Surface analysis and oxidation behavior of Y-ion implanted AZ31 magnesium alloys

AZ31 samples were implanted with yttrium ions with fluences of 5 × 10¹⁶, 1 × 10¹⁷ and 5 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source at an extraction voltage of 45 kV. The surfaces of the implanted samples were then analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It was found that after treatment a pre-oxidation layer was formed, and the higher the fluence, the thicker the pre-oxidation layer was. The valence states showed that yttrium existed in the form of Y₂O₃. Isothermal oxidation tests have been conducted in pure oxygen at 773 K for 90 min to evaluate the oxidation behavior of the implanted samples. The results indicate that after implantation the oxidation resistance of the samples was significantly improved. Moreover, the greater the fluence, the better the oxidation resistance has been achieved. The characterization of the implanted layers after isothermal oxidation was examined by SEM, AES and XPS. From the results, it can be found that the thickness of the oxide scale formed on the implanted surfaces have been greatly decreased, and there is no obvious change for both the thickness of the pre-oxidation layer and the valence states of the elements after oxidation.     

Impact of yttrium ion implantation on corrosion behavior of laser beam welded zircaloy-4 in sulfuric acid solution

In order to study the effect of yttrium ion implantation on the aqueous corrosion behavior of laser beam welded zircaloy-4 (LBWZr4), The butt weld joint of zircaloy-4 was made by means of a carbon dioxide laser, subsequently the LBWZr4 samples were implanted with yttrium ion using a MEVVA source at an energy of 40 keV, with a fluence range from 1 × 10¹⁶ to 4 × 10¹⁶ ions/cm² at about 150 °C. Three-sweep potentiodynamic polarization measurement was employed to evaluate the aqueous corrosion behavior of yttrium-implanted LBWZr4 in a 0.5 M H₂SO₄ solution. Scanning electron microscopy (SEM) was used to examine the surface topographic character of the yttrium-implanted LBWZr4 before and after the potentiodynamic polarization measurement. The valences of the carbon, yttrium, and zirconium in the surface layer were analyzed by X-ray photoemission spectroscopy (XPS). It was found that a significant improvement was achieved in the aqueous corrosion resistance of yttrium-implanted LBWZr4 compared with that of the un-implanted LBWZr4. The mechanism of the corrosion resistance improvement of the yttrium-implanted LBWZr4 is probably due to the addition of the yttrium oxide dispersoid into the zirconium matrix.     

Influence of titanium ions implantation on corrosion behavior of zirconium in 1 M H2SO4

In order to study the effect of titanium ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with titanium ions with fluence ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc (MEVVA) source at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zirconium in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zirconium implanted with titanium ions. The larger the fluence, the better is the corrosion resistance of implanted sample. Finally, the mechanism of the corrosion behavior of titanium-implanted zirconium was discussed.     

Effect of copper ions implantation on corrosion behavior of zircaloy-4 in 1 M H2SO4

In order to study the effect of copper ion implantation on the aqueous corrosion behavior, samples of zircaloy-4 were implanted with copper ions with fluences ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source (MEVVA) operated at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the copper ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-4 in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-4 implanted with copper ions when the fluence is smaller than 5 × 10¹⁶ ions/cm². The corrosion resistance of implanted samples declined with increasing the fluence. Finally, the mechanism of the corrosion behavior of copper-implanted zircaloy-4 was discussed.     

Surface oxidation behavior of MgNd alloys

The oxidation kinetics of MgNd alloys oxidized in pure O₂ at high temperatures has been investigated. The results revealed two stages of the reaction: A fast initial oxidation was followed by a slow oxide growth with a parabolic kinetics. For MgNd alloys (Nd = 25 wt.%), the oxidation rate increased with the enhancement of the oxidation temperature. A sudden ignition was found for this alloys oxidized at 873 K up to about 80 min. Moreover, the increase of the Nd content would harm the oxidation resistance of the MgNd alloys. By Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, it was found that a triplex structure of oxide film formed. The outer layer was composed of MgO, Nd₂O₃ and Nd(OH)₃, the middle layer mainly consisted of MgO and Nd₂O₃, and the inner layer was the transitional layer made of MgO, Nd₂O₃ and the content of the substrate. The protective oxidation was associated with the formation of the dense Nd₂O₃/MgO layer during isothermal oxidation process. The oxidation mechanisms for the formation of oxide film are discussed.     

In vitro corrosion behavior of Ti-O film deposited on fluoride-treated Mg-Zn-Y-Nd alloy

In this paper, a new composite coating was fabricated on magnesium alloy by a two-step approach, to improve the corrosion resistance and biocompatibility of Mg-Zn-Y-Nd alloy. First, fluoride conversion layer was synthesized on magnesium alloy surface by immersion treatment in hydrofluoric acid and then, Ti-O film was deposited on the preceding fluoride layer by magnetron sputtering. FE-SEM images revealed a smooth and uniform surface consisting of aggregated nano-particles with average size of 100 nm, and a total coating thickness of ∼1.5 μm, including an outer Ti-O film of ∼250 nm. The surface EDS and XRD data indicated that the composite coating was mainly composed of crystalline magnesium fluoride (MgF₂), and non-crystalline Ti-O. Potentiodynamic polarization tests revealed that the composite coated sample have a corrosion potential (E_corr) of −1.60 V and a corrosion current density (I_corr) of 0.17 μA/cm², which improved by 100 mV and reduced by two orders of magnitude, compared with the sample only coated by Ti-O. EIS results showed a polarization resistance of 3.98 kΩ cm² for the Ti-O coated sample and 0.42 kΩ cm² for the composite coated sample, giving an improvement of about 100 times. After 72 h immersion in SBF, widespread damage and deep corrosion holes were observed on the Ti-O coated sample surface, while the integrity of composite coating remained well after 7 d. In brief, the data suggested that single Ti-O film on degradable magnesium alloys was apt to become failure prematurely in corrosion environment. Ti-O film deposited on fluoride-treated magnesium alloys might potentially meet the requirements for future clinical magnesium alloy stent application.     

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.     

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.     

纯锆上离子注入钇和镧后的表面分析

用金属蒸汽真空弧源，以40kV加速电压对纯锆样品分别进行了10¹⁶—10¹⁷/cm²的钇、镧离子注入，注入温度约为130℃.然后对注入样品进行表面分析.x射线光电子能谱分析表明，注入的钇以Y₂O₃形式存在，镧以La₂O₃形式存在.俄歇电子能谱表明，纯锆基体表面的氧化膜厚度随着离子注入剂量的增加而增加，当离子注入剂量达到10¹⁷/cm²时，氧化膜的厚度达到了最大值.卢瑟福背散射显示镧层的厚度约为30nm，同时直接观察到当离子注入剂量为(La+Y)10¹⁷/cm²时，纯锆样品表面发生了严重的溅射. 关键词： 纯锆 钇和镧离子共注入 卢瑟福背散射 x射线光电子能谱     

Increase in corrosion resistance of Zn–22Al–2Cu alloy by depositing an Y2O3 film studied by Auger electron spectroscopy

Thin films of Y₂O₃ were deposited on the surface of a zinalco alloy (Zn–22Al–2Cu) in order to modify the surface and increase the corrosion resistance. By means of ion sputtering and surface analysis using Auger electron spectroscopy, in-depth relative elemental intensity profiles were obtained. The growth mechanism of the surface oxides layer is modified by the deposited yttrium oxide film. On samples without film, corrosion progresses mainly at the surface as indicated by the zinc excess, while on samples with film, the growth of the oxides layer occurs at inner points of the film where migrating anions and cations are allowed to find each other. The growth of the corrosion products layer is about nine times smaller in samples with a film of 1600 Å of Y₂O₃ with respect to samples without a film. Migration of aluminum particles is higher than that of zinc particles, producing a surface highly enriched in aluminum.     

Corrosion and wear properties of PEO coatings formed on AM60B alloy in NaAlO2 electrolytes

Coatings with a thickness of 22-32 μm were formed on an AM60B magnesium alloy by plasma electrolytic oxidation (PEO) in electrolytes containing 12.0-24.0 g/l NaAlO₂ and other additives. SEM analyses of the coated samples showed that the coatings were compact with relatively low porosity. X-ray diffraction revealed that the coatings consisted of mainly MgAl₂O₄ and MgO phases. The relative amount of MgAl₂O₄ in the coating increased with increasing NaAlO₂ concentration. The relatively compact and thick coatings provide good corrosion protection for magnesium, as indicated by the results of potentiodynamic polarization tests. In addition, the PEO treatment also significantly improved the wear resistance of the alloy. Pin-on-disk wear tests showed that the PEO treatment reduced the wear volume loss by a factor of 10.     

Influence of treating frequency on microstructure and properties of Al2O3 coating on 304 stainless steel by cathodic plasma electrolytic deposition

Alumina ceramic coatings were fabricated on 304 stainless steel by cathodic plasma electrolytic deposition (CPED). Influence of treating frequency of the power supply on the microstructure and properties of the coatings were studied. The results indicated that coatings obtained at various frequencies on 304 stainless steels were all composed of α-Al₂O₃ and γ-Al₂O₃, and α-Al₂O₃ was the dominant phase. The contents of α-Al₂O₃ decreased gradually in a very small rate with increasing the frequency and γ-Al₂O₃ gradually increased. The surface of alumina ceramic coating was porous. With increasing the frequency, the coating surface gradually became less rough and more compact, resulting in low surface roughness. The bonding strength of Al₂O₃ coating was higher than 22 MPa and was not strongly affected by treating frequency. With increasing the frequency, the alumina coated steels showed better and gradually increasing corrosion resistance than the uncoated one in 3.5% NaCl solution. The coating steel with desirable corrosion resistance was obtained at 800 Hz whose corrosion current potential and corrosion density were −0.237 V and 7.367 × 10⁻⁸ A/cm², respectively.     

The influence of implanted yttrium on the cyclic oxidation behaviour of 304 stainless steel

High-temperature alloys are frequently used in power plants, gasification systems, petrochemical industry, combustion processes and in aerospace applications. Depending on the application, materials are subjected to corrosive atmospheres and thermal cycling. In the present work, thermal cycling was carried out in order to study the influence of implanted yttrium on the oxide scale adherence on 304 steel specimens oxidised in air at 1273 K. In situ X-ray diffraction indicates that the oxides formed at 1273 K are different on blank specimens compared to implanted specimens. Glancing angle XRD allows to analyse the oxide scale composition after cooling to room temperature.Experimental results show that yttrium implantation at a nominal dose of 10¹⁷ ions cm⁻² does not improve significantly the cyclic oxidation behaviour of the austenitic AISI 304 steel. However, it appears that yttrium implantation remarkably enhance the oxidation resistance during isothermal oxidation. It reduces the transient oxidation stage and the parabolic oxidation rate constant by one order of magnitude.     

A novel blue magnesium strontium aluminate-based phosphor for PDP application

A novel blue light-emitting phosphor, Eu²⁺-doped magnesium strontium aluminate (MgSrAl₁₀O₁₇:Eu²⁺), for plasma display panel (PDP) application was developed. X-ray diffraction (XRD) patterns disclosed that the phosphor annealed at 1500 °C for 5 h was a pure MgSrAl₁₀O₁₇ phase. Field emission scanning electron microscopy (FE-SEM) images showed the particle size of the phosphor was less than 3 μm. The phosphor shows strong and broad blue emission under vacuum ultraviolet (VUV) light excitation. After baking at 400-600 °C and irradiation with VUV light for 300 h, the phosphor still keep excellent VUV luminescence properties exhibiting good stability against high temperature baking and VUV irradiation. The decay time was short as 1.09 μs and the quantum yield was high to 0.77±0.02. All the characteristics indicated that MgSrAl₁₀O₁₇:Eu²⁺ would be a promising blue phosphor for PDP application.     

Phase evolution of an aluminized steel by oxidation treatment

Effects of temperature and time on the microstructure and phase evolution for different thermal treatments were investigated with respect to the measurement of intermetallic layer thickness, phase identification and microhardness distribution in the aluminized zone of a steel substrate. The intermetallic phases present in the aluminized region after hot dip aluminizing is mainly Fe₂Al₅. The thickness of the intermetallic layers increases with increasing oxidation temperature and time. In the oxidation treatments of the aluminized steel in air, the initial Fe₂Al₅ phase remains at the temperature below 950 °C in 2-h, and the Fe₂Al₅ phase is completely transformed into low iron content Fe-Al intermetallics due to oxidation at 950 °C for 4 h. However, the Fe₂Al₅ phase remains in the outer layer of the aluminized samples diffusion-treated in vacuum regardless of diffusion time. The microhardness values of the Al₂O₃ and the intermetallic Fe₂Al₅, FeAl₂, FeAl and Fe₃Al phases are HV1150, HV1010, HV810, HV650 and HV320, respectively. The oxide layer formed on the steel substrate has an extremely fast adherence to the steel substrate and excellent properties of thermal shock resistance, high temperature oxidation resistance and anti-liquid aluminum corrosion.     

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.     

Structure and tribological performance by nitrogen and oxygen plasma based ion implantation on Ti6Al4V alloy

Ti6Al4V alloy was implanted with nitrogen-oxygen mixture by using plasma based ion implantation (PBII) at pulsed voltage −10, −30 and −50 kV. The implantation was up to 6 × 10¹⁷ ions/cm² fluence. The changes in chemical composition, structure and hardness of the modified surfaces were studied by XPS and nanoindentation measurements. According to XPS, it was found that the modified layer was predominantly TiO₂, but contained small amounts of TiO, Ti₂O₃, TiN and Al₂O₃ between the outmost layer and metallic substrate. Surface hardness and wear resistance of the samples increased significantly after PBII treatment, the wear rate of the sample implanted N₂-O₂ mixture at −50 kV decreased eight times than the untreated one. The sample implanted N₂-O₂ mixture showed better wear resistance than that of the sample only implanted oxygen at − 50 kV. The wear mechanism of untreated sample was abrasive-dominated and adhesive, and the wear scar of the sample implanted at −50 kV was characterized by abrasive wear-type ploughing.     

Corrosion resistance and blood compatibility of lanthanum ion implanted pure iron by MEVVA

Pure iron is a potential material applying for coronary artery stents based on its biocorrodible and nontoxic properties. However, the degradation characteristics of pure iron in vivo could reduce the mechanical stability of iron stents prematurely. The purpose of this work was to implant the lanthanum ion into pure iron specimens by metal vapor vacuum arc (MEVVA) source at an extracted voltage of 40 kV to improve its corrosion resistance and biocompatibility. The implanted fluence was up to 5 × 10¹⁷ ions/cm². The X-ray photoelectron spectroscopy (XPS) was used to characterize the chemical state and depth profiles of La, Fe and O elements. The results showed lanthanum existed in the +3 oxidation state in the surface layer, most of the oxygen combined with lanthanum and form a layer of oxides. The lanthanum ion implantation layer could effectively hold back iron ions into the immersed solution and obviously improved the corrosion resistance of pure iron in simulated body fluids (SBF) solution by the electrochemical measurements and static immersion tests. The systematic evaluation of blood compatibility, including in vitro platelets adhesion, prothrombin time (PT), thrombin time (TT), indicated that the number of platelets adhesion, activation, aggregation and pseudopodium on the surface of the La-implanted samples were remarkably decreased compared with pure iron and 316L stainless steel, the PT and TT were almost the same as the original plasma. It was obviously showed that lanthanum ion implantation could effectively improve the corrosion resistance and blood compatibility of pure iron.     

Effect of current density on the microstructure and corrosion behaviour of plasma electrolytic oxidation treated AM50 magnesium alloy

Plasma electrolytic oxidation (PEO) of an AM50 magnesium alloy was accomplished in a silicate-based electrolyte using a DC power source. Coatings were produced at three current densities, i.e. 15 mA cm⁻², 75 mA cm⁻², and 150 mA cm⁻² and were characterised for thickness, roughness, microstructural morphology, phase composition, and corrosion resistance. Even though the 15 min treated coatings produced at higher current density levels were thicker, they showed poor corrosion resistance when compared to that of the coatings obtained at 15 mA cm⁻². Short-term treatments (2 min and 5 min) at 150 mA cm⁻² yielded coatings of thickness and corrosion resistance comparable to that of the low current density coatings. The superior corrosion resistance of the low thickness coatings is attributed to the better pore morphology and compactness of the layer.     

The anodization of ZK60 magnesium alloy in alkaline solution containing silicate and the corrosion properties of the anodized films

The anodization of ZK60 magnesium alloy in an alkaline electrolyte of 100 g/l NaOH + 20 g/l Na₂B₄O₇·10H₂O + 50 g/l C₆H₅Na₃O₇·2H₂O + 60g/l Na₂SiO₃·9H₂O was studied in this paper. The corrosion resistance of the anodic films was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques and the microstructure and composition of films were examined by SEM and XRD. The influence of anodizing time was studied and the results show that the anodizing time of 60 min is suitable for acquiring films with good corrosion resistance. The influence of current density on the corrosion resistance of anodizing films was also studied and the results show that the film anodized at 20 mA/cm² has the optimum corrosion resistance. The film formed by anodizing in the alkaline solution with optimized parameters show superior corrosion resistance than that formed by the traditional HAE process. The XRD pattern shows that the components of the anodized film consist of MgO and Mg₂SiO₄.