氩气等离子体聚合大豆油的合成及摩擦学性能研究
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摘要
利用氩气等离子体降低大豆油(SO)中不饱和C=C双键的含量,得到高黏度的聚合油PAR2.采用凝胶渗透色谱仪分析了PAR2的分子量分布;采用四球摩擦磨损试验机考察了PAR2及同黏度级别的光亮油175BS的摩擦学性能;采用X射线光电子能谱仪分析了钢球摩擦表面元素的化学成分及状态.结果表明:氩气等离子体处理使得PAR2在40℃下的黏度由33.8 cSt增加到956 cSt;与175BS相比,PAR2表现出更为优良的黏温及低温流动性能.与此同时,PAR2中的聚合物主要由SO的二聚物及高分子量的齐聚物组成,其数均分子量M n分别达到2 735和5 434.此外,PAR2的承载能力以及减摩抗磨性能优于175BS;这是由于PAR2在金属表面形成的由羧酸铁组成的边界润滑膜与高价氧化铁膜共同作用,从而有效地减轻金属表面的摩擦与磨损所致.
The content of unsaturated double bonds( C = C) of soybean oil( SO) was decreased by argon plasma polymerization to obtain polymerized oil PAR2. The molecular weight distribution of PAR2 was determined with a gel permeation chromatograph. The tribological properties of PAR2 and 175BS,a bright lubricating oil with the same viscosity grade as that of PAR2,were evaluated with a four- ball machine. Moreover,the chemical composition and state of the elements on the sliding surface of the steel balls were analyzed by means of X- ray photoelectron spectroscopy. Results indicate that Ar plasma treatment increased the viscosity of PAR2 at 40 ℃ from 33. 8 cSt to 956 cSt. As compared with 175BS,PAR2 exhibited better viscosity- temperature and low temperature properties. The polymerized species in plasma- treated PAR2 mainly included the dimers and oligomers of SO,and the number average molecular weight,M n,of the dimers and oligomers were 2 735 and 5 434,respectively. Moreover,PAR2 showed better load- carrying capacity as well as friction- reducing performance and anti- wear ability than 175BS. This is attributed to the synergistic effect of iron carboxylate and iron oxide with high valent state on sliding steel surface,thereby effectively reducd friction and wear of the steel- steel contact.
The content of unsaturated double bonds( C = C) of soybean oil( SO) was decreased by argon plasma polymerization to obtain polymerized oil PAR2. The molecular weight distribution of PAR2 was determined with a gel permeation chromatograph. The tribological properties of PAR2 and 175BS,a bright lubricating oil with the same viscosity grade as that of PAR2,were evaluated with a four- ball machine. Moreover,the chemical composition and state of the elements on the sliding surface of the steel balls were analyzed by means of X- ray photoelectron spectroscopy. Results indicate that Ar plasma treatment increased the viscosity of PAR2 at 40 ℃ from 33. 8 cSt to 956 cSt. As compared with 175BS,PAR2 exhibited better viscosity- temperature and low temperature properties. The polymerized species in plasma- treated PAR2 mainly included the dimers and oligomers of SO,and the number average molecular weight,M n,of the dimers and oligomers were 2 735 and 5 434,respectively. Moreover,PAR2 showed better load- carrying capacity as well as friction- reducing performance and anti- wear ability than 175BS. This is attributed to the synergistic effect of iron carboxylate and iron oxide with high valent state on sliding steel surface,thereby effectively reducd friction and wear of the steel- steel contact.
引文
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[3]Zeng X,Wu H,Yi H,et al.Tribological behavior of three novel triazine derivatives as additives in rapeseed oil[J].Wear,2007,262(5):718-726.
[4]Wang B,Tao D,Jiang H.Synthesis of biodegradable dimmer acid esters and study of their tribological characteristics[J].Tribology,2005,25(5):403-407(in Chinese)[王彬,陶德华,蒋海珍.可生物降解二聚酸酯类的合成及其摩擦磨损性能研究[J].摩擦学学报,2005,25(5):403-407].
[5]Li Q,Tao D,Wang B,et al.The alkyl chain structure and tribology characteristics of chemically modified soybean oil[J].Tribology,2009,29(3):233-237(in Chinese)[李清华,陶德华,王彬,等.化学改性豆油的烷链结构和摩擦学性能研究[J].摩擦学学报,2009,(3):233-237].
[6]Biswas A,Adhvaryu A,Stevenson D G,et al.Microwave irradiation effects on the structure,viscosity,thermal properties and lubricity of soybean oil[J].Industrial crops and products,2007,25(1):1-7.
[7]Dilsiz N,Akovali G.Plasma polymerization of selected organic compounds[J].Polymer,1996,37(2):333-342.
[8]Favia P,Stendardo MV,d'Agostino R.Selective grafting of amine groups on polyethylene by means of NH3—H2RF glow discharges[J].Plasmas and Polymers,1996,1(2):91-112.
[9]Liu D,Hu J,Zhao Y,et al.Surface modification of PBO fibers by argon plasma and argon plasma combined with coupling agents[J].Journal of applied polymer science,2006,102(2):1 428-1 435.
[10]Li G.Testing and analysis for vegetable oils and fats[M].Beijing:Chemical Industry Press,2006:101-130(in Chinese)[李桂华.油料油脂检验与分析[M].北京:化学工业出版社,2006:101-130].
[11]Jahanmir S,Beltzer M.Effect of additive molecular structure on friction coefficient and adsorption[J].Journal of tribology,1986,108(1):109-116.
[12]Fang J,Chen B,Huang W,et al.Synthesis and tribological behavior of phosphorous-nitrogen-incorporated rapeseed oil as lubricating additive[J].Tribology,2001,21(5):348-353(in Chinese)[方建华,陈波水,黄伟九,等.磷氮化改性菜籽油润滑添加剂的制备及其摩擦学性能[J].摩擦学学报,2001,21(5):348-353].
[13]Bowden FP,Tabor D.The friction and lubrication of solids[M].New York:Oxford university press,2001:285-298.
[14]Zhang J,Liu W,Xue Q.The friction and wear behaviors of some O-containing organic compounds as additives in liquid paraffin[J].Wear,1998,219(1):124-127.
[15]Jayadas N,Prabhakaran Nair K.Tribological evaluation of coconut oil as an environment-friendly lubricant[J].Tribology International,2007,40(2):350-354.
[16]McIntyre N,Zetaruk D.X-ray photoelectron spectroscopic studies of iron oxides[J].Analytical Chemistry,1977,49(11):1 521-1 529.
[17]López G P,Castner D G,Ratner B D.XPS O1s binding energies for polymers containing hydroxyl,ether,ketone and ester groups[J].Surface and interface analysis,1991,17(5):267-272.
[18]Srivastava S,Badrinarayanan S,Mukhedkar A.X-ray photoelectron spectra of metal complexes of substituted 2,4-pentanediones[J].Polyhedron,1985,4(3):409-414.
[19]Blomquist J,Helgeson U,Moberg LC,et al.ESCA and M?ssbauer spectra of some iron(III)betadiketonates and tetraphenylporphyrin iron(III)chloride[J].Inorganica Chimica Acta,1983,69:17-23.
[20]Jiang D,Hu L,Feng D.Tribological properties of crown‐type phosphate ionic liquids as lubricating additives in rapeseed oils[J].Lubrication Science,2012,25:195-207.