
Rinsing the copper-tungsten alloy material subjected to decontamination treatment in the step S1-2 in clear water at 88 ℃ for 9 times, taking out the copper-tungsten alloy material after rinsing, and air-drying at the air-drying temperature of 95 ℃ at the air speed of 9 m/S;
s2: oxidation by oxygen
Oxidizing the cleaned waste copper-tungsten alloy material in the air atmosphere to obtain a mixture of tungsten, tungsten oxide, copper oxide and copper, wherein the oxidizing temperature is 650 ℃, the oxidizing time is 4 hours, the oxidized copper-tungsten alloy can expand and is easy to grind, and the granularity of the ground powder is smaller;
s3: ball mill
Performing ball milling treatment on the mixture obtained in the step S2 to obtain mixed powder containing tungsten, tungsten oxide and copper oxide, wherein the ball milling adopts tungsten alloy balls with a ball-to-material ratio of 8:1, and the ball milling treatment specifically comprises the following steps: firstly, carrying out high-speed dry grinding at a dry grinding speed of 580r/min for 7h, and then adding a grinding aid accounting for 0.8 percent of the mass of the copper-tungsten alloy material into a ball mill for carrying out low-speed wet grinding, wherein the grinding aid consists of the following components in parts by weight: 9 parts of ethanol, 4 parts of isopropanol and 6 parts of stearic acid, wherein the grinding aid is beneficial to improving the ball milling efficiency, the wet milling time is 4.5 hours, and vacuum drying is carried out after the wet milling is finished; wherein the parameters of vacuum drying are as follows: the vacuum drying temperature is 80 ℃, the vacuum degree is 0.1MPa, the vacuum drying time is 2.5 hours, the mixed powder A is obtained after ball milling, the obtained mixed powder A is screened by a 325-mesh screen, and undersize products are taken as the mixed powder A for reduction in the step S4, so that the consistency of the finally obtained copper-tungsten alloy powder is improved;
s4: reduction of
Reducing the mixed powder A in a hydrogen atmosphere to obtain mixed powder B of tungsten powder and copper powder, wherein the reduction temperature is 900 ℃, the reduction time is 1.5h, stirring is carried out along with the reduction process, the stirring speed is 80r/min, so that the hydrogen is fully contacted with the mixed powder A, and the reduction efficiency is improved;
s5: mechanical alloying
Pouring the mixed powder B into a planetary high-energy ball mill for high-energy ball milling, and mechanically alloying the mixed powder B to obtain regenerated copper-tungsten alloy powder, wherein argon is used as protective gas in the mechanical alloying process, and the parameters of the high-energy ball milling are as follows: the ball-material ratio is 40:1, the ball-milling speed is 900r/min, and the ball-milling time is 18 h.
Example 4:
as shown in fig. 1, a method for preparing a recycled copper-tungsten alloy powder includes the following steps:
s1: cleaning of
Cleaning the waste copper-tungsten alloy material, and removing dirt on the surface to obtain the cleaned waste copper-tungsten alloy material, wherein the volume of the waste copper-tungsten alloy material monomer is 0.5-2cm3And the cleaning and the oxidation are convenient, and the cleaning comprises the following steps:
s1-1: rinsing
Carrying out high-pressure washing on the waste copper-tungsten alloy material on an 8-mesh filter screen, wherein the high-pressure washing time is 2min, the washing temperature is 30 ℃, obtaining the washed copper-tungsten alloy material, washing off easily-fallen stains on the surface of the copper-tungsten alloy material through the washing pressure, and adopting a washing liquid consisting of the following components in parts by weight: 16 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 20 parts of soap base, 5 parts of amino acid humectant, 8 parts of absolute ethyl alcohol, 10 parts of coconut diethanolamide and 600 parts of water;
s1-2: decontamination
Putting the copper-tungsten alloy material washed in the step S1-1 into ozone cleaning equipment with ultraviolet rays, wherein the cleaning time is 60S, the cleaning temperature is 40 ℃, so that the copper-tungsten alloy material after decontamination treatment is obtained, dissolving the copper-tungsten alloy material with ethanol and oxidizing ozone to remove stubborn stains, the ultraviolet rays of the ozone cleaning equipment adopt a low-pressure mercury lamp, the wavelength of the ultraviolet rays is 254nm, and the cleaning agent is prepared from deionized water and industrial ethanol with the mass percentage concentration of 95% according to the mass ratio of 5: 1;
s1-3: drying
Rinsing the copper-tungsten alloy material subjected to decontamination treatment in the step S1-2 in clear water at 90 ℃ for 10 times, taking out the copper-tungsten alloy material after rinsing, and air-drying at the air-drying temperature of 100 ℃ at the air speed of 10 m/S;
s2: oxidation by oxygen
Oxidizing the cleaned waste copper-tungsten alloy material in the air atmosphere to obtain a mixture of tungsten, tungsten oxide, copper oxide and copper, wherein the oxidation temperature is 700 ℃, the oxidation time is 6 hours, the oxidized copper-tungsten alloy can expand and is easy to grind, and the granularity of the ground powder is smaller;
s3: ball mill
Performing ball milling treatment on the mixture obtained in the step S2 to obtain mixed powder containing tungsten, tungsten oxide and copper oxide, wherein tungsten alloy balls are adopted for ball milling, the ball-to-material ratio is 10:1, and the ball milling treatment specifically comprises the following steps: firstly, carrying out high-speed dry grinding at a dry grinding speed of 600r/min for 8h, and then adding a grinding aid accounting for 0.9% of the mass of the copper-tungsten alloy material into a ball mill for carrying out low-speed wet grinding, wherein the grinding aid consists of the following components in parts by weight: 10 parts of ethanol, 5 parts of isopropanol and 7 parts of stearic acid, wherein the grinding aid is beneficial to improving the ball milling efficiency, the wet milling time is long for 5 hours, and vacuum drying is carried out after the wet milling is finished; wherein the parameters of vacuum drying are as follows: the vacuum drying temperature is 80 ℃, the vacuum degree is 0.1MPa, the vacuum drying time is 3 hours, the mixed powder A is obtained after ball milling, the obtained mixed powder A is screened by a 325-mesh screen, and undersize products are taken as the mixed powder A for reduction in the step S4, so that the consistency of the finally obtained copper-tungsten alloy powder is improved;
s4: reduction of
Reducing the mixed powder A in a hydrogen atmosphere to obtain mixed powder B of tungsten powder and copper powder, wherein the reduction temperature is 1000 ℃, the reduction time is 2 hours, stirring is carried out along with the reduction process, the stirring speed is 80r/min, so that hydrogen is fully contacted with the mixed powder A, and the reduction efficiency is improved;
s5: mechanical alloying
Pouring the mixed powder B into a planetary high-energy ball mill for high-energy ball milling, and mechanically alloying the mixed powder B to obtain regenerated copper-tungsten alloy powder, wherein argon is used as protective gas in the mechanical alloying process, and the parameters of the high-energy ball milling are as follows: the ball-material ratio is 50:1, the ball milling speed is 1000r/min, and the ball milling time is 24 h.
The tungsten copper alloy powders prepared in examples 1 to 4 were sampled for O content (%) and C content (%), and the results of the examination showed that example 1 had an O content of 0.0321% and a C content of 0.0205%; the O content of example 2 was 0.0301% and the C content was 0.0152%; the O content of example 3 was 0.0214% and the C content was 0.0185%; the O content of example 4 was 0.0111% and the C content was 0.0032%;
comparing the test results of examples 1 to 4, it is understood that example 4 is the most suitable example because the reduction of copper oxide and tungsten oxide is most complete and the cleaning of organic substances is more complete.
Claims (10)
1. The method for preparing the regenerated copper-tungsten alloy powder is characterized by comprising the following steps of:
s1: cleaning of
Cleaning the waste copper-tungsten alloy material, and cleaning surface dirt to obtain a cleaned waste copper-tungsten alloy material;
s2: oxidation by oxygen
Oxidizing the cleaned waste copper-tungsten alloy material in an air atmosphere to obtain a mixture of tungsten, tungsten oxide, copper oxide and copper, wherein the oxidation temperature is 500-700 ℃;
s3: ball mill
Performing ball milling on the mixture obtained in the step S2 to obtain mixed powder containing tungsten, tungsten oxide and copper oxide, wherein tungsten alloy balls are adopted for ball milling, the ball-to-material ratio is 1:1-10:1, and mixed powder A is obtained after ball milling;
s4: reduction of
Reducing the mixed powder A in a hydrogen atmosphere to obtain mixed powder B of tungsten powder and copper powder, wherein the reduction temperature is 620 ℃ and 1000 ℃;
s5: mechanical alloying
Pouring the mixed powder B into a planetary high-energy ball mill for high-energy ball milling, and mechanically alloying the mixed powder B to obtain regenerated copper-tungsten alloy powder, wherein argon is used as protective gas in the mechanical alloying process, and the parameters of the high-energy ball milling are as follows: the ball-material ratio is 20:1-50:1, the ball-milling speed is 600-.
2. The method for preparing recycled copper-tungsten alloy powder according to claim 1, wherein the step S1 cleaning comprises the steps of:
s1-1: rinsing
Washing the waste copper-tungsten alloy material on an 8-mesh filter screen at high pressure for 1-2min at 15-30 ℃ to obtain a washed copper-tungsten alloy material;
s1-2: decontamination
Putting the copper-tungsten alloy material washed in the step S1-1 into an ozone cleaning device with ultraviolet rays, wherein the cleaning time is 50-60S, and the cleaning temperature is 30-40 ℃, so as to obtain the copper-tungsten alloy material after decontamination treatment;
s1-3: drying
And (4) rinsing the copper-tungsten alloy material subjected to decontamination treatment in the step S1-2 in clear water at the temperature of 80-90 ℃ for 7-10 times, taking out the copper-tungsten alloy material after rinsing, and air-drying at the air-drying temperature of 80-100 ℃ at the air speed of 8-10 m/S.
3. The method for preparing the recycled copper-tungsten alloy powder as claimed in claim 2, wherein the cleaning solution used in the high-pressure washing in the step S1-1 comprises the following components in parts by weight: 13-16 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 15-20 parts of soap base, 3-5 parts of amino acid humectant, 5-8 parts of absolute ethyl alcohol, 8-10 parts of coconut diethanolamide and 500-600 parts of water.
4. The method for producing recycled copper-tungsten alloy powder according to claim 2, wherein the ultraviolet ray of the ozone cleaning device in step S1-2 is a low-pressure mercury lamp, the wavelength of the ultraviolet ray is 254nm, and the cleaning agent is prepared from deionized water and industrial ethanol having a concentration of 95% by mass in a mass ratio of 5: 1.
5. The method for preparing recycled copper-tungsten alloy powder according to claim 1, wherein the oxidation time of step S2 is 1 to 6 hours.
6. The method for preparing the recycled copper-tungsten alloy powder according to claim 1, wherein the ball milling treatment in step S3 is specifically: firstly, carrying out high-speed dry grinding at the dry grinding speed of 500-600r/min for 5-8h, then adding a grinding aid accounting for 0.7-0.9% of the mass of the copper-tungsten alloy material into the ball mill for carrying out low-speed wet grinding for 3-5h, and carrying out vacuum drying after the wet grinding is finished; wherein the parameters of vacuum drying are as follows: the vacuum drying temperature is 80 deg.C, the vacuum degree is 0.1MPa, and the vacuum drying time is 2-3 h.
7. The method of preparing recycled copper-tungsten alloy powder according to claim 6, wherein the grinding aid comprises the following components in parts by weight: 8-10 parts of ethanol, 3-5 parts of isopropanol and 5-7 parts of stearic acid.
8. The method for preparing recycled copper-tungsten alloy powder according to claim 1, wherein the volume of the single body of the scrap copper-tungsten alloy material in step S1 is 0.5-2cm3。
9. The method for preparing recycled copper-tungsten alloy powder according to claim 1, wherein the reduction time period in step S4 is 1-2 hours, and the stirring speed is 80r/min with stirring during the reduction process.
10. The method of producing a reclaimed copper-tungsten alloy powder according to claim 1, wherein in step S3, the mixed powder A obtained is sieved with a 325-mesh sieve, and the undersize product is collected as the mixed powder A for reduction in step S4.
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