CN100470069C - 用于滑动轴承的层状复合材料,其制备和应用 - Google Patents

用于滑动轴承的层状复合材料,其制备和应用 Download PDF

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CN100470069C
CN100470069C CNB2004800255999A CN200480025599A CN100470069C CN 100470069 C CN100470069 C CN 100470069C CN B2004800255999 A CNB2004800255999 A CN B2004800255999A CN 200480025599 A CN200480025599 A CN 200480025599A CN 100470069 C CN100470069 C CN 100470069C
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A·亚当
K·施塔什克
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Federal Mogul Wiesbaden GmbH
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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0-20重量%的铜和/或银和余量为铋构成的滑动层(1)。滑动层由甲磺酸的电解液电镀沉积的。

Description

用于滑动轴承的层状复合材料，其制备和应用
技术领域
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。此外本发明还涉及用来制备这种层状复合材料的方法、滑动轴承或轴套的制备以及层状复合材料的应用。
背景技术
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，然而在其制备中是非常昂贵的。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％。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。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。由这种层状复合材料可以制备用于在现代化的、高载荷的柴油发动机中的较高负载的产品。然而由于该附加的层而在制备层状复合材料时要有较高的过程技术复杂性和从而较高的成本。
由DE 100 32 624 A1获知一种由轴承合金和由铋或铋合金构成的滑动层构成的滑动轴承，其可具有改善了的相容性和疲劳强度。铋晶体特别的择优取向是决定性的，相对于晶体的无规取向和相对于单晶其可以具有减少了的脆性和改善的适应性。作为可能的合金指的是铋与软的材料，如锡、铟、锑和类似的材料的合金。然而这有这样的危险，即在这些材料在基质中分布不均匀时，也就是说在浓度变化时要形成低熔融的共晶体。所以添加物应限制在最大为5重量％。然而在实际上已经发现，共晶体的形成甚至已经在低于5重量％的限度下出现。
本发明的任务是克服现有技术的这些缺点。
发明内容
本发明通过下面的层状复合材料而解决了这一任务。此外这一任务通过下面的制备方法以及下面的应用而解决。
已经证实，在铋基质中存在由铜和/或银构成的另一相时可以提高耐磨性。尽管滑动层不含有铅，但是其还是具有比传统的基于铅的层相当的直至更好的比承载能力和磨损性能。根据本发明的层状复合材料的滑动层是适用的和显示出对于污染颗粒的高的嵌入能力。特别优越的是，在滑动层没有低熔融的共晶体形成。
此外精确的试验已经显示，由这种层状复合材料制成的轴承在进入到起始还较软的滑动层后通过在工作中的加热而自身稳定化和形成高强度的表面。这通过含有铋和镍的层的形成通过镍向着基本上是由铋构成的滑动层的扩散而发生。由此生成的滑动面是可高载荷的和耐磨的。通过含有至少约4μm厚的镍层，可以保证镍层在进入阶段后也不完全转变。
金属铜和银可以单独地或一起地在铋基质存在。它们的总份额为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4-6μm的层厚和对于铋滑动层有约6-14μm的层厚。对于在这个数量级的层厚将保证，镍层和基于铋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铋和轴承合金之间的粘附问题或意想不到的相互作用，例如在含铅和锡的轴承合金时导致具有非常低的熔点的共晶体形成。
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％。
根据本发明层状复合材料这样制备，即在由载体-、轴承合金-和镍中间层构成的复合体上由甲磺酸电解液沉积滑动层，如在权利要求9中所详细说明的那样，在此电解液含有非离子湿润剂和含有碳酸的晶粒精炼剂。在电解液中存在有作为抗氧化剂的间苯二酚。假如滑动层还应含有银，那么还必须加入硫脲作为络合物形成剂。硫脲向着这样的方向移动沉积电势，即银和铋可以一起被沉积。
作为晶粒精炼剂优选使用基于丙烯酸衍生物和烷基芳基聚二醇醚的试剂。Enthone OMI公司销售这种名为添加物L，Cerolyt BMM/T的晶粒精炼剂。
非离子的湿润剂主要是对含铜的滑动层具有意义。它应阻止特别是在轴承背部上的未受控制的铜沉积。特别地已经证实基于芳基聚二醇醚和/或烷基芳基聚二醇醚的非离子的湿润剂是有效的。Enthone OMI公司销售这种名为添加物N，Cerolyt BMM-T的非离子湿润剂。
根据本发明的滑动轴承或轴套具有这样大的优点，即在工作条件下在进入时由铋和镍形成一互扩散层，其提高耐磨性。存在的可能性是，通过滑动轴承或轴套的人为硬化而促进内扩散层的形成。在此地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。
附图说明
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。
具体实施方式
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铋的滑动层。在此使用下列的水基的电解液体系：
Bi3+作为甲磺酸铋                    30-40g/l
Cu2+作为甲磺酸铜                    1-5g/l
Ag+作为甲磺酸银                     0.1-2g/l
甲磺酸                              150-200g/l
添加剂“N”(Cerolyt BMM-T)          50-70g/1
添加剂“L”(Cerolyt BMM-T)          10-20g/l
间苯二酚                            2-3g/l
硫脲                                30-150g/l
在不用甲磺酸银时也应不用硫脲。
使用铋作为阳极材料。用来沉积滑动层的槽温度为15-40℃。使用1.5-4 x 10-2A/m2的电流密度。阳极至阴极的距离最大为350mm。阳极对阴极的表面比应基本上为1:1(+/-10％)。
图1显出了如上所述的在不用甲磺酸银和硫脲的情况下所得到的层状复合材料的层结构作为剖面图。在此1表示10.3μm厚的由铜-铋构成的滑动层，2表示4.2μm厚的镍中间层和3表示由CuPb22Sn构成的轴承合金。
在此为了清楚地识别，两个层2和3之间的边界用白线标出。
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8.5μm厚的铋-镍-层，其导致了一个可载荷的和耐磨的滑动面。涉及铋-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3.6μm和2.4μm。
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)。
如在表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。具有根据本发明的厚的镍中间层的轴承在相同覆盖层时具有比具有较薄的镍中间层的轴承高得多的载荷极限(比较实施例4，5)。通过附加地应用银和铜添加物而比纯的铋滑动层(实施例5-8)有显著改善了的耐磨性。
Figure C200480025599D00101

Claims (19)

1、一种层状复合材料，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)由含量0-20重量％的铜和/或银以及余量的铋构成，镍中间层的层厚为大于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)具有含量至少0.5重量％的铜和/或银。
3、根据权利要求1的层状复合材料，其特征在于，滑动层(1)由2-8重量％的铜和/或银以及余量的铋构成。
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5-25μm。
5、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6-14μm。
6、根据权利要求1-3之一的层状复合材料，其特征在于，镍中间层(2)的层厚为小于6μm。
7、根据权利要求1-3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1-3之一的层状复合材料，其进行一个时效过程，在镍中间层和滑动层之间具有一个基本上由铋和镍构成的互扩散层。
9、一种用来通过电镀沉积而制备根据权利要求1-8之一的层状复合材料的方法，在该方法中滑动层由下列组成的水基的电解液体系沉积：
20-100g/l的甲磺酸铋
1-30g/l的甲磺酸铜和/或0.1-2g/l的甲磺酸银
80-250g/l的甲磺酸
20-100g/l的非离子湿润剂
5-40g/l的晶粒精炼剂
1-4g/l的间苯二酚
在添加甲磺酸银时附加地应用
30-150g/l的硫脲。
10、根据权利要求9的方法，其特征在于，晶粒精炼剂是基于丙烯酸衍生物和烷基芳基聚二醇醚的。
11、根据权利要求9或10的方法，其特征在于，非离子湿润剂是基于芳基聚二醇醚和/或烷基芳基聚二醇醚的。
12、滑动轴承或轴套的制备，包括下列步骤：
在载体层上涂覆作为轴承合金层的铜合金或铝合金；
分开和变形层状复合材料；
涂覆镍中间层到轴承合金层上；
根据权利要求9-11任一项的方法在镍中间层上电镀沉积滑动层。
13、根据权利要求12的制备，其特征在于，滑动轴承或轴套热处理几个小时直至几天。
14、根据权利要求13的制备，其特征在于，热处理时的温度为150-170℃。
15、根据权利要求1-8之一的层状复合材料在曲轴主轴承中的用途。
16、根据权利要求1-8之一的层状复合材料在连杆轴承中的用途。
17、根据权利要求16的用途，其中所述层状复合材料是用在连杆轴承的大孔中。
18、一种具有根据权利要求1-8之一的层状复合材料的滑动轴承或轴套。
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ES2317019T3 (es) 2009-04-16
RU2354864C2 (ru) 2009-05-10
DE502004008538D1 (de) 2009-01-08
PT1654471E (pt) 2008-12-22
JP4945241B2 (ja) 2012-06-06
US20060286398A1 (en) 2006-12-21
DE10337029B4 (de) 2009-06-04
EP1654471B1 (de) 2008-11-26
DE10337029A1 (de) 2005-04-14
PL1654471T3 (pl) 2009-05-29
JP2007501919A (ja) 2007-02-01
RU2006107254A (ru) 2006-08-10
ATE415569T1 (de) 2008-12-15
BRPI0413524B1 (pt) 2018-04-24
EP1654471A1 (de) 2006-05-10
US7368046B2 (en) 2008-05-06
CN1846076A (zh) 2006-10-11
WO2005015037A1 (de) 2005-02-17

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