轧制润滑添加剂在铜箔表面的吸附、减摩与缓蚀行为研究

发布时间：2018-01-18 12:40

  本文关键词：轧制润滑添加剂在铜箔表面的吸附、减摩与缓蚀行为研究　出处：《北京科技大学》2017年博士论文　论文类型：学位论文

  更多相关文章： 铜箔 轧制 润滑添加剂 吸附 缓蚀

【摘要】：随着电子信息产业的迅速发展,压延铜箔因具有高延展性、抗挠曲性、高致密性和低粗糙度等优异性能,已成为柔性印制电路板(FPC)的基础材料。生产达到电子器件要求的高表面质量和高导电性能铜箔,生产过程中的润滑工艺十分关键。压延铜箔轧制摩擦润滑作为多学科渗透的一门科学,目前已引起国内外业界人士的高度重视,而压延铜箔轧制过程中添加剂、摩擦磨损机制及其润滑工艺相关的研究与应用较少。虽然采用润滑工艺可以降低铜箔的最小可轧厚度、改善铜箔表面质量,但轧制油中含有的添加剂可能会对铜箔表面造成局部腐蚀,影响其使用性能。因此,开展轧制油中添加剂分子在铜箔表面的吸附、减摩、腐蚀与缓蚀行为的研究是十分必要的。利用四球摩擦磨损试验机研究了不同浓度、载荷和转速条件下单体极压抗磨添加剂及其复配体系对铜箔轧制油摩擦学性能的影响,并通过冷轧实验研究了铜箔轧制摩擦磨损与工艺润滑效果的关系。基于表征润滑性能的最大无卡咬负荷、摩擦系数和磨斑直径三个参数,提出了分析润滑剂摩擦学性能新指标——极压抗磨润滑系数Ω。根据分子动力学理论设计制备的含氮磷硼酸酯NBPE是一种具有良好的热稳定性、水解稳定性和优异的极压、抗磨性的润滑油添加剂;当润滑油中添加质量分数为0.15%的NBPE时,在钢-铜摩擦过程中摩擦系数和铜磨损率分别降低了 59.4%和45.2%;NBPE在铜表面形成由含硼吸附层、有机含氮金属络合物和磷酸盐无机反应膜组成的约30nm厚纳米摩擦膜,S和P元素化合物与Fe反应生成FeP04和Fex(S04)y,两者均导致了边界润滑膜的形成。轧辊与铜箔的摩擦以粘着、犁削和剥离等多种磨损机制并存,粘着磨损起主要作用。通过重量损失法和表面微观分析考察了轧制油组分、温度、时间等对铜箔腐蚀的规律与机理,明确了轧制油中的极压抗磨剂(BT和EK)造成铜箔的腐蚀。轧制油中缓蚀剂的加入,明显降低了铜箔的腐蚀速度,铜缓蚀效率随噻二唑类缓蚀剂(DTA)浓度增加而增加,随温度升高而增加,且100℃C下DTA浓度在5mM时获得最大缓蚀效率,其值为89.02%;缓蚀剂BTA,MBA和DTA吸附铜表面增加了表面的疏水性,缓蚀剂膜在铜表面上呈球形、圆柱形、半球形等,是由缓蚀剂浓度决定。质量损失、LSCM和SERS实验表明,缓蚀剂以Langmuir.等温线模型吸附在铜表面上。采用第一性原理计算和表面表征技术揭示了极压抗磨剂(EK)/缓蚀剂(DTA)分子在轧制过程中铜表面的吸附机理;基于压延铜箔的微观结构在(220)的择优取向构建了 Cu(110)模型,利用密度泛函理论(DFT)计算了EK和DTA分子在Cu(110)面的吸附能、最优吸附构型和电荷转移。缓蚀剂DTA经过自分解与Cu原子形成多个Cu-N、Cu-S键强烈的化学吸附在Cu(110)面,吸附能为-3.59eV;而极压抗磨剂EK吸附能为-0.50eV,通过Cu-0键微弱的吸附在铜表面,分子与Cu表面形成化学键的预测结果和XPS分析一致。因此,基于DTA自分解以及比EK更强的化学吸附作用的模拟结果提出了一个新的缓蚀机理。根据密度泛函理论计算了添加剂分子的全局反应活性及局部反应活性位点等化学参数,采用量子化学计算和遗传运算法相结合的方法研究了添加剂分子的结构与轧制工艺润滑效果之间的关系,建立的"分子结构—润滑性能(摩擦学性能、缓蚀效率等)"的定量构效模型(QSAR)真实可靠,可用于添加剂分子的摩擦学性预测,并为轧制润滑添加剂分子的设计合成提供参考和指导。
[Abstract]:With the rapid development of electronic information industry, because the rolled copper foil has high ductility, flexing resistance, high density and low roughness and excellent performance, has become a flexible printed circuit board (FPC). The basic material production to achieve high surface quality requirements of electronic devices and high conductivity copper foil, lubrication technology in the production process is the key. The rolled copper foil rolling friction lubrication as a science of multi-disciplinary, has attracted great attention of domestic and foreign industry, and rolled copper foil rolling process additives, research and application of less friction and wear mechanism and lubrication technology related. Although the use of lubrication technology can reduce the minimum thickness of copper foil, improve surface quality of copper foil, but the additives containing in rolling oil may cause local corrosion on the surface of copper foil, affecting its performance. Therefore, to carry out additives in rolling oil branch The adsorption of copper foil surface friction, corrosion and corrosion behavior research is very necessary. By four ball friction wear testing machine of different concentration, speed and load conditions of single extreme pressure antiwear additives and their mixtures on the tribological properties of copper foil rolling oil influence, and through the experimental study of cold rolled copper foil rolling friction and wear and process lubrication effect. The lubrication performance characterization of the maximum nonseizure load based on the friction coefficient and wear scar diameter three parameters, put forward the new index analysis of tribological performance of lubricant anti-wear extreme pressure lubrication coefficient Omega. According to the molecular dynamics theory to design the preparation of borate ester containing nitrogen and phosphorus is NBPE with good thermal stability, hydrolysis stability and excellent extreme pressure and antiwear lubricating oil additives of lubricating oil; when the mass fraction of NBPE was 0.15%, in the steel copper friction process The friction coefficient and wear rate of copper were decreased by 59.4% and 45.2%; NBPE formed by boron adsorption layer on the copper surface, about 30nm thick nano friction film containing organic nitrogen and inorganic phosphate metal complex reaction film composed of S and P element compound and Fe reaction of FeP04 and Fex (S04) y, both of which lead to the the formation of boundary lubrication film. The friction roller and copper foil with adhesive, peeling and other coexistence of plough and wear mechanism, adhesive wear plays a main role. By the weight loss method and surface analysis of rolling oil composition, temperature were investigated, the regularity and mechanism of time on copper corrosion, the rolling oil in the pressure antiwear agent (BT and EK) caused by the corrosion of copper foil rolling oil. Add corrosion inhibitor, significantly reduces the corrosion rate of copper foil, copper corrosion inhibition efficiency with hydrochlorothiazide two azole inhibitor (DTA) concentration increased, increased with increase of temperature, and 100 DEG C under C DTA娴撳害鍦，

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