CN102216633B - Ptfe系滑动材料、轴承和ptfe系滑动材料的制备方法 - Google Patents
Ptfe系滑动材料、轴承和ptfe系滑动材料的制备方法 Download PDFInfo
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Abstract
本发明涉及PTFE系滑动材料,所述材料是将PTFE含浸在背衬金属表面的多孔烧结层中并烧结而成的、是含浸纤维状PTFE以及根据情况进一步含浸固体润滑剂和耐磨损添加剂的任一种或者两者而成的PTFE系滑动材料,该材料可以提高在作为空调轴承使用时所要求的对偏磨损的耐磨损性。解决手段:在纤维状PTFE1的相互缠结结构中混有低聚物或聚合物的碳化物。
Description
技术领域
本发明涉及PTFE系滑动材料、轴承、特别是涉及车用冷气机压缩机用轴承、以及PTFE系滑动材料的制备方法。
背景技术
PTFE(聚四氟乙烯)是代表性的低摩擦的摩擦材料,具有如下特征。
(1)熔点:有人发表了以下的研究:熔点为固定的327℃或者具有幅度等。
(2)熔融粘度:熔融粘度在327℃下为1011-1012泊,非常高,市售PTFE即使在熔点以上也几乎不流动。因此烧结后容易残留孔洞。
(3)结晶性:被分类为结晶性树脂,分子量大。
(4)处理方法:将含有PPFE的微粒、表面活性剂和水等的PTFE分散液含浸在多孔烧结层中,进行烧结,作为轴承使用。
(5)组织:若对烧结前的PTFE进行剪切,则可以容易地进行纤维化(原纤化)。纤维组织在烧结后可见部分消失,但若提高精度进行观察,则可见残留。因此,如上述(4)那样进行处理的PTFE滑动材料呈现纤维状晶体的形态。
提高PTFE耐磨损性的技术大致分为通过添加剂和改良PTFE本身的组织来进行。
首先列举通过添加剂提高耐磨损性的以往的技术。
专利文献1:日本特开平1-108413号公报提出:在背衬金属的多孔层中含浸被覆芳族聚醚酮、PTFE和氟化金属。
专利文献2:日本特开平8-41484号公报中公开了添加下述成分 A、B、C的PTFE系滑动材料。成分A:磷酸盐、硫酸钡。成分B:硅酸镁、云母。成分C:Pb、Sn、Pb-Sn合金。根据实施例,将PTFE和石油系溶剂含浸在背衬金属(裏金back metal)钢板的多孔层中,在200℃下使溶剂蒸发,接着进行辊压,在370℃下加热10分钟,再次进行辊压。
作为固体润滑剂具有优异特性的Pb由于环境问题,其使用受到限制,因此专利文献3:日本特开2002-20568号公报中提出了在PTFE中添加硫酸钡、二硫化钼、石墨等作为其对策。该专利文献的实施例中,将硫酸钡等添加剂与PTFE树脂(通过乳液聚合得到的球状胶体疏水性树脂)混合,通过辊将混合物含浸在背衬金属的多孔层内,在370-420℃下烧结。
接着给出改良PTFE系材料的结构的以往的技术。
专利文献4:日本特开2007-09216号公报提出:PTFE系树脂的耐磨损性、耐烧结性在如压缩机用主轴承的不平衡载荷那样的严格条件下不能令人满意,作为其对策,通过进行二次烧结,使边界层(鏡界層)消失,可强化PTFE。
作为不属于上述两种分类的任何一种的方法,专利文献5:日本特开2008-69196号公报中记载:少量含有全氟辛酸作为制备时的助剂、将用丙烯酸树脂系分散剂分散的PTFE分散液含浸在背衬金属的多孔层内,在380-430℃下烧结的方法。另外,丙烯酸树脂分散剂中所含的羧基对轴承性能产生不良影响。不过,在PTFE的烧结温度下,丙烯酸树脂完全分解需要数小时-数十小时,所以完全分解丙烯酸树脂是不可能实施的,因此,将最终烧结品中丙烯酸树脂的残留量规定为相对于PTFE为0.5%以下。
车用冷气机压缩机用主轴承以及推力滚针轴承(ニ一ドルスラスト軸受)中大多采用如下得到的PTFE系滑动材料:在背衬金属上,将氟树脂与Pb、Zn、硫酸钡、石墨等固体润滑材料的混合物含浸在多孔铜合金烧结层中并干燥、烧结。
现有技术文献
专利文献
专利文献1:日本特开平1-108413号公报
专利文献2:日本特开平8-41484号公报
专利文献3:日本特开2002-20568号公报
专利文献4:日本特开2007-9216号公报
专利文献5:日本特开2008-69196号公报
发明内容
发明所需解决的课题
从确保对PTFE系滑动材料特别要求的耐磨损性的角度考虑,通常的提高耐磨损性的方法有:除PTFE树脂之外还混合聚醚醚酮等硬质树脂或耐磨损添加材料等的方法,但这些方法对汽车压缩机用轴承而言无法保障足够的性能。
使用本发明的PTFE系滑动材料的车用冷气机压缩机用轴承结构是常规结构。所述轴承设计成结构上施加不平衡载荷(片荷重unbalanced load),是含浸PTFE系轴承材料的多孔铜合金烧结层承受局部载荷、在PTFE系树脂层上滑动的结构。PTFE系轴承材料利用PTFE的转移带来的降低摩擦的效果。在压缩机的使用环境下,形成边界润滑,PTFE的转移效果弱,另外,PTFE与硬质树脂或耐磨损性添加材料的界面的结合力弱,因此无法获得耐磨损性。因此,必须通过多孔烧结层上树脂皮膜的强化来提高滑动性能。
专利文献4所提出的二次烧结法可以满足上述要求,但是有导致成本增加的问题。
因此,本发明的目的在于:对施加了不平衡载荷、容易发生偏磨损的部件中所使用的PTFE系树脂的特性进行改良。特别是本发明的目的在于:对用于车用冷气机的压缩机主轴承的PTFE系滑动材料的 性能进行改良,所述主轴承因结构上承受不平衡载荷,以磨损部分为起点,摩擦增大,从而形成导致扭矩增加的问题,如果这样持续使用下去则导致烧损。
解决课题的手段
本发明人对于PTFE的强化材料进行了深入研究,发现:若在尽量阻断氧的状态下、在PTFE烧结温度附近,从表面活性剂等的有机材料中除去碳以外的氧、氢、氮等,使表面活性剂等碳化,则碳化的物质与PTFE纤维相互缠结,且与在PTFE分散液中添加碳化物或石墨颗粒并烧结所得的材料相比,碳化物非常微细地分散,因此PTFE被膜得到强化,结果耐磨损性提高。这也是由于,本发明中所使用的低聚物或聚合物具有亲水基团,均匀地分散于PTFE分散液中。图1是示意性地表示通过扫描式电子显微镜观察基于上述认识得到的试验材料的结果的图,图中,1为纤维状PTFE,由于PTFE分散液的混合而相互缠结形成带状,2是具有亲水基团的低聚物或聚合物碳化后得到的物质(以下称为“碳化物”)。即,若着眼于纤维状PTFE1来观察碳化物2,则1在其弯曲部夹持2,或者2存在于1的附近。着眼于碳化物2来观察纤维状PTFE,则1以包围2的方式存在。若观察全体,则在相互缠结的PTFE纤维1之间混有碳化物2。
本发明的PTFE系滑动材料的特征在于:在背衬金属表面的多孔烧结层中含浸PTFE并且烧结而成、并且根据情况进一步含浸固体润滑剂和耐磨损添加剂的任一种或两者而成的PTFE系滑动材料中,上述纤维状PTFE的相互缠结结构中混有将低聚物或聚合物碳化所得的碳,本发明的PTFE系滑动材料的制备方法是将含有具亲水基团的低聚物和聚合物的1种或2种而成的PTFE分散液进行烧结的制备方法,其特征在于:在非氧化性气氛中进行烧结,由此可以使上述具亲水基团的低聚物和聚合物的1种或2种碳化,作为强化成分残留。以下详细说明本发明。
如上所述,PTFE分散液是以PTFE微粒和活性剂(表面活性剂)为基本成分,在聚合物固形成分较多时添加,根据情况向其中添加硫酸钡、石墨、铁磷化合物等。将PTFE分散液含浸在背衬金属表面的多孔层中,在通常的PTFE的熔点附近烧结,在该阶段,将水或表面活性剂蒸发。根据本发明人的试验可知,通过控制烧结条件,在烧结中,存在于PTFE分散液中的聚合物固形成分以及表面活性剂的氧、氢、氮等碳以外的物质被除去,实质上只有碳,即,被碳化。该氧、氢等的除去处理中,含浸PTFE层的表面中,挥发成分呈焦油状,若进一步持续烧结,则焦油状物质被除去,烧结材料全体中,表面活性剂等实质上形成碳。这样形成的物质是碳化物。
对本发明的碳化物进行说明。通过X射线衍射分析,其结构并不形成石墨等的晶体结构,是无定形结构。碳化物是在低聚物分子中的挥发成分除去后,碳之间形成聚集微粒,所述微粒不是被覆PTFE纤维的形态,而是夹杂在更粗的PTFE纤维的相互缠结结构之间,并且附着或接近于纤维的表面,即,由于是混于上述相互缠结结构中,因此碳化物颗粒使PTFE纤维难以移动,得到强化,并且PTFE纤维和碳化微粒分别与对磨材料(相手材counterpart material)滑动。
本发明中使用的低聚物优选具有非离子系亲水基团的表面活性剂,具体是:脂肪酸系,例如聚氧乙烯脂肪酸酯、聚氧乙烯失水山梨醇脂肪酸酯、失水山梨醇脂肪酸酯、蔗糖脂肪酸酯、脂肪酸烷醇酰胺等;高级醇系,聚氧乙烯烷基醚、烷基糖苷等;烷基酚系,例如聚氧乙烯烷基苯基醚等。进一步优选的是高级醇系、烷基酚系。本发明中,两性表面活性剂也可以使用烷基胺氧化物。
聚合物优选使用聚乙烯醇、聚丙烯酸等聚合物。优选这些低聚物、聚合物为水溶性的,溶解于PTFE分散液中的水,为不损害分散稳定性的物质。
即使只使市售的聚合物分散液中所含的表面活性剂碳化也具有效果,可以将上述表面活性剂追加添加到市售的聚合物分散液中,也可 以在通常的烧结时间内同时进行烧结和碳化物的形成。若事后添加的表面活性剂量多,则碳化物的量增多,并且提高皮膜强度,因此优选。不过,若添加过多的亲水性有机物,则PTFE分散液的粘度提高,在多孔烧结层中的含浸性变差,因此必须调节添加量。
上述以外的背衬金属、多孔烧结层、含浸层的厚度等是公知的,可以适当采用专利文献4(段落号0007)中说明的材料。
本发明的PTFE系滑动材料可以进一步含有固体润滑剂和耐磨损添加剂的任一种或两者,所述固体润滑剂优选为选自MoS2、石墨、BaSO4、Zn和Pb的至少一种,所述耐磨损添加剂优选为选自Al2O3、BN、铁磷系化合物、SiO2和芳族聚酯的至少一种。
并且进一步优选背衬金属为钢板、且多孔烧结层为铜合金。
本发明的PTFE系滑动材料可优选用于汽车或家用压缩机的主轴承。
本发明的PTFE系滑动材料可以防止不平衡载荷导致的偏磨损,其理由可以认为起因于:碳化物的(1)分散均匀性、(2)微粒形态、(3)相互缠结结构中的分散、(4)碳化物导致的强化。
即,本发明的表面活性剂的碳化所形成的碳化物是在分散液中均匀分散的液状表面活性剂的几乎所有成分挥发而残留的物质,含浸后仍可保持微细分散形态。并且,碳化物分散于PTFE纤维的相互缠结结构中,使该纤维在滑动时难以移动,从而使材料整体强化。因此,即使在无法期待PTFE的转移的状况下,仍可发挥足够的耐磨损性。与此相对,硫酸钡和石墨由于其物性而具有使耐磨损性提高的作用,但是由于是粉末状物体的添加混合,因此不具有使PTFE均匀分散的功能,因此缺乏起因于该性质的全部上述(1)-(4)。
接着,平均15μm左右的粉末芳族聚酯形成全体与PTFE混合的状态,因此无法实现(2)、(3)、(4)。与此相对,本发明的碳化物使PTFE纤维缠结存在,因此不仅不妨碍PTFE与对磨材料接触的接触状态,而且在滑动时使PTFE纤维难以移动。
以下通过实施例更具体地说明本发明。
实施发明的最佳方式
实施例
在厚度0.85mm的低碳钢(S15C)的背衬金属上层合厚度0.3mm青铜烧结层。使用以下材料作为滑动材料的成分。
PTFE(大金工业制备:商品名ポリフロンデイスパ一ジヨンD1E,相对于100重量份掺混3重量份非离子系表面活性剂(日油化学产品,非离子HS-204.5)作为碳化强化材料)。需说明的是,PTFE分散液不会分离成水和其它成分。另外,表中的比较例1是不添加上述非离子系表面活性剂、使烧结气氛为空气、不进行碳化强化的实例。
MoS2:平均粒径1.0μm(住矿润滑剂社制备:商品名PA粉末)
石墨:平均粒径1.0μm(日本石墨社制备:商品名CSSP)
BaSO4:平均粒径10μm(堺化学社制备:商品名BMH-100)
Al2O3:平均粒径0.5μm(和光纯药社制备:商品名M60G-B)
BN:平均粒径1μm(电气化学工业社制备:商品名SP-1)
将上述滑动材料成分掺混并混合形成表1的组成,然后平稳地进行混炼,使PTFE不聚集,将使PTFE纤维化得到的浆含浸在于背衬金属上烧结铜合金粉末得到的多孔层内,在约100℃下干燥,然后,对于实施例,在氮气气氛中进行380℃、5分钟的烧结。通过显微镜观察实施例的样品时,如图1所示的那样,在纤维状PTFE的相互缠结结构中混有碳化物,另一方面,对于比较例,只观察到纤维状PTFE的相互缠结结构。由该结果可知,原来在PTFE分散液中添加的表面活性剂完全分解并挥发。
接着如图2所示,配置薄板试验材料3和圆筒状对磨材料4,进行磨损量的测定。试验条件如下。
速度:0.3m/秒
载荷:5MPa
试验时间:3小时
温度:室温
对磨材料:JIS SCM415
润滑:无
试验结果如表1所示。
[表1]
可知本发明的实施例与比较例相比,耐磨损性优异。
产业实用性
如以上说明,本发明的PTFE系滑动材料特别适合作为承受不平衡载荷的车用冷气机用压缩机用轴承。
附图简述
[图1]是表示本发明的PTFE系滑动材料的组织的概念图。
[图2]是表示磨损试验装置的主要部分的图。
符号的说明
1纤维状PTFE
2碳化物
3试验材料
4对磨材料
Claims (1)
1.PTFE系滑动材料,该材料是在背衬金属表面的多孔烧结层中在烧结前含浸PTFE而成的PTFE系滑动材料,其中上述烧结PTFE的纤维状相互缠结结构中混有具亲水基团的低聚物和聚合物的1种或2种的碳化物。
2. PTFE系滑动材料,该材料是在背衬金属表面的多孔烧结层中在烧结前含浸PTFE、以及进一步含浸固体润滑剂和耐磨损添加剂的任一种或者两者而成的PTFE系滑动材料,其中上述烧结PTFE的纤维状相互缠结结构中混有具亲水基团的低聚物和聚合物的1种或2种的碳化物。
3.权利要求2的PTFE系滑动材料,其中,上述固体润滑剂是选自MoS2、石墨、BaSO4、Zn和Pb的至少一种。
4.权利要求2的PTFE系滑动材料,其中,上述耐磨损添加剂是选自Al2O3、BN、铁磷系化合物、SiO2和芳族聚酯的至少一种。
5.权利要求1或2所述的PTFE系滑动材料,其中,上述聚合物是聚乙烯醇或聚丙烯酸。
6.权利要求1或2的PTFE系滑动材料,其中,上述低聚物是非离子系表面活性剂。
7.权利要求1或2的PTFE系滑动材料,其中,背衬金属是钢板,且上述多孔烧结层是铜合金。
8.汽车或家用压缩机用轴承,该轴承中使用了权利要求1-7中任一项的PTFE系滑动材料。
9.PTFE系滑动材料的制备方法,该方法是将含有具亲水基团的低聚物和聚合物的1种或2种而成的PTFE分散液进行烧结,其特征在于:通过使上述烧结气氛为非氧化性气氛,使上述具亲水基团的低聚物和聚合物的1种或2种碳化,作为强化成分残留。
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CN105713327A (zh) * | 2016-04-29 | 2016-06-29 | 杭州电子科技大学 | 一种海水液压马达配对副材料及制备方法 |
CN105713327B (zh) * | 2016-04-29 | 2018-03-02 | 杭州电子科技大学 | 一种海水液压马达配对副材料及制备方法 |
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JP5432173B2 (ja) | 2014-03-05 |
US20110097593A1 (en) | 2011-04-28 |
EP2341258A4 (en) | 2012-10-03 |
WO2010050444A9 (ja) | 2010-09-02 |
US8962143B2 (en) | 2015-02-24 |
CN102216633A (zh) | 2011-10-12 |
EP2341258A1 (en) | 2011-07-06 |
WO2010050444A1 (ja) | 2010-05-06 |
KR20100124840A (ko) | 2010-11-29 |
JPWO2010050444A1 (ja) | 2012-03-29 |
KR101261110B1 (ko) | 2013-05-06 |
EP2341258B1 (en) | 2015-12-23 |
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