CN1185097C - 层状复合材料 - Google Patents

层状复合材料 Download PDF

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CN1185097C
CN1185097C CNB99106285XA CN99106285A CN1185097C CN 1185097 C CN1185097 C CN 1185097C CN B99106285X A CNB99106285X A CN B99106285XA CN 99106285 A CN99106285 A CN 99106285A CN 1185097 C CN1185097 C CN 1185097C
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A·阿达姆
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Federal Mogul Wiesbaden GmbH
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Abstract

本发明涉及层状复合材料，它对油润滑下的摩擦值没有负面影响，并且具有更高的耐磨损性与耐剥离性。在该层状复合材料中的滑移层内至少含有粉末状的聚芳族酰胺，其中的作为基体物料的PTFE含量或PTFE与ETFE的共同含量是55-90%(体积)，填料含量为9.5-44.5%(体积)，而聚芳族酰胺的含量为0.5-10%(体积)。

Description

层状复合材料
                         技术领域
本发明涉及一种层状复合制料，其中包含一层金属支承层，一层多孔的中间层，以及一层置于其上面的，由PTFE或由PTFE与其熔点高于260℃的其它氟热塑性塑料例如ETFE的结合物料所组成的，其中还嵌垫入填料物的滑移层。
                         背景技术
虽然这类材料在未经润滑的情况下使用也不成问题，但是本发明的层状复合材料应该特别适用于使用油的轴承，为此，对其来说，具有非常低的磨擦系数，同时又保持较高的耐磨损性与耐气蚀性是至关重要的。例如用于汽车制造业的减震缓冲器或者齿轮泵或液压发动机。由于所需求的摩擦系数，因此按已知知识的这种材料必须含有高含量的PTFE，因为所有已知的即使在其它性能上适合的其它塑料，都不能满足上述要求。
由于PTFE本身过于柔软，并具有较高的磨损系数，因此必须混入可抵制气蚀与磨损的物质，同时又不会明显提高其磨擦系数。
在应用领域最常用的轴承材料由钢背，多孔青铜层与含约80％(体积)PTFE及其余为二硫化钼或铅的塑料物质组成。该塑料物质被压入到青铜构架中，从而在其上构成致密薄层。然而如此构成的材料在极端条件下，例如在减震缓冲器中，由在轴承间隙中的高负载，高滑移速度与加速度，以及高流速会导致腐蚀与气蚀现象。由此，特别在更高的应力下会导致有限的使用寿命。
虽然我们可以制备在上述条件下几乎不磨损的又不具有气蚀性的材料。其中可用其它的热塑性材料，如PVDF或PEEK代替上述的PTFE。然而，在这种情况下，还将忍受在油润滑中磨擦的明显增加。
在许多文献中，推荐了PTFE基的组合物。然而，迄今只显示出比上述标准材料稍有改进，而且通常还具有增高的磨擦值，例如专利文献EP0183375提出使用氟化钙的情况或专利文献DE4227909 C2提出的使用聚酰亚胺。
由专利文献GB2272029A可知，由于采用的铅粉的比表面很高，因此其耐气蚀性能有所增高。但是滑移元件的用户对使用铅或铅的化合物是执批评态度的。因此，该问题并未能获得完全满意的解决。
尽管经常提到可以用聚(对亚苯基对苯二酰胺)作为自润滑的、以PTFE为基的轴承材料中的填料，但无例外地都是以纤维形式，例如在GB2291879A中所述。
专利文献WO 95/02772公开了一种加入到PTFE基体物质中的特殊原纤化的纤维。该纤维形式在PTFE基体中的均匀混合就会出现问题，并为此在生产中需用专门的特种设备。此外，该纤维也存在缺点，即含有进入肺部的成分，该成分疑为致癌性的。
上述纤维是作为非规则的编织物嵌垫在基体中，这样就会削减对否则将很软的PTFE基体的毁坏与腐蚀作用。
例如在专利文献WO 97/03299或GB 2177099A中可知，也不断提到芳酰胺纤维作为可置换成其它纤维并因此显然对得到一定性质不是必需的纤维状中性元件。
采用上述纤维的基本理由主要是机械参数--非常高的抗拉强度及E模数。这主要是由其在纤维纵向中的特别高的分子定向性，以及各个刚性分子链的坚固的物理平行连接决定的。
                         发明内容
本发明的任务是制备一种层状复合材料，其中不改变其制造流程，也不影响其在油滑润中的磨擦值，并且具有更高的耐磨损性与耐剥离性。
本发明的任务通过一种层状复合材料来解决，其中的滑移层至少含有一种粉末的聚芳族酰胺，其中的PTFE含量或PTFE与其它的氟热塑性塑料例如ETFE的共同含量为55-90％(体积)，其它填料的含量为9.5-44.5％(体积)，而聚芳族酰胺的含量为0.5-10％(体积)。
令人惊奇地是，添加这一较低量的聚芳族酰胺粉末可以大为减轻与相应的未添加该物质的组合物相比，由于腐蚀和气蚀现象导致的滑移层表面的破坏。与此相反，在未使用润滑剂的情况下，本发明的层状复合材料相同或改善得不明显。
                       具体实施方式
优选地是，PTFE或与其它氟热塑性塑料结合的PTFE的含量为65-80％(体积)，其它填料的含量为10-34％(体积)，聚芳族酰胺的含量为2-10％(体积)。
上述的聚芳族酰胺最好是聚(对亚苯基对苯二酰胺)(PPTA)和/或聚(对苯甲酰胺)(PBA)，它们具有高的分子刚性。
聚芳族酰胺粉末的粒径宜为100微米以下。该聚芳族酰胺的粒径最好是小于50微米。
上述的填料物质宜为铅，氧化铅，具有层状结构的金属硫化物，如硫化钼，金属氟化物，氮化硼，石墨，碳黑，焦炭，氧化铁，其中可以单独地或混合地使用。
除了上述提及的填料物质外，也可以使用由下列一个或多个物质，如硬质材料，颜料，纤维材料，固态润滑剂，热固性或高温热塑性塑料所组成的填料物质。
最好采用由具有层状结构的金属硫化物，六方晶系的氮化硼与三价的氧化铁所组成的填料组合物。
当选择Fe2O3与其它的填料物质一起结合使用时，其含量最好为1-6％(体积)。
当选用的基体物料除了PTFE外，还使用其它氟热塑性塑料时，该塑料可以是PFA，FEP，ETFE，或EPE，而且其含量至多是与PTFE含量相等。
上述制备的层状复合材料最好是应用于减震缓冲器中的滑移元件或用于其它的液压装置。
借助实例将可能的实施方案与不含有聚(对亚苯基对苯二酰胺)粉末或聚(对苯甲酰胺)粉末的相应物料进行比较。表1中给出了几个组合物。
表1
 实例  组合物，％(体积)
 1  PTFE 80MoS2 15PPTA5
 2  PTFE 80MoS2 20
 3  PTFE 80 石墨 15PPTA5
 4  PTFE 80 石墨 20
 5  PTFE 80BN 6,75MoS2 6,75Fe2O3 1,5PPTA5
 6  PTFE 80BN 9MoS2 9Fe2O3 2
 7  PTFE 80MoS2 15.PBA5
用已知方法制备上述物料：
--借助于非离子型润湿剂，使填料物与聚芳族酰胺粉末均匀地悬浮于水中，
--加入30％的PTFE分散液，并均匀混合，
--借助于硝酸铝溶液体使上述混合物聚凝，
--除去多余的水分，并最终搅拌至适于涂敷的物料浓度，
--将混合物轧制在涂于钢背上的多孔的青铜架构内，
--在380℃中烧结PTFE，
--轧制，使总体结构被热压紧缩。
把由上述物料制成的轴套经受减震缓冲器试验，并检测其磨损性。其中，涉及30个小时的试验过程，经受80毫米行程与频率0.5赫兹的斜坡道作用。此外，在滴油润滑条件下，在1000N负载与20毫米/秒的滑移速度下，测得该材料的摩擦值。
表2显示了上述测得的数据，其中实例1-6各代表含有或不含有聚芳族酰胺粉末的可比较的物料。实例7证实了，采用结构上类似于PPTA的聚合物，也可以达到本发明的目的。
表2
实例  磨损(微米)  摩擦值，(涂润油的)
1  15  0,028
2  42  0.019
3  33  0,040
4  80  0,034
5  7  0,025
6  24  0,016
7  18  0,026
上述试验结果表明：聚芳族酰胺粉末对耐磨损性具有明显的有利影响，并且证实了，其摩擦值只受到微小的影响。

Claims (12)

1、层状复合材料，其中含有一层金属支垫层，一层多孔的中间夹层，以及一层置于其上面的、由聚四氟乙烯或由聚四氟乙烯与乙烯四氟乙烯的结合物料基体组成的、其中还嵌垫入填料物的滑移层，其特征是该滑移层至少含有一种粉末状的聚芳族酰胺，其中的聚四氟乙烯含量或聚四氟乙烯与乙烯四氟乙烯的共同含量是55-90％体积，填料的含量是9.5-44.5％体积，而聚芳族酰胺的含量为0.5-10％体积。
2、根据权利要求1的层状复合材料，其特征是该聚四氟乙烯含量或聚四氟乙烯与乙烯四氟乙烯的共同含量为65-80％体积，填料含量为10-34％体积，而聚芳族酰胺含量为2-10％体积。
3、根据权利要求1的层状复合材料，其特征是该聚芳族酰胺是聚对亚苯基对苯二酰胺和/或聚对苯甲酰胺。
4、根据权利要求1-3中之一的层状复合材料，其特征是该聚芳族酰胺粉末的粒径小于100微米。
5、根据权利要求1-3中之一的层状复合材料，其特征是该聚芳族酰胺粉末的粒径小于50微米。
6、根据权利要求1-3中之一的层状复合材料，其特征是乙烯四氟乙烯的含量至多与聚四氟乙烯含量相等。
7、根据权利要求1-3中之一的层状复合材料，其特征是上述的填料可以是铅，氧化铅，具有层状结构的金属硫化物，金属氟化物，氮化硼，石墨，碳黑，焦炭，氧化铁，其中可单独地或多个混合地使用。
8、根据权利要求7的层状复合材料，其特征是上述的填料还可以是单个或多个的下列物质：硬质材料，颜料，纤维物质，固态润滑剂，热固性或高温热塑性的塑料。
9、根据权利要求7的层状复合材料，其特征是所述金属硫化物为硫化钼。
10、根据权利要求7的层状复合材料，其特征是含有1-6％体积的Fe2O3及至少一种其它的填料。
11、根据权利要求6的层状复合材料，其特征是该填料是一个由具有层状结构的金属硫化物，氮化硼与Fe2O3所组成的混合物。
12、根据权利要求1的层状复合材料的用途，其中可用于减震缓冲器内的滑移元件或其它的液压装置。
CNB99106285XA 1998-02-28 1999-02-26 层状复合材料 Expired - Fee Related CN1185097C (zh)

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KR19990072958A (ko) 1999-09-27
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EP0938970B1 (de) 2004-05-06
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ATE265928T1 (de) 2004-05-15
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CN1234334A (zh) 1999-11-10
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