CN115466877B - 一种用于制造精密电阻的锗锰铜合金 - Google Patents
一种用于制造精密电阻的锗锰铜合金 Download PDFInfo
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- CINLLNGRSOXFOG-UHFFFAOYSA-N [Ge].[Mn].[Cu] Chemical compound [Ge].[Mn].[Cu] CINLLNGRSOXFOG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 50
- 239000000956 alloy Substances 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005242 forging Methods 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 238000005097 cold rolling Methods 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000005098 hot rolling Methods 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 5
- 239000011572 manganese Substances 0.000 description 12
- 229910052732 germanium Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000896 Manganin Inorganic materials 0.000 description 1
- 229910008487 TiSn Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- B21B1/166—Rolling wire into sections or flat ribbons
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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Abstract
本发明涉及一种用于制造精密电阻的锗锰铜合金，其特征在于，该合金各组分的重量百分含量为：Mn 6.0%~8.0%，Ge 2.0%~4.0%，Sn 2.0%~4.0%，Ni 0~0.40%，Ti 0~0.30%，Nb 0~0.15%，Re 0~0.15%，余量Cu。所述合金在较宽温域下（0~120℃）能保持较低的温度系数（±6.0ppm/℃），并且成本低、加工性能好。
Description
技术领域
本发明涉及精密电阻合金技术领域，尤其涉及一种用于制造精密电阻的锗锰铜合金。
背景技术
锰铜精密电阻合金拥有成本低、良好的电学性能等优点，广泛应用于电子元器件行业。为了追求更加优良的合金，研究人员们往锰铜合金中加入了Ni、Fe、Si等元素，对其加工性能和各项电学性能均有不同程度的改善。其中，锰加宁合金（Manganin），即Cu-12%Mn-4%Ni三元合金，一直处于精密电阻合金领先地位，在使用上有显著优势。但是，锰加宁合金依然存在使用温度范围较小的问题，仅在0~50℃时电阻变化较为稳定，超过此温度范围电阻变化会陡然增大。此外，由于Mn含量较高，锰加宁合金在较大变形量下塑性不佳。
在上世纪60年代，英国专利和美国相继报道了锗锰铜合金。其中，锗拉宁合金（Zeranin），即Cu-7%Mn-6%Ge三元合金，在当时倍受关注。相对于锰加宁合金，锗拉宁合金冷加工性能更好，并且其电阻温度系数位于±3ppm/℃以内，在0℃~70℃时电阻随温度基本呈直线变化，在-75℃~125℃电阻变化仅为0.1%左右。因此，锗拉宁合金是一种能在宽温域下使用的良好材料。对于锗拉宁合金，由于锗含量较高，加之锗价格昂贵，故生产成本高。另外，锗拉宁合金长期使用时电阻经年变化较大，以及电阻受材料形变影响变化剧烈，让其应用受限。
上世纪80年代，国内学者白全智等对低锗锰铜和高锗锰铜进行了细致的研究，并证明了4yc6锗锰铜是一类高可靠性的精密电阻材料。公开号为CN101020974A，2007年的专利，公开了一种铜锰镓锗精密电阻合金，主要成分为7.0%~12.0%Mn，6.0%~9.0%Ga，1.0%~3.0%Ge，余量Cu。该合金可以在宽温域下（-60~125℃）保持较低温度系数，并且加工性能好，电学性能稳定。但该合金中镓元素含量较高，金属镓价格同样很高，所以材料成本增加，大批量生产使用受限。
为了获得加工性能好、电学性能优异以及生产成本低的电阻材料，有必要研究出一种新型锗锰铜精密电阻合金。
发明内容
本发明目的是提供一种用于制造精密电阻的锗锰铜合金，所述合金在较宽温域下（0~120℃）能保持较低的温度系数（±6.0ppm/℃），并且成本低、加工性能好。
本发明的技术方案是：
用于制造精密电阻的锗锰铜合金，该合金各组分的重量百分含量为：Mn 6.0%~8.0%，Ge 2.0%~4.0%，Sn 2.0%~4.0%，Ni 0~0.40%，Ti 0~0.30%，Nb 0~0.15%，Re 0~0.15%，余量Cu。
较好的技术方案，该合金各组分的重量百分含量为：Mn 7.0%，Ge 2.0%~3.0%，Sn3.0%~4.0%，Ni 0.30%，Ti 0.30%，Nb 0~0.15%，Re 0.15%，余量Cu。
较好的技术方案，该合金各组分的重量百分含量为：Mn 7.0%，Ge 3.0%~4.0%，Sn2.0%~3.0%，Ni 0.30~0.40%，Ti 0.30%，Nb 0.15%，Re 0.15%，余量Cu。
Ge元素可降低铜合金电阻温度系数，稳定电学性能。由于金属Ge的价格较高，本发明采用Sn元素替代部分Ge来降低材料成本。Sn和Ge在元素周期表中位于同一主族，外层电子排布相似，化学性质相似，因此采用Sn元素代替Ge可以得到性能相近的合金。为保证合金有较低温度系数，Ge元素含量控制在2.0%~4.0%。
Sn元素除了替代Ge元素，还可改善材料塑性。若Sn元素含量超过4%，会导致偏析严重以及电阻温度系数升高，故也控制在2.0%~4.0%。
Ni元素可提高合金的强度、耐腐蚀性和电学稳定性，同时也可减小合金的结晶温度范围和树枝晶线生长速度，从而减弱Sn元素的反偏析。Nb元素起到微调性能作用，含量控制在0~0.40%。
Ti能够与Sn形成TiSn化合物，对合金有沉淀强化作用。Ti元素加入过多会降低合金电学稳定性，故加入量0~0.30%为宜。
Nb元素加入可以得到极细弥散相，显著提升合金的耐热性，在较高温度下合金的电学性能依然可以保持相对稳定。同样地，Nb元素加入过多会导致电学性能不稳定，控制量为0~0.15%。
稀土元素Re也可以减弱Sn的反偏析，它的存在能使主干树枝晶变粗、二次晶轴生长受阻，树枝间隔变大，故Sn元素在大的枝间通道中可以较为充分扩散。同时，Re还能够降低S等杂质含量，提高合金的热稳定性。稀土元素含量过多会使得成本增加，故控制Re元素为0~0.15%。
本发明添加Ni、Ti、Nb以及稀土元素Re等微量元素，通过微量元素的细化晶粒、钉扎、纯净化等作用，可以进一步保证所述合金在较宽温域下能保持较低的温度系数，同时提高电学稳定性。
本发明所述合金带材和丝材的制备方法：
合金配料完成后，采用真空中频感应炉熔炼，浇铸于钢锭模，铸锭经热锻、热轧、表面处理、拉拔、退火等工序，制备成直径0.15mm丝材；铸锭经热锻、冷轧、表面处理、退火等工序，制备成厚度0.15mm带材。丝材和带材成品均为在氨分解气保护下进行650±10℃连续退火处理。对丝材和带材微观组织进行了观察，组织均匀，晶粒尺寸大多在20~30μm。
所得合金加工性能优异，充分退火后在75%的加工变形量下不会出现裂纹或者开裂。0.15mm丝材延伸率在40%以上，0.15mm带材延伸率在35%以上。丝材抗拉强度在580N/mm2以上，带材抗拉强度在620N/mm2以上。
合金电阻率为0.37~0.40μΩ·m。合金能够在宽温域下使用，在0~120℃下电阻温度系数在±6.0ppm/℃以内。
具体实施方式
实施例1
按照合金为7.0%Mn，2.0%Ge，4.0%Sn，0.30%Ni，0.30%Ti，0.15%Re，余量Cu取各组分，将各组分采用真空中频感应炉熔炼，浇铸于钢锭模，铸锭经热锻、热轧、表面处理、拉拔、退火等工序，制备成直径0.15mm丝材；铸锭经热锻、冷轧、表面处理、退火等工序，制备成厚度0.15mm带材。丝材和带材成品均为在氨分解气保护下进行650±10℃连续退火处理。
经拉伸试验，获得丝材的延伸率和抗拉强度分别为45%和585N/mm2，带材的延伸率和抗拉强度分别为39%和623N/mm2。采用电桥法，在20℃下测得合金电阻率约为0.37μΩ·m。采用电位差计法，在0~120℃下测得丝材和带材的平均电阻温度系数分别为5.3和3.4ppm/℃。
实施例2
合金配料成分为7.0%Mn，3.0%Ge，3.0%Sn，0.30%Ni，0.30%Ti，0.15%Nb，0.15%Re，余量Cu。采用真空中频感应炉熔炼，浇铸于钢锭模，铸锭经热锻、热轧、表面处理、拉拔、退火等工序，制备成直径0.15mm丝材；铸锭经热锻、冷轧、表面处理、退火等工序，制备成厚度0.15mm带材。丝材和带材成品均为在氨分解气保护下进行650±10℃连续退火处理。
经拉伸试验，获得丝材的延伸率和抗拉强度分别为43%和594N/mm2，带材的延伸率和抗拉强度分别为37%和630N/mm2。采用电桥法，在20℃下获得合金电阻率约为0.38μΩ·m。采用电位差计法，在0~120℃下测得丝材和带材的平均电阻温度系数分别为2.3和0.5ppm/℃。
实施例3
合金配料成分为7.0%Mn，4.0%Ge，2.0%Sn，0.40%Ni，0.30%Ti，0.15%Nb，0.15%Re，余量Cu。采用真空中频感应炉熔炼，浇铸于钢锭模，铸锭经热锻、热轧、表面处理、拉拔、退火等工序，制备成直径0.15mm丝材；铸锭经热锻、冷轧、表面处理、退火等工序，制备成厚度0.15mm带材。丝材和带材成品均为在氨分解气保护下进行650±10℃连续退火处理。
经拉伸试验，获得丝材的延伸率和抗拉强度分别为41%和605N/mm2，带材的延伸率和抗拉强度分别为36%和637N/mm2。采用电桥法，在20℃下获得合金电阻率约为0.40μΩ·m。采用电位差计法，在0~120℃下测得丝材和带材的平均电阻温度系数分别为-4.2和-2.7ppm/℃。
以上所诉仅为本发明的优选实施例，并不用于限制本发明，本领域技术人员在不脱离本发明创新点的前提下，对本发明进行的改动均落入本发明的保护范围。
Claims (3)
1.一种用于制造精密电阻的锗锰铜合金，其特征在于，该合金各组分的重量百分含量为：Mn 6.0%~8.0%，Ge 2.0%~4.0%，Sn 2.0%~4.0%，Ni 0.3~0.40%，Ti 0.30%，Nb 0~0.15%，Re0.15%，余量Cu；所述合金采用以下方法制备得到：
合金配料完成后，采用真空中频感应炉熔炼，浇铸于钢锭模，铸锭经热锻、热轧、表面处理、拉拔、退火工序，制备成直径0.15mm丝材；铸锭经热锻、冷轧、表面处理、退火工序，制备成厚度0.15mm带材；丝材和带材成品均为在氨分解气保护下进行650±10℃连续退火处理。
2.根据权利要求1所述的合金，其特征在于：该合金各组分的重量百分含量为：Mn7.0%，Ge 2.0%~3.0%，Sn 3.0%~4.0%，Ni 0.30%，Ti 0.30%，Nb 0~0.15%，Re 0.15%，余量Cu。
3.根据权利要求1所述的合金，其特征在于：该合金各组分的重量百分含量为：Mn7.0%，Ge 3.0%~4.0%，Sn 2.0%~3.0%，Ni 0.30~0.40%，Ti 0.30%，Nb 0.15%，Re 0.15%，余量Cu。
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| CN101020974A (zh) * | 2007-03-19 | 2007-08-22 | 贵研铂业股份有限公司 | 一种铜锰镓锗精密电阻合金 |
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| CN1495804A (zh) * | 2002-09-13 | 2004-05-12 | 兴亚株式会社 | 电阻组成物、使用该组成物的电阻器及其制造方法 |
| CN101020974A (zh) * | 2007-03-19 | 2007-08-22 | 贵研铂业股份有限公司 | 一种铜锰镓锗精密电阻合金 |
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