CN1846077A - 层状复合材料,其制备和应用 - Google Patents
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Abstract
在用于滑动轴承或轴套的层状复合材料中本发明致力于应用不含铅的滑动层。根据本发明提出了一种层状复合材料,其具有载体层、由铜合金或铝金构成的轴承合金层(3)、厚度>4μm的镍中间层(2)和由约0-20重量%的铜和/或银和余量为锡构成的滑动层(1)。滑动层由甲磺酸的电解液电镀沉积的。
Description
本发明涉及一种层状复合材料,特别是用于滑动轴承或轴套的层状复合材料,其具有载体层、由铜合金或铝合金制成的轴承合金层、镍中间层和滑动层。此外本发明还涉及层状复合材料的应用。
具有钢背部作为载体层、铅青铜作为轴承合金层和由铅-锡-铜构成的滑动层的结构的经典的层状复合材料,如在Glyco-Ingenieurberichte 1/91中所描述的,通过其高度的可靠性和机械承载能力而证明是优越的。在此滑动层是电镀沉积的。在此它是一个多功能层,外来的颗粒可以嵌入其中,其用作为腐蚀防护层,其显示出了紧急开动性能和特别适合用于入口(Einlauf)或与滑动部件的匹配。
轴承合金层对于在滑动层至少在有些地方被完全被磨蚀掉的情况下也具有足够的紧急开动性能。
经典的层状复合材料具有基于铅的滑动层。常用的合金例如是PbSn10Cu2。这种滑动层具有12-15HV的低的硬度(维氏硬度)。所以其具有良好的嵌入能力和是耐腐蚀的。然而出于劳动保护和环境保护的原因,期望的是重金属铅用其他的合适的材料代替。
一种方法在于,在高负载的轴承中使用硬质层作为滑动层。例如通过PVD法(物理气相沉积)沉积具有80HV的硬度的铝-锡-层。这是不含铅的,然而在其制备上是非常昂贵的。这种轴承是非常耐磨损的。然而其几乎没有嵌入能力和所以大多与作为相对壳(Gegenshale)的软的含铅的层联合使用。然而也期望的是,将相对壳中的铅也用其他的材料代替。
已经试验,用纯锡作为滑动面。然而其约10HV的硬度是比传统的铅合金还要软和所以不能够承受例如在曲轴主轴承和连杆轴承中所产生的载荷。
在DE 197 28 777 A1中描述了一种用于滑动元件的层状复合材料,它的滑动层是由不含铅的、具有锡和铜的合金构成,在此铜的份额为3-20重量%和锡的份额为70-97重量%。通过加入铜,滑动层的硬度相对于纯锡得到提高。这种滑动层是采用具有晶粒精炼添加剂的甲磺酸的电解液电镀沉积的。这样生成的滑动层具有三元铅基滑动层的性能。此外在DE 197 28 777 A1中还提出,为了进一步改善耐磨性,加入在电解槽中分散了的硬质材料颗粒,其嵌入层中。然而这会带来附加的耗费和成本。在轴承合金和滑动层之间可以有1-3μm厚的镍层连同2-10μm厚的镍-锡层一起作为扩散阻挡层。
在DE 197 54 221 A1中公开了一种层状复合材料,其带有一个含有3-30重量%的铜、60-97重量%的锡和0.5-10重量%的钴的滑动层。这样达到了机械承载能力的进一步提高和阻止了在滑动层和镍扩散阻挡层之间的连接层的脆变。通过钴而减小了锡向镍的扩散倾向。然而由于加入合金元素钴而使得电镀沉积过程变得复杂了,这减小了过程安全性。此外,如在DE 197 28 777 A1中那样,1-3μm厚的镍层连同2-10μm厚的镍-锡层可一起作为扩散阻挡层。
在EP 1 113 180 A2中描述了一种用于滑动轴承的层状复合材料,它的滑动层具有锡基质,锡-铜-颗粒嵌入其中,其由39-55重量%的铜和余量锡构成。此外对于这种层状复合材料的特征还在于,不仅提供一个1-4μm厚的镍中间层,而且在镍中间层和滑动层之间还设置一个2-7μm厚的锡和镍的第二中间层。由镍形成的第一中间层从Watt的镍电解液施加到轴承合金层上。在这种第一中间层上电镀由镍和锡组成的第二中间层上。为此,使用一种改性的氯化物/氟化物电解液。采用由镍和锡-镍构成的中间层将生成本身与载荷相匹配的体系,在该体系中根据热条件通过锡-镍-层的生长而提高承载能力。
本发明的任务是克服现有技术的这些缺点。
本发明通过根据权利要求1的层状复合材料而解决了这一任务。此外这一任务通过根据权利要求9和10的应用而解决。
已经意外地表明,即使开始时没有存在一个锡-镍层也缓慢地形成了一个这样的层。在加热层状复合材料时,正如在进入阶段在由本发明的层状复合材料制备的轴套和轴承中所发生的,镍扩散到基本上由锡组成的滑动层中。由此,由于在锡基质中含有的由铜-锡-和/或银-锡构成的第二硬质相浓度提高,缓慢地构成了一个高强度的表面。通过降低承载的层厚度可以提高疲劳强度。
根据现有技术,施加上一个用作扩散阻挡层的1-3μm的薄的镍层,与之相反,根据本发明的镍层形成用于构成开始时不存在的锡-镍层的镍源。该镍层必须厚于4μm,因为否则的话由于镍扩散进入锡层,镍层可能被完全消耗。这会导致由锡-镍和锡-滑动层合金构成的覆盖层剥落。迄今为止,应尽可能避免较厚的镍层,因为它没有良好的滑动性能并且在紧急情况下允许快速地磨损到下面的轴承合金中。
金属铜和银可以单独地或一起地在锡基质中存在。它们的总份额约为0.5-20重量%。有利地,铜和/或银的总份额应为约2-8重量%。
有利地,滑动层具有约5-25μm的层厚。特别优选地对于镍中间层有约4-8μm的层厚和对于滑动层有约6-14μm的层厚。对于在这个数量级的层厚将保证,镍层和基于锡的滑动层都不会因为扩散而完全转化。这将导致在滑动层中含有的锡和轴承合金之间的粘附问题或意想不到的相互作用如形成脆相。
有利地轴承合金为铜-铝-、铜-锡-、铜-锡-铅-、铜-锌-、铜-锌-硅-、铜-锌-铝-、铜-铝-铁-或铜-锌合金。基于铜或铝的轴承合金是优选的,也就是说它的铜或铝份额为50-95重量%。
为了制备根据本发明的层状复合材料,在钢和轴承合金的复合体上在第一步骤中化学或电化学施加由镍构成的中间层。然后从一个二元或多元的烷基磺酸电解槽在添加非离子湿润剂和游离的烷基磺酸条件下沉积滑动层。在制备轴承时,首先由钢和轴承合金的复合体预制轴承并在进一步的步骤中施加由镍和滑动层构成的中间层。
根据本发明的层状复合材料具有这样大的优点,即在工作条件下在由其制成的轴承或轴套进入时由锡和镍本身形成一互扩散层,其提高了耐磨性。它们不必在一个单独的方法步骤中独立地施加。存在的可能性是,通过滑动轴承或轴套的人为硬化而促进互扩散层的形成。在此特别地已经证实在约150-170℃下的热处理是有利的,热处理要进行超过几个小时直至几天。
根据本发明的层状复合材料特别适合用来制备曲轴主轴承和连杆轴承,特别是用于制备大的连杆孔。
以下根据实施例和附图更清楚地解释本发明。
附图示出:
图1根据本发明的层状复合材料的轴承合金层、镍中间层和滑动层的剖面图;
图2由根据本发明的层状复合材料制备的轴承在进入阶段后的剖面图和
图3由根据图2的轴承在III-III区域中通过能量色散X-射线分析测得的元素分布图。
在由钢和CuPb22Sn制成的轴承合金构成的复合体构成的预制成的轴承上在相应的预处理后由Watt的镍电解液施加一个镍扩散阻挡层。
在这样生成的镍中间层上电镀沉积基于锡的滑动层。在此使用下列的水基的电解液体系:
Sn2+作为甲磺酸锡 30-45g/l
Cu2+作为甲磺酸铜 2-8g/1
Ag+作为甲磺酸银 0.1-2g/l
甲磺酸 80-140g/l
添加剂“N”(Cerolyt BMM-T) 30-45g/l
间苯二酚 1.5-4g/l
使用锡作为阳极材料。用来沉积滑动层的槽温度为20-40℃。使用1.5-3.0×10-2A/m2的电流密度。阳极至阴极的距离大约为300-400mm。阳极对阴极的表面比应基本上为1∶1(+/-10%)。为了除去连续生成的Sn4+,电解液必须通过过滤设备循环。
图1显出了如上所述得到的层状复合材料的带有铜-锡滑动层的层结构作为剖面图。在此1表示13.1μm厚的由铜-锡构成的滑动层,2表示4.9μm厚的镍中间层和3表示由CuPb22Sn构成的轴承合金。
在此,两个层1和2之间的边界用灰线标明。
在图2中作为剖面图示出了由在图1所示出了的层状复合材料制成的在调节工作状态后,也就是说在进入阶段后的轴承。在此轴承在150℃下热处理500小时。通过扩散生成以4表示的4.1μm厚的锡-镍-层,其导致了一个可载荷的和耐磨的滑动面。涉及锡-镍-层时通过在图3中示出的能量色散X-射线分析的结果而证实。X-轴上距离与相应的在图2的III-III区域中的层厚相一致。滑动层1’和镍层2分别只有较小的厚度为10.2μm和3.3μm。
在此,在图2中两个层1’和4之间的边界用灰线标明。
为了评价由根据本发明的层状复合材料制备的轴承的效率,进行安德伍德试验。在此具有偏心轮重量的轴以刚性安装了的连杆转动。在连杆中的轴承由试验轴承构成。试验轴承具有1.4mm的壁厚和50mm的直径。通过轴承宽度而调节比载荷。转数为4000转/min。在250小时工作时间后测量滑动层疲劳和磨损。在这个试验中所得到的结果列于表1中(实施例5-8)。为了比较也给出了用根据现有技术的材料达到的值(实施例1-4)。
如从表1所列的结果可以看出,由根据本发明的层状复合材料制成的轴承在滑动层疲劳、磨损和最大载荷直至总磨损方面都显著优于传统的具有基于铅的滑动层的轴承。甚至具有纯的锡滑动层的轴承(实施例5)使用一个厚的镍层也变得几乎与带有含铅滑动层的轴承可比较并且可以应用于轻的应力负荷。
表1
现有技术 | 根据本发明 | |||||||
实施例序号 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
组成 | PbSn5Cu2 | PbSn10Cu5 | PbSn14Cu8 | Sn | Sn | SnCu6 | SnAg3 | SnCu3Ag2 |
镍层的厚度(μm) | 1 | 2 | 1.5 | 1 | 5 | 4.5 | 5.5 | 4.5 |
没有滑动层疲劳的最大载荷(MPa) | 52.5 | 60 | 65 | 35 | 50 | 70 | 67.5 | 72.5 |
在60Mpa时的磨损(μm) | 15 | 11 | 9 | 不可测量 | 12 | 6 | 8 | 6 |
直至滑动层总磨损时的最大载荷(MPa) | 60 | 67.5 | 80 | 45 | 65 | 85 | 82.5 | 85 |
Claims (10)
1、一种特别是用于滑动轴承或轴套的层状复合材料,其具有载体层、由铜合金或铝合金制成的轴承合金层(3)、镍中间层(2)和滑动层(1),其特征在于,滑动层(1)由约0-20重量%的铜和/或银和余量锡构成和镍层的层厚为大于4μm。
2、根据权利要求1的层状复合材料,其特征在于,滑动层(1)具有至少约0.5-20重量%的铜和/或银。
3、根据权利要求1或2的层状复合材料,其特征在于,滑动层(1)由约2-8重量%的铜和/或银和余量锡构成。
4、根据权利要求1-3之一的层状复合材料,其特征在于,滑动层(1)的层厚为约5-25μm。
5、根据权利要求1-4之一的层状复合材料,其特征在于,滑动层(1)的层厚为约6-14μm。
6、根据权利要求1-5之一的层状复合材料,其特征在于,镍层(2)的层厚为约4-6μm。
7、根据权利要求1-6之一的层状复合材料,其特征在于,轴承合金层(3)由铜-铝、铜-锡、铜-锡-铅、铜-锌、铜-锌-硅、铜-锌-铝、铝-锌或铜-铝-铁-合金构成。
8、根据权利要求1-7之一的层状复合材料,其进行一个时效过程和在镍中间层(2)和滑动层(1’)之间具有一个基本上由锡和镍构成的互扩散层。
9、根据权利要求1-8的层状复合材料作为曲轴主轴承的用途。
10、根据权利要求1-8的层状复合材料作为连杆轴承,特别是在连杆的大孔中的用途。
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DE10337030A DE10337030B4 (de) | 2003-08-12 | 2003-08-12 | Schichtverbundwerkstoff, Herstellung und Verwendung |
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EP (1) | EP1654470B2 (zh) |
JP (1) | JP5203606B2 (zh) |
CN (1) | CN100443753C (zh) |
AT (1) | ATE443816T1 (zh) |
BR (1) | BRPI0413483B1 (zh) |
DE (2) | DE10337030B4 (zh) |
ES (1) | ES2334918T3 (zh) |
PL (1) | PL1654470T3 (zh) |
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CN101680482B (zh) * | 2007-03-12 | 2012-12-26 | 大丰工业株式会社 | 滑动轴承 |
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- 2004-08-05 EP EP04762610.6A patent/EP1654470B2/de not_active Not-in-force
- 2004-08-05 AT AT04762610T patent/ATE443816T1/de active
- 2004-08-05 RU RU2006107256/11A patent/RU2354865C2/ru not_active IP Right Cessation
- 2004-08-05 CN CNB2004800256008A patent/CN100443753C/zh not_active Expired - Fee Related
- 2004-08-05 DE DE502004010121T patent/DE502004010121D1/de active Active
- 2004-08-05 ES ES04762610T patent/ES2334918T3/es active Active
- 2004-08-05 JP JP2006522885A patent/JP5203606B2/ja not_active Expired - Fee Related
- 2004-08-05 BR BRPI0413483-4A patent/BRPI0413483B1/pt not_active IP Right Cessation
- 2004-08-05 PL PL04762610T patent/PL1654470T3/pl unknown
- 2004-08-05 WO PCT/DE2004/001765 patent/WO2005015036A1/de not_active Application Discontinuation
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CN101680482B (zh) * | 2007-03-12 | 2012-12-26 | 大丰工业株式会社 | 滑动轴承 |
CN102080242B (zh) * | 2009-11-27 | 2012-12-12 | 比亚迪股份有限公司 | 一种铜锡铁三元合金镀液、电镀方法及电镀产品 |
CN102537067A (zh) * | 2011-12-15 | 2012-07-04 | 湖北安达汽车零部件有限公司 | 轴瓦基底层 |
CN102537067B (zh) * | 2011-12-15 | 2014-07-23 | 湖北安达精密工业有限公司 | 轴瓦基底层 |
CN109429498A (zh) * | 2017-06-21 | 2019-03-05 | 大丰工业株式会社 | 滑动构件以及滑动轴承 |
CN109429498B (zh) * | 2017-06-21 | 2021-04-20 | 大丰工业株式会社 | 滑动构件以及滑动轴承 |
Also Published As
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WO2005015036A1 (de) | 2005-02-17 |
BRPI0413483A (pt) | 2006-10-17 |
BRPI0413483B1 (pt) | 2018-02-06 |
ATE443816T1 (de) | 2009-10-15 |
JP2007501898A (ja) | 2007-02-01 |
US7575814B2 (en) | 2009-08-18 |
CN100443753C (zh) | 2008-12-17 |
ES2334918T3 (es) | 2010-03-17 |
PL1654470T3 (pl) | 2010-05-31 |
DE502004010121D1 (de) | 2009-11-05 |
EP1654470B1 (de) | 2009-09-23 |
DE10337030B4 (de) | 2007-04-05 |
RU2354865C2 (ru) | 2009-05-10 |
JP5203606B2 (ja) | 2013-06-05 |
RU2006107256A (ru) | 2007-09-27 |
DE10337030A1 (de) | 2005-03-17 |
US20060263625A1 (en) | 2006-11-23 |
EP1654470A1 (de) | 2006-05-10 |
EP1654470B2 (de) | 2016-03-16 |
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