Studies of the porosity in electroless nickel deposits on magnesium alloy

In the present paper, the porosity of the plating coating was evaluated by the combination of corrodkote and filter paper, the effects of the plating solution on the porosity were investigated, and the properties of the porous coatings were studied through scanning electron microscopy (SEM) and electrochemical potentiodynamic polarization. The results show that the eriothrome black T indicator used as an indicator of the coating porosity for coatings on magnesium alloy is more effective than magneson indicator and sodium alizarinesulfonate indicator. The porosity in electroless nickel deposits on magnesium alloy was well evaluated by the combination of corrodkote and filter paper. It is revealed that the pores exist on both grain surface and grain boundaries. An affecting trend of the plating bath parameters on the coating porosity was obtained.     

A novel process for electroless nickel plating on anodized magnesium alloy

In this paper, a novel palladium-free activation electroless nickel (EN) plating process, by which a TiB₂ powders contained intermediate film was used as catalyst, was introduced for anodized magnesium alloy AZ91D. The corrosion behavior of AZ91D without and with coating was compared and the bonding strength of the EN plating to the substrate was also measured. The results showed that the EN plating could easily take place on the intermediate catalytic layer, directly on which a smooth and compact Ni–P alloy layer without obvious flaws, about 20 μm thickness, was successfully deposited. The catalytic function was principally from TiB₂ powder. The adhesive tensile test indicated a good bonding strength of about 11 MPa between the substrate and the catalytic layer. An obvious passivation range and higher E_corr (−0.323 V) for the EN plating during anodic polarization in 3.5 wt.% NaCl solution, implied a typical character of a compact Ni–P alloy layer, with an effective protection for the substrate.     

XPS study of the surface chemistry on AZ31 and AZ91 magnesium alloys in dilute NaCl solution

The surface chemistry on AZ31 and AZ91 magnesium alloys was characterized by X-ray photoelectron spectroscopy (XPS) in the corrosion and the passivation zones. In the corrosion zone, the presence of Mg(OH)₂ and MgCO₃ species was found in the outer surface, whereas, in the inner layer, the co-existence of Mg(OH)₂, MgO and MgCO₃ species was observed for both alloys. The presence of Al³⁺ in the surface electrolyte to form Al₂O₃/Al(OH)₃ and the formation of carbonate product provide a better passivation on the surfaces and retard the chloride-induced corrosion on the materials in the passivation zone.     

Characterization of ceramic PVD thin films on AZ31 magnesium alloys

Ceramic thin films have been widely used to protect the metal substrate as coatings in the past years. In order to improve the poor corrosion resistance of AZ31 magnesium alloy, the study in this paper used the electron beam evaporation method to prepare ceramic PVD films on its surface with TiO₂ and Al₂O₃ as donors, respectively. Atomic force microscopy (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES) and X-ray diffraction (XRD) were used to investigate the surface morphology, composition and microstructure of the thin films. Both films deposited on AZ31 took on compact top surface morphologies and grew as amorphous structures on substrate. AES test not only showed that films compositions deviated the standard stoichiometric ratios, but also found that element Mg diffused into films and existed as magnesium oxide in the TiO_x film as well as the AlO_x film. In the electrochemical corrosion test, the AlO_x coating on AZ31 exhibited the largest electrochemical impedance in a 3.5% NaCl solution. But it did not show better corrosion resistance than others for the poorer adhesion. Even if its thickness was small, the TiO_x coating on AZ31 exhibited the best corrosion resistance in this study. According to the observation and analysis, the damage of these films on AZ31 in aggressive solutions was mainly due to the existence of pores, microcracks, vacancies and poor adhesion between coating and substrate.     

Modelling of CO2 laser welding of magnesium alloys

Laser welding is an important joining process for magnesium alloys. These materials are being increasingly used in different applications such as in aerospace, aircraft, automotive, electronics, etc. To date, carbon dioxide (CO₂) neodymium-doped yttrium aluminum garnet (Nd:YAG) and the high power diode laser have been extensively used to investigate the weldability of magnesium alloys. The present work describes an analytical thermal model for the weldability of magnesium alloys (WE43) using an industrial (CO₂) laser source. The main target of the project is to present to the industrial community a simple and rapid tool for the determination of the penetration depth and the bead width as a function of both the incident laser power and welding speed. The proposed model is based on the Davis thermal approach, largely considered for the characterization of the average radius of the liquid zone, aiming at predicting the joint shape. Moreover, since during the welding process considered in this study, a protecting gas is used to avoid joint oxidation, both thermal convection and radiation phenomena in the welding area have been estimated and introduced in our model for a better characterization of the welding process. The obtained results have been compared to the experimental ones and a satisfactory correlation has been observed, indicating the reliability of the model developed in this study.     

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.     

Studies on the influence of surface pre-treatments on electroless copper coating of boron carbide particles

Boron carbide is one of the hard ceramic particles which find application as structural materials and neutron shielding material due to its high neutron capture cross section. Copper coating on boron carbide particle is essential for the synthesis of metal-ceramic composites with enhanced sinterability and dispersibility. Surface characteristics of the substrate and the coating parameters play a foremost role in the formation of effective electroless coating. The effect of surface pre-treatment conditions and pH on electroless copper coating of boron carbide particles has been studied. Surface pre-treatement of B₄C when compared to acid treated and alkali treated particles were carried out. Uniform copper coating was observed at pH 12 in alkali treated particles when compared to others due to the effective removal of inevitable impurities during the production and processing of commercially available B₄C. A threshold pH 11 was required for initiation of copper coating on boron carbide particles. The growth pattern of the copper coating also varies depending on the surface conditions from acicular to spherical morphology.     

Comparison of coating properties obtained by MAO on magnesium alloys in silicate and phytic acid electrolytes

Anodic coatings were prepared by using microarc oxidation (MAO) on AZ91HP in silicate containing solution (Si-solution) and phytic acid containing solution (P-solution), respectively. The influence of the electrolytes on coating structure, morphology and composition was studied by using X-ray diffraction (XRD), environmental scanning electron microscope (ESEM) and energy dispersive X-ray spectroscopy (EDX). Potentiodynamic polarization test and immersion test were employed to evaluate the corrosion resistance of anodic coatings. Different electrolytes caused the differences in the MAO process and coating properties. The breakdown voltage and the final voltage in P-solution were higher than those in Si-solution. The pore uniformity of anodic coatings obtained in Si-solution (Si-film) was worse than that in P-solution (P-film). XRD analyses indicated that Si-film was amorphous, while P-film consisted of MgO. The corrosion resistance of the sample coated with P-film was better than that with Si-film.     

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.     

Study of magnesium and aluminum alloys absorption coefficient during Nd:YAG laser interaction

In laser processes, the absorption factor of laser Nd:YAG by metals plays a very important role. In order to model laser welding, we need to know its evolution during the process. The theoretical calculation does not enable the prediction of the absorption factor in the case of a keyhole mode. It is difficult to predict the effect of plasma and recoil pressure on the shape of the keyhole. In this paper, an integrating sphere is used to determine the absorption factor during the laser process, which is carried out on two types of magnesium alloys (WE43 and RZ5) and an aluminum alloy. We obtain the evolution in time of the absorption factor according to different steps of the evolution of the keyhole.     

Effect of the chemistry and structure of the native oxide surface film on the corrosion properties of commercial AZ31 and AZ61 alloys

The purpose of this study has been to advance in knowledge of the chemical composition, structure and thickness of the thin native oxide film formed spontaneously in contact with the laboratory atmosphere on the surface of freshly polished commercial AZ31 and AZ61 alloys with a view to furthering the understanding of protection mechanisms. For comparative purposes, and to more fully describe the behaviour of the native oxide film, the external oxide films formed as a result of the manufacturing process (as-received condition) have been characterised. The technique applied in this research to study the thin oxide films (thickness of just a few nanometres) present on the surface of the alloys has basically been XPS (X-ray photoelectron spectroscopy) in combination with ion sputtering. Corrosion properties of the alloys were studied in 0.6 M NaCl by measuring charge transfer resistance values, which are deduced from EIS (electrochemical impedance spectroscopy) measurements after 1 h of exposure. Alloy AZ61 generally showed better corrosion resistance than AZ31, and the freshly polished alloys showed better corrosion resistance than the alloys in as-received condition. This is attributed to a combination of (1) higher thickness of the native oxide film on the AZ61 alloy and (2) greater uniformity of the oxide film in the polished condition. The formation of an additional oxide layer composed by a mixture of spinel (MgAl₂O₄) and MgO seems to diminish the protective properties of the passive layer on the surface of the alloys in as-received condition.     

Characterisation of precipitate phases in magnesium alloys using electron microdiffraction

Recent results of the characterisation of the structure, morphology and orientation of fine-scale, strengthening precipitate phases in selected magnesium alloys using transmission electron microscopy and microdiffraction are reviewed. The strengthening precipitate phases in Mg–Y–Nd alloys, aged to maximum hardness at 250°C, have been found to include two metastable precipitate phases β′ and β₁, and the equilibrium precipitate β. The β′ phase has a globular form, a base-centred orthorhombic structure (potential point group of mmm), and an orientation relationship such that (100)_β′//(1 10)_α, [001]_β′//[0001]_α. The β₁ phase has an f.c.c. structure (space group and an orientation relationship that may be described by (100)_β1//[0001]_α, and forms as plates parallel to The β phase has an f.c.c. structure (space group ) and also forms as plates on with an orientation relationship with the matrix phase that is identical to that observed for β₁ phase. Precipitates in Mg–Al alloys, aged isothermally at 200°C, invariably have the b.c.c. structure of the equilibrium precipitate phase β (Mg₁₇Al₁₂). Three orientation relationships have been observed between β and the matrix phase. Most precipitates have an irrational orientation relationship that approximates to the Burger's relationship, (001)_β//(0001)_α, and a faceted lath morphology with habit plane parallel to (0001)_α. A minor fraction of precipitates posses an orientation relationship that is of the form

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and have a prismatic rod morphology. The long axes of these rods are parallel to [0001]_α, and their faceted surfaces are parallel to A few precipitates are observed to have an orientation relationship such that

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and a rod shape, with their long axes apparently inclined with respect to [0001]_α.     

Electroless deposition of Ni-W-P coating on AZ91D magnesium alloy

Ternary Ni-W-P alloy coating was deposited directly on AZ91D magnesium alloy by using an alkaline-citrate-based baths. Nickel sulfate and sodium tungstate were used as metal ion sources, respectively, and sodium hypophosphite was used as a reducing agent. The pH value of the electroless bath was tailored for magnesium alloy. The coating was characterized for its structure, morphology, microhardness and the corrosion properties. SEM observation showed the presence of dense and coarse nodules in the ternary coating. EDS analysis showed that the content of tungsten in the Ni-W-P alloy was 4.5 wt.%. Both the electrochemical analysis and the immersion test in 10% HCl solution revealed that the ternary Ni-W-P coating exhibited good corrosion resistance properties in protecting the AZ91D magnesium alloy.     

Experimental study of the voids in the electroless copper deposits and the direct measurement of the void fraction based on the scanning electron microscopy images

Electroless copper deposits were plated on epoxy substrates in various plating solutions at either a high operating temperature (60 °C) or a low one (45 °C). Cross section samples were made using epoxy resin cured in room temperature, and then ground, polished and over-etched. The scanning electron microscopy (SEM) images of the over-etched cross section samples show voids in low temperature deposits and solid structure in high temperature ones. The surface morphology images also indicated such structures in low temperature samples. The SEM image of the cross section of a stand-alone deposit prepared on stainless steel substrate shows similar voids observed on etched cross section samples on epoxy board substrates. An image processing program was written using MATLAB to identify the voids in the over-etched cross sections of the deposits from low temperature solutions and thus the void fraction can be directly measured and compared with the previously published simulation results.     

Yttrium ion implantation on the surface properties of magnesium

Owing to their excellent physical and mechanical properties, magnesium and its alloys are receiving more attention. However, their application has been limited to the high reactivity and the poor corrosion resistance. The aim of the study was to investigate the beneficial effects of ion-implanted yttrium using a MEVVA ion implanter on the surface properties of pure magnesium. Isothermal oxidation tests in pure O₂ at 673 and 773 K up to 90 min indicated that the oxidation resistance of magnesium had been significantly improved. Surface morphology of the oxide scale was analyzed using scanning electron microscope (SEM). Auger electron spectroscopy (AES) and X-ray diffraction (XRD) analyses indicated that the implanted layer was mainly composed of MgO and Y₂O₃, and the implanted layer with a duplex structure could decrease the inward diffusion of oxygen and reduce the outward diffusion of Mg²⁺, which led to improving the oxidation resistance of magnesium. Potentiodynamic polarization curves were used to evaluate the corrosion resistance of the implanted magnesium. The results show yttrium implantation could enhance the corrosion resistance of implanted magnesium compared with that of pure magnesium.     

Effect of solute atoms on fracture toughness in dilute magnesium alloys

The effect of alloying elements on the toughness and the fracture behaviour was investigated on seven kinds of Mg-0.3?at.% X (X?=?Ag, Al, Ca, Pb, Sn, Y and Zn) alloys with a grain size of 3–5?μm. The fracture toughness and fracture behaviour in magnesium alloys were closely related to the segregation energy. The Mg–Al and –Zn alloys that had small segregation energy showed high toughness and ductile fracture in most regions, while the Mg–Ca alloy with large segregation energy exhibited low toughness and intergranular fracture. These different tendencies resulted from solute segregation at grain boundaries (GBs). The change in the lattice parameter ratio was the influential material parameter regardless of whether the GB embrittlement was for enhancement or suppression.     

各向异性场对非晶态合金应力阻抗效应的影响

在非晶态合金材料中引入应力感生各向异性场及磁各向异性场,根据Maxwell方程组及带Gilbert项的Landau-Lifshitz方程,得到了能揭示非晶态合金材料应力阻抗效应的理论,理论结果可定性地解释实验结果. 对不同各向异性场参数下的应力阻抗效应进行了大量计算,获得了一些对理论和应用具有一定参考价值的结论. 关键词： 应力阻抗效应 应力感生各向异性 横向有效磁导率 非晶态合金     

Effect of temperature on the anisotropy of AZ31 magnesium alloy rolling sheet under high strain rate deformation

In order to investigate the effect of temperature on the anisotropic behaviour of AZ31 magnesium alloy rolling sheet under high strain rate deformation, the Split Hopkinson Pressure Bar was used to analyse the dynamic mechanical properties of AZ31 magnesium alloy rolling sheet in three directions, rolling direction(RD), transverse direction (TD) and normal direction (ND). The texture of the rolling sheet was characterised by X-ray analysis and the microstructure prior and after high strain rate deformation was observed by optical microscope (OM). The results demonstrated that AZ31magnesium alloy rolling sheet has strong initial {0?0?0?2} texture, which resulted at the obvious anisotropy in high strain rate deformation at 20 °C. The anisotropy reflected in stress–strain curve, yield stress, peak stress and microstructure. The anisotropy became much weaker when the deformation temperature increased up to 250 °C. Continuing to increase the deformation temperature to 350 °C the anisotropy of AZ31 rolling sheet essentially disappeared. The decreasing tendency of anisotropy with increasing temperature was due to the fact that when the deformation temperature increased, the critical resolved shear stress (CRSS) for pyramidal 〈c + a〉 slip, which was the predominant slip mechanism for ND, decreased close to that of twinning, which was the predominant deformation mechanism for RD and TD. The deformation mechanism at different directions and temperatures and the Schmid factor (SF) at different directions were discussed in the present paper.     

The surface tension of liquid Cu-Fe-Sb alloys

The results of study on the influence of temperature and iron and antimony on the surface tension of liquid ternary Cu-Fe-Sb systems are presented. The measurements were carried out with the sessile drop method, in a broad range of the alloy additions concentration (Fe and Sb). It was demonstrated that the surface tension varies as a linear function of temperature and concentration of iron. It was also demonstrated that antimony, in examined alloys, shows the properties characteristic of a surface-active substance, significantly reducing the surface tension value. The changes of the surface tensions as a function of concentration of antimony were described with the Szyszkowski's equation. Composition of surface layer, enriched with an antimony, was determined basing on the model, which used data regarding properties of binary systems. The surface tension values of Cu-Fe-Sb systems was also computed from model and compared with experimental data. A good agreement was obtained.     

The surface modified composite layer formation with boron carbide particles on magnesium alloy surfaces through pulse gas tungsten arc treatment

A novel fabrication process of surface modified composite layer by pulse current gas tungsten arc (GTA) surface modification process was used to deposit B₄C particles on the surface of magnesium alloy AZ31. This method is an effective technique in producing a high performance surface modified composite layer. During the pulse current GTA surface modification process, considerable convection can exist in the molten pool due to various driving forces and the pulse current could cause violent stirring in the molten pool, and the large temperature gradient across the boundary between the GTA modified surface and matrix metal resulted in rapid resolidification with high cooling rates in the molten pool, so that the process result notable grain refinement in the GTA surface modified composite layer. The hardness and wear resistance of the GTA surface modified composite layer are superior to that of as-received magnesium alloy AZ31. The hardness values and wear resistance of GTA surface modified composite layer depend on the GTA process parameters and the B₄C particles powder concentration and distribution. The optimum processing parameters for the formation of a homogeneous crack/defect-free and grain refinement microstructure were established.