CN1318780C - 链条传动系统 - Google Patents
链条传动系统 Download PDFInfo
- Publication number
- CN1318780C CN1318780C CNB2004100574854A CN200410057485A CN1318780C CN 1318780 C CN1318780 C CN 1318780C CN B2004100574854 A CNB2004100574854 A CN B2004100574854A CN 200410057485 A CN200410057485 A CN 200410057485A CN 1318780 C CN1318780 C CN 1318780C
- Authority
- CN
- China
- Prior art keywords
- chain
- slidingsurface
- transmission system
- carbon coating
- guide rail
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
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- -1 fatty acid ester Chemical class 0.000 claims description 117
- 239000011248 coating agent Substances 0.000 claims description 59
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 49
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- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims description 13
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- 229910052708 sodium Inorganic materials 0.000 description 4
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- 206010044565 Tremor Diseases 0.000 description 3
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 3
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
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- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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Abstract
一种链条传动系统,其包括主动链轮、从动链轮和环绕在主动链轮和从动链轮上的链条。所述链条和链轮具有在润滑油存在下可相对滑动的各自滑动表面,链条的任何相邻链条部件都具有在润滑油存在下可相对滑动的各自滑动表面。所述链条和链轮之间的至少一个滑动表面和任何相邻链条部件之间的至少一个滑动表面均在其基底部分上形成有类金刚石碳涂层。各类金刚石碳涂层中的氢含量都是10原子%或更低。所述润滑油含有至少一种选自无灰脂肪酸酯摩擦改进剂和无灰脂族胺摩擦改进剂的摩擦改进剂。
Description
技术领域
本发明涉及链条传动系统,其具有以低摩擦阻力和低磨损量相对滑动的零件,从而提高耐久性,防止系统性能长期劣化,并且当用于将内燃机中的曲轴转动传递给阀驱动凸轮轴时,可以改善发动机性能和燃料效率。
背景技术
日本特许公开专利No.6-264993公开了一种用于将内燃机中的曲轴转动传递给一对阀传动凸轮轴的链条传动系统,其包括:与曲轴连接的曲轴链轮、与各个凸轮轴连接的凸轮轴链轮、环绕在曲轴链轮和凸轮轴链轮上的链条、沿适当的链条传动方向引导链条的链条导轨以及通过液压控制链条张力的链条张紧轮单元。在上述链条传动系统中,如日本特许公开专利No.11-190406所建议的,可以使用滚链或无声链。
发明内容
链条一般包括用销钉偶联在一起的多个链片。但因为销钉和链片之间及任意两个相邻链片之间存在滑动摩擦,所以会出现各种问题,例如能耗、噪音、磨损和链条拉长。另外,链条拉长会造成链条传动系统的性能劣化(例如控制时间延迟)。
另外,链条张紧轮单元包括松弛导轨、张紧轮本体和柱塞,所述柱塞滑动性地啮合在张紧轮本体内,从而将松弛导轨压在链条上,用于控制链条的运动,在链条上施加初始张力,从而防止在发动机启动时链条震颤。尽管要求将张紧轮本体和柱塞之间的间隙最小化,以避免发动机停止期间漏油和有利于将初始张力施加在链条上,但张紧轮本体和柱塞之间的滑动摩擦会随着张紧轮本体和柱塞之间的间隙减小而增加。当张紧轮本体和柱塞之间的滑动摩擦增加时,张紧轮本体和柱塞会严重磨损,导致漏油的可能性更大。另外,张紧轮对链条输入的响应劣化。如果链条张紧轮单元不能适当控制链条的运动,链条将会震颤。
链条和链轮之间及链条和链条导轨之间的滑动摩擦还会产生其它问题,例如能耗、噪音和磨损,导致其强度下降及过早更换零件。
因此,本发明的目的是提供一种链条传动系统,其具有以低摩擦阻力和低磨损量相对滑动的相对零件,从而防止能耗和噪音,并增加任何设备如装备有链条传动系统的内燃机的耐久性,改善其操作性能和效率。
本发明的发明人经过广泛研究后发现:当一个或两个滑动件上涂覆有硬碳涂层薄膜时,在特定润滑油的存在下,一对相对滑动件显示出明显改善的低摩擦性能和耐久性。本发明就是基于上述发现而完成的。
本发明的第一个方面是提供一种链条传动系统,其包括:主动链轮;从动链轮;环绕在主动链轮和从动链轮上的链条;链条和链轮都具有在润滑油存在下可相对滑动的各自滑动表面;链条的任何相邻链条部件都具有在润滑油存在下可相对滑动的各自滑动表面;链条和链轮之间的至少一个滑动表面和任何相邻链条部件之间的至少一个滑动表面都具有形成在其基底部分上的硬碳涂层;各硬碳涂层中的氢含量都是10原子%或更低。
本发明的第二个方面是提供一种链条传动系统,其包括:主动链轮;从动链轮;环绕在主动链轮和从动链轮上的链条;链条和链轮都具有可相对滑动的各自滑动表面;链条的任何相邻链条部件都具有可相对滑动的各自滑动表面;链条和链轮之间的至少一个滑动表面和任何相邻链条部件之间的至少一个滑动表面都具有形成在其基底部分上的硬碳涂层;各硬碳涂层中的氢含量都是10原子%或更低;在链条和链轮之间的滑动表面和任何相邻链条部件之间的滑动表面上提供润滑剂,用于润滑这些滑动表面。
从如下说明中还可以理解本发明的其它目的和特点。
附图说明
图1是根据本发明一种实施方案的链条传动系统的示意图。
图2A是可用于图1的链条传动系统的无声链的平面图。
图2B是图2A的无声链的链条部件的放大透视图。
图3A是可用于图1的链条传动系统的滚链的平面图。
图3B是图3A的滚链的链条部件的放大透视图。
图4A、4B、4C和4D是在图2A的无声链上形成硬碳涂层薄膜的例子。
图5A、5B、5C和5D是在图3A的滚链上形成硬碳涂层薄膜的例子。
具体实施方式
下面将详述本发明。除另有说明外,下面描述中的所有百分数(%)都是质量百分数。
如图1所示,本发明一个示例性实施方案的链条传动系统1包括第一链轮2(主动链轮)、一对第二和第三链轮3和4(从动链轮)和无声链5或滚链6。链条5或6由链条部件构成,环绕在第一和第二链轮2、3和4上,沿链条传动方向运动(如图1中的箭头所示)。如图1所示,链条传动系统1还包括链条导轨7和链条张紧轮单元,链条张紧轮单元上配有松弛导轨8和张紧轮9,用于控制施加到链条5或6上的张力。链条导轨7置于第一和第三链轮2和4之间,用于引导链条5或6正确地沿链条传动方向运动。松弛导轨8置于第一和第二链轮2和3之间,被枢轴8a枢轴性支撑。张紧轮9具有柱塞9a,柱塞9a可滑动地啮合在张紧轮本体内,使柱塞9a突出时将松弛导轨8压在链条5或6上。用润滑油润滑这些系统零件2、3、4、5或6、7、8和9,以降低它们之间的滑动摩擦。
在该实施方案中,链轮2、3、4和链条5、6之间的至少一个滑动表面、链条5、6的任意两个相对链条部件之间的至少一个滑动表面、链条5、6和导轨7、8之间的至少一个滑动表面、松弛导轨8和枢轴8a之间的至少一个滑动表面及柱塞9a和张紧轮本体之间的至少一个滑动表面上均具有硬碳薄涂层Fc。
更具体地说,如图2A和2B所示,无声链5具有用销钉52偶联在一起的多个链片51。(在这种情况下,链片51和销钉52均为链条部件)。每个链片51都在链条5的内侧半径处即在链片51朝向链轮2、3和4的一侧处排列有两个齿轮齿51a。在链片51中形成销孔51b,销钉52啮合在销孔51b中,将一个链片51和另一个链片偶联在一起。
销钉52的外部圆柱状部分与销孔51b的内部圆柱状部分滑动接触。如图4A所示,销钉52的外部圆柱状部分与销孔51b的内部圆柱状部分上分别涂覆有硬碳涂层Fc。一种替代方案是,销钉52的外部圆柱状部分或销孔51b的内部圆柱状部分上涂覆有硬碳涂层Fc。
排列在链条5的外侧半径处(与齿轮齿相对的一侧)的链片51的外侧部位与链条导轨7和松弛导轨8的导轨部分滑动接触。如图4B所示,链片51的外侧部位上分别涂覆有硬碳涂层Fc。也可以在链条导轨7和松弛导轨8的导轨部分上涂覆硬碳涂层Fc,而不在链片51的外侧部位上涂覆硬碳涂层Fc,也可以在链片51的外侧部位和链条导轨7和松弛导轨8的导轨部分上全都涂覆硬碳涂层Fc。
每个链片51的相对片部分与任意相邻的链片51的片部分滑动接触。如图4C所示,链片51的片部分上分别涂覆有硬碳涂层Fc。一种替代方案是,每个链片51的一个片部分上涂覆有硬碳涂层Fc。
链片51的齿轮齿部分与链轮2、3和4的齿轮部分滑动接触。如图4D所示,链片51的齿轮齿部分上分别涂覆有硬碳涂层Fc。也可以在链轮2、3和4的齿轮部分上涂覆硬碳涂层Fc,而不在链片51的齿轮齿部分上涂覆硬碳涂层Fc,也可以在链片51的齿轮齿部分和链轮2、3和4的齿轮部分上全都涂覆硬碳涂层Fc。
如图3A和3B所示,滚链6具有用套筒62和销钉63偶联在一起的多个椭圆链片61。(在这种情况下,链片61、套筒62和销钉63均为链条部件)。在每个链片61中都形成销孔61a,套筒62和销钉63可滑动地啮合在销孔61a中,从而将一个链片61和另一个链片偶联在一起。
销钉63的外部圆柱状部分与销孔61a的内部圆柱状部分和套筒62的内部圆柱状部分滑动接触。如图5A所示,销钉63的外部圆柱状部分、销孔61a的内部圆柱状部分和套筒62的内部圆柱状部分上分别涂覆有硬碳涂层Fc。一种替代方案是,销钉63的外部圆柱状部分或销孔61a的内部圆柱状部分和套筒62的内部圆柱状部分上涂覆有硬碳涂层Fc。
链片61的外侧部位与链条导轨7和松弛导轨8的导轨部分滑动接触。如图5B所示,链片61的外侧部位上分别涂覆有硬碳涂层Fc。也可以在链条导轨7和松弛导轨8的导轨部分上涂覆硬碳涂层Fc,而不在链片61的外侧部位上涂覆硬碳涂层Fc,也可以在链片61的外侧部位和链条导轨7和松弛导轨8的导轨部分上全都涂覆硬碳涂层Fc。
链片61的相对片部分与任意相邻的链片61的片部分滑动接触。如图5C所示,链片61的片部分上分别涂覆有硬碳涂层Fc。一种替代方案是,每个链片61的一个片部分上涂覆有硬碳涂层Fc。
套筒62的外部圆柱状部分与链轮2、3和4的齿轮部分滑动接触。如图5D所示,套筒62的外部圆柱状部分上分别涂覆有硬碳涂层Fc。也可以在链轮2、3和4的齿轮部分上涂覆硬碳涂层Fc,而不在套筒62的外部圆柱状部分上涂覆硬碳涂层Fc,也可以在套筒62的外部圆柱状部分和链轮2、3和4的齿轮部分上全都涂覆硬碳涂层Fc。
另外,松弛导轨8的轴承部分与枢轴8a的外侧部分相互之间滑动接触。尽管附图中没有具体示出,但松弛导轨8的轴承部分与枢轴8a的外部圆柱状部分之一或二者均涂覆有硬碳涂层Fc。
柱塞9a的外侧部分与张紧轮本体的轴承部分相互之间也滑动接触,柱塞9a的外侧部分与张紧轮本体的轴承部分之一或二者均涂覆有硬碳涂层Fc。
硬碳涂层Fc一般由无定形碳如类金刚石碳(DLC)材料制成,其中的碳元素存在于Sp2和Sp3杂化中,形成石墨和金刚石复合结构。DLC材料的具体例子包括:无氢的无定形碳(a-C)、含氢的无定形碳(a-C:H)和/或金属碳化物或含有钛(Ti)或钼(Mo)金属元素作为其一部分的金属碳(MeC)。
随着硬碳涂层Fc中氢含量的增加,链轮2、3、4,链条5或6,链条导轨7,松弛导轨8和张紧轮9的任何两个相邻滑动表面之间的摩擦系数增加。因此,为了降低链轮2、3、4,链条5或6,链条导轨7,松弛导轨8和张紧轮9的任何两个相邻滑动表面之间的滑动摩擦,从而使链轮2、3、4,链条5或6,链条导轨7,松弛导轨8和张紧轮9具有稳定的滑动性能,硬碳涂层Fc中的氢含量优选是10原子%或更低,更优选1.0原子%或更低。在该实施方案中,将各硬碳涂层Fc中的氢含量控制为1.0原子%或更低。利用其中的涂覆气氛基本不含有氢和含氢化合物的物理气相沉积(PVD)法如电弧离子电镀法可以形成这种氢含量低的硬碳涂层Fc。为了降低硬碳涂层Fc中的氢含量,需要在形成硬碳涂层Fc之前烘焙反应器容和支撑结构,并清洗链轮2、3、4,链条5或6,链条导轨7,松弛导轨8和张紧轮9的基底部分(即链轮2、3、4的齿轮部分,链片51的齿轮齿部分、外侧部位和片部分,销钉52的外部圆柱状部分,销孔51b的内部圆柱状部分,链片61的外侧部位和片部分,销钉63的外部圆柱状部分,销孔61a的内部圆柱状部分,套筒62的内外部圆柱状部分,链条导轨7和松弛导轨8的导轨部分,松驰导轨8的轴承部分,枢轴8a的外侧部分,柱塞9a的外侧部分,张紧轮本体的轴承部分)。
另外,在尚未在链轮2、3、4,链条5或6,链条导轨7,松弛导轨8和张紧轮9的基底部分上形成硬碳涂层Fc的条件下,优选将链轮2、3、4,链条5或6,链条导轨7,松弛导轨8和张紧轮9的基底部分修整,使其平均表面粗糙度Ra不大于0.3μm。如果表面粗糙度Ra大于0.3μm,则硬碳涂层Fc的表面粗糙度造成的突起会增加对相对滑动表面的局部赫兹(Hertz)接触压力。这将导致在硬碳涂层Fc中形成裂纹。该实施方案中的表面粗糙度Ra解释为JIS B0601中的“Ra75”。
润滑油优选由基础油和无灰脂肪酸酯摩擦改进剂与无灰脂族胺摩擦改进剂中的至少一种混合制备而成,从而有效降低滑动件之间的摩擦。
所述基础油不作特别的限制,它可选自任意常用的润滑基础油化合物,如矿物油、合成油和脂肪。
所述矿物油的具体实例包括正链烷烃油和链烷烃基油或环烷烃基油,它们是通过常压蒸馏或减压蒸馏从石油中提取润滑油馏分、然后采用任意的下述处理方法对所得到的润滑油馏分进行纯化而制得的:溶剂脱沥青、溶剂提取、加氢裂化、溶剂脱蜡、加氢精制、蜡异构化、硫酸处理和白土精制。虽然所述润滑油馏分一般通过加氢精制或溶剂精制进行纯化,但优选使用通过深度加氢裂化或GTL(气体到液体)蜡异构化方法降低所述油中芳烃含量来纯化所述润滑油馏分而制得的矿物油。
所述合成油的具体实例包括:聚α-烯烃(PAO),如1-辛烯低聚物、1-癸烯低聚物和乙烯-丙烯低聚物及其加氢产物;异丁烯低聚物及其加氢产物;异链烷烃;烷基苯;烷基萘;二酯,如戊二酸二(十三烷基)酯、己二酸二辛基酯、己二酸二异癸基酯、己二酸二(十三烷基)酯和癸二酸二辛基酯;多元醇酯,如三羟甲基丙烷酯(例如三羟甲基丙烷辛酸酯、三羟甲基丙烷壬酸酯和三羟甲基丙烷异硬脂酸酯)和季戊四醇酯(例如己酸季戊四醇-2-乙基酯和壬酸季戊四醇酯);聚氧亚烷基二醇;二烷基二苯基醚;和聚苯基醚。其中优选的为聚α-烯烃,如1-辛烯低聚物和1-癸烯低聚物及其加氢产物。
上述基础油化合物可以单独使用,也可组合使用。在使用由两种或更多种基础油化合物的混合物作为基础油时,对于基础油化合物的混合比不作特别限定。
所述基础油的硫含量不受特别限制,基于所述基础油的总质量,优选为0.2%或更低,更优选为0.1%或更低,更进一步优选为0.05%或更低。希望使用加氢精制矿物油或合成油,这是因为加氢精制矿物油和合成油都具有不多于0.005%的硫含量,或基本不含硫(不多于5ppm)。
所述基础油的芳烃含量不受特别限制。此处,所述芳烃含量定义为按照ASTM D2549测得的芳烃馏分的含量。为了在延长的时间期限内使所述润滑油保持适合用于内燃机的低摩擦特性,基础油的芳烃含量基于基础油的总质量优选为15%或更低,更优选为10%或更低,更进一步优选为5%或更低。当基础油的芳烃含量超过15%时,润滑油的氧化稳定性将不利地发生劣化。
所述基础油的运动粘度不受特别限制。为了在内燃机中使用所述润滑油,所述基础油的运动粘度优选为2mm2/s或更高,更优选为3mm2/s或更高,并且同时优选为20mm2/s或更低,更优选为10mm2/s或更低,更进一步优选为8mm2/s或更低,它们都是在100℃时测得的。当所述基础油的运动粘度在100℃低于2mm2/s时,所述润滑油就有可能不能提供充足的耐磨性,并引起相当大的蒸发损失。当所述基础油的运动粘度在100℃超过20mm2/s时,所述润滑油就有可能不能提供低摩擦特性,并使低温性能发生劣化。
在组合使用两种或多种基础油化合物时,不需要限定每种基础油化合物的运动粘度均在这一特定范围内,只要所述基础油化合物的混合物在100℃时的运动粘度处于上述规定范围内即可。
所述基础油的粘度指数不受特别限制,为了在内燃机中使用所述润滑油,所述粘度指数优选为80或更高,更优选为100或更高,最优选为120或更高。当所述基础油具有较高粘度指数时,所述润滑油可以改善油耗性能和低温粘度性能。
至于脂肪酸酯摩擦改进剂和脂族胺摩擦改进剂,可以使用每个都具有C6-C30直链或支链烃链的脂肪酸酯和脂族胺,优选具有C8-C24直链或支链烃链,更优选具有C10-C20直链或支链烃链。当所述摩擦改进剂烃链的碳数不在6-30范围内时,可能不能产生想要的摩擦降低效果。所述脂肪酸酯和脂族胺摩擦改进剂的C6-C30直链或支链烃链的具体实例包括:烷基如己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基、二十四烷基、二十五烷基、二十六烷基、二十七烷基、二十八烷基、二十九烷基和三十烷基;链烯基如己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十三碳烯基、十四碳烯基、十五碳烯基、十六碳烯基、十七碳烯基、十八碳烯基、十九碳烯基、二十碳烯基、二十一碳烯基、二十二碳烯基、二十三碳烯基、二十四碳烯基、二十五碳烯基、二十六碳烯基、二十七碳烯基、二十八碳烯基、二十九碳烯基和三十碳烯基。上述烷基和链烯基均包括所有可能的异构体。
所述脂肪酸酯优选的例子有具有上述C6-C30烃基的脂肪酸和单羟基或多羟基脂族醇的酯。这类脂肪酸酯的具体实例包括甘油单油酸酯、甘油二油酸酯、山梨聚糖单油酸酯和山梨聚糖二油酸酯。
所述脂族胺优选的例子有每个均具有上述C6-C30烃基的脂族单胺及其环氧烷加合物、脂族多胺、咪唑啉及其衍生物。这类脂族胺的具体实例包括:脂族胺化合物如月桂基胺、月桂基二乙胺、月桂基二乙醇胺、十二烷基二丙醇胺、棕榈胺、硬脂胺、硬脂基四亚乙基五胺、油基胺、油基亚丙基二胺、油基二乙醇胺和N-羟乙基油基咪唑啉(N-hydroxyethyloleylimidazolyne);上述脂族胺化合物的环氧烷加合物,如N,N-二聚氧亚烷基-N-烷基或链烯基(C6-C28)胺和酸改性的化合物,该酸改性的化合物通过使上述脂族胺化合物与C2-C30一元羧酸(如脂肪酸)或C2-C30多元羧酸(如草酸、苯二酸、偏苯三酸和1,2,4,5-苯四酸)反应以中和或酰胺化全部或部分的剩余氨基和/或亚氨基而制得。其中N,N-二聚氧亚乙基-N-油基胺是优选使用的。
所述脂肪酸酯摩擦改进剂和/或脂族胺摩擦改进剂在润滑油中的含量不受特别限制,基于所述润滑油总质量,优选为0.05-3.0%,更优选为0.1-2.0%,最优选为0.5-1.4%。当润滑油中脂肪酸酯摩擦改进剂和/或脂族胺摩擦改进剂的含量低于0.05%时,就有可能不能获得足够的摩擦降低效果。当润滑油中脂肪酸酯摩擦改进剂和/或脂族胺摩擦改进剂的含量超过3.0%时,所述基础油中摩擦改进剂的溶解度就有可能变得很低,以致使所述润滑贮存稳定性劣化,引起沉淀。
所述润滑油可以优选含有聚丁烯基琥珀酸亚胺和/或其衍生物。
对于所述聚丁烯基琥珀酰亚胺,可以使用由下述通式(1)和(2)表示的化合物:
在通式(1)和(2)中,PIB表示衍生自数均分子量为900-3500的聚丁烯的聚丁烯基团,优选分子量为1000-2000,它可通过在氟化硼催化剂或氯化铝催化剂存在下聚合高纯度异丁烯或1-丁烯和异丁烯的混合物而制得。当所述聚丁烯的数均分子量低于900时,就有可能不能提供充分的清洁作用。当所述聚丁烯的数均分子量超过3500时,所述聚丁烯基琥珀酰亚胺的低温流动性倾向于劣化。在用于制备聚丁烯基琥珀酰亚胺之前,聚丁烯可通过采用任意合适的处理方法(如吸附方法或洗涤方法)除去源自上述聚丁烯制备催化剂的痕量氟和氯残余物而对其进行纯化,由此来控制聚丁烯中氟和氯残余物的含量为50ppm或更低,希望为10ppm或更低,更希望为1ppm或更低。
而且考虑到清洁效果,在通式(1)和(2)中,n表示1-5的整数,优选为2-4的整数。
所述聚丁烯基琥珀酰亚胺的制备方法不受特别限制。例如所述聚丁烯基琥珀酰亚胺可通过下述方法制得:使聚丁烯的氯化物或聚丁烯(氟和氨残余物已经从中充分除去)与马来酸酐在100-200℃反应形成聚丁烯基琥珀酸酯,然后使所述聚丁烯基琥珀酸酯与多胺(如二亚乙基三胺、三亚乙基四胺、四亚乙基五胺或五亚乙基六胺)进行反应。
对于所述聚丁烯基琥珀酰亚胺衍生物,它们可使用硼或酸改性的化合物,可通过使通式(1)或(2)所述聚丁烯基琥珀酰亚胺与硼化合物或含氧有机化合物进行反应以中和或酰胺化全部或部分的剩余氨基和/或酰亚胺基团而制得。其中含硼聚丁烯基琥珀酰亚胺,尤其是含硼二(聚丁烯基)琥珀酰亚胺,是优选使用的。在含硼聚丁烯基琥珀酰亚胺化合物中氮与硼的含量之比(B/N)以质量计通常为0.1-3,优选为0.2-1。
用于制备聚丁烯基琥珀酰亚胺衍生物的硼化合物可以为硼酸、硼酸盐或硼酸酯。所述硼酸的具体实例包括原硼酸、偏硼酸和四硼酸。所述硼酸盐的具体实例包括:铵盐如硼酸铵,例如偏硼酸铵、四硼酸铵、五硼酸铵和八硼酸铵。所述硼酸酯的具体实例包括:硼酸和烷基醇(优选为C1-C6烷基醇)的酯,如硼酸单甲基酯、硼酸二甲基酯、硼酸三甲基酯、硼酸单乙基酯、硼酸二乙基酯、硼酸三乙基酯、硼酸单丙基酯、硼酸二丙基酯、硼酸三丙基酯、硼酸单丁基酯、硼酸二丁基酯和硼酸三丁基酯。
用于制备聚丁烯基琥珀酰亚胺衍生物的含氧有机化合物可以为任意C1-C30一元羧酸,如甲酸、乙酸、乙二醇酸、丙酸、乳酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、硬脂酸、油酸、十九烷酸和二十烷酸;C2-C30多元羧酸,如草酸、苯二酸、偏苯三酸和1,2,4,5-苯四酸,其酸酐和酯;C2-C6环氧烷;和羟基(多)氧亚烷基碳酸酯。
所述聚丁烯基琥珀酰亚胺和/或聚丁烯基琥珀酰亚胺衍生物存在于所述润滑油中的含量不受特别限制,基于所述润滑油总质量,优选为0.1-15%,更优选为1.0-12%。当所述润滑油中聚丁烯基琥珀酰亚胺和/或聚丁烯基琥珀酰亚胺衍生物的含量低于0.1%时,就有可能不能获得充分的清洁效果。当所述润滑油中聚丁烯基琥珀酰亚胺和/或聚丁烯基琥珀酰亚胺衍生物的含量超过15%时,所述润滑油的反乳化能力可能劣化。另外,在所述润滑油中添加如此大量的所述聚丁烯基琥珀酰亚胺和/或聚丁烯基琥珀酰亚胺衍生物,也是不经济的。
另外,所述润滑油可以优选含有二硫代磷酸锌。
对于所述二硫代磷酸锌,它可以采用由下述通式(3)表示的化合物:
在通式(3)中,R4、R5、R6和R7中每个均表示C1-C24烃基。所述C1-C24烃基优选为C1-C24直链或支链烷基、C3-C24直链或支链链烯基、C5-C13环烷基或直链或支链烷基环烷基、C6-C18芳基或直链或支链烷基芳基或C7-C19芳基烷基。上述烷基或链烯基可为伯、仲或叔基。R4、R5、R6和R7的具体实例包括:烷基如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基和二十四烷基;链烯基如丙烯基、异丙烯基、丁烯基、丁二烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十三碳烯基、十四碳烯基、十五碳烯基、十六碳烯基、十七碳烯基、十八碳烯基(油基)、十九碳烯基、二十碳烯基、二十一碳烯基、二十二碳烯基、二十三碳烯基和二十四碳烯基;环烷基如环戊基、环己基和环庚基;烷基环烷基如甲基环戊基、二甲基环戊基、乙基环戊基、丙基环戊基、乙基甲基环戊基、三甲基环戊基、二乙基环戊基、乙基二甲基环戊基、丙基甲基环戊基、丙基乙基环戊基、二丙基环戊基、丙基乙基甲基环戊基、甲基环己基、二甲基环己基、乙基环己基、丙基环己基、乙基甲基环己基、三甲基环己基、二乙基环己基、乙基二甲基环己基、丙基甲基环己基、丙基乙基环己基、二丙基环己基、丙基乙基甲基环己基、甲基环庚基、二甲基环庚基、乙基环庚基、丙基环庚基、乙基甲基环庚基、三甲基环庚基、二乙基环庚基、乙基二甲基环庚基、丙基甲基环庚基、丙基乙基环庚基、二丙基环庚基和丙基乙基甲基环庚基;芳基如苯基和萘基;烷基芳基如甲苯基、二甲苯基、乙基苯基、丙基苯基、乙基甲基苯基、三甲基苯基、丁基苯基、丙基甲基苯基、二乙基苯基、乙基二甲基苯基、四甲基苯基、戊基苯基、己基苯基、庚基苯基、辛基苯基、壬基苯基、癸基苯基、十一烷基苯基和十二烷基苯基;和芳基烷基,如苄基、甲基苄基、二甲基苄基、苯乙基、甲基苯乙基和二甲基苯乙基。上述烃基包括所有可能的异构体。其中优选的是C1-C18直链或支链烷基和C6-C18芳基或直链或支链烷基芳基。
所述二硫代磷酸锌化合物优选的例子有:二异丙基二硫代磷酸锌、二异丁基二硫代磷酸锌、二仲丁基二硫代磷酸锌、二仲戊基二硫代磷酸锌、二正己基二硫代磷酸锌、二仲己基二硫代磷酸锌、二辛基二硫代磷酸锌、二-2-乙基己基二硫代磷酸锌、二正癸基二硫代磷酸锌、二正十二烷基二硫代磷酸锌和二异十三烷基二硫代磷酸锌。
所述润滑油中所述二硫代磷酸锌的含量不受特别限制。为了获得更大的摩擦降低效果,所述二硫代磷酸锌的含量基于所述润滑油总质量以磷元素计优选为0.1%或更低,更优选为0.06%或更低,最优选为最小有效量。当所述润滑油中二硫代磷酸锌含量超过0.1%时,就有可能抑制无灰脂肪酸酯摩擦改进剂和/或无灰脂族胺摩擦改进剂的摩擦降低效果。
所述二硫代磷酸锌的制备方法不受特别限制,所述二硫代磷酸锌可通过任意已知方法制得。例如所述二硫代磷酸锌可通过使具有上述R4、R5、R6和R7烃基的醇或酚与五硫化磷(P2O5)反应形成二硫代磷酸,然后用氧化锌中和二硫代磷酸而制得。要指出的是,二硫代磷酸锌的分子结构会随着用于制备所述二硫代磷酸锌的原料的醇或酚而不同。
上述二硫代磷酸锌化合物可以单独使用,也可以使用两种或多种化合物的混合物。在组合使用两种或多种二硫代磷酸锌化合物时,对于所述二硫代磷酸锌化合物的混合比不作特别限定。
当相对的系统零件2、3、4、5或6、7、8和9的一个或两个涂覆有硬碳涂层Fc时,上述特定润滑油对在系统零件2、3、4、5或6、7、8和9的任意两个相对滑动表面之间的滑动摩擦能够产生大的摩擦降低作用。
为了改善用于内燃机的润滑油所需的性能,所述润滑油还可含有其它添加剂,如金属清洁剂、抗氧化剂、粘度指数改进剂、不同于上述提及的脂肪酸酯摩擦改进剂和脂族胺摩擦改进剂的摩擦改进剂、不同于上述提及的聚丁烯基琥珀酰亚胺和聚丁烯基琥珀酰亚胺衍生物的无灰分散剂、耐磨剂或极压剂、防锈剂、非离子型表面活性剂、破乳剂、金属钝化剂和/或消泡剂。
所述金属清洁剂可选自任意的常用于发动机润滑剂的金属清洁剂化合物。所述金属清洁剂的具体实例包括诸如钠(Na)和钾(K)之类碱金属或诸如钙(Ca)和镁(Mg)之类碱土金属的磺酸盐、酚盐和水杨酸盐;及其两种或多种的混合物。其中钠和钙的磺酸盐、钠和钙的酚盐和钠和钙的水杨酸盐是适合使用的。所述金属清洁剂的总碱值和含量可根据润滑油所需要的性能进行选择。所述金属清洁剂的总碱值通常为0-500mgKOH/g,优选为150-400mgKOH/g,它是按照ISO3771利用高氯酸测得的。所述金属清洁剂的含量通常为所述润滑油总质量的0.1-10%。
所述抗氧化剂可选自任意的常用于发动机润滑剂的抗氧化剂化合物。所述抗氧化剂的具体实例包括:酚类抗氧化剂,如4,4,-亚甲基二(2,6-二-叔丁基苯酚)和十八烷基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯;氨基抗氧化剂,如苯基-α-萘胺、烷基苯基-α-萘胺和烷基二苯基胺;及其两种或多种的混合物。所述抗氧化剂的含量通常为所述润滑油总质量的0.01-5%。
对于所述粘度指数改进剂,可以使用的有:非分散型聚甲基丙烯酸酯粘度指数改进剂,如一种或多种甲基丙烯酸的共聚物及其加氢产物;分散型聚甲基丙烯酸酯粘度指数改进剂,如还含有氮化合物的甲基丙烯酸酯的共聚物;及其它粘度指数剂,如乙烯和α-烯烃(例如丙烯、1-丁烯和1-戊烯)的共聚物及其加氢产物、聚异丁烯及其加氢产物、苯乙烯-二烯加氢共聚物、苯乙烯-马来酸酐共聚物和聚烷基苯乙烯。考虑到剪切稳定性,需要对所述粘度指数改进剂的分子量进行选择。例如所述粘度指数改进剂的数均分子量,对于所述分散型或非分散型聚甲基丙烯酸酯来说,希望在5000-1000000范围内,更希望为100000-800000;对于所述聚异丁烯或其加氢产物来说,该分子量在800-5000范围内;对于所述乙烯/α-烯烃共聚物或其加氢产物来说,该分子量在800-300000范围内,更优选为10000-200000。上述粘度指数改进化合物可以单独使用,也可以以其两种或多种的混合物形式使用。所述粘度指数改进剂的含量优选为所述润滑油总质量的0.1-40.0%。
所述不同于上述提及的脂肪酸酯摩擦改进剂和脂族胺摩擦改进剂的摩擦改进剂,可以列举的有:无灰摩擦改进剂,如硼酸酯、更高级的醇和脂族醚,和金属摩擦改进剂,如二硫代磷酸钼、二硫代氨基甲酸钼和二硫化钼。
所述不同于上述提及聚丁烯基琥珀酰亚胺和聚丁烯基琥珀酰亚胺衍生物的无灰分散剂,可为任意一种具有数均分子量为900-3500的聚丁烯基的聚丁烯基苄胺和聚丁烯基胺、具有数均分子量低于900的聚丁烯基的聚丁烯基琥珀酰亚胺及其衍生物。
对于所述耐磨剂或极压剂,可以使用:二硫化物、硫化脂肪、烯烃硫化物、具有1-3个C2-C20烃基的磷酸酯、硫代磷酸酯、亚磷酸酯、硫代亚磷酸酯和这些酯的胺盐。
对于所述防锈剂,可以使用:烷基苯磺酸酯、二壬基萘磺酸酯、烯基琥珀酸的酯和多元醇的酯。
对于所述非离子型表面活性剂和破乳剂,可以使用:非离子型聚亚烷基二醇表面活性剂,如聚氧亚乙基烷基醚、聚氧亚乙基烷基苯基醚和聚氧亚乙基烷基萘基醚。
所述金属钝化剂可以列举的有:咪唑啉、嘧啶衍生物、噻唑和苯并三唑。
所述消泡剂可以列举的有:硅酮、氟代硅酮和氟代烷基醚。
所述不同于脂肪酸酯和脂族胺摩擦改进剂的摩擦改进剂、所述不同于聚丁烯基琥珀酰亚胺和聚丁烯基琥珀酰亚胺衍生物的无灰分散剂、所述耐磨剂或极压剂、所述防锈剂和所述破乳剂中,每种物质的含量通常均为所述润滑油总质量的0.01-5%,所述金属钝化剂的含量通常为所述润滑油总质量的0.005-1%,所述消泡剂的含量通常为所述润滑油总质量的0.0005-1%。
如上所述,在链条部件51、52或61、62、63之间的一个或两个相对滑动表面上具有本发明的氢含量低的硬碳涂层Fc。因此,链条部件51、52或61、62、63能够在上述特定润滑油的存在下以低摩擦阻力和低磨损相对滑动。这样就可以降低由链条5、6的运动造成的能耗和噪音,能够防止链条5、6由于磨损而拉长,从而可以改善链条5、6的耐久性。特别是当在内燃机中用链条传动系统1控制将主动轴(即曲轴)的转动传递给从动轴(即阀驱动凸轮轴)的时间时,可以防止由于链条拉长而导致的发动机性能劣化(如控制时间延迟)。另外,在链条的允许延伸率设置为恒定值的情况下,形成硬碳涂层Fc还可以减少链条5、6的受压面积。因此由于链条传动系统1的尺寸减小,可以使链条5、6的宽度和销钉52、63的直径更小。尽管传统的链条需要进行表面修整处理(例如精密冲裁)以避免链条拉长,但根据本实施方案,不需要对链条5、6上进行这一表面修整处理。这将降低成本。另外,在上述特定润滑油的存在下,链条5或6可以相对于链轮2、3、4,链条导轨7和松弛导轨8以低摩擦阻力和低磨损滑动。这样也可以降低由于链条5、6和链轮2、3、4,链条导轨7和松弛导轨8的滑动接触所造成的能耗和噪音,并降低链条5或6、链轮2、3、4,链条导轨7和松弛导轨8材料的耐磨等级,从而可以节约成本。
同样,松弛导轨8和枢轴8a之间的至少一个相对滑动表面和张紧轮本体和柱塞9a之间的至少一个相对滑动表面上均具有本实施方案的氢含量低的硬碳涂层Fc。这样可以降低松弛导轨8的枢轴摩擦,改善张紧轮9对链条5、6输入的响应性,从而提高链条传动系统1的性能。另外还可以减小张紧轮本体和柱塞9a之间的间隙,以避免在发动机停止期间发生漏油,从而可以改善张紧轮9在发动机启动时的响应性。这样可以避免用于链条5、6等的震颤造成的异常声音。
因此,链条传动系统1能够得到良好的低摩擦性能和耐久性,当在内燃机中用所述链条传动系统1控制将主动轴(即曲轴)的转动传递给从动轴(即阀驱动凸轮轴)的时间时,在没有长期劣化的情况下可以极大地改善发动机性能和燃料效率。
应当注意的是,可以将硬碳涂层Fc涂覆在其它任何滑动机器零件上。例如已经得到证实的是,当将硬碳涂层Fc涂覆在连杆的曲轴销和曲轴销轴承(称为“大端”)之间的滑动部位上和曲轴轴承和曲轴轴颈之间的滑动部位上时,这些发动机零件之间的滑动摩擦可以降低约70%,发动机燃料效率提高约2.2%,并且发动机零件的耐卡死性没有任何损失。
本申请中全文引入日本专利申请No.2003-207494(2003年8月13日申请)作为参考。
尽管已经参考本发明的具体实施方案描述了本发明,但本发明不局限于上述实施方案。对于本领域普通技术人员来说,在上述教导下可以对上述实施方案进行各种改动和变化。本发明的保护范围由所附权利要求书定义。
Claims (12)
1、一种链条传动系统,其包括:
主动链轮;
从动链轮;
环绕在主动链轮和从动链轮上的链条;
所述链条和链轮均具有在润滑油存在下可相对滑动的各自滑动表面;
所述链条的任何相邻链条部件均具有在润滑油存在下可相对滑动的各自滑动表面;
所述链条和链轮之间的至少一个所述滑动表面和任何相邻链条部件之间的至少一个所述滑动表面均具有形成在其基底部分上的类金刚石碳涂层;
各类金刚石碳涂层的氢含量均为10原子%或更低;和
所述润滑油含有至少一种选自无灰脂肪酸酯摩擦改进剂和无灰脂族胺摩擦改进剂的摩擦改进剂。
2、权利要求1的链条传动系统,还包括:
沿着链条传动方向引导链条的链条导轨;
所述链条和链条导轨均具有用润滑油润滑以致于可相对滑动的各自滑动表面;
所述链条和链条导轨之间的至少一个所述滑动表面具有形成在其基底部分上的氢含量为10原子%或更低的类金刚石碳涂层。
3、权利要求1的链条传动系统,还包括:
被枢轴性支撑的松弛导轨;
具有张紧轮本体和柱塞的张紧轮,所述柱塞可滑动地啮合在张紧轮本体内,从而将松弛导轨压在链条上;
所述链条和松弛导轨均具有用润滑油润滑以致于可相对滑动的各自滑动表面;和
所述链条和松弛导轨之间的至少一个所述滑动表面具有形成在其基底部分上的氢含量为10原子%或更低的类金刚石碳涂层。
4、权利要求3的链条传动系统,还包括:
支撑松弛导轨的枢轴,其支撑方式使松弛导轨围绕枢轴旋转;
所述松弛导轨和枢轴均具有用润滑油润滑以致于可相对滑动的各自滑动表面;
所述松弛导轨和枢轴之间的至少一个所述滑动表面具有形成在其基底部分上的氢含量为10原子%或更低的类金刚石碳涂层。
5、权利要求3的链条传动系统,所述张紧轮本体和柱塞具有用润滑油润滑以致于可相对滑动的各自滑动表面;和
所述张紧轮本体和柱塞之间的至少一个所述滑动表面具有形成在其基底部分上的氢含量为10原子%或更低的类金刚石碳涂层。
6、权利要求1的链条传动系统,其中各类金刚石碳涂层中的氢含量是1.0原子%或更低。
7、权利要求1的链条传动系统,其中所述至少一种摩擦改进剂具有C6-C30烃基,其含量以润滑油的总质量计是0.05-3.0%。
8、权利要求1的链条传动系统,其中所述润滑油含有聚丁烯基琥珀酰亚胺和/或其衍生物。
9、权利要求8的链条传动系统,其中所述聚丁烯基琥珀酰亚胺和/或其衍生物的含量以润滑油的总质量计是0.1-15%。
10、权利要求1的链条传动系统,其中所述润滑油含有二硫代磷酸锌,所述二硫代磷酸锌的含量基于润滑油的总质量以磷元素计是0.1%或更低。
11、权利要求1的链条传动系统,其中所述类金刚石碳涂层是用电弧离子电镀法形成的。
12.权利要求1的链条传动系统,其中任何所述基底部分在尚未在其上形成类金刚石碳涂层时的表面粗糙度Ra都是0.03μm或更小。
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003207494A JP4117553B2 (ja) | 2003-08-13 | 2003-08-13 | チェーン駆動装置 |
| JP2003207494 | 2003-08-13 |
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| CN1318780C true CN1318780C (zh) | 2007-05-30 |
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| EP (1) | EP1507099B1 (zh) |
| JP (1) | JP4117553B2 (zh) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1580611A (zh) | 2005-02-16 |
| JP2005061441A (ja) | 2005-03-10 |
| EP1507099B1 (en) | 2007-04-18 |
| EP1507099A1 (en) | 2005-02-16 |
| US20050037879A1 (en) | 2005-02-17 |
| US7572200B2 (en) | 2009-08-11 |
| JP4117553B2 (ja) | 2008-07-16 |
| DE602004005932T2 (de) | 2007-08-30 |
| DE602004005932D1 (de) | 2007-05-31 |
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