本文關(guān)鍵詞：軋制潤滑添加劑在銅箔表面的吸附、減摩與緩蝕行為研究　出處：《北京科技大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 銅箔 軋制 潤滑添加劑 吸附 緩蝕

【摘要】：隨著電子信息產(chǎn)業(yè)的迅速發(fā)展,壓延銅箔因具有高延展性、抗撓曲性、高致密性和低粗糙度等優(yōu)異性能,已成為柔性印制電路板(FPC)的基礎(chǔ)材料。生產(chǎn)達到電子器件要求的高表面質(zhì)量和高導(dǎo)電性能銅箔,生產(chǎn)過程中的潤滑工藝十分關(guān)鍵。壓延銅箔軋制摩擦潤滑作為多學(xué)科滲透的一門科學(xué),目前已引起國內(nèi)外業(yè)界人士的高度重視,而壓延銅箔軋制過程中添加劑、摩擦磨損機制及其潤滑工藝相關(guān)的研究與應(yīng)用較少。雖然采用潤滑工藝可以降低銅箔的最小可軋厚度、改善銅箔表面質(zhì)量,但軋制油中含有的添加劑可能會對銅箔表面造成局部腐蝕,影響其使用性能。因此,開展軋制油中添加劑分子在銅箔表面的吸附、減摩、腐蝕與緩蝕行為的研究是十分必要的。利用四球摩擦磨損試驗機研究了不同濃度、載荷和轉(zhuǎn)速條件下單體極壓抗磨添加劑及其復(fù)配體系對銅箔軋制油摩擦學(xué)性能的影響,并通過冷軋實驗研究了銅箔軋制摩擦磨損與工藝潤滑效果的關(guān)系。基于表征潤滑性能的最大無卡咬負荷、摩擦系數(shù)和磨斑直徑三個參數(shù),提出了分析潤滑劑摩擦學(xué)性能新指標——極壓抗磨潤滑系數(shù)Ω。根據(jù)分子動力學(xué)理論設(shè)計制備的含氮磷硼酸酯NBPE是一種具有良好的熱穩(wěn)定性、水解穩(wěn)定性和優(yōu)異的極壓、抗磨性的潤滑油添加劑;當(dāng)潤滑油中添加質(zhì)量分數(shù)為0.15%的NBPE時,在鋼-銅摩擦過程中摩擦系數(shù)和銅磨損率分別降低了 59.4%和45.2%;NBPE在銅表面形成由含硼吸附層、有機含氮金屬絡(luò)合物和磷酸鹽無機反應(yīng)膜組成的約30nm厚納米摩擦膜,S和P元素化合物與Fe反應(yīng)生成FeP04和Fex(S04)y,兩者均導(dǎo)致了邊界潤滑膜的形成。軋輥與銅箔的摩擦以粘著、犁削和剝離等多種磨損機制并存,粘著磨損起主要作用。通過重量損失法和表面微觀分析考察了軋制油組分、溫度、時間等對銅箔腐蝕的規(guī)律與機理,明確了軋制油中的極壓抗磨劑(BT和EK)造成銅箔的腐蝕。軋制油中緩蝕劑的加入,明顯降低了銅箔的腐蝕速度,銅緩蝕效率隨噻二唑類緩蝕劑(DTA)濃度增加而增加,隨溫度升高而增加,且100℃C下DTA濃度在5mM時獲得最大緩蝕效率,其值為89.02%;緩蝕劑BTA,MBA和DTA吸附銅表面增加了表面的疏水性,緩蝕劑膜在銅表面上呈球形、圓柱形、半球形等,是由緩蝕劑濃度決定。質(zhì)量損失、LSCM和SERS實驗表明,緩蝕劑以Langmuir.等溫線模型吸附在銅表面上。采用第一性原理計算和表面表征技術(shù)揭示了極壓抗磨劑(EK)/緩蝕劑(DTA)分子在軋制過程中銅表面的吸附機理;基于壓延銅箔的微觀結(jié)構(gòu)在(220)的擇優(yōu)取向構(gòu)建了 Cu(110)模型,利用密度泛函理論(DFT)計算了EK和DTA分子在Cu(110)面的吸附能、最優(yōu)吸附構(gòu)型和電荷轉(zhuǎn)移。緩蝕劑DTA經(jīng)過自分解與Cu原子形成多個Cu-N、Cu-S鍵強烈的化學(xué)吸附在Cu(110)面,吸附能為-3.59eV;而極壓抗磨劑EK吸附能為-0.50eV,通過Cu-0鍵微弱的吸附在銅表面,分子與Cu表面形成化學(xué)鍵的預(yù)測結(jié)果和XPS分析一致。因此,基于DTA自分解以及比EK更強的化學(xué)吸附作用的模擬結(jié)果提出了一個新的緩蝕機理。根據(jù)密度泛函理論計算了添加劑分子的全局反應(yīng)活性及局部反應(yīng)活性位點等化學(xué)參數(shù),采用量子化學(xué)計算和遺傳運算法相結(jié)合的方法研究了添加劑分子的結(jié)構(gòu)與軋制工藝潤滑效果之間的關(guān)系,建立的"分子結(jié)構(gòu)—潤滑性能(摩擦學(xué)性能、緩蝕效率等)"的定量構(gòu)效模型(QSAR)真實可靠,可用于添加劑分子的摩擦學(xué)性預(yù)測,并為軋制潤滑添加劑分子的設(shè)計合成提供參考和指導(dǎo)。
[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嫻撳害鍦，

本文編號：1441031