Effects of solidifi cation cooling rate on the corrosion resistance of Mg – Zn–Ca alloy

This study was carried out to investigate the effect of solidification cooling rate on the corrosion resistance of an Mg–Zn–Ca alloy developed for biomedical applications. A wedge shaped copper mould was used to obtain different solidification cooling rates. Electrochemical and immersion tests were employed to measure the corrosion resistance of Mg–Zn–Ca alloy. It was found that increasing cooling rate resulted in a significant improvement in the corrosion resistance of the Mg–Zn–Ca alloy. The findings were explained in terms of solidification behaviour in association with the change in solubility of the alloying elements, microstructural homogeneity and refinement and chemical homogeneity as well as the increased cooling rates.     

In fl uence of HEPES buffer on the local pH and formation of surface layer during in vitro degradation tests of magnesium in DMEM

The human body is a buffered environment where p H is effectively maintained. HEPES is a biological buffer often used to mimic the buffering activity of the body in in vitro studies on the degradation behavior of magnesium. However, the influence of HEPES on the degradation behavior of magnesium in the DMEM pseudo-physiological solution has not yet been determined. The research aimed at elucidating the degradation mechanisms of magnesium in DMEM with and without HEPES. The morphologies and compositions of surface layers formed during in vitro degradation tests for 15–3600 s were characterized. The effect of HEPES on the electrochemical behavior and corrosion tendency was determined by performing electrochemical tests. HEPES indeed retained the local p H, leading to intense intergranular/interparticle corrosion of magnesium made from powder and an increased degradation rate. This was attributed to an interconnected network of cracks formed at the original powder particle boundaries and grain boundaries in the surface layer, which provided pathways for the corrosive medium to interact continuously with the internal surfaces and promoted further dissolution. Surface analysis revealed significantly reduced amounts of precipitated calcium phosphates due to the buffering activity of HEPES so that magnesium became less well protected in the buffered environment.     

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.     

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.     

摩擦表面合金化法开发一种 Mg–Zn 表面合金:模拟体液中的体外降解研究

A new variant of friction-assisted process named friction surface alloying (FSA) for developing surface alloys was demonstrated in the present work. In FSA, the dispersed phase is melted and allowed to react with the matrix material to form an alloy at the surface of a metallic substrate. In the present work, magnesium (Mg) sheets and zinc (Zn) powder were selected, and fine grained (~3.5 μm) Mg–Zn surface alloy with improved hardness was produced by FSA. X-ray diffraction studies confirmed the formation of intermetallic phases of Mg and Zn at the surface. From the in vitro degradation studies carried out by immersing in simulated body fluids, a lower corrosion rate was observed for the Mg–Zn surface alloy compared with pure Mg. The surface morphologies after immersion studies indicated large degraded areas on the base Mg compared with Mg–Zn. The results demonstrate the potential of FSA in developing Mg-based surface alloys without melting the substrate to impart better surface properties.     

Developing Mg–Zn surface alloy by friction surface allosying: In vitro degradation studies in simulated body fluids

A new variant of friction-assisted process named friction surface alloying(FSA) for developing surface alloys was demonstrated in the present work. In FSA, the dispersed phase is melted and allowed to react with the matrix material to form an alloy at the surface of a metallic substrate. In the present work, magnesium(Mg) sheets and zinc(Zn) powder were selected, and fine grained(～3.5 μm) Mg–Zn surface alloy with improved hardness was produced by FSA. X-ray diffraction studies confirmed the formation of intermetallic phases of Mg and Zn at the surface. From the in vitro degradation studies carried out by immersing in simulated body fluids, a lower corrosion rate was observed for the Mg–Zn surface alloy compared with pure Mg. The surface morphologies after immersion studies indicated large degraded areas on the base Mg compared with Mg–Zn. The results demonstrate the potential of FSA in developing Mg-based surface alloys without melting the substrate to impart better surface properties.     

In vitro corrosion of Mg–1.21Li –1.12Ca –1Y alloy

The influence of the microstructure on mechanical properties and corrosion behavior of the Mg–1.21Li–1.12Ca–1Y alloy was investigated using OM, SEM, XRD, EPMA, EDS, tensile tests and corrosion measurements. The results demonstrated that the microstructure of the Mg–1.21Li–1.12Ca–1Y alloy was characterized by α-Mg substrate and intermetallic compounds Mg2 Ca and Mg24Y5. Most of the fine Mg2 Ca particles for the as-cast alloy were distributed along the grain boundaries, while for the as-extruded along the extrusion direction. The Mg24Y5 particles with a larger size than the Mg2 Ca particles were positioned inside the grains. The mechanical properties of Mg–1.21Li–1.12Ca–1Y alloy were improved by the grain refinement and dispersion strengthening. Corrosion pits initiated at the α-Mg matrix neighboring the Mg2 Ca particles and subsequently the alloy exhibited general corrosion and filiform corrosion as the corrosion product layer of Mg(OH)2and Mg CO3 became compact and thick.     

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.     

PLGA/硬石复合涂层镁基纳米复合材料在植入应用时的体外生物活性和腐蚀行为

A type of polymer/ceramic coating was introduced on a magnesium-based nanocomposite, and the nanocomposite was evaluated for implant applications. The microstructure, corrosion, and bioactivity of the coated and uncoated samples were assessed. Mechanical alloying followed by sintering was applied to fabricate the Mg–3Zn–0.5Ag–15NiTi nanocomposite substrate. Moreover, different contents of poly(lactic-co-glycolic acid) (PLGA) coatings were studied, and 10wt% of PLGA content was selected. The scanning electron microscopy (SEM) images of the bulk nanocomposite showed an acceptable homogenous dispersion of the NiTi nanoparticles (NPs) in the Mg-based matrix. In the in vitro bioactivity evaluation, following the immersion of the uncoated and coated samples in a simulated body fluid (SBF) solution, the Ca/P atomic ratio demonstrated that the apatite formation amount on the coated sample was greater than that on the uncoated nanocomposite. Furthermore, assessing the corrosion resistance indicated that the coatings on the Mg-based substrate led to a corrosion current density (i_corr) that was considerably lower than that of the substrate. Such a condition revealed that the coating would provide an obstacle for the corrosion. Based on this study, the PLGA/hardystonite (HT) composite-coated Mg–3Zn–0.5Ag–15NiTi nanocomposite may be suitably applied as an orthopedic implant biomaterial.     

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.     

Engineered polycaprolactone – magnesium hybrid biodegradable porous scaffold for bone tissue engineering

In this paper, we describe the fabrication of a new biodegradable porous scaffold composed of polycaprolactone(PCL) and magnesium(Mg)micro-particles. The compressive modulus of PCL porous scaffold was increased to at least 150% by incorporating 29% Mg particles with the porosity of 74% using Micro-CT analysis. Surprisingly, the compressive modulus of this scaffold was further increased to at least 236% when the silane-coupled Mg particles were added. In terms of cell viability, the scaffold modified with Mg particles significantly convinced the attachment and growth of osteoblasts as compared with the pure PCL scaffold. In addition, the hybrid scaffold was able to attract the formation of apatite layer over its surface after 7 days of immersion in normal culture medium, whereas it was not observed on the pure PCL scaffold. This in vitro result indicated the enhanced bioactivity of the modified scaffold. Moreover, enhanced bone forming ability was also observed in the rat model after 3 months of implantation. Though bony in-growth was found in all the implanted scaffolds. High volume of new bone formation could be found in the Mg/PCL hybrid scaffolds when compared to the pure PCL scaffold. Both pure PCL and Mg/PCL hybrid scaffolds were degraded after 3 months. However, no tissue inflammation was observed. In conclusion, these promising results suggested that the incorporation of Mg micro-particles into PCL porous scaffold could significantly enhance its mechanical and biological properties. This modified porous bio-scaffold may potentially apply in the surgical management of large bone defect fixation.     

Microstructure characterization of early corrosion behavior of AM60B magnesium alloys

The microstructures and corrosion behavior of AM60B magnesium alloys, produced by both high-pressure die casting (HPDC) and super vacuum die casting (SVDC) processes, were investigated by a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), and slow positron beam technique. XRD confirmed that calcium carbonate (CaCO3) deposited on the surface of alloys during the early stages of corrosion, and the deposition rate of CaCO3 for SVDC with corrosion time was slower than that of HPDC. SEM observation found that the -phases in the skin surface of SVDC alloy had a greater volume fraction and more continuous distribution than that of HPDC alloy, leading to lower volume fraction of CaCO3 deposited on surface of SVDC alloy for the same corrosion time. The slow positron beam Doppler broadening measurement revealed that the thickness of surface corrosion layer increased with corrosion time. Compared with HPDC alloy, the increase rate of thickness for SVDC alloy is slower, which implied that SVDC alloy exhibited a better corrosion resistance than HPDC alloy.     

Surface modification of Ti-49.8at%Ni alloy by Ti ion implantation：phase transformation,corrosion, and cell behavior

The Ti?49.8at%Ni alloy was modified by Ti ion implantation to improve its corrosion resistance and biocompatibility. The chemical composition and morphologies of the TiNi alloy surface were determined using atomic force microscopy (AFM), auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The results revealed that Ti ion implantation caused the reduction of Ni concentration and the formation of a TiO2 nano-film on the TiNi alloy. The phase transformation temperatures of the Ti–TiNi alloy remained almost invariable after Ti ion implantation. Electrochemical tests indicated that the corrosion resistance of TiNi increased after Ti ion im-plantation. Moreover, the Ni ion release rate in 0.9% NaCl solution for the TiNi alloy remarkably decreased due to the barrier effect of the TiO2 nano-film. The cell proliferation behavior on Ti-implanted TiNi was better than that on the untreated TiNi after cell culture for 1 d and 3 d.     

In fl uence of the extraction parameters on the cytotoxicity test results of Mg materials

Recently more and more researchers query the predictability of cytotoxicity results of biomedical Mg alloys obtained according to ISO 10993 due to significant difference between in vitro and in vivo corrosion. This study aimed to observe the influence of different extraction parameters(time, volume/surface ratio and medium composition) on cytotoxicity results and illustrate whether more predictable results could be obtained by adjusting the extraction parameters. The results showed that longer extraction time and smaller extraction volume/surface ratio improve the sensitivity of screening Mg materials by making inferior Mg materials release relatively more ions to the extract; and more predictable results could not be obtained by the way of simply adding bovine serum albumin(BSA) into the extraction medium to the same level in vivo or simply using fetal bovine serum(FBS) directly as extraction medium, since BSA and FBS accelerated the corrosion of Mg materials during extraction and they affected the cells’ health states during the test. In order to get more predictable results, in our opinions, it is necessary to establish a database of primary cells’ hazards(metal ions, p H and H2gas) tolerance and a set of in vitro corrosion test with high similarity in vivo, which is very difficult to realize now however.     

The molecular mechanism of embryonic stem cell pluripotency maintenance

In vitro cultured embryonic stem （ES） cells are derived from the inner cell mass （ICM） of pre-implantation embryos, and are capable of giving rise to all cell and tissue types of the three germ layers upon being injected back into blastocysts. These ceils are therefore said to possess pluripotency that can be maintained infinitely in culture under optimal conditions. Such pluripotency maintenance is believed to be due to the symmetrical cleavage of the cells in an undifferentiated state. The pluripotency of ES cells is the basis for their various practical and potential applications. ES cells can be used as donor cells to generate knockout or transgenic animals, as in vitro models of mammalian development, and as cell resources for cell therapy in regenerative medicine. The further success in these applications, particularly in the last two, is dependent on the establishment of a culture system with components in the medium clearly defined and the subsequent procedures for controlled differentiation of the cells into specific lineages. In turn, elucidating the molecular mechanism for pluripotency maintenance of ES cells is the prerequisite. This paper summarizes the recent progresses in this area, focusing mainly on the LIF/STAT3, BMPs/Smads, canonical Wnt, TGFβ/activin/nodal, PI3K and FGF signaling pathways and the genes such as oct4, nanog that are crucial in ES cell pluripotency maintenance. The regulatory systems of pluripotency maintenance in both mouse and human ES cells are also discussed. We believe that the cross-talkings between these signaling pathways, as well as the regulatory system underlying pluripotency maintenance will be the main focus in the area of ES cell researches in the future.     

Environmental and energy gains from using molten magnesium–sodium–potassium chlorides for electro-metallisation of refractory metal oxides

The molten eutectic mixture of magnesium,sodium and potassium chlorides(Mg Cl2–Na Cl–KCl) has inappreciable solubility for oxide ions,and can help disengage a carbon anode from the oxide ions generated at a metal oxide cathode,and effectively avoid carbon dioxide formation.This "disengaging strategy" was successfully demonstrated in electro-reduction of solid oxides of zirconium and tantalum.It has led to significantly higher current efficiency(93%),and lower energy consumption(1.4 k W h kg 1) in electrolysis of tantalum oxide to tantalum metal compared to the conventional electrolysis in molten calcium chloride(e.g.78% and 2.4 k W h/kg-Ta).     

Production of transgenic blastocyst of sheep by somatic cell cloning

Five samples from primary cultures of five sheep ovarian granulosa cells were transfected by pEGFP- N1 DNA. Five transgenic positive cell lines, each from one of the five samples above, were used as donor nuclei for somatic nucleus transfer. A total of 352 in vitro matured and enucleated sheep oocytes were fused electrically with transgenic granulosa cells and 329 reconstructed embryos were obtained after activation by Ionomycin/6-DMAP, and these embryos were cultured in SOFaaBSA medium for 7 d. The result shows that 312 embryos (94.8%) had gone through cleavage and among them 63 (19.1%) had developed to the blastocyst stage. Expression of GFP gene was detected in various stages of early embryonic development by sampling randomly. Blastocyst rates given by the four cells treated with 0.5% FCS starvation was 19.6% (55/280) and it had not shown difference significantly (P＞0.05) with the result obtained with another cell line that had not gone through serum starvation (16.3%, 8/49). This experiment indicates that sheep transgenic embryos up to the blastocyst stage can be produced effectively by the combination of gene transfection in somatic cells in culture and somatic cell cloning.     

Enhanced biodegradation behavior of ultra fine-grained ZE41A magnesium alloy in Hank's solution

The biodegradation behavior of an ultrafne-grained(UFG) magnesium alloy ZE41A containing rare-earth(RE),obtained through multi-pass of equal channel angular pressing(EACP),was investigated by electrochemical measurements in Hank’s solution.The highest value of charge transfer resistance was obtained in the electrochemical impedance spectroscopy plots of the ECAPed samples with the largest pressing pass,while a movement of corrosion potential toward noble direction and a decrement of corrosion current density were observed in the potentiodynamic polarization curves of the ECAPed samples with further pressing passes.These results indicated that ECAP could be an effcient way to reduce the biodegradation rate of the ZE41A alloy.     

Effects of P addition on the microstructure and mechanical properties of Mg–5%Sn–1.25%Si alloy

The effects of Al-P addition on the microstructure and mechanical properties of as-cast Mg–5%Sn–1.25%Si magnesium alloy were investigated. The results show that the phases of the as-cast alloy are composed of α-Mg, Mg2 Sn, Mg2 Si, little P, and AlP. The Chinese character shape Mg2 Si phase changes into a granular morphology by P addition because AlP can act as a heterogeneous nucleation core for the Mg2 Si phase. When 0.225wt% of Al–3.5%P alloy is added, the mechanical properties of the Mg–5%Sn–1.25%Si alloy are greatly improved, and the tensile strength increases from 156 to 191 MPa, an increase of 22.4% compared to the alloy without P addition. When the amount of Al–3.5%P reaches 0.300wt%, a segregation phenomenon occurs in the granular Mg2 Si phase, and the tensile strength and hardness decrease though the elongation increases.     

Doping inorganic ions to regulate bioactivity of Ca –P coating on bioabsorbable high purity magnesium

Performance of biomaterials was strongly affected by their surface properties and could be designed artificially to meet specific biomedical requirements. In this study, F(F), Si O2 4(Si), or HCO 3(C)-doped Ca–P coatings were fabricated by biomimetic deposition on the surface of biodegradable high-purity magnesium(HP Mg). The crystalline phases, morphologies and compositions of Ca–P coatings had been characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and energy-dispersive spectroscopy(EDS). The biomineralization and corrosion resistance of doped Ca–P coatings had also been investigated. The results showed that the Ca–P coating with or without doped elements mainly contained the plate-like dicalcium phosphate dehydrate(DCPD) phase. The doped F, Si, or C changed the surface morphology of Ca–P coatings after mineralization. Doped F enhanced the mineralization of Ca–P coating, and doped Si retarded the mineralization of Ca–P coating.However, H2 evolution of HP Mg discs with different Ca–P coatings was close to 0.4–0.7 ml/cm2 after two-week immersion. That meant that the corrosion resistance of the Ca–P coatings with different or without doped elements did not change significantly.