The enhanced corrosion resistance of UMAO coatings on Mg by silane treatment

The surface silanization was carried out on ultrasonic micro-arc oxidation(UMAO) coatings on pure magnesium using KH550 as silane coupling agent(SCA). The surface morphology, chemical bonds and corrosion resistance of the silane films were investigated by scanning electron microscope(SEM), Fourier transform infrared spectroscopy(FTIR) and electrochemical workstation, respectively. The results showed that hybrid coatings were successfully prepared on pure magnesium by UMAO-Na OH(1 mol/L, 2 mol/L, 3 mol/L)-SCA processing. The organic films with Si–O–Mg bonds are helpful for the reduction of the pores in UMAO coatings. The pores decreased with increasing Na OH concentration. Compared with single UMAO treatment, the corrosion potentials(Ecorr) of magnesium plates with UMAO-Na OH(1 mol/L,2 mol/L, 3 mol/L)-SCA treatment increased by 29 m V, 53 m V and 75 m V, respectively, meanwhile the corrosion current density(Icorr) reduced one to two orders of magnitude. It indicated that the corrosion resistance of the coatings was improved by silane treatment.     

In vitro and in vivo studies on biodegradable magnesium alloy

The microstructure, mechanical property, electrochemical behavior and biocompatibility of magnesium alloy(Bio De MSM^TM) were studied in the present work. The experimental results demonstrated that grain refining induced by extrusion improves the alloy strength significantly from162 MPa for the as-cast alloy to 241 MPa for the as-extruded one. The anticorrosion properties of the as-extruded alloy also increased.Furthermore, the hemolysis ratio was decreased from 4.7% for the as-cast alloy to 2.9% for the as-extruded one, both below 5%. Bio De MSM^TMalloy shows good biocompatibility after being implanted into the dorsal muscle and the femoral shaft of the New Zealand rabbit, respectively, and there are no abnormalities after short-term implantation. In vivo observation indicated that the corrosion rate of this alloy varies with different implantation positions, with higher degradation rate in the femur than in the muscle.     

Corrosion of magnesium and magnesium –calcium alloy in biologically-simulated environment

A study of biocompatibility and corrosion of both metallic magnesium(Mg) and a magnesium alloy containing 1% calcium(Mg–Ca) were investigated in in vitro culture conditions with and without the presence of bone marrow derived human mesenchymal stem cells(h MSCs).Chemical analysis of the degraded samples was performed using XRD and FEGSEM. The results from the XRD analysis strongly suggested that crystalline phase of magnesium carbonate was present on the surface of both the Mg and Mg–Ca samples. Flame absorption spectrometry was used to analyse the release of magnesium and calcium ions into the cell culture medium. Magnesium concentration was kept consistently at a level ranging from 40 to 80 m M for both Mg and Mg–Ca samples. No cell growth was observed when in direct contact with the metals apart from a few cells observed at the bottom of culture plate containing Mg–Ca alloy. In general, in vitro study of corrosion of Mg–Ca in a biologicallysimulated environment using cell culture medium with the presence of h MSCs demonstrated close resemblances to in vivo corrosion. Although in vitro corrosion of Mg–Ca revealed slow corrosion rate and no immediate cytotoxicity effects to h MSCs, its corrosion rate was still too high to achieve normal stem cell growth when cells and alloys were cultured in vitro in direct contact.     

Facile synthesis of nanosized sodium magnesium hydride, NaMgH3

The ternary magnesium hydride NaMgH 3 has been synthesised via reactive milling techniques.The method employed neither a reactive H2 atmosphere nor high pressure sintering or other post-treatment processes.The formation of the ternary hydride was studied as a function of milling time and ball:powder ratio.High purity NaMgH 3 powder(orthorhombic space group Pnma,a 5.437(2),b 7.705(5),c 5.477(2) ;Z 4) was prepared in 5 h at high ball:powder ratios and characterised by powder X-ray diffraction(PXD),Raman spectroscopy and scanning electron microscopy/energy dispersive X-ray spectroscopy(SEM/EDX).The products formed sub-micron scale(typically 200-400 nm in size) crystallites that were approximately isotropic in shape.The dehydrogenation behaviour of the ternary hydride was investigated by temperature programmed desorption(TPD).The nanostructured hydride releases hydrogen in two steps with an onset temperature for the first step of 513 K.     

Corrosion study of resorbable Ca60Mg15Zn25 bulk metallic glasses in physiological fluids

The corrosion activity of amorphous plates of Ca_(60)Mg_(15)Zn_(25)alloy was investigated.The biocompatible elements were selected for the alloy composition.The electrochemical corrosion and immersion tests were carried out in a multi-electrolyte fluid and Ringer's solution.Better corrosion behavior was observed for the samples tested in a multi-electrolyte fluid despite the active dissolution of Ca and Mg in Ringer's solution.The experimental results indicated that reducing concentration of NaCl from 8.6 g/dm~3for Ringer's solution to 5.75 g/dm~3caused the decrease of the corrosion rate.The volume of the hydrogen evolved after 480 min in Ringer's solution(40.1 ml/cm~2)was higher in comparison with that obtained in a multi-electrolyte fluid(24.4 ml/cm~2).The values of opencircuit potential(E_(OCP))for the Ca_(60)Mg_(15)Zn_(25)glass after 1 h incubation in Ringer's solution and a multielectrolyte fluid were determined to be-1553 and-1536 m V vs.a saturated calomel electrode(SCE).The electrochemical measurements indicated a shift of the corrosion current density(j_(corr))from 1062μA/cm~2for the sample tested in Ringer's solution to 788μA/cm~2for the specimen immersed in a multi-electrolyte fluid.The corrosion products analysis was conducted by using the X-ray photoelectron spectroscopy(XPS).The corrosion products were identified to be CaCO_3,Mg(OH)_2,CaO,MgO and Zn O.The mechanism of corrosion process was proposed and described based on the microscopic observations.The X-ray diffraction and Fourier transform infrared spectroscopy(FTIR)also indicated that Ca(OH)_2,CaCO_3,Zn(OH)_2and Ca(Zn(OH)_3)_2·2H_2O mainly formed on the surface of the studied alloy.     

Study on vertical mandibular distraction osteogenesis using magnesium alloy on canine

The bone formation feasibility by a novel magnesium alloy device was evaluated using a canine vertical mandibular distraction osteogenesis(DO) model. Osteotomies were performed in the area where last 3 star’s teeth of left mandibular were pulled out before 3 months. Both AZ31 magnesium alloy(n ? 6) and 316 L stainless steel(n ? 6) distraction devices were implanted. The distraction osteogenesis was carried out with a latency of 5 days after mandibular osteotomy. Distraction proceeded at a rate of 0.3 mm/8 h for 7 days and followed by 4 weeks of consolidations. The evaluations were conducted by scanning electron microscopy(SEM) and histological examinations. There were osteoblasts and trabecular bones formations manifestly in both groups. There was no significant difference in the bone mineral density between the two groups. The surface of the magnesium alloy was much more cracked and uneven, resulting from the surface pitting corrosion. The crew nails were closely combined with the surrounding bone tissue. AZ31 magnesium alloy exhibited a certain degradation rate in mandibular and did not post a negative effect on the kidney and liver. The observations in magnesium alloys group is consistent with the stainless steel group.     

Preparation, microstructure and degradation performance of biomedical magnesium alloy fine wires

With the development of new biodegradable Mg alloy implant devices, the potential applications of biomedical Mg alloy fine wires are realized and explored gradually. In this study, we prepared three kinds of Mg alloy fine wires containing 4 wt% RE(Gd/Y/Nd) and 0.4 wt% Zn with the diameter less than 0.4 μm through casting, hot extruding and multi-pass cold drawing combined with intermediated annealing process. Their microstructures, mechanical and degradation properties were investigated. In comparison with the corresponding as-extruded alloy, the final fine wire has significantly refined grain with an average size of 3–4 μm, and meanwhile shows higher yield strength but lower ductility at room temperature. The degradation tests results and surface morphologies observations indicate that Mg–4Gd–0.4Zn and Mg–4Nd–0.4Zn fine wires have similar good corrosion resistance and the uniform corrosion behavior in SBF solution. By contrast, Mg–4Y–0.4Zn fine wire shows a poor corrosion resistance and the pitting corrosion behavior.     

Corrosion mechanism of micro-arc oxidation treated biocompatible AZ31 magnesium alloy in simulated body fluid

The rapid degradation of magnesium(Mg) based alloys has prevented their further use in orthopedic trauma fixation and vascular intervention,and therefore it is essential to investigate the corrosion mechanism for improving the corrosion resistance of these alloys. In this work, the effect of applied voltage on the surface morphology and the corrosion behavior of micro-arc oxidation(MAO) with different voltages were carried out to obtain biocompatible ceramic coatings on AZ31 Mg alloy. The effects of applied voltage on the surface morphology and the corrosion behavior of MAO samples in the simulated body fluid(SBF) were studied systematically. Scanning electron microscope(SEM) and X-ray diffractometer(XRD)were employed to characterize the morphologies and phase compositions of coating before and after corrosion. The results showed that corrosion resistance of the MAO coating obtained at 250 V was better than the others in SBF. The dense layer of MAO coating and the corrosion precipitation were the key factors for corrosion behavior. The corrosion of precipitation Mg(OH)2and the calcium phosphate(Ca–P) minerals on the surface of MAO coatings could enhance their corrosion resistance effectively. In addition, the mechanism of MAO coated Mg alloys was proposed.     

Preparation of electroless Ni–P composite coatings containing nano-scattered alumina in presence of polymeric surfactant

Ni–P electroless coating was applied on low carbon steel with the incorporation of different amounts of nano Al2O3 powder (ranging from 3 g/l to 30 g/l) in electroless bath. Corrosion properties and microstructures of the coating were studied. The dispersion stability of alumina colloidal particles stabilized by polymeric (non-ionic) surfactants in an electroless bath was also investigated. The surface morphology and the relevant structure were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Corrosion behavior of the coated steel was evaluated by electrochemical impedance spectroscopy (EIS) and polarization techniques. The results showed that increasing alumina concentration not only changed the surface morphology, but also promoted the corrosion resistance. Addition of surfactants has an indirect effect on the amount of the incorporated particles. Meanwhile, in the presence of surfactant, corrosion resistance of Ni–P coating containing even a small quantity of alumina was improved since a stabilized bath was obtained.     

Microstructure heterogeneity and creep damage of DZ125 nickel-based superalloy

The creep behavior of the DZ125 superalloy at high temperatures has been investigated based on the creep properties measurement and microstructure observations. The experimental results show that, after full heat treatment, the fine and coarser cuboidal γ0precipitates distributed in the dendrite arm and inter-dendrite regions, respectively, the boundaries with various configurations located in the inter-dendrite regions. In the primary creep stage, the cuboidal γ0phase in the alloy transformed into the rafted structure along the direction vertical to the stress axis.The dislocations slipping and climbing over the rafted γ0phase are attributed the deformation mechanism of the alloy during steady-state creep.The(1/2)?1 1 0? dislocations slipping in the γ matrix and ?1 1 0? super-dislocations shearing into the γ0phase are the deformation mechanisms of the alloy in the latter stage of creep. And then the alternate slipping of dislocations results in the initiation and propagation of the micro-cracks along the boundaries until the occurrence of the creep fracture. Since the grain boundaries with various angles relative to the stress axis distribute in the different regions, the initiation and propagation of micro-cracks along the boundaries display the various features.& 2014 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.     

Hot corrosion behavior of nanostructured Gd2O3 doped YSZ thermal barrier coating in presence of Na2SO4 + V 2O5 molten salts

Nickel-based superalloy DZ125 was first sprayed with a NiCrAlY bond coat and followed with a nanostructured 2 mol% Gd_2O_3-4.5 mol% Y_2 O_3-ZrO_2(2 GdYSZ) topcoat using air plasma spraying(APS). Hot corrosion behavior of the as-sprayed thermal barrier coatings(TBCs) were investigated in the presence of 50 wt%Na_2SO_4 + 50 wt% V_2O_5 as the corrosive molten salt at 900 ℃ for 100 h. The analysis results indicate that Gd doped YVO_4 and m-ZrO_2 crystals were formed as corrosion products due to the reaction of the corrosive salts with stabilizers(Y_2O_3, Gd_2O_3) of zirconia. Cross-section morphology shows that a thin layer called TGO was formed at the bond coat/topcoat interface. After hot corrosion test, the proportion of m-ZrO_2 phase in nanostructured 2GdYSZ coating is lower than that of nano-YSZ coating. The result reveals that nanostructured 2GdYSZ coating exhibits a better hot corrosion resistance than nano-YSZ coating.     

Surface characteristics and corrosion resistance of biodegradable magnesium alloy ZK60 modifi ed by Fe ion implantati on and deposition

The ZK60 magnesium alloy has been modified by Fe ion implantation and deposition with a metal vapor vacuum arc plasma source. The surface morphology, phase constituent and elemental distribution are determined by scanning electron microscopy, transmission electron microscopy, X-ray diffractometer and Auger electron spectroscopy. The results show that Fe thin film is deposited on ZK60 alloy and the corresponding thickness increases from 2.73 μm to 6.36 μm with increasing deposition time. A transition layer mainly composed of Mg, Fe and O elements is formed between Fe thin film and ZK60 substrate. The potentiodynamic polarization tests reveal that a high corrosion potential and a low corrosion current density are detected for the Fe deposited ZK60 alloy, indicating the improvement of corrosion resistance. The tensile deformation test indicates that the Fe deposited film on the ZK60 substrate can sustain 1% tensile strain without any cracks.     

Bilirubin sensor based on CuO-CdO composites deposited in a nafion/glassy carbon electrode matrixes

Copper oxide-cadmium oxide nanocomposites(CuO-CdO NCs) were synthesized by solvothermal technique in a basic medium. CuO-CdO NCs were characterized using conventional techniques, such as Fourier Transform Infrared Spectroscopy(FTIR), UV–Visible Spectroscopy(UV/Vis), Field-Emission Scanning Electron Microscopy(FESEM), X-ray electron dispersive spectroscopy(XEDS), X-ray photoelectron spectroscopy(XPS), and powder X-ray diffraction(XRD). A selective and enzyme-less Bilirubin(BLR) sensor was developed with a thin-layer of NCs onto a glassy carbon electrode(GCE, surface area = 0.0316 cm~2) using 5% nafion binders at room conditions. Improved electrochemical performances of higher sensitivity, lower detection limit,linear dynamic range(LDR), and long-term stability of preferred BLR were achieved by a reliable currentvoltage(I-V) approach. The calibration curve was found linear(R~2= 0.9347) in a wide range of BLR concentration(10.0 pM ~ 10.0 mM). Based on the signal to noise ratio value of 3, the sensitivity and limit of detection(LOD) of the sensor were calculated as 95.0 pA μM~(-1) cm~(-2) and 1.0 ± 0.1 pM respectively.Solvothermally synthesized CuO-CdO NCs/GCE is an excellent advancement of developing a selective and sensitive BLR sensor by electrochemical approach and practically implemented in real sample applications.     

Improvement of corrosion performance of 316L stainless steel via PVTMS/henna thin film

Metallic materials are the most used materials as orthopedic or dental implants due to their excellent mechanical properties. However they are not able to create a natural bonding with the mineralized bone and occasionally suffer localized corrosion. This work describes the electrochemical behavior of a hybrid sol–gel thin film with the addition of green inhibitor. These films enhance the ability of the implant to make a union with the existing bone and improve its resistance to aggressive environment. An ethanol solution of the polymerized vinyltrimethoxysilane (PVTMS) was mixed with an aqueous solution of henna extract (Lawsonia inermis) and refluxed to give homogeneous sols. Nanostructure hybrid PVTMS/henna thin films were deposited on the stainless steel 316L by spin-coating. The morphology, composition and adhesion of hybrid sol–gel coatings have been examined by SEM, EDX and pull-off test, respectively. Addition of high additive concentrations (0.1%) did not disorganize the sol–gel network. Direct pull-off test recorded a mean coating-substrate bonding strength larger than 20.6 MPa for the hybrid sol–gel coating. The effect of henna extract, with various added concentrations from 0.012% to 0.1%, on the anticorrosion properties of sol–gel films have been characterized by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in simulated body fluid (SBF) solution and has been compared to the bare metal. Henna extract additions (0.05%) have significantly increased the corrosion protection of the sol–gel thin film to higher than 90%. The in vitro bioactivity of prepared films indicates that hydroxyapatite nuclei can form and grow on the surface of the doped sol–gel thin films. The present study shows that due to their excellent anticorrosion properties, bioactivity and bonding strength to substrate, doped sol–gel thin films are practical hybrid films in biomedical applications.     

Degradation of EB-PVD thermal barrier coatings caused by CMAS deposits

In aero-turbine engines, thermal barrier coatings (TBCs) must be capable to withstand harsh environments, such as high-temperature oxidation and hot-corrosion. Recently, a new failure mode of TBCs caused by calcium–magnesium–alumina–silicate (CMAS) glass has attracted increasing attention. In this paper, yttria stabilized zirconia (YSZ) TBCs produced by electron beam physical vapor deposition (EB-PVD) were exposed to CMAS deposits at 1250 1C. The microstructure evolution and failure mechanism of the coatings were investigated. It has been shown that CMAS glass penetrated into the YSZ ceramic layer along the inter-columnar gaps and interacted with YSZ. As a result, an interaction zone of about 20 mm thickness, which was the mixture of CMAS and YSZ with equiaxial structure, was formed in the YSZ surface layer after 4 h heat-treatment at 1250 1C. Meanwhile, yttria in YSZ layer as a stabilizer was dissolved in CMAS glass and caused accelerated monoclinic phase transformation. After 8 h heat-treatment, degradation of YSZ TBC occurred by delamination cracking of YSZ layer, which is quite different from the traditional failure caused by interfacial cracking at the YSZ/metallic bond coat. Physical models have been built to describe the failure mechanism of EB-PVD TBCs attacked by CMAS deposits.     

In vitro degradation and biocompatibility of Mg-Nd-Zn-Zr alloy

In this study,in vitro degradation and biocompatibility of Mg-Nd-Zn-Zr(NZK) alloy were investigated to determine its suitability as a degradable medical biomaterial.Its corrosion properties were evaluated by static immersion test,electrochemical corrosion test,scanning electron microscopy(SEM),and energy dispersive spectroscopic(EDS) analysis,and in vitro biocompatibilities were assessed by hemolysis and cytotoxicity tests.Pure magnesium was used as control.The results of static immersion test and electrochemical corrosion test in simulated body fluid(SBF) demonstrated that the addition of alloying elements could improve the corrosion resistance.The hemolysis test found that the hemolysis rate of calcium phosphate coated NZK alloy was 4.8%,which was lower than the safe value of 5%.The cytotoxicity test indicated that NZK alloy extracts did not significantly reduce MC3T3-E1 cell viability.Hemolysis test and cytotoxicity test display excellent hemocompatibility and cytocompatibility of NZK alloy in vitro.Our data indicate that NZK alloy has excellent biocompatibility and thus can be considered as a potential degradable medical biomaterial for orthopedic applications.     

Optimization of dual effects of Mg– 1Ca alloys on the behavior of chondrocytes and osteoblasts in vitro

Mg ions can enhance the proliferation and redifferentiation of chondrocytes and the osteogenic differentiation of osteoblasts at specific concentrations, respectively. However, degradation of Mg alloys at varying degradation rates could lead to complex changes in the surrounding tissue environment, such as changes in the dynamic concentration of Mg ions and subsequent p H value. Considering the above mentioned factors, the comprehensive effects of Mg alloys on chondrocytes and osteoblasts behaviors have not yet been optimized. In this study, we evaluated the effects of Mg–1Ca microspheres on cell behavior with an aim to optimize conditions favorable for both cell types. Cells were cultured with Mg–1Ca microspheres prepared using the following concentrations: 250 μg/ml, 500 μg/ml and 1000 μg/ml. At specific time points,cytotoxicity, expression of specific genes and extracellular matrix deposition by cells(Alizarin Red Staining of osteoblasts and Alcian blue staining for chondrocytes) were evaluated. The experimental results revealed that Mg–1Ca microspheres prepared at a concentration of 250 μg/ml were optimum for both cell types, where chondrocytes were found to be in hypertrophy state while osteoblasts in close proximity to the microspheres showed osteogenetic differentiation. Interestingly, a slight change in osteoblasts behavior was observed nearer to and at a relative distance away from Mg–1Ca microspheres, an important observation for administering the application of microspheres as potential scaffolds.     

Addition of IrO2 to RuO2+TiO2 coated anodes and its effect on electrochemical performance of anodes in acid media

Ternary mixed metal oxide coatings with the nominal composition IrxRu(0.6-x)Ti0.4O2(x=0, 0.1, 0.2, 0.3) on the titanium substrate were prepared by thermal decomposition of a chloride precursor mixture. Surface morphology and microstructure of the coatings were investigated by Scanning electron microscopy(SEM), Field emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) analysis. Systematic study of electrochemical properties of these coatings was performed by cyclic voltammetry(CV) and polarization measurements. The corrosion behavior of the coatings was evaluated under accelerated conditions(j=2 A cm-2) in acidic electrolyte. The role of iridium oxide admixture in the change of electrocatalytic activity and stability of Ru0.6Ti0.4O2coating was discussed. Small addition of IrO2can improve the stability of the RuO2+TiO2mixed oxide, while the electrocatalytic activity for oxygen evolution reaction(OER) is decreased. The shift of redox potentials for Ru0.6Ti0.4O2electrode that is slightly activated with IrO2and improvement in the stability can be attributed to the synergetic effect of mixed oxide formation.     

Structure and properties of solid-state synthesiz ed poly (3,4-propylenedi oxythiophene) /nano-ZnO composite

Poly（3,4-propylenedioxythiophene）/nano-Zinic Oxide（PProDOT/ZnO） composites with the content of 3-7 wt%nano-ZnO were synthesized by the solid-state method with FeCl₃ as oxidant.The structure and morphology of the composites were characterized by Fourier transform infrared（FTIR）spectroscopy,ultraviolet-visible（UV-vis） absorption spectroscopy,X-ray diffraction（XRD） and transmission electron microscopy（TEM）.The electrochemical performances of the composites were investigated by galvanostatic charge-discharge,cyclic voltammetry and electrochemical impedance spectroscopy（EIS）.The photocatalytic activities of the composites were investigated by the degradation of methylene blue（MB） dyes in aqueous medium under UV light irradiation.The results from FTIR and UV-vis spectra showed that the PProDOT/ZnO composites were successfully synthesized by solid-state method,and nano-ZnO had great influences on the conjugation length and oxidation degree of the polymers.Furthermore,the PProDOT/5 wt%ZnO had the highest conjugation and oxidation degree among the composites.The results of XRD analysis indicated that there were some FeCl₄^- ions as doping agent in the PProDOT matrix,and the content of ZnO had no effect on diffraction pattern of PProDOT.Morphological studies revealed that the pure PProDOT and composites had similar morphological structure,and all the composites displayed an irregular sponge like morphology.The results of electrochemical tests showed that the PProDOT/5 wt%ZnO had a higher electrochemical activity with a specific capacitance value of 220 F g^-1 than others.The results from photocatalytic activities of the composites indicated that the PProDOT/5 wt%ZnO had better photocatalytic activity than other composites.     

Grain size-dependent electrical resistivity of bulk nanocrystalline Gd metals

The electrical resistivity of the as-consolidated and coarse-grained bulk gadolinium(Gd) metals was studied in the temperature range of 3-315K.The experimental results showed that with decrease in the grain size of Gd grains from micrometer to nanometer range,the room temperature electrical resistivity increased from 209.7 to 333.0 μΩcm,while the electrical resistivity at the low temperature of 3K was found to increase surprisingly from 16.5 to 126.3 μΩcm.The room temperature coefficient resistivity(TCR) values were obtained as 39.2×10-3,5.51×10-3 and 33.7×10-3K-1.The ratios of room temperature to residual resistivity [RRR=ρ(300K)/ρ(3K)] are 2.64,11.0,respectively,for the as-consolidated samples at 280℃ and 700℃ with respect to that of the coarse-grained sample.All results indicate the remarkable influence of the nanostructure on the electrical resistivity of Gd due to the finite size effect and large fraction of grain boundaries.