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金属陶瓷nc-Ti(C，N)复合自润滑碳介质涂层的制备及性能*

  • 陈强1

    机 构：

    1. 上海应用技术大学上海物理气相沉积（PVD）超硬涂层及装备工程技术研究中心 上海 201418

    ×
  • ， 张而耕1

    机 构：

    1. 上海应用技术大学上海物理气相沉积（PVD）超硬涂层及装备工程技术研究中心 上海 201418

    ×
  • ， 周琼1

    机 构：

    1. 上海应用技术大学上海物理气相沉积（PVD）超硬涂层及装备工程技术研究中心 上海 201418

    ×
  • ， 黄彪1

    机 构：

    1. 上海应用技术大学上海物理气相沉积（PVD）超硬涂层及装备工程技术研究中心 上海 201418

    ×
  • ， 梁丹丹1

    机 构：

    1. 上海应用技术大学上海物理气相沉积（PVD）超硬涂层及装备工程技术研究中心 上海 201418

    ×
  • ， 张帆2

    机 构：

    2. 上海名古屋精密工具有限公司 上海 201801

    ×
  • ， 孙思叡2

    机 构：

    2. 上海名古屋精密工具有限公司 上海 201801

    ×
  • ， 孙国庆2

    机 构：

    2. 上海名古屋精密工具有限公司 上海 201801

    ×

1. 上海应用技术大学上海物理气相沉积（PVD）超硬涂层及装备工程技术研究中心 上海 201418；
2. 上海名古屋精密工具有限公司 上海 201801；

Preparation and Properties of Cermet nc-Ti(C, N) and Self-lubricating Carbon Media Composite Coating

  • CHEN Qiang1

    Affiliation：

    1. Shanghai Engineering Research Center of Physical Vapor Deposition (PVD) Superhard Coating and Equipment, Shanghai Institute of Technology, Shanghai 201418 , China

    ×
  • ， ZHANG Ergeng1

    Affiliation：

    1. Shanghai Engineering Research Center of Physical Vapor Deposition (PVD) Superhard Coating and Equipment, Shanghai Institute of Technology, Shanghai 201418 , China

    ×
  • ， ZHOU Qiong1

    Affiliation：

    1. Shanghai Engineering Research Center of Physical Vapor Deposition (PVD) Superhard Coating and Equipment, Shanghai Institute of Technology, Shanghai 201418 , China

    ×
  • ， HUANG Biao1

    Affiliation：

    1. Shanghai Engineering Research Center of Physical Vapor Deposition (PVD) Superhard Coating and Equipment, Shanghai Institute of Technology, Shanghai 201418 , China

    ×
  • ， LIANG Dandan1

    Affiliation：

    1. Shanghai Engineering Research Center of Physical Vapor Deposition (PVD) Superhard Coating and Equipment, Shanghai Institute of Technology, Shanghai 201418 , China

    ×
  • ， ZHANG Fan2

    Affiliation：

    2. Shanghai Nagoya Precision Tools Co., Ltd, Shanghai 201801 , China

    ×
  • ， SUN Sirui2

    Affiliation：

    2. Shanghai Nagoya Precision Tools Co., Ltd, Shanghai 201801 , China

    ×
  • ， SUN Guoqing2

    Affiliation：

    2. Shanghai Nagoya Precision Tools Co., Ltd, Shanghai 201801 , China

    ×

1. Shanghai Engineering Research Center of Physical Vapor Deposition (PVD) Superhard Coating and Equipment, Shanghai Institute of Technology, Shanghai 201418 , China；
2. Shanghai Nagoya Precision Tools Co., Ltd, Shanghai 201801 , China；

作者简介:

陈强,男,1991年出生,硕士,实验师。主要研究方向为超硬纳微米PVD涂层、材料失效分析。E-mail:chenqiang2019@yeah.net;

张而耕(通信作者),男,1973年出生,博士后,教授,硕士研究生导师。主要研究方向为超硬纳微米PVD涂层、机械制造和材料失效分析等。E-mail:zhangeg@yeah.net

中图分类号:TG174;TH117

DOI:10.11933/j.issn.1007−9289.20211011002

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目录contents

    摘要

    金属陶瓷涂层与类金刚石涂层的性能不同，在实际应用中两种涂层不能够互换使用，对于涂层的应用来说是一个缺陷。 为了克服上述缺陷，将金属陶瓷涂层与类金刚石涂层的优异性能相结合，提出一种金属陶瓷复合自润滑碳涂层，并以三元TiCN 涂层为对象，采用 SEM、EDAX、XRD、Raman、XPS 及维氏硬度计、压痕试验、摩擦磨损试验，研究具有自润滑特性的碳相对含量对涂层微观组织结构、力学及摩擦磨损性能的影响。结果表明：随着碳含量的增加，涂层表面更为致密光滑，涂层的主要组成相为 TiN、TiC、TiC0.3N0.7 及 TiC0.7N0.3；涂层中 Ti-N、Ti-C 键随着碳含量的增加呈现先增加后减少趋势，当碳含量为 31.24 at%时，涂层中便有多余的非晶碳析出，形成金属陶瓷复合自润滑碳涂层 nc-Ti(C, N) / a-C，此时涂层不锈钢的硬度最高为 HV0.05 1052.2，同时涂层表现出较好的结合力、较低的摩擦因数及磨损率；涂层中碳含量为 43.85 at%时，摩擦因数较低，在 0.1 以下波动，磨损率达最小值 3.31×10-15m3 / (N·m)，但压痕周围有微裂纹产生。解释了自润滑碳对于金属陶瓷涂层性能的影响机制，可为高性能涂层的制备提供理论指导及试验依据。

    Abstract

    Cermet coating has different properties from diamond-like carbon coating. In practical applications, the two coatings can not be used interchangeably, which is a defect for coating applications. To overcome the above defects and combine the excellent properties of cermet coating and diamond-like carbon coating, a cermet composite self-lubricating carbon coating is proposed. Taking the ternary TiCN coating as the object, the effects of the relative content of carbon with self-lubricating characteristics on the microstructure, mechanics and friction and wear properties of the coating are studied by SEM, EDAX, XRD, Raman, XPS, Vickers hardness tester, indentation test and friction and wear test. The results show that the coating surface becomes more compact and smooth with the increase of carbon content, and the main constituent phases of the coating are TiN, TiC, TiC0.3N0.7 and TiC0.7N0.3. The Ti-N and Ti-C bonds in the coating increase first and then decrease with the increase of carbon content. When the C content is 31.24at.%, the C gradually precipitates from the crystal, and a cermet composite carbon coating of nc-Ti(C, N)/a-C is formed. At this time, the highest hardness of coated stainless steel is HV0.051052.2, and the coating shows good adhesion, low friction factor and wear rate. When the C content is 43.85 at.%, the friction factor of the coating is low, fluctuates below 0.1, and the wear rate reaches the minimum value of 3.31×10-15 m3 / (N·m), but there are microcracks around the indentation. The above research explains the influence mechanism of self-lubricating carbon on the properties of cermet coatings, and provides theoretical guidance and experimental basis for the preparation of high-performance coatings.

  • 0 前言

  • 物理气相沉积技术的应用日益广泛，它主要通过物理方法使原材料蒸发、电离，然后在低气压及磁场、电场作用下，粒子运动到基体表面堆积形成功能性涂层。该涂层具有硬度高、耐磨损、抗腐蚀等性质，用于工模具表面，可以改善工模具的加工效果，延长其使用寿命。现如今，80%以上的切削刃具及60%以上的成型模具均采用了涂层处理[1-3]。对于一些难加工材料，如钛合金、高温合金、淬硬钢、不锈钢等，采用无涂层刀具对其成型加工，刀具极易失效，且切削效率低、经济效益差。涂层可显著延长刀具的切削寿命，提高加工效率。目前，市场上的工模具涂层产品可分为两大类，一类为适用于加工铁基材料的硬质金属陶瓷涂层，如氮化物、碳化物涂层等，另一类为适用于加工软金属及高分子材料的自润滑涂层，如类金刚石（Diamond like carbon，DLC）涂层等[4-6]。工模具用金属陶瓷涂层的制备往往在高温条件下进行，高温不仅可以活化工模具表面，增强粒子活性，还可以提高涂层与基体的结合力。相较于DLC涂层，金属陶瓷涂层往往表现出较好的膜/基结合性能。DLC涂层与工模具的物性差异大，且沉积过程对温度极为敏感，温度过高则会造成碳膜生长缺陷明显，且成膜后的碳膜本征应力较大，导致碳膜石墨化而剥落。此外，沉积温度高，DLC以sp 2-C方式生长，体系能量降低，薄膜生长模式从亚表层注入转变为表面生长机制，薄膜的C1s电子结合能由高能态向低能态移动， sp 3-C的整体含量降低，涂层硬度降低[7-9]。为活化工件基体表面、提高碳膜与工件间的结合力，制备过程需采用高温（150～300℃），但高温易导致DLC涂层石墨化。若将金属陶瓷涂层与DLC涂层的性能优点相结合，可使涂层拥有高硬度、良好的结合性能的同时，具备较好的自润滑性能[10-12]，并同时适用于铁基材料、软金属及高分子材料的成型加工。然而，国内外对于具备上述性质的涂层的研究报道较少。本文以二元氮基金属陶瓷涂层为基础，向其中添加不同含量的碳元素，希望通过形成富碳的nc-Ti(C，N)/a-C复合结构涂层，使涂层具备高硬度、结合强度好及自润滑等特性，并研究不同碳含量对涂层性能的影响。

  • 1 试验方案

  • 1.1 涂层制备

  • 采用意大利ICS公司生产的阴极电弧+辉光放电涂层沉积系统（ICS-04ARC PRO），分别在单晶硅（8mm×8mm×0.5mm）及304不锈钢（30mm× 7mm×3mm）表面制备TiCN涂层。阴极电弧使金属靶材蒸发、电离，提供涂层合成所需的金属元素。辉光放电使气体电离，产生涂层合成所需的非金属离子。粒子在偏压电源及磁场作用下在基体表面堆积、结合形成涂层。对于待涂层试样，先采用无水乙醇对试样进行10min的超声波清洗，除去表面油污及其他黏附性杂质，再在80℃热循环风条件下将试样表面烘干后，把试样固定装夹在涂层腔体内。在涂层沉积前，需对试样进行10min的低压等离子清洗，以去除试样表面吸附的氧化物、微颗粒物等，粗化、活化基体表面。然后在试样表面制备一层薄薄的Ti/TiN打底层，以提高涂层与试样的结合强度，降低涂层剥落趋势。涂层的制备参数如表1所示。涂层制备所采用的靶材为单质钛（Ti）靶，纯度99.999%，涂层气体为氮气（N2）及乙炔（C2H2）。

  • 表1 涂层制备参数

  • Table1 Parameters of coating preparation

  • 1.2 性能表征

  • 为降低基底对涂层性能表征的影响，涂层后的单晶硅用于涂层的表面形态观察，以及涂层的成分、物相及化学态分析。观察设备为扫描电子显微镜 （SEM），放大倍数2万倍，加速电压10kV。该扫描电子显微镜配备能谱仪（EDAX）组件，能谱仪探针以面扫描的方式对涂层进行成分分析，同时为增大分析区域，提高分析结果的准确性，放大倍数为2 500倍。X射线衍射仪（XRD）分析涂层的相结构，Cu Kα 射线（λ=0.154 18nm），加速电压40kV，衍射角2θ=20°～80°。显微共聚焦激光拉曼光谱仪检测涂层中的碳信号峰，激光器波长514.5nm，50× 物镜，光斑直径2 μm，扫描时间30s，光谱范围为100～2 000cm−1。X射线光电子能谱（XPS）分析涂层的键态信息及成键比例，在200W功率条件下，采用Al Kα（hv=1 486.6eV）射线，且所有涂层的光谱均以284.8eV的不定碳（CHx）的C1s峰进行荷电校正。

  • 涂层后的不锈钢用于涂层厚度的测量，以及评判涂层的力学、摩擦及磨损性能。采用球磨仪测量涂层的厚度，研磨钢球直径为30mm，研磨速度为1 200r/min，研磨时间为涂层被磨穿，且涂层与不锈钢试片有明显分界线为止。通过数显显微维氏硬度计（402SXV）分析涂层对基体表面硬度的影响，金刚石显微维氏菱形压头，施加载荷50g，保荷时间10s。采用洛氏硬度计定性表征涂层的结合力，金刚石压头，试验载荷1 500N，保荷时间6s。环块式滑动摩擦磨损试验测量涂层的耐磨性，试验载荷196N，摩擦速度0.42m/s，摩擦方式为干摩擦，摩擦时间2h，摩擦副为45钢（硬度HRC55-60）。

  • 2 结果及讨论

  • 2.1 涂层的微观组织及结构

  • SEM观察涂层的表面形貌如图1所示。随着乙炔流量增加，涂层表面液滴、针孔等缺陷减少，表面结构完整度变好，表明乙炔流量的增加对于提高涂层的表面质量具有较为积极的作用。阴极靶材弧光放电及气体辉光放电过程中能够产生中性原子团，未被离化的中性原子团在低气压条件下迁移至已堆积成膜的涂层表面，并在其表面附着，且附着力较小。离化的粒子在继续堆积成膜的过程中会对低附着力的中性原子团产生“轰击”效应，从而导致原子团脱离形成凹坑及针孔等缺陷。增大乙炔的流量，离化的粒子密度增加，中性基团被碰撞离化的概率增加，涂层表面的结构缺陷减少[13-14]。不同乙炔流量、相同工艺参数条件下，EDAX分析涂层及涂层表面液滴的元素成分如表2、表3所示。乙炔流量由10cm3/min增加至15cm3/min，涂层中C含量增幅较小。进一步增加乙炔流量，涂层中C含量快速增加，相应地Ti、N含量降低。结合XRD及XPS分析结果可知，产生上述现象的原因为，在乙炔流量较小的情况下，涂层主要生成Ti-N、Ti-C及TiC0.3N0.7。随着乙炔流量增大，涂层中产生更多的TiC0.7N0.3，并逐渐析出非晶碳，从而导致涂层中的碳含量大幅增加。析出的无定形非晶碳填充在涂层中，该种情况下，涂层内部能够方便形成典型致密的纳米复合材料结构[15]。涂层表面液滴中碳的含量随着乙炔流量的增加而增加。相较于涂层本身，涂层表面液滴中碳的含量均较高。表面高碳含量的液滴，对于涂层的减磨及耐磨性能具有较为积极的影响。

  • 图1 不同C含量TiCN涂层的表面形貌：（a）～（e）代表C2H2流量为10～30cm3/min

  • Fig.1 Surface morphology of TiCN coatings with different C content：(a)-(e) represents C2H2 flow rates of 10-30cm3/min

  • 表2 不同C2H2流量下的涂层元素成分及含量（at.%）

  • Table2 Element composition and content of coatings with different C2H2 flow rates (at.%)

  • 表3 不同C2H2流量下涂层液滴的元素成分及含量（at.%）

  • Table3 Element composition and content of coating droplets with different C2H2 flow rates (at.%)

  • 图2 给出不同C2H2 流量制备的TiCN涂层的XRD衍射图谱。Ti-N键的结合能与形成能均小于Ti-C键，TiN、TiC的形成能分别为−9.08eV/atom、 −8.64e V/atom，结合能分别为 −1.96kJ/mol、 −0.89kJ/mol，且非化学计量比的TiCxN1-x相的形成能均大于TiN，可以推测在相同条件下，涂层中更容易形成TiN，而后离化的C融入TiN晶中形成置换或固溶强化的TiCxN1-x，最终形成TiC[16-17]。阴极电弧+辉光放电技术在涂层沉积过程中同时生成TiN、TiC及TiCxN1-x（TiCxN1-x的衍射角介于TiN、 TiC的衍射角之间），并随乙炔流量的增加而形成更多的TiCxN1-x相。乙炔流量为10～20cm3/min时，涂层的衍射峰强度较弱。当流量为10cm3/min时，涂层中组成相主要为低指数晶面（111）相，涂层的主要相为TiN、TiC、TiC0.3N0.7、TiC0.7N0.3，且晶格常数相对较小。随着乙炔流量增加，涂层中并没有生成更多形成能小的TiN相，而是更多半径较大的C原子取代半径略小的N原子，使得晶胞膨胀，晶粒尺寸及晶格常数增大，衍射峰峰位向小角度偏移，且涂层的组成相向高指数晶面（220）相移动。 TiC0.3N0.7、TiC0.7N0.3 的衍射峰在TiN、TiC之间， TiC0.7N0.3 的衍射角小于TiC0.3N0.7，随着乙炔流量增加，涂层中生成更多的TiC0.7N0.3 相。在涂层的宏观性能表现上，C元素的添加使得涂层的韧性优于TiC，涂层的硬度及耐磨性强于TiN[18-20]。乙炔流量为25cm3/min时，涂层的C含量增幅较大，涂层的衍射峰强度较强，仍沿晶面能高的（220）晶面择优取向快速生长，衍射峰的衍射角度已靠近TiC（220）一侧，表明涂层中生成了大量的TiC0.7N0.3 相或TiC相，且涂层中出现（200）生长取向。乙炔流量为30cm3/min时，涂层中C含量增幅较大，各生长取向均被抑制，涂层的衍射峰强度变弱。此时，若涂层中结晶相的晶格中及非晶相的所有的非金属原子空位被占据，涂层中应存在过饱和的游离碳，并在晶界处析出形成富碳的nc-Ti(C， N)/a-C复合结构[21-23]。

  • 图2 不同C2H2流量下TiCN涂层的XRD图谱

  • Fig.2 XRD spectra of TiCN coatings with different C2H2 flow rates

  • 涂层中碳饱和前，C元素在涂层中应以Ti-C、 TiCxN1-x 结晶相形式存在。碳饱和后，涂层中还存在无定型的游离碳（a-C）。不同乙炔流量制备的TiCN涂层的拉曼光谱如图3所示。对于类金刚石涂层 （DLC）而言，由于其内部存在以SP2 及SP3 形式杂化态碳，其拉曼光谱在1 300cm−1 及1 580cm−1 处出现金刚石态的D峰及石墨态的G峰[24]。图3表明，随着乙炔流量的增加，涂层中非晶态碳的拉曼光谱峰愈加明显。乙炔流量达30cm3/min时，涂层的拉曼峰最为明显，说明涂层中碳已处于饱和状态，并在涂层中微小晶的晶界处析出，形成非晶碳[25]。结合XRD及XPS分析发现，C含量的增加，涂层中并没有形成更多的Ti-C，而是更多的C取代N形成TiC0.7N0.3。正是非晶碳的存在，抑制了涂层中结晶相的生长，导致了涂层的衍射峰强低。此外，XPS表征乙炔流量为25cm3/min时，涂层中的Ti-C化学态的C含量有减小趋势，表明乙炔流量为25cm3/min时，涂层中便已有少量饱和非晶碳的析出。涂层中碳的饱和点在乙炔流量为20～25cm3/min。因此，在乙炔流量在20cm3/min及以下时，C元素在涂层中主要以TiCN的形式存在。乙炔流量在25cm3/min及以上时，C元素不仅以TiCN的形式存在，也以非晶碳形式填充于涂层的晶粒之间[26]。

  • 图3 不同C2H2流量下TiCN涂层的拉曼光谱

  • Fig.3 Raman spectra of TiCN coatings with different C2H2 flow rates

  • XPS表征涂层的全谱信息如图4所示，从全谱扫描可以看出，涂层表面含有Ti、C、N、O元素，涂层中的氧元素源于涂层表面的污染性物质。不同乙炔流量制备的TiCN涂层的C1s、N1s峰拟合结果如图5、6所示。涂层中的C元素主要以Ti-C、 C-N（TiCN）键的形式存在，N元素主要以Ti-N、 C-N的形式存在[27]。涂层的C1s、N1s窄谱分析涂层中处于Ti-C、Ti-N化学态的C、N含量如表4所示。随着乙炔流量的增加，涂层中Ti-C化学态的C含量呈增加后减少趋势。产生该现象的原因为，如图6a～6e所示，乙炔流量增加，涂层中较多的C取代TiN中的N，形成更多的TiCN置换相[20]。待在该沉积条件下，涂层中的非金属空位被占据，涂层中饱和的碳以C-C/C=C非晶的形式存在于涂层中，并在晶体界面处析出，阻碍晶粒的形核及生长，从而进一步导致涂层中Ti-C化学态的C含量的减少[28]。乙炔流量为20cm3/min时，涂层中虽然存在较多的Ti-C、Ti-N，但结合XRD图谱分析发现，涂层的晶粒尺寸小，且晶体晶型差。乙炔流量为30cm3/min时，涂层中Ti-C化学态的含量最低，结合EDAX及Raman分析可知，涂层中含有较多的非晶碳，晶粒的形核及生长困难，涂层的成分主要以TiN、TiCN、非晶碳为主，从而导致涂层的结晶程度较差，使得涂层的XRD衍射峰强度较弱。

  • 图4 不同C2H2流量下TiCN涂层的XPS全谱图

  • Fig.4 XPS full spectra of TiCN coatings with different C2H2 flow rates

  • 表4 XPS表征涂层中Ti-C、Ti-N化学态中的C、N含量（at.%）

  • Table4 XPS characterization of C and N contents in Ti-C and Ti-N chemical states of coatings

  • 图5 TiCN涂层C1s峰拟合图谱：（a）～（e）代表C2H2流量为10～30cm3/min

  • Fig.5 C1s peak fitting diagram of TiCN coatings, (a)-(e) represents C2H2 flow rates of 10-30cm3/min

  • 图6 TiCN涂层N1s峰拟合图谱：（a）～（e）代表C2H2流量为10～30cm3/min

  • Fig.6 N1s peak fitting diagram of TiCN coating, (a)-(e) represents C2H2 flow rates of 10-30cm3/min

  • 2.2 涂层的力学及摩擦磨损性能

  • 不同乙炔流量条件下制备的涂层厚度如图7所示。涂层厚度随着乙炔流量的增加有增大趋势，表明在其他工艺参数不变的情况下，沉积源粒子数量增加，单位时间内在基底表面堆积的粒子数量越多，涂层厚度也愈大。

  • 图7 不同C2H2流量下制备的TiCN涂层的厚度

  • Fig.7 Thickness of TiCN coatings prepared with different C2H2 flow rates

  • 涂层的硬度反应涂层自身抵抗外界压入的能力。因涂层厚度较薄，对其硬度测量往往受压入深度及仪器（纳米压痕仪）精度的影响。硬度测量结果离散性大，准确度低。涂层在实际工况中的性能表现一般是基体及涂层复合作用的结果。因此，对于基体及涂层复合硬度的测量更能直观地反映涂层对于基体表面硬度的影响。涂层/不锈钢的复合硬度随乙炔流量的变化如图8所示，随着乙炔流量的增加，复合硬度呈增加后减小趋势。产生上述现象的主要原因还与C含量的增加导致涂层成分结构转变及非晶碳的形成相关[29]。乙炔流量为25cm3/min时，涂层/不锈钢的复合硬度值最大，为HV0.05 1 052.2。结合XRD、Raman及XPS发现乙炔流量为25cm3/min时，涂层中便已有非晶碳析出，此时涂层的衍射峰较强，表明涂层的高硬度是非晶碳与涂层中硬质相复合作用的结果。乙炔流量为30cm3/min时，涂层中形成较多的非晶碳，因SP2-C为软介质，在受压过程中易产生滑移，以及涂层中含C硬质相含量降低。所以，当乙炔流量为30cm3/min时，复合硬度并没有增大，反而减小。

  • 图8 涂层与基体的复合硬度随乙炔流量的变化

  • Fig.8 Variation of the composite hardness of coating and substrate with C2H2 flow rates changing

  • 根据行业标准JC/T2174—2013《精细陶瓷涂层结合性能试验方法洛氏压痕法》规定的方法表征涂层的结合性能。不同乙炔流量条件下制备的TiCN涂层的表面压痕形貌如图9所示。乙炔流量为10～25cm3/min，涂层与不锈钢基底均保持着较好的结合强度，压痕周围未观测到有裂纹及涂层脆性剥落现象。乙炔流量为30cm3/min，压痕周围的涂层有明显脆性断裂现象，并伴随有裂纹扩展。上述现象说明C含量达31.24～43.85at.%中间某一值时，涂层的内部应力增大到不足以维持涂层在受压条件下的完整性，涂层的整体断裂韧性变差，结合性能降低，但仍满足应用要求。若进一步增大乙炔流量，涂层在冲击载荷作用下，极可能出现大面积脆性剥落现象[30]。

  • 图9 不同C2H2流量下制备的TiCN涂层的表面压痕形貌

  • Fig.9 Surface indentation morphologies of TiCN coatings prepared with different C2H2 flow rates

  • 环—块式滑动摩擦磨损条件下，涂层试样表面的摩擦因数曲线如下图10所示。随着乙炔流量的增加，涂层中碳含量增加，摩擦因数减小，且摩擦因数曲线波动幅度变小，愈渐趋于平滑。图10表明涂层中碳元素导致涂层组织结构的变化，尤其是在乙炔流量为25cm3/min及以上时，饱和的非晶碳的析出，使涂层对于涂层试样表面摩擦因数的变化产生较为重要的影响，相较于无非晶碳成分的纯金属陶瓷结构TiCN涂层，低摩擦因数（0.2以下）的nc-Ti （C，N）/a-C涂层反映出较好的润滑作用。

  • 图10 不同C2H2流量下制备的TiCN涂层试样的表面摩擦因数曲线

  • Fig.10 Friction factor curve of TiCN coating samples prepared with different C2H2 flow rates

  • 二维轮廓仪表征涂层试样在环—块式滑动摩擦磨损试验条件下的磨损轮廓如图11所示。乙炔流量为25cm3/min、30cm3/min条件下制备的涂层试样的磨损宽度及磨损深度要明显低于在其他乙炔流量条件下制备的涂层试样。基于origin软件拟合磨损轮廓面积并计算10～30cm3/min乙炔流量条件下制备的涂层试样的磨损体积及磨损率如图12所示。随着乙炔流量的增加，涂层试样的耐磨性能具有较大幅度的提高。在乙炔流量低于25cm3/min条件下制备的涂层试样耐磨性能的提升主要归因于涂层中的硬质相。乙炔流量为25cm3/min以上时，涂层中的金属陶瓷硬质相的晶粒小、晶型差，涂层中自润滑介质非晶碳，对涂层试样的优异耐磨性起到主导作用。

  • 图11 不同C2H2流量下制备的TiCN涂层试样的磨损轮廓

  • Fig.11 Wear profile of TiCN coating samples prepared with different C2H2 flow rates

  • 图12 不同C2H2 流量下制备的TiCN涂层试样磨损体积及比磨损率

  • Fig.12 Wear volume and wear rate of different coating samples prepared with different C2H2 flow rates

  • 3 结论

  • 通过阴极电弧+辉光放电技术制备不同碳含量的TiCN涂层，研究碳含量对于涂层的微观形貌、组织结构、力学性能及摩擦磨损性能的影响，主要结论如下：

  • （1）随着TiCN涂层中碳含量的增加，涂层表面完整性较好，更为致密、光滑。涂层中碳含量为31.24at.%时，涂层的摩擦因数降至0.2以下，碳含量为43.85at.%时，涂层的摩擦因数降至0.1以下，且摩擦因数曲线平滑、波动幅度小，反映出较好的润滑作用。

  • （2）碳饱和前，涂层的组成相主要为TiN、TiC、 TiC0.3N0.7 及TiC0.7N0.3，且衍射峰强度弱，晶粒尺寸小，晶型差。当碳含量为31.24at.%时，涂层中碳含量已处于过饱和状态，并析出非晶碳，形成nc-Ti （C，N）/a-C结构涂层。

  • （3）非晶碳的析出并没有降低涂层的力学性能，当碳含量为31.24at.%时，涂层不锈钢的硬度最大，为1 052.2HV0.05。涂层中C含量大于31.24at.%时，涂层的内部应力较大，进一步导致涂层的断裂韧性变差，结合性能降低。

  • （4）涂层的磨损率随着碳含量的增加而降低，尤其当涂层中析出非晶碳形成nc-Ti(C，N)/a-C结构涂层时，涂层不锈钢的磨损率下降趋势明显。此现象表明，涂层硬度是影响耐磨性的关键因素之一，涂层的成分、组成及润滑性能对于耐磨性能也具有重要的影响。

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    • [17] YANG Y,LU H,YU C,et al.First-principles calculations of mechanical properties of TiC and TiN[J].Journal of Alloys and Compounds,2014,485(1-2):542-547.

    • [18] AKINRIBIDE O J,OBADELE B A,AKINWAMIDE S O,et al.Sintering of binderless TiN and TiCN-based cermet for toughness applications:Processing techniques and mechanical properties:A review[J].Ceramics International,2019,45(17):21077-21090.

    • [19] ZHANG F Y,LI C,YAN S,et al.Microstructure and tribological properties of plasma sprayed TiCN-Mo based composite coatings[J].Applied Surface Science,2019,464(15):88-98.

    • [20] KUMAR T S,JEBARAJ A V,SHANKAR E.Metallurgical and mechanical characterization of TiCN/TiAlN and TiAlN/TiCN bilayer nitride coatings[J].Surfaces and Interfaces,2019,15:256-264.

    • [21] GUO F F,BI Y H,LI C,et al.The crystallization behaviours of reactive-plasma-sprayed TiCN coatings with different Ti/graphite powder ratios[J].Ceramics International,2020,46(15):23510-23515.

    • [22] LI J L,ZHANG S H,LI M X.Influence of the C2H2 flow rate on gradient TiCN films deposited by multi-arc ion plating[J].Applied Surface Science,2013,283:134-144.

    • [23] LEI Z F,ZHU X D,LI Y H,et al.Characterization and tribological behavior of TiAlN/TiAlCN multilayer coatings[J].Journal of Tribology,2018,140(5):051301.

    • [24] ZENG Y Q,QIU Y D,MAO X Y,et al.Superhard TiAlCN coatings prepared by radio frequency magnetron sputtering[J].Thin Solid Films,2015,584:283-288.

    • [25] CHEN S N,LIAO BI,CHEN L,et al.Corrosion and tribological properties of TiAlCN/TiAlN/TiAl composite system deposited by magneticfliter cathode vacuum arctechnique[J].Acta Physica Sinica,2020,69(10):38-48.

    • [26] DREILING I,STIENS D,CHASSÉ T.Raman spectroscopy investigations of TiBxCyNz coatings deposited by low pressure chemical vapor deposition[J].Surface and Coatings Technology,2010,205(5):1339-1344.

    • [27] RODRÍGUEZ R J,GARCÍA J A,MEDRANO A,et al.Tribological behaviour of hard coatings deposited by arc-evaporation PVD[J].Vacuum,2002,67(3-4):559-566.

    • [28] AL-BUKHAITI M A,AL-HATAB K A,TILLMANN W,et al.Tribological and mechanical properties of Ti/TiAlN/TiAlCN nanoscale multilayer PVD coatings deposited on AISI H11 hot work tool steel[J].Applied Surface Science,2014,318:180-190.

    • [29] KUPTSOV K A,KIRYUKHANTSEV-KORNEEV P V,SHEVEYKO A N,et al,Comparative study of electrochemical and impact wear behavior of TiCN,TiSiCN,TiCrSiCN,and TiAlSiCN coatings[J].Surface and Coating Technology,2013,216:273-281.

    • [30] XIAN G,ZHAO H B,FAN H Y,et al.The structure and adhesion of Zr/TiAlN coatings on high-speed steel and cemented carbide substrates[J].Applied Mechanics and Materials,2014,459:46-50.

  • 基本信息

    中图分类号: TG174;TH117
    DOI: 10.11933/j.issn.1007−9289.20211011002

    基金信息

    上海应用技术大学中青年科技人才发展基金(ZQ2020-24)；
    上海市自然科学基金(20ZR1455700)；
    国家自然科学基金青年基金(51901138)资助项目；
    Supported by Development Fund for Young and Middle-aged Scientific and Technological Talents of Shanghai Institute of Technology(ZQ2020-24)；
    Shanghai Natural Science Foundation(20ZR1455700)；
    National Natural Science Foundation of China (51971148).；

    引用信息

    稿件历史

    收稿日期: 2021-10-11

  • 参考文献

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    • [20] KUMAR T S,JEBARAJ A V,SHANKAR E.Metallurgical and mechanical characterization of TiCN/TiAlN and TiAlN/TiCN bilayer nitride coatings[J].Surfaces and Interfaces,2019,15:256-264.

    • [21] GUO F F,BI Y H,LI C,et al.The crystallization behaviours of reactive-plasma-sprayed TiCN coatings with different Ti/graphite powder ratios[J].Ceramics International,2020,46(15):23510-23515.

    • [22] LI J L,ZHANG S H,LI M X.Influence of the C2H2 flow rate on gradient TiCN films deposited by multi-arc ion plating[J].Applied Surface Science,2013,283:134-144.

    • [23] LEI Z F,ZHU X D,LI Y H,et al.Characterization and tribological behavior of TiAlN/TiAlCN multilayer coatings[J].Journal of Tribology,2018,140(5):051301.

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    • [25] CHEN S N,LIAO BI,CHEN L,et al.Corrosion and tribological properties of TiAlCN/TiAlN/TiAl composite system deposited by magneticfliter cathode vacuum arctechnique[J].Acta Physica Sinica,2020,69(10):38-48.

    • [26] DREILING I,STIENS D,CHASSÉ T.Raman spectroscopy investigations of TiBxCyNz coatings deposited by low pressure chemical vapor deposition[J].Surface and Coatings Technology,2010,205(5):1339-1344.

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    • [28] AL-BUKHAITI M A,AL-HATAB K A,TILLMANN W,et al.Tribological and mechanical properties of Ti/TiAlN/TiAlCN nanoscale multilayer PVD coatings deposited on AISI H11 hot work tool steel[J].Applied Surface Science,2014,318:180-190.

    • [29] KUPTSOV K A,KIRYUKHANTSEV-KORNEEV P V,SHEVEYKO A N,et al,Comparative study of electrochemical and impact wear behavior of TiCN,TiSiCN,TiCrSiCN,and TiAlSiCN coatings[J].Surface and Coating Technology,2013,216:273-281.

    • [30] XIAN G,ZHAO H B,FAN H Y,et al.The structure and adhesion of Zr/TiAlN coatings on high-speed steel and cemented carbide substrates[J].Applied Mechanics and Materials,2014,459:46-50.

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