Erosion-corrosion of thermally sprayed coatings in simulated splash zone

The damage of marine steel structures in the splash zone is very severe. Applying thermally sprayed metal coatings is among the most important protective technologies, but the service life of current coatings is limited. In this paper, arc spray was used to prepare four types of metal coatings, that is, aluminum (Al), zinc bottom coating combined with aluminum topcoat (Zn + Al), aluminum-zinc pseudo alloy (Al/Zn) and aluminum-titanium pseudo alloy (Al/Ti) coatings. These metal coatings were sealed with epoxy priming and aliphatic polyurethane topcoat. Erosion-corrosion experiments were carried out on self-made device by simulating the splash zone working environment of steel structures and protective coatings. The results show that all the sealed coatings could improve the steel resistance to erosion-corrosion, and the aluminum-zinc pseudo alloy is the most excellent coating. In the coating failure process, mechanical erosion rather than corrosion is the key factor causing coating erosion-corrosion in splash zone. Improving the anti-cutting properties could help to prolong the coating life.     

Corrosion resistance of Ti–6Al–4V alloy with nitride coatings in Ringer’s solution

The corrosion behaviour of Ti–6Al–4V alloy with nitride coatings was investigated in Ringer’s solution at 36 and 40 °С. Nitride coatings of different composition, thickness and surface quality were formed because of changing nitrogen partial pressure from 1 to 10⁵ Ра and nitriding temperature from 850 to 900 °С. Results shown that nitride coatings improve anticorrosion properties of alloy at both solution temperatures. Corrosion resistance of alloy increases with the content increase of TiN phase in nitride coating. With increase of temperature from 36 to 40 °С the corrosion resistance of alloy is determined significantly by quality of nitride coating.     

In vitro corrosion resistance and cytotoxicity of novel TiNbTaZr alloy

A novel β type Ti35Nb2Ta3Zr alloy with low modulus (48 GPa) was fabricated using vacuum consumable arc melting. The corrosion resistance and cytotoxicity of Ti35Nb2Ta3Zr were evaluated. The open circuit potential, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization methods were used to determine the corrosion resistance. In Ringer's solution, Ti35Nb2Ta3Zr alloy exhibits better corrosion resistance, as compared to that of Ti6Al4V and Ti. The cytotoxicity tests indicate that the biocompatibility of Ti35Nb2Ta3Zr is as good as Ti and Ti6Al4V which are widely used in biomedical fields. Based on corrosion resistance and cytotoxicity, the novel β type Ti35Nb2Ta3Zr alloy can be considered as a potential biomaterial.     

钛合金表面GO/HA/MAO复合膜层的制备及其性能

为了改善钛合金种植体在体液中的腐蚀及摩擦腐蚀行为,延长其在人体环境中的服役时间,在微弧氧化 (MAO)膜层上采用溶胶凝胶(Sol-gel)法于羟基磷灰石(HA)和氧化石墨烯(GO)的混合溶胶中浸渍提拉成膜,从而在 Ti6Al4V 合金表面成功地制备了 GO/ HA/ MAO 复合膜层。 结果表明,MAO 膜层表面的微孔及微球被 GO/ HA 薄膜有效的覆盖且较为致密;膜层的物相组成主要为金红石相及锐钛矿相的 TiO₂、HA、SiO₂ 和GO;根据电化学腐蚀和摩擦腐蚀结果分析知,GO/ HA/ MAO 复合膜层在模拟体液(SBF)中的耐蚀性及耐摩擦腐蚀性相比于 MAO 膜层和 Ti6Al4V 基体均得到了显著提高。     

新型TiNbTaZr合金的生物腐蚀性和细胞毒性(英文)

通过真空自耗电弧炉开发一种新型β钛合金Ti35Nb2Ta3Zr,其弹性模量仅为48GPa,探讨该合金的耐腐蚀性能和细胞毒性。在Ringer模拟体液中,通过测量开路电位、极化阻抗谱和极化曲线发现Ti35Nb2Ta3Zr的腐蚀性优于Ti6Al4V和Ti。细胞毒性试验证明Ti35Nb2Ta3Zr的生物相容性与目前临床常用的Ti6Al4V和Ti相当。因此,该新型β钛合金Ti35Nb2Ta3Zr具有良好的耐腐蚀性和生物相容性,未来作为生物材料具有广阔前景。     

Effect of the aluminium content and the bias voltage on the microstructure formation in Ti1 − xAlxN protective coatings grown by cathodic arc evaporation

The effect of aluminium contents and bias voltage on the microstructure of cathodic arc evaporated Ti_1 − xAl_xN coatings was investigated with the aid of X-ray diffraction experiments and transmission electron microscopy. The coatings were deposited from mixed Ti-Al targets with different Ti:Al ratios (60:40, 50:50, 40:60 and 33:67) at bias voltages ranging between − 20 V and − 120 V. The microstructure of the coatings was described in terms of the phase composition, crystallite size and residual stress and related to the indentation hardness. The microstructure features were found to be related to the uniformity of the local distribution of Ti and Al in (Ti,Al)N, which was controlled, for a certain overall chemical composition of the coatings, by the bias voltage. The consequences of large local fluctuations of the Ti and Al concentrations in Ti_1 − xAl_xN that occurred at higher bias voltages were the phase segregation, which was indicated through the formation of the fcc-(Ti,Al)N/fcc-AlN nanocomposites and the increase of the compressive residual stress in the face-centred cubic (Ti,Al)N. Concurrently, the increasing bias voltage contributed significantly to the reduction of the crystallite size. Higher residual stress and smaller crystallite size increased the hardness of the coatings. The overall chemical composition of the coatings influenced mainly their phase composition. The high concentration of Al in (Ti,Al)N led to the formation of wurtzitic AlN in the coatings.     

激光沉积CoCrFeNiSi-(Al,Ti)非等原子比高熵合金涂层腐蚀行为研究

目的 研究Al、Ti元素对激光沉积CoCrFeNi系高熵合金涂层耐蚀性能影响,并对影响程度进行比较。方法 采用激光沉积技术在316L不锈钢表面制备CoCrFeNiSi0.5、CoCrFeNiSi0.5Al0.5、CoCrFeNiSi0.5Ti0.5、CoCrFeNiSi0.5Al0.5Ti0.5等4种成分的高熵合金涂层,并通过X射线衍射仪(XRD)、金相显微镜(OM)、场发射扫描电镜(FESEM)以及电化学工作站等设备对高熵合金涂层凝固组织形貌、微观组织形貌、微区成分分布、耐腐蚀性能等方面进行分析研究。结果 激光沉积CoCrFeNiSi0.5高熵合金涂层物相由单一面心立方(FCC)相构成;CoCrFeNiSi0.5Al0.5高熵合金涂层的主要物相变成体心立方(BCC)相,并形成沿晶界网状分布的Cr3Si相;CoCrFeNiSi0.5Ti0.5高熵合金涂层的主要物相仍为FCC相,但枝晶间区域内形成G相(Ni16Ti6Si7),枝晶内区域形成长条状Cr15Co9Si6相;CoCrFeNiSi0.5Al0.5Ti0.5高熵合金涂层的主要物相为BCC相,枝晶间区域G相含量较CoCrFeNiSi0.5Ti0.5合金涂层有所降低,枝晶内区域形成弥散分布的方形纳米Fe3Al相。激光沉积CoCrFeNiSi-(Al,Ti)非等原子比高熵合金涂层在0.5 mol/L H2SO4溶液中的耐蚀性大小依次为CoCrFeNiSi0.5Ti0.5>CoCrFeNiSi0.5Al0.5Ti0.5>CoCrFeNiSi0.5>CoCrFeNiSi0.5Al0.5。浸蚀后,CoCrFeNiSi0.5高熵合金涂层以均匀腐蚀为主,CoCrFeNiSi0.5Al0.5涂层产生严重的晶间腐蚀,CoCrFeNiSi0.5Ti0.5涂层主要为枝晶间区域的点蚀,CoCrFeNiSi0.5Al0.5Ti0.5涂层枝晶间区域的点蚀程度明显高于CoCrFeNiSi0.5Ti0.5涂层,且枝晶内区域的纳米第二相颗粒发生脱落。结论 在酸性溶液环境中,相较于Al元素,Ti元素可更有效地提升激光沉积CoCrFeNi系高熵合金涂层的耐蚀性能。     

铝合金上电弧离子镀(Ti,Al)N膜的腐蚀特性

研究铝合金上电弧离子镀(Ti,Al)N膜层的腐蚀性能。通过对3种N2气分压下沉积膜层的阳极极化曲线、电化学阻抗谱、盐雾腐蚀失重曲线以及表面形貌的分析表明:沉积过程氮分压较低时,膜层中含有富金属相,耐腐蚀性能较低;增加氮分压使膜层中金属与非金属呈理想配比时,膜层的耐腐蚀性明显增加;膜层在缺陷处产生点蚀、电偶腐蚀,并通过形成裂纹、碎屑脱落使质量显著减小。     

钛合金表面GO/纳米ZnO复合涂层的制备及性能

为了有效解决生物医用钛合金长期植入人体后,易发生细菌感染和面临有害金属离子释放的问题,采用水热反应和涂覆方法,分别在聚多巴胺(PDA)预处理的Ti6Al4V合金表面制备了氧化石墨烯涂层(GP/T)和氧化石墨烯/纳米氧化锌复合涂层(GZP/T)。系统分析了2种涂层的物相结构、微观形貌及其在林格氏液中的耐腐蚀性能和在大肠杆菌环境中的抗菌性能。结果表明:聚多巴胺发挥“双面胶”桥接作用,有效增强了涂层与基底间的化学键合;GP/T涂层抗菌率随着GO浓度增大而增大;GZP/T纳米复合涂层相较Ti6Al4V基材具有优异的耐蚀性,该复合涂层中ZnO起主要抗菌作用。     

Corrosion behavior of Ti‐xNb‐13Zr alloys in Ringer's solution

Ti‐6Al‐4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V‐free alloys and both V‐ and Al‐free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti‐13Nb‐13Zr alloy is promising due to its better biomechanical compatibility than Ti‐6Al‐4V. In this work, the corrosion behavior of Ti, Ti‐6Al‐4V, and Ti‐xNb‐13Zr alloys (x = 5, 13, and 20) was evaluated in Ringer's solution (pH 7.5) at 37 °C through open‐circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10^?7 A/cm²) and high impedance values (in the order of 10⁵ Ωcm² at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti‐xNb‐13Zr alloys were more corrosion resistant than both Ti and Ti‐6Al‐4V in Ringer's solution.     

Microstructure and mechanical properties of CrN coating deposited by arc ion plating on Ti6Al4V substrate

CrN coatings have been grown by arc ion plating (AIP) onto Ti6Al4V alloy substrate at various nitrogen pressures (PN₂). The goals of this investigation are to study the influence of nitrogen pressure content on the composition, structure and mechanical properties of AIP CrN coatings, as well as their tribological properties. With an increase of PN₂, the main phases in the coatings changed from CrN + Cr₂N + Cr to CrN, and the texture of CrN was transformed from CrN (111)-oriented to (220)-oriented. Furthermore, the multi-layers including a metal Cr layer, a Cr₂N layer and a CrN layer were observed by cross-sectional TEM (XTEM), besides an “unbalanced” state transition layer at the interface of CrN/substrate which was analyzed by nucleation thermodynamics subsequently. An increase in nitrogen pressure also resulted in a change of micro-hardness due to the variation in composition and structure. Finally, the tribological properties of the Ti6Al4V substrate and the CrN/Ti6Al4V coating system have also been explored, which shows that CrN coatings can act as good wear resistance layer for Ti6Al4V substrate.     

Synthesis and high-temperature corrosion resistance of Ti-Zr-Si-N coatings deposited by means of sputtering

ABSTRACT

We present a study of the synthesis and an evaluation of the corrosion resistance of Ti-Zr-Si-N coatings deposited by means of the co-sputtering technique on 316L steel and Ti6Al4V alloy substrates. The thin films were obtained using Ti₅Si₂ and Zr targets with 99.9% purity for the deposition, and a power of 200 W was applied in the DC source and 170?W in the RF source. The corrosion resistance was evaluated via the cyclic oxidation test with consistent cycles of 1 hour of cooling, 1 hour of heating, and 16 minutes of stabilisation for 300 cycles at a temperature of 600°. The coatings were characterised by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), and confocal laser microscopy. The coating was effective up to 150 cycles for the case of 316L steel, and up to 50 cycles for the Ti6AlV alloy.     

The examination of corrosion behaviors of hap coated Ti implant materials and 316L SS by sol-gel method

In this research, hydroxyapatite (HAP) coatings have been produced on Ti, Ti6Al4V alloy and 316L stainless steel substrates by sol-gel method. (NH₄) · H₂PO₄ is taken as P precursor and Ca(NO₃)₂ · 4H₂O is taken as Ca precursor to obtain HAP coating. Additionally, three different pretreatment processes (HNO₃, anodic polarization, base-acide (BA)) have been applied to Ti, Ti6Al4V alloy and 316L stainless steel substrates. The corrosion behaviors of bare and HAP coated samples are examined in Ringer and 0.9% NaCl. HAP coated Ti have showed over 87.85% inhibition. HAP coated Ti6Al4V alloys have showed over 87.33% inhibition. In Ringer solution, 99.24% inhibition has been showed in HAP coated anodic pretreatment for 316L stainless steel. All pretreatment processes are effective on clinging of HAP coating to the surface. It is seen that impedance values have increased in HAP coatings (Ti and Ti6Al4V). HAP coatings have raised the corrosion resistance of Ti and Ti6Al4V. The values of polarization resistance in HAP coated samples have increased for 316L stainless steel in 0.9% NaCl and Ringer solutions. It is seen in SEM images that open pores and attachments among pores have been observed in the coating, which increases osteointegration. It is noted in EDX analyses of the surfaces of the HAP coated samples that there is only Ca, O, and P on the surface. Ca/P ratio varies in 1.84–2.00 ranges. As Ca/P ratio increases, the inhibition increases too. It is seen in XRD images of HAP powder that there are HA ate structures. Additionally, it is seen in FTIR analysis, characteristic HA absorption bands have occurred in sintered powders.     

Triode plasma nitriding and PVD coating: A successful pre-treatment combination to improve the wear resistance of DLC coatings on Ti6Al4V alloy

Diamond-like carbon (DLC) coatings have found great applicability in the automotive industry because of their low friction coefficient and high wear resistance. Nevertheless, their tribological performance can be greatly reduced on soft substrates such as titanium alloys. The hard DLC coating cannot usually follow elastic and plastic deformation of the substrate without failing. In order to overcome this property mismatch between hard coating and soft substrate, triode plasma nitriding was applied as a pre-treatment to improve the mechanical properties of the Ti6Al4V alloy and further enhance the load support for the DLC coating. DLC and multilayered TiN/DLC, CrN/DLC CrAlN/DLC coatings were deposited onto “standard” and plasma nitrided Ti6Al4V substrates. Triode plasma nitriding increased the load-bearing capacity of the coating/substrate system, as higher critical adhesion loads were recorded for DLC coatings on plasma nitrided Ti6Al4V substrates. This treatment also reduced the wear rate of the DLC coating/substrate. Further load support and lower wear rates were achieved by using TiN, CrN and CrAlN as intermediate layers on plasma nitrided Ti6Al4V substrates.     

The Effect of Coating Thickness on Corrosion Resistance of Hydroxyapatite Coated Ti6Al4V and 316L SS Implants

Hydroxyapatite (HAP) has been coated onto Ti6Al4V and 316L SS substrates by sol-gel method. The coating thicknesses for the analysis were about 40 and 72 μm. Adhesion and corrosion tests have been conducted on uncoated and HAP-coated substrates. The coatings were characterized by XRD, SEM, and adhesion analysis. The corrosion resistance was examined in vitro by potentiodynamic polarization technique in Ringer’s solution at room temperature. Electrochemical analysis indicated that the highest corrosion susceptibility was found on 72-μm-coated 316L SS, and the 40-μm HAP-coated Ti6Al4V showed the highest corrosion resistance. It was observed that the coating thickness was an effective parameter on both adhesion and corrosion resistance. It was shown that adhesion and corrosion resistance decreased with increasing coating thickness on both substrates.     

Mechanical and electrochemical characterization of Ti-12Mo-5Zr alloy for biomedical application

We have fabricated a new β metastable titanium alloy that comprised of non-toxic elements Mo and Zr. Ingot with composition of Ti-12Mo-5Zr is prepared by melting pure metals in a vacuum non-consumable arc melting furnace. The alloy is then homogenized and solution treated under different temperature. The alloy is characterized by optical microscopy, X-ray diffraction, tensile tests and found to have an acicular martensitic α″ + β structure and dominant β phase for the 1053 K and 1133 K solution treatment samples, respectively. The elastic modulus of the latter is about 64 GPa, which is much lower than those of pure Ti and Ti-6Al-4V alloy. In addition, it had moderate strength and much higher microhardness as compared with Ti-6Al-4V alloy. The results show better mechanical biocompatibility of this alloy, which will avoid stress shielding and thus prevent bone resorption in orthopedic implants applications. As long-term stability in biological environment is required, we have also evaluated the electrochemical behavior in a simulated body fluid (Hank's solution). Potentiodynamic polarization curves exhibits that the 1133 K solution treatment Ti-12Mo-5Zr sample has better corrosion properties than Ti-6Al-4V and is comparable to the pure titanium. The good corrosion resistance combined with better mechanical biocompatibility makes the Ti-12Mo-5Zr alloy suitable for use as orthopedic implants.     

The effects of spark anodizing treatment of pure titanium metals and titanium alloys on corrosion characteristics

This study evaluated the surface characteristics of oxide films on commercially pure titanium metals (CP-Ti; Grade 2 and Grade 3) and titanium alloy (Ti6Al4V and Ti6Al7Nb) samples formed by an anodic oxidation treatment, and investigated the effects of anodization on the corrosion characteristics. FE-SEM, XRD, and Raman spectroscopy were used to evaluate the micromorphology and crystalline structure of the oxide films. The corrosion resistance of the sample groups was evaluated using open-circuit potential and cyclic polarization tests. After anodic oxidation up to dielectric breakdown with the same electric current, 150-200 nm-sized pores were distributed homogeneously on pure titanium metal samples, partially occluded pores were observed on the Ti6Al4V alloy, and there was an inhomogeneous size and distribution of pores on the Ti6Al7Nb alloy. The titanium dioxide films formed through anodic oxidation contained a phase mixture of anatase and rutile. The cyclic polarization tests showed that all the tested sample groups were not susceptible to localized corrosion. The as-received and anodically oxidized CP-Ti grade 3 groups showed a higher corrosion resistance than the other groups. The mean E_corr values of the anodically oxidized sample groups, except for the anodized Ti6Al7Nb alloy, showed higher values than those of the respective as-received sample groups. In particular, the Ti6AL7Nb alloy showed a statistically higher E_corr value in the anodized group than in the as-received group (p < 0.05).     

The Tribological Performance of Surface Treated Ti6A14V as Sliding Against Si<Subscript>3</Subscript>N<Subscript>4</Subscript> Ball and 316L Stainless Steel Cylinder

Closed field unbalanced magnetron sputtering was used to deposit diamond-like carbon (Ti-C:H) coatings on Ti6Al4V alloy and gas nitrided Ti6Al4V alloy. Four different specimens were prepared, namely untreated Ti6Al4V alloy (Ti6Al4V), gas nitrided Ti6Al4V alloy (N-Ti6Al4V), Ti-C:H-coated Ti6Al4V alloy (Ti-C:H/Ti6Al4V) and Ti-C:H-coated gas nitrided Ti6Al4V alloy (Ti-C:H/N-Ti6Al4V). The tribological properties of the four specimens were evaluated using a reciprocating wear tester sliding against a Si₃N₄ ball (point contact mode) and 316L stainless steel cylinder (line contact mode). The wear tests were performed in a 0.89 wt.% NaCl solution. The results showed that the nitriding treatment increased the surface roughness and hardness of the Ti6Al4V alloy and improved the wear resistance as a result. In addition, the Ti-C:H coating also improved the tribological performance of Ti6Al4V. For example, compared to the untreated Ti6Al4V sample, the Ti-C:H coating reduced the wear depth and friction coefficient by 340 times and 10 times, respectively, in the point contact wear mode, and 151 times and 9 times, respectively, in the line contact wear mode. It is thus inferred that diamond-like carbon coatings are of significant benefit in extending the service life of artificial biomedical implants.     

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.     

Composition and processing effects on the electrochemical characteristics of biomedical titanium alloys

The electrochemical behaviour of the Ti–13Nb–13Zr and Ti–6Al–4V ELI alloys with martensitic microstructures was investigated by polarization and electrochemical impedance spectroscopy (EIS) in Ringer’s solution. The impedance spectra were interpreted by a two time-constants equivalent circuit. Both investigated alloys showed high corrosion resistance, but the thin and uniform passive film on the Ti–6Al–4V ELI alloy surface was more protective. The inner barrier and outer porous layer were highly resistant and capacitive. However, thicker and more porous passive film on the Ti–13Nb–13Zr alloy surface may be beneficial for osteointegration. The suitable thermomechanical processing improved the corrosion resistance of Ti–13Nb–13Zr alloy.