Comparison of the Corrosion Behavior of Coated and Uncoated Magnesium Alloys in an In Vitro Corrosion Environment

The in vitro degradation of magnesium alloys with various alloying elements, the effect of coatings, and the impact of an altered experimental environment are investigated. LANd442 and Nd2 alloys are subjected to a continuously moving environment during an immersion test allowing flowing SBF. Applying an MgF₂ coating to the alloys increases the corrosion resistance of LANd442 but has no effect on the corrosion rate of Nd2 within the period of investigation. It leads to a more‐even degradation with less pitting corrosion in the early stages of corrosion. A bioglass coating on Nd2 increases the corrosion rate. The mass loss, volume loss, and loss in maximum force all show the same trends as the specimens degrade over time.     

Effects of hydroxyapatite/Zr and bioglass/Zr coatings on morphology and corrosion behaviour of Rex-734 alloy

To improve corrosion resistance of metallic implant surfaces, Rex-734 alloy was coated with two different bio-ceramics; single-Hydroxyapatite (HA), double-HA/Zirconia(Zr) and double-Bioglass (BG)/Zr by using sol–gel method. Porous surface morphologies at low crack density were obtained after coating and sintering processes. Corrosion characteristics of coatings were determined by Open circuit potential and Potentiodynamic polarization measurements during corrosion tests. Hardness and adhesion strength of coating layers were measured and their surface morphologies before and after corrosion were characterized by scanning electron microscope (SEM), XRD and EDX. Through the SEM analysis, it was observed that corrosion caused degradation and sphere-like formations appeared with dimples on the coated surfaces. The coated substrates that exhibit high crack density, the corrosion was more effective by disturbing and transmitting through the coating layer, produced CrO₃ and Cr₃O₈ oxide formation. It was found that the addition of Zr provided an increase in adhesion strength and corrosion resistance of the coatings. However, BG/Zr coatings had lower adhesion strength than the HA/Zr coatings, but showed higher corrosion resistance.     

Surface Engineering of Biodegradable Magnesium Alloys for Enhanced Orthopedic Implants

Magnesium (Mg) alloys have been promised for biomedical implants in orthopedic field, however, the fast corrosion rate and mode challenge their clinical application. To push Mg alloys materials into practice, a composite coating with biodegradable and high compatible components to improve anticorrosion property of an Mg alloy (i.e., AZ31) is designed and fabricated. The inner layer is micro‐nano structured Mg(OH)₂ through hydrothermal treatment. Then stearic acid (SA) is introduced to modify Mg(OH)₂ for better reducing the gap below a surface‐degradation polymer layer of poly(1,3‐trimethylene carbonate). Benefited by the SA modification effect, this sandwiched coating avoids corrosive medium penetration via enhancing the adhesion strength at the interface between outer and inner layers. Both in vitro and in vivo tests indicate that the composite coating modified AZ31 perform a better anticorrosion behavior and biocompatibility compared to bare AZ31. Strikingly, a 1.7‐fold improvement in volume of newly formed bone is observed surrounding the composite coating modified implant after 12 week implantation. The sandwiched biocompatible coating strategy paves a hopeful way for future translational application of Mg alloys orthopedic materials in clinics.     

Galvanisches Verzinken von Magnesiumlegierungen

Zinc‐Plating of Magnesium Alloys Magnesium alloys are highly susceptible to corrosion that limits their application when exposure to corrosive service conditions is needed. One of the ways to prevent corrosion is to coat the magnesium‐based substrate to avoid a contact with an aggressive environment. Results concerning corrosion behaviour of wrought AZ31 magnesium alloy with electrolytic zinc coatings deposited from different electrolyte solutions are described. Evaluation of corrosion processes in chlorides containing solutions was performed by electrochemical measurements. It was found that thick and dense electrolytic zinc coatings formed on AZ31 significantly improve the corrosion behaviour of magnesium alloy after one hour immersion of zinc coated magnesium alloys in corrosive media. Further increase of immersion time leads to relatively fast decrease of corrosion properties. Electrolytic zinc coatings obtained in consecutive alkaline / acidic process demonstrate an improvement of corrosion resistance of coated AZ31. The time to coating degradation strongly increases.     

Einfluss der Oberflächenbehandlung auf das Korrosionsverhalten von Magnesiumlegierungen

For the coating of magnesium alloys, especially those that should be used in medical technologies, fluoride coatings are tested and used. These coatings should enable a predictable degradation behavior for future implant materials. Presently the pre‐ and post‐treatment processes vary, so an optimum to achieve defined thicknesses of the fluoride layers is still not established. The present investigations are based on the process parameters known from the literature, they are discussed and compared. Different pre‐treating times of the base material (pure magnesium and a magnesium‐aluminum‐calcium alloy as a comparison) in 200 g/l sodium hydroxide combined with 96 hours of immersion in 40 % fluoride acid are examined.     

Hydroxyapatite coating on magnesium with MgF<Subscript>2</Subscript> interlayer for enhanced corrosion resistance and biocompatibility

Hydroxyapatite (HA) was coated onto pure magnesium (Mg) with an MgF₂ interlayer in order to reduce the surface corrosion rate and enhance the biocompatibility. Both MgF₂ and HA were successfully coated in sequence with good adhesion properties using the fluoride conversion coating and aerosol deposition techniques, respectively. In a simulated body fluid (SBF), the double layer coating remarkably enhanced the corrosion resistance of the coated Mg specimen. The in vitro cellular responses of the MC3T3-E1 pre-osteoblasts were examined using a cell proliferation assay and an alkaline phosphatase (ALP) assay, and these results demonstrated that the double coating layer also enhanced cell proliferation and differentiation levels. In the in vivo study, the HA/MgF₂ coated Mg corroded less than the bare Mg and had a higher bone-to-implant contact (BIC) ratio in the cortical bone area of the rabbit femora 4 weeks after implantation. These in vitro and in vivo results suggested that the HA coated Mg with the MgF₂ interlayer could be used as a potential candidate for biodegradable implant materials.     

Effect of Thermal Oxidation on Microstructure and Corrosion Behavior of the PVD Hf‐Coated Mg Alloy

Hafnium coatings are fabricated on magnesium alloys by magnetron sputtering and are further submitted to the thermal oxidation treatment at temperature of 200, 300, and 400 °C. The thin hafnium oxide film and new grain boundaries are observed on the hafnium coatings during the appropriate treatment temperature (300 °C). These changes in microstructure result in surface densification, oxidation, and low porosity of the treated coating that significantly decrease its susceptibility to corrosion. Consequently, the thermal oxidation treatment hafnium coating exhibits a more positive corrosion potential, lower corrosion current density, and higher polarization resistance than that of the as‐deposited coating using an electrochemical system. Moreover, the enhanced adhesion of the treated coating produced by applying an appropriate treatment temperature facilitates an efficient long‐term protection of magnesium alloy.

     

Biodegradable poly(lactide-co-glycolide) coatings on magnesium alloys for orthopedic applications

Polymeric film coatings were applied by dip coating on two magnesium alloy systems, AZ31 and Mg4Y, in an attempt to slow the degradation of these alloys under in vitro conditions. Poly(lactic-co-glycolic acid) polymer in solution was explored at various concentrations, yielding coatings of varying thicknesses on the alloy substrates. Electrochemical corrosion studies indicate that the coatings initially provide some corrosion protection. Degradation studies showed reduced degradation over 3 days, but beyond this time point however, do not maintain a reduction in corrosion rate. Scanning electron microscopy indicates inhomogeneous coating durability, with gas pocket formation in the polymer coating, resulting in eventual detachment from the alloy surface. In vitro studies of cell viability utilizing mouse osteoblast cells showed improved biocompatibility of polymer coated substrates over the bare AZ31 and Mg4Y substrates. Results demonstrate that while challenges remain for long term degradation control, the developed polymeric coatings nevertheless provide short term corrosion protection and improved biocompatibility of magnesium alloys for possible use in orthopedic applications.     

Biofunctionalization of porous titanium coatings through sol–gel impregnation with a bioactive glass–ceramic

In implant technology, open porous Ti coatings are applied as functional surface layers on prosthetic devices to improve osseointegration. Since a successful clinical performance strongly depends on the (initial) quality of bone ingrowth in the porous structure, surface functionalization of the porous Ti to incorporate an additional osteoconductive capacity is recommended. In this paper, a bioactive glass–ceramic coating is applied into the open porous network of Ti coatings with a pore throat size of 1–20 μm through a sol–gel process. Using an all-alkoxide precursor route, homogeneous amorphous powders of three- (SiO₂–CaO–P₂O₅) and four-component (SiO₂–CaO–Na₂O–P₂O₅) bioactive glass compositions are prepared. By sol impregnation followed by a heat treatment, it is possible to deposit a micrometer thin bioactive glass–ceramic layer on the walls of the internal pore surface, while the original porosity and the open pore structure of the Ti coatings are maintained. The tensile adhesion strength of the Ti/bioactive glass–ceramic composite coatings is 22 to 29 MPa, suggesting a good mechanical adhesion.     

Characterization of electrolytic HA/ZrO2 double layers coatings on Ti–6Al–4V implant alloy

Hydroxyapatite (HA) coating was proved having bioactive property and hence improving the bonding strength on bone tissue without inducing the growth of fiber tissue. However, the weak adhesion between HA and metal implants is still the major problem. In this study, a novel method of electrolytic HA/ZrO₂ double layers coating was successfully conducted on F-136 Ti–6Al–4V implant alloy in ZrO₂(NO₃)₂ aqueous solution and subsequently in the mixed solution of Ca(NO₃)₂ and NH₄H₂PO₄. After annealing at 400 °C, 500 °C and 600 °C for 4 h in air, the coated specimens were evaluated by X-ray diffraction analyses, surface morphology observations, scratch tests, dynamic polarization tests, immersion tests and cell culture assays. In addition to corrosion resistance, the adhesion strength of electrolytic deposited HA on Ti alloy was dramatically improved from the critical scratch load 2 N to 32 N by adding the intermediate electrolytic deposition of ZrO₂, which showed the strong bonding effects between Ti alloy substrate and HA coating. Based on the cell morphology and cell proliferation data, HA/ZrO₂ double layers coating revealed the better substrate for the adhesion and proliferation of osteoblasts than the others. It was also found that the crystallization of HA had positive effect on the proliferation of osteoblasts.     

Anti-corrosion mechanism of epoxy-resin and different content Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> coatings on magnesium alloy

In this study, anti-corrosion coatings were prepared and coated successfully on magnesium alloy substrates by mixing nanopowders, solvent, curing agent with epoxy resin. The effect of the amount of iron trioxide (Fe₂O₃) on the adhesion strength and corrosion resistance on magnesium alloy was investigated with standard protocols, and electrochemical measurements were also made in 3.5 wt.% NaCl solutions. The surface morphology and corrosion mechanism after corrosion tests was characterized using FESEM analysis. Nanoparticles in matrix acted as filler, and interstitial cross-linked spaces and other coating artifacts regions (micro cracks and voids) would all affect the anti-corrosion properties of coating. The results showed the proper powder content not only provided adhesion strength to these coatings but also improved obviously their anticorrosion. Hydrogen bound to the amine nitrogen (¹N) could take part in the curing process rather than hydrogen of the amide site due to the smaller ΔG and the more stable configuration.     

仿生涂层形貌对MgZnSrCa合金降解速率的影响

镁合金降解速率过快限制了其作为生物医用材料的应用,对镁合金降解速率的控制成为了研究的热点。采用仿生法在MgZnSrCa合金基体表面形成羟基磷灰石涂层。利用X射线衍射仪、扫描电子显微镜及能谱仪对涂层结构、形貌和成分进行分析和观察。通过失重法、析氢法、pH值测定等方法,研究不同涂层形貌的合金试样在人体模拟体液(SBF)中的降解速率。实验结果表明:羟基磷灰石(HA)涂层可以降低合金的降解速率,可以通过控制涂层形貌对合金的降解速率进行控制。     

Fabrication and characterization of bioactive composite coatings on Mg–Zn–Ca alloy by MAO/sol–gel

High corrosion rate and accumulation of hydrogen gas upon degradation impede magnesium alloys’ clinical application as implants. In this work, micro-arc oxidation (MAO) was used to fabricate a porous coating on magnesium alloys as an intermediate layer to enhance the bonding strength of propolis layer. Then the composite coatings were fabricated using sol–gel method by dipping sample into the solution containing propolis and polylactic acid at 40°C. The corrosion resistance of the samples was determined based on potentiodynamic polarization experiments and immersion tests. Biocompatibility was designed by observing the attachment and growth of wharton’s jelly-derived mesenchymal stem cells (WJCs) on substrates with MAO coating and substrates with composite coatings. The results showed that, compared with that of Mg–Zn–Ca alloy, the corrosion current density of the samples with composite coatings decreased from 5.37 × 10⁻⁵ to 1.10 × 10⁻⁶ A/cm² and the corrosion potential increased by 240 mV. Composite coatings exhibit homogeneous corrosion behavior and can promote WJCs cell adhesion and proliferation. In the meantime, pH value was relatively stable during the immersion tests, which may be significant for cellular survival. In conclusion, our results indicate that composite coatings on Mg–Zn–Ca alloy fabricated by MAO/sol–gel method provide a new type bioactive material.     

Corrosion protection of carbon fibre reinforced aluminium composite by diamondlike carbon coatings

Abstract

Carbon fibre reinforced aluminium exhibits poor resistance against electrochemical corrosion in 3·5 wt-%NaCl solution. Diamondlike carbon (DLC) coatings provide properties which make them interesting materials for external corrosion protection on metal matrix composites (MMCs). The electrochemical corrosion behaviour of uncoated and DLC coated carbon fibre reinforced aluminium was tested in 3·5 wt-%NaCl solution. It has been found that the pitting potential is shifted significantly in the anodic direction and the corrosion current density is much lower due to the presence of the sealing DLC coating. Additionally, scratch tests and SEM studies were carried out in order to characterise the adhesion of the DLC films on the heterogeneous MMCs. Reliable corrosion protection is connected with sufficient coating durability under loading. In order to ensure sufficient loading capacity of the DLC coating under tribological conditions, wear tests were undertaken which revealed a considerable improvement in wear resistance due to deposition of the DLC coatings.     

Influence of Tris in simulated body fluid on degradation behavior of pure magnesium

In current paper, influence of tris-hydroxymethyl-aminomethane (tris) in simulated body fluid (SBF) on degradation behavior of pure magnesium is investigated using electrochemical tests as well as degradation measurement. Our results shows that tris mainly affects earlier degradation behavior of pure magnesium alloy. Tris and HCl used in preparation of SBF will form Tris–HCl which only lowers corrosion potential of magnesium slightly but accelerates degradation rates of pure magnesium by teens times. Consumption of OH^? generated during magnesium dissolution by Tris–HCl progressively promotes transformation from Mg to Mg²⁺, which is the main reason for quite high degradation rate of pure magnesium in SBF. Pure magnesium is also more sensitive to pitting corrosion due to inclusion of Tris–HCl in SBF. This study deepens the understanding on degradation mechanism of biomedical magnesium alloys.     

Verschleiß- und Korrosionsschutz durch Chrom und Chromnitrid (PVD-Abscheidung auf Al und Mg)

Wear and corrosion protection using Cr and CrN (PVD coating on Al and Mg) Investigations of the wear behaviour of uncoated Magnesium and Aluminium alloys (AZ 91hp, AlSi 7Mg) are showing very high wear rates of these materials. To improve the wear behaviour both materials were coated with 9 μm CrN using PVD (Physical Vapour Deposition) technology. The tribological behaviour of the coated light metals was tested afterwards by using a plate on cylinder tribometer. Looking at the results, wear is reduced enormously. The great number of defects in the coating of the magnesium alloy is showing almost no influence to the wear behaviour. The corrosion behaviour of chromium and chromium nitride coatings was tested on the magnesium alloy. Because of the defects in the coating, caused by defects like pores in the magnesium, only a short term protection of the alloy can be achieved. The corrosion behaviour of multilayer coatings is better than the behaviour of single layer coatings.     

Bioactive Materials for Regenerative Medicine: Zeolite‐Hydroxyapatite Bone Mimetic Coatings

We report the synthesis and characterization of a novel zeolite‐hydroxyapatite composite coating on titanium alloys and stainless steel. The zeolite‐hydroxyapatite coating is superhydrophilic and outperforms the state‐of‐the‐art Ti6Al4V alloys in corrosion resistance tests in aggressive pitting NaCl media, phosphate buffer solution with BSA protein, as well as highly complex DMEM cell culture media. And the composite coating also eliminates the elastic modulus mismatch between coating and bone. In addition, the composite coating has an osteoconductive and osteoinductive effect on hFOBs, indicating that it may enhance osteointegration of implants and speed up post‐surgical recovery, and thus reduce the need for recurring implant replacement surgeries. Replacing titanium with zeolite‐hydroxyapatite coated steel can also significantly reduce implant cost while improving implant lifespan.     

Development and bio-electrochemical characterization of a novel TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> mixed oxide coating for titanium implants

Titanium and its alloys, the most commonly used materials for dental and orthopaedic implants are generally coated with bioactive materials such as sol-gel derived titania, silica and calcium phosphate in order to render these materials bioactive. In the present work a coating containing nanosized titania particles having anatase structure was developed on titanium substrate by thermal decomposition of titanium tetrachloride in isopropanol. A modified titania-silica mixed oxide coating was developed by incorporating the required amount of silica in the coating system. The presence of silica at small weight percentage caused improvement of adhesion and corrosion resistance of the coating. In vitro bioactivity tests were performed in 1.5 Kokubo's simulated body fluid after alkaline treatment of the titania/titania-silica coatings and the performance was compared with that of the titania coating developed by simple thermal oxidation. TF-XRD, FTIR and SEM-EDAX were used to investigate the microstructural morphology and crystallinity of the coatings. Elemental analysis of simulated body fluid was carried out using ICP-AES and spectrophotometry. Enhanced biogrowth was facilitated on the titania coating incorporated with low silica content.     

A study of corrosion performance of electroless Ni–P and Ni–W–P coatings on AZ91D magnesium alloy

The autocatalytic nature of the electroless nickel‐based alloy coating process will inevitably produce H₂ bubbles which may be left in electroless nickel‐based alloy coating. If the H₂ cannot be removed and left in the coating, it can lead to its poor corrosion resistance due to hydrogen cracks. So, the post treatment is an essential step for electroless deposition process. In this paper, electroless Ni–P and Ni–W–P coatings with chromium‐free pretreatment and dehydrogenation post treatment have been successfully prepared on AZ91D magnesium alloy, and the corrosion behaviors of the two kind coating samples in NaCl solution, HCl solution, and H₂SO₄ solution have been investigated. Both the polarization test and immersion tests show that the electroless Ni–W–P coating has better corrosion resistance than that of electroless Ni–P coating.