CN105385883B - 一种电触头材料 - Google Patents
一种电触头材料 Download PDFInfo
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- CN105385883B CN105385883B CN201510983271.8A CN201510983271A CN105385883B CN 105385883 B CN105385883 B CN 105385883B CN 201510983271 A CN201510983271 A CN 201510983271A CN 105385883 B CN105385883 B CN 105385883B
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- 239000000463 material Substances 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000000280 densification Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- -1 graphite alkene Chemical class 0.000 claims 3
- 239000004411 aluminium Substances 0.000 claims 2
- 238000004062 sedimentation Methods 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000002679 ablation Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000009689 gas atomisation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
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- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- 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
- C22C32/0084—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 carbon or graphite as the main non-metallic constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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Abstract
本发明涉及一种电触头材料，尤其涉及一种石墨烯增强铜基电触头复合材料，以及这种材料的制备方法。电触头材料由重量比为0.1‑3.0%镀镍石墨烯和97.0‑99.9%铜合金组成。其制备方法为：石墨烯镀镍、铜合金制粉、球磨混粉、致密化、烧结、加工成型。本发明的电触头材料，在铜合金中添加镀镍石墨烯作为骨架，使材料具有高硬度、抗机械冲击性能与抗电弧烧蚀性能的同时，避免了导电性、导热性的降低。
Description
技术领域
本发明涉及一种电触头材料及其制备方法，尤其涉及一种石墨烯增强铜基电触头复合材料及其制备方法。
背景技术
真空触头材料是影响真空开关开断性能的重要因素，要求触头材料具有高导电率、高导热系数、高的机械强度及低的接触电阻。真空开关不需检修，触头需要最少耐受8-12次，多则30-50次的开合额定短路电流对触头的烧损，因此触头材料应具有良好的耐弧性、抗熔焊性。目前常用的铜铋合金具有良好的抗熔焊性、较低的载流值，一定的开断能力，但强度较低，电弧侵蚀大，降低了触头材料的寿命。
现有（公开号105063413A），公开了“一种铜基电触头材料及其制备工艺”，铜基触头材料包含以下重量百分比成份：0.2-0.6％的镁、0.05-0.3％的锑、0.05-0.4％的铋、0.05-0.3％的锡、0.05-0.3％的铬、0.005-0.05％的硼、0.02-0.1％的镧以及0.2-0.5％的石墨和余量的铜。通过加入适量的硼、锡、锑粉末，提高电触头制成品的强度和耐磨性，但一定程度上降低了材料导电性。
现有专利文献（公开号102385938A），公开了一种金属基石墨烯复合电接触材料及其制备方法,电接触材料包含0.02-10wt.%的石墨烯,其余为金属基体材料。由于石墨烯增强相的加入,使该复合电接触材料具有比其他增强相复合电接触材料更好的导电、导热性能和更高的硬度和耐磨性。石墨烯与金属基体的润湿性不好，电触头材料性能具有进一步提升的空间。
发明内容
本发明提供了一种电触头材料，通过在铜合金材料中加入镀镍石墨烯增强体，在不降低其导电性、导热性的同时，提高铜合金的硬度。
此外本发明还提供了上述电触头材料的制备方法。
本发明为解决上述问题提出的技术方案：
一种电触头材料，其特征在于，由重量比为0.1-3.0%镀镍石墨烯和97.0-99.9%铜合金组成，铜合金的重量组成成分为0.15-0.5%的铋、0.1-3.0%的金属X、余量为铜，X选自锌、锡、铝、镍和银中一种或几种。优选地，X选自锌、铝和镍中一种或几种。石墨烯为N层，N为1-10。
上述电触头材料的制备方法，包括以下步骤：
（1）采用直流磁控溅射法将金属镍沉积在石墨烯表面，制成镀镍石墨烯。直流磁控溅射沉积设备的工艺参数为：真空度达到0.1*10-3-1.0*10-3Pa时，通入高纯氩气，真空室气压0.5-1.2Pa，溅射功率100-150W，沉积时间为5-30min，优选10-30min。
（2）将铜合金采用雾化法制成200-300目的铜合金粉末。
（3）将镀镍石墨烯和铜合金装入球磨机球磨，制成镀镍石墨烯和铜合金均匀混合的粉末。球磨机工作状态为：转速100-250r/min，球磨15-20分钟，停止5分钟，顺时针、逆时针交替运行，混粉时间为2-6小时。
（4）将步骤（3）混合后的粉末放入模具中进行致密化处理。
（5）热压烧结，塑性加工成型，制成石墨烯增强铜基的电触头复合材料。热压烧结工艺为：采用惰性气体保护，烧结温度700-900℃，烧结压力30-60MPa，时间2-4h。
本发明的有益成果是：
（1）这种电触头材料，在铜合金中添加镀镍石墨烯作为骨架，使材料具有高硬度、抗机械冲击性能与抗电弧烧蚀性能的同时，避免了导电性、导热性的降低。此外，镀镍石墨烯改善了石墨烯与金属间的界面结合力，获得良好界面结合，解决了石墨烯与基体间界面润湿的问题。
（2）电触头的制备方法，采用直流磁控溅射法在石墨烯表面沉积镍，形成的结构，减少石墨烯作为纳米颗粒在混粉过程中的团聚。镍可作为铜基体的合金化元素，提高铜合金的耐腐蚀能力和抗熔焊性。
具体实施方式
实施例1
（1）采用直流磁控溅射法在石墨烯（层数为1-5）表面沉积金属镍制备成镀镍石墨烯。纯度为99.99%的镍靶安装前先用细砂纸进行打磨，去除表面氧化膜，再用丙酮清洗，烘干，直流磁控溅射沉积前进行5分钟预溅射，去除靶材表面的金属氧化物及其它杂质，保证后续石墨烯表面沉积镍膜的纯度。溅射参数如下：真空度达到0.1*10-3Pa时，通入高纯氩气，真空室气压0.5Pa，溅射功率100W，沉积时间为30min。
（2）将含有0.15%铋、1.0%锌、98.85%铜的合金粉采用气体雾化法制成200目铜合金粉末。
（3）镀镍石墨烯与铜-0.15铋-1.0%锌合金粉按0.1:99.9的重量比例装入球磨机中，球磨罐先抽真空再通入氩气保护，转速100r/min，球磨混粉过程中，顺时针球磨15分钟，停止5分钟，逆时针球磨15分钟，停止5分钟，依此交替工作，球磨时间6小时，获得镀镍石墨烯和铜合金均匀混合的粉末。
（4）将混合后粉末放入模具中进行致密化处理，压力为250MPa。
（5）制成的块坯放入热压烧结炉中进行烧结，采用氩气保护，烧结压力30MPa，烧结温度900℃，时间2h，采用挤压或者轧制等工艺加工成型，制备出石墨烯增强铜基电触头复合材料。
实施例2
（1）采用直流磁控溅射法在石墨烯（层数为1-10）表面沉积金属镍制备成镀镍石墨烯。纯度为99.99%的镍靶安装前先用细砂纸进行打磨去除表面氧化膜，再用丙酮清洗，烘干，直流磁控溅射沉积前进行5分钟预溅射，去除靶材表面的金属氧化物及其它杂质，保证后续石墨烯表面沉积镍膜的纯度。溅射参数如下：真空度达到1.0*10-3Pa时，通入高纯氩气，真空室气压1.2Pa，溅射功率150W，沉积时间为10min。
（2）将含有0.5%铋、3.0%锌、96.5%铜的合金粉采用气体雾化法制成300目铜合金粉末。
（3）镀镍石墨烯与铜-0.5%铋-3.0%锌合金粉按0.1:99.9的重量比例装入球磨机中，球磨罐先抽真空再通入氩气保护，转速250r/min，球磨混粉过程中，顺时针球磨20分钟，停止5分钟，逆时针球磨20分钟，停止5分钟，依此交替工作，球磨时间2小时，获得镀镍石墨烯和铜合金均匀混合的粉末。
（4）将混合后粉末放入模具中进行致密化处理，压力300MPa。
（5）制成的块坯放入热压烧结炉中进行烧结，采用氩气保护，烧结压力60MPa，烧结温度700℃，时间2h，采用挤压或者轧制等工艺加工成型，制备出石墨烯增强铜基电触头复合材料。
实施例3
（1）采用直流磁控溅射法在石墨烯（层数为1-10）表面沉积金属镍制备成镀镍石墨烯。靶材安装前先用细砂纸进行打磨去除表面氧化膜，再用丙酮清洗，烘干，直流磁控溅射沉积前进行5分钟预溅射，去除靶材表面的金属氧化物及其它杂质，保证后续石墨烯表面沉积镍膜的纯度。溅射参数如下：真空度达到0.5*10-3Pa时，通入高纯氩气，真空室气压1.0Pa，溅射功率140W，沉积时间为15min。
（2）将含有0.3%铋、3.0%铝、96.7%铜的合金粉采用气体雾化法制成200目铜合金粉末。
（3）将镀镍石墨烯：铜-0.3%铋-3.0%铝的合金粉按按重量比0.5:99.5装入球磨机中，球磨罐先抽真空再通入氩气保护，转速150r/min，球磨混粉过程中，顺时针球磨20分钟，停止5分钟，逆时针球磨20分钟，停止5分钟，依此循环工作，总计混粉时间3h，获得镀镍石墨烯和铜合金均匀混合的粉末。
（4）将混合后粉末放入模具中进行致密化处理，压力300MPa。
（5）将处理后的块坯放入热压烧结炉中进行烧结，采用氩气保护，烧结压力40MPa，烧结温度850℃，时间2h，采用挤压或者轧制等工艺加工成型，制备出石墨烯增强铜基电触头复合材料。
实施例4
镀镍石墨烯：铜-0.3%铋-3.0%铝合金粉按重量比1.0:99.0装入球磨机，其他条件同实施例3，制成石墨烯增强铜基电触头复合材料。
实施例5
镀镍石墨烯：铜-0.3%铋-3.0%铝合金粉按重量比3.0:97.0装入球磨机中,其他参数同实施例3，制成石墨烯增强铜基电触头复合材料。
实施例6
镀镍石墨烯：铜-0.15%铋-0.1%镍合金粉按重量比0.5:99.5装入球磨机中,其他参数同实施例3，制成石墨烯增强铜基电触头复合材料。
对比例1
将铜-0.2%铋-1.0%锌装入球磨机混粉，其它参数同实施例1，制成铜基电触头材料。
对比例2
将铜-0.3%铋-3.0%铝装入球磨机混粉，其它参数同实施例3，制成铜基电触头材料。
对比例3
未镀镍石墨烯：铜-0.2%铋-1.0%锌按重量比0.2:99.8装入球磨机混粉，其它参数同实施例1，制成铜基电触头材料。
制成的复合材料各项参数如下表：
加入镀镍石墨烯制成石墨烯增强铜基电触头复合材料，与对比例1、2中未加入石墨烯的铜合金制成的电触头材料相比，电导率、硬度都明显提高，硬度可提高60%以上，电导率也显著提高。与对比例3中加入未镀镍的石墨烯的铜合金制成的电触头材料相比，电导率、硬度也都明显提高。
Claims (7)
1.一种电触头材料，其特征在于，由重量组成为0.1-3.0%镀镍石墨烯和97.0-99.9%铜合金组成，铜合金的重量组成为0.15-0.5%的铋、0.1-3.0%的金属X、余量为铜，X选自锌、锡、铝和银中一种或几种；
制备方法包括以下步骤：
（1）采用直流磁控溅射法将金属镍沉积在石墨烯表面，制成镀镍石墨烯；
（2）将铜合金采用雾化法制成200-300目的铜合金粉末；
（3）将镀镍石墨烯和铜合金装入球磨机球磨，制成镀镍石墨烯和铜合金均匀混合的粉末；
（4）将步骤（3）混合后的粉末放入模具中进行致密化处理；
（5）热压烧结，塑性加工成型，制成石墨烯增强铜基的电触头复合材料。
2.根据权利要求1所述的一种电触头材料，其特征在于，石墨烯为N层，N为1-10。
3.根据权利要求1所述的一种电触头材料，其特征在于，X选自锌和铝中一种或几种。
4.根据权利要求1所述的一种电触头材料，其特征在于，所述步骤（1）中直流磁控溅射沉积设备的工艺参数为：真空度达到0.1×10-3-1.0×10-3Pa时，通入高纯氩气，真空室气压0.5-1.2Pa，溅射功率100-150W，沉积时间为5-30min。
5.根据权利要求4所述的一种电触头材料，其特征在于，所述步骤（1）中直流磁控溅射沉积设备的工艺参数为：沉积时间为10-30min。
6.根据权利要求1所述的一种电触头材料，其特征在于，所述步骤（3）中球磨机工作状态为：转速100-250r/min，球磨15-20分钟，停止5分钟，顺时针、逆时针交替运行，混粉时间为2-6小时。
7.根据权利要求1所述的一种电触头材料，其特征在于，所述步骤（5）中热压烧结工艺为：采用惰性气体保护，烧结温度700-900℃，烧结压力30-60MPa，时间2-4h。
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