Interface adhesion properties of functional coatings on titanium alloy formed by microarc oxidation method

Three functional coatings (namely Al-C, Si-P-Al and P-F-Al coating) were fabricated by microarc oxidation method on Ti6Al4V alloy in different aqueous solutions. The microstructure, phase and chemical composition of coatings were investigated using scanning electron microscope, X-ray diffraction and energy dispersive spectroscopy. The interface adhesion failure mode of the coating is revealed by shear, tensile and thermal shock methods. The coatings exhibit high adhesion strength by the quantitative shearing test, registering as 110, 70, and 40 MPa for Al-C, Si-P-Al and P-F-Al coating, respectively. The tensile test of the coated samples shows that microarc oxidation treatment does not significantly deteriorate mechanical properties of substrate titanium alloy. The observations of the coating failure after subjected to the identical tensile elongation of 3.0% are well in agreement with those results of the shear test. The thermal cycle test indicates that all the coatings have good anti-thermal shocking properties.     

Improvement of corrosion properties of microarc oxidation coating on magnesium alloy by optimizing current density parameters

The microstructure, composition and corrosion performance of oxide coatings formed on AM60B alloy using microarc oxidation techniques at different waveforms of applied current densities were investigated within this study. It is found that the use of optimizing current density waveforms, i.e. decaying freely current density in the later stage and stepped decreasing current density, significantly improved the microstructure of oxide coatings compared with the constant current density mode, which are connected with changes in behaviors of spark discharges on the surface in oxidation process. The optimal waveform of current density is showed to be decaying freely current density in the later stage, which results in sealing the originally formed large micropores. The optimisation of the microstructure results in a significant improvement of the corrosion resistance of oxide coating.     

Effect of potassium fluoride in electrolytic solution on the structure and properties of microarc oxidation coatings on magnesium alloy

Oxide coatings were produced on AM60B magnesium alloy substrate making use of microarc oxidation (MAO) technique. The effect of KF addition in the Na₂SiO₃-KOH electrolytic solution on the microarc oxidation process and the structure, composition, and properties of the oxide coatings was investigated. It was found that the addition of KF into the Na₂SiO₃-KOH electrolytic solution caused increase in the electrolyte conductivity and decrease in the work voltage and final voltage in the MAO process. Subsequently, the pore diameter and surface roughness of the microarc oxidation coating were decreased by the addition of KF, while the coating compactness was increased. At the same time, the phase compositions of the coatings also varied after the addition of KF in the electrolytic solution, owing to the participation of KF in the reaction and its incorporation into the oxide coating. Moreover, the coating formed in the electrolytic solution with KF had a higher surface hardness and better wear-resistance than that formed in the solution without KF, which was attributed to the changes in the spark discharge characteristics and the compositions and structures of the oxide coatings after the addition of KF.     

Preparation of anti-corrosion films by microarc oxidation on an Al-Si alloy

Thick ceramic films over 140 μm were prepared on Al-7% Si alloy by ac microarc oxidation in a silicate electrolyte. The film growth kinetics was determined by an eddy current technique and film growth features in different stages were discussed. The microstructure and composition profiles for different thick films were analyzed by scanning electron microscopy and energy dispersive X-ray spectroscopy. Their phase components were determined by X-ray diffraction. The electrochemical corrosion behaviors of bare and coated alloys were evaluated using potentiodynamic polarization curves, and their corrosion morphologies were observed. In the initial stage of oxidation, the growth rate is slow with 0.48 μm/min due to the effect of Si element though the current density is rather high up to 33 A/dm². After the current density has decreased to a stable value of 11 A/dm², the film mainly grows towards the interior of alloy. The film with a three-layer structure consists of mullite, γ-Al₂O₃, α-Al₂O₃ and amorphous phases. By microarc discharge treatment, the corrosion current of the Al-Si alloy in NaCl solution was significantly reduced. However, a thicker film has to be fabricated in order to obtain high corrosion-resistant film of the Al-Si alloy. Microarc oxidation is an effective method to form an anti-corrosion protective film on Si-containing aluminum alloys.     

Microstructure and corrosion behavior of coated AZ91 alloy by microarc oxidation for biomedical application

Magnesium and its alloy currently are considered as the potential biodegradable implant materials, while the accelerated corrosion rate in intro environment leads to implant failure by losing the mechanical integrity before complete restoration. Dense oxide coatings formed in alkaline silicate electrolyte with and without titania sol addition were fabricated on magnesium alloy using microarc oxidation process. The microstructure, composition and degradation behavior in simulated body fluid (SBF) of the coated specimens were evaluated. It reveals that a small amount of TiO₂ is introduced into the as-deposited coating mainly composed of MgO and Mg₂SiO₄ by the addition of titania sol into based alkaline silicate electrolytic bath. With increasing concentration of titania sol from 0 to 10 vol.%, the coating thickness decreases from 22 to 18 μm. Electrochemical tests show that the E_corr of Mg substrate positively shifted about 300500 mV and i_corr lowers more than 100 times after microarc oxidation. However, the TiO₂ modified coatings formed in electrolyte containing 5 and 10 vol.% titania sol indicate an increasing worse corrosion resistance compared with that of the unmodified coating, which is possibly attributed to the increasing amorphous components caused by TiO₂ involvement. The long term immersing test in SBF is consistent with the electrochemical test, with the coated Mg alloy obviously slowing down the biodegradation rate, meanwhile accompanied by the increasing damage trends in the coatings modified by 5 and 10 vol.% titania sol.     

In situ formation of Al2O3-SiO2-SnO2 composite ceramic coating by microarc oxidation on Al-20%Sn alloy

In situ formation of Al₂O₃-SiO₂-SnO₂ composite ceramic coating on Al-20%Sn alloy was successfully fabricated in aqueous Na₂SiO₃ electrolyte by microarc oxidation technology. The compositions, structure, mechanical and tribological properties of the composite coating were detailed studied by scanning electron microscope, energy dispersive spectroscopy, X-ray diffraction, hardness tester and ball-on-disc friction tester. It is found that the species originating from the Al-20%Sn alloy substrate and the electrolyte solution both participate in reaction and contribute to the composition of the coating, which results in the generated coating firmly adherent to the substrate. The composite ceramic coating can greatly improve the microhardness and tribological property of Al-20%Sn alloy.     

Fretting wear behaviour of microarc oxidation coatings formed on titanium alloy against steel in unlubrication and oil lubrication

Ceramic coatings were formed on Ti6Al4V alloy surface by microarc oxidation (MAO) in a Na₂SiO₃ system solution. Unlubricated, smear oil and oil bath lubricated fretting tests were performed on MAO coatings against 52100 steel on a fretting wear tester. Microstructural investigation of the worn surfaces was performed and the wear mechanisms were studied. The results show that the coatings are mainly composed of rutile and a small amount of anatase TiO₂, both in nano grain structure. Friction coefficient of microarc oxidation coatings under oil bath lubrication was significantly reduced, favorable stable at 0.15, which indicates that the coatings with oil lubricated lowered the shear and adhesive stresses between contact surfaces, consequently alleviating the possibility of initiation and propagation of cracks in the inner layer of the coating or titanium alloy substrate.     

Characterization of microarc oxidation coatings formed on AM60B magnesium alloy in silicate and phosphate electrolytes

Microarc oxidation coatings on AM60B magnesium alloy were prepared in silicate and phosphate electrolytes. Structure, composition, mechanical property, tribological, and corrosion resistant characteristics of the coatings was studied by scanning electron microscope (SEM), X-ray diffraction (XRD) and microhardness analyses, and by ball-on-disc friction and potentiodynamic corrosion testing. It is found that the coating produced from the silicate electrolyte is compact and uniform and is mainly composed of MgO and forsterite Mg₂SiO₄ phases, while the one formed in phosphate electrolyte is relatively porous and is mainly composed of MgO phase. The thick coating produced from a silicate electrolyte possesses a high hardness and provides a low wear rate (3.55 × 10⁻⁵ mm³/Nm) but a high friction coefficient against Si₃N₄ ball. A relatively low hardness and friction coefficient while a high wear rate (8.65 × 10⁻⁵ mm³/Nm) is recorded during the testing of the thick coating produced from a phosphate electrolyte. Both of these types of coatings provide effective protection for the corrosion resistance compared with the uncoated magnesium alloy. The coating prepared from the silicate electrolyte demonstrates better corrosion behavior due to the compacter microstructure.     

Tribological behavior of microarc oxidation coatings formed on titanium alloys against steel in dry and solid lubrication sliding

The coatings mainly composed of nanostructured TiO₂ were deposited on Ti6Al4V alloy by microarc oxidation (MAO). The duplex coatings of microarc oxidation combined with spraying graphite process were fabricated for the antifriction purpose. The tribological properties of unpolished, polished and duplex coating against steel under dry friction conditions were examined. It is found that antifriction property of the polished microarc oxidation coating is superior to that of the unpolished one. The improvement is attributed to the low surface roughness and the nanocrystalline structure of coatings. The duplex coating exhibits best antifriction property, registering a lower and steady friction coefficient of ≈0.12 than that of the polished microarc oxidation coating sliding in the similar condition. The good tribological property is attributed to the specially designed duplex structure, the coating adhering strongly to the substrate and serving as the load-supporting underlayer and the graphite layer on top of it working as solid lubricant.     

Characteristic of microarc oxidized coatings on titanium alloy formed in electrolytes containing chelate complex and nano-HA

Microarc oxidized (MAO) TiO₂-based coatings containing Ca and P on titanium alloy were formed in electrolytes containing nano-hydroxyapatite (nano-HA), calcium and phosphate salts. The effects of HA concentration on the thickness, micropore size and number of the MAO coatings were not pronounced. However, the surfaces of the MAO coatings become rough and the crystallinity of anatase increases with increasing HA concentration. In addition, the Ca and P concentrations on the surfaces of the MAO coatings decrease, since the chelate complex of CaY²⁻ (Y = [₂(OOC)NCH₂CH₂N(COO)₂]⁴⁻) and phosphate ions are hindered to be incorporated into the MAO coatings by HA. In vitro experiments indicate that the apatite-forming abilities of the MAO coatings decrease with increasing HA concentration. Furthermore, with increasing HA concentration, the solubility of Ca and P of the MAO coatings decreases, which could lower the supersaturation of the SBF with respect to apatite near the surfaces of the MAO coatings, further leading to the decreased apatite-forming ability. The results indicate that the HA addition in the electrolytes has an important effect on the structure and in vitro bioactivity of the MAO coatings.     

TaC微粒对Ti-6Al-4V合金微弧氧化层结构和性能的影响

为了提高钛合金表面微弧氧化层在海洋环境中的抗腐蚀和耐磨损性能,在硅酸盐系电解液中添加不同浓度粒径在1 μm左右的TaC微粒,制备了 TaC掺杂微弧氧化层.通过扫描电子显微镜、能谱仪和X射线光电子能谱仪等对微弧氧化层的形貌、元素组成及其化学状态进行表征与分析,并对比评价了钛合金表面TaC掺杂微弧氧化层的厚度、表面粗糙度、...     

阴极电压脉冲占空比对钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化电源,在保持双极性电压脉冲幅度不变的条件下,研究了阴极电压脉冲占空比（d_c）对钛合金微弧氧化膜特性的影响.结果表明：阴、阳极的峰值电流随处理时间的变化分为几个不同阶段,各阶段的开始和结束时间与d_c密切相关.氧化膜主要由金红石和锐钛矿相TiO₂组成,金红石相TiO₂的相对含量在d_c=50%附近随d_c的 关键词： 微弧氧化 钛合金 占空比     

工业纯钛微弧氧化膜的结构及拉曼光谱分析

采用微弧氧化技术,用处理电压为300, 350, 400, 450, 500 V在工业纯钛表面制备了5块氧化膜试样,利用扫描电镜和拉曼光谱研究了处理电压对氧化膜结构的影响。结果表明：氧化膜表面布满了微孔,其尺寸随处理电压的升高而增加,而微孔密度则呈相反的变化趋势。氧化膜主要由锐钛矿和金红石相组成,其相含量与处理电压的大小密切相关。当处理电压较低时,氧化膜主要由锐钛矿相组成; 随着处理电压的升高,氧化膜中金红石相的相对含量增加; 当处理电压在400～450 V时,金红石相含量增加迅速,并成为主晶相。     

The effects of anodic and cathodic processes on the characteristics of ceramic coatings formed on titanium alloy through the MAO coating technology

This paper reports on the investigation into the effects of the different anodic j_a and cathodic j_c current densities on the variations of the anodic and cathodic processes and the associated changes in the characteristics of the coatings synthesized on Ti-6Al-4V alloy substrate by microarc oxidation technique. The coated samples were subjected to coating thickness and cross-section fracture observation. Phase and elemental composition at different depth of the coatings were evaluated through X-ray diffraction and energy dispersive spectrum analyses. The experimental results indicate that the increase of j_a leads to the increasing slope of anodic voltage U₊ versus oxidation time plots, the larger coating thickness and the more coarse surface morphology of MAO coatings; while the aggrandizement of the cathodic process results in the lower growth rate and more uniform structure of coatings. The changes of the elements distribution from the interface towards the coating surface with variation of j_a and j_c are affected by the Ti anodic dissolution and the electromigration of electriferous particles, such as Al(OH)₄⁻, in electrolytes.     

Formation and structure of sphene/titania composite coatings on titanium formed by a hybrid technique of microarc oxidation and heat-treatment

Sphene/titania composite coatings were fabricated on titanium by a hybrid technique of microarc oxidation (MAO) and heat treatment. The high-applied voltages promote the formation of sphene in the MAO coatings after heat-treatment. Heat treatment could change the surface morphology of the MAO coatings such as roughness, macropores size and density and the thickness of the MAO coatings. Increasing the heat-treatment temperature decreased the atomic concentration ratios of Ti/Si and Ti/Ca of the MAO coatings. The chemical states of Ti⁴⁺, Ca²⁺, Si²⁺ and O²⁻ were observed on all the coatings. Additionally, Ti²⁺ was detected in the MAO and heat-treated MAO coatings at 600 and 700 °C. The heat-treatment has obvious effect on the chemical states of Si, Ti and O elements due to the formation of sphene and oxidation of TiO phase of the MAO coating, but did not affect that of Ca. In the heat-treated MAO coatings at 800 °C (MAO-H8), the titanium surface shows a MAO top layer and oxidized interior layer. A concentration gradient in components in the MAO layer of the MAO-H8 coating was formed.     

Al(OH)3溶胶浓度对TC4钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化(MAO)电源,在保持电学参数和处理时间不变的条件下对TC4钛合金表面进行了MAO处理,研究了Al(OH)₃溶胶浓度对钛合金MAO膜的生长特性、微观结构、相结构和电致变色特性的影响.结果表明:随着Al(OH)₃溶胶浓度(体积分数)C的增加,膜层的生长速率由慢到快逐渐增加,膜表面微孔尺寸和粗糙度逐渐增大,而微孔密度逐渐减小;当C≤10%时,膜层由锐钛矿相TiO₂组成,而当C>10%时,膜层中开始出现金红石相TiO₂并随着C的增加其相对含量逐渐增大,并在C=40%时,膜层全部由金红石相TiO₂组成;在pH＝2.0的HCl溶液中的循环伏安测试结果表明,C≤20%制备试样的膜层颜色变化不明显,随着C的进一步增加,制备试样的膜层颜色变化逐渐明显,并在C=40%时,其着色呈蓝色且色泽均匀;该试样在循环伏安测试过程中还表现出了良好的稳定性和可逆性. 关键词： 微弧氧化 氧化膜 微观结构 电致变色     

电流密度对铝合金微弧氧化膜物理化学特性的影响

利用微弧氧化(MAO)技术，在LYl2铝合金上沉积了显微硬度达42.14GPa的超硬陶瓷膜.采用x射线衍射仪和显微硬度计研究了阳极电流密度j_a和阴极、阳极电流密度比j_c/j_a对MAO膜相构成和力学特性的影响.此外，利用扫描电子显微镜和恒电位仪分别对膜的微结构和抗点腐蚀特性进行了分析.结果表明，高j_a制备的膜主要含α-Al₂O₃相，低j_a制备的膜主要含γ-Al₂O₃相.显微硬度测试表明，这类膜有较高的硬度，但以j_a=15A/dm²和j_c/j_a=0.7制备的陶瓷膜硬度最高.抗点腐蚀测试表明，j_c/j_a对陶瓷膜的微结构有很强的影响. 关键词： 微弧氧化 显微硬度 电流密度 抗点腐蚀     

N离子注入对Ti—Al—Zr合金耐蚀性影响研究

经完全退火处理的Ti-Al-Zr合金表面注入不同剂量的N离子,并在pH值为10的溶液中进行电化学腐蚀试验。结果表明,N离子注入后,试样表面首先形成具有四方结构的ε-Ti2N,随着离子注入剂量的增加,四方结构的ε-Ti2N逐渐向立方结构的σ-TiN转变,X射线光电子能谱的分析结果也证实了这一变化过程;N离子的注入能明显改善Ti-Al-Zr合金表面的耐腐蚀性能,且在注入8×10^16 ion／cm^2时得到最佳的耐腐蚀性。根据原子碰撞理论对电化学腐蚀实验结果进行了理论分析。In the present investigation, fully annealed Ti-Al-Zr plates were implanted with different nitrogen fluences. The corrosion resistance was examined by the electrochemical methods in a solution with pH value of 10 at room temperature in order to determine the optimum fluenee that can give good corrosion resistance in a simulated nuclear reactor condition. The results show ε-Ti2N phase formed initially and then transformed into σ-TIN with increasing of nitrogen fluences, which was confirmed by the results of X-ray photoelectron spectroscopy （XPS）. In addition, it can be found the increase of the corrosion resistance depends on the nitrogen fluence employed and the maximum improvement of the corrosion resistance was observed with a fluence of 8 × 10^16 N^＋ ion/cm^2. The mechanism of the corrosion resistance is attributed to defect accumulation, formatio on of amorphous phase and nanocrystallization in the implanted layer.     

Microstructure and infrared emissivity property of coating containing TiO2 formed on titanium alloy by microarc oxidation

Ceramic coatings containing TiO₂ were formed on Ti6Al2Zr1Mo1V alloy surface by microarc oxidation (MAO) method. The microstructure, phase and chemical composition of the coatings were analyzed by SEM, XRD and EDS techniques. The coating mainly consists of rutile TiO₂ and a small amount of anatase TiO₂. The infrared emissivity values of coated and uncoated titanium samples when exposed to 700 °C were tested. It was found that the coating exhibits a higher infrared emissivity value (about 0.9) in the wavelength range of 8–14 μm than that of the uncoated titanium alloy, although which shows a slight increase from 0.1 to 0.3 with increasing exposure time at 700 °C. The relatively high infrared emissivity value of the MAO coating is possibly attributed to the photon emission from the as formed TiO₂ phase.     

Enhanced fatigue performance of porous coated Ti6Al4V biomedical alloy

Biofunctional coatings are necessary to improve integration of titanium implants in the host tissue but they may be detrimental for the implant fatigue properties. This study presents an attempt towards enhancement of the in vitro fatigue strength of plasma electrolytic oxidation coated Ti6Al4V alloy by applying shot peening process prior to coating. The electrolytic oxidation was performed in calcium acetate and calcium glycerophosphate electrolytes that allowed formation of porous oxide coatings with high surface free energy and apatite like ability. A deformed surface layer coupled with induced residual compressive stresses seem to affect oxide growth rate and fatigue behavior of the titanium alloy.