CN109825733B - Short-process preparation method of dispersion-strengthened copper alloy - Google Patents
Short-process preparation method of dispersion-strengthened copper alloy Download PDFInfo
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Abstract
The invention provides a short-flow preparation method of a dispersion strengthened copper alloy, which comprises the steps of firstly smelting Cu-Al alloy components, then carrying out gas atomization for powder preparation to obtain Cu-Al alloy powder, then controlling and oxidizing the Cu-Al alloy powder, then uniformly mixing the Cu-Al alloy powder with carbon powder, carrying out cold isostatic pressing to obtain a billet, carrying out hydrogen reduction treatment after carrying out internal oxidation on the billet, and finally annealing after carrying out hot extrusion deformation after sheathing on the billet. The short-flow preparation method of the dispersion strengthened copper alloy changes the process of mixing the oxidant with the copper-aluminum powder after the oxidant is separately prepared in the prior art into the process of using the directly oxidized Cu-Al alloy powder as the oxygen source for internal oxidation, and integrates the internal oxidation and hydrogen reduction processes, thereby shortening the process flow and reducing the labor intensity.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a short-process preparation method of a dispersion-strengthened copper alloy.
Background
The dispersion strengthening copper alloy is a novel structural functional material with excellent comprehensive physical properties and mechanical properties, and has high strength, high conductivity and good high-temperature softening resistance. The common preparation method of the dispersion strengthened copper alloy comprises the following steps: mechanical mixing, coprecipitation, nitrate fusion, and internal oxidation. The most effective method is to prepare the dispersion strengthened copper alloy by adopting an internal oxidation method.
In the prior art, two processes for preparing the dispersion strengthened copper alloy by an internal oxidation method are available. The first method comprises the following steps: preparing copper-aluminum alloy powder, preparing an oxidant, mixing the copper-aluminum powder and the oxidant, internally oxidizing, crushing, reducing, carrying out cold isostatic pressing, sheathing, pressurizing and carrying out cold deformation; and the second method comprises the following steps: copper-aluminum alloy powder preparation-oxidant preparation-copper-aluminum powder and oxidant mixing-cold isostatic pressing-internal oxidation/reduction-sheathing-pressurization-cold deformation. For example, CN101240387B discloses a Cu-Al alloy2O3The nanometer dispersion strengthening alloy and its preparation process includes the steps of vacuum smelting of Cu-Al alloy, atomizing, sieving, internal oxidation, hydrogen reduction, vacuum hot pressing, covering and hot extrusion, etc. CN105506329B discloses a high Al alloy2O3Concentration of Cu-Al2O3A method for preparing a nano dispersion strengthened alloy, the method comprising: preparing Cu-Al alloy powder, mixing, primary internal oxidation, high-energy mechanical ball milling, secondary internal oxidation, hydrogen reduction, secondary mixing and coolingAnd (3) performing press molding, vacuum sheathing and hot extrusion to obtain bars and the like. The method firstly adopts a one-time internal oxidation method to generate fine Al2O3Dispersing the particles, then adopting mechanical alloying high-energy ball-milling internal oxidation powder, and then adopting secondary internal oxidation to the ball-milled powder to further oxidize the residual Al.
Among the two processes, the first process has long process flow, consumes time and labor, and easily causes alloy powder to be polluted in the process, thereby influencing the conductivity and strength of the dispersed copper. The second process integrates the internal oxidation and hydrogen reduction processes, namely, copper aluminum powder is mixed with an oxidant, and hydrogen reduction is directly carried out after cold isostatic pressing internal oxidation, although the process flow is shortened, because the internal oxidation temperature is high, the powder can be bonded in the internal oxidation process, when hydrogen is reduced, residual oxygen can not be completely reduced, and even 100ppm of oxygen is contained in 100g of copper, 14cm of oxygen can be generated during hydrogen annealing at 800 DEG C3The copper is cracked by the high-pressure steam, and the airtightness is sharply reduced after the cracking. In addition, in the prior art, an oxidant is additionally added for preparing the dispersion strengthened copper alloy.
Therefore, in order to meet the higher requirements of rapid development in the fields of aerospace, electronic communication and the like on the 'quality' of high-conductivity, heat-resistant and oxygen-free dispersed copper, a new preparation method is still needed.
Disclosure of Invention
In order to solve the problems existing in the prior art for preparing the dispersion strengthened copper alloy, the invention aims to provide a short-flow preparation method of the dispersion strengthened copper alloy.
In order to achieve the purpose, the invention adopts the following technical scheme:
a short-flow preparation method of a dispersion-strengthened copper alloy comprises the following steps:
(1) oxidizing and weighting Cu-Al alloy powder;
(2) uniformly mixing the Cu-Al alloy powder treated in the step (1) with carbon powder, and carrying out cold isostatic pressing to obtain a billet;
(3) and (3) oxidizing the billet obtained in the step (2) and then carrying out reduction treatment to obtain a finished product.
In dispersion strengthened copper alloys, Al2O3The volume percentage of (B) is 0.23-3.33 vol%.
Preferably, the temperature of the oxidation in the step (1) is 300-400 ℃.
Preferably, the weight gain of the Cu-Al alloy powder in the oxidation process in the step (1) is 0.13-6.49% by mass.
Preferably, the adding amount of the carbon powder in the step (2) is 0.04-1.94% of the mass of the Cu-Al alloy powder.
The addition of carbon powder can control the oxygen in the cuprous oxide and the cupric oxide formed on the surface of the Cu-Al alloy powder during the oxidation, and during the subsequent heating process of the internal oxidation, on one hand, the Cu-Al alloy powder can diffuse to the inside and react with Al to form Al2O3Nanoparticles, which can also react with carbon to form CO2，CO2Certain pressure can be generated, so that the billet can keep communicated gaps, and after the billet is directly converted into hydrogen atmosphere, the internal oxidation billet can be subjected to hydrogen reduction on line, so that the process flow is shortened.
Preferably, the pressure of the cold isostatic pressing in the step (2) is 150-300 MPa.
And in the cold isostatic pressing process, controlling the volume of the pressed blank to control the density of the finally obtained billet, so that the density of the billet is 70-80%.
Preferably, the temperature of the internal oxidation in the step (3) is 850-890 ℃.
Preferably, the time of the internal oxidation in the step (3) is 5-8 h.
Internal oxidation refers to heating the ingot obtained by cold isostatic pressing in an inert gas atmosphere.
Preferably, the temperature of the reduction treatment in the step (3) is 860-900 ℃.
Preferably, the time of the reduction treatment in the step (3) is 5-8 h.
Preferably, the gas of the reduction treatment in step (3) is hydrogen.
The Cu-Al alloy powder can be prepared by weighing Cu-Al alloy components according to a ratio, carrying out gas atomization for powder preparation after smelting to obtain Cu-Al alloy powder, wherein the smelting temperature is 1200-1230 ℃, an alloy melt obtained after smelting is subjected to nitrogen gas atomization for powder preparation, and the nitrogen purity is more than or equal to 99.9%.
The oxidation in the step (1) is to oxidize the Cu-Al alloy powder under the air condition, the mass change of the Cu-Al alloy powder is monitored in the oxidation process, and when the mass of the Cu-Al alloy powder is increased to a set value, the oxidation process is finished.
And (4) after the step (3), covering the finished product with pure copper under the argon condition, carrying out hot extrusion, and annealing after deformation, wherein the hot extrusion temperature is 880-920 ℃, and the extrusion ratio is more than or equal to 15. The deformation is cold drawing or cold rotary swaging, and the deformation amount is 40-80%. The annealing temperature is 500-700 ℃, and the annealing time is 40-80 min.
The technical scheme of the invention has the beneficial effects
1. Compared with the prior art, the short-process preparation method of the dispersion strengthened copper alloy changes the process of mixing the oxidant with the copper-aluminum powder after the oxidant is separately prepared in the prior art into the process of using the directly oxidized Cu-Al alloy powder as the oxygen source for internal oxidation, and integrates the internal oxidation and hydrogen reduction processes, thereby shortening the process flow, reducing the labor intensity and needing no additional oxidant;
2. in the preparation method, the addition of the carbon powder enables the Cu-Al alloy powder to control the cuprous oxide formed on the surface and the oxygen in the cupric oxide during the oxidation, and during the heating process of the subsequent internal oxidation, on one hand, the Cu-Al alloy powder can diffuse to the inside and react with Al to form Al2O3The nanoparticles, together with the oxygen in the cuprous and cupric oxides, can also react with carbon to form CO2，CO2Certain pressure can be generated, so that the billet can keep communicated gaps, and after the billet is directly converted into hydrogen atmosphere, the internal oxidation billet can be subjected to hydrogen reduction on line, and the residual oxygen can be completely reduced.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment provides a short-process preparation method of a dispersion strengthened copper alloy, which mainly comprises the following steps:
(1) oxidizing and weighting Cu-Al alloy powder;
(2) uniformly mixing the Cu-Al alloy powder treated in the step (1) with carbon powder, and carrying out cold isostatic pressing to obtain a billet;
(3) and (3) oxidizing the billet obtained in the step (2) and then carrying out reduction treatment to obtain a finished product.
In dispersion strengthened copper alloys, Al2O3The volume percentage of (B) is 0.23-3.33 vol%.
Wherein the oxidation temperature in the step (1) is 300-400 ℃, and the weight gain of the Cu-Al alloy powder in the oxidation process is 0.13-6.49% by mass.
The adding amount of the carbon powder in the step (2) is 0.04-1.94% of the mass of the Cu-Al alloy powder. The addition of carbon powder can control the oxygen in the cuprous oxide and the cupric oxide formed on the surface of the Cu-Al alloy powder during the oxidation, and during the subsequent heating process of the internal oxidation, on one hand, the Cu-Al alloy powder can diffuse to the inside and react with Al to form Al2O3Nanoparticles, which can also react with carbon to form CO2，CO2Certain pressure can be generated, so that the billet can keep communicated gaps, and after the billet is directly converted into hydrogen atmosphere, the internal oxidation billet can be subjected to hydrogen reduction on line, so that the process flow is shortened.
And (3) in the step (2), the pressure of the cold isostatic pressing is 150-300 MPa, and in the cold isostatic pressing process, the density of the finally obtained billet is controlled by controlling the volume of the pressed billet, so that the density of the billet is 70-80%.
And (3) carrying out internal oxidation at 850-890 ℃ for 5-8 h, wherein the internal oxidation refers to heating the billet obtained by cold isostatic pressing in an inert gas atmosphere.
The temperature of the reduction treatment in the step (3) is 860-900 ℃, the time of the reduction treatment is 5-8 h, and the gas of the reduction treatment is hydrogen.
The Cu-Al alloy powder can be prepared by weighing Cu-Al alloy components according to a ratio, carrying out gas atomization for powder preparation after smelting to obtain Cu-Al alloy powder, wherein the smelting temperature is 1200-1230 ℃, an alloy melt obtained after smelting is subjected to nitrogen gas atomization for powder preparation, and the nitrogen purity is more than or equal to 99.9%.
The oxidation in the step (1) is to oxidize the Cu-Al alloy powder under the air condition, the mass change of the Cu-Al alloy powder is monitored in the oxidation process, and when the mass of the Cu-Al alloy powder is increased to a set value, the oxidation process is finished.
And (4) after the step (3), covering the finished product with pure copper under the argon condition, carrying out hot extrusion, and annealing after deformation, wherein the hot extrusion temperature is 880-920 ℃, and the extrusion ratio is more than or equal to 15. The deformation is cold drawing or cold rotary swaging, and the deformation amount is 40-80%. The annealing temperature is 500-700 ℃, and the annealing time is 40-80 min.
Example 2
The embodiment specifically prepares a dispersion strengthened copper alloy A, and the specific steps are as follows:
(1) weighing Cu-Al alloy components according to the proportion that the Al content is 0.05 wt%, smelting at 1210 ℃, and atomizing by adopting high-purity nitrogen to prepare powder to obtain Cu-Al alloy powder;
(2) controlling the Cu-Al alloy powder obtained in the oxidation step (1), specifically oxidizing the alloy powder at 350 ℃, and discharging and cooling the alloy powder after the weight of the alloy powder is increased by 0.22%;
(3) uniformly mixing the Cu-Al alloy powder subjected to the oxidation control in the step (2) with 0.06% of carbon powder, and then controlling the density at 70% of cold isostatic pressing to obtain a billet;
(4) oxidizing the billet obtained in the step (3) at 880 ℃ for 7h, and then reducing the billet with hydrogen at 900 ℃ for 5h to obtain a reduced billet;
(5) and (4) carrying out oxygen-free copper sheet sheathing on the billet treated in the step (4), carrying out hot extrusion at 900 ℃, then carrying out cold rotary swaging deformation with the deformation amount of 60%, and annealing the rotary swaged bar for 1 hour at 600 ℃.
Example 3
The embodiment specifically prepares a dispersion strengthened copper alloy B, and the specific steps are as follows:
(1) weighing Cu-Al alloy components according to the proportion that the Al content is 0.6%, smelting at 1220 ℃, and atomizing by adopting high-purity nitrogen to prepare powder to obtain Cu-Al alloy powder;
(2) controlling the Cu-Al alloy powder obtained in the oxidation step (1), specifically oxidizing the alloy powder at 400 ℃, and discharging and cooling the alloy powder after the weight of the alloy powder is increased by 3.2%;
(3) uniformly mixing the Cu-Al alloy powder subjected to the oxidation control in the step (2) with 0.87% of carbon powder, and then controlling the density to be 70% in cold isostatic pressing, so as to obtain a billet;
(4) oxidizing the billet obtained in the step (3) at 890 ℃ for 7h, and then reducing the billet with hydrogen at 900 ℃ for 7h to obtain a reduced billet;
(5) and (4) carrying out oxygen-free copper sheet sheathing on the billet treated in the step (4), carrying out hot extrusion at 920 ℃, then carrying out cold rotary swaging deformation with the deformation amount of 60%, and annealing the rotary swaged bar for 1 hour at 600 ℃.
Example 4
The embodiment specifically prepares a dispersion strengthened copper alloy C, and the specific steps are as follows:
(1) weighing Cu-Al alloy components according to the proportion that the Al content is 0.12%, smelting at 1220 ℃, and atomizing by adopting high-purity nitrogen to prepare powder to obtain Cu-Al alloy powder;
(2) controlling the Cu-Al alloy powder obtained in the oxidation step (1), specifically oxidizing the alloy powder at 300 ℃, and discharging and cooling the alloy powder after the weight of the alloy powder is increased by 0.96%;
(3) uniformly mixing the Cu-Al alloy powder subjected to oxidation control in the step (2) with 2% of carbon powder, and then controlling the density at 70% of cold isostatic pressing to obtain a billet;
(4) oxidizing the billet obtained in the step (3) at 890 ℃ for 7h, and then reducing the billet with hydrogen at 900 ℃ for 7h to obtain a reduced billet;
(5) and (4) carrying out oxygen-free copper sheet sheathing on the billet treated in the step (4), carrying out hot extrusion at 910 ℃, then carrying out cold rotary swaging deformation with the deformation amount of 60%, and annealing the rotary swaged bar for 1 hour at 600 ℃.
Example of detection
In this example, the dispersion strengthened copper alloys A, B and C prepared in examples 2-4 were tested for performance and the results are shown in Table 1.
TABLE 1 Dispersion-strengthened copper alloy Performance test results
| Alloy number | Conductivity/% IACS | Tensile strength/Mpa | Yield strength/MPa | Elongation/percent |
| A | 95.2 | 322 | 251 | 19.3 |
| B | 80.1 | 573 | 527 | 15·7 |
| C | 92.3 | 501 | 479 | 17.2 |
Compared with the prior art, the short-flow preparation method of the dispersion strengthening copper alloy adopts the technical scheme that the process of independently preparing the oxidant and mixing the oxidant with the copper-aluminum powder in the prior art is changed into the process of using the directly oxidized Cu-Al alloy powder as the oxygen source for internal oxidation, and simultaneously reducing the internal oxidation and hydrogen into the copper-aluminum alloyThe original process is integrated, the process flow is shortened, and the labor intensity is reduced. Due to the addition of carbon powder, the Cu-Al alloy powder controls the oxygen in cuprous oxide and cupric oxide formed on the surface during oxidation, and can diffuse to the inside and react with Al to form Al during the subsequent heating process of internal oxidation2O3The nanoparticles, together with the oxygen in the cuprous and cupric oxides, can also react with carbon to form CO2，CO2Certain pressure can be generated, so that the billet can keep communicated gaps, and after the billet is directly converted into hydrogen atmosphere, the internal oxidation billet can be subjected to hydrogen reduction on line, and the residual oxygen can be completely reduced.
Claims (7)
1. A short-process preparation method of a dispersion-strengthened copper alloy is characterized by comprising the following steps:
(1) oxidizing and weighting Cu-Al alloy powder;
(2) uniformly mixing the Cu-Al alloy powder treated in the step (1) with carbon powder, and carrying out cold isostatic pressing to obtain a billet;
(3) carrying out reduction treatment after oxidation in the billet obtained in the step (2) to obtain a finished product;
in the dispersion strengthened copper alloy, Al2O3The volume percentage of (A) is 0.23-3.33 vol%;
in the step (1), the weight percentage of the oxidation weight increment of the Cu-Al alloy powder is 0.13-6.49%;
the adding amount of the carbon powder in the step (2) is 0.04-1.94% of the mass of the Cu-Al alloy powder;
after the step (3), the finished product is sheathed, hot extruded and deformed by pure copper under the argon condition and then annealed, wherein the hot extrusion temperature is 880-920 ℃, the extrusion ratio is not less than 15, the deformation is cold drawing or cold swaging, the deformation amount is 40-80%, the annealing heat preservation temperature is 500-700 ℃, and the heat preservation time is 40-80 min.
2. The short-process preparation method of the dispersion-strengthened copper alloy according to claim 1, wherein the temperature of the oxidation in the step (1) is 300-400 ℃.
3. The short-process preparation method of the dispersion-strengthened copper alloy as claimed in claim 1, wherein the cold isostatic pressing pressure in step (2) is 150-300 MPa.
4. The short-process preparation method of the dispersion-strengthened copper alloy as claimed in claim 1, wherein the temperature of the internal oxidation in step (3) is 850-890 ℃.
5. The short-process preparation method of the dispersion-strengthened copper alloy as claimed in claim 1, wherein the time of the internal oxidation in step (3) is 5-8 h.
6. The short-process preparation method of the dispersion-strengthened copper alloy as claimed in claim 1, wherein the temperature of the reduction treatment in the step (3) is 860 to 900 ℃.
7. The short-process preparation method of the dispersion-strengthened copper alloy as claimed in claim 1, wherein the time of the reduction treatment in step (3) is 5-8 h.
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| JPS6376774A (en) * | 1986-09-18 | 1988-04-07 | Sumitomo Light Metal Ind Ltd | Heat resistant high electrical conductivity copper alloy clad material |
| DE19606270A1 (en) * | 1996-02-21 | 1997-08-28 | Bleistahl Prod Gmbh & Co Kg | Material for powder metallurgical production of molded parts, especially valve seat rings with high thermal conductivity and high wear and corrosion resistance |
| CN104259692B (en) * | 2014-10-10 | 2016-08-17 | 中铝洛阳铜业有限公司 | A kind of preparation method for automobile robot automatic welding station resistance welding electrode |
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