發(fā)布時間：2018-06-02 18:15

  本文選題：物理氣相沉積 + 類金剛石薄膜��； 參考：《華南理工大學(xué)》2016年博士論文

【摘要】：類金剛石(diamond-like carbon)薄膜具有高硬度、高彈性模量、優(yōu)異的減摩耐磨性能、良好的光透過性、較強的化學(xué)穩(wěn)定性和生物相容性等優(yōu)異的性能,在太空機械、工模具、汽車、電子器件、光學(xué)、生物醫(yī)學(xué)等領(lǐng)域擁有廣闊的應(yīng)用前景。然而,大量的研究發(fā)現(xiàn)類金剛石薄膜(DLC)中存在著很大的殘余應(yīng)力,不僅削弱了薄膜與基體之間的結(jié)合強度導(dǎo)致薄膜在服役過程中提前剝落失效,還限制了薄膜的沉積厚度,此外DLC薄膜還存在摩擦學(xué)行為對服役環(huán)境敏感性高的缺點,這些因素均限制了DLC薄膜在工業(yè)中的大規(guī)模應(yīng)用。為了改善DLC薄膜的固有缺陷,滿足工業(yè)應(yīng)用的要求,本文通過金屬、非金屬以及化合物異質(zhì)摻雜的方法對類金剛石薄膜進(jìn)行改性,針對高溫、高濕、干燥、貧油等不同的摩擦磨損服役工況,制備出了綜合性能優(yōu)異的摻鎢DLC薄膜、摻硅DLC薄膜和WS_2摻雜DLC薄膜。采用磁控濺射和陽極層流型離子源復(fù)合沉積技術(shù)在H13熱作模具鋼和Si(100)基體表面制備了鎢元素?fù)诫s的DLC薄膜,以減小DLC薄膜中的殘余應(yīng)力、提高薄膜在高溫環(huán)境中的熱穩(wěn)定性和減摩耐磨性能。為了減小薄膜與基體之間的物理失配、緩解界面應(yīng)力并提高膜基結(jié)合強度,本試驗通過工藝設(shè)置在DLC薄膜和基體之間構(gòu)筑了Cr/CrN/CrNC/CrC梯度過渡層,大幅度地提高了DLC薄膜與基體間的結(jié)合強度。最終在H13鋼表面沉積的摻W類金剛石薄膜的厚度可達(dá)3.51μm,膜基結(jié)合強度達(dá)HF2級,薄膜的顯微硬度可達(dá)2289HV。采用TEM、SEM、XRD等檢測方法對摻W類金剛石薄膜的微觀結(jié)構(gòu)和化學(xué)成分進(jìn)行分析,發(fā)現(xiàn)W元素是以WC1-x納米晶團簇的形式彌散地鑲嵌在DLC薄膜三維碳基網(wǎng)絡(luò)中,構(gòu)成了納米晶-非晶復(fù)合結(jié)構(gòu)。隨后本文系統(tǒng)地研究了摻W類金剛石薄膜從室溫25℃到500℃溫度范圍內(nèi)的摩擦磨損行為,得到的試驗結(jié)果表明:在DLC薄膜中摻雜W元素不僅可以降低薄膜內(nèi)應(yīng)力和提高膜基結(jié)合力,還能提高薄膜在高溫條件下的穩(wěn)定性。在200℃以下能保持結(jié)構(gòu)和摩擦學(xué)性能的穩(wěn)定性,300℃加熱時薄膜會發(fā)生部分石墨化,同時表面開始氧化,薄膜的耐磨損性能開始下降;400℃時氧化嚴(yán)重,薄膜中的C大量損失,薄膜主要由WO3相組成疏松的結(jié)構(gòu),薄膜的耐磨損性能將顯著降低;500℃時其摩擦系數(shù)仍能保持在0.15以下,但其磨損率要遠(yuǎn)高于25℃~200℃溫度范圍內(nèi)磨損的樣品。采用中頻磁控濺射和離子源輔助沉積技術(shù),通過正交試驗優(yōu)化工藝參數(shù),在Cr12MoV模具鋼和Si(100)表面成功地制備了膜層結(jié)構(gòu)細(xì)膩、致密的含氫摻硅DLC薄膜。Si元素?fù)诫s含量是影響薄膜機械性能和摩擦學(xué)性能的關(guān)鍵因素,當(dāng)Si含量為3.75at.%時,Si-DLC薄膜的硬度為2039HV,膜基結(jié)合強度在30N以上。此外,Si元素的摻入還可以降低薄膜摩擦學(xué)性能對摩擦環(huán)境濕度的敏感性,當(dāng)Si含量在3.38~3.75 at.%范圍時,Si-DLC薄膜在高濕度和低濕度條件下的摩擦系數(shù)均可穩(wěn)定在0.13左右。為了使DLC薄膜能夠同時適應(yīng)多種服役環(huán)境,采用中頻磁控濺射和離子源輔助沉積技術(shù)在9310滲碳鋼、TC4鈦合金、K20硬質(zhì)合金三種基體上制備了摻WS_2類金剛石薄膜。WS_2摻入DLC薄膜后是以WC1-x和WS_2納米晶團簇的形式彌散分布于碳基網(wǎng)絡(luò)之中,使得W-S-C復(fù)合薄膜既具有DLC薄膜高硬度、高耐磨性能,又擁有WS_2良好的自潤滑性能。將制備的W-S-C復(fù)合薄膜樣品分別放在干燥的氮氣、濕潤的大氣、油潤滑等環(huán)境中進(jìn)行摩擦磨損試驗,試驗結(jié)果證實復(fù)合薄膜樣品在不同的摩擦條件下均具有很低而且穩(wěn)定的摩擦系數(shù)。其中,在干燥氮氣氣氛中的摩擦系數(shù)可低至0.03,在油潤滑協(xié)同下的摩擦系數(shù)為0.04,在大氣環(huán)境中無油潤滑條件下的摩擦系數(shù)約0.15,此外在大氣環(huán)境中和9310對偶副對磨時的磨損率可低至9.105×10~(-8)mm3·N~(-1)·m~(-1)。
[Abstract]:Diamond like (diamond-like carbon) films have high hardness, high modulus of elasticity, excellent antifriction and wear resistance, good light transmittance, strong chemical stability and biocompatibility. It has broad application prospects in space machinery, tooling, automobile, electronic devices, optics, biomedicine and other fields. It is found that there is a large residual stress in the diamond like film (DLC), which not only weakens the bonding strength between the film and the matrix, but also causes the premature failure of the film in the process of service, but also restricts the deposition thickness of the film. In addition, the DLC film has the disadvantages of high sensitivity to the service environment with tribological behavior. In order to improve the inherent defects of the DLC film in the industry, in order to improve the inherent defects of the DLC film and meet the requirements of industrial application, this paper has modified the diamond like film through the heterogeneous doping of metal, nonmetal and compound, and made a comprehensive synthesis for the different friction and wear service conditions of high temperature, high humidity, dry, poor oil and so on. Tungsten doped DLC films, silicon doped DLC thin films and WS_2 doped DLC films have excellent properties. The DLC films doped with tungsten elements are prepared by magnetron sputtering and anodic laminar ion source composite deposition on the H13 hot working die steel and Si (100) matrix to reduce the residual stress in the DLC film and improve the thermal stability of the film in the high temperature environment. In order to reduce the physical mismatch between the thin film and the matrix, alleviate the interfacial stress and improve the bonding strength of the film base, the Cr/CrN/CrNC/CrC gradient transition layer was constructed between the DLC film and the matrix, and the bonding strength between the DLC film and the substrate was greatly improved. Finally, the surface of the H13 steel was deposited on the surface of the steel. The thickness of W doped diamond like diamond films can reach 3.51 mu m, the bonding strength of the film base is HF2, the microhardness of the film can reach 2289HV. by means of TEM, SEM, XRD and other detection methods, the microstructure and chemical composition of the diamond doped diamond films are analyzed. It is found that the W element is inlaid in the DLC film three-dimensional carbon based network in the form of WC1-x nanoclusters. The nanocrystalline amorphous composite structure is formed in the collaterals. Then the friction and wear behavior of W doped diamond like diamond films from 25 to 500 C is systematically studied. The results show that the doping of W in the DLC film can not only reduce the internal stress of the film and increase the bonding force of the film, but also improve the high temperature of the film. Under 200 c, the stability of the structure and tribological properties can be kept below 200 c. When the film is heated at 300 C, the film will be partially graphitized and the surface begins to oxidize, and the wear resistance of the film begins to decrease; at 400 C, the oxidation is serious, the loss of the thin film is large, the thin film is mainly composed of the structure of the WO3 phase and the wear resistance of the film. The loss performance will be reduced significantly, and the friction coefficient can remain below 0.15 at 500 C, but its wear rate is much higher than that of the samples worn within the temperature range of ~200 C at 25 C. Using medium frequency magnetron sputtering and ion source assisted deposition technology, the membrane structure is successfully prepared on the surface of Cr12MoV die steel and Si (100) by orthogonal test. The content of the dense and dense.Si doped DLC film containing hydrogen is the key factor affecting the mechanical properties and Tribological Properties of the thin film. When the Si content is 3.75at.%, the hardness of the Si-DLC film is 2039HV and the adhesion strength of the membrane is above 30N. In addition, the incorporation of Si elements can also reduce the sensitivity of the tribological properties of the film to the humidity of the friction environment. When the content of Si is in the range of 3.38~3.75 at.%, the friction coefficient of Si-DLC film can be stable at about 0.13 under the condition of high humidity and low humidity. In order to make DLC film adaptable to various service environments at the same time, medium frequency magnetron sputtering and ion source assisted deposition technology are used in the 9310 infiltration carbon steel, TC4 titanium alloy, and K20 cemented carbide three kinds of matrix. The WS_2 doped diamond like thin film.WS_2 doped DLC thin film is dispersed and distributed in the carbon based network in the form of WC1-x and WS_2 nanocrystalline clusters. The W-S-C composite film has the high hardness, high wear resistance and good self lubrication performance of the DLC film, and the samples of the prepared W-S-C composite thin films are in dry. The friction and wear tests of nitrogen, moist atmosphere and oil lubrication have been carried out. The results show that the composite film samples have a very low and stable friction coefficient under different friction conditions. The friction coefficient in the atmosphere of dry nitrogen can be as low as 0.03, and the friction coefficient of oil lubrication is 0.04, in the atmosphere environment. The friction coefficient of oil free lubrication is about 0.15, and the wear rate in the atmosphere and 9310 pairs of pairs can be as low as 9.105 x 10~ (-8) mm3. N~ (-1). M~ (-1).
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TG174.4

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本文編號：1969714