CN111673080B - Copper alloy feed, preparation method thereof and preparation method of copper alloy blank - Google Patents
Copper alloy feed, preparation method thereof and preparation method of copper alloy blank Download PDFInfo
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- 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
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
- B22F3/1025—Removal of binder or filler not by heating only
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- 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
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
A copper alloy feed and a preparation method thereof, and a preparation method of a copper alloy blank body are provided, wherein copper alloy is coated to form copper alloy powder with a core-shell structure, the copper alloy powder is mixed with a binder to form the feed, and the feed is degreased and sintered to prepare a copper alloy product.
Description
Technical Field
The invention relates to the technical field of metal injection molding feed, in particular to a copper alloy feed and a preparation method thereof, and a preparation method of a copper alloy blank.
Background
Metal Powder Injection Molding (MIM) is a new Near-Net-Shape technology that combines modern plastic Injection Molding technology with Powder metallurgy. The method mainly comprises the steps of adding a binder into metal powder, and injecting a feed material into a mold in an injection molding mode, so that the problem that a complex product is difficult to form in the metal powder metallurgy technology is solved. Degreasing is an important process in MIM, and can quickly remove the binder in the feed on the premise of ensuring that the injection molding blank does not have defects, so that the production efficiency is improved.
At present, the conventional degreasing methods include thermal degreasing, solvent degreasing, catalytic degreasing, and the like. Wherein, the catalytic degreasing technology utilizes the principle that the main components in the binder can be rapidly decomposed and removed in a specific atmosphere; POM (polyoxymethylene) binders are capable of undergoing rapid degradation in acidic atmospheres, which is a typical representative of catalytic degreasing.
However, some special metal elements (such as copper, cobalt, etc.) are liable to react with nitric acid or nitric acid vapor to generate nitrate compounds, which affect the subsequent sintering densification process, even damage the surface quality, so that the metal materials such as copper, cobalt, etc. cannot be carried out by using an acid catalytic degreasing method, and also limit the application of the metal materials such as copper, cobalt, etc. in metal injection molding.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide a copper alloy feed and a preparation method thereof, and a preparation method of a copper alloy blank, wherein the copper alloy is coated to form copper alloy powder with a core-shell structure, so that the copper alloy powder is not oxidized and is not directly contacted with a nitric acid medium in an acidification and degreasing process, the density of a product prepared by the copper alloy feed is greatly improved, and the surface quality of the prepared product is improved.
In order to achieve the purpose, the copper alloy feed comprises copper alloy powder and a forming agent, wherein the copper alloy and the forming agent are prepared according to the weight ratio of 80:20 to 70:30, the granularity of the copper alloy is 200-500 meshes, and the copper alloy feed comprises the following components in percentage by mass: 65-75% of Cu, 25-35% of Al, 5-10% of Ni and 0.5-1% of rare earth elements; the forming agent comprises the following components in percentage by mass: 73-78% of polyformaldehyde, 2-3% of naphthalene, 5-10% of carnauba wax, 10-15% of polybutylene terephthalate and 3-5% of zinc stearate, wherein the particle sizes of the polyformaldehyde, the carnauba wax and the polybutylene terephthalate are 200-500 meshes, the copper alloy powder is of a core-shell structure, the inner core is copper alloy, and the shell is nickel.
Preferably, the copper alloy has a particle size of 300 mesh.
Preferably, the forming agent comprises the following components in percentage by mass: 78-82% of polyformaldehyde, 2.5-3% of naphthalene, 7-9% of carnauba wax, 12-13% of polybutylene terephthalate and 3.5-4.5% of zinc stearate.
Preferably, the copper alloy powder is heated to 140 ℃ of 120-.
The invention also provides a preparation method of the copper alloy powder, which comprises the following specific steps: selecting a high-purity aluminum sample, polishing the sample by using abrasive paper, removing oxides on the surface of the sample, putting the sample into a container containing acetone solution, cleaning the sample by using ultrasonic waves, taking out the sample, and drying the sample for later use; putting the dried aluminum sample into a crucible, heating to 680-plus 700 ℃, adding the preheated copper sample, nickel powder and rare earth elements, then continuously heating to 820-plus 860 ℃, preserving heat for 10-12 hours, and discontinuously applying ultrasonic waves outside the crucible in the heat preservation process to uniformly mix the alloy in the crucible; carrying out atomization on the molten alloy liquid to obtain pretreated copper alloy powder; and preparing the copper alloy with the core-shell structure by adopting a chemical nickel plating method.
The invention further provides a chemical nickel plating method in the preparation process, which comprises the following specific preparation steps: activation treatment of copper powder: dipping and reducing in reducing agent solution with the concentration of 1-6g/L for 4-6 min; preparing a nickel nitrate solution and a potassium hydroxide solution; weighing sodium citrate and thiourea, respectively dissolving, adding into a nickel nitrate solution, and preparing a chemical plating solution; adding the activated copper powder and acetic acid into a nickel nitrate solution, heating the copper powder and the acetic acid to 45-60 ℃ in a water bath, adding a reducing agent for reaction, and adjusting the pH value of the solution by adopting a potassium hydroxide solution in the nickel plating process for 20-25min until the reaction is complete; washing with deionized water for 2-3 times, washing with anhydrous alcohol for 2-3 times, and drying in vacuum environment to obtain the nickel-coated copper alloy powder with core-shell structure.
The invention also provides a preparation method of the copper alloy blank, the copper alloy feed prepared by the preparation method is injected and molded by adopting a mold matched with a prepared workpiece to obtain a copper alloy product, the copper alloy product is subjected to nitric acid catalytic degreasing, after degreasing for 1-2 hours, vacuum sintering is carried out, the sintering vacuum degree is 100-200Pa, the sintering temperature is 880-1050 ℃, and the heat preservation time is 1-2 hours.
Preferably, a mold release agent is applied to the mold prior to injection molding.
The invention at least comprises the following beneficial effects:
1. the rare earth element is added into the copper alloy, so that the mechanical property of the copper alloy can be effectively improved, the binding force between the copper alloy and the coating can be improved, and the conductivity of the prepared product can also be improved.
2. The copper alloy injection molding feed provided by the invention adopts the copper alloy particles with the core-shell structure, can effectively avoid the oxidation effect of oxygen on the copper alloy particles, and can avoid the condition that the copper particles are directly contacted with nitric acid to generate nitrate and influence the service performance of the copper alloy feed when nitric acid is adopted for catalytic degreasing.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples to enable those skilled in the art to practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example one
The copper alloy and the forming agent are prepared according to the weight ratio of 80:20, the granularity of the copper alloy is 200 meshes, and the copper alloy comprises the following components in percentage by mass: 65% of Cu, 30% of Al, 4% of Ni and 1% of rare earth elements; the forming agent comprises the following components in percentage by mass: 73% of polyformaldehyde, 3% of naphthalene, 10% of carnauba wax, 10% of polybutylene terephthalate and 4% of zinc stearate, wherein the particle sizes of the polyformaldehyde, the carnauba wax and the polybutylene terephthalate are 200 meshes, the copper alloy powder is of a core-shell structure, the inner core is copper alloy, and the outer shell is nickel.
Firstly, selecting a high-purity aluminum sample, polishing the sample by using abrasive paper, removing oxides on the surface of the sample, putting the sample into a container containing an acetone solution, cleaning the sample by using ultrasonic waves, taking out the sample, and drying the sample for later use; putting the dried aluminum sample into a crucible, heating to 680-plus 700 ℃, adding the preheated copper sample, nickel powder and rare earth elements, then continuously heating to 820-plus 860 ℃, preserving heat for 10-12 hours, and discontinuously applying ultrasonic waves outside the crucible in the heat preservation process to uniformly mix the alloy in the crucible; atomizing the molten alloy liquid to obtain the pretreated copper alloy powder
And preparing the copper alloy powder with the core-shell structure by adopting a chemical nickel plating method: activation treatment of copper powder: dipping and reducing in reducing agent solution with the concentration of 1-6g/L for 4-6 min; preparing a nickel nitrate solution and a potassium hydroxide solution; weighing sodium citrate and thiourea, respectively dissolving, adding into a nickel nitrate solution, and preparing a chemical plating solution; adding the activated copper powder and acetic acid into a nickel nitrate solution, heating the copper powder and the acetic acid to 45-60 ℃ in a water bath, adding a reducing agent for reaction, and adjusting the pH value of the solution by adopting a potassium hydroxide solution in the nickel plating process for 20-25min until the reaction is complete; washing with deionized water for 2-3 times, washing with anhydrous alcohol for 2-3 times, and drying in vacuum to obtain core-shell nickel-coated copper alloy powder
And then heating the copper alloy powder to 140 ℃, heating the forming agent to 170 ℃, mixing the copper alloy powder and the forming agent, uniformly stirring, plasticizing, extruding and granulating to obtain the copper alloy feed.
And finally, obtaining a copper alloy product by injection molding by adopting a mold matched with the prepared workpiece, carrying out nitric acid catalytic degreasing on the copper alloy product, carrying out vacuum sintering after degreasing for 1-2 hours, wherein the sintering vacuum degree is 100-200Pa, the sintering temperature is 880-1050 ℃, and the heat preservation time is 1-2 hours, thus obtaining the copper alloy product.
The density of the sintered copper alloy product is about 6.63g/cm through detection3The density is 98%.
Example two
The copper alloy and the forming agent are prepared according to the weight ratio of 70:30, the granularity of the copper alloy is 300 meshes, and the copper alloy comprises the following components in percentage by mass: 70% of Cu, 25% of Al, 4% of Ni and 1% of rare earth elements; the forming agent comprises the following components in percentage by mass: 78% of polyformaldehyde, 2% of naphthalene, 5% of carnauba wax, 10% of polybutylene terephthalate and 5% of zinc stearate, wherein the particle sizes of the polyformaldehyde, the carnauba wax and the polybutylene terephthalate are 300 meshes, the copper alloy powder is of a core-shell structure, the inner core is copper alloy, and the outer shell is nickel.
Firstly, selecting a high-purity aluminum sample, polishing the sample by using abrasive paper, removing oxides on the surface of the sample, putting the sample into a container containing an acetone solution, cleaning the sample by using ultrasonic waves, taking out the sample, and drying the sample for later use; putting the dried aluminum sample into a crucible, heating to 680-plus 700 ℃, adding the preheated copper sample, nickel powder and rare earth elements, then continuously heating to 820-plus 860 ℃, preserving heat for 10-12 hours, and discontinuously applying ultrasonic waves outside the crucible in the heat preservation process to uniformly mix the alloy in the crucible; atomizing the molten alloy liquid to obtain the pretreated copper alloy powder
And preparing the copper alloy powder with the core-shell structure by adopting a chemical nickel plating method: activation treatment of copper powder: dipping and reducing in reducing agent solution with the concentration of 1-6g/L for 4-6 min; preparing a nickel nitrate solution and a potassium hydroxide solution; weighing sodium citrate and thiourea, respectively dissolving, adding into a nickel nitrate solution, and preparing a chemical plating solution; adding the activated copper powder and acetic acid into a nickel nitrate solution, heating the copper powder and the acetic acid to 45-60 ℃ in a water bath, adding a reducing agent for reaction, and adjusting the pH value of the solution by adopting a potassium hydroxide solution in the nickel plating process for 20-25min until the reaction is complete; washing with deionized water for 2-3 times, washing with anhydrous alcohol for 2-3 times, and drying in vacuum to obtain core-shell nickel-coated copper alloy powder
And then heating the copper alloy powder to 140 ℃, heating the forming agent to 170 ℃, mixing the copper alloy powder and the forming agent, uniformly stirring, plasticizing, extruding and granulating to obtain the copper alloy feed.
And finally, obtaining a copper alloy product by injection molding by adopting a mold matched with the prepared workpiece, carrying out nitric acid catalytic degreasing on the copper alloy product, carrying out vacuum sintering after degreasing for 1-2 hours, wherein the sintering vacuum degree is 100-200Pa, the sintering temperature is 880-1050 ℃, and the heat preservation time is 1-2 hours, thus obtaining the copper alloy product.
The density of the sintered copper alloy product is about 6.94g/cm through detection3And the compactness is 97%.
EXAMPLE III
The copper alloy and the forming agent are prepared according to the weight ratio of 70:30, the granularity of the copper alloy is 500 meshes, and the copper alloy comprises the following components in percentage by mass: 70% of Cu, 25% of Al, 4% of Ni and 1% of rare earth elements; the forming agent comprises the following components in percentage by mass: 78% of polyformaldehyde, 2% of naphthalene, 5% of carnauba wax, 10% of polybutylene terephthalate and 5% of zinc stearate, wherein the particle sizes of the polyformaldehyde, the carnauba wax and the polybutylene terephthalate are 200 meshes, the copper alloy powder is of a core-shell structure, the inner core is copper alloy, and the outer shell is nickel.
Firstly, selecting a high-purity aluminum sample, polishing the sample by using abrasive paper, removing oxides on the surface of the sample, putting the sample into a container containing an acetone solution, cleaning the sample by using ultrasonic waves, taking out the sample, and drying the sample for later use; putting the dried aluminum sample into a crucible, heating to 680-plus 700 ℃, adding the preheated copper sample, nickel powder and rare earth elements, then continuously heating to 820-plus 860 ℃, preserving heat for 10-12 hours, and discontinuously applying ultrasonic waves outside the crucible in the heat preservation process to uniformly mix the alloy in the crucible; atomizing the molten alloy liquid to obtain the pretreated copper alloy powder
And preparing the copper alloy powder with the core-shell structure by adopting a chemical nickel plating method: activation treatment of copper powder: dipping and reducing in reducing agent solution with the concentration of 1-6g/L for 4-6 min; preparing a nickel nitrate solution and a potassium hydroxide solution; weighing sodium citrate and thiourea, respectively dissolving, adding into a nickel nitrate solution, and preparing a chemical plating solution; adding the activated copper powder and acetic acid into a nickel nitrate solution, heating the copper powder and the acetic acid to 45-60 ℃ in a water bath, adding a reducing agent for reaction, and adjusting the pH value of the solution by adopting a potassium hydroxide solution in the nickel plating process for 20-25min until the reaction is complete; washing with deionized water for 2-3 times, washing with anhydrous alcohol for 2-3 times, and drying in vacuum to obtain core-shell nickel-coated copper alloy powder
And then heating the copper alloy powder to 140 ℃, heating the forming agent to 170 ℃, mixing the copper alloy powder and the forming agent, uniformly stirring, plasticizing, extruding and granulating to obtain the copper alloy feed.
And finally, obtaining a copper alloy product by injection molding by adopting a mold matched with the prepared workpiece, carrying out nitric acid catalytic degreasing on the copper alloy product, carrying out vacuum sintering after degreasing for 1-2 hours, wherein the sintering vacuum degree is 100-200Pa, the sintering temperature is 880-1050 ℃, and the heat preservation time is 1-2 hours, thus obtaining the copper alloy product.
The density of the sintered copper alloy product is about 6.86g/cm through detection3And the compactness is 93 percent.
Comparative example 1
The copper alloy and the forming agent are prepared according to the weight ratio of 80:20, the granularity of the copper alloy is 200 meshes, and the copper alloy comprises the following components in percentage by mass: 65% of Cu, 30% of Al, 4% of Ni and 1% of rare earth elements; the forming agent comprises the following components in percentage by mass: 73% of polyformaldehyde, 3% of naphthalene, 10% of carnauba wax, 10% of polybutylene terephthalate and 4% of zinc stearate, wherein the particle sizes of the polyformaldehyde, the carnauba wax and the polybutylene terephthalate are 200 meshes, the copper alloy powder is of a core-shell structure, the inner core is copper alloy, and the outer shell is nickel.
Firstly, selecting a high-purity aluminum sample, polishing the sample by using abrasive paper, removing oxides on the surface of the sample, putting the sample into a container containing an acetone solution, cleaning the sample by using ultrasonic waves, taking out the sample, and drying the sample for later use; putting the dried aluminum sample into a crucible, heating to 680-plus 700 ℃, adding the preheated copper sample, nickel powder and rare earth elements, then continuously heating to 820-plus 860 ℃, preserving heat for 10-12 hours, and discontinuously applying ultrasonic waves outside the crucible in the heat preservation process to uniformly mix the alloy in the crucible; atomizing the molten alloy liquid to obtain the pretreated copper alloy powder
And then heating the copper alloy powder to 140 ℃, heating the forming agent to 170 ℃, mixing the copper alloy powder and the forming agent, uniformly stirring, plasticizing, extruding and granulating to obtain the copper alloy feed.
And finally, obtaining a copper alloy product by injection molding by adopting a mold matched with the prepared workpiece, carrying out nitric acid catalytic degreasing on the copper alloy product, carrying out vacuum sintering after degreasing for 1-2 hours, wherein the sintering vacuum degree is 100-200Pa, the sintering temperature is 880-1050 ℃, and the heat preservation time is 1-2 hours, thus obtaining the copper alloy product.
The density of the sintered copper alloy product is about 6.61g/cm through detection3And the compactness is 88 percent.
Comparative example No. two
The copper alloy and the forming agent are prepared according to the weight ratio of 70:30, the granularity of the copper alloy is 300 meshes, and the copper alloy comprises the following components in percentage by mass: 70% of Cu, 25% of Al, 4% of Ni and 1% of rare earth elements; the forming agent comprises the following components in percentage by mass: 78% of polyformaldehyde, 2% of naphthalene, 5% of carnauba wax, 10% of polybutylene terephthalate and 5% of zinc stearate, wherein the particle sizes of the polyformaldehyde, the carnauba wax and the polybutylene terephthalate are 200 meshes, the copper alloy powder is of a core-shell structure, the inner core is copper alloy, and the outer shell is nickel.
Firstly, selecting a high-purity aluminum sample, polishing the sample by using abrasive paper, removing oxides on the surface of the sample, putting the sample into a container containing an acetone solution, cleaning the sample by using ultrasonic waves, taking out the sample, and drying the sample for later use; putting the dried aluminum sample into a crucible, heating to 680-plus 700 ℃, adding the preheated copper sample, nickel powder and rare earth elements, then continuously heating to 820-plus 860 ℃, preserving heat for 10-12 hours, and discontinuously applying ultrasonic waves outside the crucible in the heat preservation process to uniformly mix the alloy in the crucible; and (3) atomizing the molten alloy liquid to obtain the pretreated copper alloy powder.
And then heating the copper alloy powder to 140 ℃, heating the forming agent to 170 ℃, mixing the copper alloy powder and the forming agent, uniformly stirring, plasticizing, extruding and granulating to obtain the copper alloy feed.
And finally, obtaining a copper alloy product by injection molding by adopting a mold matched with the prepared workpiece, carrying out nitric acid catalytic degreasing on the copper alloy product, carrying out vacuum sintering after degreasing for 1-2 hours, wherein the sintering vacuum degree is 100-200Pa, the sintering temperature is 880-1050 ℃, and the heat preservation time is 1-2 hours, thus obtaining the copper alloy product.
The density of the sintered copper alloy product is about 6.89g/cm3 and the density is 86% through detection.
| Density (g/cm) of copper alloy product3） | Compactness degree | |
| Example one | 6.63 | 98% |
| Example two | 6.94 | 97% |
| EXAMPLE III | 6.91 | 93% |
| Comparative example 1 | 6.61 | 88% |
| Comparative example No. two | 6.89 | 86% |
As can be seen from the above table, the compactness of the copper alloy product prepared from the core-shell structure copper alloy powder is obviously better than that of the copper alloy product prepared from the common copper alloy powder, and in addition, the comparison between the second embodiment and the third embodiment shows that the great difference between the particle diameters of the copper alloy powder and the particles of the forming agent powder also affects the compactness of the sintered product.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, and the invention is thus not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (6)
1. A copper alloy feed is characterized in that: the feeding material comprises copper alloy powder and a forming agent, and the preparation steps of the copper alloy powder are as follows: (1) selecting a high-purity aluminum sample, polishing the sample by using abrasive paper, removing oxides on the surface of the sample, putting the sample into a container containing acetone solution, cleaning the sample by using ultrasonic waves, taking out the sample, and drying the sample for later use; (2) putting the dried aluminum sample into a crucible, heating to 680-plus 700 ℃, adding the preheated copper sample, nickel powder and rare earth elements, then continuously heating to 820-plus 860 ℃, preserving heat for 10-12 hours, and discontinuously applying ultrasonic waves outside the crucible in the heat preservation process to uniformly mix the alloy in the crucible; (3) carrying out atomization on the molten alloy liquid to obtain pretreated copper alloy powder; (4) preparing copper alloy powder with a core-shell structure by adopting a chemical nickel plating method; the copper alloy powder and the forming agent are prepared according to the weight ratio of 80: 20-70: 30, the granularity of the copper alloy powder is 200-500 meshes, and the copper alloy powder comprises the following components in percentage by mass: 65-75% of Cu, 25-35% of Al, 5-10% of Ni and 0.5-1% of rare earth elements; the forming agent comprises the following components in percentage by mass: 73-78% of polyformaldehyde, 2-3% of naphthalene, 5-10% of carnauba wax, 10-15% of polybutylene terephthalate and 3-5% of zinc stearate, wherein the particle sizes of the polyformaldehyde, the carnauba wax and the polybutylene terephthalate are 200-500 meshes, the copper alloy powder is of a core-shell structure, the inner core is copper alloy, and the shell is nickel; and degreasing the copper alloy feed by using nitric acid.
2. Copper alloy feedstock according to claim 1 characterised in that: the particle size of the copper alloy powder was 300 mesh.
3. A method of preparing a copper alloy feedstock according to claim 1, characterized in that: heating the copper alloy powder to 140 ℃ at first, heating the forming agent to 170 ℃ at second, mixing the copper alloy powder and the forming agent, uniformly stirring, plasticizing, extruding and granulating to obtain the copper alloy feed.
4. A method of preparing a copper alloy feedstock as defined in claim 3 wherein: the preparation method of the chemical nickel plating method comprises the following steps:
(1) activation treatment of copper powder: dipping and reducing in reducing agent solution with the concentration of 1-6g/L for 4-6 min;
(2) preparing a nickel nitrate solution and a potassium hydroxide solution;
(3) weighing sodium citrate and thiourea, respectively dissolving, adding into a nickel nitrate solution, and preparing a chemical plating solution;
(4) adding the activated copper powder and acetic acid into a nickel nitrate solution, heating the copper powder and the acetic acid to 45-60 ℃ in a water bath, adding a reducing agent for reaction, and adjusting the pH value of the solution by adopting a potassium hydroxide solution in the nickel plating process for 20-25min until the reaction is complete;
(5) washing with deionized water for 2-3 times, washing with anhydrous alcohol for 2-3 times, and drying in vacuum environment to obtain the nickel-coated copper alloy powder with core-shell structure.
5. A preparation method of a copper alloy blank is characterized in that a copper alloy feed prepared by the preparation method according to any one of claims 3-4 is adopted, a mould matched with a prepared workpiece is adopted, injection molding is carried out to obtain a copper alloy product, the copper alloy product is subjected to nitric acid catalytic degreasing, vacuum sintering is carried out after degreasing is carried out for 1-2 hours, the sintering vacuum degree is 100-200Pa, the sintering temperature is 880-1050 ℃, and the heat preservation time is 1-2 hours.
6. The method of claim 5, wherein: before injection molding, a mold release agent is applied to the mold.
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