CN106811670A - 改进用于钟表应用的铁‑镍‑铬‑锰合金的方法 - Google Patents
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Abstract
改进用于钟表应用,特别是用于生产摆轮游丝的铁‑镍‑铬‑锰合金的方法,其中选择和生产包含质量计的以下元素的基础合金:‑ 9.0%至13.0%镍,‑ 4.0%至12.0%铬,‑ 21.0%至25.0%锰,‑ 0‑5.0%钼和/或0‑5.0%铜,‑余量铁,并通过碳和氮的间隙引入而进行该合金的硬化,同时保持其反铁磁性能,其具有以该基础合金的质量比例计:‑ 0.10%至1.20%碳,和/或‑ 0.10%至1.20%氮。
Description
发明领域
本发明涉及改进用于钟表应用的铁-镍-铬-锰合金的方法。
本发明还涉及该合金在生产摆轮游丝中的用途。
发明背景
用于钟表摆轮游丝的热补偿合金大部分是Charles-Edouard Guillaume工厂且基于Fe-Ni-Cr Elinvar的产品。由于添加,硬化元素具有W+C或者Ti+Al,或者Be或Nb,其特别产生合金“Elinvar”,“Ni-Span”,“Nivarox”,“Isoval”。
然而,由于其机械性能而适于应用的所有这些合金是铁磁性的,因此对磁场敏感,这对手表的功能而言是不利的。
在1970-1990年,公开了关于反铁磁合金的著作,但没有产生工业发展。这些合金对磁场的影响几乎不敏感,但具有一些工业问题并且20世纪80年代制表业危机的到来阻碍了发展。
文件EP2924514以NIVAROX SA的名义描述了钟表游丝或珠宝业生产了不锈钢合金,所述合金包含根据奥氏体面心立方体结构排列的由铁和铬形成的基础,并且包含锰和氮,且所述游丝的质量计组成为:
-铬:最小值15%,最大值25%;
-锰:最小值5%,最大值25%;
-氮:最小值0.10%,最大值0.90%;
-碳:最小值0.10%,最大值1.00%;
-总计比例为0.40%至1.50%的碳和氮总质量计值(C+N);
-碳相对于氮的总计比例为0.125-0.550的质量含量比(C/N);
-杂质和除铁外的其它金属;最小值0%,最大值12.0%;
-铁:至100%的余量。
发明概述
特别由Dr.Ing.Manfred Müller的著作中已知一类特别有意义的Fe-Mn-Ni-Cr类型的反铁磁合金。
可通过加入Be或者通过加入Ti+Al而将这类合金硬化。
由于其毒性,Be是不理想的。并且Ti+Al的添加是困难的,因为Ti+Al与存在于合金中的Ni反应,并且通过局部改变组成,使得由此难以控制合金的热系数;此外,通过Ni3Al和Ti3Al的沉淀导致的结构硬化倾向于降低合金的延性。
本发明的目的是找到容许满意的硬化的备选物。
为此,本发明涉及根据权利要求1的改进用于钟表应用的铁-镍-铬-锰合金的方法。
概括而言,本发明使得可根据HIS钢原理通过间隙引入碳和氮而将Fe-Mn-Ni-Cr型合金硬化。
该通过C+N的硬化使得可开发包含良好机械性能的合金,其为反铁磁且生态的。
本发明还涉及该合金在生产钟表摆轮游丝中的用途。
优选实施方案详述
本发明涉及改进用于钟表应用的铁-镍-铬-锰合金的方法。
根据本发明,选择和生产包含质量计的以下元素的基础合金(base alloy):
-4.0%至13.0%镍,
-4.0%至12.0%铬,
-21.0%至25.0%锰,
-0-5.0%钼和/或0-5.0%铜,
-余量铁,
并且通过碳和氮的间隙引入而进行该合金的硬化,同时保持其反铁磁性能,其具有以基础合金的质量比例计:
-0.10%至1.20%碳,和/或
-0.10%至1.20%氮。
因此,铬的比例比早先引用的文件EP2924514少得多。
更特别地,调整该碳和氮的引入,使得碳和氮的比例之和以基础合金的质量计为0.60%至0.95%。
更特别地,调整该碳和氮的引入,使得碳和氮的比例之和以基础合金的质量计为0.75%至0.95%。
更特别地,调整该碳和氮的引入,使得碳和氮的比例之和以基础合金的质量计为0.80%至0.85%。
更特别地,调整该碳和氮的引入,使得碳和氮的百分数的比以基础合金的总质量计为0.5-2.0。
更特别地,调整该碳和氮的引入,使得碳和氮的百分数的比以基础合金的总质量计为1.0-1.5。
更特别地,选择包含质量计为至少8.0%铬的该基础合金。
更特别地,在基础合金中结合作为基础合金的质量比例为0.5%至5.0%钼和/或铜以改进它的耐腐蚀性。
更特别地,选择和生产包含质量计的以下元素的基础合金:
-4.0%至13.0%镍,
-4.0%至12.0%铬,
-21.0%至25.0%锰,
-0-5.0%钼和/或0-5.0%铜,
-余量铁。
更特别地,将铬铁加入氮中以达到恰当的化学组成。
更特别地,将锰铁加入碳中以达到恰当的化学组成。
更特别地,将铬铁加入氮中并将锰铁加入碳中以达到恰当的化学组成。
更特别地,该合金的生产包括铸造过程,其包括以下步骤:
-以适当的比例制备一方面纯金属镍、铬、铁以及另一方面以下类型的预合金:
称为氮化低碳铬铁的低碳铬铁,其具有65%铬,3%氮,余量铁,
称为高碳锰铁的高碳锰铁,其具有75%锰,7%碳,余量铁,
称为低碳锰铁的低碳锰铁,其具有95%锰,余量铁,
-在真空感应炉中在氮气分压下将铁、镍和铬熔融,
-加入低碳锰铁和高碳锰铁,
-控制温度并将它保持在合金的液相线以上约20℃,或者合金的液相线以上至少20℃,
-将铬铁加入低碳氮(其为氮的主要来源)中,
-控制温度并将它保持在在合金的液相线以上约20℃,或者合金的液相线以上至少20℃,
-进行铸锭的铸造。
本发明还涉及该合金在生产钟表摆轮游丝,特别是用于振荡器的摆轮游丝中的用途。
Claims (14)
1.改进用于钟表应用的铁-镍-铬-锰合金的方法,其特征在于选择和生产包含质量计的以下元素的基础合金:
-4.0%至13.0%镍,
-4.0%至12.0%铬,
-21.0%至25.0%锰,
-0-5.0%钼和/或0-5.0%铜,
-余量铁,
且特征在于通过碳和氮的间隙引入而进行所述合金的硬化,同时保持其反铁磁性能,其具有以所述基础合金的质量比例计:
-0.10%至1.20%碳,和/或
-0.10%至1.20%氮。
2.根据权利要求1的方法,其特征在于调整所述碳和氮的引入使得碳和氮的比例之和以所述基础合金的质量计为0.60%至0.95%。
3.根据权利要求2的方法,其特征在于调整所述碳和氮的引入使得碳和氮的比例之和以所述基础合金的质量计为0.75%至0.95%。
4.根据权利要求3的方法,其特征在于调整所述碳和氮的引入使得碳和氮的比例之和以所述基础合金的质量计为0.80%至0.85%。
5.根据权利要求1的方法,其特征在于调整所述碳和氮的引入使得碳和氮的百分数的比以所述基础合金的总质量计为0.5-2.0。
6.根据权利要求5的方法,其特征在于调整所述碳和氮的引入使得碳和氮的百分数的比以所述基础合金的总质量计为1.0-1.5。
7.根据权利要求1的方法,其特征在于选择包含质量计至少8.0%铬的所述基础合金。
8.根据权利要求1的方法,其特征在于在所述基础合金中结合作为所述基础合金的质量比例为0.5%至5.0%钼和/或铜以改进它的耐腐蚀性。
9.根据权利要求1的方法,其特征在于选择和生产包含质量计的以下元素的基础合金:
-4.0%至13.0%镍,
-4.0%至12.0%铬,
-21.0%至25.0%锰,
-0-5.0%钼和/或0-5.0%铜,
-余量铁。
10.根据权利要求1的方法,其特征在于将铬铁加入氮中以达到恰当的化学组成。
11.根据权利要求1的方法,其特征在于将锰铁加入碳中以达到恰当的化学组成。
12.根据权利要求1的方法,其特征在于将铬铁加入氮中并将锰铁加入碳中以达到恰当的化学组成。
13.根据权利要求12的方法,其特征在于该合金的生产包括铸造过程,其包括以下步骤:
-以适当的比例制备一方面纯金属,镍、铬、铁以及另一方面以下类型的预合金:
称为氮化低碳铬铁的低碳铬铁,其具有65%铬,3%氮,余量铁,
称为高碳锰铁的高碳锰铁,其具有75%锰,7%碳,余量铁,
称为低碳锰铁的低碳锰铁,其具有95%锰,余量铁,
-在真空感应炉中在氮气分压下将铁、镍和铬熔融,
-加入低碳锰铁和高碳锰铁,
-控制温度并将它保持在合金的液相线以上至少20℃,
-将铬铁加入低碳氮中,
-控制温度并将它保持在合金的液相线以上至少20℃,
-进行铸锭的铸造。
14.根据权利要求1生产的合金在生产钟表摆轮游丝中的用途。
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EP15197408.6 | 2015-12-02 | ||
EP15197408.6A EP3176281B1 (fr) | 2015-12-02 | 2015-12-02 | Procede d'amelioration d'un alliage fer-nickel-chrome-manganese pour des applications horlogeres |
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CN113126466A (zh) * | 2019-12-31 | 2021-07-16 | 尼瓦罗克斯-法尔股份公司 | 用于钟表机芯的摆轮游丝及其制造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US3788822A (en) * | 1970-03-18 | 1974-01-29 | Hattori Tokeiten Kk | Non-magnetic composite having a constant modulus of elasticity |
CN87105055A (zh) * | 1987-08-03 | 1988-10-19 | 大连铁道学院 | 铁-锰-铝-铬系反铁磁精密电阻合金 |
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WO2014198466A2 (fr) * | 2013-06-12 | 2014-12-18 | Nivarox-Far S.A. | Pièce pour mouvement d'horlogerie |
EP2924514A1 (fr) * | 2014-03-24 | 2015-09-30 | Nivarox-FAR S.A. | Ressort d'horlogerie en acier inoxydable austénitique |
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DE19607828C2 (de) * | 1995-04-15 | 2003-06-18 | Vsg En Und Schmiedetechnik Gmb | Verfahren zum Herstellen eines austenitischen Cv-Mn-Stahls |
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JPWO2009069762A1 (ja) * | 2007-11-30 | 2011-04-21 | 日本ピストンリング株式会社 | ピストンリング用鋼材およびピストンリング |
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EP2570862B1 (fr) * | 2011-09-15 | 2014-03-05 | ETA SA Manufacture Horlogère Suisse | Ensemble barillet d'horlogerie à diamètre de bonde réduit |
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US3788822A (en) * | 1970-03-18 | 1974-01-29 | Hattori Tokeiten Kk | Non-magnetic composite having a constant modulus of elasticity |
CN87105055A (zh) * | 1987-08-03 | 1988-10-19 | 大连铁道学院 | 铁-锰-铝-铬系反铁磁精密电阻合金 |
EP2447387A1 (fr) * | 2010-10-28 | 2012-05-02 | Générale Ressorts SA | Ressort de barillet de pièce d'horlogerie |
WO2014198466A2 (fr) * | 2013-06-12 | 2014-12-18 | Nivarox-Far S.A. | Pièce pour mouvement d'horlogerie |
EP2924514A1 (fr) * | 2014-03-24 | 2015-09-30 | Nivarox-FAR S.A. | Ressort d'horlogerie en acier inoxydable austénitique |
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CN113126466A (zh) * | 2019-12-31 | 2021-07-16 | 尼瓦罗克斯-法尔股份公司 | 用于钟表机芯的摆轮游丝及其制造方法 |
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EP3176281A1 (fr) | 2017-06-07 |
US10501818B2 (en) | 2019-12-10 |
EP3176281B1 (fr) | 2019-03-27 |
JP2017101319A (ja) | 2017-06-08 |
RU2724737C1 (ru) | 2020-06-25 |
JP6378277B2 (ja) | 2018-08-22 |
CN106811670B (zh) | 2018-10-19 |
US20170159144A1 (en) | 2017-06-08 |
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