真空阴极离子镀法制备Ti/TiN/Zr/ZrN多层膜

过去,在不锈钢上沉积10μm以上多元多层软硬交替Ti/TiN/Zr/ZrN厚膜用以提高材料耐腐蚀性能的报道不多.采用阴极电弧离子镀结合脉冲偏压的方法制备了厚度选15 μm的Ti/TiN/Zr/ZrN多层膜.运用扫描电镜(SEM)、X射线衍射(XRD)、显微硬度计、划痕仪等考察了多层膜的形貌、厚度、相组成、硬度以及膜/基结合力,并利用电化学方法评价了基体、单层TiN薄膜以及多层膜的电化学腐蚀性能.结果表明:制备的Ti/TiN/Zr/ZrN多层膜界面明晰、结构致密、晶粒细小;膜/基结合力大于70 N,显微硬度达28 GPa;多层膜比单层TiN膜在提高1Cr11Ni2W2MOV基体的抗腐蚀能力方面具有更显著的作用.     

多弧离子镀TiN/TiCrN/CrN多元多层复合膜的制备及性能研究

采用XH-800多弧离子镀设备在硬质合金刀具表面制备TiN/TiCrN/CrN多元多层复合膜.利用XRD、SEM、显微硬度计、多功能材料表面性能测试仪等对其组织结构与性能进行了研究.结果表明:膜层表面均匀,未出现龟裂现象,色泽光亮度好;膜的相结构组成为TiN和Cr2N,随着Cr靶电流的增大,TiN的择优取向由(200)向(111)转变,膜层出现单质Cr;膜层厚度为5.02μm,具有明显多层特征;显微硬度2536 HV;结合力65 N.     

金属钛激光气体氮化层组织及表面特征

采用连续波Nd-YAG激光在氮气环境中对金属钛进行激光气体氮化处理.利用SEM,XRD,XPS研究氮化层的显微组织、表面成分、结构.结果表明:通过激光气体氮化可以在金属钛表面得到表面相对平滑、无裂纹的氮化层;氮化层与基体材料之间为冶金结合.氮化层主要由枝晶状TiN组成,同时有TiNxOy,TiO2及TiC存在,外表面有C,O污染或吸附;TiN枝晶密度由表面沿深度方向下降.     

高温化学气相沉积TiC/Ti(CxN1-x)/TiN层的组织结构及摩擦磨损性能

Ti(CxN1-x)涂层具有硬度大、强度高、耐磨等性能,而目前采用化学气相沉积法在不锈钢表面制备Ti(CxN1-x)多层涂层的报道较少。用高温化学气相沉积法在316L不锈钢表面分别制备了TiN单层涂层和TiC/Ti(CxN1-x)/TiN多层涂层,比较分析了2种涂层的显微形貌、相结构、硬度、界面结合力及耐磨性能。结果表明:TiC/Ti(CxN1-x)/TiN多层涂层结构致密,厚约10μm;TiN单层及TiC/Ti(CxN1-x)/TiN多层涂层均提高了316L不锈钢的硬度、耐磨性;与TiN单层涂层相比,TiC/Ti(CxN1-x)/TiN多层涂层的显微硬度和界面结合力更好,摩擦系数更低,磨损量更小,耐磨减摩性能更好;2种涂层的磨损破坏机制较一致,主要为磨粒磨损和摩擦氧化。     

建筑装饰用铜合金表面Ni-P化学镀层的制备与性能研究

为了增加建筑装饰用铜合金的耐磨性,研究了硬质相TiN浓度和热处理对铜合金表面化学镀Ni-P层显微形貌、物相组成、硬度和耐磨性能的影响。结果表明：装饰用铜合金基体主要由CuZn相和CuZn₅相组成,化学镀层表面可见Ni的非晶馒头峰和CuZn衍射峰。化学镀层的显微硬度均高于铜合金基体,且化学镀层的硬度会随着TiN浓度增加而增大,在TiN浓度为3～11 g/L时,化学镀层的磨损率小于铜合金基体,且TiN浓度为7 g/L时化学镀层的磨损率最小[1.15×10^-8 g/（r·N）],此时磨损机制为氧化磨损。Cu-P-TiN化学镀层在300～600℃热处理后发生了晶化转变并形成Ni和Ni₃P相;随着热处理温度升高,化学镀层的显微硬度先增加后减小、磨损率先减小后增大,在热处理温度为400℃时获得硬度最大值和磨损率最小值,表明热处理有助于提升化学镀层的耐磨性能。     

35CrMoA钢激光淬火-渗氮复合改性层微观组织及脆性

研究了气体渗氮层和激光淬火-渗氮层的相组成、微观结构、显微硬度及脆性。结果表明, 激光淬火-渗氮白亮层中ε-Fe₃N含量由14.74%增至69.45%, 而脆硬的ξ-Fe₂N含量由79.95%降至25.03%。表层的N含量降低, 渗氮层N浓度曲线降低趋势平缓, N的总扩散通量增加, 渗氮层厚度增加。激光淬火-渗氮层组织晶粒细小致密, 渗碳体分布在条状下贝氏体组织中, 硬度高的Cr₂N颗粒数目增加, 白亮层显微硬度值显著提高, 渗氮层脆断的临界压力由气体渗氮层的3 N提高到激光淬火-渗氮层的6 N。      

工业纯铁等离子体氮化及Ti/TiN多层薄膜沉积复合处理研究

为改善工业纯铁的耐磨抗腐蚀性能,本文采用低偏压高频等离子浸没离子注入及氮化技术(HLPⅢ)对工业纯铁进行表面改性,然后利用非平衡磁控溅射技术(UBMS)在低压高频等离子浸没离子注入及氮化处理样品表面制备Ti/TiN多层膜.研究发现,工业纯铁在3.5kV脉冲电压(频率15.15kHz,占空比25%)下等离子注入及氮化3h后,表面形成了深度达4μm的氮化层,其相结构以ε-Fe_3N和γ-Fe_4N结构为主.等离子氮化及Ti/TiN多层薄膜沉积复合处理后,工业纯铁的硬度、耐磨损性能以及抗腐蚀性能均得到大大提高,等离子注入及氮化形成的氮化层有利于提高Ti/TiN多层薄膜与工业纯铁基体之间的结合力和耐磨性.     

TA2钛合金真空脉冲气体氮化层的性能

为了进一步提高钛合金表面改性层的质量,采用真空脉冲气体氮化法在不同温度下对工业纯钛TA2进行氮化处理。利用金相显微镜、扫描电镜、X射线衍射仪、硬度仪、摩擦磨损试验及极化曲线分析了氮化层的组织结构、耐磨性能、耐腐蚀性能和表面硬度梯度等,研究了氮化温度对氮化层性能的影响。结果表明:TA2钛合金经过不同温度氮化处理后,其表面主要形成Ti N_(0.3)相;氮化层厚度和表面硬度都随温度的升高而增加,当温度升高到900℃时,氮化层厚度达60μm,表面硬度达750 HV,耐磨性及耐蚀性较基材大幅提高,磨损速率由基材的0.277 8 mg/(h·cm~2)减小至0.000 4 mg/(h·cm~2),腐蚀速率降低了2个数量级;800~900℃温度范围内,氮化温度对氮化层的耐腐蚀性能影响不大,但是温度的升高使得表面组织变得粗大,同时脆性有所增加。     

原位反应合成TiN/Al2O3梯度复合材料的研究

以Al和TiO2为原料,在匣钵埋碳保护气氛下铝热还原氮化法原位合成制备了TiN/Al2O3梯度复合材料.采用XRD,SEM,EDS和TEM等分析手段,结合热力学计算研究了该梯度复合材料的原位反应过程和材料的物相组成和微观结构.研究结果表明,XRD检测结果与热力学分析结果相吻合,采用埋炭工艺条件下的原位铝热反应可以制得TiN-Al2O3梯度复合材料.TiN/Al2O3梯度试样中各层间没有明显的界面,TiN/Al2O3比沿厚度方向由边缘向中心连续转变,材料的显微结构沿厚度方向由边缘向中心也是梯度变化的,TiN晶粒逐渐长大.     

脉冲激光诱导钛表面氮化的研究

介绍了在氮气气氛下,用脉冲激光照射钛表面实现钛的诱导氮化的实验结果.利用扫描电镜(SEM)、X射线衍射(XRD)和拉曼光谱对氮化表面进行了结构表征和性能分析.X射线衍射(XRD)结果显示氮化层的主要成分是a-Ti相和δ-TiN相,同时含有少量的a-Ti(N)固溶体.随着激光平均功率的增加,氮化层中δ-TiN相和α-Ti(N)固溶体含量逐渐增加,相应的氮含量也逐渐增加.纳米硬度测试结果显示氮化层的纳米硬度和弹性模量较基材钛明显增加,2mN载荷下测得氮化层的纳米硬度和弹性模量分别在11.5～15GPa和200～250GPa之间.     

Laser Gas Nitriding of Ti-6Al-4V Part 2: Characteristics of Nitrided Layers

The characteristics of laser nitrided layers formed on Ti-6Al-4V are presented in this investigation. It has been determined that titanium nitride (TiN) is formed, which significantly increases the hardness of the nitrided surfaces. The amount of titanium nitride produced depends on the processing parameters such as laser pulse energy and nitrogen concentration. Nitrided layers are much smoother along the laser pass direction than perpendicular to this direction. The shrinkage effect in the laser melt zone produces surface residual tensile stresses in Ti-6Al-4V samples regardless of whether the processing environment is Ar, N₂, or a mixture of these gases. Pre-heating or stress relieving after laser nitriding significantly reduces the residual tensile stress level.     

Metal matrix composite layers formed by laser processing of commercial purity Ti–SiCp in nitrogen environment

Abstract

Metal matrix composite layer formation by means of laser alloying using 6 μm particle size SiC powder (SiC_p) preplaced on titanium surfaces in a nitrogen environment produced golden coloured tracks and a complete solution of SiC_p in the melt zones under a range of processing conditions. The melt layers consisted of dendrites at the top (titanium nitride based) followed by threadlike particle structures (titanium silicides), and the sizes of dendrites and the threadlike particles werefound to increase with increasing laser power density. The surface layer of the dendrites developed a hardness 4·5–9 times that of the base metal (150 HV), and the deep underlying threadlike structures had a plateau of hardness of aboout 2·8–4 times the base hardness. The metal matrix composite layers were found to be 2–4 times thicker than those produced previously in a helium environment under similar processing conditions. The exothermic reactions due to the formation of titanium nitride, titanium carbide, or titanium carbonitride along with titanium silicide during laser melting of SiC_p coated titanium surfaces under a nitrogen environment are considered to be responsible for the greater melt depth and complete dissolution of ceramic particles, by increasing the temperature of the melt.

MST/3208     

The effect of laser surface nitriding with a spinning laser beam on the wear resistance of commercial purity titanium

Laser nitriding of commercial purity titanium using various concentrations of helium and nitrogen has been carried out. The surface appearance and microstructure of a treated layer were found to be dependent on the beam power density, interaction time, velocity and concentration of nitrogen. X-ray diffraction analyses have led to the conclusion that the dendrite layer in the resolidified zone of the nitrided specimens consisted mainly of TiN. The surface roughness of specimens after various laser treatments was investigated by SEM and a surface profilemeter. Using optical microscopy, the dendrite TiN and needle-like structure in the melt zone, and the large grain structure in the heat affected zone, were investigated. The surface wear resistance of nitriding CPTi was significantly improved compared to the untreated or laser glazed material, and the wear data were found to correlate with scanning electron microscopy observations. Two layers, having different microstructures, thickness and abrasive wear resistance were identified. Further, 100% overlapping considerably improved the wear resistance of the nitrided specimens.     

Laser Gas Nitriding of Ti-6AI-4V Alloy

Laser gas nitriding of Ti-6A1-4V has been investigated with both CO₂ and Nd:YAG lasers. Results indicate that Nd:YAG laser in pulse mode provides a better surface finish and a lower cracking severity than CO₂ laser. A crack-free nitrided layer has been obtained by optimizing the processing parameters. Titanium nitride (TiN) significantly increases the hardness of the nitrided surfaces. The amount of titanium nitride produced depends on the processing parameters, such as laser pulse energy and nitrogen concentration. With optimized parameters, the nitrided surface is somewhat rougher than the polished base metal but much smoother than the shot peened surface. The shrinkage effect in the laser melt zone produces surface residual tensile stresses regardless of the processing environment. Preheating or stress relieving after laser nitriding can significantly reduce the residual tensile stress level.     

Diffusion kinetics of explosively treated and plasma nitrided Ti-6Al-4V alloy

Ti-6Al-4V alloys, which were exposed to an explosive shock process, were nitrided in nitrogen plasma in the temperature range of 700-900°C for 3-12 h. During the plasma nitriding, the surface layer consisted of TiN (δ), Ti₂N (ε) and nitrogen solid solution layers (α-Ti). The growth rate of nitride and solid solution layers were found to be controlled by the diffusion of nitrogen. An effective nitriding was achieved due to high dislocation density and vacancy concentration. Based on the present layer growth data, an analytical model for multiphase diffusion was used to estimate the effective nitrogen atom diffusion coefficient in the nitride layers. The interface velocity equations were derived from Fick's law and a numerical method has been used to compute the diffusion coefficients of nitrogen in a binary multiphase Ti-TiN system. Depending on temperature and layer thickness, the activation energies of nitrogen in TiN and Ti₂N phases were found to be 18,950 (±2116) and 27,925 (±1105) cal/mole, respectively.     

Ion-nitriding behaviour of Fe-Ti alloys in theα-phase region

The ion-nitriding behaviour of four iron alloys containing between 0.11 and 1.48 wt% titanium was investigated in the-phase region to discuss kinetics of the growth of the nitriding layer. The ion-nitriding experiments have been made at 823 K. Two nitriding layers were observed: a thin surface layer which mainly consists of Fe₄N; an internal nitriding layer beneath the surface layer, where the nitride formed was found to be TiN. The growth of the internal nitriding layer is controlled by a diffusion process of nitrogen in the matrix metal. The apparent diffusion coefficient of nitrogen in the nitriding layer, evaluated using the rate equation proposed for internal oxidation, increases linearly with the volume fraction of titanium nitride. Furthermore, by excluding the effect of the titanium nitride from the apparent diffusion coefficient, the diffusion coefficient of nitrogen in-iron was calculated, being in good agreement with that reported so far. In addition, the increase in hardness in the internal nitriding layer has been discussed.     

Titanium nitride laser-beam surface-alloying treatment on carbon tool steel

In order to improve the wear resistance of tool steel, a study of TiN surface-alloying treatment on 1% carbon steel by irradiation with a CO₂ laser beam was performed. Argon and nitrogen were used as shielding gases, and their effects on the formation of the surface-alloyed layer were investigated. The effect of cobalt additions to the TiN powder on the hardness of the alloyed layer was also investigated. When argon was used as shielding gas, the depth of the alloyed layer was increased compared with the depth when nitrogen was used as a shielding gas. A portion of the TiN decomposed into titanium in the argon environment, the nitrogen apparently being lost as a gas. The structure of the surface-alloyed layer was composed of a ferritic phase without martensitic structure even at high cooling rates. When this layer was annealed at 1000 ° C for 3 h, part of the titanium precipitated as TiC particles. The hardness of the annealed alloyed layer increased to about 500 Hv. This increase in hardness was accompanied by the appearance of martensite. When nitrogen was used as shielding gas, decomposition of TiN was suppressed and the hardness of the alloyed layer reached 850 Hv. These layers had a martensitic structure. Thus, nitrogen is preferable to argon as a shielding gas if a martensitic structure is desired in this system. When 5% cobalt was added to the TiN powder, the hardness of the alloyed layer increased to 1100 Hv. This increased hardness is caused by stabilization of the martensitic structure caused by an increase in theM _s temperature.     

X-ray reflectivity study on TiN/Ti/Si structures before and after annealing

X-ray reflectivity was employed as a powerful tool for studying the surface and interface roughness and thickness, as well as density, of TiN/Ti/Si layers. X-ray reflectivity of the as-deposited samples, with nominal thickness of 17.5 nm of Ti and 3.0 nm of TiN, shows uniform oscillations. When the samples are annealed at 710°C, residual strongly attenuated oscillations are still observed, while the 850°C-annealed sample does not show oscillations, indicating high surface and interface roughness of the formed nitride and silicide layers. It is demonstrated that increased interface roughness, even for a layer with a larger average electron density difference, reduces the oscillations in the reflectivity curve very rapidly. For comparison, cross sectional transmission electron microscopy was employed to find the thickness of the surface and interface layers in silicide structures, which are in good agreement with the X-ray reflectivity results. The work was also supported by tapping mode atomic force microscopy observations, where we have observed nearly flat structures for the as-deposited sample surface and needle-like protrusions for the annealed samples. The surface roughness of the top TiN layer was used to obtain simulated X-ray reflectivity spectra in good agreement with the experimental results. Preliminarily, the crystallography of the layers in the samples was determined by the grazing angle X-ray diffraction technique, to acquire knowledge on the Ti and Si compounds formed in the samples after the annealing.     

Effect of N2/Ar gas flow ratios on the nitrided layers by direct current arc discharge

Nitrided layers were prepared on titanium substrates by direct current (DC) arc discharge technique. The effect of nitrogen to argon flow ratios on the microstructures and mechanical properties of the samples was investigated. The X-ray diffraction results show that the surfaces of the layers consist mainly of TiN and a very little TiN_0.3 (101) under the condition of nitrogen/argon gas mixture. A strong TiN (200) preferential orientation in nitrided layers can be seen. With increasing the nitrogen concentration ratio in nitrogen/argon gas mixture, the density and size of TiN dendrites in the nitrided layers, and the hardness and wear resistance of the layers enhanced significantly.     

氮氩混合比对TA2真空氮化层结构与性能的影响

采用间歇式真空氮化技术对TA2钛合金进行渗氮处理。探究氮氩混合比对合金氮化层结构和性能的影响规律。结果表明:表面渗氮层主要由TiN和TiN0.3相组成,氮氩比越低其有效硬化层越厚,但会降低有效活性N原子的相对含量,不利于渗层的致密性。适当的氮氩混合比能在TA2表面形成氮化物,N原子有效地向纵深扩散,氮化物层与扩散层结合紧密,过渡良好,硬度梯度平缓;腐蚀电位随着氮氩比的增加呈现逐渐上升趋势,从氮氩比为1∶5时的-0.622V提升到氮氩比为5∶1时的-0.549V,腐蚀电流和腐蚀速率则呈现出逐渐降低的趋势。