CN114293232A - Method for preparing tungsten dispersion strengthened copper composite material by electroforming - Google Patents
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Abstract
The invention provides a method for preparing a tungsten dispersion strengthened copper composite material by electroforming, and belongs to the field of preparation of copper-based composite materials. The process comprises the steps of preparing a plating solution containing copper and tungsten, treating an electrode slice, then adjusting proper electroforming process parameters, depositing ions containing copper and tungsten on a specially treated cathode slice, and finally separating a casting layer to obtain the bulk copper-tungsten composite material with uniform distribution of tungsten particles and small size. The invention can control the composition proportion, microstructure, mechanical property and the like of the composite material by adjusting electroforming parameters and plating solution components. The technology of the invention has the characteristics of short preparation flow, continuous and controllable components and fine and uniform particles, the nano-scale tungsten particles can greatly improve the mechanical property of the copper alloy, maintain excellent electric conduction and heat conduction properties, and have wide prospects in the application of electronic packaging materials, electrode materials, electric contact materials and the like.
Description
Technical Field
The invention belongs to the technical field of copper-based composite material preparation. Relates to a method for preparing a tungsten dispersion strengthened copper composite material by electroforming.
Technical Field
Copper is one of the first metals developed and utilized by humans. The copper alloy has the advantages of good electrical and thermal conductivity, good machinability and the like, so the copper alloy is widely applied to the fields of electric power, transportation and energy. With the progress of science and technology, the demand for novel copper-based composite materials is continuously increased, and the requirements on the comprehensive properties of the copper-based composite materials are increasingly strict. The traditional pure copper and solid solution reinforced copper alloy are difficult to consider both the strength and the electric and heat conducting properties. The particle reinforced copper-based composite material has the characteristics of high strength, good high-temperature stability, excellent electric and heat conductivity and the like, so that the particle reinforced copper-based composite material has wide application prospect in the future.
The tungsten dispersion strengthened copper composite material has the characteristics of high melting point and high hardness of tungsten and good electric and thermal conductivity of copper. The method is widely applied to the fields of various high-temperature resistant materials, high-voltage electrical materials, electronic packaging materials and the like. The enthalpy of the mixing formation of the tungsten and the copper phases is as high as 32kJ/mol, and the tungsten is extremely difficult to be dissolved in the copper matrix, so that the tungsten serving as a strengthening phase can effectively avoid the influence of solid solution elements on the electric and heat conducting properties of the copper alloy. However, the extremely high enthalpy of mixing also makes the tungsten dispersion strengthened copper composite material unable to be prepared by the traditional smelting method, so a novel preparation method needs to be developed to solve the problem. At present, researchers have disclosed various methods for preparing tungsten dispersion strengthened copper composite materials, and in patents CN201611158950.2, CN200710118440.7, and CN201810058741.3, tungsten dispersion strengthened copper composite materials are prepared by infiltration, coprecipitation, sol-gel method, etc. However, the disclosed method mainly uses powder as a precursor, and the subsequent molding and sintering process is complex and high in cost. The infiltration method only can prepare the tungsten dispersion strengthened copper composite material with high tungsten content by taking tungsten as a framework, and cannot be used for preparing the copper-based composite material. Therefore, it is necessary to develop a more advanced preparation process to meet the requirements of the production of the new generation of high-performance tungsten dispersion-strengthened copper composite material.
The electroforming method is one of electrochemical synthesis methods, and a metal layer is uniformly plated on the surface of a cathode mainly by electrolysis of a metal salt in an electroplating bath, and then the plated layer is separated from the cathode to obtain a shaped metal material. The electroforming has the advantages of high production efficiency, uniform and fine tissue, controllable thickness, easy preparation of components with complex shapes and the like. By adjusting electroforming parameters and plating solution components, the continuous regulation and control of the components of the multi-component material can be realized. The patent CN201010575369.7 and the prior literature disclose methods for preparing pure copper coating or pure tungsten coating by electroplating, but there is no report on electroplating tungsten dispersion strengthened copper composite material, and there is no report on preparing tungsten dispersion strengthened copper composite material by electroforming.
The preparation method provided by the invention dissolves the reactant raw materials in the plating solution, and can realize the uniform mixing of multi-component ions. By adjusting the shape of the cathode and the electroforming parameters, the shape and thickness of the final finished component can be precisely controlled. The method realizes one-step forming of the components, omits subsequent high-temperature sintering and processing steps in the traditional method, and has the advantages of high production efficiency, low energy consumption, high finished product precision, no waste in one-step forming and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a tungsten dispersion strengthened copper composite material by electroforming. The method takes soluble copper salt and soluble tungstate as raw materials, and copper ions and tungstate ions in the plating solution are electrolyzed to deposit pure copper and pure tungsten metal on a cathode, so that a tungsten-copper composite plating layer is formed. And after the electroforming process is finished, cleaning, drying and demolding to finish the preparation of a finished product.
In order to realize the technical scheme of the invention, the specific scheme comprises the following steps:
1) preparing a plating solution: dissolving soluble copper salt and soluble tungstate in deionized water according to a certain proportion. And simultaneously adding sodium citrate and sodium dodecyl sulfate, and stirring until the sodium citrate and the sodium dodecyl sulfate are completely dissolved for later use.
2) Pretreatment of an electrode plate: before electroforming, the cathode and the anode sheets are polished, deoiled, washed, activated by acid, washed again and the like, so that the cleanliness of the matrixes of the cathode and the anode is ensured.
3) Electroforming: and placing the anode and the cathode into a plating tank filled with plating solution, wherein the anode is a copper plate, and the cathode is a titanium material component with a required shape. Then, the power is turned on to perform electroforming. The pH value is continuously adjusted in the electroforming process until the electroforming is finished.
4) And (3) post-treatment: and cleaning and drying the tungsten dispersion strengthened copper composite material prepared on the cathode to obtain a finished product of the tungsten dispersion strengthened copper composite material.
Preferably, the soluble copper salt in step 1) is one or more of copper sulfate, copper nitrate and copper chloride, and the soluble tungstate is one or more of ammonium metatungstate, sodium tungstate and sodium metatungstate. The complexing agent can also be one or more of glutamic acid, catechol, sodium sulfamate, citric acid and salicylic acid.
Preferably, in the plating solution in the step 1), the mass ratio of the copper element to the tungsten element is 100: 1-5: 1.
Preferably, in the plating solution in the step 1), the content of sodium citrate is 1-10 g/L, and the content of sodium dodecyl sulfate is 0.1-1 g/L. The sodium citrate and the sodium dodecyl sulfate are added, so that the tungsten and the copper phases in the electroformed layer are uniformly and finely distributed, and the formation of pitting pits due to overlarge current is prevented.
Preferably, in the electroforming process in the step 3), the pH value control agent is acetic acid and ammonia water, and the pH value of the plating solution is controlled to be 8-10. By controlling the pH value within a reasonable range, the formation of hexavalent tungsten ions caused by tungsten elements due to too low pH value is prevented, and the precipitation of copper ions caused by too high pH value is also prevented.
Preferably, in the electroforming process in the step 3), the direct current source voltage is 5-10V, and the cathode current density is 1-5A/dm2And keeping the temperature of the electroforming solution at 40-80 ℃.
Preferably, in the tungsten dispersion strengthened copper composite material in the step 4), tungsten particles are uniformly distributed in the copper matrix, and the size of the tungsten particles is 4-500 nm.
The key points of the technology of the invention are as follows:
1. the technology of the invention realizes the binary codeposition of copper and tungsten, which is different from the electrodeposition of single component (such as pure copper) (the pure tungsten can not realize the single electrodeposition), the binary composite electrodeposition needs to overcome the problem that the codeposition can not be realized due to the difference of the potential difference of intrinsic electrodes, and the purpose of the binary codeposition of copper and tungsten can be achieved only by strictly matching the internal parameters of electrolyte solution, additive formula, concentration and the like with the external parameters of current, stirring speed and the like.
2. The tungsten dispersion strengthening copper composite material is prepared by adopting an electroforming method, dispersed-phase tungsten particles can gradually appear and gradually diffuse without aggregation by controlling the proportion of copper salt and tungsten salt, the current voltage and the pH value range, the prepared dispersed-phase tungsten particles are fine and are uniformly distributed in a copper matrix, and the problems of large dispersed-phase aggregation and high product porosity in the traditional method are solved.
3. Aiming at the types and contents of copper sulfate, copper nitrate and copper chloride as soluble copper salt and ammonium metatungstate, sodium tungstate and sodium metatungstate as soluble tungstate, tungsten and copper phases in the electroformed layer are uniformly and finely distributed by adopting different complexing agents and adding amounts, and pitting pits are prevented from being formed due to overlarge current. For copper nitrate and sodium tungstate, copper and tungsten are weighed according to the mass ratio of 100:1, sodium citrate and sodium dodecyl sulfate are selected as complexing agents, and when the ratio of the sodium citrate to the sodium dodecyl sulfate is 10:1, the tungsten dispersion strengthened copper composite material with higher performance can be prepared by controlling proper direct-current power supply voltage, cathode current density, electroforming temperature, pH value and electroforming time.
Compared with the prior art, the invention has the following advantages:
1. the tungsten dispersion strengthening copper composite material is prepared by adopting the electroforming method, the dispersed phase tungsten particles are fine and are uniformly distributed in the copper matrix, the problems of large dispersed phase agglomeration and high product porosity in the traditional method are solved, and the mechanical property and the electric and heat conducting properties of the copper alloy are greatly improved.
2. The tungsten dispersion strengthened copper composite material plate with the foil and the component with the complex shape can be directly formed and prepared by an electroforming method, compared with the traditional method, the tungsten dispersion strengthened copper composite material plate with the foil is short in preparation flow, high in processing efficiency and low in energy consumption, near-net forming can be achieved, and the phenomenon that performance is deteriorated due to coarsening of crystal grains in the traditional high-temperature processing forming process is avoided.
Drawings
Figure 1 example 1 SEM micrograph of tungsten dispersion strengthened copper composite material,
figure 2 SEM micrograph of tungsten dispersion strengthened copper composite of example 2,
FIG. 3 SEM micrograph of tungsten dispersion strengthened copper composite of example 1.
Detailed Description
Example 1
1. Copper nitrate and sodium tungstate are weighed according to the mass ratio of copper to tungsten being 100:1, and sodium citrate with the content of 1g/L and lauryl sodium sulfate with the content of 0.1g/L are added. Dissolving with deionized water, and stirring to mix completely and uniformly.
2. And (3) degreasing and pickling the cathode copper plate, and cleaning the cathode copper plate with deionized water until the surface is clean.
3. Adding the anode, the cathode and the prepared plating solution into the plating bath, controlling the direct current power supply voltage to be 5V and the cathode current density to be 1A/dm2The electroforming temperature is 40 ℃, the pH value is controlled to be 8, and the electroforming time is 12 h.
4. After the electroforming is finished, cleaning and drying are carried out, and then the electroforming component is demoulded to obtain the tungsten dispersion strengthened copper composite material sheet with the thickness of 0.5 mm.
In this example, the tensile strength of the tungsten dispersion strengthened copper composite material was 320MPa, and the electrical conductivity was 93% IACS.
Example 2
1. Copper sulfate and ammonium metatungstate are weighed according to the mass ratio of copper to tungsten of 10:1, and 5g/L sodium citrate and 0.5g/L sodium dodecyl sulfate are added. Dissolving with deionized water, and stirring to mix completely and uniformly.
2. And (3) degreasing and pickling the cathode copper plate, and cleaning the cathode copper plate with deionized water until the surface is clean.
3. Adding the anode, the cathode and the prepared plating solution into the plating bath, controlling the direct current power supply voltage to be 8V and the cathode current density to be 3A/dm2The electroforming temperature is 70 ℃, the pH value is controlled to be 10, and the electroforming time is 24 h.
4. After the electroforming is finished, cleaning and drying are carried out, and then the electroforming component is demoulded to obtain the tungsten dispersion strengthened copper composite material sheet with the thickness of 0.75 mm.
In this example, the tensile strength of the tungsten dispersion strengthened copper composite material was 482MPa, and the electrical conductivity was 84% IACS.
Example 3
1. Copper chloride and sodium metatungstate are weighed according to the mass ratio of copper to tungsten of 5:1, and sodium citrate with the content of 10g/L and sodium dodecyl sulfate with the content of 1g/L are added. Dissolving with deionized water, and stirring to mix completely and uniformly.
2. And (3) degreasing and pickling the cathode copper plate, and cleaning the cathode copper plate with deionized water until the surface is clean.
3. Adding the anode, the cathode and the prepared plating solution into the plating bath, controlling the direct current power supply voltage to be 10V and the cathode current density to be 5A/dm2The electroforming temperature is 80 ℃, the pH value is controlled to be 10, and the electroforming time is 48 h.
4. After the electroforming is finished, cleaning and drying are carried out, and then the electroforming component is demoulded to obtain the tungsten dispersion strengthened copper composite material sheet with the thickness of 1.2 mm.
In this example, the tensile strength of the tungsten dispersion-strengthened copper composite material was 619MPa, and the electrical conductivity was 77% IACS.
Claims (7)
1. A method for preparing a tungsten dispersion strengthened copper composite material by electroforming is characterized by comprising the following steps: the method comprises the following process steps:
1) preparing a plating solution: dissolving soluble copper salt and soluble tungstate in deionized water, adding sodium citrate and sodium dodecyl sulfate as a surfactant and a complexing agent, and stirring until the soluble copper salt and the soluble tungstate are completely dissolved for later use;
2) pretreatment of an electrode plate: before electroforming, polishing, degreasing, washing, acid activating and washing are carried out on the cathode and the anode plate, so that the cleanliness of the matrixes of the cathode and the anode is ensured;
3) electroforming: putting an anode and a cathode into a plating bath filled with plating solution, wherein the anode is a phosphor copper plate, and the cathode is a titanium material component; then starting a direct current power supply to carry out electroforming;
4) and (3) post-treatment: and cleaning and drying the tungsten dispersion strengthened copper composite material prepared on the cathode to obtain a finished product of the tungsten dispersion strengthened copper composite material.
2. The method of claim 1, wherein the electroforming is performed in the presence of a tungsten dispersion strengthened copper composite material, wherein: the soluble copper salt in the step 1) is one or more of copper sulfate, copper nitrate and copper chloride, and the soluble tungstate is one or more of ammonium tungstate, ammonium metatungstate, sodium tungstate and sodium metatungstate; the complexing agent can also be one or more of glutamic acid, catechol, sodium sulfamate, citric acid and salicylic acid.
3. The method of claim 1, wherein the electroforming is performed in the presence of a tungsten dispersion strengthened copper composite material, wherein: in the plating solution in the step 1), the mass ratio of the copper element to the tungsten element is 100: 1-5: 1.
4. The method of claim 1, wherein the electroforming is performed in the presence of a tungsten dispersion strengthened copper composite material, wherein: in the plating solution in the step 1), the content of sodium citrate is 1-10 g/L, and the content of sodium dodecyl sulfate is 0.1-1 g/L.
5. The method of claim 1, wherein the electroforming is performed in the presence of a tungsten dispersion strengthened copper composite material, wherein: and 3) in the electroforming process, controlling the pH value of the plating solution to be 8-10 by using acetic acid and ammonia water as pH value control agents.
6. The method of claim 1, wherein the electroforming is performed in the presence of a tungsten dispersion strengthened copper composite material, wherein: in the electroforming process of the step 3), the direct current source voltage is 5-15V, and the cathode current density is 1-5A/dm2And keeping the temperature of the electroforming solution at 40-80 ℃.
7. The method of claim 1, wherein the electroforming is performed in the presence of a tungsten dispersion strengthened copper composite material, wherein: and 4) uniformly distributing the tungsten particles in the tungsten dispersion strengthened copper composite material in the copper matrix, wherein the size of the tungsten particles is 4-500 nm.
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| CN113774442A (en) * | 2021-09-23 | 2021-12-10 | 中冶赛迪技术研究中心有限公司 | Nano composite coating based on endogenesis precipitation method and preparation process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11229176A (en) * | 1998-02-19 | 1999-08-24 | Osaka Prefecture | Tungsten alloy electroplating bath and electroplating method |
| CN101787552A (en) * | 2010-01-20 | 2010-07-28 | 中南大学 | Cu-W-Ni copper matrix composite used for liner, electroforming method and electroforming solution thereof |
| CN101838827A (en) * | 2010-04-16 | 2010-09-22 | 北京工业大学 | Method for controlling components and surface defect of electroformed nickel-tungsten alloy |
| US20110180415A1 (en) * | 2008-07-15 | 2011-07-28 | Enthone Inc. | Cyanide free electrolyte composition for the galvanic deposition of a copper layer |
| CN103643265A (en) * | 2013-12-25 | 2014-03-19 | 昆明理工大学 | Electroplating liquid for electrically depositing Cu-W-Co alloy coating and method thereof |
| CN108251685A (en) * | 2018-01-22 | 2018-07-06 | 北京科技大学 | A kind of tungsten dispersed and strengthened copper-based composite material and preparation method thereof |
-
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- 2021-12-02 CN CN202111467319.1A patent/CN114293232B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11229176A (en) * | 1998-02-19 | 1999-08-24 | Osaka Prefecture | Tungsten alloy electroplating bath and electroplating method |
| US20110180415A1 (en) * | 2008-07-15 | 2011-07-28 | Enthone Inc. | Cyanide free electrolyte composition for the galvanic deposition of a copper layer |
| CN101787552A (en) * | 2010-01-20 | 2010-07-28 | 中南大学 | Cu-W-Ni copper matrix composite used for liner, electroforming method and electroforming solution thereof |
| CN101838827A (en) * | 2010-04-16 | 2010-09-22 | 北京工业大学 | Method for controlling components and surface defect of electroformed nickel-tungsten alloy |
| CN103643265A (en) * | 2013-12-25 | 2014-03-19 | 昆明理工大学 | Electroplating liquid for electrically depositing Cu-W-Co alloy coating and method thereof |
| CN108251685A (en) * | 2018-01-22 | 2018-07-06 | 北京科技大学 | A kind of tungsten dispersed and strengthened copper-based composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| PAWEL BACAL等: "Unusual example of induced codeposition of tungsten Galvanic formation of Cu–W alloy", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774442A (en) * | 2021-09-23 | 2021-12-10 | 中冶赛迪技术研究中心有限公司 | Nano composite coating based on endogenesis precipitation method and preparation process thereof |
| CN113774442B (en) * | 2021-09-23 | 2023-02-17 | 中冶赛迪技术研究中心有限公司 | Nano composite coating based on endogenesis precipitation method and preparation process thereof |
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