CN100420843C - 热喷涂活塞环 - Google Patents
热喷涂活塞环 Download PDFInfo
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Abstract
本发明提供一种热喷涂活塞环,其具有优越的初期磨合性,而且形成具有耐磨损性、耐消耗性的热喷涂膜。活塞环1的热喷涂膜3含有为2~40质量%的Sn以及为5~50质量%的石墨,必要时还可含有P、Sb、Co、Be、Cr、Mn、Si、Cd、Zn、Fe、Ni、以及Pb,其余部分由Cu所构成。
Description
技术领域
本发明涉及用在内燃机和压缩机等的活塞环,更详细的说本发明涉及在至少一个外周滑动表面上具有热喷涂膜的活塞环。
背景技术
近年来,随着引擎高性能化,对它的耐消耗性和耐磨损性有更高的要求磨损。另一方面,为降低石油消耗量和缩短磨合时间而降低成本,必须改进初始的磨合性能,也就是需要活塞环和气缸套早些完成磨合。
因此以往为了改进滑动部分的初期磨合性,比如说为加强活塞环的初期磨合性,会在活塞环最***面施以镀铜膜和软质的热喷涂膜。
但是,将上述以往施以镀铜膜的活塞环用在高性能的柴油机的情况下,镀铜膜会太过柔软,在初期磨合完成之前会磨尽,造成磨损和消耗等问题。
而且,如特开平11-80921中所示,铜基合金滑动面材料的组成如下:Al为7~11质量%,Fe、Ni、Mn之中1种或多种为0.5~8质量%,其余部分为Cu。此后通过等离子或电弧热喷涂形成热喷涂膜,作为初期磨合的涂膜来使用。但该膜硬度太高,膜中又没有能够自己润滑的成分,所以就产生了初期磨合性不够充分的问题。
而且,在如特表2000-507679所示的热喷涂膜中,石墨等固态润滑剂5~60%,Ni、Al、Si等金属接着剂40~95%,任选的有机接着剂低于15%,使用这种热喷涂膜来解决上述问题。但该膜与铜膜一样属于软性膜,所以耐消耗性不够充分,故在初期磨合完成前会产生膜磨尽等问题。
发明内容
本发明的目的,是为解决特开平11-80921、特表2000-507679中热喷涂膜的缺点,提供具有优越初期磨合性而且有耐磨损性、耐消耗性的热喷涂活塞环。
鉴于上述问题,此次研究结果中,本发明者将Cu、Sn、石墨以特定的比例来混合,通过活塞环的滑动面热喷涂,可以发现得到具有优越初期磨合性、耐消耗性、耐磨损性的热喷涂活塞环,来完成本发明。
也就是说,本发明的热喷涂活塞环中,Sn为2~40质量%、石墨为5~50质量%,其余部分由Cu所构成的热喷涂膜至少有***滑动面为其特征。
热喷涂膜基本由Cu、Sn以及石墨所构成。包含在热喷涂膜中的石墨会在热喷涂层中分散,以提高膜自身润滑性。石墨颗粒防止涂层薄膜在膜和表面形成前被磨掉,膜和表面由于相对的轴磨损铜基合金而形成。假定热喷涂膜总质量为100%,而石墨的含有量未达质量5%则缺乏自己润滑性效果,若超过质量50%的话,会成为软性膜,故初期磨合在完成之前膜会被磨尽。因此,石墨的含有量最好为5~50质量%,5~20质量%的含有量为最佳。
包含在热喷涂膜中的Sn,在等离子热喷涂中不会形成氧化物等硬质物,或者不会实质形成。在此所谓的不会实质形成氧化物等硬质物,在后述第4图显微镜观察下,可以认定由热喷涂形成空孔,但还未观察到硬质物。Sn会预先和Cu合金化进而热喷涂的情况下,Sn再固溶于铜合金适度硬化铜合金。也就是说,原料Cu-Sn合金中,有时会生成劣于初期磨合的Cu-Sn系金属化合物,但热喷涂时金属化合物会再固溶,故可以固溶或实质固溶组织。在此所谓实质固溶状态在后述第4图显微镜的观察下,可以认定以热喷涂生成空孔,但还未观察到金属化合物。金属化合物为硬质,所以对初期磨合性有害,但将Sn固溶的Cu则利于初期磨合性。
另一方面,热喷涂Sn粉末和Cu粉末的情况下,根据热喷涂条件,可以得到Cu和Sn所分散的组织。也就是说,此发明的组成如平衡状态图所示,为Sn-Cu金属化合物生成范围,但热喷涂情形各粉末在尚未完全融合会急速冷却,所以金属化合物不会实质生成,会生成利于初期磨合性的Sn。
若热喷涂膜总量为100质量%,而Sn的含有量未达质量2%则膜硬度较低,缺乏耐消耗性;若超过质量40%,则热喷涂膜中会分析出多量的Sn,这样热喷涂膜会劣于耐消耗性。因此Sn含有量为2~40质量%,以5~25质量%为最佳。
上述所记载的Cu-C-Sn成分热喷涂材料中可以添加P、Sb、Co、Be、Cr、Mn、Si、Cd、Zn、Fe、Ni、Pb等一种以上。P可改善Cu合金的熔铸性进而精密化热喷涂组织。但是,P含有量若超过1.0质量%的话则合金会硬化就不理想。P含有量最好在0.03~0.5质量%。Pb会形成软质的Pb相,或者由形成Pb-Sb共晶组织给予初期磨合性良好影响,但不管哪一方面都属低溶点,所以有可能会在活塞环的工作温度下溶出。因此,Pb含有量应该在20质量%以下,最好在0.03~5.0质量%之间。在本发明的Sn量范围,Be没有Cu-Be合金的时效性,最主要是作为强化固溶。其它元素Sb、Co、Cr、Mn、Si、Cd、Zn、Fe、Ni会在铜内合金化状态下热喷涂、再溶解后进行固溶强化。这些元素若以单独金属粉末形式热喷涂的话,特别是Cr、Mn、Fe、Ni等以单独金属分散在热喷涂组织中提高耐消耗性。但是,以质量百分比来看,Sb超过5%、Co超过5%、Be超过5%、Cr超过5%、Mn超过15%、Si超过15%、Cd超过15%、Zn超过15%、Fe超过5%、Ni超过20%的话,合金全体硬度会上升,所以要维持最佳硬度为平均硬度300HV0.1以下最为困难。这些添加元素的总量最好在25质量%以下。
附图说明
第1图为本发明一实例表示活塞环的概略剖面图。
第2图为本发明另一实例表示活塞环的概略剖面图。
第3图为本发明其它实例表示活塞环的概略剖面图。
第4图为在实施例中形成等离子热喷涂膜提供测验材料的金属组织的显微镜相片。
第5图表示实施等离子热喷涂装置(等离子枪)的概略剖面图。
第6图为超高压磨损测验机的概略图。
第7图为第6图的A-A切矢视剖面图。
第8图为在实施例和比较例的磨损测验中表示到燃烧时间的柱状图。
第9图为在实施例和比较例的磨损测验中表示燃烧时测试件的磨损量。
具体实施方式
第1图和第2图为本发明的实施例表示活塞环的概略剖面图。活塞环1为公知的铸铁、不锈钢所构成的活塞环母材2、而母材2平坦外周滑动面或外周滑动面内面形成热喷涂膜3。必要时,热喷涂膜3也可以形成于上下面。
第3图本发明其它实施例表示活塞环的概略剖面图,热喷涂膜3的基质则形成以耐消耗性为目的的镀白金膜和硬质热喷涂膜等其它膜22。
热喷涂膜通常可由电弧热喷涂、火焰热喷涂、高速火焰热喷涂、等离子热喷涂、和减压等离子热喷涂所形成,但最好是由石墨分散状态由等离子热喷涂来形成。
等离子热喷涂如第5图所示运用等离子枪5来实施。等离子枪5是由铜所构成的环状阳极6和钨等所形成,拥有位于阳极6上部的阴极7和电源8。阳极6会形成喷出等离子气体的喷嘴。型腔(未示出)则在阳极6和阴极7内部形成,拥有冷却功能。
实施等离子热喷涂,首先在离阳极6前端20~300mm距离位置设置活塞环母材2。接下来将Ar等惰性气体导入喷嘴。在此状态下阳极6和阴极7之间施以高压电的话,会因电弧放电9加热惰性气体而等离子化。而等离子化的气体会膨胀,由阳极6高温且高速喷出,形成等离子喷射流10。
将原料粉末11混合以提供希望的组合物,并具有5-125μm的平均颗粒直径,将其装载在等离子体射流10中。原料由预合金粉末或单独元素的粉末组成。而且石墨粉末镀上无电解的铜也可以。粉末11的供给口,如第5图所示设在阳极6内也好,设在阳极6的正下方也可以。粉末11在等离子喷射流10熔融加速后和母材2撞击。撞击后的粉末11会瞬时扁平化,急速冷却到母材温度,形成热喷涂膜3。
然而,母材2的表面以先形成喷丸(shot blast)等10~20μm大小的凹凸面为适宜者。以此熔融粒子撞击到母材的凸部时,凸部会产生局部熔融容易合金化,而且因熔融粒子的凝固收缩力而机械性的产生固定(anchor)效果,膜接着力也更强韧。而且热喷涂之前将母材2预先加热到400~550℃的高温,由移动电弧清洁母材2表面的话,表面会活性化,热喷涂后母材2和热喷涂膜3之间会形成相互扩散层,母材2和热喷涂膜3会接合得更牢固。
热喷涂膜3的厚度最好为50~500μm,100~300μm为最佳。
由以下具体实施例更详细的说明本发明。
实施例1
本实施例如第6图所示由超高压磨损测验机实施燃烧测验。
本测验所用的超高压磨损测验机和测验条件如下。
测验装置为第6图和第6图A-A切矢剖面图且图解要部表示于第7图,脱落于固定支持器(stator holder)12后,直径80mmX厚度100mm圆盘13中央,由内侧透过注油口14倒入润滑油。在圆盘13中通过无图示的油压装置,在图中向右方以特定的压力实施压力P。与圆盘13相对的是回转器15,由无图示的驱动装置以特定的速度回转。回转器15中,测验片16形成表面处理层5mm正方形,其单面以滑动面可以自在的滑动。
在此装置下,将所定的施压力P加在固定支持器(stator holder)12上,以所定的面压和圆盘13及测验片16之突起21接触,旋转回转器15。以一定压力,藉由回转器15的回转及测验片16与圆盘13的摩擦,在固定支持器(stator holder)12产生扭矩(torque)T。而扭矩(torque)T透过不锈钢纤维17作用于测力计(load cell)18,以测动计19读取其变化,记录在记录仪20。扭矩(torque)T急速上升时燃烧所产生的东西,这时所用时间来判断初期磨合性的好坏,而且在这之前以膜的消耗量来判断耐消耗性的好坏。
测验条件如下
摩擦速度:8m/秒
材料:FC25
接触面压:2MPa保持三分钟,增压到3MPa,保持到燃烧情形发生。
润滑油:机油#30
供给量:初期涂在1cc圆盘旁边,之后无润滑
准备的粉末如下:
混合粉末1:Sn粉末8质量%、石墨粉末20质量%、以及Cu粉末72质量%
混合粉末2:Cr3C2粉末30质量%、Mo粉末60质量%、Ni-Cr合金粉末质量10%(Ni:80质量%、Cr:20质量%)然而,各自粉末为325网眼(mesh)。
将混合粉末2作粘合(bond)层来使用,而本发明的混合粉末1为外涂层,由等离子热喷涂于测验片16突起21的表面形成约100μm厚度的热喷涂膜。热喷涂条件如下。
热喷涂条件
使用枪:METECO公司所制造的9MB的等离子热喷涂枪。
电压:70V
电流500A
所用气体:Ar
母材预热温度:400℃
得到的测验片16的弯曲面中金属组织的显微镜相片如第4图所示。由第4图可以得知,粘合层部22(相片下方)和热喷涂膜4的接合部合金化后扩散结合,膜3中空孔极少。混合粉末1的热喷涂膜的平均硬度为150Hv0.05。热喷涂膜4中黑色部分(相片约中央位置)为石墨。
其中,热喷涂膜为多层所构成,其下层膜上具有热喷涂时的粗糙度,无需机械加工即可形成上层膜。
将测验片16以及FC25所形成的圆盘13贴在上述的超高压磨损测验机,以以上的测验条件进行燃烧测验。测验片16及圆盘13的燃烧时间结果如第8图所示、燃烧发生时测验片的消耗量如第9图所示。
比较例1
和实施例中测验片16同样取材,准备Si粉末8.5质量%、石墨粉末23质量%、Al合金粉末68.5质量%所构成的混合粉末3,和Cr3C2粉末30质量%、Mo粉末60质量%、Ni-Cr合金粉末10质量%(Ni:80质量%、Cr:20质量%)所构成的混合粉末4。混合粉末4以粘合层、混合粉末3以外涂层,由等离子热喷涂于测验片16突起21的表面形成约100μm厚度的热喷涂膜。热喷涂条件如下。混合粉末3热喷涂膜的硬度为110Hv0.05。
热喷涂条件
使用枪:METECO公司所制造的9MB的等离子热喷涂枪。
电压:70V
电流500A
所用气体:Ar
母材预热温度:400℃
和实施例一样将测验片16和圆盘13组合,和实施例一样进行燃烧测验。测验片16和圆盘13燃烧发生时间结果如图8、燃烧发生时测验片16的磨耗量如图9。
比较例2
和实施例测验片16一样同样取材,记载于特愿平10-31600中,准备Al粉末9质量%、Fe粉末1质量%、Cu合金粉末90质量%所构成的混合粉末5,和Cr3C2粉末质量10%、Mo粉末质量31%、Ni-Cr合金粉末质量10%(Ni:80质量%、Cr:20质量%)所构成混合粉末6。混合粉末6以粘合层、混合粉末5以外涂层,由等离子热喷涂于测验片16弯曲面形成约100μm厚度的热喷涂膜。
热喷涂条件如下。
热喷涂条件
使用枪:METECO公司所制造的9MB的等离子热喷涂枪。
电压:70V
电流500A
所用气体:Ar
母材预热温度:400℃
和实施例一样将测验片16和圆盘13组合,和实施例一样进行燃烧测验。测验片16和圆盘13燃烧发生时间结果如图8、燃烧发生时测验片16的磨损量如图9。
由图8图9可得知,实施例的测验片比比较例的测验片16更富有耐消耗性、耐磨损性、更利于初期磨合性。
产业上利用的可能性
如上所述,将Cu、Sn、石墨以所定的比例混合后热喷涂出来的膜形成于外周滑动面的活塞环,富有耐消耗性、耐磨损性、更利于初期磨合性。
Claims (13)
1. 一种热喷涂活塞环,其特征在于:具有热喷涂膜,该膜包含2~40质量%Sn、5~50质量%石墨,其余部分基本由Cu所构成。
2. 如权利要求1所述的热喷涂活塞环,其特征在于:热喷涂膜形成于活塞环的最***表面。
3. 如权利要求1~2的任一项所述的热喷涂活塞环,其特征在于:除了一般的杂质锡青铜以外,前述热喷涂膜含有P、Sb、Co、Be、Cr、Mn、Si、Cd、Zn、Fe、Ni、Pb中的一种或多种,其这些成分的含量为:P最大1.0质量%、Sb最大5质量%、Co最大5质量%、Be最大5质量%、Cr最大5质量%、Mn最大15质量%、Si最大15质量%、Cd最大15质量%、Zn最大15质量%、Fe最大5质量%、Ni最大20质量%、Pb最大20质量%,其余为Cu。
4. 如权利要求3所述的热喷涂活塞环,其特征在于:选自P、Sb、Co、Be、Cr、Mn、Si、Cd、Zn、Fe、Ni、Pb中的一种或多种元素的总量最多为25质量%。
5. 如权利要求1、2、或4中的任一项所述的热喷涂活塞环,其特征在于:热喷涂膜平均硬度为300HV0.1或更小。
6. 如权利要求3所述的热喷涂活塞环,其特征在于:热喷涂膜平均硬度为300HV0.1或更小。
7. 如权利要求1、2、4、或6中的任一项所述的热喷涂活塞环,其特征在于:前述热喷涂膜为多层组成,上层涂层形成在下层之上,其下层涂层具有热喷涂时的粗糙度,无需机械加工。
8. 如权利要求3所述的热喷涂活塞环,其特征在于:前述热喷涂膜为多层组成,上层涂层形成在下层之上,其下层涂层具有热喷涂时的粗糙度,无需机械加工。
9. 如权利要求5所述的热喷涂活塞环,其特征在于:前述热喷涂膜为多层组成,上层涂层形成在下层之上,其下层涂层具有热喷涂时的粗糙度,无需机械加工。
10. 如权利要求1、2、4、6、8、或9的任一项所述的热喷涂活塞环,其特征在于:其热喷涂膜的厚度为50~500μm。
11. 如权利要求3所述的热喷涂活塞环,其特征在于:其热喷涂膜的厚度为50~500μm。
12. 如权利要求5所述的热喷涂活塞环,其特征在于:其热喷涂膜的厚度为50~500μm。
13. 如权利要求7所述的热喷涂活塞环,其特征在于:其热喷涂膜的厚度为50~500μm。
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- 2003-01-17 CN CNB038023938A patent/CN100420843C/zh not_active Expired - Fee Related
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CN102261291A (zh) * | 2010-05-24 | 2011-11-30 | 陈殿宽 | 一种活塞及其生产工艺 |
CN105038417A (zh) * | 2015-06-25 | 2015-11-11 | 潘应生 | 高耐磨活塞环 |
Also Published As
Publication number | Publication date |
---|---|
KR20040089111A (ko) | 2004-10-20 |
US7279227B2 (en) | 2007-10-09 |
DE60332705D1 (de) | 2010-07-08 |
CN1617989A (zh) | 2005-05-18 |
BR0306972A (pt) | 2004-11-09 |
EP1467129B1 (en) | 2010-05-26 |
JPWO2003062680A1 (ja) | 2005-05-26 |
EP1467129A4 (en) | 2008-03-26 |
WO2003062680A1 (fr) | 2003-07-31 |
EP1467129A1 (en) | 2004-10-13 |
KR100614022B1 (ko) | 2006-08-22 |
US20050069724A1 (en) | 2005-03-31 |
JP4369757B2 (ja) | 2009-11-25 |
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