WO2019029023A1 - 一种用于机车导电零部件的铜基复合材料及其制备方法 - Google Patents

一种用于机车导电零部件的铜基复合材料及其制备方法 Download PDF

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WO2019029023A1
WO2019029023A1 PCT/CN2017/108225 CN2017108225W WO2019029023A1 WO 2019029023 A1 WO2019029023 A1 WO 2019029023A1 CN 2017108225 W CN2017108225 W CN 2017108225W WO 2019029023 A1 WO2019029023 A1 WO 2019029023A1
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copper
composite material
based composite
locomotive
temperature
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French (fr)
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孙飞
赵勇
埃塞尔赛
佐罗叶斯夫丹尼斯
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Suzhou Richmond Advanced Material Technology Transfer Co Ltd
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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
    • 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
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • 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
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

Definitions

  • the invention relates to the field of copper-based composite material processing, in particular to a copper-based composite material for locomotive conductive parts and a preparation method thereof.
  • TAg0.1 silver-copper alloy is an alloy material that can increase the softening temperature (recrystallization temperature) and creep of a material by adding a small amount of silver to the copper without reducing the conductivity, heat conduction and shaping of the material. strength.
  • the material has good wear resistance, electrical conductivity and corrosion resistance, as well as good electrical conductivity, thermal conductivity, corrosion resistance and processing properties.
  • the effect of age hardening of the material is not significant, and it is easy to cause "hydrogen disease", and it is not suitable for processing (annealing, welding, etc.) and use in a reducing atmosphere at a high temperature (for example, >370 ° C).
  • a high temperature for example, >370 ° C
  • the present invention provides a copper-based composite material which can satisfy a high temperature use environment and has great practical significance in the industry.
  • the present invention adopts the following technical solutions:
  • a copper-based composite material for a conductive component of a locomotive comprising Sn, Al 2 O 3 and Cu.
  • the mass percentage of each component in the copper-based composite material is Sn 0.05-0.25%, Al 2 O 3 0.1-0.5%, and the balance copper.
  • the particle size of the Al 2 O 3 is less than 100 ⁇ m.
  • the particle size of the Al 2 O 3 is between 10 ⁇ m and 100 ⁇ m.
  • the particle size is too small an Al 2 O 3 of high production costs, while the particle size of Al 2 O 3 influence too large final conductive composite material was prepared.
  • the invention selects Al 2 O 3 in the particle size range as a raw material to facilitate industrial production, at the same time saves cost and has less influence on conductivity.
  • Cu is electrolytic copper
  • the copper-based composite material has a tensile strength greater than 310 MPa, an elongation greater than 10%, a hardness greater than 120 HB, an ambient temperature of up to 450 ° C, an elastic modulus of 125 GPa, and a conductivity of 100% IACS;
  • the mass percentage of iron is not more than 0.01%, and the mass percentage of lead is not more than 0.01%.
  • the invention selects the tin material with lower material price to replace the silver, thereby reducing the manufacturing cost of the material; adding Al 2 O 3 as the dispersed particles of the alloy material, improving the strength and hardness of the material while ensuring the electrical conductivity of the alloy material;
  • the effect of age hardening treatment meets the requirements of materials used in 400 ° C environment, which improves the service life of materials in conductive parts.
  • the invention also provides a preparation method of the copper matrix composite material for the conductive parts of the locomotive, the method comprising the following steps:
  • the alumina powder is added to the alloy liquid which has been kept in temperature, and the temperature is raised to 1200 ° C to 1210 ° C, and the stirring device is turned on for mechanical stirring, and after the completion of the stirring, the temperature is lowered to about 1050 ° C;
  • the smelting time of the step 1) is 50-60 minutes; the smelting time of the step 2) is 10-15 minutes, and the holding time is 20-30 minutes.
  • the stirring speed of the step 3) mechanical stirring was 400 r/min, and the stirring time was 15 minutes.
  • the vibration frequency of the vibrating device in the step 5) is set to 25-30 times/second, the stirring speed of the stirring device is 300 r/min, and the drawing speed is 20 mm/min.
  • the preparation method of the copper-based composite material of the invention effectively prevents element segregation by controlling the melting temperature, the melting time, the holding temperature and time, and the stirring mode and the rate, and at the same time makes the distribution of the reinforcing phase Al 2 O 3 more uniform.
  • the conductivity and strength of the copper-based composite material are simultaneously effectively improved.
  • the weighed electrolytic copper was added to a 300 kg medium frequency electric furnace, and smelting was carried out, and the temperature was gradually raised to 1,150 ° C, and the melting time was 50 minutes.
  • the weighed tin ingot was added to the smelting furnace, and the smelting was continued for 15 minutes, and the temperature was kept at 1100 ° C for 20 minutes.
  • the weighed alumina (Al 2 O 3 ) powder was added to the kept alloy solution, and the temperature was raised to 1200 ° C, and the stirring device was turned on to mechanically stir, the stirring speed was 400 r / min, and the stirring time was 15 minutes. After the completion of the stirring, the temperature was lowered to 1050 °C.
  • the smelted copper alloy water was subjected to composition testing using a Spike direct reading spectrometer to determine its chemical composition within the requirements of the national standard.
  • the vibration device and the stirring device were turned on, and the vibration frequency was set to 25 times/second, and the stirring speed was 300 r/min.
  • the casting drawing device is turned on and the drawing speed is 20 mm/min.
  • the blank profile was cast according to the predetermined product shape and the casting temperature was set at 1050 °C.
  • the finished blank profile is surface-treated, further processed according to the size of the corresponding product, and packaged into the warehouse after completion.
  • the performance of the copper-based composite material (labeled as LZCuSn0.05-0.1Al 2 O 3 ) prepared according to the method of the present embodiment and the prior art TAg 0.1 material is as follows:
  • the electrolytic copper contains less than 0.01% by mass of the impurity iron and less than 0.01% of the lead content.
  • the weighed electrolytic copper was added to a 300 kg medium frequency electric furnace, and smelting was carried out, and the temperature was gradually raised to 1,150 ° C, and the melting time was 55 minutes.
  • the weighed tin ingot was added to the smelting furnace, and the smelting was continued for 10 minutes, and the temperature was kept at 1100 ° C for 25 minutes.
  • the weighed alumina (Al 2 O 3 ) powder was added to the alloy solution which was kept warmed in proportion, and the temperature was raised to 1210 ° C, and the stirring device was turned on for mechanical stirring, the stirring speed was 400 r / min, and the stirring time was 15 min. After the completion of the stirring, the temperature was lowered to 1050 °C.
  • the smelted copper alloy water was subjected to composition testing using a Spike direct reading spectrometer to determine its chemical composition within the requirements of the national standard.
  • the vibration device and the stirring device were turned on, and the vibration frequency was set to 30 times/second, and the stirring speed was 300 r/min.
  • the casting drawing device is turned on and the drawing speed is 20 mm/min.
  • the blank profile was cast according to the predetermined product shape and the casting temperature was set at 1050 °C.
  • the finished blank profile is surface-treated, further processed according to the size of the corresponding product, and packaged into the warehouse after completion.
  • the performance of the copper-based composite material (labeled as LZCuSn0.2-0.3Al 2 O 3 ) prepared according to the method of the present embodiment and the prior art TAg 0.1 material is as follows:
  • the electrolytic copper contains less than 0.01% by mass of the impurity iron and less than 0.01% of the lead content.
  • the weighed electrolytic copper was added to a 300 kg medium frequency electric furnace, and smelting was carried out, and the temperature was gradually raised to 1,150 ° C, and the melting time was 60 minutes.
  • the weighed tin ingot was added to the smelting furnace, and the smelting was continued for 15 minutes, and the temperature was kept at 1100 ° C for 30 minutes.
  • the weighed alumina (Al 2 O 3 ) powder was added to the insulative alloy solution, and the temperature was raised to 1210 ° C, and the stirring device was turned on for mechanical stirring, the stirring speed was 400 r / min, and the stirring time was 15 minutes. After the completion of the stirring, the temperature was lowered to 1050 °C.
  • the smelted copper alloy water was subjected to composition testing using a Spike direct reading spectrometer to determine its chemical composition within the requirements of the national standard.
  • the vibration device and the stirring device were turned on, and the vibration frequency was set to 30 times/second, and the stirring speed was 300 r/min.
  • the casting drawing device is turned on and the drawing speed is 20 mm/min.
  • the blank profile was cast according to the predetermined product shape and the casting temperature was set at 1050 °C.
  • the finished blank profile is surface treated, further processed according to the corresponding product specifications, and packaged into the warehouse after completion.
  • the copper-based composite material obtained by the distribution ratio and the method disclosed in the present invention has lower cost, higher tensile strength, higher elongation, higher hardness and wider use environment temperature. It is more wear resistant and has no decrease in electrical conductivity.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Conductive Materials (AREA)

Abstract

一种用于机车导电零部件的铜基复合材料，该铜基复合材料包含Sn、Al 2O 3以及Cu。铜基复合材料的制备：通过对熔炼温度、熔炼时间、保温温度和时间、以及搅拌方式及速率等进行控制来有效地预防元素偏析，同时使增强相Al 2O 3的分布更加均匀，改善导电率和强度。

Description

一种用于机车导电零部件的铜基复合材料及其制备方法 技术领域
本发明涉及铜基复合材料加工领域，具体涉及一种用于机车导电零部件的铜基复合材料及其制备方法。
背景技术
TAg0.1银铜合金是一种合金材料，它通过在铜中加入少量的银，在不降低材料的导电、导热和塑形的同时，能够提高材料的软化温度(再结晶温度)和蠕变强度。该材料具有很好的耐磨性、导电性和耐腐蚀性，以及良好的导电、导热、耐蚀和加工性能等特点。但是该材料时效硬化的效果不显著，且易引起“氢病”，不宜在高温(如＞370℃)还原性气氛中加工(退火、焊接等)和使用。而且，银的价格高，在工业中应用会明显提高材料的成本。
发明内容
针对上述问题，本发明提供一种铜基复合材料，该材料能够满足较高温度的使用环境，在行业内具有非常重大的现实意义。
在现有技术中已有使用Al2O3作为增强相来提高铜基复合材料的强度的相关报道，但未曾有过将Al2O3添加到Cu-Sn合金中进行强化的相关记载。经发明人研究发现，将Al2O3添加到Cu-Sn合金中进行弥散强化时会出现Sn元素偏析的问题。
因此，为了克服上述问题以及实现本发明的目的，本发明采用以下技术方案：
一种用于机车导电零部件的铜基复合材料，铜基复合材料包含Sn、Al2O3以及Cu。
进一步地，该铜基复合材料中各组分的质量百分比为Sn 0.05-0.25％、Al2O30.1-0.5％以及余量的铜。
进一步地，该Al2O3的粒径小于100μm。
进一步地，该Al2O3的粒径介于10μm与100μm之间。粒径太小的Al2O3生产成本高，而Al2O3粒径太大会影响最终制备复合材料的导电性。本发明选取该粒径范围内的Al2O3作为原料便于工业生产，同时节省成本，对导电性的影响也比较小。
进一步地，其中Cu为电解铜。
进一步地，该铜基复合材料的抗拉强度大于310MPa，伸长率大于10％，硬度大于120HB，使用环境温度高达450℃，弹性模量为125GPa，导电率为100％IACS；
铜基复合材料中，铁的质量百分含量不大于0.01％，铅的质量百分含量不大于0.01％。
本发明选取材料价格较低的锡材料取代银，从而降低材料的制作成本；添加Al2O3作为合金材料的弥散粒子，在保证合金材料导电性能的同时，提高材料的强度、硬度；提高材料的时效硬化处理效果，满足材料在400℃环境下的使用要求，提升了材料在导电部件中的使用年限。
本发明同时还提供了这种用于机车导电零部件的铜基复合材料的制备方法，该方法包括以下步骤：
1)将铜添加到电炉中，逐渐升温至约1150℃并进行熔炼；
2)将锡锭按照比例添加到熔炼炉中，继续熔炼，之后在约1100℃进行保温；
3)将氧化铝粉末按照比例添加至保温完成的合金液当中，升温至1200℃-1210℃，并开启搅拌装置进行机械搅拌，搅拌完成后降温至约1050℃；
4)对熔炼完成的铜合金水进行成分检测；
5)开启振动装置及搅拌装置，同时进行铸造拉拔，按照预定的产品 形状铸造毛坯型材；以及
6)将铸造完成的毛坯型材进行表面处理，根据相应产品规格尺寸进一步加工处理，完成后包装入库。
进一步地，步骤1)的熔炼时间为50-60分钟；步骤2)的熔炼时间为10-15分钟，保温时间为20-30分钟。
进一步地，步骤3)机械搅拌的搅拌速度为400r/min，搅拌时间为15分钟。
进一步地，步骤5)中振动装置的振动频率设置为25-30次/秒，搅拌装置的搅拌速度为300r/min，拉拔速度为20mm/min。
本发明的铜基复合材料的制备方法通过对熔炼温度、熔炼时间、保温温度和时间、以及搅拌方式及速率等进行控制来有效地预防元素偏析，同时使增强相Al2O3的分布更加均匀，使该铜基复合材料的导电率和强度同时得到有效地改善。
具体实施方式
应当理解，在示例性实施例中所示的本发明的实施例仅是说明性的。虽然在本发明中仅对少数实施例进行了详细描述，但本领域技术人员很容易领会在未实质脱离本发明主题的教导情况下，多种修改是可行的。相应地，所有这样的修改都应当被包括在本发明的范围内。在不脱离本发明的主旨的情况下，可以对以下示例性实施例的设计、操作条件和参数等做出其他的替换、修改、变化和删减。
实施例一
按照质量百分比为Sn 0.05％、Al2O30.1％以及余量的电解铜称取这三种原料，其中Al2O3的粒径为100nm。其中原料中所包含的杂质铁的质量百分比小于0.01％，铅含量少于0.01％。
将称取的电解铜添加到300kg中频电炉当中，进行熔炼，逐渐升温至1150℃，熔炼时间50分钟。将称取的锡锭添加到熔炼炉中，继续熔炼15分钟，保温至1100℃，保温时间20分钟。将称取的氧化铝(Al2O3)粉末添 加至保温完成的合金溶液当中，升温至1200℃，并开启搅拌装置进行机械搅拌，搅拌速度为400r/min，搅拌时间为15分钟。搅拌完成后降温至1050℃。采用斯派克直读光谱仪对熔炼完成的铜合金水进行成分检测，以确定其化学成分在国标要求范围之内。开启振动装置及搅拌装置，振动频率设定为25次/秒，搅拌速度为300r/min。开启铸造拉拔设备，拉拔速度为20mm/min。按照预定的产品形状铸造毛坯型材，铸造温度设定在1050℃。将铸造完成的毛坯型材进行表面处理，根据相应产品规格尺寸进一步加工处理，完成后包装入库。
按照本实施例的方法所制备得到的铜基复合材料(标记为LZCuSn0.05-0.1Al2O3)与现有技术的TAg0.1材料的性能对比如下表：
表1
Figure PCTCN2017108225-appb-000001
Figure PCTCN2017108225-appb-000002
实施例二
按照质量百分比为Sn 0.2％、Al2O3 0.3％以及余量的电解铜称取这三种原料，其中Al2O3的粒径为10μm。其中电解铜所包含的杂质铁的质量百分比小于0.01％，铅含量少于0.01％。
将称取的电解铜添加到300kg中频电炉当中，进行熔炼，逐渐升温至1150℃，熔炼时间55分钟。将称取的锡锭添加到熔炼炉中，继续熔炼10分钟，保温至1100℃，保温时间为25分钟。将称取的氧化铝(Al2O3)粉末按照比例添加至保温完成的合金溶液当中，升温至1210℃，并开启搅拌装置进行机械搅拌，搅拌速度为400r/min，搅拌时间为15min。搅拌完成后降温至1050℃。采用斯派克直读光谱仪对熔炼完成的铜合金水进行成分检测，以确定其化学成分在国标要求范围之内。开启振动装置及搅拌装置，振动频率设定为30次/秒，搅拌速度为300r/min。开启铸造拉拔设备，拉拔速度为20mm/min。按照预定的产品形状铸造毛坯型材，铸造温度设定在1050℃。将铸造完成的毛坯型材进行表面处理，根据相应产品规格尺寸进一步加工处理，完成后包装入库。
按照本实施例的方法所制备得到的铜基复合材料(标记为LZCuSn0.2-0.3Al2O3)与现有技术的TAg0.1材料的性能对比如下表：
表2
Figure PCTCN2017108225-appb-000003
Figure PCTCN2017108225-appb-000004
实施例三
按照质量百分比为Sn 0.25％、Al2O30.5％以及余量的电解铜称取这三种原料，其中Al2O3的粒径为100μm。其中电解铜所包含的杂质铁的质量百分比小于0.01％，铅含量少于0.01％。
将称取的电解铜添加到300kg中频电炉当中，进行熔炼，逐渐升温至1150℃，熔炼时间60分钟。将称取的锡锭添加到熔炼炉中，继续熔炼15分钟，保温至1100℃，保温时间为30分钟。将称取的氧化铝(Al2O3)粉末添加至保温完成的合金溶液当中，升温至1210℃，并开启搅拌装置进行机械搅拌，搅拌速度为400r/min，搅拌时间为15分钟。搅拌完成后降温至1050℃。采用斯派克直读光谱仪对熔炼完成的铜合金水进行成分检测，以确定其化学成分在国标要求范围之内。开启振动装置及搅拌装置，振动频率设定为30次/秒，搅拌速度为300r/min。开启铸造拉拔设备，拉拔速度为20mm/min。按照预定的产品形状铸造毛坯型材，铸造温度设定在1050℃。将铸造完成的毛坯型材进行表面处理，根据相应产品规格尺寸进 一步加工处理，完成后包装入库。
按照本发明的方法所制备得到的铜基复合材料(标记为LZCuSn0.25-0.5Al2O3)与现有技术的TAg0.1材料的性能对比如下表：
表3
Figure PCTCN2017108225-appb-000005
由上表可知，按照本发明公开的成分配比及方法所制得的铜基复合材料其成本更低，抗拉强度更高，伸长率更高，硬度更大，使用环境温度更广，更耐磨，并且导电性也未降低。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详 细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (7)

  1. 一种用于机车导电零部件的铜基复合材料，其特征在于，所述铜基复合材料包含Sn、Al2O3以及Cu。
  2. 根据权利要求1所述的用于机车导电零部件的铜基复合材料，其特征在于，所述铜基复合材料中各组分的质量百分比为Sn0.05-0.25％、Al2O30.1-0.5％以及余量的铜。
  3. 根据权利要求2所述的用于机车导电零部件的铜基复合材料，其特征在于，所述Al2O3的粒径小于100μm。
  4. 根据权利要求3所述的用于机车导电零部件的铜基复合材料，其特征在于，所述Al2O3的粒径介于10μm与100μm之间。
  5. 根据权利要求1-4任一项所述的用于机车导电零部件的铜基复合材料，其特征在于，所述Cu为电解铜。
  6. 根据权利要求1-4任一项所述的用于机车导电零部件的铜基复合材料，其特征在于，所述铜基复合材料的抗拉强度大于310MPa，伸长率大于10％，硬度大于120HB，使用环境温度高达450℃，弹性模量为125GPa，导电率为100％IACS；
    所述铜基复合材料中，铁的质量百分含量不大于0.01％，铅的质量百分含量不大于0.01％。
  7. 一种如权利要求1-6任一项所述的用于机车导电零部件的铜基复合材料的制备方法，其特征在于，包括以下步骤：
    1)将铜添加到电炉中，逐渐升温至1150℃并进行熔炼；
    2)将锡锭按照比例添加到熔炼炉中，继续熔炼，之后在1100℃进行保温；
    3)将氧化铝粉末按照比例添加至保温完成的合金溶液当中，升温至1200℃-1210℃，并开启搅拌装置进行机械搅拌，搅拌完成后降温至1050℃；
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