Studies on influence of zinc immersion and fluoride on nickel electroplating on magnesium alloy AZ91D

The effect of zinc immersion and the role of fluoride in nickel plating bath were mainly investigated in nickel electroplating on magnesium alloy AZ91D. The state of zinc immersion, the composition of zinc film and the role of fluoride in nickel plating bath were explored from the curves of open circuit potential (OCP) and potentiodynamic polarization, the images of scanning electron microscopy (SEM) and the patterns of energy dispersive X-ray (EDX). Results show that the optimum zinc film mixing small amount of Mg(OH)₂ and MgF₂ is obtained by zinc immersion for 30-90 s. The corrosion potential of magnesium alloy substrate attached zinc film will be increased in nickel plating bath and the quantity of MgF₂ sandwiched between magnesium alloy substrate and nickel coating will be reduced, which contributed to produce nickel coating with good performance. Fluoride in nickel plating bath serves as an activator of nickel anodic dissolution and corrosion inhibitor of magnesium alloy substrate. 1.0-1.5 mol dm⁻³ of F⁻ is the optimum concentration range for dissolving nickel anode and protecting magnesium alloy substrate from over-corrosion in nickel plating bath. The nickel coating with good adhesion and high corrosion resistance on magnesium alloy AZ91D is obtained by the developed process of nickel electroplating. This nickel layer can be used as the rendering coating for further plating on magnesium alloys.     

Correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys

X-ray photoelectron spectroscopy (XPS) was used in order to investigate the correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys exposed to 98% relative humidity at 50 °C. Commercially pure magnesium, used as the reference material, revealed MgO, Mg(OH)₂ and tracers of magnesium carbonate in the air-formed film. For the AZ80 and AZ91D alloys, the amount of magnesium carbonate formed on the surface reached similar values to those of MgO and Mg(OH)₂. A linear relation between the amount of magnesium carbonate formed on the surface and the subsequent corrosion behaviour in the humid environment was found. The AZ80 alloy revealed the highest amount of magnesium carbonate in the air-formed film and the highest atmospheric corrosion resistance, even higher than the AZ91D alloy, indicating that aluminium distribution in the alloy microstructure influenced the amount of magnesium carbonate formed.     

Growth and characterization of Mg(OH)2 film on magnesium alloy AZ31

Magnesium-based biomaterials have been proposed as potential candidates for biodegradable implant materials, such as bone screws, bone plates, intraluminal stents and so on. However, the poor corrosion resistance inhibits their applications in surgery. They collapse before the injured tissues are healed. In this paper, Mg(OH)₂ nonstructural film was synthesized on the substrate of AZ31 magnesium alloy by hydrothermal method with NaOH solution as mineralizer to reduce the corrosion rate of magnesium-based materials. The obtained films were characterized by XRD, SEM, and XPS. The results showed that a Mg(OH)₂ film with nanostructure surface can be synthesized by hydrothermal method. It was observed that the thickness of film increased with the holding time. Corrosion rates of the films were studied by immersing the samples in Hank's solution (37 °C). Surface deposits of samples with films soaked in Hank's solution for 31 days were investigated by XRD, SEM, EDS, XPS, and FTIR. It verified that the corrosion rate of the magnesium alloy with grown film was slowed down in the Hank's solution and the behavior of corrosion was inhibited effectively. Amorphous calcium apatite precursor was observed to deposit on the surface of the film during corrosion experiments in Hank's solution. And the tape test revealed a strong adhesion between the film and the substrate.     

pH值对AZ31镁合金表面植酸转化膜在模拟体液耐腐蚀性能的影响

采用沉积的方法在镁合金AZ31表面制备植酸转化膜并研究了pH值的影响. 利用极化曲线和电化学阻抗谱方法测定其耐腐蚀性能,用扫描电子显微镜观察转化膜的表面微观结构,用能谱测定转化膜的组成元素. 在理论上通过热力学的方法分析最佳pH值. 植酸转化膜可以提高镁合金AZ31的耐腐蚀性能. 当植酸溶液的pH=5时腐蚀效率达到了89.19%,此时腐蚀电位正移了156 mV,腐蚀电流密度与没有处理的试样相比减小了约一个数量级. 热力学分析表明植酸转化膜的耐腐蚀性能不仅受植酸根离子和镁离子浓度的影响,也与氢气释放的速率有关.     

Corrosion protection of Mg/Al alloys by thermal sprayed aluminium coatings

The protective features of thermal sprayed Al-coatings applied on AZ31, AZ80 and AZ91D magnesium/aluminium alloys were evaluated in 3.5 wt.% NaCl solution by electrochemical and gravimetric measurements. The changes in the morphology and corrosion behaviour of the Al-coatings induced by a cold-pressing post-treatment were also examined. The specimens were characterized by scanning electron microscopy, energy dispersive X-ray analysis and low-angle X-ray diffraction. The as-sprayed Al-coatings revealed a high degree of porosity and poor corrosion protection, which resulted in galvanic acceleration of the corrosion of the magnesium substrates. The application of a cold-pressing post-treatment produced more compact Al-coatings with better bonding at the substrate/coating interface and higher corrosion resistance regardless of the nature of the magnesium alloy.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

Composition design and laser cladding of Ni-Zr-Al alloy coating on the magnesium surface

The cluster line criterion was used for optimized design of a Ni-Zr-Al alloy used as coating on the AZ91HP magnesium alloy by laser cladding. Results show that the coating mainly consists of an amorphous, two ternary intermetallic phases with Ni₁₀Zr₇ and Ni₂₁Zr₈ type structures resulting in high hardness, good wear resistance and corrosion resistance. The interface between the clad layer and the substrate has good metallurgical bond.     

Study of molybdenum/lanthanum-based composite conversion coatings on AZ31 magnesium alloy

The molybdenum/lanthanum-based (Mo/La) composite conversion coating on AZ31 magnesium alloy was investigated and the corrosion resistance was evaluated as well. The morphology, composition and corrosion resistance of the coating were studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and potentiodynamic polarization analysis, respectively. The results revealed that the conversion coating consisted of spherical nodular particles, which was mainly composed of Mo, La, O and Mg. After conversion treatment the corrosion potential shifts about 500 mV positively, and the corrosion current density decreases two orders of magnitude. The corrosion resistance of AZ31 alloy is remarkably improved by Mo/La composite conversion coating.     

Effects of laser pulse wavelength and laser fluence on the characteristics of silver nanoparticle generated by laser ablation

Electrically pumped ultraviolet random lasing was achieved in metal-insulator-semiconductor (MIS) diodes based on ZnO films at room temperature. The ZnO films were grown by plasma assisted molecular beam epitaxy. Two different kinds of insulator layers, SiO _x (0<x≤2) and AlO _x (0<x≤1.5) were deposited by electron beam evaporation. X-ray diffraction experiments found these oxide layers were amorphous (or microcrystals), and X-ray photoelectron spectroscopy confirmed the Si and Al were fully oxidized. Compared with devices using SiO _x as the insulator layer, diodes with evaporated AlO _x layers showed a lower working threshold forward current (～20 mA to ～26 mA) and higher emission intensity. Periodic features indicating formation of closed-loop paths were deduced by the power Fourier transform of electroluminescence spectra. The cavity length of both devices increased as forward currents increased, while a larger cavity length was always obtained in the AlO _x -involved device under the same working current. The improved performance was attributed to larger hole amount in AlO _x layers. These results revealed that evaporated AlO _x can serve as good electron blocking and hole supplying layers for hetero-structures.     

Electrodeposition of Al-Mn alloy on AZ31B magnesium alloy in molten salts

The Al-Mn alloy coatings were electrodeposited on AZ31B Mg alloy in AlCl₃-NaCl-KCl-MnCl₂ molten salts at 170 °C aiming to improve the corrosion resistance. However, in order to prevent AZ31B Mg alloy from corrosion during electrodeposition in molten salts and to ensure excellent adhesion of coatings to the substrate, AZ31B Mg alloy should be pre-plated with a thin zinc layer as intermediate layer. Then the microstructure, composition and phase constituents of the coatings were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD). It was indicated that, by adjusting the MnCl₂ content in the molten salts from 0.5 wt% to 2 wt%, the Mn content in the alloy coating was increased and the phase constituents were changed from f.c.c Al-Mn solid solution to amorphous phase. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization measurements in 3.5% NaCl solution. It was confirmed that the Al-Mn alloy coatings exhibited good corrosion resistance with a chear passive region and significantly reduced corrosion current density at anodic potentiodynamic polarization. The corrosion resistance of the alloy coatings was also related with the microstructure and Mn content of the coatings.     

The interplay between molecular orientation, film morphology and luminescence properties of tetracene thin films on epitaxial AlOx/Ni3Al(1 1 1)

We report a systematic study of the interplay between molecular orientation, film morphology and luminescence properties of tetracene thin films on epitaxial alumina films on Ni₃Al(1 1 1), employing high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and photoluminescence spectroscopy (PL). If deposited at low temperatures, tetracene forms laterally disordered and compact films in which at least the first monolayer is oriented parallel to the substrate. For thicknesses in the range of 10 Å or below, these as-deposited films show no luminescence, while thicker films exhibit weak luminescence from higher layers. On annealing to 210 K, tetracene films dewet the AlO_x/Ni₃Al(1 1 1) surface and transform into an island morphology. At the same time, molecules tend to re-orient into a more upright configuration. In this island configuration, even thin films show luminescence. We can thus conclude that in spite of the insulating nature of the surface, the interaction of flat-lying tetracene molecules with AlO_x/Ni₃Al(1 1 1) is strong enough to provide at least one efficient non-radiative decay channel.     

Electrodeposition of high corrosion resistance Cu/Ni-P coating on AZ91D magnesium alloy

High corrosion resistance Cu/Ni-P coatings were electrodeposited on AZ91D magnesium alloy via suitable pretreatments, such as one-step acid pickling-activation, once zinc immersion and environment-friendly electroplated copper as the protective under-layer, which made Ni-P deposit on AZ91D Mg alloy in acid plating baths successfully. The pH value and current density for Ni-P electrodeposition were optimized to obtain high corrosion resistance. With increasing the phosphorous content of the Ni-P coatings, the deposits were found to gradually transform to amorphous structure and the corrosion resistance increased synchronously. The anticorrosion ability of AZ91D Mg alloy was greatly improved by the amorphous Ni-P deposits, which was investigated by potentiodynamic polarization curve and electrochemical impedance spectroscopy (EIS). The corrosion current density (I_corr) of the coated Mg alloy substrate is about two orders of magnitude less than that of the uncoated.     

Ultra-thin Si overlayers on the TiO2 (1 1 0)-(1 × 2) surface: Growth mode and electronic properties

The growth of thin subnanometric silicon films on TiO₂ (1 1 0)-(1 × 2) reconstructed surfaces at room temperature (RT) has been studied in situ by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS), Auger electron and electron-energy-loss spectroscopies (AES and ELS), quantitative low energy electron diffraction (LEED-IV), and scanning tunneling microscopy (STM). For Si coverage up to one monolayer, a heterogeneous layer is formed. Its composition consists of a mixture of different suboxides SiO_x (1 < x ? 2) on top of a further reduced TiO₂ surface. Upon Si coverage, the characteristic (1 × 2) LEED pattern from the substrate is completely attenuated, indicating absence of long-range order. Annealing the SiO_x overlayer results in the formation of suboxides with different stoichiometry. The LEED pattern recovers the characteristic TiO₂ (1 1 0)-(1 × 2) diagram. LEED I-V curves from both, substrate and overlayer, indicate the formation of nanometric sized SiO_x clusters.     

Plasma electrolytic oxidation coating on AZ91 magnesium alloy modified by neodymium and its corrosion resistance

Ceramic coatings on the surfaces of Mg-9Al-1Zn (AZ91) magnesium alloy and Mg-9Al-1Zn-1Nd magnesium alloy (AZ91 magnesium alloy modified by neodymium, named as AZ91Nd in this paper) are synthesized in aluminate electrolyte by plasma electrolytic oxidation (PEO) process, respectively. X-ray diffraction and X-ray photoelectron spectroscopy analyses show the PEO coating on the Mg-9Al-1Zn-1Nd alloy comprises not only MgO and Al₂O₃, which are found in the coating on the AZ91 alloy, but also a trace amount of Nd₂O₃. Microstructure observations indicate the addition of Nd can decrease the sizes of β phases and form Al₂Nd intermetallics in the AZ91 alloy. The fine β phases can effectively restrain the formation of unclosed-holes and greatly decrease the sizes of pores in the coating during the PEO process. In addition, the Al₂Nd intermetallics can be completely covered due to the lateral growth of the PEO coatings formed on the α and β phases. As a result, the coating on the AZ91Nd alloy possesses a dense microstructure compared with that on the AZ91 alloy. The following corrosion tests indicate the corrosion resistance of the PEO coating on the AZ91Nd alloy is evidently higher than that of the PEO coating on the AZ91 alloy.     

Improvement of high-frequency characteristics of FeCoHfO/AlOx multilayered films

High-permeability magnetic films can enhance the inductance of thin-film inductors in dc-dc converters. The FeCoHfO/AlO_x multilayered films were fabricated by dc reactive magnetron co-sputtering. Inserting the AlO_x layers can decrease the anisotropic field of the FeCoHfO magnetic films, which was beneficial to raise the permeability of the FeCoHfO/AlO_x multilayered films. With this optimum configuration of a nine-layer structure [FeCoHfO (133 nm)/AlO_x (10 nm)]₉, low anisotropic field (H_K = 65 Oe) and high permeability (permeability over 170 at 30-50 MHz) were obtained. The permeability increased nearly six times from 30 (M1) to 175 (M9). The permeability was evidently improved by the employment multilayered coating.     

Corrosion and passivation behavior of Mg-Zn-Y-Al alloys prepared by cooling rate-controlled solidification

Highly corrosion-resistant nanocrystalline Mg-Zn-Y-Al multi-phase alloys have been prepared by consolidation of rapidly solidified (RS) ribbons. The relation between corrosion behavior and microstructure evolution of Mg-Zn-Y-Al alloys with a long period stacking ordered phase has been investigated. In order to clarify the influence of rapid solidification on the occurrence of localized corrosion such as filiform corrosion, several Mg_96.75Zn_0.75Y₂Al_0.5 (at.%) alloys with different cooling rates are fabricated by the gravity casting, copper mould injection casting and melt-spinning techniques and their corrosion behavior and microstructures are examined by the salt water immersion test, electrochemical measurements, GDOES, XRD, SEM and TEM. To clarify the effect of aluminium addition on the improvement in corrosion resistance of the alloys, several Mg_97.25−xZn_0.75Y₂Al_x alloys with different aluminium contents are fabricated by consolidating RS ribbons and the formation of corroded films on the Mg-Zn-Y-Al alloys have been investigated. Rapid solidification brings about the grain refinement and an increase in the solid solubility of zinc, yttrium and aluminium into the magnesium matrix, enhancing microstructural and electrochemical homogeneity, which in turn enhanced corrosion resistance. The addition of aluminium to magnesium can modify the structure and chemical composition of surface films and improves the resistance to local breakdown of the films.     

Preparation and properties of composite ceramic coating containing Al2O3–ZrO2–Y2O3 on AZ91D magnesium alloy by plasma electrolytic oxidation

A composite ceramic coating containing Al₂O₃–ZrO₂–Y₂O₃ was successfully prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) technique in an alkaline aluminate electrolyte. The morphology, elemental and phase composition, corrosion behavior and thermal stability of the uncoated and coated samples were studied by environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electrochemical corrosion test, high temperature oxidation test and thermal shock test. The results showed that the composite ceramic coating was composed of Al₂O₃, c-ZrO₂, t-ZrO₂, Y₂O₃ and some magnesium compounds, such as MgO, MgF₂ and MgAl₂O₄. After PEO treatment, the corrosion potential of AZ91D alloy was increased and the corrosion current density was significantly reduced. Besides, the coated magnesium alloys also showed excellent high temperature oxidation resistance and thermal shock resistance at 500 °C environment.     

In vitro degradation of AZ31 magnesium alloy coated with nano TiO2 film by sol-gel method

A nano TiO₂ film was coated on AZ31 alloy substrate by sol-gel method. The TiO₂ film was characterized by X-ray diffractometry (XRD), differential scanning calorimetry-thermogravimetric analysis (DSC-TG), field emission scanning electron microscopy (FE-SEM) and energy dispersion spectroscopy (EDS). The degradation of the nano-TiO₂ coated alloy was evaluated by immersion test and electrochemical measurement. An attempt was made to relate corrosion of coated alloys with the annealing treatment and resultant structural evolution.     

Chemical nature of phytic acid conversion coating on AZ61 magnesium alloy

Phytic acid (PA) conversion coating on AZ61 magnesium alloy was prepared by the method of deposition. The influences of pH, time and PA concentration on the formation process, microstructure and properties of the conversion coating were investigated. Scanning electron microscopy (SEM) was used to observe the microstructure. The chemical nature of conversion coating was investigated by energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques. The corrosion resistance was examined by means of potentiodynamic polarization method. The adhesive ability was tested by score experiments. The results showed that the growth and microstructure of the conversion coatings were all obviously affected by pH, time and PA concentration. In 0.5 mg/ml PA solution with a pH of 5, an optimization conversion coating formed after 20 min immersion time by deposition of PA on AZ61 magnesium alloy surface through chelating with Al³⁺. It made the corrosion potential E_corr of sample shifted positively about 171 mV than that of the untreated sample, and the adhesive ability reached to Grade 1 (in accordance with GB/T 9286).     

Interactions between glycine and amorphous solid water nanoscale films

The interactions of glycine (Gly) with amorphous solid water (ASW) nanolayers (≤ 100 ML), vapor-deposited on single crystalline AlO_x surfaces at 100 K, have been investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K-edge, temperature-programmed thermal desorption (TPD), X-ray photoelectron spectroscopy (XPS), and temperature-dependent work function measurements. Gly-on-ASW, ASW-on-Gly, and Gly on top of ASW-on-Gly ultrathin films have been fabricated. In contrast to the uniform ASW films grown directly on the hydrophilic AlO_x, water molecules adsorb on the hydrophobic Gly films in the form of 3D ASW clusters. This leads to significant differences in the NEXAFS and work function data obtained from ASW-on-AlO_x and ASW-on-Gly films, respectively. Furthermore, these structural differences influence the chemical state of Gly molecules (neutral vs. zwitterionic) adsorbed on top of ASW films. N1s XPS measurements revealed an increased amount of neutral Gly molecules in the film top-deposited on the ASW-on-Gly structure in comparison to the neutral Gly in the films directly condensed on AlO_x or grown on the ASW substrate. H₂O TPD spectra demonstrate that the crystallization and desorption processes of ASW are affected in a different way by the Gly layers, top-deposited on to ASW-on-AlO_x and ASW-on-Gly films. At the same time, Gly adlayers sink into the ASW film during crystallization/desorption of the latter and land softly on the alumina surface in the form of zwitterionic clusters.