CN109210081B - 滚动轴承的电镀组成部件 - Google Patents
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- 238000005096 rolling process Methods 0.000 title claims abstract description 39
- 238000009713 electroplating Methods 0.000 title description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 229910052718 tin Inorganic materials 0.000 claims description 70
- 238000007747 plating Methods 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
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- 239000004332 silver Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
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- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 241000282485 Vulpes vulpes Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229940079864 sodium stannate Drugs 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- -1 zinc Chemical compound 0.000 description 1
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- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
本发明涉及一种滚动轴承(10)的轴承组成部件,诸如为滚动元件(17)、轴承圈(12;15)和/或用于保持滚动轴承(10)的滚动元件(17)的保持架(20),其中所述轴承组成部件的外表面(22)设置有镀层(25),所述镀层包含至少97重量%锡。根据本发明,所述镀层(25)的锡包含α/β的相比率小于10%、优选不多于4%的α相锡和β相锡。
Description
技术领域
本发明涉及滚动轴承的领域,更特别涉及一种电镀有金属涂层以用于改善耐磨性的滚动轴承的组成部件。
背景技术
在使用时,滚动元件和/或滚动轴承的保持架与轴承圈滚道(raceway)经历周期性滑动接触(在滚动元件的情况下)、与滚动元件经历周期性滑动接触(在球引导式保持架或滚子引导式保持架的情况下)、或者与轴承圈(bearing race)的肩部经历周期性滑动接触(在圈(ring)引导式保持架的情况下)。这种周期性的滑动接触可能导致严重的磨损,尤其在润滑条件差的高速应用中,诸如齿轮箱轴承(/变速箱轴承)(gearbox bearings)、汽车发动机轴承、航空发动机主轴轴承和转轴轴承(/锭轴承)中(spindle bearings)。
为了解决这个问题,例如已知为保持架的引导表面设置硬质类金刚石涂层(harddiamond-like coating),诸如在JP2005147306中公开的那样。作为另一种选择,可以将软金属膜施加(/涂布)于保持架表面,诸如在JP2002195266中公开的那样,由此厚度为25-50μm的银镀层被设置在由低碳钢制成的保持架上。然而,DLC涂层和银是昂贵的材料。
在JP2012097872中,提出了锡涂层,其优点在于:这是一种更便宜的材料。在US9416821中提出了一种涂层,其包含锡和第二金属,该第二金属具有比铁低的表面自由能,例如,锌,由此第二金属以5-35重量%(/重量百分比,下同)(wt.%)的量存在于涂层中,并且涂层的厚度在5至30μm之间。在具有纯锡镀层的样本和具有由锡与锌构成的镀层的样本上进行保持架旋转试验之后,发现纯锡层表现出差的磨损状态。
因此,在以下方面存在改进空间:为滚动轴承提供经济的且直接(/易于)制造的(有)涂层(的)组成部件,由此涂层提供了低摩擦和持久的耐磨性。
发明内容
本发明涉及一种轴承组成部件,诸如由金属材料制成的滚子元件、轴承圈或保持架,其中轴承组成部件的接触表面设置有延性镀层,该延性镀层包含至少97重量%锡或镍或铜(/紫铜)(copper)。
锡是一种后过渡金属,具有两个主同素异形体(allotropes)或相(phases),通常称为β-锡和α-锡。在室温时,稳定相为具有四方结构的β-锡。在低温时,β-锡转变成具有金刚石立方结构的α-锡。尽管如此,即使在高于转变温度的温度时,也已经发现传统的锡涂层包含α/β相比率为5-20%的α-锡和β-锡(这两者)。
在根据本发明的轴承组成部件中,锡镀层包含小于10mol%(的)α-锡,优选小于5mol%,最优选不多于4mol%的α-锡。在优选的实施方式中,锡镀层包含不多于3mol%的α-锡。
已经发现,具有有相应高水平的β-锡(即超过90mol%、优选至少96mol%)的锡镀层的轴承组成部件展现出改善的摩擦和磨损特性,并且寿命比具有包含较低水平的β-锡的锡镀层的轴承组成部件长。
作为另一种选择,延性镀层可以包括无电镀镍(electroless nickel)、电解镍或铜(/紫铜)(copper)。
延性金属镀层允许在不牺牲轴承疲劳寿命的情况下提高滚动元件与滚道的一致性(/适合性)(conformity)。通常轴承寿命由于小的接触面积一般导致较高的接触压力(但却提供了减小的摩擦扭矩)的事实而减少。
由于镀层的延性特征,因此镀层可以在滚动接触期间能够塑性变形和/或甚至可以被在试车(/磨合)时期去除(removed)。通过减小赫兹接触面积,变形的和/或去除的层改变了接触几何结构(contact geometry)和/或增强了滚动元件与滚道的一致性。这进而在不减少轴承疲劳寿命的情况下降低了摩擦扭矩。
进一步优选的是,设置有延性镀层(ductile layer plate)的轴承组成部件为滚动轴承的保持架,所述保持架与滚动轴承的滚子和轴承圈中的至少一者滑动接触。优选的是,与所述保持架滑动接触的滚动轴承的滚子和轴承圈中的至少一者的表面设置有黑色氧化物层。因此,滑动接触的保持架和滚子或轴承圈的表面区域形成了包含锡的延性层和黑色氧化物层的滑动接触搭配体(/搭配物)(partners)。优选的是,设置有黑色氧化物层的轴承圈的外表面为轴承圈的滚道或肩部。此外,有利的是,所述黑色氧化物层的厚度在0.2至1.3μm之间,优选在0.5至1μm之间。
根据本发明的轴承组成部件可以以电镀工艺生产,在该电镀工艺中将所述轴承组成部件浸入包含锡(或镍或铜)离子的电解液(的)浴(bath)中,并在电解回路中形成阴极。在一些实施方式中,使用酸性镀锡工艺(acid tin plating process),其中电解液包含硫酸亚锡和硫酸。在其它实施方式中,使用碱性镀锡工艺,其中电解液包含碱金属锡酸盐,诸如锡酸钠或锡酸钾。在这两个实施方式中,在电镀过程期间特别选择并仔细控制浴温(bathtemperature)。
本发明人已经发现电解液浴(electrolyte bath)的温度在存在于镀层中的α-锡与β-锡的比例中起到重要的作用。该机理尚未完全了解,但看来存在温度“窗口”,在该温度“窗口”中α-锡的形成被抑制。该窗口存在于25℃至35℃的温度之间。在使用相同样品、浴组分和工艺参数进行的一个实验中(其中仅温度变化),发现35℃的浴温产生出小于3%的α/β相比率,而40℃的浴温导致产生10%的α/β相比率。另一个窗口存在于60℃至80℃之间,示出了与较低温度的第一窗口相同的α/β相比率(phase ratios)。
在一些实施方式中,锡镀层由纯锡构成。在其它实施方式中,锡镀层包含至多3重量%的以下元素中的一种或多种:锑、铋、铟或银。据认为,添加这些元素中的一种或多种使β相稳定。在一个实施方式中,所述锡镀层由99.5-99.9重量%的锡和0.1-0.5重量%的锑、铋、铟和/或银构成。
设置有镀层的轴承组成部件由金属材料制成,金属材料诸如为钢、铝或(青)铜,并且(轴承组成部件)可以是内圈、外圈、滚动元件和/或球引导(式)保持架、滚子引导(式)保持架或被构造成在轴承内圈或轴承外圈的肩部或凸缘上运行的圈引导(式)保持架。保持架还可以是用于汽车发动机应用的分离式保持架(split cage)。在保持架的情况下,镀层的厚度可以在1至100μm之间,优选在5至30μm之间。假如镀层被施加于圈的滚道和/或滚动元件,则镀层的厚度优选为小于5μm,最优选小于3μm。
现将参照实施例(/示例)和附图来进一步描述本发明。
附图说明
图1示出了包括了设置有根据本发明的锡的表面层的保持架的滚动轴承的一部分的截面;
图2示出了不同的电镀温度对电镀的锡层中锡相的比例(/比率)的影响。
具体实施方式
图1示出了滚动轴承的一部分的截面图。轴承10具有内圈12、外圈15和设置在内圈12与外圈15之间的轴承圈的内滚道和外滚道上的圆柱滚子17的列。在所示的示例中,轴承(的)外圈15在外滚道的任一轴向侧具有凸缘15a,凸缘15a沿径向向内方向延伸并在轴承运行(/工作)(operation)期间引导滚子。(这些)滚子被保持架20保持间隔开,在本示例(/实施例)中,保持架20被在外圈(的)凸缘15a上对中并引导,并由低碳钢材料形成。
让我们假设轴承支撑发动机曲轴(engine crankshaft)并且(轴承)用发动机油来润滑。在轴承运行期间,保持架的径向外表面22与外圈(的)凸缘15a的径向内表面滑动接触。在没有适当的润滑膜的情况下,发生高(的)摩擦和磨损。为了减轻这个问题,保持架、圈和/或滚子的外表面电镀有锡涂层25。
根据本发明,锡涂层25包括α/β相比率(phase ratio)为小于10mol%α锡的α相锡和β相锡,优选为小于5mol%,在组成部件为保持架的情况下,为不超过4%。如将通过以下实施例表明的,已经发现具有相应的高百分比的β-相锡的锡涂层会产生低摩擦并展现出优异的耐久性。
制备多个样品并进行销盘摩擦试验(pin-on-disc friction test),在试验中将盘(的)样品安装在旋转平台上,并将球形式的销压靠旋转的盘。盘样品的基础材料为低合金碳钢(ST24),这是轴承保持架的常用材料。使盘样品转动,然后用如下金属涂层电镀:
表1:设置在盘样品上的涂层的材料、厚度和硬度
在以下条件下,在试验开始时和在试验结束时测量滑动摩擦的系数:
·球:DIN 100Cr6钢,马氏体硬化(硬度780-800HV),直径12.7mm,表面粗糙度Rq=0.01μm
·平(的)盘样品:ST24保持架钢,未硬化(硬度230HV),在涂层(/涂覆)前的表面粗糙度Ra=1.6μm
·直线(线性)滑动速度:1m/s(在盘的半径为25mm时为400rpm)
·润滑油:发动机油,福斯(Fuchs)TITAN EM 225.26(HTHS 2.9),粘度:在40℃时为55.2mm2/s,在100℃时为10.1mm2/s
·试验油温:90℃
·试验持续时间:4小时
此外,在试验之前和试验之后测量样品的表面粗糙度。球在盘表面上产生磨损痕迹(wear track),这是测量的磨损痕迹的表面粗糙度。试验结果在表2中给出。
表2在试验的开始和结束时利用销盘试验台(test rig)测量的摩擦系数,加上在试验前和试验后的表面粗糙度。
如可以看到的,根据本发明的锡-B涂层产生与更贵得多的银涂层相当的、低且稳定的摩擦系数。还值得注意的是,尽管锡-A涂层具有较低的表面粗糙度的事实,但锡-B涂层(α/β相比率为2%)产生比锡-A涂层(α/β相比率为20%)(更)低的滑动摩擦。
在不受理论束缚的情况下,据认为这可归因于两个锡相的不同的晶体结构。β相具有四方结构并且具有高延性(ductile),这是因为晶体可以被沿着四方晶体平面剪切。α相具有立方结构,其抵抗β相的剪切,使金属更脆。还据认为根据本发明的锡涂层的高延性和剪切性能(behaviour)改善了涂层的耐久性。
对设置有如表1中给出的涂层的样品进行耐磨性试验(wear resistance test)。
为由低合金碳钢(ST24)制成的圈电镀涂层并将其安装在摩擦扭矩试验台的轴上。试验条件如下:
-被涂覆的圈(coated ring):ST24,转动表面(在进行涂覆之前Ra~1.6μm),圈(的)外径为67.5mm、内径为60mm且高度为48mm,硬度为230HV
-对立面(Counter face):CRB 208ECP外圈肩部,直径67.5mm,宽度3mm,DIN100Cr6硬化钢,硬度780-800HV,表面粗糙度Ra~0.2μm
-转速:500、1000、2000、3000rpm
-载荷:0-50kg(在样品上)
-润滑油:发动机油,福斯(Fuchs)TITAN EM 225.26(HTHS 2.9),粘度:在40℃时为55.2mm2/s,在100℃时为10.1mm2/s
-油流量:20和150cc/min
-油温度:环境温度,
-试验持续时间:100小时
在试验期间测量摩擦扭矩,磨损寿命由以下两个测量(值)确定:
1)当摩擦扭矩超过0.375Nm时
2)当在光学显微镜检查下观察到涂层损坏时。
试验的结果在表3中示出。
表3在寿命结束时测量的耐久寿命(小时)和摩擦扭矩。试验条件:载荷300N,速度(/转速)3000rpm,室温,油流量150cc/min
如可以从结果看出的,本发明的锡涂层锡-B达到100小时试验的结束并展现出低(的)摩擦扭矩,而用于对比的涂层锡-A仅持续70小时。本发明的锡涂层更持久。
为了生产含有至少90mol%β-锡的锡涂层,本发明人已经发现,必须要在电镀过程期间仔细选择和控制浴温(bath temperature)。
进行以下试验:将由低碳钢制成的样品浸入包含有40g/L的锡和120g/L的硫酸的硫酸亚锡浴混合物(stannous sulphate bath composition)中。将各样品作为阴极(cathode)连接到由纯锡制成的阳极(anode)上并在特定温度下电镀,该温度对于不同的样品而言是变化的,保持所有其它工艺参数恒定。在完成电镀过程之后,使用X射线衍射检查镀层,以确定α-锡与β-锡的相对含量。结果在图2的棒形图中示出。
如可以看到的,35℃的温度导致产生出根据本发明的锡涂层,其中α/β相比率小于3%,而仅高5度的温度会导致明显高的α-锡的含量。70℃的工艺温度(/过程温度)也导致出根据本发明的锡涂层。
虽然机理尚未完全了解,但看来存在窄的温度范围或“窗口”,在该温度范围或“窗口”中α-锡的形成被大大抑制。该窗口存在于25℃至35℃的温度之间。另一窗口存在于60℃至80℃之间,示出了与较低温度的第一窗口相同的α/β相比率(phase ratios)。根据本发明的轴承保持架在落入所确定的(identified)温度范围内的温度下被用锡电镀,以产生出具有增强的耐久性和低摩擦性能的锡涂层。
已经描述了本发明的许多方面/实施方式。本发明不限于所描述的实施方式,而是可以在所附的专利权利要求的范围内变化。
Claims (20)
1.一种滚动轴承(10)的轴承组成部件,其中所述轴承组成部件的外表面(22)设置有延性镀层(25),
其特征在于,
-所述延性镀层包含至少97重量%锡,其中所述延性镀层(25)的锡包含α/β的相比率小于10%。
2.根据权利要求1所述的轴承组成部件,其特征在于,所述轴承组成部件为用于保持滚动轴承(10)的滚动元件(17)的保持架(20),所述保持架与所述滚动元件的外表面或轴承圈的表面滑动接触,所述滚动元件的外表面或所述轴承圈的表面设置有黑色氧化物层,使得所述保持架上的延性镀层与所述黑色氧化物层滑动接触。
3.根据权利要求2所述的轴承组成部件,其特征在于,所述黑色氧化物层的厚度在0.2至1.3μm之间。
4.根据权利要求1、2或3所述的轴承组成部件,其特征在于,所述延性镀层(25)的α/β相比率不多于3%。
5.根据权利要求1、2或3所述的轴承组成部件,其特征在于,所述延性镀层的厚度小于5μm。
6.根据权利要求1、2或3所述的轴承组成部件,其特征在于,保持架的延性镀层的厚度在1至100μm之间。
7.根据权利要求1、2或3所述的轴承组成部件,其特征在于,所述延性镀层(25)由纯锡构成。
8.根据权利要求1、2或3所述的轴承组成部件,其特征在于,所述延性镀层(25)还包含选自锑、铋、铟和银中的一种或多种元素。
9.根据权利要求8所述的轴承组成部件,其特征在于,所述延性镀层(25)由99.5-99.9重量%的锡和0.1-0.5重量%的锑、铋、铟和/或银构成。
10.根据权利要求1所述的轴承组成部件,其特征在于,所述轴承组成部件为滚动元件(17)、轴承圈(12;15)和/或用于保持滚动轴承(10)的滚动元件(17)的保持架(20)。
11.根据权利要求1所述的轴承组成部件,其特征在于,所述延性镀层(25)的锡包含α/β的相比率不多于4%的α相锡和β相锡。
12.根据权利要求3所述的轴承组成部件,其特征在于,所述黑色氧化物层的厚度在0.5至1μm之间。
13.根据权利要求5所述的轴承组成部件,其特征在于,所述延性镀层的厚度小于3μm。
14.根据权利要求6所述的轴承组成部件,其特征在于,保持架的延性镀层的厚度在5至30μm之间。
15.一种滚动轴承(10)的轴承组成部件,其中所述轴承组成部件的外表面(22)设置有延性镀层(25),
其特征在于,
-所述延性镀层包含至少97重量%的无电镀镍、电解镍或铜,所述轴承组成部件为用于保持滚动轴承(10)的滚动元件(17)的保持架(20),所述保持架与所述滚动元件的外表面或轴承圈的表面滑动接触,所述滚动元件的外表面或所述轴承圈的表面设置有黑色氧化物层,使得所述保持架上的延性镀层与所述黑色氧化物层滑动接触。
16.根据权利要求15所述的轴承组成部件,其特征在于,所述黑色氧化物层的厚度在0.2至1.3μm之间。
17.根据权利要求15或16所述的轴承组成部件,其特征在于,所述延性镀层的厚度小于5μm。
18.根据权利要求15所述的轴承组成部件,其特征在于,所述轴承组成部件为滚动元件(17)、轴承圈(12;15)和/或用于保持滚动轴承(10)的滚动元件(17)的保持架(20)。
19.根据权利要求16所述的轴承组成部件,其特征在于,所述黑色氧化物层的厚度在0.5至1μm之间。
20.根据权利要求17所述的轴承组成部件,其特征在于,所述延性镀层的厚度小于3μm。
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CN105088290B (zh) * | 2015-09-18 | 2017-04-26 | 哈尔滨工业大学 | 一种电沉积制备层状锡镀层的方法 |
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2017
- 2017-07-05 GB GB1710821.8A patent/GB2564149A/en not_active Withdrawn
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2018
- 2018-07-04 CN CN201810721966.2A patent/CN109210081B/zh active Active
- 2018-07-05 US US16/027,415 patent/US10995797B2/en active Active
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CN1524136A (zh) * | 2001-03-13 | 2004-08-25 | 沉积锡合金的电解质介质和沉积锡合金的方法 | |
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Also Published As
Publication number | Publication date |
---|---|
GB2564149A (en) | 2019-01-09 |
US20190024715A1 (en) | 2019-01-24 |
GB201710821D0 (en) | 2017-08-16 |
CN109210081A (zh) | 2019-01-15 |
US10995797B2 (en) | 2021-05-04 |
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