Preparation and Corrosion Resistance of Magnesium Coatings by Magnetron Sputtering Deposition

Magnesium coatings were fabricated on stainless steel substrates (1Cr11Ni2W2MoV) by a plane magnetron sputtering technique. The argon pressure and the substrate condition (including temperature and the substrate was rotated or fixed) were varied in order to evaluate the influence of the parameters on the crystal orientation and morphology of the coating. The corrosion behavior of the coatings in 1 wt pct NaCI solution was studied by electrochemical methods. The results showed that all coatings exhibited preferred orientation (002) as the argon pressure increased from 0.2 to 0.4 Pa. The morphologies of the coatings varied with the argon pressure and with whether the substrate was rotated or fixed. The open circuit potential of the coatings was more positive than that of cast AZ91D magnesium alloy. However, the immersion test in 1 wt pct NaCI solution showed that the corrosion rates of the coatings were higher than that of cast AZ91D magnesium alloy.

Effects of substrate temperature and deposition time on the morphology and corrosion resistance of FeCoCrNiMo0.3 high-entropy alloy coating fabricated by magnetron sputtering

The effects of substrate temperature and deposition time on the morphology and corrosion resistance of FeCoCrNiMo0.3 coating fabricated by magnetron sputtering were investigated by scanning electron microscopy and electrochemical tests.The FeCoCrNiMo0.3 coating was mainly composed of the face-centered cubic phase.High substrate temperature promoted the densification of the coating,and the pitting resistance and protective ability of the coating in 3.5wt%NaCl solution was thus improved.When the deposition time was prolonged at 500℃,the thickness of the coating remarkably increased.Meanwhile,the pitting resistance improved as the deposition time increased from 1 to 3 h;however,further improvement could not be obtained for the coating sputtered for 5 h.Overall,the pitting resistance of the FeCoCrNiMo0.3 coating sputtered at 500℃for 3 h exceeds those of most of the reported high-entropy alloy coatings.

Microstructure and corrosion resistance of sputtered TiN coatings on surface of Zr-4 alloy

To improve the oxidation resistance and corrosion resistance of Zr-4 alloy, titanium nitride(TiN) coatings were prepared on the Zr-4 alloy with a TiN ceramic target with different ratios of N_2. Microstructure and high-temperature properties of the TiN coated samples were studied by scanning electron microscopy(SEM), energy dispersive spectrometer(EDS), X-ray diffraction meter(XRD), X-ray photoelectron spectroscopy(XPS), heat treatment furnace and autoclaves, respectively. The x value of the TiN coatings(TiN_x) ranges from 0.96 to 1.33. After the introduction of N_2, TiN coating exhibits a weak(200) plane and a preferred(111) orientation. The coating prepared with an N_2 flow ratio of 15% shows an optimal oxidation resistance in the atmospheric environment at 800 °C. In either 1 200 °C steam environment for one hour, or deionized water at 360 °C and a pressure of 18.6 Mpa for 16 d, the opitimized TiN coated samples have no delamination or spallation; and the gains in the masses of samples are much smaller than Zr-4 alloy. These results demonstrate the effectiveness of the optimized TiN coating as the protective coating on the Zr-4 alloy under extreme conditons.

On the evaluation of ALD TiO_(2),ZrO_(2) and HfO_(2) coatings on corrosion and cytotoxicity performances

Magnesium alloys have been widely studied as materials for temporary implants,but their use has been limited by their corrosion rate.Recently,coatings have been proven to provide an effective barrier.Though only little explored in the field,Atomic Layer Deposition(ALD)stands out as a coating technology due to the outstanding film conformality and density achievable.Here,we provide first insights into the corrosion behavior and the induced biological response of 100 nm thick ALD TiO_(2),HfO_(2)and ZrO_(2)coatings on AZ31 alloy by means of potentiodynamic polarization curves,electrochemical impedance spectroscopy(EIS),hydrogen evolution and MTS colorimetric assay with L929 cells.All three coatings improve the corrosion behavior and cytotoxicity of the alloy.Particularly,HfO_(2)coatings were characterized by the highest corrosion resistance and cell viability,slightly higher than those of ZrO_(2)coatings.TiO_(2)was characterized by the lowest corrosion improvements and,though generally considered a biocompatible coating,was found to not meet the demands for cellular applications(it was characterized by grade 3 cytotoxicity after 5 days of culture).These results reveal a strong link between biocompatibility and corrosion resistance and entail the need of taking the latter into consideration in the choice of a biocompatible coating to protect degradable Mg-based alloys.

Biocompatible DCPD Coating Formed on AZ91D Magnesium Alloy by Chemical Deposition and Its Corrosion Behaviors in SBF

Bioactive calcium phosphate coatings were prepared on AZ91D magnesium alloy in phosphating solution in order to im- prove the corrosion resistance of the magnesium alloy in Simulated Body Fluid （SBF）. The surface morphologies and compo- sitions of the calcium phosphate coatings deposited in the phosphating bath with different compositions were investigated by Scanning Electron Microscopy （SEM） with Energy Dispersive Spectrometer （EDS） and X-ray Diffraction （XRD）. Results showed that the calcium phosphate coating was mainly composed of dicalcium phosphate dihydrate （CaHPO4o2H20, DCPD）, with Ca/P ratio of approximately 1 ： 1. The corrosion resistance was evaluated by acid drop, electrochemical polarization, elec- trochemical impedance spectroscopy and immersion tests. The dense and uniform calcium phosphate coating obtained from the optimal phosphating bath can greatly decrease the corrosion rate and hydrogen evolution rate of AZ91D magnesium alloy in SBE

Microstructures and properties of aluminum film and its effect on corrosion resistance of AZ31B substrate

Aluminum films with thickness of 8.78-20.82μm were deposited on the AZ31B magnesium alloys by DC magnetron sputtering.The influences of aluminum film on the micro-mechanical properties and corrosion behavior of the magnesium alloys were investigated.The morphology of aluminum film was examined by scanning electron microscopy and the microstructure of aluminum film was analyzed by X-ray diffiactometry.Nanoindentation and nanoscratch tests were conducted to investigate their micromechanical properties.Moreover,potentiodynamical polarization test performed in 3.5%NaCl solution was carried out to study their anticorrosion performances.The results show that the surface hardness of AZ31B magnesium alloy with aluminum film is 1.38-2.01 GPa,higher than that of the magnesium alloy substrate.The critical load of Al film/AZ31B substrate is in the range of 0.68-2.77 N. The corrosion current density of AZ31B with aluminum film is 2-3 orders of magnitude less than that of bare AZ31B.And the corrosion potential with aluminum film positively shifts.Thus aluminum film can increase the corrosion resistance of Mg alloys obviously.

Fabrication of Cr coating on AZ31 magnesium alloy by magnetron sputtering

Chromium-plating is considered an effective method to improve surface properties of metal materials.Magnetron sputtering was applied to prepare Cr coating on AZ31 magnesium alloy and the influence of bias voltage on properties of Cr coating was investigated.The obtained coatings present an(110) preferred texture and have a developed columnar structure.With increasing bias voltage,the surface structure of Cr coating becomes denser.All of the Cr-coated AZ31 have much higher surface microhardness than bare AZ31.The Cr coating deposited on AZ31 at bias voltage of -150 V has a higher corrosion potential than others.The result of the immersion test shows that it decreases the damaged area compared with bare AZ31.The failure of the coated AZ31 is mainly attributed to the existence of through-thickness defects in the coating.

Corrosion behaviors of Cr-Al-N coatings deposited by reactive magnetron sputtering

CrN and Cr-Al-N coatings were deposited by reactive magnetron sputtering on the glass substrate,and their corrosion behavior was studied. The electrochemical tests using both DC(polarization curves) and AC techniques(EIS) were carried out on Potentiostat/Galvanstat(EG&G) in 3.5%(mass fraction) NaCl solution. After immersed into NaCl solution for 1 h,the mass of the CrN coating keeps constant with the time continuing. This can be explained by the passivation of the coating. The comparison between the corrosion potential(φcorr) of the Cr-Al-N coatings with different aluminum contents reveals that the corrosion potentials of the aluminum contain coatings are nobler than that of the CrN coatings. This means that the addition of aluminum shifts the corrosion potential to more positive potential value. Among these coatings,CrN in NaCl solution exhibits the worst corrosion resistance,while the corrosion resistance of Cr0.63Al0.37N in NaCl solution is the best. The polarization data and EIS data suggest that addition of aluminum can improve the corrosion resistance of CrN coating.

Design multifunctional Mg–Zr coatings regulating Mg alloy bioabsorption

Magnesium(Mg)alloys are widely used for temporary bone implants due to their favorable biodegradability,cytocompatibility,hemocompatibility,and close mechanical properties to bone.However,rapid degradation and inadequate strength limit their applicability.To overcome this,the direct current magnetron sputtering technique is employed for surface coating in Mg-based alloys using various zirconium(Zr)content.This approach presents a promising strategy for simultaneously improving corrosion resistance,maintaining biocompatibility,and enhancing strength without compromising osseointegration.By leveraging Mg’s inherent biodegradability,it has the potential to minimize the need for secondary surgeries,thereby reducing costs and resources.This paper is a systematic study aimed at understanding the corrosion mechanisms of Mg–Zr coatings,denoted Mg-xZr(x=0–5 at.%).Zr-doped coatings exhibited columnar growth leading to denser and refined structures with increasing Zr content.XRD analysis confirmed the presence of the Mg(00.2)basal plane,shifting towards higher angles(1.15°)with 5 at.%Zr doping due to lattice parameter changes(i.e.,decrease and increase of“c”and“a”lattice parameters,respectively).Mg–Zr coatings exhibited“liquidphilic”behavior,while Young’s modulus retained a steady value around 80 GPa across all samples.However,the hardness has significantly improved across all samples’coating,reaching the highest value of(2.2±0.3)GPa for 5 at.%Zr.Electrochemical testing in simulated body fluid(SBF)at 37℃ revealed a significant enhancement in corrosion resistance for Mg–Zr coatings containing 1.0–3.4 at.%Zr.Compared with the 5 at.%Zr coating which exhibited a corrosion rate of 32 mm/year,these coatings displayed lower corrosion rates,ranging from 1 to 12 mm/year.This synergistic enhancement in mechanical properties and corrosion resistance,achieved with 2.0–3.4 at.%Zr,suggests potential ability for reducing stress shielding and controlled degradation performance,and consequently,promising functional biodegradable materials for temporary bone implants.

Tailoring the degradation rate of magnesium through biomedical nano-porous titanate coatings

A novel approach was developed to reduce the corrosion rate of magnesium(Mg)metal,utilising titanate coatings.Magnetron sputtering was used to deposit ca.500 nm titanium(Ti)coatings onto pure Mg discs,followed by hydrothermal conversion and ion exchange reactions to produce sodium and calcium titanate coatings.SEM confirmed the characteristic nanoporous structure of sodium and calcium titanate,with thicknesses ranging from ca.0.8 to 1.4μm.XPS analysis confirmed the presence of Ti^(4+)-O,Na-O,and Ca-O bonding,whilst Raman spectroscopy demonstrated characteristic vibrational modes(such as TiO 6 octahedral vibrations)of the sodium and calcium titanate perovskite structure.Furthermore,corrosion studies through potentiodynamic polarisation measurements demonstrated the NB/NH CaTC samples to be superior in reducing Mg degradation,compared to other samples tested,through an increase in E_(corr)from-1.49 to-1.33 V,and the reduction in corrosion current density,i corr,from 0.31 to 0.06 mA/cm^(2)for Mg and NB/NH CaTC samples,respectively.There was a clear trend noted for the NB/NH samples,which showed an increase in E corr to more positive values in the following order:Mg<Ti coated<NaTC<CaTC.These nanoporous titanate coatings have potential to be applied onto degradable plates for bone fracture fixation,or other orthopaedic applications.

Mechanical and corrosion properties of Al/Ti film on magnesium alloy AZ31B

Preparation of titanium film on magnesium substrate faces a challenge due to non-Fickian inter-diffusion between titanium and magnesium. Aluminum can build a bridge between titanium and magnesium. Al/Ti duplex coatings were deposited on magnesium alloy AZ31B using magnetron sputtering （MS）. The low temperature diffusion bonding behavior of the MglAl/Ti coating was investigated through SEM and its affiliated EDS. The phase structure and critical load of the coatings were examined by means of XRD and scratch tests, respectively, The results demonstrated that the bonding strength was significantly improved after a post heat treatment （HT） at a temperature of 210℃. The diffusion mechanism of the interfaces of MglAI and Al/Ti in the coating was discussed based on the analysis of formation energy of vacancies and diffusion rates. The Al/Ti dual layer enhanced the corrosion resistance of the alloy. And the HT process further increased the corrosion resistance of the coated alloy. This result implies that a post HTat a lower temperature after MS is an effective approach to enhance the bonding strength and corrosion resistance of the Al/Ti film on Mg alloys.

磁控溅射NiCrCN涂层在质子交换膜燃料电池阴极环境中的腐蚀行为

采用非平衡磁控溅射技术在316L不锈钢表面沉积NiCrCN涂层,研究不同铬靶电流(2,4,6 A)下涂层的微观形貌以及在模拟质子交换膜燃料电池(PEMFC)阴极环境(0.5 mol·L^(-1) H_(2) SO_(4)+2 mg·L^(-1) HF,空气鼓入,70℃)中的耐腐蚀性能。结果表明:制备的NiCrCN涂层均由金属镍、CrN、Cr_(2) N、Cr_(7) C_(3)等相组成;4 A铬靶电流下制备的涂层表面光滑平整且结构致密,而2,6 A铬靶电流下制备的涂层中出现明显的柱状晶结构。在模拟PEMFC阴极环境中恒电位0.6 V极化以及高电位1.0 V循环极化后,随着铬靶电流的增大,涂层的腐蚀电流密度先减小后增大,4 A铬靶电流下制备涂层的腐蚀电流密度最小,恒电位极化曲线更加平稳,恒电位极化时溶解在腐蚀溶液中的金属离子质量浓度最小,表面腐蚀程度最轻;该涂层在静止浸泡14 d后的电荷转移电阻始终比316L不锈钢高1个数量级。在PEMFC正常工作、快速启动/关闭和长期静止条件下服役的最佳NiCrCN涂层为4 A铬靶电流下制备的涂层。

磁控溅射AlCr涂层对电工纯铁防腐性能的影响

为了提高电工纯铁的耐腐蚀性能,基于磁控溅射技术,在电工纯铁表面制备了Al Cr涂层。采用X射线衍射仪、扫描电子显微镜对涂层表面形貌、结构和元素组成进行分析,并通过中性盐雾及电化学测试,分析了电工纯铁基体及Al Cr涂层的耐腐蚀性能。结果表明,适量Cr元素掺杂可以使涂层致密化,在Cr靶功率为75 W时效果最好。随着Cr的加入,Al Cr涂层呈现不同的化合物态,包括Al_(8)Cr_(5)、Al1_(3)Cr_(2)等相。中性盐雾及电化学测试结果均表明Cr-75涂层的耐腐蚀性能最好,在经过158 h的盐雾测试之后涂层依然没有被腐蚀;Cr-75涂层阻抗比纯铁高约2个数量级,腐蚀电流密度为7.4×10^(-9)A/cm^(2),相对于电工纯铁(1.6×10^(-6)A/cm^(2))降低了约3个数量级,点蚀电位与腐蚀电位之间的电位差最大(0.272 V),抗点蚀性能最好,保护效率高达98.8%。

磁控溅射镀铝AZ31镁合金等离子体电解氧化揭示的放电通道结构及其腐蚀行为

在硅酸盐-六偏磷酸盐电解液中对覆盖薄磁控溅射铝层的AZ31镁合金进行等离子体电解氧化(PEO),以研究PEO机理并提高合金的耐腐蚀性。使用SEM和EDS检测涂层形貌并追踪涂层中Mg和Al元素的分布。新的涂层主要在靠近涂层/金属基体界面的放电通道下部形成。在放电通道上部先前形成的氧化物大部分以固态形式保留在原先的位置,只有少部分熔融氧化物通过涂层的微孔流出,到达表层。阴离子可以通过涂层充满电解液的孔传输,自由地进入涂层的最深部位。在3.5%NaCl (质量分数)中进行开路电位、极化曲线和EIS测试。结果表明,致密的磁控溅射Al层可以显着提高AZ31镁合金的耐腐蚀性,其耐腐蚀性甚至优于PEO处理后的样品。

SUS321不锈钢表面Cr/CrN涂层的制备与抗氧化及耐腐蚀研究

采用磁控溅射技术,在SUS321不锈钢表面制备Cr/Cr N涂层,利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)及分析天平等分别表征样品高温氧化及酸性盐雾腐蚀实验后的微结构及增重。结果表明,当磁控溅射气体分压比为P_(Ar)/P_(N_(2))=3∶1的涂层样品抗氧化性能及耐腐蚀性能最佳。在此基础上通过循环沉积制备了多层Cr/CrN涂层,6周期涂层样品在600℃氧化200 h后的单位面积增重为3.599 g/m^(2),表面氧化膜致密,没有出现剥落现象;6周期的涂层样品在酸性盐雾环境中能够保持480 h表面无变化,在放置500 h后边缘部位才开始出现轻微锈迹。固定磁控溅射气体分压比为P_(Ar)/P_(N_(2))=3∶1时,制备的6周期Cr/CrN多层膜涂层具有最佳的抗氧化及耐酸性盐雾腐蚀性能。

钛基材Pt涂层接触电阻及耐蚀性能研究

质子交换膜(PEM)电解制氢系统因具有宽范围、快速动态响应能力,在新能源消纳、电网调峰等领域具有广阔的应用前景。为了提升制氢电解堆电传输性能,降低接触电阻,本文利用磁控溅射技术制备了钛毡和钛板上的Pt涂层,并对这些涂层进行了研究,探究了制备工艺对薄膜的微观结构、传输性能和耐蚀性能的影响。研究发现,最佳磁控溅射工艺包括等离子清洗时间20 min,溅射时间10 min,以及溅射功率100 W。在接触电阻方面,镀有铂的钛毡表现出优异的接触电阻性能。通过SEM和EDS测试分析,发现随着功率和时间的增加,Pt颗粒的尺寸逐渐增大。然而,当颗粒尺寸过大时,Pt颗粒之间发生相互挤压,导致微小裂纹的产生,从而影响Pt涂层耐蚀性能。这些研究结果对于优化PEM制氢电解堆的性能,提高其稳定性具有重要意义。

钼镧合金表面FeCrAl涂层耐腐蚀性能

采用非平衡磁控溅射工艺在Mo–La合金表面沉积FeCrAl涂层,研究所制备涂层的耐腐蚀性及涂层的腐蚀机理。结果表明:FeCrAl涂层样品在360℃、18.6 MPa、纯水的高压釜中腐蚀72 h,平均腐蚀速率为3.8 mg·dm^(-2),低于同条件下锆合金以及未沉积涂层的钼镧合金的腐蚀速率,且涂层中的Al与外界环境介质中的氧发生反应,在涂层表面形成致密的Al2O3薄膜,在一定程度上减缓了涂层的腐蚀速度,有效保护了基体材料。FeCrAl涂层样品在1200℃、0.1 MPa的高温水蒸气环境下腐蚀8 h,Al_(2)O_(3)氧化膜厚度在4.0μm左右,涂层维持保护效果,钼镧合金基体未暴露在腐蚀环境中;经淬火后,Al2O3氧化膜厚度减小至2.5μm左右,涂层依旧维持结构完整性,没有出现贯穿性脱落,满足Mo–La合金表面耐腐蚀性的使用要求。

A novel electroless silver depositing method for magnesium alloys

Depositing silver on magnesium alloy by both electroless plating and organic coatings was studied. The organic coating was made by immersing samples in organosilicon heat-resisting varnish. In this method the organic coating acts as interlayer between the substrate and silver film. When the reaction starts, silver deposits directly on the interlayer. X-ray diffraction and SEM analysis were used to determine the composition and morphology of the interlayer and silver film. The potentiodynamic polarization curves for corrosion studies of coated magnesium alloys were performed in a corrosive environment of 3.5% NaCl(mass fraction) at neutral pH (6.9). The results indicate that compared with the substrate, the corrosion resistance of coated magnesium alloys increases greatly. Moreover, the method proposed in this work is environmentally friendly, non-toxic chemicals were used. In addition, it provides a new concept for the corrosion inhibition of magnesium alloys.

AZ31镁合金微弧氧化-磁控溅射镀钽复合膜的制备及耐蚀性

在AZ31镁合金表面制备了含P、Sr、F、Ca等元素的微弧氧化膜层,再利用磁控溅射技术对膜层进行后处理,实现了钽纳米薄膜的均匀沉积,对微弧氧化涂层微孔和微裂纹形成有效封闭;利用SEM、EDS、XRD等手段分析膜层微观形貌、元素组成;并通过电化学测试和浸泡实验测试复合膜层的耐腐性能。结果表明:钽薄膜改善了微弧氧化膜表面结构,弥补了微弧氧化的不足。复合膜层的腐蚀电流密度相比AZ31基底至少降低了7个数量级,比微弧氧化涂层降低了5个数量级,腐蚀电压也有相应的提高。

镁合金表面溅射沉积M-TaC多层涂层的微观结构与性能

采用磁控溅射技术在ZK60镁合金表面制备了M-TaC多层涂层,并以TaC单层涂层作为对照,研究了涂层的微观结构、结合性能和耐腐蚀性能。结果表明,涂层呈多孔柱状结构和亲水性,能显著提高ZK60镁合金的耐腐蚀性能。相比于TaC单层涂层,M-TaC多层涂层的表面粗糙度增大,亲水性减弱,结合力提高(约60%),耐腐蚀性能增强(腐蚀电流密度减小2.382μA/cm^(2))。