脉冲高能量密度等离子体薄膜制备与材料表面改性

脉冲高能量密度等离子体是一项全新的等离子体材料表面处理和薄膜制备技术。文章主要介绍了作者近几年来在这方面的研究成果。从理论和试验上研究了脉冲高能量密度等离子体的产生机制及其物理性质，研究了脉冲等离子体与材料相互作用的基本物理现象和物理机制，诊断测量表明，脉冲等离子体具有电子温度高（10－100eV）、等离子体密度高（10^14-10^16cm^-3）、定向速度高（－10^7cm/s）、功率大（10^4W/cm^2）等特点，在制备薄膜时具有沉积速率高，薄膜与基底粘结力强，并兼有激光表面处理、电子束处理、冲击波轰击、离子注入、溅射、化学气相沉积等综合性特点，可以在室温下合成亚稳态相和其他化合物材料。在此基础上，系统地进行了脉冲等离子体薄膜制备和材料表面改性及其机理的研究，在室温下的不同材料衬底上成功的沉积了性能良好的较大颗粒立方氮化硼、碳氮化钛、氮化钛、类金刚石、氮化铝等薄膜材料，沉积薄膜和基底之间存在一个很宽的过渡层，因此导致薄膜与基底有很强的粘结力，经脉冲等离子体处理过的金属材料表面性能得到了极大改善。     

脉冲高能量密度等离子体材料表面改性及其应用

脉冲高能量密度等离子体（pulsed high energy density plasma, PHEDP）是一项新的材料表面改性技术.它集高电子温度、高能量密度、高定向速度于一身,在制备薄膜时具有沉积薄膜的温度低、沉积效率高、能量利用率高的优点,并兼具表面溅射、离子注入、冲击波和强淬火效应等综合效应;它可以制备纳米晶或非晶硬质薄膜,提高基底材料的表面硬度和耐磨、耐蚀性能;能够实现非金属材料表面金属化,所制备薄膜与基底之间存在很宽的混合过渡区,因此膜/基结合良好.文章主要介绍了作者近年来在该领域的部分研究成果,简要介绍了脉冲高能量密度等离子体的原理、特点及应用.分析了脉冲等离子体与材料相互作用的基本物理现象.     

脉冲高能量密度等离子体沉积(Ti,Al)N薄膜组织及其性能研究

利用脉冲高能量密度等离子体技术在室温条件下在45＃钢基材表面沉积了高硬度耐腐蚀(Ti, Al)N薄膜. 利用扫描电子显微镜、X射线衍射、X射线光电子能谱、俄歇电子能谱分析了薄膜的显微组织.利用纳米压痕仪测试了薄膜的纳米硬度.测试了薄膜在05mol/L H2SO4水溶液中的耐蚀性. 测试结果表明：薄膜主要组成相为(Ti, Al)N，同时含有少量的AlN,薄膜的纳米硬度高达26 GPa,薄膜具有良好的耐蚀性，与1Cr18Ni9Ti奥氏体不锈钢相比，耐蚀性提高了一个数量级. 关键词： 脉冲高能量密度等离子体 薄膜 纳米硬度 耐蚀性     

压缩等离子体流脉冲能量密度修正方法

介绍了压缩等离子体流能量密度诊断存在的问题,基于能量的耗散走向分析及热传导计算模型,针对汽化过程对诊断带来的误差,给出了一种基于测量的质量损失,通过表面退行的有限元计算反推损失相同质量所需输入能量的能量密度修正方法,并对能量密度修正进行了评估,通过此方法得到的修正能量密度与实验结果相吻合,但要获得更准确的能量密度,还需针对屏蔽等离子体、反冲应力波等因素进行能量密度修正,或开发出更准确的能量密度诊断方法。     

多孔脆性材料对高能量密度脉冲的吸收和抵抗能力

作用在脆性结构材料表面的高能量密度脉冲会以冲击波的形式传播进入材料内部, 导致压缩破坏和功能失效. 通过设计并引入微孔洞, 显著增强了脆性材料冲击下的塑性变形能力, 从而使脆性结构材料可以有效地吸收耗散冲击波能量, 并抑制冲击诱导裂纹的扩展贯通. 建立格点-弹簧模型并用于模拟研究致密和多孔脆性材料在高能量密度脉冲加载下的冲击塑性机理、能量吸收耗散过程和裂纹扩展过程. 冲击波压缩下孔洞塌缩, 导致体积收缩变形和滑移以及转动变形, 使得多孔脆性材料表现出显著的冲击塑性. 对致密样品、气孔率5%和10%的多孔样品吸能能力的计算表明, 多孔脆性材料吸收耗散高能量密度脉冲的能力远优于致密脆性材料. 在短脉冲加载下, 相较于遭受整体破坏的致密脆性材料, 多孔脆性材料以增加局部区域的损伤程度为代价, 阻止了严重的冲击破坏扩展贯通整个样品, 避免了材料的整体功能失效.     

脉冲高能量密度等离子体法类金刚石膜的制备及分析

利用脉冲高能量密度等离子体法在光学玻璃衬底上、在室温下成功的制备了光滑、致密、均匀的纳米类金刚石膜.工艺研究表明：放电电压和放电距离以及工作气体种类对纳米类金刚石膜的沉积起着关键作用.利用拉曼光谱、扫描电镜以及电子能量损失谱分析薄膜的形态结构表明：薄膜具有典型的类金刚石特征；纳米类金刚石膜的晶粒尺寸小于20nm甚至为非晶态；类金刚石膜中含有一定量的氮原子，随着沉积能量的升高，氮的含量增大.纳米类金刚石膜的薄膜电阻超过109Ω/cm2.对放电溅射过程进行了理论分析，结果与工艺研究的结论吻合.     

TiN对Co基合金激光熔覆层组织与性能的影响

采用5 kW CO2激光器在低碳钢表面熔覆Co基合金涂层及TiN/Co基合金复合涂层,研究了两种涂层的组织、显微硬度以及滑动磨损性能。结果表明,Co基合金涂层主要组成相为γ-Co,ε-Co,Cr23C6等,TiN/Co基合金复合涂层组成相为γ-Co,ε-Co,Cr23C6,TiN和TiC等。Co基合金涂层由发达的γ-Co枝晶和其间共晶组织所组成,TiN/Co基合金涂层典型组织为等轴固溶体以及细小的共晶组织。TiN对熔覆层的组织有显著的改善作用,促使其组织细化,树枝晶向等轴晶转化,同时可显著提高Co基合金涂层的显微硬度及耐磨性能。     

TiN对Co基合金激光熔覆层组织与性能的影响

采用5 kW CO2激光器在低碳钢表面熔覆Co基合金涂层及TiN/Co基合金复合涂层,研究了两种涂层的组织、显微硬度以及滑动磨损性能。结果表明,Co基合金涂层主要组成相为-γCo,-εCo,Cr23C6等,TiN/Co基合金复合涂层组成相为-γCo,-εCo,Cr23C6,TiN和TiC等。Co基合金涂层由发达的-γCo枝晶和其间共晶组织所组成,TiN/Co基合金涂层典型组织为等轴固溶体以及细小的共晶组织。TiN对熔覆层的组织有显著的改善作用,促使其组织细化,树枝晶向等轴晶转化,同时可显著提高Co基合金涂层的显微硬度及耐磨性能。     

强流脉冲离子束辐照对电弧离子镀TiNbN硬质薄膜摩擦磨损性能的影响

 利用分离靶电弧离子镀工艺在高速钢基体上制备TiNbN多元硬质薄膜,利用TEMP-6型强流脉冲离子束（HIPIB）设备,采用含C/H离子、加速电压300 kV、脉冲宽度70 ns、束流密度60 A/cm2的强流脉冲离子束对所制备的薄膜进行辐照处理,研究辐照前后膜层的摩擦磨损性能的变化。实验结果表明：HIPIB辐照以后,薄膜的表面熔化,摩擦系数降低,晶粒细化,膜层的硬度由HK3444提高到HK3820,膜基结合力由59 N提高到65 N。在测试载荷300 N和600 N条件下,薄膜的摩擦磨损性能均有较大改善。     

Titanium carbonitride films on cemented carbide cutting tool prepared by pulsed high energy density plasma

Hard films prepared by pulsed high energy density plasma (PHEDP) are characterized by high film/substrate adhesive strength, and high wear resistance. Titanium carbonitride (TiCN) films were deposited onto YG11C (ISO G20) cemented carbide cutting tool substrates by PHEDP at room temperature. XRD, XPS, SEM, AES, etc. were adopted to analyze the phases (elements) composition, microstructure and the interface of the films, respectively. The results show that, the uniform dense films are composed of grains ranging from 70 to 90 nm. According to the AES result, there is a broad transition layer between the film and the substrate, due to the ion implantation effect of the PHEDP. The transition layer is favorable for the film/substrate adhesion.     

Microstructure and tribological behavior of pulsed laser deposited a-CNx films

The a-CN_x films were deposited onto high-speed steel substrate by pulsed laser deposition at different nitrogen pressures. The tribological properties of the films in humid air and in vacuum were investigated using a ball-on-disk tribometer under various loads. The composition, microstructure and morphology of the films, wear tracks and paired balls were characterized by energy dispersive X-ray analysis (EDXA), X-ray photoelectron spectrum (XPS), Raman spectroscopy and scanning electron microscopy (SEM). With increasing the deposition pressure, the fraction of sp³ C bond reduces, the fraction of trapped nitrogen increases and the friction coefficient of the films declines both in humid air and vacuum. The friction coefficient of a-CN_x film decreases with increasing normal load. The tribological performances of the films in humid air are better than those of in vacuum. A transferred graphite-like tribo-layer is observed from a-CN_x film to the paired ball for both environments.     

D2钢系列涂层磨损性能的数值模拟

采用真空离子镀的方式在AISI D2钢基体上制备渗N,TiN及复合涂层,并采用模拟和实验的方法研究涂层的磨损性能.将Archard经典粘着磨损模型离散化后用Fortran子程序的形式嵌入到商业化的有限元软件中,以求解接触摩擦过程中接触区每个节点或单元的磨损深度,定量分析了基体及三种涂层的磨损深度.研究结果表明,复合涂层具有最优耐磨性能.实验结果与模拟结果相符合. 关键词： 磨损 数值模拟 渗N TiN     

Deposition of tungsten nitride thin films by plasma focus device at different axial and angular positions

Tungsten nitride thin films were deposited on stainless steel-304 substrates by using a low energy (2 kJ) Mather type plasma focus device. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and microhardness are used to study the surface of treated samples. The XRD analysis shows that the degree of crystallinity of deposited thin films strongly depends on axial and angular positions of samples. The SEM micrographs of the deposited films at different angular positions (0°, 10° and 30°) and axial position of 8 cm show that the content of WN sub-micro crystalline structures on the surface of deposited films decreased with increasing the angle with respect to anode axis. From AFM results we observe that for the sample deposited at 8 cm and 0° axial and angular positions, respectively, the most uniform surface and the most homogenous distribution of grains are obtained. Also the hardness results show that the highest mechanical hardness is obtained when the film is deposited at 8 cm and 0° axial and angular positions, respectively.     

Deposition of titanium nitride and hydroxyapatite-based biocompatible composite by reactive plasma spraying

Titanium nitride is a bioceramic material successfully used for covering medical implants due to the high hardness meaning good wear resistance. Hydroxyapatite is a bioactive ceramic that contributes to the restoration of bone tissue, which together with titanium nitride may contribute to obtaining a superior composite in terms of mechanical and bone tissue interaction matters.The paper presents the experimental results in obtaining composite layers of titanium nitride and hydroxyapatite by reactive plasma spraying in ambient atmosphere. X-ray diffraction analysis shows that in both cases of powders mixtures used (10% HA + 90% Ti; 25% HA + 75% Ti), hydroxyapatite decomposition occurred; in variant 1 the decomposition is higher compared with the second variant. Microstructure of the deposited layers was investigated using scanning electron microscope, the surfaces presenting a lamellar morphology without defects such as cracks or microcracks. Surface roughness values obtained vary as function of the spraying distance, presenting higher values at lower thermal spraying distances.     

Synthesis and characterization of nanocrystalline titanium nitride powder from rutile and anatase as precursors

In this research nanosized titanium nitride powder was synthesized through reaction of titanium oxide with ammonia gas. The reaction was carried out at a very slow heating rate. Two different TiO₂ starting powders contained rutile and anatase phase and differed in initial particle size and surface area. The crystallite size of TiN powders synthesized at 1000 °C was obtained about 40 nm for anatase sample. Surface area and particle size were found to be 19 m²/g, 70 nm for rutile sample and 31 m²/g, 39 nm for anatase sample, respectively. The rutile sample showed an increasing trend in surface area during conversion to the nitride, whilst the anatase sample followed an adverse trend. TiN powder synthesized from anatase had the highest surface area and smallest particle size due to the specification of initial precursor.     

In掺杂氮化亚铜薄膜的电学、光学和结构特性研究

采用射频磁控溅射方法, 在低功率和低温条件下利用纯氮气作为反应溅射气体制 备出不同In含量的三元氮化物Cu_xIn_yN薄膜. 研究发现In掺杂浓度对薄膜微结构、形貌、表面化学态以及光学特性有灵敏的调节作用. 光电子峰、俄歇峰、俄歇参数的化学位移变化从不同角度揭示了不同含量In掺杂引 起的原子结合情况的变化. XPS结果显示In含量小于8.2 at.%的样品形成了Cu-In-N键. 对In含量为4.6 at.%的样品进行XRD和TEM结构测试, 实验结果肯定了In原子填充到Cu₃N的反ReO₃结构的体心位置. 并且当In含量增至10.7 at.%时, 薄膜生长的择优取向从之前占主导地位的(001)方向转变为(111)方向. 此外, 随着In含量的增加, 薄膜的R-T曲线从指数形式变为线性. 当In含量为47.9 at.%时, 薄膜趋于大温区恒电阻率材料, 电阻温度系数TCR仅为-6/10000. 光谱测量结果显示In摻杂使得氮化亚铜掺杂薄膜的光学帯隙从间接帯隙变为直接帯隙. 由于Burstein-Moss效应, 帯隙发生蓝移, 从1.02 eV 到2.51 eV, 实现了帯隙连续可调. 关键词： 三元氮化物 薄膜 光学特性 氮化亚铜     

Synthesis of nano-structure tungsten nitride thin films on silicon using Mather-type plasma focus

Nano-structure thin film of tungsten nitride was deposited onto Si-substrate at room temperature using Mather-type plasma focus (3.3?kJ) machine. Substrate was exposed against 10, 20, 30, and 40 deposition shots and its corresponding effect on structure, morphology, conductivity and nano-hardness has been systematically studied. The X-ray diffractormeter spectra of the exposed samples show the presence of various phases of WN and WN₂ that depends on number of deposition shots. Surface morphological study revealed the uniform distribution of nano-sized grains on deposited film surface. Hardness and conductivity of exposed substrate improved with higher deposition shots. X-ray photo-electron spectroscopy survey scan of 40 deposition shots confirmed the elemental presence of W and N on Si-substrate.     

Thermal stability of titanium nitride coatings prepared by the mixing technology with laser and plasma

Titanium samples were treated by the mixing technology with laser and plasma (LPN) using different laser power densities. These nitrided samples were then annealed at 473 K, 673 K, 873 K, and 1073 K for 2 h in vacuum, respectively. The samples before and after annealing were characterized at room temperature and compared in terms of microstructure. X-ray diffraction and cross-sectional optical microscopy studies showed that the layer structure of the titanium nitride coating is preserved after annealing at 1073 K when the coating is formed using a laser power density of 8.0 × 10⁵ W/cm². Therefore, titanium nitride coatings produced by LPN demonstrate excellent thermal stability and are potential candidates for high temperature tribological applications.