Electrochemical corrosion behavior of amorphous carbon nitride thin films

The corrosion behavior along with biocompatibility and mechanical properties plays an important role in determining of biomedical implants feasibility. Diamond-like carbon seems to be the promising material in which all these three requirements can be achieved. In this study nitrogen doped amorphous carbon (a-C:N) films were deposited on silicon and medical CoCrMo alloy substrates by vacuum glow discharge sputtering technique using different deposition conditions from graphite target. Potentiodynamic polarization tests were employed to assess the corrosion performances of the films at room temperature in 0.89 wt. % NaCl solution. The influence of substrate bias on the electrochemical corrosion behavior was investigated. The highest value off E_corr for CoCrMo substrate was measured on the coating deposited with substrate bias around −0.6 kV. The shift of E_corr to more positive values was about 350 mV.     

氮化碳薄膜的电化学沉积及其电阻率研究

在ITO导电玻璃基底上,采用二氰二胺分散在DMF(N,N-二甲基甲酰胺)中形成的溶液做沉积液,阴极电化学沉积了CNx薄膜。X射线光电子能谱(XPS)和傅立叶转换红外光谱(FTIR)的分析结果表明,沉积的CNx薄膜的N/C比为0.7左右,碳和氮主要以C-N、C=N的形式成键,有少量的碳和氮以C≡N的形式成键。拉曼光谱测试发现其存在多个吸收峰,对其进行分析的结果表明薄膜样品中含有α-C3N4和β-C3N4相的成分。电阻率测试表明,氮化碳薄膜的电阻率值达到1012～1013Ω·cm。     

Study of high temperature mechanical behavior of the thermally oxidized Ti‐6Al‐4V alloy

The influence of oxidation of a Ti‐6Al‐4V alloy at 800 °C on its tensile properties at 600 °C has been studied. Specimens of this alloy were oxidized at 800 °C for 0.5, 1, 5, 10, 20 and 40 h. Tensile tests at 600 °C were carried out and the fracture surfaces were also examined. Oxidation of the specimens resulted in the formation of an oxide layer that spalled and another oxide layer that adhered to the substrate. Oxide formation increased with increase in duration of oxidation. In this investigation, density curves of the oxide layer as a function of duration of oxidation at 800 °C were used to identify a parabolic oxide growth law. The results of this study revealed coherence between the experimental data and calculations based on the Pilling‐Bedworth law. The mechanical strength of the Ti‐6Al‐4V alloy did not vary significantly with oxidation, but reduction in cross sectional area with increase in oxide layer thickness, as well as the slope of the stress‐strain curve decreased beyond the ultimate tensile strength. Fracture of the tensile tested specimens was predominantly ductile with microcavities. At certain regions of the oxide layer, brittle fracture with radial cracks was observed indicating intergranular fracture.     

Tribological Properties of Mo-N Hard Coatings on Ti6Al4V by Double Glow Discharge Technique

Mo-N hard coatings on Ti6Al4V were formed using double glow discharge technique. The fundamental coating properties, such as the phase, hardness and elastic modulus were investigated. The tribological performances of the coatings in dry wear condition were studied by means of ball-on-disc wear machine. The experimental results showed that the thickness of the Mo-N hard coating was about 10 µm. The coating was single fcc γ-Mo2N phase with (200) preferred orientation. The hardness and the elastic modulus of the coating was 13.80 GPa and 261.65 GPa respectively. The surface treatment enhanced the hardness and elastic modulus of the surface of Ti6Al4V base greatly. With GCr15 slider ball, the friction coefficient of the Mo-N hard coating was in the range of 0.56~0.65 at the steady state. Though the coating did not show friction reducing effect, it improved the wear resistance of Ti6Al4V greatly.     

Hot-wire growth of multi-phase carbon nitride films

This paper describes the growth of multi-phase carbon nitride films using hot-wire chemical vapor deposition (HWCVD) on (100)-oriented crystalline Si substrates. A mixture of either CH₄/NH₃ or CH₄/N₂ was activated over a hot tungsten filament under varying deposition conditions. The samples were characterized by atomic force microscopy (AFM) and X-ray diffraction (XRD). AFM micrographs show the presence of facetted crystallites. The XRD peaks observed were compared with theoretical predictions for -C₃N₄ and β-C₃N₄—the two ultra-hard phases of carbon nitride. The results suggest the presence of -C₃N₄ and β-C₃N₄, as well as other unidentified phases in our films. We also calculated the equilibrium concentration of the various gas species as a function of temperature and pressure. Our results indicate that CN and C₂N₂ radicals are possible precursors to carbon nitride growth.     

An interfacial study of sol-gel-derived magnesium apatite coatings on Ti6Al4V substrates

Magnesium apatite coatings on Ti6Al4V substrate were synthesized by the sol-gel dip-coating method. Magnesium was incorporated in the coating according to the formula (Ca_10−xMg_x)(PO₄)₆(OH)₂, where x = 0, 0.50, 1.00, 1.50 and 2.00. Approximately 2-μm-thick apatite coatings were derived after five cycles of dip-drawing-drying-firing process. A transitional region (R_t) was formed between substrate and coating during the firing process. Adhesion tests show that the adhesion strength between substrate and apatite coating is enhanced by the incorporation of magnesium in the coating. The quantity of magnesium incorporated appeared to correspond to the Mg-Ti-O chemical bonds formed in the transitional region, which contributed to the adhesion strength of the coatings.     

钛合金表面等离子体电解氮碳共渗的研究

在含有硝酸铵、甘油、乙醇的水溶液中,利用等离子体电解渗入技术在Ti6Al4V钛合金表面制备了氮碳共渗层.利用SEM、XRD、GDS以及显微硬度计分析了渗层的形貌、成分、组织和显微硬度,探讨了渗层形成的机理和过程.结果表明:(1)以300V的电压经45min处理制备的渗层总厚度约为100μm,其中化合物层约为20μm,主要由Ti(C,N)相组成;(2)渗层最高显微硬度超过2000HK0.0025.等离子体电解渗入技术可以较快地在钛合金表面制备出厚度大、硬度高的氮碳共渗层.     

Coating of carbon nanotubes with amorphous carbon nitride thin films and characterization of long-term emission stability

The effects of amorphous carbon nitride (CN) thin films that were coated on carbon nanotubes (CNTs) and their thermal treatment were investigated, in terms of the chemical bonding and morphologies of the CNTs and their field emission properties. CNTs were directly grown on conical tip-type tungsten substrates via the inductively coupled plasma-chemical vapor deposition (ICP-CVD) system, and the CNTs were coated with CN films using the RF magnetron sputtering system. The CN-coated CNTs were thermally treated using the rapid thermal annealing (RTA) system by varying the temperature (300-700 °C). The morphologies, microstructures, and chemical compositions of the CN-coated CNTs were analyzed as a function of the thickness of the CN layers and the RTA temperatures. The field emission properties of the CN/CNT hetero-structured emitters, and the fluctuation and long-term stability of the emission currents were measured and compared with those of the conventional non-coated CNT-emitter. The results showed that the electron emission capability of CNT was noticeably improved by coating a thin CN layer on the surface of the CNT. This was attributed to the low work function and negative electron affinity nature of the CN film. The CN-coated CNT-emitter had a more stable emission characteristic than that of the non-coated one. In addition, the long-term emission stability of the CN-coated emitter was further enhanced by thermal treatment, which was verified by x-ray photoelectron spectroscopy (XPS) analysis.     

喷砂酸蚀处理促进Ti6Al7Nb表面钙磷沉积

研究了Ti、Ti6Al4V和Ti6Al7Nb 3种钛基材料在喷砂酸蚀处理后成骨细胞在其表面生长的生物活性。通过Al2O3喷砂和盐酸、硫酸混合物酸蚀的表面改性方法,在Ti、Ti6Al4V和Ti6Al7Nb3种钛基材料表面进行喷砂酸蚀处理,通过SEM观察样品的表面形貌,样品的表面呈现出微米级多孔形貌;将样品浸入模拟体液(simulated body fluid,SBF)中浸泡7,14和21 d后通过SEM、X射线衍射仪(XRD)分析样品表面沉积物的形貌、物相,样品浸入SBF 14 d后,Ti6Al7Nb表面最先观察到表面覆盖的羟基磷灰石涂层;样品浸入SBF 21 d后,Ti、Ti6Al4V和Ti6Al7Nb表面都观察到羟基磷灰石涂层。羟基磷灰石涂层有利于促进钛基植入体与体内骨组织的骨结合,喷砂酸蚀处理的Ti6Al7Nb表现出良好的生物活性。     

Effect of ceramic conversion surface treatment on fatigue properties of Ti6Al4V alloy

Samples of Ti6Al4V alloy were ceramic conversion (CC) treated. The fatigue properties of untreated and CC treated samples were evaluated with a conventional Wöhler cantilever rotating-bending fatigue machine under both plain fatigue and fretting fatigue conditions. Experiment results showed that CC treatment had a detrimental effect on plain fatigue properties and reduced the plain fatigue limit of the investigated Ti6Al4V alloy by about 24%. However, the fatigue property loss could be fully recovered by an additional shot peening after CC treatment. More importantly, shot peening after CC treatment resulted in considerably longer fatigue life over untreated and CC treated materials in the finite-life region. In contrast to its detrimental effect on plain fatigue, CC treatment appeared to be beneficial to fretting fatigue property. It increased fretting fatigue strength (FFS at 10⁷ cycles) of the Ti6Al4V alloy by approximately 10%. Shot peening after CC treatment further enhanced the fretting fatigue properties, with an improvement in FFS (10⁷ cycles) of about 20% over the untreated material under the present treatment and testing conditions.     

激光冲击处理对Ti6Al4V力学性能的影响

通过对钛合金Ti6Al4V的激光冲击处理,研究了激光冲击处理工艺对钛合金Ti6Al4V力学性能的影响.实验表明:激光冲击处理能有效提升Ti6Al4V的力学性能,在激光功率密度由1.15GW/cm2增加到2.31GW/cm2过程中,其冲击波峰值压力线性增加,表面最大残余压应力也相应增大,最高达-264MPa,表面硬化层的显微硬度高达510Hv,硬化层深度约为0.25mm,经过激光冲击处理后硬度相对于原始钛板提高了64%,随着激光能量的增加,冲击区域的抗拉强度极大增强,塑性降低.     

Effects of silicon nitride interlayer on phase transformation and adhesion of TiNi films

TiNi films with different Ti/Ni ratios were deposited on Si substrates with and without silicon nitride interlayer. Near-equiatomic TiNi films were found to have the lowest residual stress and the highest recovery stress regardless of the existence of silicon nitride interlayer. The addition of silicon nitride interlayer between film and Si substrate did not cause much change in phase transformation behavior as well as adhesion properties. X-ray photoelectron spectroscopy (XPS) analysis revealed that there is significant interdiffusion of elements and formation of Ti-N and Si-Si bonds at TiNi film/silicon nitride interface. Scratch test results showed that adhesion between the TiNi film and substrate was slightly improved with the increase of Ti content in TiNi films.     

Investigation on high temperature compression behaviour of hydrogenated Ti6Al4V alloy

Abstract

Isothermal compression of hydrogenated Ti6Al4V alloy was carried out on a Gleeble-1500D simulation tester at the strain rate 3×10^?3 s^?1 and high temperatures. Before the isothermal compression, a simplified thermohydrogen processing (THP) was used for Ti6Al4V. Attention was paid to the effect of THP on subsequent compression behaviour. The results show that hydrogen can effectively lower the flow stress and deformation temperature and enhance the strain rate sensitivity index (m value) for isothermal compression. The increasing amount of β phase and the ultrafine and equiaxial microstructure precipitated between the original α or β laths are the main reasons for the simplified THP to improve the formability of Ti6Al4V.     

钛合金表面Nb-C复合渗层摩擦磨损性能的研究

为提高钛合金表面的耐磨性能,采用等离子表面合金化技术在Ti6A14V(TC4)合金表面形成含Nb的梯度改性层,然后进行渗C复合处理,得到Nb-C复合改性层,研究了改性层的显微组织形貌、成分分布、相结构特征及硬度分布,并进行了球盘摩擦磨损实验.结果表明,Nb、C元素呈梯度分布,合金层主要由Ti、TiC、Nb2C、NbC等...     

Synthesis and optical characterization of amorphous carbon nitride thin films by hot filament assisted RF plasma CVD

Carbon nitride thin films were synthesized by hot filament assisted radio frequency plasma chemical vapour deposition using methane and nitrogen gas mixture on silicon and glass substrates. The films were deposited at different substrate bias and at different substrate temperatures. At higher substrate bias (>−120 V) there was no deposition on the substrate, but complete etching of the deposited layer was observed. X-ray diffraction studies indicated the films were amorphous. The Fourier transform infrared spectra showed that the films produced exhibited high transmittance with the presence of the C-N stretching band at 1260 cm⁻¹. For the films deposited at a lower substrate temperature C=N peaks were also present. Raman spectroscopic study indicated the presence of D and G peaks whose relative height varied with substrate temperature. The transmittance versus wavelength measurement in the UV-VIS-NIR region showed the high transmittance in the NIR region. The optical band gap of the films was calculated to be 2.0 eV and the refractive index varied within 1.6-1.7 for the wavelength range 800-1800 nm.     

置氢Ti6Al4V合金的微观组织演变规律

为研究置氢Ti6Al4V合金的高温加工改性机理,从微观组织的角度对合金进行了对比分析.利用OM、SEM、XRD等研究了置氢对Ti6Al4V合金变形前后微观组织演变的影响.研究结果表明:氢的加入不仅使置氢Ti6Al4V合金中β相比例明显增大,而且改变了α相与β相之间的电势差,在氢含量为0.3%~0.5%两相颜色将发生互换,氢含量增加到0.50%以上时,合金中将出现面心立方结构的δ氢化物;随氢含量的增加,合金超塑拉伸变形后的组织由α+β两相等轴晶粒变为粗大的β晶粒,造成α与β界面的协调能力下降,并改变了合金的变形机制.     

置氢对Ti6Al4V合金室温组织的影响

通过在钛合金中引入临时元素氢,可以改变钛合金的相组成,进而改变钛合金的力学性能和加工性能.利用OP、XRD和TEM研究了固态置氢后Ti6Al4V合金的微观组织变化.研究表明:随氢含量的增加,合金中的β相含量增加,在置氢0.302%及0.490%(质量分数)的试样中发现面心立方(fcc)的氢化物δ,及大量的斜方结构的马氏体α",未发现亚稳态的氢化物γ.提出了一种基于扩散的由βH共析转变生成α及fcc结构的片状氢化物δ的机制,并指出氢的引入可能诱发马氏体转变.     

Ti6Al4V表面纹理制备及其润湿性

采用激光加工技术在Ti6Al4V表面分别加工直线、网格和具有规则点阵状结构的表面纹理,采用自组装技术制备自组装分子膜。采用扫描电镜、形貌分析仪和接触角测量仪对成膜后的钛合金表面进行形貌和接触角的表征与测量。结果表明,通过激光加工和沉积自组装分子膜,可显著增大Ti6Al4V的水接触角。其中直线纹理的试样表面水接触角可达124.8°,网格纹理的试样表面接触角可达126.1°,点阵状纹理的试样表面接触角可达151.6°。表面接触角与表面粗糙度相关,随着表面粗糙度值的增大,接触角呈增大趋势,当表面粗糙度>4μm时,接触角均>150°,形成超疏水表面。     

Thermal stability of magnetron sputtering amorphous carbon nitride films

Magnetron sputtered amorphous carbon nitride films were annealed at different temperatures (450-900°C) and time (30-120 min). Compositional, bonding structural and surface morphological modifications of the films were characterized by Fourier transformation infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy. The as-deposited film was found to have nitrogen content of 30 at%, and the carbon atoms were bonded to nitrogen atoms in the chemical structure state of CN, CN and CN bonds. The FTIR and XPS results showed that the films were thermally stable without an obvious change in the films as annealing temperature was lower than 600°C. The relative intensity ratio of CN over CN bonds reached a maximum at annealing temperature of 750°C, and then decreased gradually at annealing temperature up to 900°C. The CN bonds in the films decreased with the increase of annealing temperature and eliminated completely at annealing temperature of 900°C. These results revealed that annealing caused a substantial decrease in the number of weak bonds between carbon and nitride atoms. The CN bonds have higher thermal stability than CN bonds and CN bonds in the films. Simultaneously annealing also led to the formation of a large fraction graphitic-like carbon in the films while nitrogen escaped from the film. Besides, the surface roughness of the films increased with annealing temperature. However, when annealing time was increased from 30 to 120 min at annealing temperature of 750°C, only a slight effect of the annealing time on composition, bonding structure and the surface roughness of the films was observed.     

Spectroscopic ellipsometry characterization of amorphous carbon and amorphous, graphitic and fullerene-like carbon nitride thin films

Carbon nitride (CN_x) and amorphous carbon (a-C) thin films are deposited by reactive magnetron sputtering onto silicon (001) wafers under controlled conditions to achieve amorphous, graphitic and fullerene-like microstructures. As-deposited films are analyzed by Spectroscopic Ellipsometry in the UV-VIS-NIR and IR spectral ranges in order to get further insight into the bonding structure of the material. Additional characterization is performed by High Resolution Transmission Electron Microscopy, X-ray Photoelectron Spectroscopy, and Atomic Force Microscopy. Between eight and eleven resonances are observed and modeled in the ellipsometrically determined optical spectra of the films. The largest or the second largest resonance for all films is a feature associated with C-N or C-C modes. This feature is generally associated with sp³ C-N or sp³ C-C bonds, which for the nitrogen-containing films instead should be identified as a three-fold or two-fold sp² hybridization of N, either substituted in a graphite site or in a pyridine-like configuration, respectively. The π→π? electronic transition associated with sp² C bonds in carbon films and with sp² N bonds (as N bonded in pyridine-like manner) in CN_x films is also present, but not as strong. Another feature present in all CN_x films is a resonance associated with nitrile often observed in carbon nitrides. Additional resonances are identified and discussed and moreover, several new, unidentified resonances are observed in the ellipsometric spectra.