硬质合金及耐磨涂层：理论设计及产品开发（Ⅰ）

随着计算机技术与热力学动力学数据库的发展,把材料计算模拟和关键实验结合在一起,集成、优化、应用到硬质合金产品设计开发的全过程,通过成分–工艺–结构–性能的关联分析,能够把硬质合金及耐磨涂层的研发由传统经验或者半经验方式提升到科学的顶层/底层设计,加快研发速度,降低研发成本。本文阐述了第一性原理计算、CALPHAD方法(相图计算方法)、相场模拟和有限元模拟等计算模拟方法,论述了它们在硬质合金及耐磨涂层研发中所发挥的具体作用,从用户需要、设计制备和工业生产3个层面探讨并建立了基于集成计算材料工程进行产品开发的框架。     

硬质合金及耐磨涂层：理论设计及产品开发（Ⅲ）

热力学和第一性原理计算在材料设计方面发挥着重要的作用,通过这些理论预测能够快速确定材料工艺-成分-结构-性能之间的关系。本文主要介绍了热力学计算在化学气相沉积(Chemical Vapor Deposition,简称CVD)涂层以及第一性原理计算在物理气相沉积(Physical Vapor Deposition,简称PVD)涂层设计开发方面的应用,并以CVD TiSiN和PVD纳米多层TiAlN/ZrN新型涂层开发为例,详细阐述了热力学和第一性原理计算的具体作用。理论计算与关键实验验证相结合是提高耐磨涂层研发效率与质量的有效途径,同时也是未来新型耐磨涂层开发的发展趋势。     

CVD金刚石涂层硬质合金刀具研究进展

CVD金刚石涂层硬质合金刀具结合了金刚石和硬质合金的优异性能,是切削加工的理想材料,具有广阔的发展前景。当前限制CVD金刚石涂层刀具应用的主要问题是金刚石涂层与刀具基体之间的附着性能较差,其主要原因是粘接相Co对CVD沉积存在不利影响以及涂层与基体之间热膨胀系数存在较大差异。本文综述了提高界面结合强度和降低涂层表面粗糙度的方法,重点介绍了在界面添加过渡层来提高界面结合强度,并指出在硬质合金基体和CVD涂层之间添加过渡层和开发纳米CVD涂层是CVD金刚石涂层刀具今后的发展方向。     

切削刀具的涂层处理

引言切削刀具耐磨涂层的应用已经风行了近二十年。起初,在高速钢工具上使用金黄色的氮化钛(TiN)涂层扩大了刀具的使用范围,使能允许高的机械加工速度。当镶嵌硬质合金切削刀具达到其最大效能时,表面涂层可以再次大大增加这种刀具的使用范围,同时明显提高硬质合金刀具的使用寿命和零件表面的光洁度,并降低了产品的成本。对硬质合金刀具进行耐磨涂层的最常用工艺是化学气相沉积(CVD)。近几年来,像阴极溅射,离子注入等其它工艺也一直在试验,且取得了一些进展。切削刀具涂层处理的选择取决于几个因素。理想的做法是寻求基体材料和所采用的涂层的最佳性能配合。对要涂层的硬质合金     

硬质合金CVD金刚石涂层最新进展

金刚石因具有优异的物理化学性能被认为是理想的刀具材料。硬质合金基底上涂覆CVD金刚石薄膜有利于改善刀具的加工性能和寿命,但涂层和基底之间存在热膨胀系数差异以及合金中Co对沉积有不利影响,使得薄膜附着力较差。本文综述了近几年来各种提高CVD金刚石涂层刀具切屑性能的方法,从提高薄膜附着力和改善金刚石膜的质量两个方面进行了讨论。并介绍了国外较先进的CVD金刚石涂层刀具的应用,随着技术的不断成熟,CVD金刚石涂层将会有更为广泛的应用。     

梯度硬质合金及耐磨涂层的计算模拟和实验验证

建立了多组元硬质合金W-C-Co-Ti-Cr-Ta-Nb-N体系热力学及动力学基因库。利用所建立的热力学及扩散动力学基因库,模拟了WC-Ti(C,N)-TaC-Co硬质合金梯度层形成过程,计算所得各相体积分数及组元成分与实验结果相吻合。采用SEM和EDS等方法对不同N气氛下梯度烧结所获得的WC-Ti(C,N)-Co梯度硬质合金进行了合金表面组元成分分布测定,并对样品梯度层的形成进行了模拟,模拟能很好地描述实验结果。基于第一原理计算和实验对广泛应用的三元Ti-Al-N耐磨涂层体系的结构、力学、热力学性质和调幅分解曲线,以及调幅分解析出立方二元氮化物的性能进行了研究。计算结果与已有实验值符合较好,可为高性能硬质合金和多元涂层的开发设计提供理论指导。最后提出了硬质合金及耐磨涂层研发的基因框图。     

化学气相沉积金刚石薄膜刀具膜/基附着性能研究现状

CVD金刚石薄膜涂层刀具被认为是能最早实现CVD金刚石工业化应用的领域之一.目前,限制CVD金刚石薄膜涂层刀具产品大规模产业化应用的主要原因,是金刚石薄膜与硬质合金基底之间粘附性能较差.如何提高膜/基粘附性能,确保CVD金刚石薄膜涂层刀具优异性能的发挥、涂层刀具的使用寿命和加工性能,已成为材料科学工作者迫切需要解决的问题.介绍了影响CVD金刚石薄膜硬质合金刀具膜/基附着性能的主要因素、改善金刚石薄膜与硬质合金基体之间附着力的途径以及表征膜/基附着力的测试方法等方面的研究成果,并对提高低压气相金刚石薄膜硬质合金刀具膜/基附着性能的研究现状进行了分析.     

化学气相沉积TiC-Ti(CN)-TiN涂层在硬质合金拉丝模上应用研究

用化学气相沉积法（CVD）在硬质合金拉丝模上沉积TiC－Ti（N）-TiN耐磨涂层，经工业试验表明涂层具有硬度高、摩擦系数小、与基体粘附性强、化学稳定性好和耐磨等优良性能。涂层拉丝模比非涂层模提高使用寿命1～4倍。     

冷喷涂硬质合金耐磨涂层研究进展

硬质合金涂层具有高耐磨性与高耐腐蚀性等优势,因此广泛应用于冶金等领域的耐磨、耐蚀防护中。采用传统热喷涂技术制备硬质合金涂层,其高温会导致涂层材料产生相变、氧化、脱碳等问题,从而损害涂层的服役性能。冷喷涂技术作为一种新兴的涂层制备技术,具有低温的特点,可避免传统热喷涂方法所带来的涂层质量问题,成为硬质合金涂层制备的潜在技术。在简述冷喷涂技术原理及其沉积机理的基础上,综述了冷喷涂制备硬质合金耐磨涂层(如WC-Co、WC-Ni、Cr3C2-NiCr等),以及影响涂层硬度、耐磨性等力学性能的主要因素,包括硬质相、黏结相的种类、含量和尺寸等。综合比较了冷喷涂与超音速火焰喷涂制备的硬质合金涂层的耐磨性能,分析了后处理(喷后热处理、搅拌摩擦处理)对冷喷涂硬质合金涂层耐磨性的影响。最后,提出了冷喷涂技术在硬质合金耐磨涂层制备方面的局限性,并对未来发展进行了展望。     

化学气相沉积TiC-Ti（CN）-TiN涂层在硬质合金拉丝模上应用研究

用化学气相沉积法(CVD)在硬质台金拉丝模上沉积TiC—Ti(CN)-TiN耐磨涂层，经工业试验表明涂层具有硬度高、摩擦系数小，与基体粘附性强、化学稳定性好和耐磨等优良性能。涂层拉丝模比非涂层模提高使用寿命1～4倍。     

Hard and wear-resistant titanium nitride coatings for cemented carbide cutting tools by pulsed high energy density plasma

Hard and wear-resistant titanium nitride coatings were deposited by pulsed high energy density plasma technique on cemented carbide cutting tools at ambient temperature. The coating thickness was measured by an optical profiler and surface Auger microprobe. The elemental and phase compositions and distribution of the coatings were determined by Auger microprobe, x-photon electron spectroscope, and X-ray diffractometer. The microstructures of the coatings were observed by scanning electron microscope and the roughness of the sample surface was measured by an optical profiler. The mechanical properties of the coatings were determined by nanoindentation and nanoscratch tests. The tribological properties were evaluated by the cutting performances of the coated tools applied in turning hardened CrWMn steel under industrial conditions. The structural and mechanical properties of the coatings were found to depend strongly on deposition conditions. Under optimized deposition conditions, the adhesive strength of TiN film to the substrate was satisfactory with the highest critical load up to more than 90 mN. The TiN films possess very high values of nanohardness and Young’s modulus, which are near to 27 GPa and 450 GPa, respectively. The wear resistance and edge life of the cemented carbide tools were improved dramatically because of the deposition of titanium nitride coatings.     

金属陶瓷及硬质合金表面CVD/PVD涂层的摩擦与切削性能

为研究涂层沉积方式对金属陶瓷和硬质合金性能的影响,采用粉末冶金技术制备了Ti(C,N)基金属陶瓷和YT15硬质合金,在基体表面先后采用CVD和PVD制备涂层。采用SEM、EDS等手段对涂层的微观组织和元素含量进行分析,并对涂层试样进行划痕、摩擦因数、切削性能检测。结果表明,通过复合CVD+PVD工艺,CVD涂层和PVD涂层结合良好。不论是金属陶瓷还是硬质合金,CVD涂层的膜基结合力和摩擦因数均为最大,PVD涂层最小,复合CVD+PVD涂层介于两者之间。对于金属陶瓷和硬质合金而言,复合CVD+PVD涂层的切削性能最好,CVD涂层最差,PVD涂层介于两者之间。切削过程中的磨损机理主要是氧化磨损和磨粒磨损。     

Inclined impact–sliding wear tests of TiN/Al2O3/TiCN coatings on cemented carbide substrates

A chemical vapor deposition (CVD) TiN/Al₂O₃/TiCN coating has been commercially used as a protective coating on cemented carbide cutting tools to improve tool life and superficial quality of the workpiece. However, the CVD coating is relatively brittle and could fail due to fatigue cracking induced wear under localized contact stresses during the milling operation. Traditional coating evaluation techniques such as tribo tests, scratch tests and impact tests only involve single movement, i.e., either sliding or impacting. In the present work, the fatigue and wear behavior of the triple-layered coatings on cemented carbide substrates was investigated using a novel impact–sliding wear tester, which simulates a repetitive movement of combined impact and sliding motions between cutting tools and workpieces during interrupted milling operations. The coatings on the surface and cross-section were studied using Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) analysis. The results from the impact component showed that fatigue cracking increased for the coating on a harder substrate likely due to the lower toughness of the substrate. The results from the sliding component showed that the wear resistance of the coating decreased as the substrate was softer. The test results provided constructive knowledge in selection and development of coatings for impact and sliding involved applications.     

PVD涂层刀具高速铣削CoCrMo合金的性能研究

目的为了提高涂层硬质合金刀具的切削性能,研究了物理气相沉积PVD法制备的涂层硬质合金铣刀在高速干式环境下的铣削性能。方法采用阴极电弧技术制备了TiN、TiAlN以及TiAlSiN涂层硬质合金铣刀刀头,通过一同沉积涂层的硬质合金圆片,间接测量得出涂层的显微硬度、厚度和平均摩擦系数,并以CoCrMo合金为切削对象,进行了PVD涂层与无涂层刀具高速铣削下的对比试验。结果TiAlSiN显微硬度最高达3800HV,摩擦系数达0.3,TiAlN涂层平均膜厚为2μm,间接测得TiN、TiAlN以及TiAlSiN涂层的结合力依次为60、58、42N。在三者的切削性能中,TiAlSiN涂层的切削性能比TiAlN和TiN涂层的好,同等切削参数时,TiN刀具的高速铣削时间最短,TiAlSiN涂层的平均磨损值为0.1895,TiN的平均磨损值为0.3047。结论涂层中添加Al、Si,极大地提高了刀具的使用性能,改善了刀具切削过程中的耐磨性、红硬性,极大地延长了刀具的使用寿命。TiAlSiN涂层的硬度高,耐磨损性好,切削性能好,适合高速铣削加工。     

高能量密度脉冲等离子体制备高硬耐磨TiN涂层

用高能量密度脉冲等离子体于室温下在硬质合金刀具上成功淀积了高硬耐磨TiN涂层．实验结果表明，涂层与基体有强的结合力，纳米划痕实验临界载荷达90mN以上；TiN涂层具有很高的硬度和Young’s模量，分别达27和450GPa以上．涂层刀具切削实验表明，刀具可用于硬度高达HRC58-62的CrVVMn钢切削，且磨损量较低，寿命长．     

The Study of Deposition Parameters, Properties for PVD Ti_xN and Cr_xN Coatings Using a Closed Field Unbalanced Magnetron Sputter Ion Plating System

DIFFERENT PVD TECHNIQUES have been used todevelop a wide range of hard wear resistant coatings onsteel substrates since the early1980's.These coatingshave proved successful in improving the performanceof cutting tools[1].Closed field unbalancedmagnetron sputter ion plating(CFUBMSIP)is anexceptionally versatile technique,developed by TeerCoatings Ltd,for the deposition of high-quality;well-adhered thin films[2].Compared to other ordinarymagnetron sputter techniques,the CFUBMSIPt…     

等离子体增强磁控溅射TiN涂层与铝对摩时的摩擦磨损行为∗

铝挤压模具表面的摩擦磨损行为是影响铝制品质量和模具寿命的重要因素。为了进一步优化铝挤压模具表面耐磨涂层的沉积工艺，以 TiN 涂层为例，采用等离子体增强磁控溅射方法分别在基体偏流为 0.1 A、1.5 A、3.0 A 和 4.5 A 条件下制备 TiN 涂层，利用 XPS、SEM、AFM 和 XRD 分别测量 TiN 涂层的化学成分、表截面微观结构和相组成，利用纳米压痕仪和旋转式球-盘摩擦磨损试验机分别考察 TiN 涂层试样的综合力学性能和与铝对摩时的摩擦磨损行为。结果表明：基体偏流增加对 TiN 涂层的化学组成影响较小。随着基体偏流的增加，TiN 涂层的横截面形貌逐渐细化。涂层表面具有由岛状微凸起组成的微结构，随着基体偏流的增加，微凸起尺寸和数量逐渐减小，表面粗糙度逐渐降低。不同基体偏流条件下制备的涂层均具有明显的 TiN(111)择优生长趋势。当基体偏流从 0.1 A 增加到 1.5 A 时，TiN 涂层的晶粒尺寸明显减小，涂层的综合力学性能得到显著提高。TiN 涂层试样与铝对摩过程中主要发生粘着磨损和磨料磨损，涂层试样对铝的减摩抗磨性能与对摩过程中的铝粘着面积呈负相关。结论：基体偏流对等离子体增强磁控溅射 TiN 涂层的表截面微观结构、力学性能和摩擦磨损行为影响显著，基体偏流为 1.5 A 时制备的 TiN 涂层具有最低的摩擦因数和磨损率，分别为 0.41×10^?15 和 3.03×10^?15 m³ / (N·m)。研究结果对铝成型模具表面高性能长寿命防护涂层的研究开发具有一定的理论意义和实用价值。     

Microstructure and physical properties of PVD TiN/（Ti, Al）N multilayer coatings

Magnetron sputtered （Ti, Al） N monolayer and TiN/（Ti, Al） N multilayer coatings grown on cemented carbide substrates were studied by using energy dispersive X-ray spectroscopy （EDX）, scanning electron microscopy （SEM）, nanoindentation, Rockwell A indentation test, strength measurements and cutting tests. The results show that the （Ti, Al）N monolayer and TiN/（Ti, Al）N multilayer coatings perform good affinity to substrate, and the TiN/（Ti, Al）N multilayer coating exhibits higher hardness, higher toughness and better cutting performance compared with the （Ti, Al）N monolayer coating. Moreover, the strength measurement indicates that the physical vapour deposition （PVD） coating has no effect on the substrate strength.     

脱β层厚度对CVD涂层硬质合金性能的影响

通过对WC-TiC-(Ta,Nb)C-Co硬质合金在1 300～1 380℃的渗氮气氛处理和随后的脱N烧结制得了不同脱β层厚度的合金基体,通过化学气相沉积(CVD)工艺制成从内到外依次为TiN/MT-TiCN/Al2O3/TiN的涂层硬质合金。采用光学显微镜、扫描电镜和能谱仪、抗弯(TRS)和切削试验对合金基体涂层前后的组织特征与性能进行了研究。结果表明,随着脱β层厚度的增加,试样涂层前后的抗弯强度均增加,在厚度达到20μm以上时,增加不明显。CVD涂层硬质合金可转位刀片的抗冲击性能也有相应的规律,而耐磨性则基本上保持一致。     

Mechanical properties and oxidation resistance of chemically vapor deposited TiSiN nanocomposite coating with thermodynamically designed compositions

TiSiN coating with nanocrystallite surrounded by amorphous phase has attracted a broad interest because of its high hardness and excellent oxidation resistance desired for cutting tools. In the present work, TiSiN coatings were designed and prepared from a gaseous mixture of TiCl₄, SiCl₄, NH₃ and H₂ by low pressure chemical vapor deposition (CVD) process under the guidance of calculated CVD phase diagrams. The calculated compositions and phases in the deposited coatings agree well with the experimental ones. The deposited TiSiN coatings consist of nano-crystalline TiN and amorphous Si₃N₄ (a-Si₃N₄). A maximum hardness of about 2800 HV_0.02 was obtained, corresponding to a minimum crystallite size of 17.7 nm and a-Si₃N₄ volume fraction of 13.3% for TiSiN coating deposited at 1123 K under 3.0 kPa. After oxidation at 973 K for 1 h, TiSiN coating kept intact while TiN was completely oxidized. TiSiN nanocomposite coating formed by Si incorporation to TiN displayed superior hardness and oxidation resistance in comparison with those of TiN. The correlation of TiSiN coating hardness with volume fraction of a-Si₃N₄ and TiN grain size was discussed. The present work demonstrates a novel strategy of thermodynamic calculations and key experiments to deposit CVD TiSiN coatings highly efficiently, which is equally valid for the design of other CVD hard coatings.