自修复纳米铜润滑添加剂的研制及其摩擦学性能的研究
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摘要
纳米技术的出现，尤其是纳米粉体制备技术的长足进步，增加了纳米润滑新的研究内容。纳米润滑已经成为润滑研究的一个重要研究方向。本文基于摩擦学、纳米粉体制备技术、有机化学、界面化学、电化学、结构化学、表面化学和材料学等多学科的知识，研制出了具有良好抗磨减摩性能、较好抗极压性能和自修复效应的添加剂NT1。分析了其结构的红外光谱；研究了摩擦学系统对NT1摩擦学性能的影响；研究了NT1与其他添加剂的协同效应；研究了摩擦副磨损表面沉积膜的成分；通过现代微观技术测试了摩擦副的磨损表面形貌及成分；提出了自修复纳米润滑过程中的动力学模型和电泳模型。
本文的主要创新和研究成果体现在以下方面：
1、基于超碎粉体制备技术和界面化学基本原理，通过选择合适的助剂和物料研制出了纳米铜，并通过正交试验得出研磨时最佳的物料配比。
2、通过对纳米粉体的二次化学修饰，较好的实现了纳米铜在基础油中的稳定分散性，并在此基础上研制出了具有自修复效应的纳米添加剂NT1。
3、系统地研究了添加剂N.1的摩擦学性能。结果表明，NT1具有磨损自修复功能，能降低钢／钢摩擦副的摩擦系数和改善耐磨性，添加剂NT1在N68油中添加量为4％时获得的N68NT1润滑油具有最佳摩擦学性能。对于钢／钢摩擦副，N68NT1的摩擦系数分别为MobilSAE40和N68油的56.2％和51.1％，并出现负磨损。另外，根据摩擦学系统理论，考察了摩擦学系统中主要特征元素(相对滑动速度、表面粗糙度、不同的添加量和载荷)对自修复纳米铜润滑添加剂NT1摩擦学性能的影响。
4、从表面分子反应动力学的观点出发，在大量的试验数据基础上建立了摩擦过程中摩擦副表面生成铜配位化合物的反应动力学公式，由公式可以看出随着摩擦时间的延长，在摩擦表面沉积的铜的配位化合物膜厚度会达到一定值，不再增加。
5、建立了自修复纳米铜润滑添加剂在摩擦过程中的电泳模型，为此，初步解释了其在摩擦过程中的选择性转移效应。同时也初步探讨了其润滑机理，得出N68NT1优异的摩擦学性能是因为在摩擦过程中多种沉积膜的协同作用。
The emergence of nano-technology, especially the advance of the technology in preparing nano-powder, has brought along a series of new research activities in the field of nano-lubrication. The aspect of nano-lubrication is an important area which is arising a great deal of research interest Based on the knowledge in the disciplines of tribology, nano-powder preparation technology, organic chemistry, surface chemistry, electrochemistry, structural chemistry, material science and so on, this research specifically emphasized on the development of a self-repairing nano-copper lubricating additive NT1. The additive has fine anti-wear and anti-friction ability, high anti-xtreme pressure function and good self-repairing capacity. Infra-red spectrum analysis was performed so as to understand the structure of the additive. The effect of tribological system on NT1's tribological characteristics was conducted. The synergistic influence; of Nil with other lubricating additives and ths structures of deposited film on the
surface of friction pairs were carried out. Surface textures and elemental compositions of the worn surface were studied microcosmically using some available modem microcosmic analytical techniques. Finally, an electrophoresis model and a dynamics model were established and herewith put forward for studying the self-repairing nano-copper lubrication mechanisms of the NT1 additive.
Main contributions and results of this research include:
( I ) The production of nano-copper brei from adequate selection of some accessory ingredients based on the technology of super-fine powder preparation and the fundamental of surface chemistry. Best composition of materials for making nano-copper brei was subsequently determined by a series of orthogonal experimental approaches.
(II) The establishment of the approach for preparing nano-copper self-repairing lubricating additive by the mixing of triethanolamine and based oil, and by the steadily scattering of the uniformly dispersed nano-copper brei into the based oil.
(III) The study of the trifaological characteristics of the additive NT1. The research results indicated that additive NT1 have wear-self-repairing effects, and it can reduce the friction coefficients and improve anti-wear ability for the steel / steel rubbing pairs markedly,. The achievement of best tribological characteristics of N68NT1 with 4% of self-repairing nanopaticle additive NT1 in N68 oil. The friction coefficients of N68NT1 lubrication is 56.2% and 51.1% of MobilSAE40 and N68 oil respectively for the steel /steel rubbing pairs. On the side, the Study of tile effects of iribologica) system on the tribological characteristics of the self-repairing nano-scale NT1 additive particles under various tribological parameters like: relative sliding velocity, surface roughness of friction pair, the different affixion masses of additive and load, etc.
(IV) The setting up of the reacting dynamic formulae of Cu coordination compound on the steel/copper friction pair surface during frictional sliding by carefully correlating the vase of testing data with the surface molecule reacting dynamics. According to the formulae, the depth of coordination compound dynamically reacting on the steel/steel friction pair surface arrived at a constant value after sliding for a period of time under frictional condition.
(V) The proposal of an electrophoresis model for the self-repairing NT1 nano-copper lubrication. The explanation of the effects of selective transfer on the course of friction was given. The lubricating mechanism for self-repairing nano-copper lubricating additive was studied. The reason why the N68NT1 having excellent lubricating properties was identified as synthetical effects of several deposit coatings.
Guo Zhiguang(Mechanical Design & Theory) Directed by Prof Gu Kali & Prof Xu Jiansheng
本文的主要创新和研究成果体现在以下方面：
1、基于超碎粉体制备技术和界面化学基本原理，通过选择合适的助剂和物料研制出了纳米铜，并通过正交试验得出研磨时最佳的物料配比。
2、通过对纳米粉体的二次化学修饰，较好的实现了纳米铜在基础油中的稳定分散性，并在此基础上研制出了具有自修复效应的纳米添加剂NT1。
3、系统地研究了添加剂N.1的摩擦学性能。结果表明，NT1具有磨损自修复功能，能降低钢／钢摩擦副的摩擦系数和改善耐磨性，添加剂NT1在N68油中添加量为4％时获得的N68NT1润滑油具有最佳摩擦学性能。对于钢／钢摩擦副，N68NT1的摩擦系数分别为MobilSAE40和N68油的56.2％和51.1％，并出现负磨损。另外，根据摩擦学系统理论，考察了摩擦学系统中主要特征元素(相对滑动速度、表面粗糙度、不同的添加量和载荷)对自修复纳米铜润滑添加剂NT1摩擦学性能的影响。
4、从表面分子反应动力学的观点出发，在大量的试验数据基础上建立了摩擦过程中摩擦副表面生成铜配位化合物的反应动力学公式，由公式可以看出随着摩擦时间的延长，在摩擦表面沉积的铜的配位化合物膜厚度会达到一定值，不再增加。
5、建立了自修复纳米铜润滑添加剂在摩擦过程中的电泳模型，为此，初步解释了其在摩擦过程中的选择性转移效应。同时也初步探讨了其润滑机理，得出N68NT1优异的摩擦学性能是因为在摩擦过程中多种沉积膜的协同作用。
The emergence of nano-technology, especially the advance of the technology in preparing nano-powder, has brought along a series of new research activities in the field of nano-lubrication. The aspect of nano-lubrication is an important area which is arising a great deal of research interest Based on the knowledge in the disciplines of tribology, nano-powder preparation technology, organic chemistry, surface chemistry, electrochemistry, structural chemistry, material science and so on, this research specifically emphasized on the development of a self-repairing nano-copper lubricating additive NT1. The additive has fine anti-wear and anti-friction ability, high anti-xtreme pressure function and good self-repairing capacity. Infra-red spectrum analysis was performed so as to understand the structure of the additive. The effect of tribological system on NT1's tribological characteristics was conducted. The synergistic influence; of Nil with other lubricating additives and ths structures of deposited film on the
surface of friction pairs were carried out. Surface textures and elemental compositions of the worn surface were studied microcosmically using some available modem microcosmic analytical techniques. Finally, an electrophoresis model and a dynamics model were established and herewith put forward for studying the self-repairing nano-copper lubrication mechanisms of the NT1 additive.
Main contributions and results of this research include:
( I ) The production of nano-copper brei from adequate selection of some accessory ingredients based on the technology of super-fine powder preparation and the fundamental of surface chemistry. Best composition of materials for making nano-copper brei was subsequently determined by a series of orthogonal experimental approaches.
(II) The establishment of the approach for preparing nano-copper self-repairing lubricating additive by the mixing of triethanolamine and based oil, and by the steadily scattering of the uniformly dispersed nano-copper brei into the based oil.
(III) The study of the trifaological characteristics of the additive NT1. The research results indicated that additive NT1 have wear-self-repairing effects, and it can reduce the friction coefficients and improve anti-wear ability for the steel / steel rubbing pairs markedly,. The achievement of best tribological characteristics of N68NT1 with 4% of self-repairing nanopaticle additive NT1 in N68 oil. The friction coefficients of N68NT1 lubrication is 56.2% and 51.1% of MobilSAE40 and N68 oil respectively for the steel /steel rubbing pairs. On the side, the Study of tile effects of iribologica) system on the tribological characteristics of the self-repairing nano-scale NT1 additive particles under various tribological parameters like: relative sliding velocity, surface roughness of friction pair, the different affixion masses of additive and load, etc.
(IV) The setting up of the reacting dynamic formulae of Cu coordination compound on the steel/copper friction pair surface during frictional sliding by carefully correlating the vase of testing data with the surface molecule reacting dynamics. According to the formulae, the depth of coordination compound dynamically reacting on the steel/steel friction pair surface arrived at a constant value after sliding for a period of time under frictional condition.
(V) The proposal of an electrophoresis model for the self-repairing NT1 nano-copper lubrication. The explanation of the effects of selective transfer on the course of friction was given. The lubricating mechanism for self-repairing nano-copper lubricating additive was studied. The reason why the N68NT1 having excellent lubricating properties was identified as synthetical effects of several deposit coatings.
Guo Zhiguang(Mechanical Design & Theory) Directed by Prof Gu Kali & Prof Xu Jiansheng
引文
[1][英]．J 霍林．摩擦学原理[M]．机械工业出版社，1981．
[2]张剑锋，周志芳．摩擦磨损与抗磨技术[M]．天津科技翻译出版公司，1993．
[3]陈耕，汪一麟．摩擦与磨损[M]．同济大学出版社，1991
[4]赵源．摩擦磨损的发展及其任务[J]．摩擦磨损，1979(1)：8～23
[5]温诗铸编．摩擦学原理[M]．清华大学出版社，1990年．
[6]余俊，徐真编．摩擦学[M]．长沙：湖南科学技术出版社，1984．
[7]谢友柏．摩擦学的三个公理[J]．摩擦学学报．Vol21，No3．2001．
[8][西德]霍斯特．契可夫著．刘钟华等译．摩擦学[M]．北京：机械工业出版社，1984．
[9]张建华，赵源，李健，高万振．磨损自补偿润滑添加剂ZT2的摩擦学特性试验[J]．机械科学与技术，1998(6)：1020～1021．
[10]1(1980),2:303
[11]Furey, M. J., Ghasemi H.,et al. Tribochemistry of the Antiwear Action of a Dimer Acid/Glycol Monoester on Alumina, Tribology Transactions, 37 (1994), 1, P59.
[12]S. Tarasov, h. Kolubaev, S. Belyaev et al. Study of friction reduction of nanocopper additives to motor oil[J].Wear 252 (2002) 63-69.
[13]H. Mishina, Surface deformation and formation of original element of wear particles in sliding friction[J]. Wear 215(1998)10-17.
[14]夏延秋，丁津源，马先贵．纳米级金属改善润滑油的摩擦磨损性能研究[J]．润滑油，1998，13(6)：37～40．
[15]Xu T, Zhao J Z, Ma X G. Study on the tribological properties of unltradispersed diamond containing soot as oil additive[J]. Tribology Transactions, 1997 (40): 178～183.
[16]叶毅，董俊修，陈波水等．纳米硼酸镧对润滑油抗磨性能的影响的研究[J]．润滑与密封，2000，(2)：23～24．
[17]张泽抚，曾继华，刘维民等．含氮有机物修饰的纳米氢氧化镧与ZDDP复配的摩擦学性能的研究[J]．中国矿业大学学报，1999，28：108～110．
[18]张泽抚，刘维民，薛群基等．含氮有机物修饰的纳米氟化镧的摩擦学性能研究[J]．摩擦学学报，2000，20(3)：217～219．
[19]张泽抚，刘维民，薛群基等．纳米氢氧化镧与ZDDP相互作用研究[J]．电子显微学报，2000，19(4)：603～604．
[20]Liu W M, Chen S. An Investigation of the Tribological Behavior of Surface-Modified ZnS Nanoparticles in Liquid Paraffin[J]. Wear,2000, 238:120～124.
[21]陈爽，刘维民．ZnS纳米微粒作为润滑油添加剂的EPMA研究[J]．中国矿业大学学报，1999，28：14～16．
[22]陈爽，刘维民．温度对PbS纳米微粒摩擦学性能的影响[J]．摩擦学学报，1999，19：169～172．
[23]Chen S, Liu W M. Preparation and Characterization of Surface Coated ZnS Nanoparticles[J]. Langmuir, 1999,15:8100-8104.
[24]Chen S, Liu W M, Yu L G. Study on The Structure of PbS nanoparticles Coated with Dialkyldithiophosphate[J] Mater Res, 1999,14:2147～2151.
[25]周静芳，陶小军，张治军等．表面修饰Ag2S纳米微粒的合成及摩擦学行为[J]．化学研究，1999，3(4)1～5．
[26]张平余，刘维民，薛群基．薄膜形貌的AFM观察[J]．电子显微镜学报，2000，19(4)：593～594．
[27]Yu L G, Liu W M, Yang S R et al. An Investigation of The Friction and Wear Behaviors of Micrometer Copper Particle-and Manometer Copper Particle-Filled Polyoxymethylene Composites[J]. Journal of Applied Polymer Science, 2000,77:2404～2410.
[28]ChikaraH. Physics Today, December 1987,44～51.
[29]王世敏，许祖勋，傅晶著．纳米材料制备技术[M]．化学工业出版社，2002．7～129页
[30]盖国胜．超细粉碎分级技术[M]．北京：中国轻工业出版社，2000．
[31]张立德．纳米材料和纳米结构[M]．科学出版社，2001
[32]尾崎义治，贺城集一郎著，赵修建，张联盟译．超微颗粒导论[M]．武汉工业大学出版社，1991．
[2]张剑锋，周志芳．摩擦磨损与抗磨技术[M]．天津科技翻译出版公司，1993．
[3]陈耕，汪一麟．摩擦与磨损[M]．同济大学出版社，1991
[4]赵源．摩擦磨损的发展及其任务[J]．摩擦磨损，1979(1)：8～23
[5]温诗铸编．摩擦学原理[M]．清华大学出版社，1990年．
[6]余俊，徐真编．摩擦学[M]．长沙：湖南科学技术出版社，1984．
[7]谢友柏．摩擦学的三个公理[J]．摩擦学学报．Vol21，No3．2001．
[8][西德]霍斯特．契可夫著．刘钟华等译．摩擦学[M]．北京：机械工业出版社，1984．
[9]张建华，赵源，李健，高万振．磨损自补偿润滑添加剂ZT2的摩擦学特性试验[J]．机械科学与技术，1998(6)：1020～1021．
[10]1(1980),2:303
[11]Furey, M. J., Ghasemi H.,et al. Tribochemistry of the Antiwear Action of a Dimer Acid/Glycol Monoester on Alumina, Tribology Transactions, 37 (1994), 1, P59.
[12]S. Tarasov, h. Kolubaev, S. Belyaev et al. Study of friction reduction of nanocopper additives to motor oil[J].Wear 252 (2002) 63-69.
[13]H. Mishina, Surface deformation and formation of original element of wear particles in sliding friction[J]. Wear 215(1998)10-17.
[14]夏延秋，丁津源，马先贵．纳米级金属改善润滑油的摩擦磨损性能研究[J]．润滑油，1998，13(6)：37～40．
[15]Xu T, Zhao J Z, Ma X G. Study on the tribological properties of unltradispersed diamond containing soot as oil additive[J]. Tribology Transactions, 1997 (40): 178～183.
[16]叶毅，董俊修，陈波水等．纳米硼酸镧对润滑油抗磨性能的影响的研究[J]．润滑与密封，2000，(2)：23～24．
[17]张泽抚，曾继华，刘维民等．含氮有机物修饰的纳米氢氧化镧与ZDDP复配的摩擦学性能的研究[J]．中国矿业大学学报，1999，28：108～110．
[18]张泽抚，刘维民，薛群基等．含氮有机物修饰的纳米氟化镧的摩擦学性能研究[J]．摩擦学学报，2000，20(3)：217～219．
[19]张泽抚，刘维民，薛群基等．纳米氢氧化镧与ZDDP相互作用研究[J]．电子显微学报，2000，19(4)：603～604．
[20]Liu W M, Chen S. An Investigation of the Tribological Behavior of Surface-Modified ZnS Nanoparticles in Liquid Paraffin[J]. Wear,2000, 238:120～124.
[21]陈爽，刘维民．ZnS纳米微粒作为润滑油添加剂的EPMA研究[J]．中国矿业大学学报，1999，28：14～16．
[22]陈爽，刘维民．温度对PbS纳米微粒摩擦学性能的影响[J]．摩擦学学报，1999，19：169～172．
[23]Chen S, Liu W M. Preparation and Characterization of Surface Coated ZnS Nanoparticles[J]. Langmuir, 1999,15:8100-8104.
[24]Chen S, Liu W M, Yu L G. Study on The Structure of PbS nanoparticles Coated with Dialkyldithiophosphate[J] Mater Res, 1999,14:2147～2151.
[25]周静芳，陶小军，张治军等．表面修饰Ag2S纳米微粒的合成及摩擦学行为[J]．化学研究，1999，3(4)1～5．
[26]张平余，刘维民，薛群基．薄膜形貌的AFM观察[J]．电子显微镜学报，2000，19(4)：593～594．
[27]Yu L G, Liu W M, Yang S R et al. An Investigation of The Friction and Wear Behaviors of Micrometer Copper Particle-and Manometer Copper Particle-Filled Polyoxymethylene Composites[J]. Journal of Applied Polymer Science, 2000,77:2404～2410.
[28]ChikaraH. Physics Today, December 1987,44～51.
[29]王世敏，许祖勋，傅晶著．纳米材料制备技术[M]．化学工业出版社，2002．7～129页
[30]盖国胜．超细粉碎分级技术[M]．北京：中国轻工业出版社，2000．
[31]张立德．纳米材料和纳米结构[M]．科学出版社，2001
[32]尾崎义治，贺城集一郎著，赵修建，张联盟译．超微颗粒导论[M]．武汉工业大学出版社，1991．