南京航空航天大学硕士学位论文 i摘 要 TiN 类薄膜具有高强度、高硬度、化学稳定性好、耐磨及防腐蚀等一系列优点，其涂层被广泛作用于机械工业中的刀具、模具等表面，是具有巨大应用前景的薄膜材料针对现有制备工艺中所存在的弊端，本文采用了双层辉光渗金属技术渗镀 TiN 类薄膜 本文主要探索了双辉渗镀 TiC 和 Ti(CN)薄膜的工艺及机理，对渗镀工艺方案及参数进行了优化，对渗镀层的微观组织、结构、结合强度、耐磨性、耐腐蚀性进行了表征，分析了各表征结果，并探讨了相关机理，研究了多元合金渗入顺序对 Ti(CN)渗镀层质量的影响结果表明：采用一种方波式的源极结构，利用化合物原位合成及薄膜外延生长的原理可在低碳钢表面渗镀薄膜；渗镀层的厚度可超过 20µm，其组织结构致密，与基体结合处无孔洞与裂纹；TiC 渗镀层内只生成 TiC 相， Ti(CN)渗镀层内则可依工艺参数生成 TiC0.7N0.3和 TiC0.2N0.8两种不同结构的物相；渗镀层与基体结合良好，结合力最高可达到 70N 以上；渗镀层的表面硬度高，可超过 2500HV，具有很好的耐磨性，可较基体提高 7倍以上；渗镀层具有很好的耐腐蚀性，在 3.5%NaCl 和 5%H2SO4水溶液中，渗镀层的耐腐蚀性均是基体的 4 倍以上；C、N、Ti 渗入顺序会对渗镀层组织结构及性能产生很大的影响，在制备 Ti(CN)渗镀层时的合金元素最佳供给方式是三元共渗。
以上研究结果必将为双辉制备 TiN 类薄膜的理论与应用研究提供重要的参考价值 关键词关键词：双辉，渗镀，薄膜，TiC，Ti(CN)，磨损，腐蚀 碳钢表面双辉渗镀 TiC 及 Ti(CN)膜的工艺和性能研究 iiABSTRACT TiN-like films represent a class of materials with high strength and hardness, good chemical stability, wear and corrosion resistance. So these materials have wide application prospect in engineering field, such as the surface of cutting tools, dies and so on. But the current preparation technology of films exist some shortages or much or little, so a new technology which is named double-glow plasma alloying(DGPAT) is used in this study. In this paper, the processes and mechanism of forming TiC and Ti(CN) films by DGPAT had been researched. The optimization of technological condition of preparing coating had been discussed. Microstructure, adhesion, wear resistance and corrosion resistance of films had been studied. At last, the effect of alloying sequence with C、Ti、N on films had also been researched. The results show that excellent films have been prepared successfully with a special structure of source by the theory of in-situ synthesis and epitaxial growth. The thickness of two films can be up to 20µm and there are no impurities and cracks at connections. In TiC films, the only one new phase have been produced, while there are two different phase structures in Ti(CN) films which are TiC0.7N0.3 and TiC0.2N0.8 respectively. The adhesion between films and substrates is good and the best is above 70N. The surface hardness of films is high and some are over 2500HV. So in the abrade experiment, films expressed good wear-resistance which are more 7 times than substrates. Meanwhile the corrosion resistance of films is well, which is over 4 times than the substrate in both 3.5%NaCl and 5%H2SO4 solution. The last result shows the best sequence of alloying with C-Ti-N is multi-element alloying within one stage. All above results will be of great theoretical and practical reference value for TiN-like films prepared by double-glow plasma alloying. Keywords: double glow, penetration and depositing, film, TiC, Ti(CN), wear, corrosion 碳钢表面双辉渗镀 TiC 及 Ti(CN)膜的工艺和性能研究 vi图表清单 图清单图清单 图 1.1 空心阴极辉光放电示意图..............................................................................7 图 1.2 双辉渗金属炉结构原理图..............................................................................8 图 1.3 陶瓷渗镀层生长模型....................................................................................12 图 2.1 试验方案........................................................................................................14 图 2.2 源极结构图....................................................................................................15 图 3.1 Ti、C 共渗渗镀层表面光学显微图..............................................................21 图 3.2 Ti、C 共渗渗镀层表面 SEM.........................................................................21 图 3.3 Ti、C 共渗渗镀层截面 SEM.........................................................................21 图 3.4 Ti、C 共渗渗镀层各成分分布趋势..............................................................22 图 3.5 Ti、C 共渗渗镀层 XRD.................................................................................23 图 3.6 Ti、C 共渗渗镀层与基体结合力..................................................................25 图 3.7 Ti、C 共渗渗镀层与基体结合力..................................................................25 图 3.8 Ti、C、N 共渗渗镀层表面颜色变化...........................................................26 图 3.9 Ti、C、N 共渗渗镀层 SEM..........................................................................26 图 3.10 Ti、C、N 共渗时不同通氮时间渗镀层的金相图.....................................26 图 3.11 Ti、C、N 共渗渗镀层内各成分分布趋势.................................................27 图 3.12 不同氮气气压下 Ti、C、N 共渗渗镀层的 XRD......................................28 图 3.13 不同通氮时间 Ti、C、N 共渗渗镀层的 XRD..........................................30 图 3.14 Ti(CN)渗镀层与基体结合力 .......................................................................31 图 3.15 Ti(CN)渗镀层划痕 SEM..............................................................................31 图 3.16 不同厚度渗镀层与基体结合力..................................................................32 图 4.1 磨损曲线........................................................................................................35 图 4.2 压痕法原理图................................................................................................36 图 4.3 磨损试验机原理...........................................................................。