电泳沉积壳聚糖/绿原酸复合涂层的耐蚀性能

目的 纯镁超声微弧氧化(UMAO)表面电泳沉积中药提取物绿原酸,提高纯镁的耐蚀性及生物活性.方法 采用电泳沉积(EPD)技术在UMAO表面上制备壳聚糖/绿原酸(CS/CA)涂层.采用扫描电子显微镜、X射线衍射仪、原子力显微镜、X射线光电子能谱、傅里叶变换红外光谱和接触角测量仪,研究不同样品的表面形态、组织结构,并研究涂层腐蚀行为,评价不同样品的耐蚀性.结果 UMAO/CS/CA涂层由Mg、MgO和Mg2SiO4相组成,含有O、C、Mg、Si和N元素,绿原酸涂层中有O—H、芳香烃键、C==O键和苯环的伸缩振动峰.中药提取物和壳聚糖之间的结合主要通过化学结合和物理吸附.UMAO/CS/CA涂层的接触角为104.1°,为疏水性表面.模拟体液环境下电化学腐蚀实验表明,Mg的腐蚀电流密度为1.7569×10?5 A/cm2,UMAO/CS/CA涂层的腐蚀电流密度为3.767×10?6 A/cm2,涂层的自腐蚀电流密度比Mg至少低1个数量级.UMAO/CS/CA涂层能更好地诱导钙磷物质沉积.结论 UMAO/CS/CA涂层既能减小腐蚀溶液与涂层表面的接触面积,又能起到隔绝溶液中离子的作用,使得涂层表面不容易被模拟体液润湿,涂层能为镁基体提供更有效的保护并具有优异的生物活性.     

电流密度对ZK60镁合金表面超疏水涂层的制备及耐腐蚀性的影响

为了提高镁合金的耐腐蚀性能,基于层状双氢氧化物（LDHs）膜在ZK60镁合金表面制备了超疏水（SH）涂层。涂层制备过程中引入电场辅助,研究了工作电流密度对涂层性能的影响。结果表明,工作电流密度显著影响LDHs膜的微观结构,这对SH涂层的疏水性具有重要影响。当工作电流密度为25 mA/cm²时,SH涂层表面呈现均匀的微纳米结构,并表现出超疏水性。超疏水涂层的腐蚀电流密度（I_corr=9×10^-7 A·cm^-2）比ZK60基体的腐蚀电流密度（I_corr=3×10^-5 A·cm^-2）低了2个数量级,表现出优异的耐腐蚀性。     

高铌γ-TiAl合金表面微弧氧化陶瓷涂层的耐蚀性及高温氧化行为

利用微弧氧化技术（MAO）在硅酸钠和氢氧化钾溶液中对高铌γ-TiAl合金表面原位生长陶瓷涂层以提高γ-TiAl合金的抗高温氧化性能。采用扫描电子显微镜（SEM）、X射线衍射仪（XRD）、X射线光电子能谱（XPS）、电化学工作站和箱式电阻炉高温氧化测试分析涂层的表面及截面形貌、相组成、元素化学结合状态、耐蚀性和高温氧化行为。XRD和XPS结果表明,陶瓷涂层主要由Al₂TiO₅、SiO₂和Nb₂O₅组成。涂层与基体界面结合良好,厚度约2.15 μm。高铌γ-TiAl合金经微弧氧化处理后,在3.5%NaCl溶液中的腐蚀电流降低近1个数量级。微弧氧化处理试样在800~900 ℃中的氧化增重仅为基体的8.9%~37.5%。微弧氧化陶瓷涂层将基体的氧化激活能从247.79 kJ/mol增加到涂层试样的574.41 kJ/mol。     

纳米柱状多孔WO3- x /TiO2 薄膜的电致变色性能

采用反应磁控溅射在掠射角度α=0°和α=80°的条件下制备氧化钨（WO_3-x）薄膜,然后在其表面沉积二氧化钛（TiO₂）。利用X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱仪（XPS）对WO_3-x/TiO₂薄膜的晶体结构、表面/断面形貌以及表面化学成分进行表征。在三电极体系1 mol/L LiClO₄/PC溶液中,采用电化学工作站和紫外-可见分光光度计测试了WO_3-x/TiO₂薄膜的电致变色性能。XRD结果表明,WO_3-x/TiO₂薄膜为非晶态结构,与掠射角度无关。当掠射角度为80°时,获得了纳米柱状多孔薄膜。从 W 4f和Ti 2p的XPS谱图确认氧化钨为亚化学计量比的WO_3-x,而氧化钛为满足化学计量比的TiO₂。与致密薄膜相比,纳米柱状多孔薄膜需要较低的驱动电压且具有较快的响应速度。纳米柱状多孔薄膜的电荷容量为83.78 mC,是致密薄膜电荷容量30.83 mC的2倍以上。在±1.2 V驱动电压下,注入和脱出离子扩散速率分别为D_in=5.69×10^-10 cm²/s和D_de= 5.08×10^-10 cm²/s。与纯WO₃薄膜相比,WO_3-x/TiO₂薄膜的电致变色循环稳定性更好。纳米柱状多孔薄膜在可见光范围内具有较大的光调制幅度,因此其光密度变化（ΔOD）大于致密薄膜。     

基于第一性原理的石榴石型Li7La3Zr2O12 固态电解质的设计与合成

基于密度泛函理论（DFT）的第一原理方法计算了四方相和立方相中2种不同的Li₇La₃Zr₂O₁₂（LLZO）固体电解质材料的能带结构,晶格参数,态密度和成键特性。基于理论计算结果,通过电子结构特性解释了四面体相的离子电导率低于立方相的离子电导率的原因。基于LLZO的第一性原理计算,设计了2种晶体结构的LLZO材料,并通过高温固相法制备并分析了不同烧结时间的LLZO颗粒的性能。探索了合成工艺参数对Li₇La₃Zr₂O₁₂性能的影响。立方晶Li₇La₃Zr₂O₁₂（C-LLZO）的平均晶格大小为a=b=c=1.302 246 nm,而四方Li₇La₃Zr₂O₁₂（T-LLZO）的平均晶格大小为a=b=1.313 064 nm,c=1.266 024 nm。在1000 ℃下烧结12 h的C-LLZO为纯立方相,在室温（25 ℃）下最大离子电导率为9.8×10^-5 S·cm^-1。T-LLZO在室温（25 ℃）下的离子电导率为5.96×10^-8 S·cm^-1,在800 ℃下烧结6 h具有纯的四方相结构,与计算结果基本吻合。     

激光热喷涂Co30Cr8W1.6C3Ni1.4Si涂层在PAO+2.5%MoDTC油中摩擦学特性

为了提高TC4合金的耐磨性能,采用激光热喷涂技术在其表面制备了Co₃₀Cr₈W_1.6C₃Ni_1.4Si涂层。通过扫描电子显微镜（SEM）和X射线衍射（XRD）分析了涂层的形貌和物相,并通过摩擦磨损实验研究了涂层在PAO+2.5% MoDTC（质量分数）油中的磨损行为。结果表明,激光热喷涂的Co₃₀Cr₈W_1.6C₃Ni_1.4Si涂层主要由Ti、WC_1-x、CoO、Co₂Ti₄O和CoAl相组成,在涂层界面形成冶金结合。在激光功率为1000、1200和1400 W时所制备的涂层平均摩擦因数分别为0.151、0.120和0.171,其对应的磨损率分别为1.17×10^-6、1.33×10^-6和2.80×10^-6 mm³?N^-1?m^-1,磨损机理为磨粒磨损,其枝晶尺寸对降磨起主要作用。     

不同双层结构AlCrN/AlCrVN多层涂层的力学和磨损性能

采用电弧离子镀的方法制备了不同数目（1、2、4、6）双层结构的AlCrN/AlCrVN多层涂层,并研究了多层结构对涂层微观结构、力学、摩擦学和切削性能的影响。结果显示,沉积态AlCrN/AlCrVN多层涂层主要由固溶(Al,Cr)N组成,优先生长方向为[111]晶向。与其他多层涂层相比,具有6层双层结构的AlCrN/AlCrVN涂层在高温下表现出较低的摩擦系数（约0.46）和磨损率（0.15×10^-11 m³/N·m）,以及较高的硬度（HK_0.05=38 000 MPa）和膜-基结合强度（L_C2=53±1 N）。多层涂层相邻层之间形成了较多的界面,有助于提高多层涂层的硬度和耐磨性。切削试验结果显示,当切削磨损标准VB=0.2时,AlCrN/AlCrVN-6涂层具有较高的硬度和耐磨性,最长的切削长度为7.4 m。     

纳米Si3N4 对TC4钛合金微弧氧化层微观结构和性能的影响

在基电解液中加入氮化硅纳米颗粒,对TC4钛合金进行微弧氧化（MAO）处理,研究了Si₃N₄浓度对微弧氧化层表面形貌、耐蚀性和耐磨性的影响。添加Si₃N₄的MAO层呈现多孔结构,当Si₃N₄浓度为1 g/L时,涂层厚度最大,且经过7 d的酸腐蚀试验,该涂层的耐蚀性良好,腐蚀速率最低,约为0.057 mg·cm^-2·d^-1。随着Si₃N₄的加入,MAO涂层的抗菌性能先升高后降低。当Si₃N₄的添加量为1 g/L时,该MAO层的抗菌性能最好。Si₃N₄的加入能明显提高涂层在模拟海水中的耐磨性。当Si₃N₄的添加量为3和4 g/L时,所得涂层的摩擦系数低且稳定,且添加3 g/L Si₃N₄制备来的MAO涂层表现出优异的耐磨性。     

多弧离子镀制备Cr/CrN多层厚膜的微观结构和力学性能

通过多弧离子镀（MAIP）在室温下将具有不同调制比（1:2、1:3、1:5）的多层Cr/CrN厚涂层沉积在A100钢基底上。腔室温度在沉积过程中由室温逐渐升高到160~170 ℃。设计调制结构是为了使膜/基结合强度和机械性能最大化。调制比为1:2的Cr/CrN多层涂层表现出最高的膜/基结合强度（L_c=63.8 N）,这可能归因于最高的材料硬度(H)/弹性模量(E)和H³/E²数值比（分别为0.083和0.138）。Cr层越厚,多层Cr/CrN厚涂层的塑性和摩擦学性能越好。干摩擦试验表明,与单层CrN相比,Cr/CrN多层涂层的平均摩擦系数和比磨损率分别最高降低了24%和94%。随着Cr层变厚,磨损机理从表面疲劳磨损转变为磨料磨损,这种现象可归因于硬度和塑性的协调变化。     

从吸附角度观察Mg-Ca合金中Mg2Ca和 α-Mg的氧化：DFT研究

基于DFT计算O₂在α-Mg（0001）和Mg₂Ca（0001）上的吸附过程,以探明Mg-Ca合金中的α-Mg和Mg₂Ca氧化机理。结果表明,在吸附过程中,O₂与α-Mg和Mg₂Ca有很强的相互作用,且均为化学吸附,但Mg₂Ca的吸附结构不如α-Mg的吸附结构稳定。在氧化过程中,O₂与α-Mg和Mg₂Ca中的Ca和Mg原子发生反应,形成Mg-Ca-O氧化膜,从而提高Mg-Ca合金的抗氧化性。但Mg₂Ca的吸附结构稳定性比α-Mg差,因此Mg₂Ca形成的氧化膜对基体的保护作用比α-Mg弱。     

Properties of the TiN coatings on previously Ti ion-implanted magnesium alloy substrate

To enhance the mechanical properties of TiN coating on magnesium alloy, metal vapor vacuum arc (MEVVA) ion implantation was performed to modify magnesium alloy substrate before TiN film deposition. Implantation energy was fixed at 45 keV and dose was at 9 × 10¹⁷ cm^− 2. TiN coatings were deposited by magnetically filtered vacuum-arc plasma source on unimplanted and implanted substrate. The microstructure composition distribution and phase structure were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The chemical states of some typical elements of the TiN coating were analyzed by means of X-ray photoelectron spectroscopy (XPS). The properties of corrosion resistance of TiN coatings were studied by CS300P electrochemical-corrosion workstation, and the mechanism of the corrosion resistance was also discussed.     

Effect on Corrosion Resistance of Ce-Rich-Sealed Ni-P Coatings on Cf/Al Composite Surface

In this study, Ni-P coatings and sealing of the coatings by Ce-rich solution on Cf/Al composite surface for enhanced corrosion resistance are investigated. The corrosion resistance of uncoating sample in 3.5 wt.% NaCl solution was investigated and a comparison with Ni-P and Ce-sealed Ni-P coatings is given. Effect of Ce-sealing on Ni-P coating is discussed. The results of electrochemical measurements of corrosion performance of Cf/Al composites show that sealing of Ni-P coatings with Ce-rich solution can improve the corrosion resistance. The Ce-rich-sealed Ni-P coating has higher corrosion resistance than the coating without Ce, and the electroless plated Ni-P coating on composite surface has higher corrosion resistance than the bare sample, as evidenced by EIS and potentiodynamic polarization measurements. The microstructure of the Cf/Al composites and the two kinds of coatings (i.e., Ni-P coating and Ce-sealed Ni-P coating) were examined by scanning electron microscopy, energy dispersive spectroscopy, and transmission electron microscopy. The Ce-sealed Ni-P coatings on Cf/Al composite surface have a total thickness of ~11 μm of which 10 μm is the thickness of the Ni-P coating and ~1 μm is the thickness of the Ce-rich sealing. It shows that the selected area electron diffraction ring pattern of Ce-rich sealing on Ni-P plated composite is consistent with Ce₆O₁₁ or CeO₂. X-ray photoelectron spectroscopy results show that Ce⁴⁺ was the dominant oxidation state for Ce-rich sealing on Ni-P plated composite. The Ce-sealing treatment on Ni-P coating has improved the corrosion resistance over and above the corrosion resistance offered by the Ni-P mono-coating to the bare substrate.     

Effects of annealing heat treatment on the corrosion resistance of Zn/Mg/Zn multilayer coatings

Zn coatings alloyed with magnesium offer superior corrosion resistance compared to pure Zn or other Zn-based alloy coatings. In this study, Zn/Mg/Zn multilayer coatings with various Mg layer thicknesses were synthesized using an unbalanced magnetron sputtering process and were annealed to form Zn-Mg intermetallic phases. The effects of the annealing heat treatment on the corrosion resistance of the Zn/Mg/Zn multilayer coatings were evaluated using electrochemical measurements. The extensive diffusion of magnesium species into the upper and lower zinc layer from the magnesium layer in the middle of the coating was observed after the heat treatment. This phenomenon caused (a) the porous microstructure to transition into a dense structure and (b) the formation of a MgZn₂ intermetallic phase. The results of the electrochemical measurements demonstrated that the heat treated Zn/Mg/Zn multilayer coatings possessed higher levels of corrosion resistance than the non-heat treated coatings. A Zn/Mg/Zn multilayer coating with MgZn₂ and (Zn) phases showed the best corrosion resistance among the heat treated coatings, which could be attributed to the reduced galvanic corrosion effects due to a small potential gradient between the MgZn₂ and zinc.     

Influence of substrate composition on the formation of phytic acid conversion coatings

In this paper, the formation and corrosion resistance of the phytic acid conversion coatings on Mg, Al, and AZ91D magnesium alloy were contrastively investigated using scanning electronic microscopy (SEM), Auger electron spectroscopy (AES), Fourier transform infrared spectroscopy (FTIR), electronic probe microscopic analyzer (EPMA), electronic balance, and electrochemical methods. The influence of phytic acid conversion coating as a middle layer on the properties of the paint on magnesium alloys was also investigated. The results show that the formation process of the conversion coatings is evidently influenced by the compositions of the substrate. The coating on pure aluminum is thinner and compacter than that on pure magnesium and the coating formed on α phase in AZ91D magnesium alloy is thinner but denser than that on β phase. The phytic acid conversion coatings formed on Mg, Al, and AZ91D magnesium alloy can all increase their corrosion resistance. The active functional groups of hydroxyl and phosphate radical are rich in the conversion coatings, which can improve the bonding between the organic paint and magnesium alloy and then improve their corrosion resistance.     

An Investigation into the Corrosion Behavior of MgO/ZrO<Subscript>2</Subscript> Nanocomposite Coatings Prepared by Plasma Electrolytic Oxidation on the AZ91 Magnesium Alloy

Plasma electrolytic oxidation (PEO) of AZ91 Mg alloys was performed in ZrO₂ nanoparticles containing Na₂SiO₃-based electrolytes. The phase composition and the microstructure of PEO coatings were analyzed by x-ray diffraction and scanning electron microscopy followed by energy dispersive spectroscopy. Pitting corrosion properties of the coatings were investigated using cyclic polarization and electrochemical impedance spectroscopy tests in a Ringer solution. The results showed the better pitting corrosion resistance of the composite coating, as compared to the oxide one, due to the thickened inner layer and the decrease in the surface defects of the composite coating. Also, the PEO process decreased the corrosion current density from 25.06 µA/cm² in the Mg alloy to 2.7 µA/cm² in the oxide coating and 0.47 µA/cm² in the composite coating.     

Corrosion resistance of Mg−Al LDH/Mg(OH)2/silane−Ce hybrid coating on magnesium alloy AZ31

An environmentally-friendly hybrid coating on AZ31 magnesium alloy substrates was reported. The synergic effect was studied on Mg−Al-layered double hydroxide Mg−Al LDH/Mg(OH)₂-coated AZ31 magnesium alloy via an in-situ steam coating process and a subsequent combined surface modification of bis-[triethoxysilylpropyl]tetrasulfide (BTESPT) silane and Ce(NO₃)₃. The microstructure and composition characteristics of the hybrid coatings were investigated by means of X-ray diffraction (XRD), scanning electronic microscopy (SEM), Fourier transform infrared spectrophotometry (FT-IR) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the coated samples was evaluated by potentiodynamic polarization (PDP), electrochemical impedance spectrum (EIS) and hydrogen evolution rate during immersion in 3.5 wt.% NaCl solution. The results show an improved corrosion resistance of the alloy in the presence of BTESPT silane and Ce(NO₃)₃. This is most likely due to the synergistic effect of steam coating and silane coating to enhance the barrier properties of hybrid coating. In addition, the formation mechanism and anti-corrosion mechanism of coatings were discussed.     

纯镁表面负载中药提取物对复合涂层性能影响

在纯镁超声微弧氧化表面,采用电泳沉积方法引入壳聚糖作为中间层,并在壳聚糖表面浸提中药提取物。研究中药提取物对复合涂层的微观结构、磨损性能、耐蚀性和生物活性等的影响。结果表明：负载中药提取物能对超声微弧氧化表面实现封孔处理,负载中药提取物涂层具有适宜的表面状态,从而改善耐蚀性;负载中药提取物涂层为化学结合提高了涂层的结合力和抗磨损性能,并具有优异的体外生物活性。     

Corrosion and wear resistance of AZ31 Mg alloy treated by duplex process of magnetron sputtering and plasma electrolytic oxidation

In order to improve the wear and corrosion resistance of AZ31 magnesium alloy, a magnetron-sputtered Al layer with a thickness of 11 μm was firstly applied on the alloy, and then treated by plasma electrolytic oxidation (PEO) in an aluminate and silicate electrolytes, respectively. The performance of PEO coatings was investigated by dry sliding wear and electrochemical corrosion tests. The aluminate coating exhibits excellent wear resistance under both 10 and 20 N loads. The silicate coating only shows low wear rate under 10 N, but it was destroyed under 20 N. Corrosion tests show that the Al layer after magnetron sputtering treatment alone cannot afford good protection to the Mg substrate. However, the duplex layer of PEO/Al can significantly improve the corrosion resistance of AZ31 alloy. Electrochemical tests show that the aluminate and silicate coatings have corrosion current densities of ∼1.6×10⁻⁶ and ∼1.1×10⁻⁶ A/cm², respectively, which are two orders lower than that of the un-coated AZ31 alloy. However, immersion tests and electrochemical impedance spectroscopy (EIS) show that the aluminate coating exhibits better long-term corrosion protection than silicate coating.     

Effect of TiO2 nanoparticles on anticorrosion property in amorphous Ni-P-Cr composite coating in artificial seawater and microbial environment

To obtain the composite with a function of corrosion resistance in seawater and microbial environment, we apply low toxic electrolyte which contained Cr³⁺ instead of Cr⁶⁺ as a chromium source to produce Ni-P-Cr/TiO₂, Ni-P-Cr/ZrO₂ nanocomposite coatings, and Ni-P-Cr/TiO₂ microcomposite coating using direct current (DC) electrodeposits technique. The surface morphology, texture, and composition of the composite coatings are characterized by SEM, XRD, and EDX measurements, respectively. The corrosion behavior of the composite coatings is evaluated by polarization curves and electrochemical impedance spectroscopy (EIS). The results with more positive-shifting E_corr, lowest i_corr, and relatively high value of polarization resistance (R_p) proved that compared with other composite coatings, Ni-P-Cr/TiO₂ nanocomposite coating with its better passive film and unique antibacterial activity caused by TiO₂ nanoparticles incorporated, displayed excellent antibacterial and corrosion resistance property, consistent to the phenomenon that corrosion of this nanocomposite coating in SRB culture medium is not observed.     

Preparation of MgO coatings on magnesium alloys for corrosion protection

MgO coating is formed on magnesium alloy by anodic electrodeposition in 6 M KOH solution, whereas Mg(OH)₂ coating is produced by anodization in 10 M KOH solution, which could be successively converted to MgO by calcination in air at 450 °C. The evolution of morphology, structure and composition of anodic film obtained on Mg alloy is investigated using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray diffraction (XRD). Potentiodynamic polarization measurements show that the as-grown MgO protective coatings are very effective in improving the corrosion resistance of magnesium alloy compared to bare metallic magnesium.