CN102918286A - 滑动部件 - Google Patents
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Abstract
本发明提供在基材上设置由分散有固体润滑剂的树脂类涂料形成且具有滑动表面的被覆层而成的滑动部件,其中,提高固体润滑剂的(001)晶面的取向率。所述滑动部件是被覆层的平均厚度为3μm以下、固体润滑剂粒子通过激光衍射法测定的平均粒径为2μm以上、并且固体润滑剂以90%以上的相对C轴强度比分散的滑动部件。
Description
技术领域
本发明涉及滑动部件,更具体地说,涉及一种滑动部件,其中,从提高由树脂类涂料(coating)形成的被覆层内的固体润滑剂的取向率的观点出发,特别规定它的膜厚、并且特别规定固体润滑剂的粒径测定法以及平均粒径。
背景技术
对于在铝系轴承合金的表面上施加含有固体润滑剂的树脂类涂料,以前的专利文献有本申请人之一提出的专利文献1:日本特开平4-83914号公报。在该专利文献中说明了“用喷雾在内衬上涂布适当的稀释剂、稀释的固体润滑剂等和聚酰亚胺树脂,在150~300℃下进行干燥·煅烧。除了喷雾法之外可以采用转鼓(tumbling)法、浸渍法、刷涂等方法。涂层的厚度优选为1~25μm。”。对固体润滑剂的粒径没有叙述。
在代表性的固体润滑剂中,键合为网状的原子构成(001)面,具有该(001)面平行地堆叠的结晶结构,表现出由于沿该结晶面平行解理而导致的低摩擦特性。利用该特性的滑动部件大致区分为:直接在基材上被覆固体润滑剂的滑动部件;和将固体润滑剂分散于树脂粘合剂中形成被覆层并在基材上设置该被覆层的滑动部件。
作为前者有专利文献2:日本特开平2007-139149号公报、专利文献3:日本特开2007-270205号公报等,固体润滑剂的板状结晶粒子的(001)面的取向指数能够得到90%以上这样高的值。然而,就该种滑动部件而言,由于在基材上仅接合有固体润滑剂,密合性低,磨损大,并且,如果仅由固体润滑剂成膜,则固体润滑剂的成膜成品率也降低。需说明的是,专利文献1以及2的详细说明中没有记载固体润滑剂的粒径。
另一方面,关于后者的树脂类涂料,本申请人在专利文献4:日本特开2008-95725号公报中提出一种滑动部件,其具有固体润滑剂的相对C轴强度比为85%以上的被覆层。相对C轴强度比用下式进行定义,进一步说明如下。
所谓相对C轴强度比为,利用X射线衍射,(002)、(004)、(008)面的累积强度相对于(002)、(004)、(100)、(101)、(102)、(103)、(105)、(110)、(008)面的累积强度的百分率。
上述九个面中,(002)、(004)、(008)面相当于解理面。对其他的(004)、(100)、(101)、(102)、(103)、(105)、(110)、(008)面也能够同样地求出衍射角度2θ。能够得到来自上述九个面以外的衍射峰,由于峰强度极低,因此在相对C轴强度比的计算中,可以忽视。即使达成“垂直”取向,由于来自解理面以外的六个面的衍射必定存在,因此取向性能指数不能达到100%。为了接近“垂直”取向,后面叙述的成膜方法的条件调整是必要的,然而目前认为90%强为上限。
然而,专利文献4所设想的90%以上的相对C轴强度比难以达成的状况如下所述。
首先,若着眼于与固体润滑剂的取向有关的成膜状况,则因为固体润滑剂源于上述结晶结构而具有在与粒子的面平行的方向上容易解理的性质,所以在原料粉碎过程中成为薄片状。在将该薄片状固体润滑剂和树脂粘合剂混炼的情况下,可以进行喷雾、刷涂、辊涂、浸渍(dipping)等。涂层的厚度为2~10μm,优选为2~8μm,采用降低涂料的粘度的方法。对固体润滑剂的粒径没有特别地进行说明。
在这样的方法中,取向性提高的阻碍因素主要是粘度高的涂料、固体润滑剂粒子彼此间的接触、急速的溶剂蒸发。即,认识到若从高取向性的观点出发调整这些因素,则树脂类涂料不能实际地成膜。
专利文献5:日本特开2002-339083号公报涉及例如投射在活塞等表面上的、含有约95重量%以上的平均粒径为约1μm~约20μm的二硫化钼而成的投射材料,赋予低摩擦性。引用与其粒径测定法相关联的说明书的记载。
“需说明的是,本发明的二硫化钼(MoS2)的粒径是根据各二硫化钼(MoS2)粒子的容积设想同容积的球,将该球的直径作为粒径进行换算而得到的。即,测量粒子的个数和体积,根据这些,能够将各粒子假定为球形而进行计算,实际上本发明人使用利用电阻法的测定机器(コールターOカウンター・マルチタイザーⅢ型,Beckman Coulter公司制(口管100μm)),实测粒子的个数与体积来测定粒径。就粒径的调整而言,通过变更分级机的设定值(分级粒径),能够调整为期望的平均粒径范围。另外,所谓平均粒径是指某种处理中使用的二硫化钼投射用材料中所含的二硫化钼粒子的粒径的平均值。”
专利文献6:欧洲专利公开公报1239914A1(同族专利日本特开2002-61652号公报)说明:使用平均粒径为15μm以下、特别优选为0.2~10μm的二硫化钼、石墨、氮化硼、二硫化钨,在制备溶解、分散有这些成分的涂布液时,可以使用适量的有机溶剂(稀释剂)。进一步说明如下。“有机溶剂调整粘度,使混合变容易,只要可以溶解使用的热固化性树脂则可没有特别限制地使用。例如热固化性树脂如果是聚酰胺酰亚胺树脂,则相对于上述各成分的合计量100质量份,可以使用100~300质量份的二甲苯、N-甲基-2-吡咯烷酮、甲苯等。”进一步,对涂层的形成方法说明了:“热水洗涤后热风干燥,通过喷雾在内衬上涂布用适当的稀释剂稀释了的上述涂布液,在150~300℃下进行干燥·烧结。成膜后的表面粗糙度粗的时候通过抛光等进行平滑化处理。除了喷雾法之外,可以利用辊转印、转鼓法、浸渍法、刷涂法、印刷法等方法形成树脂涂层。树脂涂层的厚度优选为1~50μm”。专利文献6记载的固体润滑剂的尺寸测定法没有考虑它的形状。
专利文献7:美国专利公开公报US2004/0062860A1(同族专利日本特开2004-1139734号公报)记载了通过空气喷涂使基础树脂和二硫化钼等固体润滑剂在轴承内面形成涂层。但是,对固体润滑剂粒子的尺寸没有记载。
现有技术文献
专利文献
专利文献1:日本特开平4-83914号公报
专利文献2:日本特开2007-139139号公报
专利文献3:日本特开2007-270205号公报
专利文献4:日本特开2008-95725号公报
专利文献5:日本特开2002-339083号公报
专利文献6:欧洲专利公开公报1239914A1
专利文献7:美国专利公开公报US2004/0062860A1。
发明内容
发明所要解决的课题
一直以来,因为没有提供相对C轴强度比超过90%的、使固体润滑剂取向的树脂类涂料,所以滑动部件的性能不充分。因此,本发明目的在于:通过使固体润滑剂的结晶取向与滑动方向尽可能平行地取向,提高该固体润滑剂结晶的取向度,从而使滑动阻力降低,结果能够降低摩擦系数、提高耐咬粘性。
解决课题的方法
本发明的滑动部件由在基材上设置被覆层而成,所述被覆层由分散有固体润滑剂的树脂类涂料形成且具有滑动表面,所述滑动部件的特征在于,所述被覆层的平均厚度为3μm以下,所述固体润滑剂的粒子通过激光衍射法测定的平均粒径为2μm以上,并且所述固体润滑剂以90%以上的相对C轴强度比分散于所述被覆层整体中。
以下详细说明本发明。
在本发明中,基材为铝系轴承合金或者铜系轴承合金或者树脂,其厚度、组成等在后详细叙述,是公知的。另外,本发明中使用的固体润滑剂优选为MoS2、WS2、石墨以及h-BN等。
若对固体润滑剂的结晶结构进一步详细地叙述,则用于本滑动部件的固体润滑剂具有键合为网状的原子层叠而成的层状结构。MoS2的结晶结构如图1所示。在这些固体润滑剂中,层间的滑动中表现出非常低的摩擦。
发明效果
本发明中的相对C轴强度比与段落号0004中引用的专利文献4所记载的相同。本发明中的相对C轴强度比为90%以上,最大达到99%。相对C轴强度比,尽管由于在专利文献4中所述的相同理由而未达到理论值100%,但认为以99%的(001)面取向指数取向的固体润滑剂几乎完全地垂直取向。
附图说明
图1是示出MoS2的结晶结构的图。
图2是示出石墨的结晶结构的图。
图3是示出h-BN的结晶结构的图。
图4是示出被覆层平均厚度与相对C轴强度比(%)的关系的图表。
图5是示出固体润滑剂平均粒径与相对C轴强度比(%)的关系的图表。
图6是示出被覆层平均厚度对相对C轴强度比(%)的影响的示意图以及图表。
图7是示出相对C轴强度比(%)与咬粘面压力的关系的图表。
符号说明
1固体润滑剂
2基材。
具体实施方式
在图1所示的MoS2中,采取将网状Mo(B)的两面用网状S(A) 夹持的结构。因而,以在两个网状S(A)之间夹持一个Mo(B)的状态构成MoS2的一个单元(A-B-A)。这里,将网状S(A)中邻接的原子相连的方向之一规定为a轴,另外,将从网状S(A)中的某个原子到构成同一MoS2的一个单元的另一个网状S(A)中具有最短距离的某个原子相连的方向规定为c轴。c轴的面方向为(001),这相当于上述A-B-A结构,利用X射线衍射检测为(001)的2的整数倍的(002)、(004)、(008)。
另外,在根据JCPDS S卡片的标准样品β- MoS2
No.37-1492中,上述(001)面取向指数为45.8%弱。
另一方面,图2所示的石墨中,a=1.42Å、c=3.35Å,为上述的A-B-A结构中B缺失的结构。与MoS2类似的标准样品 石墨No.23-0064中,(001)面取向指数为63.3%弱。
另外,h-BN的情况如图3所示,三个B原子与三个N原子交替排列形成六角形排列,该共用一边(长度a=1.47Å)的六角形排列二维地重复形成网状。并且在c轴方向隔着间隔c=3.3Å重复网状结构。标准样品h-BN No.34-0421中,(001)面取向指数为74.3%弱。石墨、h-BN在标准样品中均为比MoS2高的(001)面取向指数,认为它们由于提高(001)面取向指数,因此滑动特性提高效果小。
因为滑动部件的树脂类涂层在滑动面与匹配(相手,opposite)材料接触,所以在滑动面的相对C轴强度比必须为90%以上。但是,因为树脂类涂层磨损至作为基底的基材露出,所以整个厚度中相对C轴强度比必须为90%以上。使用CuKα射线的通常的X射线衍射装置的输出功率为40kV-100mA左右,因为在该程度的输出功率下,X射线到达基材Al合金、Cu合金,所以如果除去该峰,就能够测定影响滑动特性的固体润滑剂的取向。
本发明的滑动部件中的被覆层的平均厚度必须为3μm以下。图4是示出被覆层的平均厚度与相对C轴强度比的关系的图表,可知被覆层的平均厚度若为3μm以下,则相对C轴强度比为90%以上。需说明的是,以下说明的MoS2的平均粒径在图4中为1~6μm。
本发明的分散于树脂类涂料中的平板状固体润滑剂的粒子由于结晶结构而导致形成薄片状。因此,固体润滑剂粒子的平均粒径在物理上可能比被覆层的平均厚度大。另外,测定平均粒径的方法有激光衍射法或费尔舍(Fischer)法,本发明人调查这些平均粒径测定法与滑动特性的关系,利用激光衍射法,对粒子照射波长固定的激光,根据其散射光强度的图案测定粒径与分布,得到的平均粒径(以下简称为“平均粒径”)作为尺寸的数值使用时,得到如图5所示的显著的相关关系。图5是示出固体润滑剂的平均粒径与相对C轴强度比的关系的图表,可知平均粒径若为2μm以上,则相对C轴强度比为90%以上。因此,固体润滑剂的平均粒径必须为2μm以上。需要说明的是,被覆层的平均厚度为1~6μm。
如上所述,若控制被覆层平均厚度以及固体润滑剂的平均粒径这两个因素,则在成膜中,固体润滑剂粒子相对于基材,倾斜自由度即取向性降低,能够得到高的相对C轴强度比。图6中,如下侧的四个示意图所示,图解使相同平均粒径的固体润滑剂粒子1分散于平均厚度不同的涂层中的比较试验。2为基材。根据图6的下半部分的四个图可知,涂层的厚度本身为使固体润滑剂粒子1倾斜的要素。进一步在比例(横轴)与相对C轴强度比(纵轴)的图表中将实验数据整理并示出。
接着,使树脂类涂料成膜时,首先将优选10~90重量%、优选为30~70重量%的薄板状固体润滑剂与余量树脂混合,加入稀释剂,制备涂料。接着,将涂料在轴承合金表面上成膜的时候,通过移印、丝网印刷、空气喷涂、无气喷涂、静电涂布、转鼓法、挤压法、辊涂法等中的任意一种进行,并且在成膜后进行干燥。涂层的表面粗糙度优选为5μmRzJIS以下。
对于滑动轴承中使用的轴承合金,随着上述涂层的相容的进展,轴承合金在露出时与匹配轴之间滑动,因此要求轴承特性。
轴承合金的组成没有特别的限定,对于铝合金,可以优选使用含有如下元素的合金:10质量%以下的Cr、Si、Mn、Sb、Sr、Fe、Ni、Mo、Ti、W、Zr、V、Cu、Mg、Zn等中的一种以上,与20质量%以下的Sn、Pb、In、Tl、Bi等中的一种以上。前一组的元素主要赋予强度以及耐磨损性,后一组的元素主要赋予相容性(なじみ性, compatibility),根据各添加元素的种类与量发挥轴承特性。以上说明了轴承合金的例子,不过,对于将AC8A、AC9B等高Si-Al合金形成的活塞裙(skirt)部作为基底,为了提高该基底的耐磨损性,可以使用本发明的涂层。
铜合金的组成没有特别的限定,可以优选使用含有如下元素的合金:25质量%以下的Pb、Bi中的一种或者两种以上;10质量%以下的Sn;2质量%以下的P、Ag、In、Ni、Al等。在这些元素中,Pb、Bi为软质金属,发挥相容性,Sn为青铜的基本成分,发挥强度和耐磨损性,其他成分辅助性地提高特性。其中,P对脱氧、促进烧结、强化等是有效的,Ag在与润滑油或者铜中的杂质S的反应中形成对提高滑动特性有效的化合物,In提高耐腐蚀性和润滑油的润湿性,Ni、Al具有强化铜等的作用。
轴承合金一般厚度为约0.3μm。加强轴承合金的里衬通常厚度为约1.2mm。
作为树脂粘合剂可以使用聚酰亚胺树脂、聚酰胺酰亚胺树脂、环氧树脂、聚酰亚胺地巴唑(polyimide
bendazole)树脂。
接着,通过实施例进一步详细地说明本发明。
实施例1
供试的滑动部件按以下的方法进行制备。
在压接于里衬钢(SPCC)的铝系轴承合金(Al-11.5%Sn-1.8%Pb-1.0%Cu-3.0%Si-0.3%Cr,厚度1.5mm的半环形状原料)上利用空气喷涂涂布涂层,在180℃下进行一小时的煅烧。作为固体润滑剂使用粒径如下表中所示的MoS2,设为40重量% MoS2、余量为含有机稀释剂(NMP)的聚酰胺酰亚胺树脂的组成。另外,在同一条件下也在铝系轴承合金平板上进行涂布,作为(001)面取向指数测定用供试材料。
将涂布干燥后的涂层的平均厚度作为“膜厚”在下表中示出。另外,耐咬粘性按以下方法进行评价,结果示于图7以及表1中。
耐咬粘性试验方法
试验机:静负荷轴承评价试验机
匹配轴:锻造轴
滑动速度(匹配轴的旋转圆周速度):20m/s
润滑油:引擎油OW-20
润滑方法:强制给油
油温:60℃
施加负荷的方法:以4.3Mpa/3分钟的比例阶段性地增加。
表1
No. | MoS2粒径(μm) | 膜厚(μm) | 咬粘面压力(MPa) | 相对C轴强度比(%) | 备注 |
1 | 5.2 | 1 | 92.5 | 98 | 实施例 |
2 | 5.2 | 1.5 | 86.7 | 95.4 | 实施例 |
3 | 5.2 | 1.5 | 86.7 | 96 | 实施例 |
4 | 1.7 | 6 | 69.3 | 85.9 | 比较例 |
5 | 1.7 | 6 | 69.3 | 88.6 | 比较例 |
6 | 1.7 | 6 | 69.3 | 88.3 | 比较例 |
7 | 1.7 | 6 | 69.3 | 87.8 | 比较例 |
8 | 1.7 | 6 | 63.5 | 71.5 | 比较例 |
9 | 1.7 | 7 | 54 | 71.3 | 比较例 |
10 | 1.7 | 7 | 54 | 68.2 | 比较例 |
11 | 1.7 | 7 | 54 | 69 | 比较例 |
12 | 1.7 | 7 | 54 | 72.7 | 比较例 |
由图7以及表1可知:相对C轴强度比如果为90%以上,则耐咬粘性极其良好。
产业上的可利用性
如以上所说明,本发明涉及的滑动部件由于滑动特性优异,因此能够用于轴承内面涂布、活塞裙部涂布等。
Claims (3)
1.一种滑动部件,其由在基材上设置被覆层而成,所述被覆层由分散有固体润滑剂的树脂类涂料形成且具有滑动表面,所述滑动部件的特征在于,所述被覆层的平均厚度为3μm以下,所述固体润滑剂的粒子通过激光衍射法测定的平均粒径为2μm以上,并且所述固体润滑剂以90%以上的相对C轴强度比分散于所述被覆层整体中。
2.如权利要求1所述的滑动部件,其中,所述固体润滑剂为选自MoS2、WS2、石墨以及h-BN中的至少一种。
3.如权利要求1或2所述的滑动部件,其中,所述被覆层中的固体润滑剂的比例为10~90重量%。
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US9029302B2 (en) | 2015-05-12 |
JP5391327B2 (ja) | 2014-01-15 |
CN102918286B (zh) | 2016-04-06 |
WO2011111668A1 (ja) | 2011-09-15 |
US20120270761A1 (en) | 2012-10-25 |
HUE028350T2 (en) | 2016-12-28 |
AU2011225590B2 (en) | 2014-11-20 |
EP2546535B1 (en) | 2015-10-21 |
JPWO2011111668A1 (ja) | 2013-06-27 |
EP2546535A1 (en) | 2013-01-16 |
AU2011225590A1 (en) | 2012-11-01 |
EP2546535A4 (en) | 2013-09-18 |
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