WO2020155322A1 - 高气密低自由氧含量纳米弥散铜合金及短流程制备工艺 - Google Patents

高气密低自由氧含量纳米弥散铜合金及短流程制备工艺 Download PDF

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WO2020155322A1
WO2020155322A1 PCT/CN2019/078199 CN2019078199W WO2020155322A1 WO 2020155322 A1 WO2020155322 A1 WO 2020155322A1 CN 2019078199 W CN2019078199 W CN 2019078199W WO 2020155322 A1 WO2020155322 A1 WO 2020155322A1
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alloy
powder
oxygen content
nano
free oxygen
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李周
邱文婷
肖柱
龚深
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B22F3/172—Continuous compaction, e.g. rotary hammering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/058—
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • B22F2302/253—Aluminum oxide (Al2O3)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention relates to a nano-dispersed copper alloy with high airtightness and low free oxygen content and a short process preparation process, in particular to a Cu-Al 2 O 3 -CaO-La 2 O 3 nano-dispersed copper with high airtightness and low free oxygen content Alloy and short process preparation process. It belongs to the technical field of nano-dispersed copper alloy preparation.
  • Nano-dispersion strengthened copper alloy is a new structural and functional material with excellent comprehensive physical and mechanical properties. It has both high strength, high electrical conductivity and good resistance to high temperature softening.
  • the prior art mainly adopts the internal oxidation method to prepare Cu-Al 2 O 3 nano-dispersion-strengthened copper alloy.
  • the specific preparation process is as follows: After the Cu-Al alloy with suitable composition is smelted, gas atomized and powdered, and then mixed with an appropriate amount of oxidant Mix and heat in a closed container for internal oxidation.
  • the solute element Al is preferentially oxidized by oxygen diffused and penetrated on the surface to form Al 2 O 3 , and then the composite powder is reduced in hydrogen to remove residual Cu 2 O, and then the powder is sheathed, Vacuum, extrusion or hot forging forming.
  • the Cu-Al 2 O 3 dispersion-strengthened copper alloy prepared by this process in China has a room temperature tensile strength of 246-405Mpa and a conductivity of 83.4-92.9IACS after hydrogen annealing at 900°C for 1h.
  • the oxygen partially diffused and penetrated into the copper matrix is difficult to be completely removed by hydrogen reduction.
  • micropores are easily generated during hot extrusion and subsequent cold working. Therefore, the prior art adopts The Cu-Al 2 O 3 nano-dispersed copper alloy prepared by the internal oxidation method still has the problems of high residual free oxygen content and low air tightness.
  • the free oxygen content of the domestically prepared Cu-Al 2 O 3 dispersion-strengthened copper alloy is as high as 56.1ppm, and the diameter expansion of the ordinary Cu-Al 2 O 3 dispersion-strengthened copper alloy of ⁇ 24mm before and after hydrogen firing at 900 °C for 1 h has reached Above 0.01mm.
  • the residual free oxygen content in the dispersed copper is high, and under high vacuum conditions, the free oxygen is slowly released, poisoning the cathode and causing the device to fail.
  • the purpose of the present invention is to overcome the problems of high residual free oxygen content and low air tightness in the existing Cu-Al 2 O 3 nano-dispersed copper alloy prepared by internal oxidation, and to provide a nano-dispersed copper alloy with high air tightness and low free oxygen content and Short preparation process.
  • the invention adopts gas-solid secondary reduction to reduce the residual free oxygen content, further densifies the alloy through vacuum medium temperature creep deformation, and finally obtains excellent low oxygen, high air tightness, high strength and high conductivity Cu-Al 2 O 3 -CaO -La 2 O 3 nano-dispersed copper alloy.
  • the present invention is a nano-dispersed copper alloy with high airtightness and low free oxygen content, comprising the following components, which are composed according to mass percentage:
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • Cu-Al 2 O 3 alloy powder is prepared by an internal oxidation method, and then mixed with Cu-Ca-La alloy powder.
  • the powder is enveloped under the protection of argon gas, and then swaging for hot extrusion at 900-920°C. After swaging, the envelope is evacuated to ⁇ 10 -3 Pa, the envelope is sealed and placed at 450-550°C, the pressure is 3-5 hours in 40-60Mpa nitrogen atmosphere.
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • the internal oxidation method for preparing Cu-Al alloy powder includes the following steps:
  • the first step milling
  • the third step graded internal oxidation
  • the mixture obtained in the second step is subjected to two-stage internal oxidation at 380-400°C and 880-900°C in a protective atmosphere;
  • the internal oxidation powder obtained in the third step is crushed and reduced by hydrogen to obtain Cu-Al 2 O 3 alloy powder.
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • the alloy melting temperature is 1200-1230°C; the alloy melt is adopted Pure nitrogen atomization powder, nitrogen purity ⁇ 99.9%.
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • alloy powder with a particle size of less than 40 mesh is mixed with oxidant Ball milling; the addition amount of the oxidant accounts for 0.5-9.5 wt% of the alloy powder mass, and the main component of the oxidant is Cu 2 O.
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • the ball milling process is: the ball-to-battery ratio is 3:1- 10:1, the speed is 50-300rpm, the milling time is 120min-600min, and the atmosphere is air.
  • the internal oxidation process parameters are: the powder is in argon after ball milling. Or heat to 380-400°C for 2-4 hours in a nitrogen atmosphere and then continue to heat up to 880-900°C for 2-4 hours.
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • the fourth step of preparing Cu-Al 2 O 3 alloy powder by internal oxidation method the internally oxidized powder is crushed and passed through a 40-mesh sieve. Heat the powder under the sieve to 880-900°C for hydrogen reduction for 4-8 hours.
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • the preparation of Cu-Ca-La alloy powder includes the following steps:
  • the present invention is a short-process preparation process of nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • Cu-Ca-La alloy powder and Cu-Al 2 O 3 powder prepared by internal oxidation method are in a mass ratio of 1:10-1: Mix the ratio of 15, cold isostatic pressing, pure copper sheath in argon chamber, water-sealed hot extrusion at 900-920°C, extrusion ratio ⁇ 15, rotary forging after extrusion, re-place the rotary forged bar in a new In the envelope, vacuumize to 10 -3 Pa and then seal it, and place it in a nitrogen atmosphere at a pressure of 40-60Mpa at 450-550°C for 3-5 hours.
  • the present invention is a short-process preparation process for nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • the prepared nano-dispersed copper alloy has a room temperature tensile strength of 330-580MPa, electrical conductivity greater than 97-80% IACS, and free oxygen content less than or equal to 15 ppm ,
  • the air leakage rate is less than or equal to 1.0 ⁇ 10 -10 Pa m 3 /s.
  • the present invention is a short-process preparation process for nano-dispersed copper alloy with high airtightness and low free oxygen content.
  • the prepared nano-dispersed copper alloy is annealed in hydrogen at 900°C for 1 hour and measured by a screw micrometer.
  • the diameter of a 20mm rod before and after the change is 0.00 ⁇ m.
  • the present invention addresses the current domestic problems of high free oxygen content and low air tightness of Cu-Al 2 O 3 nano-dispersed copper alloys.
  • Gas-solid secondary reduction technology is added to the traditional internal oxidation process and combined with vacuum medium temperature creep.
  • the synergistic effect of the deformation process produces a low-oxygen, high-density, high-strength and high-conductivity Cu-Al 2 O 3 -CaO-La 2 O 3 nano-dispersed copper alloy.
  • the gas-solid secondary reduction technology refers to the traditional hydrogen reduction of internal oxidation powder, that is, on the basis of gaseous reduction, plus a solid-state reduction process, that is, adding an appropriate amount of Cu to the reduced Cu-Al 2 O 3 powder -0.1wt% Ca-0.1wt% La alloy powder.
  • a solid-state reduction process that is, adding an appropriate amount of Cu to the reduced Cu-Al 2 O 3 powder -0.1wt% Ca-0.1wt% La alloy powder.
  • adding these two elements to the alloy can significantly reduce the free oxygen content in the alloy, and the formed nano-scale CaO and La 2 O 3 can also disperse the alloy The role of reinforcement.
  • the vacuum medium temperature creep deformation means that the swaged bar is placed in a sheath, evacuated and sealed, and then placed in a nitrogen atmosphere at 450-550°C and a pressure of 40-60Mpa for 3-5 hours to make the alloy Creep deformation occurs, thereby eliminating micro-pores and micro-cracks generated in the alloy during preparation and processing, and improving the density of the alloy.
  • the present invention adopts hydrogen primary reduction + Ca and La solid secondary reduction technology to reduce residual oxygen in the prepared alloy.
  • the formed nano-scale CaO and La 2 O 3 can also play a role of dispersion strengthening.
  • the dispersed copper prepared by the present invention has low free oxygen content, free oxygen content less than or equal to 15 ppm, high dimensional stability during hydrogen annealing, good air tightness, and air leakage rate ⁇ 1.0 ⁇ 10 -10 Pa m 3 /s, suitable For industrial production, the prepared materials can be used as various sealing device materials, such as electric vacuum shell sealing devices, high-voltage DC relays for new energy vehicles, etc.
  • the Cu-0.1wt%Ca-0.1wt%La alloy is melted under inert gas protection at 1200°C, prepared by high-purity nitrogen atomization, sieving, and high-energy ball milling to obtain ultra-fine powder (average particle size less than or equal to 20 microns). Melt Al and Cu at 1218-1230°C to form a Cu-Al alloy with an Al content of 0.04wt%.
  • the alloy powder is prepared by high-purity nitrogen atomization and sieved to obtain an alloy powder with a particle size of less than 40 mesh.
  • Table 1 Yield strength, tensile strength, elongation and electrical conductivity at different test temperatures
  • the Cu-0.1wt%Ca-0.1wt%La alloy is smelted under inert gas protection at 1200°C, prepared by high-purity nitrogen atomization, sieving, and high-energy ball milling to obtain ultrafine powder (average particle size less than or equal to 20 microns).
  • Al and Cu are smelted at 1200-1222°C to form a Cu-Al alloy with an Al content of 0.12wt%.
  • the alloy powder is prepared by high-purity nitrogen atomization and sieved out with a particle size of less than 40 mesh alloy powder.
  • Table 2 Yield strength, tensile strength, elongation, electrical conductivity and air leakage
  • the Cu-0.1wt%Ca-0.1wt%La alloy is smelted under inert gas protection at 1200°C, prepared by high-purity nitrogen atomization, sieving, and high-energy ball milling to obtain ultrafine powder (average particle size less than or equal to 20 microns).
  • Al and Cu are smelted at 1215-1230°C to form a Cu-Al alloy with an Al content of 0.30wt%.
  • the alloy powder is prepared by high-purity nitrogen atomization and sieved out of alloy powder with a particle size of less than 40 mesh, and then combined with an oxidizer Mix, perform ball milling, internally oxidize the mixed powder with oxidant at 382-393°C for 2 hours, then oxidize at 887-896°C for 3 hours, crush the above-mentioned internal oxidized powder, and reduce it with hydrogen at 892-898°C for 6 hours.
  • the Cu-0.1wt%Ca-0.1wt%La alloy is melted under inert gas protection at 1200°C, prepared by high-purity nitrogen atomization, sieving, and high-energy ball milling to obtain ultra-fine powder (average particle size less than or equal to 20 microns).
  • Al and Cu are smelted at 1215-1228°C to form a Cu-Al alloy with an Al content of 0.8wt%.
  • the alloy powder is prepared by high-purity nitrogen atomization and sieved out of alloy powder with a particle size of less than 40 mesh, and then combined with an oxidant Mix, perform ball milling, internally oxidize the mixed powder with an oxidant at 388-400°C for 2 hours, then oxidize at 886-894°C for 3 hours, crush the above-mentioned internal oxide powder, and reduce it with hydrogen at 885-893°C for 6 hours.
  • Mix with the ultra-fine Cu-Ca-La alloy powder at a ratio of 15:1.
  • the extrusion ratio is 15:1.

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Abstract

一种高气密低自由氧含量纳米弥散铜合金及短流程制备工艺，合金组分中包括Al 2O 3、Ca、La。其制备工艺是采用内氧化法制备Cu-Al 2O 3合金粉末，然后与Cu-Ca-La合金粉末混合，将混合粉末在氩气保护下包套，900-920℃热挤压后旋锻，旋锻后将包套内抽真空至≤10 -3Pa，将包套密封并置于450-550℃，压强为40-60Mpa的氮气气氛中3-5小时。制备的弥散铜，自由氧含量≤15ppm，氢气退火后尺寸稳定性高，气密性好，漏气率≤1.0×10 -10Pa m 3/s，适于工业化生产，可作为各种密封器件材料，如电真空壳体密封器件，新能源汽车高压直流继电器。

Description

高气密低自由氧含量纳米弥散铜合金及短流程制备工艺 技术领域
本发明涉及一种高气密低自由氧含量纳米弥散铜合金及短流程制备工艺，具体是指一种高气密低自由氧含量Cu-Al 2O 3-CaO-La 2O 3纳米弥散铜合金及短流程制备工艺。属于纳米弥散铜合金制备技术领域。
背景技术
纳米弥散强化铜合金是一种具有优良综合物理性能和力学性能的新型结构功能材料，它兼具高强度高导电性能和良好的抗高温软化性能。
现有技术采用主要采用内氧化法制备Cu-Al 2O 3纳米弥散强化铜合金，其具体制备工艺如下：将成分合适的Cu-Al合金熔炼后，气体雾化喷粉，再与适量的氧化剂混合，在密闭容器中加热进行内氧化，溶质元素Al被表面扩散渗入的氧优先氧化生成Al 2O 3，随后将复合粉末在氢气中还原，除去残余的Cu 2O,然后将粉末包套、抽真空、挤压或热锻成形。目前国内采用这种工艺制备的Cu-Al 2O 3弥散强化铜合金在900℃1h烧氢退火后的室温抗拉强度为246-405Mpa，导电率为83.4-92.9IACS。然而，由于部分扩散渗入铜基体中的氧难以通过氢气还原完全清除，同时由于Al 2O 3与Cu变形的不协调性，热挤压和后续冷加工过程中容易产生微孔，因此现有技术采用的内氧化法制备的Cu-Al 2O 3纳米弥散铜合金目前仍存在残余自由氧含量 高，气密性低的问题。
随着航空航天、电子通讯等领域的飞速发展，对高导、耐热、弥散无氧铜的“质”提出了更高的需求。要求其除了具有高的耐热、高强、高导性能外，其残余的自由氧的量要低，气密性要高。100g铜中若含100ppm的氧时，在900℃氢气退火时可产生14cm 3的高压水蒸气而使铜破裂，出现裂纹，气密降低。目前国内制备的Cu-Al 2O 3弥散强化铜合金的自由氧含量高达56.1ppm以上，φ24mm的普通Cu-Al 2O 3弥散强化铜合金在900℃1h烧氢前后的直径的膨胀量达到了0.01mm以上。弥散铜中残留的自由氧含量高，则在高真空的条件下，自由氧缓缓释放，毒害阴极，导致器件工作失效。
目前，针对高气密低自由氧含量Cu-Al 2O 3纳米弥散铜合金的内氧化法短流程制备技术尚未见公开报道。
发明内容
本发明的目的在于克服现有内氧化制备Cu-Al 2O 3纳米弥散铜合金存在残余自由氧含量高，气密性低的问题，提供一种高气密低自由氧含量纳米弥散铜合金及短流程制备工艺。
本发明采用气-固二次还原，降低残余自由氧含量，通过真空中温蠕变变形进一步致密化合金，最终获得性能优异的低氧、高气密性高强高导Cu-Al 2O 3-CaO-La 2O 3纳米弥散铜合金。
本发明一种高气密低自由氧含量纳米弥散铜合金，包括下述组分，按质量百分比组成：
Al 2O 3 0.05-1.61wt.％
Ca 0.008-0.012wt.％
La 0.008-0.012wt.％，余量为Cu。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，是采用内氧化法制备Cu-Al 2O 3合金粉末，然后，与Cu-Ca-La合金粉末混合，将混合粉末在氩气保护下包套，900-920℃热挤压后旋锻，旋锻后将包套内抽真空至≤10 -3Pa，将包套密封并置于450-550℃，压强为40-60Mpa的氮气气氛中3-5小时。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，所述内氧化法制备Cu-Al合金粉末包括下述步骤：
第一步：制粉
将Al和Cu熔炼，制备Al含量为0.03-0.8％的Cu-Al合金熔体，熔体气雾化制粉；
第二步：球磨活化
将第一步制备的粉末与氧化剂混合进行球磨活化；
第三步：分级内氧化
将第二步得到的混合物在保护气氛中进行380-400℃及880-900℃的两级内氧化；
第四步：还原
将第三步得到的内氧化粉末破碎后氢气还原，得Cu-Al 2O 3合金粉末。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，内氧化法制备Cu-Al 2O 3合金粉末第一步中，合金熔炼温度 1200-1230℃；合金熔体采用纯氮气雾化制粉，氮气纯度≥99.9％。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，内氧化法制备Cu-Al 2O 3Al合金粉末第二步中，取粒径小于40目的合金粉末与氧化剂混合球磨；氧化剂的添加量占合金粉末质量的0.5-9.5wt％，所述氧化剂主要成分为Cu 2O。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，内氧化法制备Cu-Al 2O 3合金粉末第二步中，球磨工艺为：球料比为3:1-10:1，转速为50-300rpm，球磨时间为120min-600min，氛围为空气。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，内氧化法制备Cu-Al 2O 3合金粉末第三步中，内氧化工艺参数为：球磨后粉末在氩气或氮气氛围中加热至380-400℃保温2-4小时后继续升温至880-900℃保温2-4h。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，内氧化法制备Cu-Al 2O 3合金粉末第四步中，内氧化后的粉末破碎后过40目筛，将筛下粉末加热至880-900℃氢气还原4-8小时。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，Cu-Ca-La合金粉末的制备，包括下述步骤：
取Cu、Cu-Ca中间合金、La加热熔炼，制备Ca含量为0.08-0.12wt.％％、La含量为0.08-0.12wt.％的Cu-Ca-La合金熔体，熔体采用高纯氮气气雾化制粉；过200目筛，取筛下粉末球磨至粉末粒度小于20微米，获得超细粉末；高纯氮气纯度≥99.9％。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，Cu-Ca-La合金粉末与内氧化法制备的Cu-Al 2O 3粉末按质量比1:10-1:15的比例混合，冷等静压，氩气室纯铜包套、900-920℃水封热挤压，挤压比≥15,挤压后旋锻，将旋锻棒材重新置于新的包套中，抽真空达10 -3Pa后密封，置于450-550℃的压强为40-60Mpa的氮气气氛中3-5小时。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，制备的纳米弥散铜合金室温抗拉强度330-580MPa，导电率大于97-80％IACS，自由氧含量小于等于15ppm，漏气率小于等于≤1.0×10 -10Pa m 3/s。
本发明一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，制备的纳米弥散铜合金经900℃氢气退火1小时，利用螺旋测微计测量，φ20mm的棒材前后直径变化0.00μm。
本发明优点在于：
本发明针对目前国内Cu-Al 2O 3纳米弥散铜合金高自由氧含量和低气密性的问题，在传统的内氧化工艺中加入了气-固二次还原技术，同时结合真空中温蠕变变形工艺的协同作用，制备出低氧高致密化高强高导Cu-Al 2O 3-CaO-La 2O 3纳米弥散铜合金。
其中气-固二次还原技术是指在内氧化粉末进行传统的氢气还原，即气态还原的基础上，加上固态还原工艺，即在还原后的Cu-Al 2O 3粉末中加入适量的Cu-0.1wt％Ca-0.1wt％La合金粉末。利用Ca和La极易与氧发生反应的特性，在合金中添加这两种元素可以显著降低合金中 的自由氧含量，而且形成的纳米尺度的CaO和La 2O 3也能够对合金起到弥散强化的作用。真空中温蠕变变形是指将旋锻棒材置于包套中，抽真空后密封，然后置于450-550℃，压强为40-60Mpa的氮气气氛保温包压处理3-5小时，使合金发生蠕变变形，从而消除在制备和加工过程中合金内部产生的微孔隙和微裂纹，提高合金的致密度。
本发明采用氢气一次还原+Ca和La固体二次还原技术，使制备的合金残余氧低,同时，形成的纳米尺度的CaO和La 2O 3也能够起到弥散强化的作用。
由于Al 2O 3与Cu变形的不协调性，热挤压和后续冷加工过程中均容易产生微孔，影响其致密性。通过旋锻变形，对挤压材施加压应力，可使部分晶界处的Al 2O 3进入铜基体内，焊合部分孔洞；将旋锻材置于包套中，抽真空后，然后在450-550℃的压强为40-60Mpa的氮气气氛中保持3-5小时，通过蠕变变形，愈合微裂纹，提高合金的致密度和气密性。
本发明制备的弥散铜，自由氧含量低，自由氧含量小于等于15ppm，氢气退火后过程中尺寸稳定性高，气密性好，漏气率≤1.0×10 -10Pa m 3/s，适于工业化生产，制备的材料可作为各种密封器件材料，如电真空壳体密封器件，新能源汽车高压直流继电器等。
具体实施方式
实施例1：
Cu-0.1wt％Ca-0.1wt％La合金在1200℃下进行惰性气体保护熔炼，进行高纯氮气雾化制备、筛分，高能球磨获得超细粉末(平均粒度小于等于20微米)。将Al和Cu在1218-1230℃下进行熔炼，形成Al 含量为0.04wt％的Cu-Al合金熔炼，采用高纯氮气雾化制备、筛分出粒径小于40目的合金粉末，将其与氧化剂混合，进行球磨,将混合粉末在386-395℃与氧化剂进行内氧化，时间2小时，再在892-900℃进行内氧化，时间3小时，将上述内氧化粉末破碎，885-893℃氢气还原6小时，与Cu-Ca-La合金超细粉末按照15:1的比例混合，将上述混合粉末冷等静压，氩气室纯铜包套、900℃水封热挤压，挤压比15:1，挤压后旋锻；将旋锻棒材重新置于新的包套中，抽真空达10 -3Pa后密封，置于480℃的压强为40MPa的氮气气氛中3小时。自由氧含量小于等于11ppm(自由氧含量采用美国LECO公司生产的氮/氧分析仪TC-436检测)，合金性能如表1所示。
表1不同测试温度下的屈服强度、抗拉强度、伸长率和导电率
Figure PCTCN2019078199-appb-000001
实施例2：
Cu-0.1wt％Ca-0.1wt％La合金在1200℃下进行惰性气体保护熔炼，高纯氮气雾化制备、筛分，高能球磨获得超细粉末(平均粒度小于等于20微米)。将Al和Cu在1200-1222℃下进行熔炼，形成Al含量为0.12wt％的Cu-Al合金熔炼，采用高纯氮气雾化制备、筛分出粒径小于40目的合金粉末，将其与氧化剂混合，进行球磨,将混合粉末在392-400℃与氧化剂进行内氧化，时间2小时，再在893-898℃内氧化3小时，将上述内氧化粉末破碎，895-900℃氢气还原6小时，与 Cu-Ca-La合金超细粉末混合按照13:1的比例混合，将上述粉末冷等静压，氩气室纯铜包套、900℃水封热挤压，挤压比15:1，挤压后旋锻；将旋锻棒材重新置于新的包套中，抽真空达10 -3Pa后密封，置于500℃的压强为50MPa的氮气气氛中3小时。自由氧含量小于等于12ppm(自由氧含量采用美国LECO公司生产的氮/氧分析仪TC-436检测)，合金性能如表2所示。
表2屈服强度、抗拉强度、伸长率、导电率和漏气率
Figure PCTCN2019078199-appb-000002
实施例3：
Cu-0.1wt％Ca-0.1wt％La合金在1200℃下进行惰性气体保护熔炼，高纯氮气雾化制备、筛分，高能球磨获得超细粉末(平均粒度小于等于20微米)。将Al和Cu在1215-1230℃下进行熔炼，形成Al含量为0.30wt％的Cu-Al合金熔炼，采用高纯氮气雾化制备、筛分出粒径小于40目的合金粉末，将其与氧化剂混合，进行球磨,将混合粉末在382-393℃与氧化剂进行内氧化，时间2小时，再在887-896℃内氧化3小时，将上述内氧化粉末破碎，892-898℃氢气还原6小时，与Cu-Ca-La合金超细粉末混合按照10:1的比例混合，将上述粉末冷等静压，氩气室纯铜包套、900℃水封热挤压，挤压比15:1，挤压后旋锻；将旋锻棒材重新置于新的包套中，抽真空达10 -3Pa后密封，置于520℃的压强为50MPa的氮气气氛中3小时。自由氧含量小于等于12ppm(自由氧含量采用美国LECO公司生产的氮/氧分析仪TC-436 检测)，合金性能如表3所示。
表3屈服强度、抗拉强度、伸长率、导电率
Figure PCTCN2019078199-appb-000003
实施例4：
Cu-0.1wt％Ca-0.1wt％La合金在1200℃下进行惰性气体保护熔炼，进行高纯氮气雾化制备、筛分，高能球磨获得超细粉末(平均粒度小于等于20微米)。将Al和Cu在1215-1228℃下进行熔炼，形成Al含量为0.8wt％的Cu-Al合金熔炼，采用高纯氮气雾化制备、筛分出粒径小于40目的合金粉末，将其与氧化剂混合，进行球磨,将混合粉末在388-400℃与氧化剂进行内氧化，时间2小时，再在886-894℃内氧化3小时，将上述内氧化粉末破碎，885-893℃氢气还原6小时，与Cu-Ca-La合金超细粉末混合按照15:1的比例混合，将上述粉末冷等静压，氩气室纯铜包套、900℃水封热挤压，挤压比15:1，挤压后旋锻；将旋锻棒材重新置于新的包套中，抽真空达10 -3Pa后密封，置于550℃的压强为60MPa的氮气气氛中3小时。自由氧含量小于等于14ppm(自由氧含量采用美国LECO公司生产的氮/氧分析仪TC-436检测)；合金性能如表4所示。
表4不同测试温度下的抗拉强度、伸长率和导电率屈服强度
测试温度(℃) 抗拉强渡(MPa) 伸长率(％) 导电率(％IACS) 漏气率(Pa m 3/s)
25 568 9.7 80.0 9.6×10 -11
700 261 7.1 /  

Claims (10)

  1. 一种高气密低自由氧含量纳米弥散铜合金，包括下述组分，按质量百分比组成：
    Al 2O 3 0.05-1.61wt.％，
    Ca 0.008-0.012wt.％
    La 0.008-0.012wt.％，余量为Cu。
  2. 一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，是采用内氧化法制备Cu-Al 2O 3合金粉末，然后，与Cu-Ca-La合金粉末混合，将混合粉末在氩气保护下包套，900-920℃热挤压后旋锻，旋锻后将包套内抽真空至≤10 -3Pa，将包套密封并置于450-550℃，压强为40-60Mpa的氮气气氛中3-5小时。
  3. 根据权利要求2所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，所述内氧化法制备Cu-Al 2O 3合金粉末包括下述步骤：
    第一步：制粉
    将Al和Cu熔炼，制备Al含量为0.03-0.8wt.％的Cu-Al合金熔体，熔体气雾化制粉；
    第二步：球磨活化
    将第一步制备的粉末与氧化剂混合进行球磨活化；
    第三步：分级内氧化
    将第二步得到的混合物在保护气氛中进行380-400℃及880-900℃的两级内氧化；
    第四步：还原
    将第三步得到的内氧化粉末破碎后氢气还原，得Cu-Al 2O 3合金粉末。
  4. 根据权利要求3所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，第一步中，合金熔炼温度1200-1230℃；合金熔体采用纯氮气雾化制粉，氮气纯度≥99.9％。
  5. 根据权利要求3所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，第二步中，取粒径小于40目的合金粉末与氧化剂混合球磨；氧化剂的添加量占合金粉末质量的0.5-9.5wt％；球磨工艺为：球料比为3:1-10:1，转速为50-300rpm，球磨时间为120min-600min，氛围为空气。
  6. 根据权利要求3所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，第三步中，内氧化工艺参数为：球磨后粉末在氩气或氮气氛围中加热至380-400℃保温2-4小时后继续升温至880-900℃保温2-4h。
  7. 根据权利要求3所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，第四步中，内氧化后的粉末破碎后过40目筛，将筛下粉末加热至880-900℃氢气还原4-8小时。
  8. 根据权利要求2所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，Cu-Ca-La合金粉末的制备，包括下述步骤：
    取Cu、Cu-Ca中间合金、La加热熔炼，制备Ca含量为0.08-0.12wt.％、La含量为0.08-0.12wt.％的Cu-Ca-La合金熔体，熔体 采用高纯氮气气雾化制粉；过200目筛，取筛下粉末球磨至粉末粒度小于20微米，获得超细粉末；高纯氮气纯度≥99.9％。
  9. 根据权利要求2-8任意一项所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，Cu-Ca-La合金粉末与内氧化法制备的Cu-Al合金粉末按质量比1:10-1:15的比例混合，冷等静压，氩气室纯铜包套、900-920℃水封热挤压，挤压比≥15，挤压后旋锻，将旋锻棒材重新置于新的包套中，抽真空达10 -3Pa后密封，置于450-550℃的压强为40-60Mpa的氮气气氛中3-5小时。
  10. 根据权利要求9所述的一种高气密低自由氧含量纳米弥散铜合金的短流程制备工艺，制备的纳米弥散铜合金室温抗拉强度330-580MPa，导电率大于97-80％IACS，自由氧含量小于等于15ppm，漏气率小于等于≤1.0×10 -10Pa m 3/s；
    制备的纳米弥散铜合金经900℃氢气退火1小时，利用螺旋测微计测量，φ20mm的棒材前后直径变化0.00μm。
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