Characteristics and machining applications of Ti(Y)N coatings

The Ti(Y)N coatings were successfully deposited onto 18-8 stainless steel substrates by the hollow cathode discharge ion-plating method. The influence of the rare-earth element yttrium on the TiN coating properties was studied. The results show that the adhesion of the coating to the substrate were evidently enhanced by adding a small amount (0.2 wt.%) of the rare-earth element yttrium, showing a critical load of about 390 g which is much higher than that (230 g) of the TiN coating/substrate. Investigation on the corrosion resistance of the Ti(Y)N coating and the TiN coating was performed in 0.5 N Na₂SO₄ + 0.1 N H₂SO₄ + 0.1 N NaCl corrosion media by means of an electrochemical potentiodynamic polarization. The Ti(Y)N coating exhibited much better corrosion resistance than the TiN coating, whose passivity maintaining current is about one order in magnitude smaller than that of the TiN coating.The Ti(Y)N coatings deposited on some HSS-based tools were presented and compared with the TiN coating. The service lifetime of Ti(Y)N coated tools is approximately 36% higher (on the pinion shape cutters) and about 50% higher (on punch side pin) compared to that of TiN coated. The Ti(Y)N coatings showed such excellent performance. It is attributed to that the transition area of Ti(Y)N/substrate consisted of three sublayers which revealed a gradual change of phase structure and composition, so that the adhesion of the coating/substrate was evidently enhanced. Moreover, Ti(Y)N coating showed a preferred orientation with (111) plane which is favorable to improve wear resistance and corrosion resistance of the coating.     

Effect of hydroxyapatite‐titanium‐MWCNTs composite coating fabricated by electrophoretic deposition on corrosion and cellular behavior of NiTi alloy

In this study, the hydroxyapatite (HA)‐titanium (Ti, 20 wt.%) multiwalled carbon nanotubes (MWCNTs, 1 wt.%) composite coating was applied on the NiTi alloy by using the electrophoretic deposition (EPD) technique. The morphologies and the phase structures of the coatings were investigated by the FESEM and XRD analysis, respectively. The corrosion behaviors of the coated NiTi samples were investigated using the polarization and electrochemical impedance spectroscopy tests in a simulated body fluid (SBF). The amounts of the released Ni ions from the coated NiTi were studied in the SBF. The results of the electrochemical tests revealed the corrosion resistance of the NiTi coated with HA was further improved by the addition of the Ti and MWCNTs to the HA coating. The current density and corrosion resistance of the NiTi alloy changed from 2.52 μA.cm^?2 and 24.13 kΩ to 0.91 nA.cm^?2 and 5.92 MΩ after coated with the HA‐Ti‐MWCNTs composite coating. Also, the number of nickel ions released from the surface of the NiTi alloy to the SBF medium suppressed from 11.8 to 0.08 μgr.L^?1, after coating with HA‐Ti‐MWCNTs. Also, the cellular proliferation in the culture medium consisting of the NiTi alloy coated with the HA‐Ti‐MWCNTs improved significantly (compared with that of the NiTi alloy) as shown no toxicity in the cell culture medium.     

Microstructure, corrosion resistance and biocompatibility of titanium incorporated amorphous carbon nitride films

Titanium incorporated amorphous carbon nitride films were deposited by direct current magnetron sputtering. The films change from amorphous to nanocomposite structure, the relative fraction of sp³ C-N bonding decreases significantly from 2.17 to 1.64 with the increase of Ti content from 2.7 at.% to 12.3 at.%. For the films with high Ti content, the nanocrystalline TiN embedded in a-CN_x matrix, while principally TiN did not appear to be well formed for the film containing low Ti content. Potentiodynamic polarization, in vitro human osteoblasts and murine fibroblast cell adhesion tests were employed to assess the corrosion performances of Ti6Al4V alloy coated with the films in Tyrode's solution, and the biocompatibility of Ti-incorporated a-CN_x films, respectively. Titanium incorporation increases the corrosion resistance of a-CN_x films, and the higher corrosion potential and lower corrosion current density are observed for the alloy coated with the film containing lower Ti content. The high osteoblast adhesion and activation demonstrate the enhanced biocompatibility of Ti alloy coated with Ti-incorporated a-CN_x films. The improved biocompatibility in biological environment is attributed to structural change after titanium introduction.     

气相沉积 Ti / TiN 多层薄膜的力学及耐腐蚀性能研究

目的研究多层薄膜的界面对薄膜性能的影响。方法通过直流磁控溅射法在45#钢表面制备Ti N及Ti/Ti N多层薄膜,采用扫描电镜和XRD衍射分析仪对薄膜表面形貌及相结构进行观察和分析,使用纳米压痕仪、电子薄膜应力分布测试仪对Ti N及Ti/Ti多层薄膜的力学性能以及残余应力大小进行研究,并运用电化学设备对Ti N及不同调制周期的Ti/Ti多层薄膜的耐腐蚀性能进行研究。结果制备的Ti N及Ti/Ti N多层薄膜表面光滑且结构致密,Ti N晶粒细小且为非晶相;薄膜力学性能良好,内部均存在残余压应力。随着调制周期的减小,弹性模量和硬度先减小后增大,内部残余应力逐渐减小且分布不均匀程度逐渐增大。薄膜在H_2SO_4中的腐蚀试验表明:当Ti/Ti N多层薄膜调制周期为1μm时,多层薄膜的耐腐蚀性能不如Ti N薄膜,随着Ti/Ti N多层薄膜随调制周期的减小,多层薄膜的耐腐蚀性能逐渐升高;当调制周期为0.5μm时,Ti/Ti N多层薄膜的耐蚀性能已超过Ti N薄膜。结论 Ti/Ti N多层薄膜界面的增多有助于减小薄膜的残余应力,并且可提高薄膜的耐蚀性能。     

基片偏压改变对镁合金 Ti / TiN 膜质量的影响

目的探讨基片偏压对镁合金Ti/TiN膜层质量的影响。方法利用多弧离子镀技术,在不同偏压条件下,对镁合金先镀Ti再镀TiN,通过SEM观察膜层形貌,通过划痕测定膜基结合性能,通过电化学工作站对比AZ31镁合金与不同偏压镀膜试样的耐蚀性。结果偏压为200V时,TiN膜层致密均匀且成膜速度快,膜层耐蚀性最好;偏压为200V时,基体结合最好且膜层较厚,有较好的耐蚀性。结论镀Ti膜时的偏压对随后镀TiN的质量有着显著的影响,以200V偏压的工艺镀TiN膜层质量最好,膜层致密,成膜速度快,耐蚀性优良。     

医用镁合金等离子喷涂羟基磷灰石涂层研究

为了提高医用镁合金的表面耐蚀性和生物相容性,采用等离子喷涂技术在镁合金表面制备羟基磷灰石(HA)涂层.研究结果表明,镁合金表面所制备的HA涂层与基体结合牢固,界面无裂纹、气孔等缺陷.相组成为生物相容性较好的HA和少量的Ca3(PO4)2(TCP),显微组织具有层状特征,涂层表面存在一些有利于骨长人的孔隙.涂层的弹性模量约为19.825 GPa,接近骨的弹性模量,涂层表面硬度为300～350 HV.腐蚀试验和钙磷沉积试验结果表明HA涂层具有较好的耐蚀性和骨诱导性.     

Wear, erosion and corrosion resistance of CrTiAlN coating deposited by magnetron sputtering

A nanolayered CrTiAlN coating, which was deposited on Ti6Al4V substrate using unbalanced magnetron sputtering technique, was tested to evaluate its performances against wear, erosion and corrosion. The coating, with a higher hardness compared to CrN, demonstrates significantly higher dry sliding wear resistance than CrN and TiN coatings. Different from the brittle TiN coating, the CrTiAlN coating has a maximum erosion rate at an impingement angle of 45° and shows better erosion resistance than TiN coating at 90°. The CrTiAlN coated Ti6Al4V, when tested in 3.5% NaCl aqueous solution, shows a markedly more noble corrosion potential in comparison with the uncoated Ti6Al4V substrate. Furthermore, it demonstrates a wide passive region with a low current density. All these properties make the CrTiAlN coating a good candidate for a variety of industrial applications.     

Electrochemical characteristics and interfacial contact resistance of multi-layered Ti/TiN coating for metallic bipolar-plate of polymer electrolyte membrane fuel cells

Metallic bipolar-plates have advantages over non-porous graphite ones due to their higher mechanical strength and better electrical conductivity. However, corrosion resistance and interfacial contact resistance are major concerns that remain to be solved, since metals such as stainless steels may develop oxide layers that decrease electrical conductivity, thus lowering fuel cell efficiency. In this study, multi-layered nitride coatings consisting of Ti and TiN were deposited on 316L stainless steel (SS316L) by a D.C magnetron sputtering method to enhance the corrosion resistance and to lower the interfacial contact resistance (ICR) of metallic bipolarplates for a polymer electrolyte membrane fuel cell (PEMFC). Electrochemical methods were conducted and ICRs of the coated specimens were measured to investigate the potential of the coated metallic bipolar-plate for use in PEMFCs. The multi-layered Ti/TiN coating deposited on SS316 showed lower ICR values than the single-layered TiN coating, and improved corrosion resistance when the PEMFC was not in operation while the degradation of the coating layer was observed in both cathodic and anodic working environments.     

Enhancing Biocompatibility and Corrosion Resistance of Ti-6Al-4V Alloy by Surface Modification Route

Titanium (Ti) and its alloys are widely used as candidate materials for biomedical implants. Despite their good biocompatibility and corrosion resistance, these materials suffer from corrosion after implantation in biological environments. The aim of this research work is to study the effect of two coatings on biocompatibility and corrosion behavior of Ti-6Al-4V biomedical implant material. Hydroxyapatite (HA) and hydroxyapatite/titanium dioxide (HA/TiO₂) coatings were thermal-sprayed on Ti-6Al-4V substrates. In the latter case, TiO₂ was used as a bond coat between the substrate and HA top coat. The corrosion behavior of coated and un-coated samples in Ringer’s solution was studied by potentiodynamic and linear polarization techniques. Before and after corrosion testing, XRD and SEM/EDS techniques were used for the analysis of phases formed and to investigate microstructure/compositional changes in the coated specimens. The cellular response was analyzed by the MTT (microculture tetrazolium) assay. The results showed that both the HA, as well as, the HA/TiO₂ coatings significantly increased the corrosion resistance of the substrate material. The HA coating was found to be more biocompatible as compared to the un-coated and HA/TiO₂-coated Ti-6Al-4V alloy.     

Effect of Ti interlayer on corrosion behavior of nanostructured Ti/TiN multilayer coating deposited on TiAl6V4

To improve the corrosion properties of TiAl₆V₄ alloy, TiN monolayer and Ti/TiN multilayer coatings are deposited by reactive magnetron sputtering. The phase, structure, and morphology properties are investigated by grazing‐incidence X‐ray diffraction, field‐emission scanning electron microscopy, and atomic force microscopy, respectively, and the corrosion behavior is evaluated by electrochemical impedance spectroscopy and potentiodynamic polarization. The TiN monolayer and Ti/TiN multilayer with thickness of 1,350 and 1,410 nm have the (111) and (002) preferred orientation and crystallite size of 42.5 and 24.3 nm, respectively. Columnar growth in TiN is hindered by the Ti interlayers and no cracking is observed between the layers indicating strong adhesion. The nanostructured Ti/TiN coating forms stable surface titanium oxide which improves the corrosion resistance by approximately 80 and four times compared with TiAl₆V₄ alloy and TiN coating, respectively. Hindrance of the columnar structure in TiN by the Ti interlayer decreases the local corrosion rate and enhances the galvanic corrosion resistance by forming a layer on the β‐phase enriched with vanadium as well as a TiO₂ stable layer. The nanostructured Ti/TiN coating demonstrates capacitive behavior with phase angles approximately ?50° and high impedance values at low frequency to be the corrosion resistance mechanism.     

盐雾腐蚀条件下Ti合金表面功能薄膜的摩擦磨损性能

目的研究Ti6Al4V合金、铬掺杂类金刚石(Cr-DLC)薄膜、钨掺杂类金刚石(W-DLC)薄膜和氮化钛(TiN)薄膜,在干摩擦和盐雾腐蚀气氛摩擦条件下的摩擦磨损性能。方法在商用Ti6Al4V合金表面通过非平衡磁控溅射制备Cr-DLC薄膜和W-DLC薄膜,通过多弧离子镀技术制备TiN薄膜。利用扫描电镜、显微硬度计、摩擦磨损试验机、白光干涉扫描轮廓仪,对薄膜的形貌、硬度、干摩擦和腐蚀摩擦性能、磨痕形貌进行测试分析。结果干摩擦条件下,Ti6Al4V合金表面沉积Cr-DLC、W-DLC和TiN三种薄膜的摩擦系数均比Ti6Al4V合金低;Ti6Al4V合金及其表面制备的三种薄膜在盐雾腐蚀气氛条件下的摩擦系数都比干摩擦条件下有所增加。与Ti6Al4V合金相比,Cr-DLC、W-DLC和TiN三种薄膜在干摩擦和盐雾腐蚀气氛摩擦条件下均减小了磨损体积。干摩擦条件下,W-DLC薄膜的磨损体积为0.0017 mm~3,耐磨性最好;盐雾腐蚀气氛摩擦条件下,TiN薄膜的磨损体积为0.0028 mm~3,表现出最佳的耐腐蚀磨损性能。通过磨痕形貌可以得出,盐雾腐蚀气氛摩擦条件下,Ti6Al4V合金表面制备的金属掺杂类金刚石薄膜的磨损受到磨粒磨损和腐蚀磨损双重机制的影响。结论三种表面功能薄膜在盐雾腐蚀气氛摩擦条件下都较好地保护了Ti合金,极大地减少了磨损损失。     

Electrochemical behavior of TiN film coated Ti−Nb alloys for dental materials

In order to study the electrochemical behaviors of TiN film coated Ti−Nb alloys for dental materials, Ti containing Nb up to 3, 20, and 40 wt.% was melted by a vacuum furnace and coated with TiN by EB-PVD. the electrochemical behaviors were investigated using a potentiostat in 0.9% NaCl solution and the corrosion surface was observed using SEM and XPS. Ti−3Nb and Ti−20Nb alloys have α+β phase structure. In the case of Ti−40Nb, the microstructure had a coarse β phase. The microstructural changed from equiaxed to acicular and an increase of β-phase in Ti−Nb alloys was observed with increased Nb content. The current density at 300 mV (potential of oral environment) of Ti−40Nb alloy was lower than that of the other alloys in 0.9% NaCl. The pitting corrosion resistance of Ti−40Nb was higher than that of Ti−3Nb and Ti−20Nb alloys in the 0.9% NaCl solution. The corrosion potential and pitting potential of TiN coated Ti alloy increased with increasing Nb content but the current density at 300 mV and the current density at the passive region decreased. The TiN coated Ti−40Nb alloy offers good corrosion resistance for dental implants compared with non-TiN coats alloys.     

钛合金表面百微米级Ti/TiN多层复合涂层性能研究

目的提高TiN硬质涂层的厚度及各项力学性能。方法采用等离子增强PVD技术在钛合金(TC4)基体表面制备多层复合Ti/TiN涂层,对涂层进行扫描电镜(SEM)分析,采用划痕法表征涂层的结合强度,用维氏显微硬度计测试涂层的显微硬度,利用销盘式摩擦磨损试验仪评价涂层的摩擦磨损性能。结果制备的多层复合Ti/TiN涂层厚度最高可达100μm,且未发生剥落等失效,结合强度相对于单层TiN提高了近3倍。由于Ti、TiN的多层复合调制作用,制备的Ti/TiN显微硬度测试表明复合涂层的显微硬度高达2700 HV0.025,同时,涂层在原有耐磨性能优良的基础上具备自润滑减摩作用,经过近20 000 m的磨损测试,复合涂层的摩擦系数低至0.25左右,且未完全失效。结论多层复合结构能够有效提高TiN硬质涂层的厚度,制备的Ti/TiN多层复合涂层的各项力学性能显著提高。     

Effects of Duplex Nitriding and TiN Coating Treatment on Wear Resistance,Corrosion Resistance and Biocompatibility of Ti6Al4V Alloy

Ti6Al4V alloy substrates were nitrided at 900 °C. TiN coatings were then deposited on the nitrided substrates using a closed-field unbalanced magnetron sputtering system. The microstructure, hardness and adhesion properties of the TiN-N-Ti6Al4V substrates were evaluated and compared with those of an untreated Ti6Al4V sample, a nitrided Ti6Al4V sample and a TiN-coated Ti6Al4V sample, respectively. The tribological properties of the various samples were investigated by means of reciprocating sliding wear tests performed in 0.9 wt.% NaCl solution against 316L, Si₃N₄ and Ti6Al4V balls, respectively. In addition, the corrosion resistance was evaluated using potentiodynamic polarization tests. Finally, the biocompatibility of the samples was investigated by observing the attachment and growth of purified mouse leukemic monocyte/macrophage cells (Raw 264.7) on the sample surface after culturing periods of 24, 72 and 120 h, respectively. Overall, the results showed that the duplex nitriding/TiN coating treatment significantly improved the tribological, anti-corrosion and biocompatibility properties of the original Ti6Al4V alloy.     

加Si提高PCVD TiN基镀层的耐蚀性和力学性能

在直流PCVDTiN镀膜过程中，加入Si形成（Ti，Si）N镀层。用SiH4作为气源，代替一部分金属卤化物，可降低镀层中的氯含量。含16％Si的（Ti，St）N比二元TiN镀层有较高的硬度。用划痕法和对滚法评定了二者的结合强度。三元镀层在界面上用TiN作底层，则TiN和（Ti，Si）N的界面疲劳强度是相同的。（Ti，Si）N比TiN在高温下有较高的抗氧化性能。用电化学腐蚀方法测定在3．5％NaCl溶液中的耐腐蚀性表明，（Ti，Si）N镀层优于TiN。     

TiN, TiN gradient and Ti/TiN multi-layer protective coatings on Uranium

Single-layer TiN, gradient TiN and multi-layer Ti/TiN coating were deposited on silicon and uranium substrates by means of arc ion plating technique. The main phase in the single-layer TiN coating was TiN with a (111) preferred orientation. Ti and TiN were observed in the TiN gradient coating and Ti/TiN multi-layer coatings. The single-layer TiN coating has demonstrated the best wear resistance among the three coatings. Compared with the bare U substrate, the corrosion potential E_corr of the multi-layer Ti/TiN coatings is increased by 580 mV, and the corrosion current density I_corr is decreased at least by two orders of magnitude. The multi-layer Ti/TiN coatings possessed the highest corrosion resistance among the three coating in a 0.5 μg/g Cl⁻ solution.     

Al/Cr复合涂层对Ti2AlNb合金抗热腐蚀性能的影响

目的改善Ti2AlNb合金在高温腐蚀盐环境中的耐热腐蚀性能。方法在Ti2AlNb合金表面通过双层辉光等离子渗铬及磁控溅射镀铝技术制备Al/Cr复合涂层,分析涂层热腐蚀前后的微观形貌和物相组成,并探究涂覆Na2SO4盐膜的试样在不同温度下(750、850、950℃)的热腐蚀行为。结果Al/Cr复合涂层组织均匀致密,且与基体结合良好,厚度约73μm,由表及里依次由Al沉积层、Al/Cr合金层、Cr沉积层、Cr扩散层四部分组成。经不同温度Na2SO4盐热腐蚀后,Al/Cr复合涂层腐蚀程度均显著小于合金基体。涂层试样经750~850℃Na2SO4盐热腐蚀后质量变化较小,850℃腐蚀增重仅0.525 mg/cm^2,而经历950℃、40 h熔盐热腐蚀后失重达到73.571 mg/cm^2,且试样截面出现剥离、脱落现象,Al/Cr复合涂层抵抗热腐蚀能力减弱。结论具有涂层保护的试样抗热腐蚀性能明显优于合金基体。Al/Cr复合涂层在750~850℃Na2SO4盐环境中具有良好的热腐蚀抗力,而更高温度段(850~950℃)的热腐蚀抗力下降。Al/Cr复合涂层在Na2SO4盐环境中良好的抗热腐蚀性得益于涂层中Al、Cr元素氧化形成以Al2O3、Cr2O3为主的混合氧化膜,有效阻碍外界氧气及腐蚀性介质侵入基体。     

Surface characterization and mechanical property of TiN/Ti-coated NiTi alloy by PIIID

A hard and adherent TiN/Ti thin film of approximately 3 μm in thickness was deposited on the surface of Ti-50.6 at.% Ni alloy by the PIIID technique. The surface composition and chemical state of the coated samples were evaluated by XPS. The XPS results indicate that titanium oxide and titanium oxynitride were present on the TiN surface. The spectra of Ti 2p, N 1s, O 1s and C 1s electrons before and after the film being sputter etched were also discussed. Scanning electron microscopy (SEM) and energy disperse spectroscopy (EDS) analyses demonstrate that an interfacial layer, containing Ti, N and Ni, was formed at the interface between the TiN and Ti coatings. Sliding wear tests show that the TiN coating significantly reduces the friction coefficient and improves wear resistance of the NiTi alloy.     

镁合金表面纳米TiSiN复合薄膜的制备及其结构和耐蚀耐磨性能分析

为提高镁合金耐蚀和耐磨性,扩大其在航空领域的应用,采用反应磁控溅射法,分别在AZ31和Mg8Li两种镁合金基体上制备了复合TiSiN薄膜. 采用X射线荧光光谱、扫描电镜、原子力显微镜和X射线小角掠入射分别对薄膜表面元素分布、形貌、膜层结构和晶粒尺寸进行了分析. 采用电化学工作站和球盘式摩擦磨损试验机分别对薄膜在3.5%NaCl溶液中的腐蚀行为和在空气中的摩擦磨损性能进行了研究. 结果表明,薄膜中Ti和Si元素比例与靶材相近,元素在整个膜层表面呈高低交替的环形分布,Mg8Li基体上薄膜的分布较为均匀;薄膜主要由TiN和Ti₂N两相组成,AZ31表面薄膜的晶粒尺寸和粗糙度均小于Mg8Li表面的薄膜;两种基体镀膜后的腐蚀电流密度降低了三个数量级,摩擦系数低于0.4,磨损率在10?6 m3/Nm数量级.     

物理气相沉积Ti/TiN提高冷冲模具寿命研究

对Cr12MoV冷作模具钢表面进行了单一处理(PVD Ti／TiN)和双重处理(低温等离子氮化 PVD Ti／TiN),通过显微硬度、划痕和磨损试验综合分析了这两种不同处理涂层的摩擦学性能。而且,对PVD Ti／TiN涂覆的“控制臂翻边凸模”进行应用试验。研究结果和应用试验表明：较单一处理,双重处理改善了涂层与基体界面的结合,显著提高了Cr12MoV钢的表面承载能力和耐磨性,PVD Ti／TiN涂覆的“控制臂翻边凸模”寿命提高了2倍多。