镁合金表面等离子喷涂Al2O3-TiO2陶瓷涂层的耐腐蚀性研究

采用等离子喷涂技术在AZ31镁合金表面制备Al2O3-13％TiO2陶瓷复合涂层,对涂层的微观组织进行了观察分析,测试了涂层的表面硬度.通过极化曲线和浸泡腐蚀试验,对比研究了镁合金基材及喷涂陶瓷涂层的试样在5％ NaCl溶液中的耐腐蚀性能.结果表明:涂层镁合金试样的硬度和耐腐蚀性优于基体镁合金,但当腐蚀液透过涂层孔隙时...     

Structural and tribological properties of DC reactive magnetron sputtered titanium/titanium nitride (Ti/TiN) multilayered coatings

Ti/TiN multilayered coatings of 200 layers with the thickness of 1.5 μm were deposited by a reactive DC magnetron sputtering technique using a mixture of Ar and N₂ gas. XRD technique was employed to elucidate the structural parameters. The presence of different phases like TiN, TiO_xN_y and TiO₂ were confirmed by XPS analyses. The observation of longitudinal optic (LO) phonon modes in the Raman spectra confirmed the highly crystalline nature of the deposited films. A microhardness value of 25.5 GPa was observed for Ti/TiN multilayers. The observed lower friction coefficient value for the Ti/TiN multilayers on mild steel (MS) indicated that the stack layers have better wear resistance property. Results from the electrochemical polarization and impedance studies showed the favorable behavior of the Ti/TiN multilayers, which have improved the corrosion resistance property of MS in 3.5% NaCl solution. The results of this study demonstrate that these multilayers can improve the corrosion resistance of mild steel substrates.     

Hard and Corrosion-Resistant Ni-<Emphasis Type="Italic">x</Emphasis>Al-<Emphasis Type="Italic">y</Emphasis>Ti Nanocomposite Coatings for CNT/Al Composites

The ternary Ni-xAl-yTi (x, y in wt.%) nanocomposite protective coatings were electroplated on carbon nanotubes (CNT)/Al composite by the co-deposition of Al and Ti particles at several current densities. The dependences of microstructure, microhardness, residual stress, and corrosion resistance of the ternary nanocomposite coating on current density were investigated. The results showed that the embedded Al and Ti particles caused the crystallite refinement and the decrease of [200] fiber texture of nanocrystalline Ni matrix when current density decreased. The microstructure evolution endowed the ternary nanocomposite coating with high microhardness and corrosion resistance. The surface residual stress of the ternary nanocomposite coating increased with decreasing current density.     

Corrosion behaviour of low-cost Ti–4.5Al–xV–yFe alloys in sodium chloride and sulphuric acid solutions

ABSTRACT

The electrochemical behaviour of low-cost α+β Ti–4.5Al–xV–yFe (where x?+?y?=?4; x?=?1–3; and y?=?1–3) alloys and commercial Ti–6Al–4V alloy was compared in sodium chloride and sulphuric acid solutions. The low-cost alloys were developed by partial substitution of vanadium with iron and the reduction in aluminium content from 6 to 4.5?wt-%. The influence of iron addition and reduction in aluminium content on the corrosion performance of the experimental alloys was assessed via open circuit potential, potentiodynamic polarisation measurements and scanning electron microscopy. The results show that partial replacement of vanadium with up to 3?wt-% iron and the reduction in aluminium content yielded superior corrosion resistance in some of the low-cost alloys when compared with the commercial Ti–6Al–4V alloy. The Ti–4.5Al–1V–3Fe experimental alloy could serve as an alternative low-cost alloy to commercial Ti–6Al–4V alloy in a number of land-based applications such as marine, chemical and petrochemical industries.     

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。     

Deposition of thick TiAlN coatings on 2024 Al/SiCp substrate by Arc ion plating

Aluminum-matrix composites with particulate SiC ceramic reinforcements (Al/SiC_p) have received much attention for space and aircraft propulsion applications. It is imperative to deposit thick hard coatings on these composites for protection. TiAlN coatings with a Ti interlayer were deposited by arc ion plating (AIP) on 2024 Al/SiC_p substrates at various nitrogen flow rates. It was found that when the nitrogen flow rate is increased from 100 sccm to 250 sccm, the deposition rate decreases, the coating hardness increases and the adhesion strength decreases. Based on the above results and the principle of gradient materials, the thick gradient TiAlN coatings with a Ti interlayer were successfully deposited on a 2024 Al/SiC_p substrate to a thickness of 60 μm by continuously increasing the nitrogen flow rate during deposition. Such an achievement can be attributed to the gradient distribution of elements, hardness, and stresses across the coating thickness.     

Corrosion performance and mechanical stability of 316L/DLC coating system: Role of interlayers

In the present work, the corrosion performance and mechanical stability of diamond-like carbon (DLC) coatings were investigated in the context of their biomedical applications. DLC was prepared by radio-frequency (RF) plasma-enhanced chemical vapor deposition (PECVD) onto medical grade 316L stainless steel. Interlayers of amorphous hydrogenated silicon-based materials such as a-Si, a-SiN_x, a-SiC_x, and a-SiC_xN_y, and a nitrided interlayer, were studied in order to optimize its adhesion strength. Potentiodynamic polarization tests were performed to evaluate the corrosion performance of the 316L/DLC coating system. Electrochemical impedance spectroscopy (EIS) was used to determine the stability of the coating system during long-term tests of exposure to a simulated body fluid solution. The evolution of EIS spectra was monitored during two years of immersion in Ringer's solution. In addition to providing the best adhesion, the a-SiN_x interlayer was found to significantly improve the corrosion resistance of the DLC system since it is highly impervious to the liquid. This is demonstrated by a two-order of magnitude improvement in the corrosion current density compared to the DLC with the nitrided interlayer. The a-SiN_x interlayer substantially enhances the mechanical stability of the DLC coating system in the simulated body fluid environment, indicated by a slight reduction (less than 20%) in the adhesion strength and fivefold increase in the charge transfer resistance after two years of immersion. Moreover, Si-doped DLC coatings show improved corrosion barrier properties, due to the formation of a passive silicon oxide film at the electrode/electrolyte interface.     

Microstructure and corrosion behavior of plasma electrolytic oxidation coated magnesium alloy pre-treated by laser surface melting

An AZ91D magnesium alloy was treated using duplex techniques of laser surface melting (LSM) and plasma electrolytic oxidation (PEO). The microstructure, composition and corrosion behavior of the laser melted surface, PEO coatings, LSM–PEO duplex coatings as well as the as-received specimen were characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and electrochemical corrosion tests, respectively. Especially, the effect of LSM pre-treatment on the microstructure, composition and corrosion resistance of the PEO coatings was investigated. Results showed that the corrosion resistance of AZ91D alloy was marginally improved by LSM due to the refinement of grains, redistribution of β-phase (Mg₁₇Al₁₂) and increase of Al on the surface. Both the PEO and duplex (LSM–PEO) coatings improved significantly the corrosion resistance of the AZ91D alloys, while the duplex (LSM–PEO) coating exhibited better corrosion resistance compared with the PEO coating.     

微弧氧化电解液中加入Al_2O_3胶体对AZ91D复合陶瓷层性能的影响

在硅酸盐体系中加入Al_2O_3胶体对AZ91D镁合金进行微弧氧化,研究了Al_2O_3胶体的加入时间和加入量对陶瓷层组成、结构以及耐蚀性的影响。结果表明,在微弧氧化后期6 min(约为总氧化时间的3/5)时加入Al_2O_3胶体生成的复合陶瓷层耐蚀性最好;随Al_2O_3胶体用量的增加,陶瓷层的腐蚀速度明显减小,但当用量约超过电解液总容量的20%时,对陶瓷层的耐蚀性能提高不明显。     

Al2O3对等离子喷涂Cr2O3/TiO2/Al2O3/SiO2复合陶瓷涂层性能影响研究

目的研究Al_2O_3添加量对Cr_2O_3/TiO_2/Al_2O_3/SiO_2四元复合陶瓷涂层性能的影响。方法采用等离子喷涂技术在油气管道X80管线钢基体表面制备出具有不同Al_2O_3含量的四元复合陶瓷涂层。另外,为探究基体温度对涂层性能的影响,所有涂层均在等离子喷枪预热及室温的两种基体上制备。所制涂层的气孔率、硬度、结合力及电化学腐蚀性能分别采用煮沸称重法、维氏硬度计、划痕仪、电化学工作站进行检测,并用X射线衍射仪(XRD)、扫描电镜(SEM)分析不同Al_2O_3含量涂层的物相组成和形貌特征,研究Al_2O_3含量对涂层各性能的影响。结果随着Al_2O_3含量的增加,Cr_2O_3/TiO_2/Al_2O_3/SiO_2四元复合陶瓷涂层的气孔率呈现先降低后增加的趋势,相对应的四元复合陶瓷涂层的结合力、维氏硬度则先增加后降低。当Al_2O_3质量分数为60%时,四元复合陶瓷涂层的性能最优,气孔率为3.6%,硬度为824.6HV,结合力为53.8N。电化学腐蚀测试表明,Al_2O_3能增强涂层的耐腐蚀性能,Al_2O_3质量分数为60%时,涂层自腐蚀电位最高,为-0.28 V。另外,在基体预热和不预热条件下,所制涂层性能随Al_2O_3含量的变化一致,但是基体预热比不预热更有利于涂层性能的提高。结论 Al_2O_3的添加不仅能够有效降低涂层Cr含量,还能显著提升四元复合陶瓷涂层的各项性能,特别是耐腐蚀性。此外,等离子喷涂前对基体进行预热,有利于涂层性能提高。     

A new method for electroless Ni-P plating on AZ31 magnesium alloy

Coating Ni-P films on AZ31 magnesium alloys via electroless plating and organic coatings (organsilicon heat-resisting varnish), was studied. An organic coating was proposed as the interlayer between Ni-P coating and AZ31magnesium alloy substrate, to replace the traditional chromium oxide plus HF pretreatment. The Ni-P deposited on the interlayer was also characterized by its structure, morphology and corrosion-resistance. The interlayer on the substrate not only reduces the corrosion of magnesium during Ni-P plating process, but also reduces the potential difference between the matrix and the second phase. The result of the cross-cut test indicates the adhesion between the substrate and the interlayer is good enough. A Ni-P film with fine and dense structure was obtained on the AZ31 magnesium alloy. The electrochemical measurements show that the sample with Ni-P film exhibits lower corrosion current density and more positive corrosion potential than the substrate. Furthermore, the Ni-P coating on the AZ31 magnesium alloy exhibits high corrosion resistance in the rapid corrosion test illustrated in this paper. The method proposed in this work is environmentally friendly: no fluoride or hexacalent chromium compounds are used. In addition, it provides a new concept for plating the metals, which are considered difficult to plate due to high reactivity.     

Glass-like CexOy sol–gel coatings for corrosion protection of aluminium and magnesium alloys

This work reports the preparation of glass-like, environmentally-friendly, cerium-based coatings for active corrosion protection of aluminium and magnesium alloys. It describes the production of cerium sol–gel sols from cerium nitrate and their deposition by immersion and automatic spray onto aluminium and magnesium alloys to produce uniform coatings with amorphous (glass-like) structures (Ce_xO_y). The coatings have been characterised by profilometry, scanning electron microscopy (SEM), spectral ellipsometry and UV–visible, in order to analyse the structure and density of the glass-like cerium coatings as well as their redox ratio Ce⁴⁺/Ce³⁺ as a function of pH and sintering temperature. Finally, electrochemical measurements (EIS) and standard corrosion tests (neutral salt spray, filiform corrosion, immersion–emersion test and adhesion on embossing and T-bend test) have been performed to study the corrosion behaviour of the cerium glass-like coatings on aluminium and magnesium alloys. EIS measurements confirm the healing or blocking of the defects by the corrosion inhibiting species. Excellent corrosion protection is provided by cerium glass-like coatings, satisfying the most demanding industrial requirements.     

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.     

Electrophoretic deposition of 3YSZ coating on AZ91D using an aluminum interlayer

The zirconia stabilized by 3 mol % Y₂O₃ (3YSZ) was applied onto the surface of the magnesium alloy AZ91D using electrophoretic deposition (EPD) from a non- aqueous solvent. An interlayer of aluminum between the substrate and YSZ coating was also prepared by EPD. The preparation, microstructure and corrosion resistance of the coatings were investigated. The surface morphologies of the coatings were studied by scanning electron microscopy (SEM) and their compositions were determined by X-ray diffraction (XRD). The corrosion resistance of the coatings was evaluated by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. The results indicate that the aluminum interlayer has a favorable effect on the densification of the coating by formation of aluminum oxide. In addition, the corrosion resistance of coated AZ91D alloy in chloride solution is significantly improved because of the aluminum interlayer and an increase in charge-transfer resistance of the AZ91D surface in chloride solution was observed which was attributed to YSZ.     

掺杂镍对镁合金表面冷喷涂锌基涂层性能的影响

目的研究镍添加对冷喷涂锌基涂层耐蚀性的影响,为镁合金提供有效的防护涂层。方法采用低压冷喷涂技术在镁合金基体表面分别制备锌基和锌/镍基复合涂层,通过微观观察、摩擦磨损实验、电化学极化法和电化学阻抗谱测试及全浸泡腐蚀试验,研究镁合金表面冷喷涂涂层的结构、摩擦磨损行为和耐蚀性。结果镁合金表面冷喷涂锌基涂层后,其硬度和耐磨性得到显著提高,掺镍后的锌/镍基涂层具有更高的硬度和耐磨性。锌基和锌/镍基涂层均能为镁合金提供腐蚀防护,锌/镍基涂层比锌基涂层具有更好的耐蚀性。相对镁合金来说,锌基涂层和锌/镍基涂层的自腐蚀电位分别正移了260 mV和560 mV;长期腐蚀后锌/镍基涂层形成了更致密的腐蚀产物膜,腐蚀电阻显著高于锌基涂层。结论冷喷涂锌基和锌/镍复合涂层均能对镁合金提供防护作用,掺杂镍后的锌/镍基复合涂层具有更高的硬度、耐磨性和耐蚀性。     

The use of Al-Al2O3 cold spray coatings to improve the surface properties of magnesium alloys

Pure Al and 6061 aluminium alloy based Al₂O₃ particle-reinforced composite coatings were produced on AZ91E substrates using cold spray. The strength of the coating/substrate interface in tension was found to be stronger than the coating itself. The coatings have corrosion resistance similar to that of bulk pure aluminium in both salt spray and electrochemical tests. The wear resistance of the coatings is significantly better than that of the AZ91 Mg substrate, but the significant result is that the wear rate of the coatings is several decades lower than that of various bulk Al alloys tested for comparison. The effect of post-spray heat treatment, the volume fraction of Al₂O₃ within the coating and of the type of Al powder used in the coatings on the corrosion and wear resistance was also discussed.     

20% Al2O3-SiO2(sf)/AZ91D镁基复合材料微弧氧化陶瓷层电化学腐蚀性能

在磷酸盐体系电解液中,对20%(体积分数)硅酸铝短纤维(Al2O3-SiO2)增强AZ91D镁基复合材料进行微弧氧化表面处理获得陶瓷层。利用扫描电子显微镜(SEM)和X射线衍射(XRD)仪分析陶瓷层的表面形貌、截面组织和相组成,采用动电位极化和电化学阻抗谱(EIS)测试评价微弧氧化陶瓷层的电化学腐蚀性能。结果表明,该陶瓷层主要由MgO和MgAl2O4相组成。陶瓷层的腐蚀电流密度比镁基复合材料基体低3个数量级,电化学阻抗大幅升高,耐腐蚀性能明显高于复合材料基体     

(Ti,Al)N–Ni nanostructured coatings: Thermal stability,heat resistance,electrochemical behavior,and adhesive strength with a substrate

In this work, thermal stability and oxidation resistance at temperatures up to 800°C are studied for (Ti,Al)N–(8–10 at %)Ni coatings with a thickness on the order of 4 µm and a crystallite size below 20 nm, which have been prepared via ion–plasma vacuum arc deposition. The composition and structural characteristics of coatings remain stable during 1-h heating in vacuum of 10_–4 Pa at temperatures of 600 and 700°C. Heating at a temperature of 800°C leads to an increase in the crystallite size and a decrease in microstrains of a ceramic phase, which is accompanied by a reduction in the hardness of the coating from 51–53 to 31–33 GPa. The coatings are heat resistant up to 800°C and characterized by cohesive failure in scribing. The adhesive strength of coatings with a substrate exceeds 85 N. Studying electrochemical behavior reveals the high efficiency of (Ti,Al)N_0.87–Ni coatings in corrosion protection of cutting tools in acid and alkaline environments.     

Influence of interlayers on corrosion resistance of diamond-like carbon coating on magnesium alloy

Diamond-like carbon coating (DLC) was deposited on AZ31 magnesium alloy by ion beam deposition technique in this study. A columnar Cr layer with a (110) preferred texture and a columnar CrN layer with a (111) preferred texture were applied as interlayers in the DLC coating/AZ31 substrate systems. The addition of these interlayers improved the adhesion between coating and substrate effectively, but did not enhance the corrosion resistance of the DLC/AZ31 systems due to the formation of galvanic cell between substrate and interlayer in the region of through-thickness defects in 3.5 wt.% NaCl solution. In addition, the effect of bias voltage on the corrosion resistance of CrN/Cr coatings on magnesium alloys was investigated. Although the application of bias voltage induced the coating denser, it was still difficult for CrN/Cr coating to reduce the corrosion current density of AZ31 due to the large difference between coating and substrate in galvanic series.     

镁合金表面冷喷涂层防护研究进展

镁合金作为最轻质的金属结构材料,由于其密度低和比强度高等优良的物理和力学性能,在航空、航天、汽车以及电子等领域引起广泛关注。然而,镁合金化学性质活泼、耐腐蚀和耐磨损性差等缺点严重制约其进一步应用。近些年发展起来的冷喷涂技术,在固态下制备涂层,涂层致密且与基体结合良好,因此可为镁合金表面防护提供一种新的有效方法。主要综述了镁合金表面冷喷涂耐腐蚀涂层(纯铝、铝合金和复合材料涂层)和耐磨损涂层(合金和复合材料涂层),论述了影响冷喷涂层耐腐蚀、耐磨损以及其他力学性能(硬度和涂层/基体结合强度)的主要因素,包括杂质元素含量、合金种类以及复合材料涂层中陶瓷颗粒含量、尺寸和形貌等。对比了几种常用表面处理技术制备的纯铝涂层的耐腐蚀性能,并阐述了冷喷涂技术在镁合金表面防护方面的优势。此外,还分析了热处理对冷喷涂纯铝和复合材料涂层耐蚀性的影响。最后提出了目前冷喷涂技术在镁合金防护方面的局限性以及发展难题,对未来研究趋势进行了展望。