Erosion-resistant metal nitride coatings and carbide and their plasmochemical synthesis

The influence of ion-plasma coatings made from high-hardness metal compounds on the erosion and corrosion resistance and mechanical properties of the alloy (substrate) + coating system is studied. The influence of the thickness, composition, and design of coatings based on metal nitrides and carbides on the relative gas-abrasive wear resistance of alloy+coating compositions in a gas-abrasive flux of quartz sand is discussed. It is shown that the zirconium nitride coating provides the best protection for compressor blades made of titanium alloys, without any decrease in fatigue resistance of the alloys, and chromium carbide coating is the most appropriate protection for steel compressor blades.     

铝合金表面改性对有机涂层附着力的影响及腐蚀防护性能研究

利用电化学阻抗（EIS）、扫描微参比技术（SRET）、接触角、粗糙度、附着力、盐雾等测试方法,研究了铝合金阳极氧化与贻贝黏附蛋白（MAP）/CeO₂/硅烷γ-APS（MCA）表面复合修饰的腐蚀防护性能以及对改性聚氨酯涂层附着力和耐蚀性的影响。结果表明,MCA复合膜可抑制铝合金的腐蚀,并具有一定的自修复功能;阳极氧化和MCA表面复合修饰可为铝合金提供有效的早期腐蚀防护作用,且能提高铝合金表面粗糙度和润湿性,显著提升改性聚氨酯涂层在铝合金表面的附着力和耐蚀性,因而结合改性聚氨酯涂层和表面复合修饰可实现对铝合金长期有效的腐蚀防护。     

Effect of Aluminum Alloy Surface Modification on Adhesion of the Modified Polyurethane Coating and Its Corrosion Protective Performance北大核心CSCD

The ordinary organic coatings on aluminum alloy usually encounter a problem of low adhesion to the substrate, which results in destruction and failure of the long-term protective performance of the anticorrosion systems. The surface modification of aluminum alloy is able to enhance the adhesion of organic coating on aluminum alloys, and to improve their protective performance. In this work, a combined surface modification of anodic oxidation and mussel adhesion protein/CeO2/3-aminopropyltriethoxysilane composite film (MCA) was developed on the aluminum alloy. The adhesion of modified polyurethane coated on the treated aluminum alloy and its corrosion protective performance were evaluated comprehensively by using contact angle, adhesion strength, electrochemical impedance spectroscopy (EIS), and scanning reference electrode technique (SRET). The measurements of EIS and SRET demonstrated that the MCA composite film on anodic oxidized Al possessed self-healing function and provided effective protection against early corrosion of aluminum alloy. The pull-off test showed that both anodic oxidation treatment and MCA composite film modification were able to increase the adhesion of modified polyurethane coating on aluminum alloy, and their combined action were supposed to remarkably enhance the adhesion strength up to 17.1 MPa. The reason for the improvement of adhesion was that the anodic oxidation treatment and MCA composite film modification could improve the surface roughness of aluminum alloy, and enhance the surface wettability and surface polarity, which is beneficent to enhance the bonding of the modified polyurethane coating to aluminum alloy surface. The EIS results showed that no any corrosion occurred for the modified polyurethane coating on the treated aluminum alloy during 65 d immersion in 3.5wt.% NaCl solution. The impedance value in low frequency range of the modified polyurethane coating always maintained at a high order of magnitude on the aluminum alloy treated by anodic oxidation and MCA composite film modification, showing an excellent protective performance of the coating system. The evaluation of Neutral Salt Spray (NSS) indicated that the modified polyurethane coating on the treated aluminum alloy owned superior corrosion protection performance, and the adhesion strength remained 13.1 MPa and no any corrosion was found at the scratch locations even after 1200 h of salt spray testing. It was concluded that combination of anodic oxidation and MCA composite film were capable of significantly improving the adhesion of modified polyurethane coating on aluminum alloy and providing long-term effective corrosion protection for aluminum alloy. © 2021 Authors. All rights reserved.     

超音速火焰喷涂含铝或锌中间层的YSZ热障涂层

在镁合金基底表面直接制备热障涂层,涂层的耐蚀性较差。采用超音速火焰喷涂法在镁合金基底和热障涂层之间分别制备了Al涂层和Zn涂层。通过XRD,SEM和EDS对涂层进行物相、微观结构和点扫描元素分析,采用电化学工作站对Al涂层试样和Zn涂层试样进行耐腐蚀性分析,同时研究了含Al中间层和含Zn中间层的热障涂层的抗热震性能。结果表明:Al涂层表面粗糙度(10.237±0.527μm)大于Zn涂层表面粗糙度(7.171±0.488μm),且喷涂过程中仅有轻微氧化。Al涂层试样的耐腐蚀性优于Zn涂层试样。含Zn中间层的热障涂层具有更好的抗热震性能。     

添加氧化铈对AZ91D镁合金表面富镁涂层的保护作用

通过Machu测试、电化学交流阻抗(EIS)和扫描电子显微镜(SEM)等方法研究了添加氧化铈对AZ91D镁合金表面富镁涂层防护性能的影响.氧化铈添加量较少(0.1%,w)时,对涂层耐蚀性无影响;添加量过多(3%)时,涂层耐蚀性降低;添加氧化铈颗粒为0.5%时,涂层的阻抗增大,涂层电容降低,对AZ91D镁合金基体的保护性能明显提高.尽管添加氧化铈不改变富镁涂层对AZ91D镁合金的保护机制,但可显著延长涂层的服役寿命.氧化铈能够降低纯镁颗粒的电化学反应活性,使镁粉腐蚀速率降低,阴极保护时间延长.添加一定量氧化铈后,也有利于涂层屏蔽性能提高,氧化铈能降低AZ91D镁合金表面阳极腐蚀电流密度,提高镁合金腐蚀电位,从而有利于富镁涂层发挥对镁合金基体的阴极保护作用.     

Effect of TiO2–Ti and TiO2–TiN composite coatings on corrosion behavior of NiTi alloy

Two kinds of biocompatible coatings were produced in order to improve the corrosion resistance of nickel titanium (NiTi) alloy. A titanium oxide–titanium (TiO₂–Ti) composite was coated on NiTi alloy using electrophoretic method. After the coating process, the samples were heat‐treated at 1000 °C in two tube furnaces, the first one in argon atmosphere and the second one in nitrogen atmosphere at 1000 °C. The morphology and phase analysis of coatings were investigated using scanning electron microscopy and X‐ray diffraction analysis, respectively. The electrochemical behavior of the NiTi and coated samples was examined using polarization and electrochemical impedance spectroscopy tests. Electrochemical tests in simulated body fluid demonstrated a considerable increase in corrosion resistance of composite‐coated NiTi specimens compared to the non‐coated one. The heat‐treated composite coating sample in nitrogen atmosphere had a higher level of corrosion resistance compared to the heat‐treated sample in argon atmosphere, which is mainly due to having nitride phases. Copyright © 2014 John Wiley & Sons, Ltd.     

(NaPO3)6对AZ91D镁合金微弧氧化陶瓷层电化学腐蚀特性的影响

在Na2SiO3-KOH电解液体系中添加一定量的(NaPO3)6, 利用微弧氧化(MAO)技术在AZ91D 镁合金表面制备了原位生长的陶瓷层. 采用动电位极化和电化学阻抗谱(EIS)技术研究了添加(NaPO3)6前后, 制备的陶瓷层在3.5%(w) NaCl溶液中的室温电化学行为. 结果表明, 添加(NaPO3)6后, 陶瓷层的自腐蚀电位显著上升, 自腐蚀电流密度明显减小. 这主要是由于(NaPO3)6增加了反应过程中基体镁合金表面的“氧空位”和溶液中PO3-4的含量, 促使元素Mg在金属/膜层(M/F)界面上快速形成相应氧化物, 从而增加了陶瓷层的厚度和致密性. 根据电化学反应体系和陶瓷层的特殊结构, 建立了合理的等效电路, 并结合EIS 数据, 分析了添加(NaPO3)6提高陶瓷层耐电化学腐蚀性能的机理.     

Synergetic effect of sol–gel silica coating and physical/chemical pre-treatment on the oxidation behavior of Ti-6Al-4V alloy

The Ti-6Al-4V alloy was treated in concentrated phosphoric acid solution and by powder blasting, respectively, subsequently coated by silica using sol–gel dip-coating technique. A barrier layer of titanium pyrophosphate (TiP₂O₇) was synthesized at the Ti-6Al-4V substrate surface after the heat treatment. XRD and SEM/EDS analysis revealed that an amorphous silica coating was formed on the alloy. The isothermal and cyclic oxidation behavior of the treated alloy with silica coating and the corresponding bare alloy was investigated at 600 °C in static air to investigate the synergetic effect of the SiO₂ coating and surface treatment on the oxidation resistance of the alloy by thermogravimetry. The average parabolic rate constants of the treated specimens with silica coating were greatly reduced. The stratified oxide layer formed on the bare alloy, while thinner oxide layer formed on the treated alloys with silica coating. The oxidation resistance of the present alloy was improved. The effect of silica coating on the microhardness of the substrate was investigated.     

Effects of 3,4-dihydrophenyl groups in water-soluble phospholipid polymer on stable surface modification of titanium alloy

The surface of a titanium (Ti) alloy substrate was modified by a simple and quick process using a water-soluble polymer, and the effects of 3,4-dihydroxyphenyl (DHP) groups in the polymer side chain on the modification process were examined. The polymers (PMDP) composed of both 2-methacryloyloxyethyl phosphorylcholine (MPC) unit and 3,4-dihydroxyphenyl methacrylate unit were synthesized for surface anchoring. The Ti alloy substrate was coated with PMDP using an aqueous solution of the polymer. A PMDP layer with a thickness of 20 nm was formed on the Ti alloy substrate simply by dip coating for 10 s without drying. Even when the Ti alloy substrate with PMDP coating was immersed in the aqueous medium for 1 week, no change in the thickness was observed, i.e., the PMDP layer was bound to the surface very stably. Oxidation of the DHP groups reduced the stability of the polymer layer significantly. Thus, the DHP groups play a significant role in achieving stable binding. Protein was adsorbed on the Ti alloy substrate; however, this was not observed for the PMDP-coated Ti alloy substrate. In conclusion, we confirmed the effects of DHP groups in PMDP on the stability of the coating on the Ti alloy substrate. Moreover, we found that surface treatment using PMDP was simple, quick, and reliable, and thus, it has great potential for improving biofouling of Ti alloy substrates used in medical devices.     

Epoxy polymer coating to prevent the corrosion of aluminum nanoparticles

Aluminum nanoparticles were coated by epoxy polymer in order to prevent the corrosion reaction. The coverage of the epoxy polymer film was controlled from 0% to 100%, which changed the corrosion rate of nanoparticles quantitatively. The surface of the polymer coating was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM), and the corrosion resistance of these nanoparticles was estimated by the wet/dry corrosion test on platinum (Pt) plate with a NaCl solution. From a TEM analysis, 10 mass% polymer‐coated Al particles in the synthesis were almost 100% covered on the surface by a polymer film of 10 nm thick. On the other hand, 3 mass% polymer‐coated Al was partially covered by a film. In the AFM–Kelvin force microscopy, the potential around the Al particles had a relatively low value by the polymer coating, which indicated that the conductivity of the Al was isolated from Pt plate by the polymer. Both the corrosion and H₂ evolution reaction rates were quantitatively reduced by the mass% of polymer coating. In the case of 10 mass% coated sample, there was very little corrosion of Al nanoparticles. This fact suggested that the electrochemical reaction was suppressed by the polymer coating. Thus, it was found that the corrosion reaction rate of Al nanoparticles could be quantitatively suppressed by the mass% of epoxy coating. Copyright © 2015 John Wiley & Sons, Ltd.     

A facile method for fabrication of superhydrophobic coating on aluminum alloy

A superhydrophobic coating applied in corrosion protection was successfully fabricated on the surface of aluminum alloy by chemical etching and surface modification. The water contact angle on the surface was measured to be 161.2° ± 1.7° with sliding angle smaller than 8°, and the superhydrophobic coating showed a long service life. The surface structure and composition were then characterized by means of SEM and XPS. The electrochemical measurements showed that the superhydrophobic coating significantly improved the corrosion resistance of aluminum alloy. The superhydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it was found that only about 6% of the water surface is in contact with the metal substrate and 94% is in contact with the air cushion. Copyright © 2011 John Wiley & Sons, Ltd.     

Ca-P Conversion Coating on AZ60 Magnesium Alloy for Biomedical Application

To improve the anti-corrosion behaviors of magnesium alloy in the inner environment of human body,a bioactive Ca-P coating was deposited on the AZ60 magnesium alloy by a novel simple method.The morphologies of the Ca-P coatings formed under different treatment time were studied by scanning electron microscopy（SEM）.The corrosion behaviors of Ca-P coating were investigated by electrochemical polarization test and electrochemical impedance spectroscopy in both 3％（mass fraction） NaCl solution and simulated body fluid（SBF）.Immersion test in SBF was performed to evaluate the corrosion rate of Ca-P coated magnesium alloy.X-Ray diffraction（XRD） analysis result shows that the coating mentioned above mainly consists of dicalcium phosphate dehydrate（CaHPO4·2H2O,DCPD） and β-tricalcium phosphate dehydrate[β-TCP,Ca3（PO4）2],which exhibits good corrosion resistance.After magnesium alloy was immersed in 1 mol/L NaOH solution at 80 ℃ for 2 h,hydroxyapatite [Ca10（PO4）6（OH）2,HA]appeared on the magnesium alloy substrate,which can further decrease the corrosion rate of AZ60 magnesium alloy in SBF.     

非晶态Ni-W-B合金的电沉积及其热处理前后的性能

To strengthen the properties of Ni-W alloy, dimethylamine borane （DMAB） was added to an alloy Ni-W electrolyte solution and a ternary Ni-W-B alloy was electrodeposited. The electrodeposition, crystallographic structure, surface morphology, heat treatment and corrosion resistance, of the alloy were studied by DSC, XRD, SEM and electrochemical techniques. The results showed that the structure of the alloy was greatly affected by the cooperation of boron compound. DSC experiment combined with X-ray diffractometry indicated that the obtained Ni-W-B alloy was still in amorphous structure although W content in the alloy was decreased by the addition of DMAB. After heat treatment at 400 ℃ for 1 h, the microhardness was increased from 612 to 947 kg.mm^-2 that was com- parative to Cr coating. The appearance of the as-plated coating was in f＇me and slice grains and kept almost no change after heat treatment. In w=0.03 NaC1 solution the as-plated coating presented very good corrosion resistance. After the coating was heat-treated its corrosion resistance was enhanced.     

Formation and characterisation of NiAl‐Ti coating on nickel‐based superalloy B1900

Alumina‐former coatings have been known as the best surface engineering approach to combat high temperature corrosion in gas turbine industry. In this investigation, attempts have been made to obtain a titanium‐modified aluminide coating with improved protective properties. Modification has been achieved by introducing titanium in the coating composition by a two‐stage coating treatment; titanium coating and subsequent aluminising. The modified coatings were characterised and compared with simple aluminides by means of electron metallography, depth elemental profiling and x‐ray diffraction techniques. Experimental results indicated that pre‐titanising diffusion treatment is an effective route to modify chemical composition of simple aluminide coating. The final microstructure of the coating was β‐NiAl matrix with titanium‐bearing precipitates mainly distributed in near surface layers. The mechanism of the coating formation is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrochemical corrosion behaviors and corrosion protection properties of Ni–Co alloy coating prepared on sintered NdFeB permanent magnet

In this study, a protective Ni–Co alloy coating was prepared on sintered NdFeB magnet applying electrodeposition technique. A pure nickel coating was also studied for a comparison. The microstructure, surface morphologies, and chemical composition of coatings were investigated using X-ray diffraction, scanning electron microscope, and energy dispersive spectroscopy, respectively. The corrosion protection properties of coatings for NdFeB magnet in neutral 3.5 wt.% NaCl solutions were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The microstructure and surface morphologies analysis showed that the addition of cobalt element into matrix metal Ni altered the preferential orientation of pure nickel coating from (2 0 0) crystal face for pure nickel coating to (1 1 1) crystal face for Ni–Co alloy coating, and made the surface morphologies more compact and uniform due to the grain-refining. The results of potentiodynamic polarization test showed that compared with pure nickel coating, Ni–Co alloy coating exhibited much nobler corrosion potential (E _corr) and lower corrosion current density (j _corr), indicating better anticorrosive properties. The long-term immersion test by dint of EIS indicated that the Ni–Co alloy coating still presented high impedance value of 1.9 × 10⁵ Ω cm² with the immersion time of 576 h indicating the excellent anticorrosive properties, and corrosion protection properties of nickel coating for NdFeB magnet practically disappeared with the immersion time of 144 h, which also indicated that the Ni–Co alloy coating provided better corrosion protection properties for the NdFeB magnet compared with nickel coating.     

Determination of beryllium in Pt-Be alloy by atomic-absorption spectrometry after ion-exchange separation

Traces of beryllium in platinum have been determined by graphite-furnace atomic-absorption spectrometry, the graphite furnace being coated with lanthanum or titanium carbide. The coating improves the reproducibility, sensitivity and detection limit. Platinum interferes in the beryllium determination, and an ion-exchange separation is used in the determination of beryllium in Pt-Be alloy.     

In vitro Degradation and Biocompatibility of Ca-P Coated Magnesium Alloy

Calcium-phosphate compounds(Ca-P) coating was prepared on an Mg-Al alloy(AZ60). Biodegradation of Ca-P coated magnesium alloy was evaluated in simulated body fluid(SBF) by examining the changes in magnesium ion concentration and pH value, which indicated that the Ca-P coating on magnesium alloy strongly affected the corrosion of magnesium alloy. Osteoblast MC3T3-E1 cells were utilized to investigate the cellular cytocompatibility. The cytocompatibility was measured by carrying out a series of tests, such as cholecystokinin-octapeptide(CCK-8) test, alkaline phosphatase activity(ALP) test, cellular morphology of hematoxylin-eosin(HE) staining and the induction of apoptosis. It was found that the cell function showed better in the Ca-P coated Mg-alloy extract than in the uncoated magnesium alloy extract. In summary, the results indicate that the Ca-P coating can improve the corrosion resistance of magnesium alloy and elevate cellular proliferation and differentiation of osteoblast MC3T3-E1 cells.     

An Investigation into the Optimum Thickness of Titanium Dioxide Thin Films Synthesized by Using Atmospheric Pressure Chemical Vapour Deposition for Use in Photocatalytic Water Oxidation

Twenty eight films of titanium dioxide of varying thickness were synthesised by using atmospheric pressure chemical vapour deposition (CVD) of titanium(IV) chloride and ethyl acetate onto glass and titanium substrates. Fixed reaction conditions at a substrate temperature of 660 °C were used for all depositions, with varying deposition times of 5–60 seconds used to control the thickness of the samples. A sacrificial electron acceptor system composed of alkaline sodium persulfate was used to determine the rate at which these films could photo‐oxidise water in the presence of 365 nm light. The results of this work showed that the optimum thickness for CVD films on titanium substrates for the purposes of water oxidation was ≈200 nm, and that a platinum coating on the reverse of such samples leads to a five‐fold increase in the observed rate of water oxidation.     

Corrosion resistance and cytotoxicity of a MgF2 coating on biomedical Mg–1Ca alloy via vacuum evaporation deposition method

To reduce the biocorrosion rate and enhance the biocompatibility by surface modification, MgF₂ coatings were prepared on Mg–1Ca alloy using vacuum evaporation deposition method. The average thickness of the coating was about 0.95 µm. The results of immersion test and electrochemical test indicated that the corrosion rate of Mg–1Ca alloy was effectively decreased after coating with MgF₂. The MgF₂ coating induced calcium phosphate deposition on Mg–1Ca alloy. After 72 h culture, MG63 cells and MC3T3‐E1 cells were well spread on the surface of the MgF₂‐coated Mg–1Ca alloy, while few cells were observed on uncoated Mg–1Ca alloy samples. In summary, MgF₂ coating showed beneficial effects on the corrosion resistance and thus improved cell response of the Mg–1Ca alloy effectively and should be a good surface modification method for other biomedical magnesium alloys. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of Substrates Performance on the Microstructure and Properties of Phosphate Chemical Conversion Coatings on Metal Surfaces

Phosphate chemical conversion (PCC) technology has attracted extensive attention for its ability to regulate the surface properties of biomedical metals. However, titanium (Ti)-based alloys exhibit inertia because of the native passive layer, whereas zinc (Zn)-based alloys show high activity in acidic PCC solutions. The substrate performance affects the chemical reaction in the phosphating solution, which further leads to diversity in coating properties. In this work, the zinc-phosphate (ZnP) coatings are prepared on Ti alloy (TA) and Zn alloy (ZA) substrates using the PCC method, respectively. The coatings prepared herein are detected by a scanning electron microscope (SEM), X-ray diffractometer (XRD), laser scanning confocal microscope (LSCM), universal testing machine, contact angle goniometer, and electrochemical workstation system. The results show that the substrate performance has little effect on the phase composition but can significantly affect the crystal microstructure, thickness, and bonding strength of the coatings. In addition, the ZnP coatings improve the surface roughness of the substrates and show good hydrophilicity and electrochemical corrosion resistance. The formation mechanism of the ZnP coating is revealed using potential-time curves, indicating that the metal–solution interfacial reaction plays a dominant role in the deposition process.