CN114525426A - Preparation method of novel high-temperature oxidation resistant multi-element copper alloy - Google Patents

Abstract

The invention discloses a preparation method of a novel high-temperature oxidation resistant multi-element copper alloy, which comprises the steps of adding trace non-metal silicon elements and oxygen group elements (S, Se and Te) into a pure copper raw material to form a three-element copper alloy, carrying out pre-annealing treatment in a protective atmosphere, and carrying out segregation of the non-metal elements to the surface of the alloy through an annealing process to obtain stable SiO with a certain thickness₂Protective film coverA Cu-S (Cu-Se, Cu-Te) segregation layer of the cap, thereby forming a double-layer protection mechanism. The high-temperature oxidation resistant multi-element copper alloy provided by the invention obviously enhances the oxidation resistance of a metal copper material, can ensure that a copper consumable material product is not easily oxidized under the condition of high-temperature air, enlarges the application range of the alloy, prolongs the quality guarantee time of the alloy, has simple and easily repeated operation flow, has simple and easily-achieved required conditions, can meet the industrial production requirement of the copper consumable material, has environmental protection requirement in the manufacturing process, is green and pollution-free, and has important significance for the process development of modern metal materials.

Description

A novel preparation method of high temperature oxidation resistant multi-component copper alloy

technical field

The invention relates to the technical field of anti-oxidation treatment of industrial metal consumables, in particular to a preparation method of a novel high-temperature oxidation-resistant multi-component copper alloy.

Background technique

Copper is a soft, malleable, ductile metal. It has a very wide range of attributes and is of immeasurable value in social and economic development. It is widely used due to its excellent electrical and thermal conductivity and excellent processability. More than half of the copper is mainly used in electronic power and related industries, such as the manufacture of electrical equipment, power instruments, power transmission cables and integrated circuits. However, in the above-mentioned applications, copper products are often affected by similar oxidation corrosion. For example, most of the packaging process of integrated circuits is carried out at a high temperature of about 400°C, and the problem of oxidation of copper connecting lines caused by this is inevitable. Therefore, it is necessary to explore the improvement of high temperature oxidation resistance of metallic copper.

Adding alloying elements is a common method to improve the oxidation resistance of copper. At present, nearly 100 kinds of copper alloys with excellent properties have been developed with added metal elements, such as copper-titanium, copper-zirconium, copper-iron, etc. However, metal alloying element-enhanced copper alloys still have obvious oxidation phenomenon at high temperature, indicating that their ability to improve the anti-oxidation effect is weak, which limits the wide application of copper alloys. Therefore, it is necessary to study copper alloys doped with non-metallic elements. In previous studies, the enhancement effect of oxygen group elements S, Se, Te and Si elements on the high temperature oxidation of metallic copper has been confirmed. In the invention patent, the method of improving the corrosion resistance of copper by adding oxygen group alloys (Patent No. ZL201010101728.5) mentioned that trace oxygen group element doping can significantly improve the oxidation resistance of metal copper, so that copper alloys can be used in high temperature working environment. It is not easy to be oxidized under low temperature, but this method only slows down the oxidation rate, and the copper material will still be severely oxidized after a long time of oxidation.

In addition, the invention patent a method for improving the oxidation resistance of copper by a self-generated non-metal oxide composite film (Patent No. ZL201911044881.6) involves the addition of Si elements to prepare copper-silicon alloys. It is known that copper-silicon binary alloys at high temperature During the pre-annealing treatment, a stable and dense single-layer protective SiO ₂ adhesion film can be formed on the surface of the substrate. However, the heat treatment conditions of the invention patent are relatively harsh. The required heat treatment temperature needs to be above 800 °C and the annealing time needs to be 24 hours to ensure that the protective film generated is dense and uniform, resulting in high production costs.

SUMMARY OF THE INVENTION

1. Technical problems to be solved

The purpose of the present invention is to solve the problem that the heat treatment conditions in the prior art are relatively harsh, the required heat treatment temperature needs to be above 800° C. and the annealing time needs 24h, so as to ensure that the generated protective film is dense and uniform, resulting in excessive production costs. A new preparation method of high temperature oxidation resistant multi-component copper alloy is proposed.

2. Technical solutions

In order to achieve the above object, the present invention adopts the following technical solutions:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix and smelt high-purity silicon particles and high-purity granular raw materials of oxygen group (S, Se, Te) elements, and the concentrations of Si and oxygen group elements (S, Se, Te) in the alloy are each 0.05-1 wt%, The mass fraction of copper is 99.9-98wt%;

Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidizing samples; Pure argon gas, repeatedly carry out the gas cleaning operation more than 5 times to make the oxygen concentration to the lowest, pump to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment;

Step 3: Before smelting the alloy, first smelt the titanium ingot repeatedly, each time for more than 30s, to remove oxygen; after smelting the titanium ingot, smelt the mixed material again, smelting each side of each sample 2-4 times, 30s each time, Obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting, then put the alloy ingot into acetone and alcohol for ultrasonic cleaning to remove impurities; then put the alloy into the electrolyte for electropolishing, and then use ethanol for the electropolished alloy. , Deionized water ultrasonic cleaning, and finally use a hair dryer for cold air drying;

Step 5: Pre-anneal the treated alloy in a tube furnace with protective atmosphere gas, the annealing temperature is 500 ℃-800 ℃; keep the temperature in the annealing furnace for 240min-1440min, and program the temperature control to slowly cool down to 200℃ ℃ and then cooled to room temperature with the furnace, and a protective atmosphere was introduced into the whole heat treatment process, and the gas flow rate was 50 cm ³ /min.

Preferably, in the step 1, the raw materials Si and S (Se, Te) are in small granular shape, and the purity is 99.99%, avoiding the use of powdered raw materials to prevent dust from gathering during the smelting process and affecting the performance of the alloy; avoid using bulky raw materials Raw materials to prevent uneven melting of alloys.

Preferably, during the smelting process of the mixture in step 3, the electromagnetic stirring of the smelting furnace is turned on, or the copper mixture is manually turned over by the metal spoon in the smelting furnace. and escaped oxygen.

Preferably, in the step 4, the copper alloy is mechanically ground and polished with 400-7000 mesh sandpaper in turn; the electrolyte is a mixed solution of phosphoric acid and ethanol, a Zhaoxin constant current source is used, and the output current is 0.5-2A, The voltage is 3-5V, the copper alloy sample is placed in the anode, the left and right sides are placed in the copper sheet as the cathode, the preset current is passed, and the polishing time is 1-2min.

Preferably, in the step 5, the programmed temperature control cooling rate is set to 1-2°C/min, and the cooling rate with the furnace is 5-8°C/min.

Preferably, in the step 5, the protective atmosphere may be high-purity hydrogen, high-purity argon, or a protective atmosphere in which the two are mixed in a certain proportion.

3. Beneficial effects

Compared with the prior art, the advantages of the present invention are:

(1) In the present invention, the proposed high-temperature oxidation-resistant multi-component copper alloy significantly enhances the oxidation resistance of metallic copper materials, ensures that copper consumable products are not easily oxidized under high-temperature air conditions, expands the scope of application of the alloy, and prolongs the quality of the alloy. . The materials used have large earth reserves, are cheap and easy to obtain, the operation process is simple and easy to repeat, and the required conditions are simple and easy to achieve, which can meet the industrial production requirements of copper consumables, and the production process meets the requirements of environmental protection, green and pollution-free, and has a great impact on the development of modern metal material technology. important meaning.

(2) In the present invention, a ternary copper alloy is formed by adding a trace amount of non-metallic silicon elements and oxygen group elements (S, Se, Te) to the pure copper raw material, and pre-annealing is performed in a protective atmosphere to avoid non-metallic elements. The metal elements are segregated to the surface of the alloy through the annealing process, and the Cu-S (Cu-Se, Cu-Te) segregation layer is covered with a certain thickness of stable SiO ₂ protective film, which inhibits the diffusion of oxygen into the copper material in the working environment and causes the oxidation corrosion of copper. , not only retains the protective ability of the Se layer, but also the presence of Se promotes the segregation of Si, which significantly improves the overall oxidation resistance of metallic copper.

(3) In the previous invention, the formation temperature and time of the single-layer protective oxide film formed by the pre-annealing of the Cu-Si binary alloy are relatively high, and the protective film is more sensitive to changes in the annealing conditions. The alloy involved in the invention is pre-annealed, and the lattice distortion of Cu-S (Cu-Se, Cu-Te) is beneficial to the diffusion of Si, so the time and temperature required for SiO ₂ film formation are greatly reduced.

(4) Compared with the protection mechanism of binary Cu-S (Cu-Se, Cu-Te) alloys, etc., which are segregated to the metal surface only by inclusions, the Cu-M segregation layer of the alloy according to the present invention is composed of silicon element. The SiO ₂ film formed by preferential oxidation is covered, and the protective effect is significantly enhanced. After the alloy of the present invention undergoes a pretreatment process, a double-layer protection is formed, the anti-oxidation effect is stronger, and a better strengthening effect can be achieved while saving costs.

Description of drawings

Fig. 1 is the thermogravimetric curve diagram of the copper alloy that the present invention implements 1-3 examples provide;

Fig. 2 is the element percentage diagram of XPS etching after annealing of Cu-Se-Si alloy;

3 is an XPS analysis diagram of the surface Si 2p orbital of the annealed Cu-Se-Si alloy;

Fig. 4 is the XPS analysis chart of the surface O1s orbital of annealed Cu-Se-Si alloy;

Fig. 5 is the XPS analysis diagram of the Se 3d orbital when the annealed Cu-Se-Si alloy is etched to 1200s;

6 is a surface SEM characterization diagram and an element distribution diagram of the Cu-Se-Si alloy obtained in Example 6 of the present invention;

7 is a surface SEM characterization diagram and an element distribution diagram of the Cu-Se-Si alloy obtained in Example 7 of the present invention;

8 is a surface SEM characterization diagram of the Cu-Se-Si alloy obtained in Example 2 of the present invention;

9 is a SEM characterization diagram of the surface of the Cu-Se-Si alloy obtained in Example 2 of the present invention after being oxidized at 400° C. for 2 h in air;

10 is a cross-sectional SEM characterization diagram and an element distribution diagram of the Cu-Se-Si alloy obtained in Example 6 of the present invention;

Fig. 11 is the macroscopic characterization of the Cu-Se-Si alloy obtained in Example 3 of the present invention after pre-annealing treatment under 400°C air condition for 24 hours, compared with annealed pure copper and unannealed Cu-Se-Si alloy under the same conditions Compare.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments.

Example 1:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix and smelt high-purity silicon particles and high-purity granular raw materials of oxygen group (S, Se, Te) elements, and the concentrations of Si and oxygen group elements (S, Se, Te) in the alloy are each 0.05-1 wt%, The mass fraction of copper is 99.9-98wt%;

Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidizing samples; Pure argon gas, repeatedly carry out the gas cleaning operation more than 5 times to make the oxygen concentration to the lowest, pump to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment;

Step 3: Before smelting the alloy, first smelt the titanium ingot repeatedly, each time for more than 30s, to remove oxygen; after smelting the titanium ingot, smelt the mixed material again, smelting each side of each sample 2-4 times, 30s each time, Obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting, then put the alloy ingot into acetone and alcohol for ultrasonic cleaning to remove impurities; then put the alloy into the electrolyte for electropolishing, and then use ethanol for the electropolished alloy. , Deionized water ultrasonic cleaning, and finally use a hair dryer for cold air drying;

Step 5: Pre-anneal the treated alloy in a tube furnace with protective atmosphere gas, the annealing temperature is 500 ℃-800 ℃; keep the temperature in the annealing furnace for 240min-1440min, and program the temperature control to slowly cool down to 200℃ ℃ and then cooled to room temperature with the furnace, the programmed temperature control cooling rate was set to 1 ℃/min, the cooling rate of the furnace was 5-8 ℃/min and a protective atmosphere was introduced throughout the heat treatment process, and the gas flow rate was 50cm ³ /min.

Example 2:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix 0.5wt% Si with 99.99% purity and 0.5wt% Se with 99.99% purity and 99wt% pure copper particles with 99.99% purity;

Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidizing samples; Pure argon gas, repeatedly carry out the gas cleaning operation more than 5 times to make the oxygen concentration to the lowest, pump to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment;

Step 3: Before smelting the alloy, the titanium ingot is first smelted repeatedly for more than 30s each time to remove oxygen. After the titanium ingot is smelted, the mixed material is smelted, and each sample is smelted 2-4 times on each side for 30s each time to obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting with sandpaper, and then put the alloy ingot in acetone and alcohol for ultrasonic cleaning to remove impurities. Then put the alloy into the electrolyte for electropolishing, and then ultrasonically clean the electropolished alloy with ethanol and deionized water, and finally use a hair dryer to dry it with cold air;

Step 5: Pre-anneal the treated alloy in a tube furnace with pure H ₂ gas, and the annealing temperature is 700 ° C; keep the temperature in the annealing furnace for 720 min, and program the temperature to slowly cool down to 200 ° C and then cool with the furnace To room temperature, the programmed temperature control cooling rate is set to 1°C/min, and high-purity H ₂ gas is introduced into the whole heat treatment process, and the gas flow rate is 50 cm ³ /min.

Example 3:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix 0.5wt% Si with 99.99% purity and 0.5wt% Te with 99.99% purity and 99wt% pure copper particles with 99.99% purity;

Step 2: Put the materials required for smelting in the groove of the vacuum smelting furnace, and use titanium ingots as standard deoxidized samples; Argon gas, repeatedly carry out the gas washing operation for more than 5 times, so that the oxygen concentration reaches the lowest level, and pump it to a high vacuum environment of 10-4Pa to exhaust the oxygen in the melting furnace. Argon gas protection environment;

Step 3: Before smelting the alloy, the titanium ingot is first smelted repeatedly for more than 30s each time to remove oxygen. After the titanium ingot is smelted, the mixed material is smelted, and each sample is smelted 2-4 times on each side for 30s each time to obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting with sandpaper, and then put the alloy ingot in acetone and alcohol for ultrasonic cleaning to remove impurities. Then put the alloy into the electrolyte for electropolishing, and then ultrasonically clean the electropolished alloy with ethanol and deionized water, and finally use a hair dryer to dry it with cold air;

Step 5: Pre-anneal the treated alloy in a tube furnace with pure H ₂ gas, and the annealing temperature is 700 ° C; keep the temperature in the annealing furnace for 720 min, and program the temperature to slowly cool down to 200 ° C and then cool with the furnace To room temperature, the programmed temperature control cooling rate is set to 1°C/min, and high-purity H ₂ gas is introduced into the whole heat treatment process, and the gas flow rate is 50 cm ³ /min.

Example 4:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix 0.5wt% Si with 99.99% purity and 0.5wt% Se with 99.99% purity and 99wt% pure copper particles with 99.99% purity;

Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidizing samples; Pure argon gas, repeatedly carry out the gas cleaning operation more than 5 times to make the oxygen concentration to the lowest, pump to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment;

Step 3: Before smelting the alloy, the titanium ingot is first smelted repeatedly for more than 30s each time to remove oxygen. After the titanium ingot is smelted, the mixed material is smelted, and each sample is smelted 2-4 times on each side for 30s each time to obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting with sandpaper, and then put the alloy ingot in acetone and alcohol for ultrasonic cleaning to remove impurities. Then put the alloy into the electrolyte for electropolishing, and then ultrasonically clean the electropolished alloy with ethanol and deionized water, and finally use a hair dryer to dry it with cold air;

Step 5: Pre-anneal the treated alloy in a tube furnace filled with pure Ar gas, and the annealing temperature is 700 °C; keep the temperature in the annealing furnace for 720 min, and program the temperature to slowly cool down to 200 °C, and then cool down to 200 °C with the furnace. At room temperature, the programmed temperature control cooling rate was set to 1°C/min, and high-purity Ar gas was introduced into the whole heat treatment process, and the gas flow rate was 50 cm ³ /min.

Example 5:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix 1wt% Si with 99.99% purity and 1wt% Se with 99.99% purity and 99wt% pure copper particles with 99.99% purity;

Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidizing samples; Pure argon gas, repeatedly carry out the gas cleaning operation more than 5 times to make the oxygen concentration to the lowest, pump to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment;

Step 3: Before smelting the alloy, the titanium ingot is first smelted repeatedly for more than 30s each time to remove oxygen. After the titanium ingot is smelted, the mixed material is smelted, and each sample is smelted 2-4 times on each side for 30s each time to obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting with sandpaper, and then put the alloy ingot in acetone and alcohol for ultrasonic cleaning to remove impurities. Then put the alloy into the electrolyte for electropolishing, and then ultrasonically clean the electropolished alloy with ethanol and deionized water, and finally use a hair dryer to dry it with cold air;

Step 5: Pre-annealing the treated alloy. The annealing atmosphere is an argon-hydrogen mixed gas containing 2×10 ² Pa hydrogen, and the annealing temperature is 600° C. At room temperature, a protective argon-hydrogen atmosphere was introduced into the whole heat treatment process, and the gas flow rate was 50 cm ³ /min.

Example 6:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix 1wt% Si with 99.99% purity and 0.5wt% Se with 99.99% purity and 99wt% pure copper particles with 99.99% purity;

Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidized samples; Pure argon gas, repeatedly carry out the gas washing operation more than 5 times to make the oxygen concentration reach the lowest level, pump it to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment;

Step 3: Before smelting the alloy, the titanium ingot is first smelted repeatedly for more than 30s each time to remove oxygen. After the titanium ingot is smelted, the mixed material is smelted, and each sample is smelted 2-4 times on each side for 30s each time to obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting with sandpaper, and then put the alloy ingot in acetone and alcohol for ultrasonic cleaning to remove impurities. Then put the alloy into the electrolyte for electropolishing, and then ultrasonically clean the electropolished alloy with ethanol and deionized water, and finally use a hair dryer to dry it with cold air;

Step 5: Pre-anneal the treated alloy in a tube furnace with pure H ₂ gas, and the annealing temperature is 600°C; keep the temperature in the annealing furnace for 480 minutes, and directly cool down to room temperature with the furnace after the pre-treatment. The whole process of heat treatment High-purity H ₂ gas was introduced, and the gas flow rate was 50 cm ³ /min.

Example 7:

A novel preparation method for a new type of high temperature oxidation resistant multi-element copper alloy, comprising the following steps:

Step 1: Mix 1wt% Si with 99.99% purity and 0.2wt% Se with 99.99% purity and 99wt% pure copper particles with 99.99% purity;

Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidizing samples; Pure argon gas, repeatedly carry out the gas cleaning operation more than 5 times to make the oxygen concentration to the lowest, pump to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment;

Step 3: Before smelting the alloy, the titanium ingot is first smelted repeatedly for more than 30s each time to remove oxygen. After the titanium ingot is smelted, the mixed material is smelted, and each sample is smelted 2-4 times on each side for 30s each time to obtain alloy products with uniform composition and excellent performance;

Step 4: Sand the alloy ingot obtained by smelting with sandpaper, and then put the alloy ingot in acetone and alcohol for ultrasonic cleaning to remove impurities. Then put the alloy into the electrolyte for electropolishing, and then ultrasonically clean the electropolished alloy with ethanol and deionized water, and finally use a hair dryer to dry it with cold air;

Step 5: Pre-anneal the treated alloy in a tube furnace with pure H ₂ gas, and the annealing temperature is 600°C; keep the temperature in the annealing furnace for 720 minutes, and directly cool down to room temperature with the furnace after the pretreatment. The whole process of heat treatment High-purity H ₂ gas was introduced, and the gas flow rate was 50 cm ³ /min.

In the present invention, carry out experimental analysis for above-mentioned embodiment, draw the following conclusions:

Referring to FIG. 1 , it is the thermogravimetric curve of the copper alloy obtained in Examples 1-3 after annealing treatment. The thermogravimetric test condition is the weight gain of pure oxygen oxidizing at 400° C. for 2 h.

As shown in FIG. 1 , the weight gains of the alloys obtained in Example 1, Example 2, and Example 3 were 0.31107 mg/cm ² , 0.27777 mg/cm ² , and 0.16796 mg/cm ² , respectively. The weight gain of the alloy obtained in Example 3 is only 5% of the weight gain of pure copper. It can be seen that compared with the pure copper sample under the same conditions, the oxidation weight gain of the alloy sample designed in the present invention is significantly reduced, and among the three alloy samples , Cu-Se-Si has slightly stronger anti-oxidation ability.

Referring to Fig. 2 and Fig. 3, the annealed Cu-Si-Se alloy in Example 2 is characterized by XPS, and specifically, the surface element is detected by a photoelectron spectrometer (XPS), and the surface element content of the alloy is obtained as Cu- 3.59%, Si-33.85%, O-62.04%, Se-0.52%. It can be seen that the surface of the alloy is mainly Si and O signals. The results are shown in the figure. Figure 2 is the XPS analysis diagram of the Si 2p orbital, and the obtained peak is 103.75eV. Figure 3 is the XPS analysis diagram of the O1s orbital, and the obtained peak is 532.9eV , the corresponding binding energy is consistent with the binding energy of SiO ₂ , so the surface of the alloy is considered to be SiO ₂ .

Referring to Figure 4, in order to further determine the composition of the alloy surface, the annealed Cu-Si-Se alloy in Example 6 was subjected to XPS elemental etching analysis, and the etching time was 0s, 25s, 100s, 200s, 400s respectively , 700s, 1200s, 1800s, 2400s; the element content of each etching was obtained, as shown in the figure. It can be seen that the alloy surface only contains Si and O elements before the etching of the first 400s, and the Cu and Se contents are almost negligible. As the etching time continues to increase, the Cu signal begins to increase, that is, the content of Cu elements begins to increase. gradually increased, indicating that a thicker _SiO2 film was formed on the surface of the alloy. When the etching time was 1200 s, the Se signal peak began to appear, and the increasing trend of Se element content could be seen.

Referring to Figure 5, it is the Se 3d peak detected by XPS characterization in the alloy at 1200 s. That is, there is a Se segregation layer under the SiO ₂ oxide film, indicating that the alloy involved in the present invention retains the protective ability of the Se layer and further enhances the oxidation resistance of the copper alloy.

Referring to Figures 6-7, the surface characterization SEM and element distribution diagrams of the Cu-Se-Si alloy samples obtained in Invention Example 6 and Example 7 show that the Cu-Se-Si alloy samples have smooth surfaces after annealing and significant Si, O signals , the relative signals of Cu and Se are relatively weak, which corresponds to the XPS results.

8 is the SEM image of the surface characterization of the Cu-Se-Si alloy sample obtained in Example 6, and FIG. 9 is the SEM image of the surface characterization of the Cu-Se-Si alloy sample obtained in Example 6 after being oxidized in air at 400°C for 2 h . As shown in the figure, after 2h oxidation, the surface of the alloy is relatively flat, no copper oxide whiskers are formed, and compared with the surface of the alloy after annealing, there is no obvious change, which is the same as that of the Cu-Se-Si alloy in Figure 1. The curve weight gain results correspond.

Referring to FIG. 9, it is the SEM image and the element distribution diagram of the cross-sectional characterization of the Cu-Se-Si alloy sample obtained in Example 6. It can be seen that the element distribution near the surface can clearly see that Si elements and O elements on the surface of the alloy have obvious aggregation, forming A continuous and dense _SiO2 oxide film was obtained, corresponding to the XPS etching results. In addition, compared with the high temperature conditions above 800°C required for the formation of dense oxide films of copper-silicon alloys, the alloy involved in Example 6 of the present invention only needs 600°C for 8 h to obtain a dense SiO ₂ layer, and it can be seen that the addition of Se decreases The formation temperature and time of the SiO ₂ protective layer are adjusted to ensure a more complete protective structure of the alloy.

Referring to FIG. 11 , according to the application scenario of copper materials, the oxidation environment is simulated, and the alloy involved in the present invention is subjected to an oxidation experiment comparison test under the atmosphere of 400 ° C. As can be seen from the figure, the pure copper sample and the unannealed Cu-Se-Si sample are obviously blackened. However, the pre-annealed alloy sample has no obvious change after being oxidized at 400° C. for 24 hours, and the surface remains bright, which proves that the oxidation resistance of the alloy involved in the present invention has been significantly improved.

The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. The equivalent replacement or change of the inventive concept thereof shall be included within the protection scope of the present invention.

Claims (5)

1. a novel high temperature oxidation resistant multicomponent copper alloy preparation method, is characterized in that, comprises the following steps: Step 1: Mix and smelt high-purity silicon particles and high-purity granular raw materials of oxygen group (S, Se, Te) elements, and the concentrations of Si and oxygen group elements (S, Se, Te) in the alloy are each 0.05-1 wt%, The mass fraction of copper is 99.9-98wt%; Step 2: Put the materials required for smelting in the groove of the vacuum ^smelting furnace, and use titanium ingots as the standard deoxidizing samples; Pure argon gas, repeatedly carry out the gas cleaning operation more than 5 times to make the oxygen concentration to the lowest, pump to a high vacuum environment of 10 ^-4 Pa to exhaust the oxygen in the smelting furnace, and finally pass argon gas to the equilibrium atmospheric pressure, so that the smelting process The whole process is argon protected environment; Step 3: Before smelting the alloy, first smelt the titanium ingot repeatedly, each time for more than 30s, to remove oxygen; after smelting the titanium ingot, smelt the mixed material again, smelting each side of each sample 2-4 times, 30s each time, Obtain alloy products with uniform composition and excellent performance; Step 4: Sand the alloy ingot obtained by smelting, then put the alloy ingot into acetone and alcohol for ultrasonic cleaning to remove impurities; then put the alloy into the electrolyte for electropolishing, and then use ethanol for the electropolished alloy. , Deionized water ultrasonic cleaning, and finally use a hair dryer for cold air drying; Step 5: Pre-anneal the treated alloy in a tube furnace with protective atmosphere gas, the annealing temperature is 500 ℃-800 ℃; keep the temperature in the annealing furnace for 240min-1440min, and program the temperature control to slowly cool down to 200℃ ℃ and then cooled to room temperature with the furnace, and a protective atmosphere was introduced into the whole heat treatment process, and the gas flow rate was 50 cm ³ /min. 2. The method for preparing a novel high-temperature oxidation-resistant multicomponent copper alloy according to claim 1, wherein in the step 1, the raw materials Si and S (Se, Te) are both small particles, and the purity is 99.99% , Avoid the use of powdered raw materials to prevent dust accumulation during the smelting process and affect the performance of the alloy; avoid the use of bulk raw materials to prevent uneven smelting of the alloy. 3. The method for preparing a novel high-temperature oxidation-resistant multi-element copper alloy according to claim 1, wherein in the step 3, during the smelting process of the mixture, the electromagnetic stirring of the melting furnace is turned on, or the copper is heated by a metal spoon in the melting furnace. The mixture is turned over manually, and the titanium ingot needs to be re-melted after each turning to remove the oxygen escaping from the movement of the metal spoon. 4. The method for preparing a novel high-temperature oxidation-resistant multicomponent copper alloy according to claim 1, wherein in the step 4, the copper alloy is mechanically ground and polished with 400-7000 mesh sandpaper in turn; The liquid is a mixed solution of phosphoric acid and ethanol, using a Zhaoxin constant current source, the output current is 0.5-2A, the voltage is 3-5V, the copper alloy sample is placed in the anode, the left and right sides are placed in copper sheets as the cathode, and the preset current is supplied , the polishing time is 1-2min. 5. a kind of novel high temperature oxidation resistant multi-element copper alloy preparation method according to claim 1, is characterized in that, in described step 5, protective atmosphere can be high-purity hydrogen, high-purity argon, and the two are in a certain Proportionately mixed protective atmosphere.

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