矿石粉体作为自修复添加剂的摩擦学作用机理研究
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摘要
金属磨损自修复技术是一项具有创新性的表面工程领域新技术。这项技术可以显著改善磨擦表面的接触力学特性和物理化学特性;选择性地补偿磨损表面,降低机械损耗;可对各种机器的金属磨损表面进行不拆卸的原位修复,使摩擦振动显著降低,从而降低能耗,并大幅度地延长装备的使用寿命。本文对自修复添加剂的热处理、制备、在润滑油中的分散性、自修复机理与影响因素以及混合粉体作为润滑油添加剂的抗磨减摩性能进行了系统的研究,得出主要结论如下:
1.借助X射线衍射仪、差热—热重分析仪和红外光谱对经不同温度热处理的蛇纹石进行分析的结果表明:在800℃左右煅烧后,蛇纹石发生相变,生成了镁橄榄石及顽火辉石,其化学反应式为:Mg_3Si_2O_5(OH)_4→Mg_2SiO_4+MgSiO_3+2H_2O。使用行星式球磨机在不同条件下制备蛇纹石粉体,采用不同的表面改性剂对蛇纹石微细粉体在润滑油中的分散性进行研究。结果表明:制备出的蛇纹石粉体粒径小于10μm,同时使用油酸和钛酸脂偶联剂修饰的粉体可以长时间悬浮于润滑油中。
2.采用扫描电镜(SEM)和能谱分析(EDXP)研究了在MM200试验机上45~#钢环表面上成膜过程及特性,结果表明自修复膜的形成过程是循序渐进的,在摩擦磨损时间很短时就开始出现了自修复膜层,成膜过程与磨损过程同时进行。随着摩擦磨损时间的增加,自修复膜在金属磨损表面形成的愈加均匀和完好。
3.在不同试验条件下对金属摩擦副之间的成膜特性进行的研究发现:在相对较高载荷下(大于600N)成膜现象较为明显;蛇纹石微粒在润滑油中的加入量为2%质量百分比时对金属摩擦副的抗磨性较为理想;在润滑油中加入蛇纹石粉的同时加入碳粉会降低金属摩擦副的摩擦系数,但对自修复膜的形成没有促进作用;550℃热处理和900℃热处理后粉体作为润滑油添加剂可以在磨损的金属表面形成一层带有大量显微孔洞的保护膜;在含有自修复添加剂的润滑条件下,在摩擦磨损过程中,渗碳金属表面可以形成一层自修复膜层,抑制表面裂纹的萌生与扩展,从而避免脆性剥落。
4.为改善添加剂粉体的减摩效果,研究了一种混合粉体作为润滑油添加剂的抗磨减摩特性,结果表明:这种蛇纹石和催化剂粉体的混合物粉体作为润滑油添加剂可以显著的降低摩擦副的摩擦系数,使摩擦系数达到0.006～0.007,同时可以降低摩擦副的磨损量。
5.采用多种微观分析手段系统的研究了添加剂粉体对磨损后表面的自修复特性及不同摩擦磨损时间后表面自修复膜的成膜特性和膜层的结构和元素组成,从而归纳出自修复膜成膜的机理为:(1)当悬浮于润滑油中的蛇纹石粉体与对磨摩擦副微凸体相接触时,添加剂粉体微粒会被相对运动的摩擦副微凸体剪切、挤压和研磨,产生粒度减小的添加剂粉体。同时,摩擦副上的微凸体相互运动,发生粘着和剪切,产生具有活化表面的磨屑和基体表面;(2)产生的具有活性表面的粉体微粒和基体表面发生吸附作用,粉体微粒吸附在基体表面上,同时一部分具有活性表面的粉体微粒和同样具有活性表面的磨屑相互吸附,沉积在摩擦副的凹坑处或悬浮在润滑油中,还有一部分粒度较大的粉体微粒同样沉积在摩擦副的凹坑处;(3)在机械力学作用和摩擦化学作用下,吸附在表面和沉积在摩擦副凹坑处的微粒发生摩擦化学作用,在局部区域生成自修复膜层;(4)在持续的机械力学作用和摩擦化学作用下,添加剂粉体继续在摩擦副表面铺展,压延,直至形成覆盖摩擦副表面的自修复膜层,之后摩擦磨损和自修复膜成膜达到动态平衡。
Self-repair technology of wear metals is an innovative technology in the field of surface engineering.This technology can evidently improve the physic-chemical and mechanical properties of friction pairs and reduce the wear loss by selectely repairing the worn surface.It can repair the worn surface of various metals without machinery disassembly,and significantly reduce friction shock,then reduce energy consumption greatly and extend service life of the devices.In this paper,the heat treatment process, preparation,and its suspension property in lubricant of the serpentine are explored.The formation mechanism of the self-repairing protective coating,and the antiwear property of a mixed powders as lubricant additive have been systematically studied.The main conclusions are reached as follow:
1.The heat treated serpentine at different temperature was examined by using Xray Diffraction apparatus,differential thermal(DTA) and thermogravimetric(TG) analyser and infrared spectrometric analyzer.The results indicated that the phase transformation of serpentine can take place at 800℃.Its chemical transformation equation can be shown as follow:
Mg_3Si_2O_5(OH)_4→Mg_2SiO_4+MgSiO_3+2H_2O
The serpentine powder was prepared by using a QM planetary ball milling machine at different conditions.The dispersive property of the serpentine powder in the lubricant was investigated by using different dispersants.The results indicated that the size of the prepared powder was less than 10μm.The serpentine powder can well suspended in the lubricant by using oil acid and titanate coupling agent as dispersants.
2.The film formation process of the additive on the surface of the metal friction pairs using self-repairing materials as oil additive was conducted by MM-200 friction and wear tester.The surface topography and components of protective film on the worn surface of 45~# steel rings were analyzed by SEM and EDAX.The experimental results indicated that wear and formation of the self-repairing film on the metal friction pairs are concurrence in the initial stage.As the time increases,the formation of the self-repairing film generated gradually.The self-repairing film fully covered on the worn surface of the metal in the end of the test.
3.The formation of the self-repairing film were studied systemically at different experimental conditions.The results indicated that the self-repairing film formation process is faster obviously when the load is relatively higher(600N and higher than 600N).The optimal content of the serpentine particulates in the lubricant is 2 wt%.The addition of the graphite particulate in lubricant can effectively diminished the friction coefficient of the friction pairs,but it has no effect on the formation of the protecting film.The powder heat treated at 550℃and 900℃as lubricant additives can form a protective film on the metal surface with a large number of micro-holes.The smooth self-repairing film can be generated on the worn steel surface of carbonized steel pairs lubricated with additive oil during friction and wear,and the protective film can prohibit the crack or void nucleation and initiation in the deformed layers.Therefore,this avoids the occurrence of delamination wear.
4.Composite powder using as lubricant additive was investigated in order to enhance the friction-reducing effect of the additive.The experimental results show that the composite additive can achieve an ultra-low friction coefficient of 0.007 for the 45~# steel friction pairs.The worn surface is smooth with only a small amount of scratches on the local area of the metal surface.The XPS result after 100h test shows the carbon was concentrated on the worn surface besides of Fe,O,Si and Mg.The existence of the carbon-rich surface layer is the main reason for the superlubricity characteristics.
5.The additive powder directly takes part in the formation process of the self-repairing film and constitutes the main component of the film.The mechanism of self-repairing film
(ⅰ)The serpentine powder can be ground into smaller size in the friction process by the surface asperities of the two contacting surfaces.There are a large number of surface dangling bonds on the powder surface after ground.At the same time,the friction produces fresh surfaces of the steel where the activity of friction pairs and the grindings is enhanced.
(ⅱ) The serpentine powder with activated surface interacts with the fresh surface. The activated powder can adhere on the steel surface.The activated powder can adhere to each other,and deposit on the pits and scratches of the friction pairs surface.At thesame time,some bigger powder can also deposit on the pits and scratches of the friction pairs surface.
(ⅲ) The fine powder adhered on the activatory surface and deposited on the pits and scratches can interact under high contacting stress,high transcient temperature. Then a self-repairing film formed in the local area on the friction pairs surface.
(ⅳ) The powder continually spread on the friction pairs surface under the process of the mechano-chemistry,tribo-chemistry,triboheat and load until the self-repairing film covers fully on the friction pairs surface.Afterward,the wear and the self-repairing film formation process reaches dynamic balance.
1.借助X射线衍射仪、差热—热重分析仪和红外光谱对经不同温度热处理的蛇纹石进行分析的结果表明:在800℃左右煅烧后,蛇纹石发生相变,生成了镁橄榄石及顽火辉石,其化学反应式为:Mg_3Si_2O_5(OH)_4→Mg_2SiO_4+MgSiO_3+2H_2O。使用行星式球磨机在不同条件下制备蛇纹石粉体,采用不同的表面改性剂对蛇纹石微细粉体在润滑油中的分散性进行研究。结果表明:制备出的蛇纹石粉体粒径小于10μm,同时使用油酸和钛酸脂偶联剂修饰的粉体可以长时间悬浮于润滑油中。
2.采用扫描电镜(SEM)和能谱分析(EDXP)研究了在MM200试验机上45~#钢环表面上成膜过程及特性,结果表明自修复膜的形成过程是循序渐进的,在摩擦磨损时间很短时就开始出现了自修复膜层,成膜过程与磨损过程同时进行。随着摩擦磨损时间的增加,自修复膜在金属磨损表面形成的愈加均匀和完好。
3.在不同试验条件下对金属摩擦副之间的成膜特性进行的研究发现:在相对较高载荷下(大于600N)成膜现象较为明显;蛇纹石微粒在润滑油中的加入量为2%质量百分比时对金属摩擦副的抗磨性较为理想;在润滑油中加入蛇纹石粉的同时加入碳粉会降低金属摩擦副的摩擦系数,但对自修复膜的形成没有促进作用;550℃热处理和900℃热处理后粉体作为润滑油添加剂可以在磨损的金属表面形成一层带有大量显微孔洞的保护膜;在含有自修复添加剂的润滑条件下,在摩擦磨损过程中,渗碳金属表面可以形成一层自修复膜层,抑制表面裂纹的萌生与扩展,从而避免脆性剥落。
4.为改善添加剂粉体的减摩效果,研究了一种混合粉体作为润滑油添加剂的抗磨减摩特性,结果表明:这种蛇纹石和催化剂粉体的混合物粉体作为润滑油添加剂可以显著的降低摩擦副的摩擦系数,使摩擦系数达到0.006～0.007,同时可以降低摩擦副的磨损量。
5.采用多种微观分析手段系统的研究了添加剂粉体对磨损后表面的自修复特性及不同摩擦磨损时间后表面自修复膜的成膜特性和膜层的结构和元素组成,从而归纳出自修复膜成膜的机理为:(1)当悬浮于润滑油中的蛇纹石粉体与对磨摩擦副微凸体相接触时,添加剂粉体微粒会被相对运动的摩擦副微凸体剪切、挤压和研磨,产生粒度减小的添加剂粉体。同时,摩擦副上的微凸体相互运动,发生粘着和剪切,产生具有活化表面的磨屑和基体表面;(2)产生的具有活性表面的粉体微粒和基体表面发生吸附作用,粉体微粒吸附在基体表面上,同时一部分具有活性表面的粉体微粒和同样具有活性表面的磨屑相互吸附,沉积在摩擦副的凹坑处或悬浮在润滑油中,还有一部分粒度较大的粉体微粒同样沉积在摩擦副的凹坑处;(3)在机械力学作用和摩擦化学作用下,吸附在表面和沉积在摩擦副凹坑处的微粒发生摩擦化学作用,在局部区域生成自修复膜层;(4)在持续的机械力学作用和摩擦化学作用下,添加剂粉体继续在摩擦副表面铺展,压延,直至形成覆盖摩擦副表面的自修复膜层,之后摩擦磨损和自修复膜成膜达到动态平衡。
Self-repair technology of wear metals is an innovative technology in the field of surface engineering.This technology can evidently improve the physic-chemical and mechanical properties of friction pairs and reduce the wear loss by selectely repairing the worn surface.It can repair the worn surface of various metals without machinery disassembly,and significantly reduce friction shock,then reduce energy consumption greatly and extend service life of the devices.In this paper,the heat treatment process, preparation,and its suspension property in lubricant of the serpentine are explored.The formation mechanism of the self-repairing protective coating,and the antiwear property of a mixed powders as lubricant additive have been systematically studied.The main conclusions are reached as follow:
1.The heat treated serpentine at different temperature was examined by using Xray Diffraction apparatus,differential thermal(DTA) and thermogravimetric(TG) analyser and infrared spectrometric analyzer.The results indicated that the phase transformation of serpentine can take place at 800℃.Its chemical transformation equation can be shown as follow:
Mg_3Si_2O_5(OH)_4→Mg_2SiO_4+MgSiO_3+2H_2O
The serpentine powder was prepared by using a QM planetary ball milling machine at different conditions.The dispersive property of the serpentine powder in the lubricant was investigated by using different dispersants.The results indicated that the size of the prepared powder was less than 10μm.The serpentine powder can well suspended in the lubricant by using oil acid and titanate coupling agent as dispersants.
2.The film formation process of the additive on the surface of the metal friction pairs using self-repairing materials as oil additive was conducted by MM-200 friction and wear tester.The surface topography and components of protective film on the worn surface of 45~# steel rings were analyzed by SEM and EDAX.The experimental results indicated that wear and formation of the self-repairing film on the metal friction pairs are concurrence in the initial stage.As the time increases,the formation of the self-repairing film generated gradually.The self-repairing film fully covered on the worn surface of the metal in the end of the test.
3.The formation of the self-repairing film were studied systemically at different experimental conditions.The results indicated that the self-repairing film formation process is faster obviously when the load is relatively higher(600N and higher than 600N).The optimal content of the serpentine particulates in the lubricant is 2 wt%.The addition of the graphite particulate in lubricant can effectively diminished the friction coefficient of the friction pairs,but it has no effect on the formation of the protecting film.The powder heat treated at 550℃and 900℃as lubricant additives can form a protective film on the metal surface with a large number of micro-holes.The smooth self-repairing film can be generated on the worn steel surface of carbonized steel pairs lubricated with additive oil during friction and wear,and the protective film can prohibit the crack or void nucleation and initiation in the deformed layers.Therefore,this avoids the occurrence of delamination wear.
4.Composite powder using as lubricant additive was investigated in order to enhance the friction-reducing effect of the additive.The experimental results show that the composite additive can achieve an ultra-low friction coefficient of 0.007 for the 45~# steel friction pairs.The worn surface is smooth with only a small amount of scratches on the local area of the metal surface.The XPS result after 100h test shows the carbon was concentrated on the worn surface besides of Fe,O,Si and Mg.The existence of the carbon-rich surface layer is the main reason for the superlubricity characteristics.
5.The additive powder directly takes part in the formation process of the self-repairing film and constitutes the main component of the film.The mechanism of self-repairing film
(ⅰ)The serpentine powder can be ground into smaller size in the friction process by the surface asperities of the two contacting surfaces.There are a large number of surface dangling bonds on the powder surface after ground.At the same time,the friction produces fresh surfaces of the steel where the activity of friction pairs and the grindings is enhanced.
(ⅱ) The serpentine powder with activated surface interacts with the fresh surface. The activated powder can adhere on the steel surface.The activated powder can adhere to each other,and deposit on the pits and scratches of the friction pairs surface.At thesame time,some bigger powder can also deposit on the pits and scratches of the friction pairs surface.
(ⅲ) The fine powder adhered on the activatory surface and deposited on the pits and scratches can interact under high contacting stress,high transcient temperature. Then a self-repairing film formed in the local area on the friction pairs surface.
(ⅳ) The powder continually spread on the friction pairs surface under the process of the mechano-chemistry,tribo-chemistry,triboheat and load until the self-repairing film covers fully on the friction pairs surface.Afterward,the wear and the self-repairing film formation process reaches dynamic balance.
引文
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