CN114875463A - Method for Heterobimetallic Connection of Electrodeposited Silver Layer Copper Alloy/Titanium Alloy - Google Patents

Abstract

The invention discloses a method for connecting copper alloy/titanium alloy heterogeneous bimetal of an electrodeposited silver layer, which specifically comprises the following steps: step 1, processing an aluminum bronze alloy and a titanium alloy into cylinders, polishing and then carrying out ultrasonic cleaning; step 2, carrying out acid cleaning on the aluminum bronze alloy and the titanium alloy cleaned in the step 1, then cleaning again, and drying and storing the titanium alloy for later use; step 3, performing electrodeposition on the aluminum bronze alloy obtained in the step 2 to obtain an aluminum bronze alloy with a silver layer deposited, performing post-treatment, and drying and storing for later use; and 4, sequentially placing the aluminum bronze alloy and the titanium alloy in a hot pressing die, and placing the hot pressing die in a vacuum hot pressing sintering furnace for vacuum diffusion connection to obtain the aluminum bronze/titanium alloy bimetal sample. The method breaks through the limitation of structural requirements on the component when the intermediate transition layer copper alloy/titanium alloy bimetal is added for connection at present, and solves the problems of low connection strength and poor interface combination of the existing connection method.

Description

Method for Heterobimetallic Connection of Electrodeposited Silver Layer Copper Alloy/Titanium Alloy

technical field

The invention belongs to the technical field of bimetal preparation, and relates to a method for electrodepositing a silver layer copper alloy/titanium alloy heterogeneous bimetal connection.

Background technique

Since the current high-pressure plunger pump with a rated pressure above 35MPa relies on imports, the high-pressure plunger pump has become a "stuck neck" problem for the innovative development of my country's aviation equipment. The high-pressure plunger pump has a complex service environment and strict requirements for use. The use of light/wear-resistant/high-strength copper alloy/titanium alloy bimetallic materials is expected to solve the problem.

At present, the connection strength of copper alloy/titanium alloy bimetallic materials is generally low, and high-quality connection can be achieved by adding an intermediate transition layer. The high-pressure plunger pump cylinder has a porous structure and complex shape, and an intermediate transition layer must be added by means of material surface treatment. Therefore, it is necessary to propose a new joining process to prepare copper alloy/titanium alloy bimetallic materials and improve their interface structure to obtain complex bimetallic cylinder structures with excellent performance and meeting requirements. Among the many surface treatment methods of materials, the electrodeposition process is easy to implement, has high flexibility, and can deposit single or multi-layer metals on flat and non-planar substrates with good performance. The Ag intermediate layer was prepared on the surface of copper alloy by electrodeposition process, and compounded with titanium alloy to prepare copper alloy/titanium alloy bimetallic material, which laid the foundation for the preparation of copper alloy/titanium alloy bimetallic material with complex shape.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a method for heterogeneous bimetallic connection of electrodeposited silver layer copper alloy/titanium alloy, which breaks the limitation of component structure requirements when adding intermediate transition layer copper alloy/titanium alloy bimetallic connection at present , which solves the problems of low connection strength and poor interface bonding existing in the existing connection methods.

The technical solution adopted in the present invention is that the method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetal connection specifically includes the following steps:

Step 1, both the aluminum bronze alloy and the titanium alloy are processed into cylinders, and subjected to mechanical grinding treatment, followed by ultrasonic cleaning;

Step 2, pickling the aluminum bronze alloy and titanium alloy cleaned in step 1, and then cleaning again to obtain pretreated aluminum bronze alloy and titanium alloy, and drying the titanium alloy for later use;

In step 3, the pretreated aluminum bronze alloy obtained in step 2 is electrodeposited to obtain an aluminum bronze alloy deposited with a silver layer, which is subjected to post-treatment, and is dried and stored for later use;

In step 4, the aluminum bronze alloy deposited with the silver layer in step 3 and the titanium alloy stored in step 2 are placed in a hot pressing mold in turn, and the hot pressing mold is placed in a vacuum hot pressing sintering furnace for vacuum diffusion connection to obtain aluminum bronze. /Titanium alloy bimetallic specimen.

The characteristic of the present invention also lies in:

In step 1, the titanium alloy and the aluminum bronze alloy are kept the same diameter; the specific process of cleaning the aluminum bronze alloy and titanium alloy after mechanical grinding in the ultrasonic cleaner is as follows: ultrasonic cleaning with deionized water for 1-10 minutes, ultrasonic cleaning with absolute ethanol 1~10min, ultrasonic cleaning with acetone solution for 1~5min, ultrasonic cleaning with deionized water for 1~5min, and drying.

In step 2: the specific process of pickling is as follows: soaking in 10% nitric acid alcohol solution for 30-120 s, and the re-cleaning adopts anhydrous ethanol ultrasonic cleaning for 5-10 min.

In step 3: the electrodeposition process parameters are as follows: the electrodeposition temperature is 20-30°C, the pH value of the electrodeposition solution is 4-6, the current intensity is 0.3-0.7A, the electrodeposition time is 5-25min, and the silver layer is deposited. The thickness is 1～20μm;

The specific process of the post-treatment is as follows: ultrasonic cleaning with deionized water for 1-10 minutes, ultrasonic cleaning with acetone solution for 1-5 minutes, and ultrasonic cleaning with absolute ethanol for 1-5 minutes in sequence.

In step 4, the vacuum diffusion connection process is specifically as follows: after the vacuum degree of the vacuum hot pressing sintering furnace reaches 6.0×10 ^-3 Pa～9.0×10 ^-3 Pa, heating starts, the sintering time is 40～50min, and the heating temperature reaches 700～ Heat preservation for 1h after ~50℃, apply pressure of 5 ~ 10MPa at the beginning of heat preservation, stop pressurization until the temperature drops to 200 ~ 300℃, and obtain aluminum bronze/titanium alloy bimetal after cooling in the furnace.

The beneficial effect of the present invention is that the method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetallic connection provided by the present invention provides a new process for copper alloy/titanium alloy heterogeneous bimetallic connection—electrodeposition -Vacuum diffusion bonding compound process. On the one hand, the electrodeposition method has high flexibility and can be deposited on complex structures with good performance. The most important thing is that the thickness of the deposited layer is controllable, and the thickness of the deposited layer within the range required for subsequent connections can be obtained; on the other hand, through the surface The process of combining electrodeposited silver layer and diffusion connection is beneficial to control the formation of metal compounds and make up for defects such as holes, thereby improving the interface structure and the interface bonding strength is high. The formed bimetal solves the problem of difficult connection of complex components, and the interface bonding strength is high, up to 23-.71MPa.

Description of drawings

Fig. 1 is the topography of aluminum bronze/titanium alloy bimetal interface in implementation case 2 of the method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetal connection according to the present invention;

2 is a schematic diagram of the shear strength curve of aluminum bronze/titanium alloy bimetallic shear strength in implementation case 2 of the method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetallic connection according to the present invention;

3 is a topography of the aluminum bronze/titanium alloy bimetal interface in implementation case 3 in the method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetallic connection according to the present invention;

4 is a graph showing the change trend of microhardness of the aluminum bronze/titanium alloy bimetal interface in implementation case 3 in the method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetallic connection according to the present invention.

Detailed ways

The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

The method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetal connection of the present invention is specifically carried out according to the following steps:

Step 1: Process the aluminum bronze alloy and the titanium alloy into a cylinder, and perform mechanical grinding treatment on it, that is, the surface is treated with ~0#, 2~0#, 400#, 600#, ~00#, 1000#, 1200 #, 1500#, 2000# sandpapers are polished in turn, and then put into deionized water, absolute ethanol, acetone, and deionized water for ultrasonic cleaning;

In step 1, the diameter dimension of the aluminum bronze alloy of the cylinder is 20mm and the height is 25mm, and the diameter dimension of the titanium alloy is 20mm and the height is 25mm, and the diameter is the same as that of the aluminum bronze alloy. The specific process of cleaning the aluminum bronze alloy and titanium alloy after mechanical grinding in the ultrasonic cleaner is as follows: ultrasonic cleaning with deionized water for 1-10 minutes - ultrasonic cleaning with absolute ethanol for 1-10 minutes - ultrasonic cleaning with acetone solution for 1-5 minutes - Ultrasonic cleaning with deionized water for 1 to 5 minutes, drying, and pickling in step 2.

Step 2, pickling the cleaned aluminum bronze alloy and titanium alloy, then cleaning again, and finally obtaining pretreated copper alloy base material and titanium alloy, and drying the titanium alloy for later use;

In step 2, the specific process of the pickling is as follows: soaking in a 10% nitric acid alcohol solution for 30 to 120 s, and the cleaning adopts anhydrous ethanol ultrasonic cleaning for 5 to 10 minutes.

In step 3, the pretreated aluminum bronze alloy in step 2 is electrodeposited to obtain an aluminum bronze alloy deposited with a silver layer, which is subjected to post-treatment, dried and stored for later use;

In step 3, in the electrodeposition process, the electrodeposition solution is an aqueous solution containing the following components: silver nitrate 40g/L, sodium thiosulfate 200g/L, potassium metabisulfite 40g/L, and an appropriate amount of boric acid is added to make the electrodeposition solution The pH value is 4-6; the specific process parameters are: the electrodeposition temperature is 20-30°C, the pH value of the electrodeposition solution is 4-6, the current intensity is 0.3-0.7A, and the electrodeposition time is 5-25min. The thickness of the deposited silver layer can be controlled within the range of 1-20 μm under the parameters. The specific process of the post-treatment is as follows: ultrasonic cleaning with deionized water for 1-10 minutes - ultrasonic cleaning with acetone solution for 1-5 minutes - ultrasonic cleaning with absolute ethanol for 1-5 minutes.

Step 4: The aluminum bronze deposited with the silver layer in step 3 and the titanium alloy preserved in step 2 are placed in a hot pressing mold in turn, and the hot pressing mold is placed in a vacuum hot pressing sintering furnace for vacuum diffusion connection to obtain aluminum bronze/ Titanium alloy bimetallic specimen.

In step 4, the vacuum diffusion connection process is specifically as follows: after the vacuum degree of the vacuum hot pressing sintering furnace reaches 6.0×10 ^-3 Pa～9.0×10 ^-3 Pa, heating is started, the sintering time is 40～50min, and the heating temperature is After 700～50℃, heat preservation for 1h, apply pressure of 5～10MPa at the beginning of heat preservation, stop pressurization until low temperature of 200～300℃, and obtain aluminum bronze/titanium alloy bimetal after cooling with the furnace.

Example 1

To prepare aluminum bronze/titanium alloy bimetal, aluminum bronze with grade QAl10-5-5 (hereinafter referred to as QAl10-5-5) and titanium alloy with trademark TC6 (hereinafter referred to as TC6) are processed into a Φ20mm×25mm cylinder. Mechanical grinding of QAl10-5-5 and TC6, ultrasonic cleaning in the order of deionized water, absolute ethanol, acetone, and deionized water, followed by pickling, soaking in 10% nitric alcohol for 30s, and then using The pretreated QAl10-5-5 and TC6 were obtained by cleaning with absolute ethanol for 5 min, and the TC6 was dried and stored for later use.

The pretreated QAl10-5-5 is electrodeposited. The specific process parameters are: the electrodeposition temperature is room temperature of 25°C, the pH value of the electrodeposition solution is 4.5, the current intensity is 0.5A, and the electrodeposition time is 25min. The silver layer thickness is 15 μm. It is post-processed, dried and stored for later use.

Place the TC6 and the QAl10-5-5 on which the silver layer is deposited in the hot pressing mold in turn, and then put the hot pressing mold into the vacuum hot pressing sintering furnace. In order to prevent the interface from being oxidized, the vacuum hot pressing sintering furnace is pumped to a high vacuum , when the vacuum degree in the vacuum hot pressing sintering furnace reaches 6.20×10 ^-3 Pa, the heating starts, sintering for 51 minutes, the heating temperature reaches ~ 35 ℃, and then the temperature is kept for 60 minutes. Pressed and cooled with the furnace to obtain aluminum bronze/titanium alloy bimetallic samples. The metallographic samples were prepared for microstructure observation. As shown in Figure 1, the interface was well bonded, and no defects such as cracks and holes appeared. The mechanical properties test shows that the interfacial shear strength can reach 23-.71MPa, as shown in Figure 2.

Example 2

To prepare aluminum bronze/titanium alloy bimetal, aluminum bronze with grade QAl10-5-5 (hereinafter referred to as QAl10-5-5) and titanium alloy with trademark TC6 (hereinafter referred to as TC6) are processed into a Φ20mm×25mm cylinder. Mechanical grinding of QAl10-5-5 and TC6, ultrasonic cleaning in the order of deionized water, absolute ethanol, acetone, and deionized water, followed by pickling, soaking in 10% nitric alcohol for 30s, and then using The pretreated QAl10-5-5 and TC6 were obtained by cleaning with absolute ethanol for 5 min, and the TC6 was dried and stored for later use.

The pretreated QAl10-5-5 was electrodeposited, and the specific process parameters were: the electrodeposition temperature was room temperature 25°C, the pH value of the electrodeposition solution was 4.3, the current intensity was 0.5A, and the electrodeposition time was 25min. The silver layer thickness is 15 μm. It is post-processed, dried and stored for later use.

Place the TC6 and the QAl10-5-5 on which the silver layer is deposited in the hot pressing mold in turn, and then put the hot pressing mold into the vacuum hot pressing sintering furnace. In order to prevent the interface from being oxidized, the vacuum hot pressing sintering furnace is pumped to a high vacuum , when the vacuum degree in the vacuum hot pressing sintering furnace reaches 6.～0×10 ^-3 Pa, the heating starts, sintering for 49 minutes, the heating temperature reaches to ～05 ℃, and then the temperature is kept for 60 minutes. The pressure was stopped at ℃, and the aluminum bronze/titanium alloy bimetal sample was obtained by cooling with the furnace. The metallographic sample was prepared for microstructure observation. As shown in Figure 3, the interface had no obvious defects and was well combined. After the microhardness test, the microhardness at the bimetal interface changed significantly, and the microhardness of the intermediate transition layer was consistent with the microhardness of the electrodeposited silver layer obtained before vacuum diffusion connection, which was 140.3HV, as shown in the figure 4 shown. The mechanical property test shows that the interfacial shear strength is 161.7-MPa.

Example 3

To prepare aluminum bronze/titanium alloy bimetal, aluminum bronze with grade QAl10-5-5 (hereinafter referred to as QAl10-5-5) and titanium alloy with trademark TC6 (hereinafter referred to as TC6) are processed into a Φ20mm×25mm cylinder. Mechanical grinding of QAl10-5-5 and TC6, ultrasonic cleaning in the order of deionized water, absolute ethanol, acetone, and deionized water, followed by pickling, soaking in 10% nitric alcohol for 30s, and then using The pretreated QAl10-5-5 and TC6 were obtained by cleaning with absolute ethanol for 5 min, and the TC6 was dried and stored for later use.

The pretreated QAl10-5-5 is electrodeposited. The specific process parameters are: the electrodeposition temperature is room temperature of 25°C, the pH value of the electrodeposition solution is 4.6, the current intensity is 0.5A, and the electrodeposition time is 25min. The silver layer thickness is 15 μm. It is post-processed, dried and stored for later use.

Place the TC6 and the QAl10-5-5 on which the silver layer is deposited in the hot pressing mold in turn, and then put the hot pressing mold into the vacuum hot pressing sintering furnace. In order to prevent the interface from being oxidized, the vacuum hot pressing sintering furnace is pumped to a high vacuum , when the vacuum degree in the vacuum hot-pressing sintering furnace reaches 6.30×10 ^-3 Pa, the heating starts, sintering for 50 minutes, the heating temperature reaches ~20 °C, and then the temperature is kept for 60 minutes. Pressed and cooled with the furnace to obtain aluminum bronze/titanium alloy bimetallic samples. The interfacial shear strength is 91.37MPa after the mechanical property test.

The method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetallic connection of the present invention provides a new process for copper alloy/titanium alloy heterogeneous bimetallic connection—electrodeposition-vacuum diffusion bonding composite process. On the one hand, the electrodeposition method has high flexibility and can be deposited on complex structures with good performance. The thickness of the deposited layer is controllable, and the thickness of the deposited layer within the range required for subsequent connections can be obtained. The process combined with the diffusion connection is beneficial to control the formation of metal compounds, make up for defects such as holes, improve the interface structure, and improve the interface bonding strength. In addition to the superior properties of aluminum bronze alloy and titanium alloy, the formed bimetal also has good interfacial bonding properties, which solves the problem of difficult connection of complex components.

Claims (5)

1. the method for electrodeposited silver layer copper alloy/titanium alloy heterogeneous bimetallic connection, is characterized in that: specifically comprises the following steps: Step 1, both the aluminum bronze alloy and the titanium alloy are processed into cylinders, and subjected to mechanical grinding treatment, followed by ultrasonic cleaning; Step 2, pickling the aluminum bronze alloy and titanium alloy cleaned in step 1, and then cleaning again to obtain pretreated aluminum bronze alloy and titanium alloy, and drying the titanium alloy for later use; In step 3, the pretreated aluminum bronze alloy obtained in step 2 is electrodeposited to obtain an aluminum bronze alloy deposited with a silver layer, which is subjected to post-treatment, and is dried and stored for later use; In step 4, the aluminum bronze alloy deposited with the silver layer in step 3 and the titanium alloy stored in step 2 are placed in a hot pressing mold in turn, and the hot pressing mold is placed in a vacuum hot pressing sintering furnace for vacuum diffusion connection to obtain aluminum bronze. /Titanium alloy bimetallic specimen. 2. The method for electrodeposited silver layer copper alloy/titanium alloy heterogeneous bimetallic connection according to claim 1, characterized in that: in the step 1, the titanium alloy and the aluminum bronze alloy keep the same diameter; The specific process of cleaning aluminum bronze alloy and titanium alloy in ultrasonic cleaner is as follows: ultrasonic cleaning in deionized water for 1-10 minutes, ultrasonic cleaning in absolute ethanol for 1-10 minutes, ultrasonic cleaning in acetone solution for 1-5 minutes, ultrasonic cleaning in deionized water for 1-10 minutes 5min, drying. 3. The method for electrodeposited silver layer copper alloy/titanium alloy heterogeneous bimetallic connection according to claim 1, characterized in that: in the step 2: the specific process of pickling is: soaked in 10% nitric acid alcohol solution For 30-120 s, the re-cleaning adopts anhydrous ethanol ultrasonic cleaning for 5-10 min. 4. The method for electrodepositing silver layer copper alloy/titanium alloy heterogeneous bimetallic connection according to claim 1, characterized in that: in the step 3: the electrodeposition process parameter process is: the electrodeposition temperature is room temperature 25°C , the pH value of the electrodeposition solution is 4-6, the current intensity is 0.3-0.7A, the electrodeposition time is 5-25min, and the thickness of the deposited silver layer is 1-20μm; The specific process of the post-treatment is as follows: ultrasonic cleaning with deionized water for 1-10 minutes, ultrasonic cleaning with acetone solution for 1-5 minutes, and ultrasonic cleaning with absolute ethanol for 1-5 minutes in sequence. 5. The method for electrodeposited silver layer copper alloy/titanium alloy heterogeneous bimetallic connection according to claim 1, characterized in that: in the step 4, the vacuum diffusion connection process is specifically: making the vacuum hot pressing sintering furnace After the vacuum degree reaches 6.0×10 ^-3 Pa～9.0×10 ^-3 Pa, the heating starts, the sintering time is 40～50min, the heating temperature reaches 700～750℃, and then the heat preservation is performed for 1h. The pressurization is stopped at 200-300°C, and the aluminum bronze/titanium alloy bimetal is obtained after cooling with the furnace.

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