磷系添加剂结构与润滑性能的量子化学研究

Theoretical study on structure and lubricant property of containing phosphorus additives

用HF/6-31G方法全优化计算了次膦酸酯、膦酸酯、磷酸酯、亚磷酸酯、酸性磷酸酯、胺基磷酸酯、磷酸酰胺、磷酸酯胺盐等8类磷系润滑添加剂,用前线轨道能级,前线轨道电荷密度,原子净电荷,键级等参数,比较各类添加剂与金属间的相互作用,得到了添加剂的分子结构与其润滑抗磨性能的规律。计算表明,添加剂分子的前线轨道能级,Mulliken键级的数值决定了它们的润滑性能。根据磷系润滑添加剂的前线轨道能级,前线轨道电荷密度,原子净电荷以及Mulliken键级讨论了它们对钢- 钢摩擦副,铝-铝摩擦副的润滑效果,计算结果与实验结论一致。

The eight sorts of phosphorus additives for hypo-phosphonate, phosphonate, phosphate, phosphite, acid phosphate, amido cyanogen phosphate, phosphate acidamine, amine salt of phosphate had been calculated by HF method and 6-31G base set. The structural parameters included the frontier orbital energy, atom net charge, electronic density and bond order of molecule. By comparing action strengthen between additives and metal clusters, the correlations between the additive molecular structure and their lubricant anti-wear were obtained elementally. The calculated results indicated that the values of frontier orbital energy and Mulliken bond order present their own lubricant anti-wear order for different types of phosphorus additives. In this article, the lubricant effects of these additives on Fe-Fe, Al-Al friction pairs were also discussed by using the same quantum chemical structural parameters, the calculated results are in good agreement with experiment results.