High purity biodegradable magnesium coating for implant application

This paper describes efforts to create high purity Mg coating by Physical Vapor Deposition (PVD) technique that is appropriate for implant applications and to improve the interaction between the implant and the biological environment. The in vitro and in vivo tests conducted with Mg coatings that consist of grains with controlled size demonstrated promising properties in terms of lower corrosion and acceptable foreign body reaction which makes them prospective as biodegradable metallic materials.     

Polylactic acid coating on a biodegradable magnesium alloy: An in vitro degradation study by electrochemical impedance spectroscopy

Polylactic acid (PLA) was coated on a biodegradable magnesium alloy, AZ91, using spin coating technique for temporary implant applications. The degradation behaviour of the coated alloy samples was evaluated using electrochemical impedance spectroscopy (EIS) method in simulated body fluid (SBF). EIS results suggested that the PLA coating enhanced the degradation resistance of the alloy significantly. Increase in the PLA coating thickness was found to increase the degradation resistance, but resulted in poor adhesion. Long-term EIS experiments of the PLA coated samples suggested that their degradation resistance gradually decreased with increase in SBF exposure time. However, the degradation resistance of the PLA coated samples was significantly higher than that of the bare metal even after a 48 h exposure to SBF.     

Deposition of functional cellulose films on titanium alloy surfaces

Titanium alloy (TiAl6V4) surfaces were treated with ultraviolet (UV) radiation to remove organic “contamination” molecules which remained on the surfaces after conventional cleaning processes. The UV-technique simultaneously revealed reactive surface hydroxyl groups at the metal surface which were monitored by the reaction with perfluorooctanoylchloride and application of Fourier-Transform infrared reflection-absorption spectroscopy and contact angle measurements, respectively. Two different cellulose polymers each made soluble in methanol by functionalized hydroxylalkyl-spacer groups and their mixtures were deposited on UV-treated TiAl6V4 surfaces. Atomic force microscopy measurements could reveal polymer films which covered the metal surfaces completely without defects. Differences were indicated in the surface structure, especially between the pure cellulose phosphate films and cinnamate containing cellulose films.     

In-vitro degradation behaviour of WE54 magnesium alloy in simulated body fluid

Rare earths containing magnesium alloy, WE54, exhibited a marginally higher in-vitro degradation resistance than that of pure magnesium. Heat-treatment procedure had an influence on the degradation behaviour. However, comparing with AZ91 magnesium alloy the in-vitro degradation resistance of WE54 magnesium alloy was significantly lower, which suggests that the passivating capacity of rare earths is inferior to that of aluminium under in-vitro condition.     

Pulsed laser deposition of alumina coating for corrosion protection against liquid uranium

Alumina coatings find wide applications as tribological coatings and as corrosion protective coatings for structural materials against chemical attack. We have investigated alumina coatings deposited on Stainless Steel (SS) substrates via pulsed laser deposition (PLD) technique. Characterization tests performed on these coatings including their compatibility with liquid uranium suggests alumina to be a potential candidate as a coating material for handling and containment of liquid uranium. We present here results of our detailed parametric study including dependence of average mass removal rate on laser fluence and ablation geometry and average deposition efficiency during PLD. These measurements provide vital inputs facilitating proper choice of process parameters for PLD runs. Deposited coatings have been characterized in terms of their microstructure, surface profile, adhesion to substrate, crystalline phase and corrosion resistance against liquid uranium. Our PLD based alumina coatings have shown a high degree of compaction and excellent corrosion resistance to molten uranium even upto a temperature of 1165 °C.     

Non-destructive corrosion study on a magnesium alloy with mechanical properties tailored for biodegradable cardiovascular stent applications

AnMg-2Zn-0.6Zr-0.6Nd alloy for biodegradable cardiovascular stent applications was prepared through indirect extrusion. The alloy exhibited a superior combination of tensile yield strength(TYS), ultimate tensile strength(UTS) and elongation(EL) of about 269 MPa, 298 MPa and 25.6 %, respectively. In addition,the non-destructive electrochemical frequency modulation(EFM) technique was used for the first time to investigate the corrosion behavior of Mg alloys combined with electrochemical impedance spectroscopy(EIS) in Dulbecco’s Modified Eagle’s Medium(DMEM) and in Hank’s solution. Compared with the corrosion rate of 0.07 mm/year in Hank’s solution, lower corrosion rate of 0.03 mm/year was achieved in DMEM. The significant differences between the corrosion rate trends were discussed and related with the composition of the corrosion layer formed. Depending on the biomimetic fluids tested, different corrosion products were precipitated on the alloy’s surface: a compact and homogeneous layer of Mg_xCa_y(PO₄)_z and Zn(OH)₂ and organic compounds was formed in DMEM, whereas a partial coverage of Mg_xCa_y(PO₄)_z and Zn(OH)₂ was formed in Hank’s solution.     

Fabrication of nanoporous Sr incorporated TiO2 coating on 316L SS: Evaluation of bioactivity and corrosion protection

In this paper, nanoporous TiO₂ and Sr-incorporated TiO₂ coated 316L SS were prepared by sol–gel methodology. The effect of Sr incorporation into TiO₂ coating on bioactivity and corrosion resistance was investigated. Attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy, X-ray diffraction analysis (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) results obtained after in vitro bioactivity test confirm the excellent growth of crystalline hydroxyapatite (HAp) over nanoporous Sr-incorporated TiO₂ coated 316L SS which may be attributed to the slow and steady release of Sr ions from the coatings. The electrochemical evaluation of the coatings confirms that Sr-incorporated TiO₂ coating offer excellent protection to 316L SS by acting as a barrier layer. The results showed that the incorporation of Sr enhanced both bioactivity and corrosion resistance of 316L SS. Hence Sr-incorporated TiO₂ coated 316L SS is a promising material for orthopaedic implant applications.     

Corrosion behavior of friction stir welded AZ31B magnesium alloy with plasma electrolytic oxidation coating formed in silicate electrolyte

A protective ceramic coating of about 50 μm thick on a friction stir welded (FSW) joint of AZ31B magnesium alloy was prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte. Electrochemical corrosion behavior of uncoated and coated FSW joints was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The equivalent circuits of EIS plots for uncoated and coated FSW magnesium alloy were suggested. The corrosion resistance of FSW magnesium alloy depended on microstructure of the FSW joint. The heat-affected zone with severe grain growth was more susceptible to corrosion than the stir zone and base metal. The PEO coating consisted of a porous outer layer and a dense inner layer. The inner layer of PEO coating played a key role on corrosion protection of the FSW joint of magnesium alloy. Meanwhile, corrosion potential, corrosion current density and impedance at different zones of coated FSW joint were almost the same. The PEO surface treatment significantly improved the corrosion resistance of FSW joints of AZ31B magnesium alloy.     

Investigation of the trivalent-chrome coating on 6063 aluminum alloy

In this work, the green trivalent chromium coating on 6063 aluminum alloy surface was made and studied by means of trivalent chromate compound (KCr(SO₄)₂) as inhibitor. The coating was evaluated in 3.5 wt.% NaCl at room temperature using polarization curve, AC impedance spectroscopy (EIS). The results show that the trivalent chromium compounds treated surface presents better corrosion behavior in chloride media than the original material surface. The morphologies and composition and valence state of the coating were examined by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS), respectively. The result indicates that the trivalent chromium chemical conversion coating was made on aluminum alloy surface.     

Growth and corrosion of aluminum PVD-coating on AZ31 magnesium alloy

Magnetron sputtering was applied to prepare aluminum coating on a mechanically polished AZ31 magnesium alloy. A loose oxide film was spontaneously formed on the surface of AZ31 magnesium alloy during polishing process. The aluminum coating, which was subsequently deposited on this oxide layer, presented a developed columnar microstructure. Attributed to the barrier effect of Al coating, the Al coated AZ31 showed a higher corrosion resistance than bare AZ31 in corrosion tests. Generally, Al coating is cathodically protected by magnesium alloy substrate. But it is interesting in this study that Al coating still suffered from severe corrosion due to the occurrence of the alkalization effect.     

Influence of microstructure on the in-vitro degradation behaviour of magnesium alloys

The study shows that the microstructural difference between the fine-grained die-cast and coarse-grained sand-cast magnesium-based alloys has no significant effect on the in-vitro degradation behaviour. However, the post-degradation analysis of the alloys suggest that the high volume fraction of secondary phase particles in the die-cast alloy may not be suitable for biodegradable implant applications, primarily due to the high stability of the secondary phase particles in physiological conditions.     

Biodegradable and bioactive properties of a novel bone scaffold coated with nanocrystalline bioactive glass for bone tissue engineering

The development of the new technologies of bone tissue engineering requires the production of bioactive and biodegradable macroporous scaffolds. Hydroxyapatite (HA) ceramics are useful bone substitutes, but they degrade minimally. Tricalcium phosphates also show poor ability of Ca-P formation both in-vitro and in-vivo, although they are degradable. The present study introduces a biodegradable, bioactive, and macroporous scaffold with suitable mechanical properties. The prepared hydroxyapatite scaffold was coated with a nanocrystalline bioactive glass layer to be subsequently sintered at different temperatures. The bioactivity and degradability of the coated scaffolds were investigated by standard procedures. The ability to induce Ca-P formation in SBF (simulated body fluid) was also investigated semi-quantitatively. BS1 scaffolds (scaffolds sintered at 800 °C with a holding time of 2 h) showed remarkable bioactivity and degradability simultaneously. Formation of a nanocrystalline phase (Si₂PO₇) during the sintering considerably decreased the capability of BS1 scaffolds for Ca-P formation and the rate of degradation but enhanced their mechanical properties. The BS1 scaffolds showed not only significant bioactivity but also good degradability and suitable mechanical property.     

In vitro degradation performance and biological response of a Mg-Zn-Zr alloy

The feasibility of a Mg-Zn-Zr alloy for biomedical applications was studied through microstructure characterization, corrosion tests in different biological media, and cell proliferation, differentiation and adhesion tests. Corrosion tests showed that the ZK60 alloy in the as-extruded state with finer grain sizes exhibited slower corrosion rates than the same alloy in the as-cast state. The tests in different biological fluids showed that the corrosion rates of the as-cast and as-extruded ZK60 alloy in DMEM + FBS were the highest, while those in Hank's solution were the lowest. The corrosion rate of the as-extruded ZK60 alloy was similar to the corrosion rates of other commercial magnesium alloys, namely the die-cast AZ91D, die-cast AM50, extruded AZ31 and extruded WE43 alloys. The results obtained from the indirect cytotoxicity evaluation showed that the 100% concentrated cast and extruded ZK60 alloy extracts resulted in significantly reduced cell numbers and total protein amounts, as compared to the negative control. The cell number and total protein amount increased with the gradual dilution of the extracts, but the protein normalized ALP activity showed an opposite trend. For the direct assay, L-929 and MG63 cells exhibited good adhesion with spread pseudopod on the surface of extruded ZK60 alloy samples after 24 h culture. In short, the as-extruded ZK60 alloy could be a good candidate material for biodegradable implants.     

Novel copolyester for a shape-memory biodegradable material in vivo

In this paper, we report the excellent shape-memory behavior of a novel Poly(glycol-glycerol-sebacate) (PGGS) terpolymer network for the first time. The polymer, with its crosslinked, three-dimensional networks acting as fixed phase, while its crystalline phase acting as a reversible one, meets the two necessary conditions to be the material that possesses shape-memory behavior, the response temperature of which is in the neighbourhood of human body temperature. The PGGS terpolymer, with a shape-memory ratio of above 99.5% and a recovery temperature of 37.5 °C, shows excellent shape-memory effect and a potential of being used directly in vivo.     

可降解镁合金表面载药涂层的制备和性能

在可降解AZ31B镁合金心血管支架表面成功制备了携带雷帕霉素的聚乳酸-聚三亚甲基碳酸酯(PLA-PTMC)共聚物涂层,评价了涂层的表面形貌、降解性能、血液相容性和药物释放性能.结果表明,PLA-PTMC共聚物作为载药涂层具有良好的柔韧性,表面均匀、光滑,降解周期超过1个月,血液相容性良好.涂层具有缓释雷帕霉素的功能,释药周期超过1个月,可在内膜增生期内有效抑制支架植入后再狭窄的发生,满足冠脉支架表面载药层的使用要求.     

The pigment influence on the anticorrosive performance of some alkyd films

This paper presents the results regarding the pigments effect on the protective properties of alkyd films in 3% natrium chloride solution. The films were realized on carbon steel substrate from an alkyd resin using the pigments of metallic, mineral and organic type. Dry films thickness in 30–35 μm range was obtained. Electrochemical techniques (electrochemical impedance spectroscopy (EIS) and stepwise polarization) were used. The interpretation of the impedance spectra (Nyquist and Bode diagrams) with the immitance analysis Equivcrt. Programme established two electrical equivalent circuits (with two and four time constants) for the carbon steel/alkyd film systems in electrolyte solution, fitted to the experimental data. The electric capacitance and resistance of the alkyd films were monitored with the immersion time to establish the water and ions permeability of these paint films. The electrochemical parameters of alkyd coated carbon steel from the anodic potentiostatic polarisation curves were determined. The correlation of all experimental results established that the tested pigments except the green organic pigment increase the protective performances of alkyd coatings. Best protection of the carbon steel was found for the alkyd film with aluminum powder pigment.     

MAO-DCPD composite coating on Mg alloy for degradable implant applications

Magnesium (Mg) is a promising metallic material for use as degradable orthopedic implants. The density and Young's modulus of Mg are close to those of human bone, and it is non-toxic and degradable in body fluids. However, the realization of Mg as an implant material is hampered by its high corrosion rate. The present article aims at improving the corrosion resistance and bioactivity of a Mg alloy AZ80 via surface treatment. AZ80 was coated with a composite coating consisting of an oxide layer formed by micro-arc oxidation (MAO) and a top layer of dicalcium phosphate dihydrate (DCPD, CaHPO₄·2H₂O) fabricated by electrodeposition. The corrosion behavior and apatite-forming ability in simulated body fluids (SBFs) were studied using hydrogen evolution measurements and SEM. The results show that the MAO-DCPD composite coating significantly reduces the corrosion rate of AZ80 and at the same time enhances the deposition of apatite on the coating.     

Calcium phosphate coating on magnesium alloy for modification of degradation behavior

Magnesium alloy has similar mechanical properties with natural bone, but its high susceptibility to corrosion has limited its application in orthopedics. In this study, a calcium phosphate coating is formed on magnesium alloy (AZ31) to control its degradation rate and enhance its bioactivity and bone inductivity. Samples of AZ31 plate were placed in the supersaturated calcification solution prepared with Ca(NO₃)₂, NaH₂PO₄ and NaHCO₃, then the calcium phosphate coating formed. Through adjusting the immersion time, the thickness of uniform coatings can be changed from 10 to 20 μm. The composition, phase structure and morphology of the coatings were investigated. Bonding strength of the coatings and substrate was 2–4 MPa in this study. The coatings significantly decrease degradation rate of the original Mg alloy, indicating that the Mg alloy with calcium phosphate coating is a promising degradable bone material.     

Cerium-based coating for enhancing the corrosion resistance of bio-degradable Mg implants

Recently there has been interest in employing degradable metallic implants for internal fixation in bone fracture healing. The major purpose of using degradable implants is to avoid a second surgery for implant removal when bone healing has completed. However, the corrosion rate of Mg in vivo is too high. Thus increasing the corrosion resistance of Mg is the key problem to address in the development of degradable Mg implants. One possible route is by way of surface treatment, which would lower the corrosion rate at the initial phase of bone healing, the period during which the implant provides mechanical support for the broken bone. In the present study cerium oxide coating was prepared on pure Mg by cathodic deposition in cerium nitrate solution followed by hydrothermal treatment. The coated samples were characterized by SEM, EDS and XRD. The corrosion resistance in Hanks’ solution (a simulated body fluid) was studied using polarization method and electrochemical impedance spectroscopy (EIS). The corrosion resistance of cerium oxide coated Mg in Hanks’ solution at 37 °C and pH 7.4 was higher than that of bare Mg by about two orders of magnitude.