CN114293232B - Method for preparing tungsten dispersion strengthened copper composite material by electroforming - Google Patents
Method for preparing tungsten dispersion strengthened copper composite material by electroforming Download PDFInfo
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Abstract
The invention provides a method for preparing a tungsten dispersion strengthened copper composite material by electroforming, belonging 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 tungsten dispersion strengthened copper composite material cannot be prepared by the traditional smelting method due to the extremely high enthalpy of mixing formation, so that a novel preparation method needs to be developed to solve the problem. Currently, 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 methods such as infiltration method, coprecipitation method and sol-gel method. 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 uses tungsten as a framework, can only prepare the tungsten dispersion strengthened copper composite material with high tungsten content, 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, followed by separating the plated layer 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 existing documents disclose methods for preparing pure copper coatings or pure tungsten coatings by electroplating methods, but there are no reports on electroplating tungsten dispersion-strengthened copper composite materials, and no reports on preparing tungsten dispersion-strengthened copper composite materials by electroforming methods.
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 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).
Preferably, in the plating solution in the step 1), the content of the sodium citrate is 1-10 g/L, and the content of the 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 in the electroforming layer are uniformly and finely distributed, and a pitting pit is prevented from being formed due to overlarge current.
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 step 3), the direct current source voltage is 5-10V, and the cathode current density is 1-5A/dm 2 The temperature of the electroforming solution is kept between 40 and 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, and 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 the 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, tungsten is weighed according to a mass ratio of 100, 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.
Compared with the prior art, the invention has the following advantages:
1. the tungsten dispersion strengthening copper composite material is prepared by adopting an electroforming method, the dispersed phase tungsten particles are fine and are uniformly distributed in a 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 and the component with the complex shape has the advantages of short preparation flow, high processing efficiency and low energy consumption, can realize near-net forming, and avoids the phenomenon that the performance is deteriorated due to coarsening of crystal grains in the traditional high-temperature processing forming process.
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, and sodium citrate with the content of 1g/L and lauryl sodium sulfate with the content of 0.1g/L are added into the mixture. Dissolving with deionized water, and stirring to mix completely and uniformly.
2. And (3) degreasing and acid washing 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/dm 2 The electroforming temperature is 40 ℃, the pH value is controlled to be 8, and the electroforming time is 12h.
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 conductivity was 93% IACS.
Example 2
1. Weighing copper sulfate and ammonium metatungstate according to the mass ratio of copper to tungsten of 10. 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 prepared plating solution into a plating bath, controlling the direct current power supply voltage to be 8V and the cathode current density to be 3A/dm 2 The electroforming temperature is 70 ℃, the pH value is controlled to be 10, and the electroforming time is 24h.
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. Weighing copper chloride and sodium metatungstate according to a mass ratio of copper to tungsten of 5. Dissolving with deionized water, 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/dm 2 The electroforming temperature is 80 ℃, the pH value is controlled to be 10, and the electroforming time is 48h.
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 electric conductivity was 77% IACS.
Claims (3)
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 sodium citrate and the sodium dodecyl sulfate are completely dissolved for later use;
2) Pretreatment of an electrode: before electroforming, polishing, degreasing, washing, activating with acid and washing again are carried out on the cathode and the anode, so that the cleanliness 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: cleaning and drying the tungsten dispersion strengthened copper composite material prepared on the cathode to obtain a finished tungsten dispersion strengthened copper composite material;
in the step 1), in the plating solution, the content of sodium citrate is 1 to 10g/L, the content of sodium dodecyl sulfate is 0.1 to 1g/L, the mass ratio of the sodium citrate to the sodium dodecyl sulfate is 10, and the mass ratio of copper elements to tungsten elements is (100);
in the electroforming process, controlling the pH value of the plating solution to be 8 to 10 by using acetic acid and ammonia water as pH value control agents; the direct current source voltage is 5 to 15V, and the cathode current density is 1 to 5A/dm 2 The temperature of the electroforming solution is kept at 40-80 ℃.
2. The method of electroforming preparation of a tungsten dispersion strengthened copper composite material as claimed in claim 1, 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.
3. The method of electroforming preparation of a tungsten dispersion strengthened copper composite material as claimed in claim 1, wherein: and 4) uniformly distributing medium 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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