Comparative study of titanium carbide and nitride coatings grown by cathodic vacuum arc technique

Titanium nitride (TiN), titanium carbide (TiC) thin films and TiC/TiN bilayers have been deposited on AISI 304 stainless steel substrates by plasma assisted physical vapor deposition technique—reactive pulsed vacuum arc method. The coatings were characterized in terms of crystalline structure, microstructure and chemical nature by X-ray diffraction and X-ray photoelectron spectroscopy, respectively. Tribological behavior was investigated using ball on disc technique. The average coefficient of friction was measured, showing lower values for the TiN/TiC bilayer. Dynamic wear curves were performed for each coating, observing a better wear resistance for TiN/TiC bilayers, compared to TiN and TiC monolayers. On the other hand, the TiCN formation in the TiN/TiC bilayer was observed, being attributed to the interdiffusion between TiN and TiC at the interface. Moreover, the substrate temperature influence was analysing observing a good behavior at T_S = 115 °C.     

Ti/TiN multilayer thin films deposited by pulse biased arc ion plating

In this work, the effect of modulation period (Λ) on Ti/TiN multilayer films deposited on high-speed-steel (HSS) substrates using pulse biased arc ion plating is reported. The crystallography structures and cross-sectional morphology of Ti/TiN multilayer films were characterized by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM), respectively. Their mechanical properties were determined via nanoindentation measurements, while the film/substrate adhesion via the scratch test. It was found that the highest hardness value reached 43 GPa for the modulation period of 54 nm, while the film/substrate adhesion also reached the highest value of 83 N. Furthermore, the hardness enhancement mechanism in the multilayer films is discussed.     

Ti/Ti-类金刚石多层膜的制备与表征

采用电子回旋共振-化学气相沉积结合中频磁控溅射的真空镀膜技术, 以99.99%Ti为靶材, 乙炔为碳源制备了Ti/Ti-类金刚石(DLC)多层膜. 利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱仪 对Ti/Ti-DLC多层膜进行了相结构、组织、成分及形态分析. 采用显微硬度仪、摩擦磨损仪、表面粗糙度仪对Ti/Ti-DLC多层膜进行了力学性能考察. 结果表明: Ti/Ti-DLC多层膜中主要含有TiC晶相; Ti层和Ti-DLC层中未出现柱状晶体生长模式, 分层中均以岛状模式生长; 当调制周期Λ≤ 50 nm时, 分层结构变模糊; 调制周期Λ对Ti/Ti-DLC多层膜的复合硬度、摩擦系数、表面形貌、表面粗糙度都有影响, 当调制周期Λ较小时表现出纳米增硬效应, 表面出现大颗粒, 表面粗糙度和摩擦系数均变大.     

磁控溅射(Ti,N)/Al纳米复合薄膜的微结构和力学性能

采用Al和TiN靶通过磁控共溅射方法, 制备了一系列Ti:N≈1的不同(Ti, N) 含量的铝基纳米复合薄膜, 利用X射线能量分散谱仪、X射线衍射仪、透射电子显微镜和纳米力学探针表征了薄膜的成分、 微结构和力学性能, 研究了(Ti, N)含量对复合薄膜微结构和力学性能的影响. 结果表明: Ti, N原子的共同加入使复合薄膜形成了同时具有置换固溶和间隙固溶特征的"双超过饱和固溶体", 薄膜的晶粒随着溶质含量的增加逐步纳米化, 并进一步形成非晶结构, 晶界区域形成溶质原子的富集区. 相应地, 复合薄膜的硬度在含1.8 at.%(Ti, N) 时就可迅速提高到3.9 GPa; 随着TiN含量的增加, 薄膜的硬度进一步提高到含17.1 at.%(Ti, N)时的8.8 GPa. 以上结果显示出Ti和N"双超过饱和固溶"对Al薄膜极其显著的强化效果.     

Synthesis and evaluation of TiN–WC/TiN nanocomposite by the hybrid technique with arc ion plating and magnetron sputtering

By adjusting the power of WC target, novel TiN–WC films with different proportions of WC phase were prepared on TiN interlayer using the hybrid technique of arc ion plating (AIP) and magnetron sputtering (MS). The TiN–WC films were characterized by XRD, XPS, AFM, FESEM, Nano-indenter, and UMT-2MT tribometer. The TiN–WC film that is composed with TiN and WC phases was grown by 15–25 nm nanodotes along the primarily growth direction TiN (1 1 1) in AIP interlayer. Among the three TiN–WC films deposited at various powers of WC target, the TiN–WC2 (500 W) has the highest deposition rate of 1.4 nm/min. The content of WC phase increases as WC target power increases in the TiN–WC films. However, the deposition rate of TiN–WC film gains at first and then declines when WC target power exceeds 500 W because of the addictive poisoning of Ti target. In the present case, the incorporation of WC into TiN is found to result in a slight decrease in friction coefficient. Furthermore, the wear mechanism of multilayer AIP TiN films and MS TiN–WC/AIP TiN films was transformed from “severe wear” to “mild wear”. As a result, the 48TiN52WC film of 35 GPa hardness exhibits better tribological performance.     

Microstructural characterization of Ti-C-N thin films prepared by reactive crossed beam pulsed laser deposition

In this work, Raman spectroscopy has been used to characterize Ti-C-N thin films in order to obtain information about the microstructure of the deposited materials, and in particular to study the effects due to the carbon incorporation into the TiN lattice. Ti-C-N thin films were prepared using a crossed plasma configuration in which the ablation of two different targets, titanium and carbon, in a reactive atmosphere was performed. With this configuration, the carbon content in the films was varied in an easy way from 5.0 at% to 40.0 at%. Thin film composition was determined from Non-Rutherford Backscattering Spectroscopy (NRBS) measurements. X-ray photoelectron spectroscopy and X-Ray diffraction measurements were also carried out in order to characterize the films in more detail, with this being used to give support to the interpretation of the Raman spectra. The Raman results revealed that at lower carbon concentrations a solid solution Ti(C, N) is formed, whilst at higher carbon concentrations a nanocomposite, consisting of nanocrystalline TiCN and TiC immersed in an amorphous carbon matrix is obtained.     

Dry sliding wear characteristics of in situ synthesized Al-TiC composites

Abstract

Aluminum-based composites containing 0.06, 0.09, 0.12 fractions of in situ-synthesized TiC (Titanium carbide) particles have been prepared through in-melt reaction from Ai–SiC–Ti system following a simple and cost-effective stir-casting route. The TiC forms by the reaction of Ti with carbon which is released by SiC at temperatures greater than 1073 K. However, some amount of titanium aluminide (Al₃Ti) is also formed. The formation of TiC has been confirmed through X-ray diffraction studies of the composite. The hardness and tensile strength have been found to increase with increasing amount of TiC. The friction and wear characteristics of the composites have been determined by carrying out dry sliding tests on pin-on-disc machine at different loads of 9.8 N, 19.6 N, 29.4 N, 39.2 N at a constant sliding speed of the 1 m/s speed. The wear rate i.e. volume loss per unit sliding distance has been found to increase linearly with increasing load following Archard’s law. However, both the wear rate and friction coefficient have been observed to decrease with increasing amount of TiC in the composite. This has been attributed to (i) a relatively higher hardness of composites containing relatively higher amount of TiC resulting in a relatively lower real area of contact and (ii) the formation of a well-compacted mechanically mixed layer of compacted wear debris on the worn surface which might have inhibited metal–metal contact and resulted in a lower wear rate as well as friction coefficient.     

The electrochemical and mechanical properties of Ti incorporated amorphous carbon films in Hanks’ solution

Ti incorporated amorphous carbon (a-C) films with variant Ti contents were prepared by the unbalanced magnetron sputtering process. Scanning electron microscopy, ultraviolet Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the microstructure of a-C films. The hardness and lubricated tribological properties were assessed using nanoindentation and ball-on-disk tribometer. As the Ti content in a-C films increases from 0 to 15.2 at.%, the sp³ volume fraction, the internal stress and the hardness of the films decreases gradually, while the disorder of sp² bond increases. The electrochemical tests reveal that the a-C films with lower than 1.5 at.% Ti possess good corrosion resistance in Hanks’ solution, while the a-C film with 15.2 at.% Ti is susceptible to crevice corrosion. The reduced friction of the a-C films is due to the sp² bonded film surface and boundary lubrication of the Hanks’ solution. The a-C film with 3.1 at.% Ti exhibits the best wear resistance in Hanks’ solution among the studied films.     

Microstructure and tribological performance of self-lubricating diamond/tetrahedral amorphous carbon composite film

In order to smooth the rough surface and further improve the wear-resistance of coarse chemical vapor deposition diamond films, diamond/tetrahedral amorphous carbon composite films were synthesized by a two-step preparation technique including hot-filament chemical vapor deposition for polycrystalline diamond (PCD) and subsequent filtered cathodic vacuum arc growth for tetrahedral amorphous carbon (ta-C). The microstructure and tribological performance of the composite films were investigated by means of various characterization techniques. The results indicated that the composite films consisted of a thick well-grained diamond base layer with a thickness up to 150 μm and a thin covering ta-C layer with a thickness of about 0.3 μm, and sp³-C fraction up to 73.93%. Deposition of a smooth ta-C film on coarse polycrystalline diamond films was proved to be an effective tool to lower the surface roughness of the polycrystalline diamond film. The wear-resistance of the diamond film was also enhanced by the self-lubricating effect of the covering ta-C film due to graphitic phase transformation. Under dry pin-on-disk wear test against Si₃N₄ ball, the friction coefficients of the composite films were much lower than that of the single PCD film. An extremely low friction coefficient (∼0.05) was achieved for the PCD/ta-C composite film. Moreover, the addition of Ti interlayer between the ta-C and the PCD layers can further reduce the surface roughness of the composite film. The main wear mechanism of the composite films was abrasive wear.     

多弧离子镀工艺对TiN/Ti与Cr/Cu界面及微结构的影响

用多弧离子镀技术在铜基上电镀Cr/Ni层进行不同工艺条件下多弧离子沉积TiN/Ti实验.借助X射线衍射(XRD)和扫描电子显微镜(SEM)研究了TiN/Ti与Cr/Cu接触界面形成、微结构及其组分与形貌.XRD分析显示,薄膜表面组分包含TiN,Ti₂N多晶相外,还包含一些Cr-Ti的金属间化合物等.显然,TiN,Ti₂N在表面上已形成.SEM观察指出,在90℃制备的表面膜具有不平整的类枝状结晶结构.随着温度升高至170℃,得到精细TiN/Ti覆盖层表面,XRD峰 关键词： 多弧离子镀 氮化钛 界面形成 微结构     

PIIID复合强化处理轴承钢表面TiN膜层的XPS表征

用等离子体浸没离子注入与沉积(PIIID)复合强化新技术在AISI52100轴承钢基体表面成功合成了硬而耐磨的氮化钛薄膜。膜层表面的化学组成和相结构分别用X射线衍射(XRD)和X射线光电子能谱(XPS)表征;膜层表面的原子力显微镜(AFM)形貌显示出TiN膜结晶完整,结构致密均匀。XRD测试结果表明,TiN在(200)晶面衍射峰最强,具有择优取向。Ti(2p)的XPS谱峰泰勒拟合分析揭示出,Ti(2p_1/2)峰和Ti_2p3/2峰均有双峰出现,表明氮化物中的Ti至少存在不同的化学状态;N(1s)的XPS谱峰在396.51, 397.22和399.01 eV附近出现了三个分峰,分别对应于TiNO_y,TiN和N—N键中的氮原子。结合O(1s)的XPS结果,证实膜层中除生成有稳定的TiN相外,还有少量钛的氧化物和未参与反应的单质氮。整个膜层是由TiN,TiO₂,Ti—O—N化合物和少量单质氮组成的复合体系。     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

（Ti,Al）N Film on Normalized T8 Carbon Tool Steel Prepared by Pulsed High Energy Density Plasma Technique

Under optimized operating parameters, a hard and wear resistant （Ti,Al）N film is prepared on a normalized T8 carbon tool steel substrate by using pulsed high energy density plasma technique. Microstructure and composition of the film are analysed by x-ray diffraction, x-ray photoelectron spectroscopy, Auger electron spectroscopy and scanning electron microscopy. Hardness profile and tribological properties of the film are tested with nano- indenter and ring-on-ring wear tester, respectively. The tested results show that the microstructure of the film is dense ahd uniform and is mainly composed of （Ti,Al）N and A1N hard phases. A wide transition interface exists between the film and the normalized T8 carbon tool steel substrate. Thickness of the film is about lO00nm and mean hardness value of the film is about 26 GPa. Under dry sliding wear test conditions, relative wear resistance of the （Ti, Al）N film is approximately 9 times higher than that of the hardened T8 carbon tool steel reference sample. Meanwhile, the （Ti,Al）N film has low and stable friction coefficient compared with the hardened T8 carbon tool steel reference sample.     

用激光分子束外延在Si衬底上外延生长高质量的TiN薄膜

采用激光分子束外延技术,利用两步法,在Si单晶衬底上成功地外延生长出TiN薄膜材料.原子力显微镜分析结果显示, TiN薄膜材料表面光滑,在10 μm×10 μm范围内,均方根粗糙度为0842nm.霍耳效应测量结果显示,TiN薄膜在室温条件下的电阻率为36×10^-5Ω·cm,迁移率达到5830 cm²/V·S,表明TiN薄膜材料是一种优良的电极材料.X射线θ—2θ扫描结果和很高的迁移率均表明,高质量的TiN薄膜材料被外延在Si衬底 关键词： 激光分子束外延 TiN单晶薄膜 外延生长     

Nanocomposite TiC/a-C：H film prepared on titanium aluminium alloy substrates by PSII assistant MW-ECRCVD

Thin films of titanium carbide and amorphous hydrogenated carbon have been synthesized on titanium aluminium alloy substrates by PSII assisted MW-ECRCVD with a mirror field. The microstructure, chemical composition and mechanical property were investigated. Using XPS and TEM, the films were identified to be a-C：H film containing TiC nanometre grains （namely, the so-called nanocomposite structure）. The size of TiC grains of nanocomposite TiC/DLC film is about 5 nm. The nanocomposite structure has obvious improvement in the mechanical properties of DLC film. The hardness of a-C：H film with Ti is enhanced to 34 G Pa~ while that of a-C：H film without Ti is about 12 G Pa, and the coherent strength is also obviously enhanced at the critical load of about 35N.     

Influence of Ti/TiAlN-multilayer designs on their residual stresses and mechanical properties

In this research work, Ti/TiAlN multilayers of various designs were deposited onto substrates pretreated by different etching procedures. The influence of multilayer design and substrate pretreatment on multilayers adhesion, hardness, wear and friction coefficients was systematically analyzed and correlated with residual stresses of these multilayers as well as with residual stresses on the coating-near substrate region, which were analyzed by synchrotron X-ray diffraction at HZB-BESSYII. These investigations show that the adhesion can be improved by a specific etching procedure, which cause increased compressive stress in the coating-near the substrate region. Additionally, it was found, that the multilayer with the thickest ceramic layers has the highest hardness and the lowest wear coefficients as well as the lowest compressive residual stress within studied multilayers.     

Effect of titanium incorporation on the structural, mechanical and biocompatible properties of DLC thin films prepared by reactive-biased target ion beam deposition method

Amorphous diamond like carbon (DLC) and titanium incorporated diamond like carbon (Ti-DLC) thin films were deposited by using reactive-biased target ion beam deposition method. The effects of Ti incorporation and target bias voltage on the microstructure and mechanical properties of the as-deposited films were investigated by means of X-ray photoelectron spectroscopy, Raman spectroscopy, transmission electron microscopy and nano-indentation. It was found that the Ti content in Ti-DLC films gets increased with increasing target bias voltage. At about 4.2 at.% of Ti, uniform sized well dispersed nanocrystals were seen in the DLC matrix. Using FFT analysis, a facility available in the TEM, it was found that the nanocrystals are in cubic TiC phase. Though at the core, the incorporated Ti atoms react with carbon to form cubic TiC; most of the surface exposed Ti atoms were found to react with the atmospheric oxygen to form weakly bonded Ti-O. The presence of TiC nanocrystals greatly modified the sp³/sp² hybridized bonding ratio and is reflected in mechanical hardness of Ti-DLC films. These films were then tested for their biocompatibility by an invitro cell culturing test. Morphological observation and the cell proliferation test have demonstrated that the human osteoblast cells well attach and proliferate on the surface of Ti incorporated DLC films, suggesting possible applications in bone related implant coatings.     

In-situ SEM indentation studies of the deformation mechanisms in TiN, CrN and TiN/CrN

In this study, the microstructure and the deformation mechanisms of TiN, CrN and multilayer TiN/CrN thin films on silicon substrates were investigated. Cross-sectional lamellas of nanoindents were prepared by focused ion beam milling to observe by transmission electron microscopy the microstructure of the as-deposited and deformed materials. TiN film exhibits nanocrystalline columns, whereas CrN shows large grains. The TiN/CrN multilayer presents microstructural features typical for both materials. A film hardness of 16.9GPa for CrN, 15.8GPa for TiN and 16.6GPa for TiN/CrN was found by the nanoindentation. Reduced modulus recorded for TiN and CrN reference coatings were 221.54 and 171.1GPa, respectively, and 218.6GPa for the multilayer coating. The deformation mechanisms were observed via in-situ scanning electron microscope nanoindentation. The TiN thin film showed short radial cracks, whereas CrN deformed through pile-up and densification of the material. For TiN/CrN multilayer pile-up and cracks were found. Transmission electron microscopy observations indicated that TiN deforms through grain boundary sliding and CrN via densification and material flow. The deformation mechanism observed in TiN/CrN multilayer was found to be a mixture of both modes.     

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.     

Synthesis and characterization of TiC and TiCN coatings

Thin film coatings of titanium carbide (TiC) and titanium- carbo-nitride (TiCN) were deposited on Si(100) substrates using the pulsed laser deposition (PLD) method. The PLD method is a unique process for depositing high-quality thin films with novel microstructure and properties. Mechanical properties of TiCN are found to be dependent on the nitrogen ambient during deposition. For nitrogen ambient pressure of 20 mTorr the TiCN has hardness values close to TiN hardness values, whereas for nitrogen ambient pressure of 5 mTorr the hardness values of the TiCN films are comparable to the hardness values of the TiC films.