【作者】 田斌；

【导师】 王成彪； 岳文；

【作者基本信息】 中国地质大学（北京） ， 地质工程， 2014， 博士

【摘要】 由于具有高硬度、优异的耐磨性能和耐腐蚀性能，TiN涂层已经被广泛应用于机械加工领域的刀具和模具表面。近年来，TiN的应用领域还进一步拓展到人工器官等医疗领域和太阳能薄膜等光学领域。而随着工业和技术的不断发展，越来越多精密零部件的加工需要TiN涂层具有更优异的表面性能。另一方面，TiN涂层向特殊地质工程钻探领域、汽车工业领域和其它机械工程领域的应用受到极大限制。这就要求TiN涂层不仅具有优异的耐磨性能，还要具有更低的摩擦系数和更优异的减摩性能。本文以金属W、Mo为主线，将离子镀、金属离子注入、磁控溅射和低温离子渗硫工艺相结合，制备了TiN-W/Mo(Sx)减摩硬质复合涂层，在MS-T3000球盘摩擦磨损实验机上考察了该复合涂层的摩擦学性能，利用三维光学形貌仪、扫描电子显微镜（SEM）、X射线衍射仪（XRD）、扫描俄歇系统（SAM）、X射线光电子能谱仪（XPS）、和纳米压痕仪等微观分析仪器研究了涂层的表面形貌、磨损形貌、微观结构、元素化合价态和硬度等表面性能，并对其减摩机理进行探讨。研究结果表明，采用金属蒸汽真空弧源（MEVVA源）可以在离子镀TiN涂层表面制备100~200nm的W、Mo离子注入改性层，使涂层表面出现Ti2N新相结构，而W氧化物、Mo氧化物的润滑及其对Ti氧化物润滑时间的有效延长，使TiN涂层的减摩性能得到明显改善，其中9E17剂量的W离子注入和1E18剂量的Mo离子注入可以使金属离子含量大幅增加，对TiN涂层摩擦学性能的改善效果更好，但其溅射效应也很显著；低温离子渗硫后处理对W、Mo离子注入后TiN涂层的溅射效应非常显著，使得W、Mo金属离子的注入深度和含量、以及涂层的表面硬度均显著降低，虽然形成的20~50nm的金属硫化物层可以在磨损前期进一步降低摩擦系数但其作用时间很有限；采用磁控溅射和低温离子渗硫处理在316L不锈钢基体上制备了厚度约2.5μm的TiN-W/Mo(Sx)复合涂层，结果表明随着W靶材或Mo靶材电流的提高，涂层沉积速率提高，涂层的硬度也提高，TiN-WSx和TiN-MoSx涂层的相结构分别主要由TiN、W2N、W、WS2和TiN、Mo2N、Mo、MoS2组成，涂层磨损表面的磨粒磨损和粘着磨损均得到显著改善，并且随着W、Mo含量的增加，其减摩性能和耐磨性能均进一步改善，其减摩机理主要包括Ti氧化物的润滑、WSx/MoSx的润滑、W/Mo氧化物的润滑和不同润滑相之间的叠加效应等四个方面，其中以具有层状结构和优异润滑性能的WSx/MoSx的润滑为主，而W-WSx-WOx/Mo-MoSx-MoOx各自三种润滑相之间的相互转化，以及多种润滑相叠加后显著延长了金属氧化物特别是Ti氧化物的有效润滑时间，都有助于该减摩硬质复合涂层在较长时间内保持优异的减摩性能。更多还原

【Abstract】 Titanium nitride (TiN) coatings have high hardness, good wear and corrosionresistance, and have been used as wear resistant coatings for cutting tools and dies. Inrecent years, they have been used in medical fileds like artificial internal organs andoptical fields like solar films. However, along with the gradual developments ofindustries and technologies, there are more and more precise parts with higherrequirements on good surface properties of TiN coatings. Moreover, it is impossiblefor TiN coatings to be used on machine parts in fields like special drilling enginnering,automobile industry, or other critical mechanical engineering industries. Therefore,besides good wear resistance, lower friction coefficient and better anti-frictionproperty are supposed to be essential properties for TiN coatings in some specialmechanical industries and machining environments.In this paper, low-friction and hard TiN-W/Mo(Sx) coatings were prepared bycombining treatments of Ion plating, Metal ion implantations, Magnetron sputteringdoping (MSD), and Low temperature ion sulfuration (LTIS), with the metal W andMo as the mainline. The tribological properties of coatings were carried out on aMS-T3000ball-on-disc friction and wear tester. The surface morphology before andafter wear, microstructures, elment valence, and hardness were investigated by thethree-dimension optical profilometer, scanning electron microscope (SEM), X-raydiffraction (XRD), Scanning Auger microprobe (SAM), X-ray photoelectronspectroscope (XPS), and Nano-hardness tester. Also, the anti-friction mechanism ofTiN-W/Mo(Sx) coatings was proposed.The results demonstrated that W or Mo implanted layers with thickness of about100~200nm could be prepared on Ion plating TiN coatings by Metal Vapor VacuumArc (MEVVA) source. New phase of Ti2N appeared on surfaces of TiN coatings afterion implantations. Under lubrications of W oxides or Mo oxides, and their effectiveprolonging of the lubrication time of Ti oxides, W-implanted and Mo-implanted TiNcoatings could obtain much better low-friction properties with higher contents of Moions and W ions, better tribological properties and more obvious sputtering effects atimplantation doses of9E17for W ions and1E18for Mo ions. After post-treatmentsof LTIS, obvious sputtering effects were shown on W-implanted and Mo-implantedTiN coatings, with evident decreasing of implantation depth and contents of W andMo ions and significant decreasing of coating hardness. A metal sulfide layer of about20~50nm were formed on W-implanted and Mo-implanted TiN coatings, whichcould further reduce the friction coefficients of coatings only for a short period at thebegnnning stages of wear. By combining the treatments of MSD and LTIS,TiN-W/Mo(Sx) coatings were prepared on316L stainless steel substrates, with thethickness of about2.5μm. It was found that depostion rates and surface hardness ofcoatings increased along with the rising of target current of W or Mo. The phases ofTiN-WSxand TiN-MoSxcoatings mainly included TiN, W2N, W, WS2and TiN,Mo2N, Mo, MoS2, respectively. Abrasive wear and adhesive wear of coatings weresignificantly reduced, and the low-friction and anti-wear properties were improvedfurther along with higher contents of W or Mo in coatings. The anti-friction mechanism of TiN-W/Mo(Sx) coatings included four factors, which were lubricationof Ti oxides, lubrication of WSx/MoSx, lubrication of W oxides or Mo oxides, andsuperposition effects of multi-lubricants. On one hand, WSxand MoSxhad the layeredstructures and excellent lubricantion effects, which played the most important roles inthe anti-friction process of TiN-W/Mo(Sx) coatings. On the other hand, the reciprocaltransformation among W-WSx-WOxor Mo-MoSx-MoOxand the effective extendingof lubrication time of metal oxides, especially for Ti oxides, made the coatings be ableto maintain good low-friction properties in a much longer time.更多还原