A study of a biodegradable Mg–3Sc–3Y alloy and the effect of self-passivation on the in vitro degradation

Magnesium and its alloys have been investigated for their potential application as biodegradable implant materials. Although properties of magnesium such as biocompatibility and susceptibility to dissolution are desirable for biodegradable implant applications, its high degradation rate and low strength pose a significant challenge. A potential way to reduce the initial degradation rate is to form a self-passivating protective layer on the surface of the alloy. Oxides with a low enthalpy of formation result in a strong thermodynamic driving force to produce oxide surfaces that are more stable than the native oxide (MgO), and possibly reduce the initial degradation rate in these alloys. In the present study a ternary Mg–3 wt.% Sc–3 wt.% Y alloy was investigated and its oxidation behavior studied. The effect of surface passivation on the in vitro degradation rate was studied and the degradation products identified. The results show that the oxide provided an initial degradation barrier and 24 h oxidation resulted in a negligible degradation rate for up to 23 days. Furthermore, the degradation products of the alloy showed no significant toxicity to osteoblastic cells, and cell proliferation studies confirmed cell attachment and proliferation on the surface of the oxidized alloy.     

Corrosion protection and improved cytocompatibility of biodegradable polymeric layer-by-layer coatings on AZ31 magnesium alloys

Composite coatings of electrostatically assembled layer-by-layer anionic and cationic polymers combined with an Mg(OH)₂ surface treatment serve to provide a protective coating on AZ31 magnesium alloy substrates. These ceramic conversion coating and layer-by-layer polymeric coating combinations reduced the initial and long-term corrosion progression of the AZ31 alloy. X-ray diffraction and Fourier transform infrared spectroscopy confirmed the successful application of coatings. Potentiostatic polarization tests indicate improved initial corrosion resistance. Hydrogen evolution measurements over a 2 week period and magnesium ion levels over a 1 week period indicate longer range corrosion protection and retention of the Mg(OH)₂ passivation layer in comparison to the uncoated substrates. Live/dead staining and DNA quantification were used as measures of biocompatibility and proliferation while actin staining and scanning electron microscopy were used to observe the cellular morphology and integration with the coated substrates. The coatings simultaneously provided improved biocompatibility, cellular adhesion and proliferation in comparison to the uncoated alloy surface utilizing both murine pre-osteoblast MC3T3 cells and human mesenchymal stem cells. The implementation of such coatings on magnesium alloy implants could serve to improve the corrosion resistance and cellular integration of these implants with the native tissue while delivering vital drugs or biological elements to the site of implantation.     

A surface-eroding poly(1,3-trimethylene carbonate) coating for fully biodegradable magnesium-based stent applications: Toward better biofunction,biodegradation and biocompatibility

Biodegradable magnesium-based materials have a high potential for cardiovascular stent applications; however, there exist concerns on corrosion control and biocompatibility. A surface-eroding coating of poly(1,3-trimethylene carbonate) (PTMC) on magnesium (Mg) alloy was studied, and its dynamic degradation behavior, electrochemical corrosion, hemocompatibility and histocompatibility were investigated. The PTMC coating effectively protected the corrosion of the Mg alloy in the dynamic degradation test. The corrosion current density of the PTMC-coated alloy reduced by three orders and one order of magnitude compared to bare and poly(ε-caprolactone) (PCL)-coated Mg alloy, respectively. Static and dynamic blood tests in vitro indicated that significantly fewer platelets were adherent and activated, and fewer erythrocytes attached on the PTMC-coated surface and showed less hemolysis than on the controls. The PTMC coating after 16 weeks’ subcutaneous implantation in rats maintained ～55% of its original thickness and presented a homogeneously flat surface demonstrating surface erosion, in contrast to the PCL coated control, which exhibited non-uniform bulk erosion. The Mg alloy coated with PTMC showed less volume reduction and fewer corrosion products as compared to the controls after 52 weeks in vivo. Excessive inflammation, necrosis and hydrogen gas accumulation were not observed. The homogeneous surface erosion of the PTMC coating from exterior to interior (surface-eroding behavior) and its charge neutral degradation products contribute to its excellent protective performance. It is concluded that PTMC is a promising candidate for a surface-eroding coating applied to Mg-based implants.     

In vitro degradation and mechanical integrity of Mg–Zn–Ca alloy coated with Ca-deficient hydroxyapatite by the pulse electrodeposition process

The key to manufacturing magnesium-based alloys that are suitable as biodegradable orthopaedic implants is how to adjust their degradation rates and mechanical integrity in the physiological environment. In this study, to solve this challenge, a soluble Ca-deficient hydroxyapatite (Ca-def HA) coating was deposited on an Mg–Zn–Ca alloy substrate by pulse eletrodeposition. This deposition can be demonstrated by X-ray diffractometry and energy dispersion spectroscopy analyses, and the Ca/P atomic ratio of as-deposited coating is about 1.33 (within the range from 1.33 to 1.65). By regulating the appropriate pulse amplitude and width, the Ca-def HA coating shows better adhesion to Mg–Zn–Ca alloy, whose lap shear strength is increased to 41.8 ± 2.7 MPa. Potentiodynamic polarization results in Kokubo’s simulated body fluid (SBF) indicate that the corrosion potential of Mg alloy increases from ?1645 to ?1414 mV, while the corrosion current density decreases from 110 to 25 μA/cm², which illustrates that the Ca-def HA coating improves the substrate corrosion resistance significantly. Since orthopaedic implants generally serve under conditions of stress corrosion, the mechanical integrity of the Mg–Zn–Ca alloy was measured using the slow strain rate tensile (SSRT) testing technique in SBF. The SSRT results show that the ultimate tensile strength and time of fracture for the coated Mg–Zn–Ca alloy are higher than those of the uncoated one, which is beneficial in supporting fractured bone for a longer time. Thus Mg–Zn–Ca alloy coated with Ca-def HA is be a promising candidate for biodegradable orthopaedic implants, and is worthwhile to further investigate the in vivo degradation behavior.     

A quantitative in vitro method to predict the adhesion lifetime of diamond-like carbon thin films on biomedical implants

A quantitative method using Rockwell C indentation was developed to study the adhesion of diamond-like carbon (DLC) protective coatings to the CoCrMo biomedical implant alloy when immersed in phosphate-buffered saline (PBS) solution at 37 °C. Two kinds of coatings with thicknesses ranging from 0.5 up to 16 microns were investigated, namely DLC and DLC/Si-DLC, where Si-DLC denotes a 90 nm thick DLC interlayer containing Si. The time-dependent delamination of the coating around the indentation was quantified by means of optical investigations of the advancing crack front and calculations of the induced stress using the finite element method (FEM). The cause of delamination for both types of coatings was revealed to be stress-corrosion cracking (SCC) of the interface material. For the DLC coating a typical SCC behavior was observed, including a threshold region (60 J m^?2) and a “stage 1” crack propagation with a crack-growth exponent of 3.0, comparable to that found for ductile metals. The DLC/Si-DLC coating exhibits an SCC process with a crack-growth exponent of 3.3 and a threshold region at 470 J m^?2, indicating an adhesion in PBS at 37 °C that is about eight times better than that of the DLC coating. The SCC curves were fitted to the reaction controlled model typically used to explain the crack propagation in bulk soda lime glass. As this model falls short of accurately describing all the SCC curves, limitations of its application to the interface between a brittle coating and a ductile substrate are discussed.     

Calcium–strontium mixed phosphate as novel injectable and radio-opaque hydraulic cement

Sterile calcium hydrogenophosphate dihydrate (DCPD) (CaHPO₄·2H₂O), calcium oxide and strontium carbonate powders were mixed in various liquid phases. Among these, ammonium phosphate buffer (0.75 M, pH 6.9) led to a novel strontium-containing calcium phosphate cement. At a 6/2.5/1.5 M ratio and for a liquid to powder ratio (L/P) of 0.5 ml g^?1, the initial paste was fluid and remained injectable for 12 min at 25 °C. It was easily obtained by mixing sterile powders and the liquid phase using the push–pull technique, avoiding complex mixing apparatus. The cement set after 15 min at 37 °C and was hard after 1 h. The compressive strength was in the 20 MPa range, a value higher than that generally assigned to trabecular bone (5–15 MPa). This strength appeared sufficient for repairing non-loading sites or reinforcing osteoporotic vertebrae (vertebroplasty). After setting, the initial mixture formed a strontium–calcium-deficient carbonate apatite. The radio-opacity of the resulting cement was three times greater than that of cortical bone because of the presence of strontium ions, a feature that complies with the requirements for vertebroplasty. Furthermore, the cement powder remained stable and retained its properties for at least 4 years.     

Corrosion inhibition of powder metallurgy Mg by fluoride treatments

Pure Mg has been proposed as a potential degradable biomaterial to avoid both the disadvantages of non-degradable internal fixation implants and the use of alloying elements that may be toxic. However, it shows excessively high corrosion rate and insufficient yield strength. The effects of reinforcing Mg by a powder metallurgy (PM) route and the application of biocompatible corrosion inhibitors (immersion in 0.1 and 1 M KF solution treatments, 0.1 M FST and 1 M FST, respectively) were analyzed in order to improve Mg mechanical and corrosion resistance, respectively. Open circuit potential measurements, polarization techniques (PT), scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS) were performed to evaluate its corrosion behavior. SECM showed that the local current of attacked areas decreased during the F^? treatments. The corrosion inhibitory action of 0.1 M FST and 1 M FST in phosphate buffered solution was assessed by PT and EIS. Under the experimental conditions assayed, 0.1 M FST revealed better performance. X-ray photoelectron spectroscopy, energy dispersive X-ray and X-ray diffraction analyses of Mg(PM) with 0.1 M FST showed the presence of KMgF₃ crystals on the surface while a MgF₂ film was detected for 1 M FST. After fluoride inhibition treatments, promising results were observed for Mg(PM) as degradable metallic biomaterial due to its higher yield strength and lower initial corrosion rate than untreated Mg, as well as a progressive loss of the protective characteristics of the F^?-containing film which ensures the gradual degradation process.     

Preparation and in vitro evaluation of plasma-sprayed Mg2SiO4 coating on titanium alloy

In this paper, chemically synthesized Mg₂SiO₄ (MS) powder was plasma-sprayed onto a titanium alloy substrate to evaluate its application potentials in biomedicine. The phase composition and surface morphology of the MS coating were analyzed. Results showed that the MS coating was composed mainly of Mg₂SiO₄ phase, with a small amount of MgO and glass phases. Mechanical testing showed that the coating exhibited good adhesion strength to the substrate due to the close thermal expansion coefficient between the MS ceramic and the titanium alloy substrate. The measured bonding strength was as high as 41.5 ± 5.3 MPa, which is much higher than the traditional HA coating. In vitro cytocompatibility evaluation of the MS coating was performed using canine bone marrow stem cells (MSCs). The MSCs exhibited good adhesion, proliferation and differentiation behavior on the MS coating surface, which can be explained by the high protein adsorption capability of the MS coating, as well as the stimulatory effects of Mg and Si ions released from the coating. The proliferation rate of the MSCs on MS coating was very close to that on the hydroxylapatite (HA) coating. Alkaline phosphatase (ALP) activity analysis demonstrated that the ALP level of the MSCs on the MS coating remained high even after 21 days, implying that the surface characteristics of the coating are beneficial for the differentiation of MSCs. In summary, our results suggest that MS coating might be a new approach to prepare bone implants.     

Electrically polarized HAp-coated Ti: In vitro bone cell–material interactions

Electrically polarized bulk sintered hydroxyapatite (HAp) compacts have been shown to accelerate mineralization and bone tissue ingrowth in vivo. In this work, a comprehensive study has been carried out to investigate the influence of surface charge and polarity on in vitro bone cell adhesion, proliferation and differentiation on electrically polarized HAp-coated Ti. Uniform and crack free sol–gel derived HAp coatings of 20 ± 1.38 μm thickness were polarized by application of an external d.c. field of 2.0 kV cm^?1 at 400 °C for 1h. In vitro bioactivity of polarized HAp coatings was evaluated by soaking in simulated body fluid, and bone cell–material interactions were studied by culturing with human fetal osteoblast cells (hFOB) for a maximum period of 11 days. Scanning electron microscopic observation showed that accelerated mineralization on negatively charged surfaces favored rapid cell attachment and faster tissue ingrowth over non-polarized HAp coating surfaces, while positive charge on HAp coating surfaces restricted apatite nucleation with limited cellular response. Immunochemistry and confocal microscopy confirmed that the cell adhesion and early stage differentiation were more pronounced on negatively charged coating surfaces as hFOB cells expressed higher vinculin and alkaline phosphatase proteins on negatively charged surface compared to cells grown on all other surfaces. Our results in this study are process independent and potentially applicable to any other commercially available coating techniques.     

In vitro degradation and cytotoxicity response of Mg–4% Zn–0.5% Zr (ZK40) alloy as a potential biodegradable material

Mg–4 wt.% Zn–0.5 wt.% Zr (ZK40) alloy was studied as a candidate material for biodegradable metallic implants in terms of its biocorrosion resistance, mechanical properties and cytocompatibility. The corrosion characteristics of ZK40 alloy were assessed by potentiodynamic polarization and immersion testing in DMEM + 10% FBS solution. Analysis of the degradation characteristics by potentiodynamic polarization measurements shows the corrosion rates of ZK40 alloy in as-cast and solution treatment (T4) condition were slightly higher than those of pure Mg or as-drawn AZ31. Determination of the corrosion rate by the weight loss technique reveals that the as-cast ZK40 resulted in slower degradation than other alloy specimens after 7 days of immersion but exhibited accelerated degradation after 14 and 21 days, respectively. T4-treated ZK40 exhibited stable degradation rates compared to as-cast ZK40 and close to those of pure Mg and AZ31 during immersion testing for 14 and 21 days. In order to examine the in vitro cytocompatibility of ZK40 alloy, live/dead cell viability assay and indirect MTT assay were performed using a murine osteoblast-like cell line (MC3T3). After 3 days of direct culture of MC3T3 on ZK40 alloys the live/dead assay indicated favorable cell viability and attachment. The degradation product of ZK40 also showed minimal cytotoxicity when assessed in indirect MTT assay. The mechanical properties of the as-cast and T4-treated ZK40 alloy were superior to those of pure Mg and comparable to as-drawn AZ31. Solution treatment did not significantly enhance the cytocompatibility and mechanical properties of ZK40 alloy. Overall, the ZK40 alloy exhibited favorable cytocompatibility, biocorrosion, and mechanical properties rendering it a potential candidate for degradable implant applications.     

Magnesium alloys as a biomaterial for degradable craniofacial screws

Recently, magnesium (Mg) alloys have received significant attention as potential biomaterials for degradable implants, and this study was directed at evaluating the suitability of Mg for craniofacial bone screws. The objective was to implant screws fabricated from commercially available pure Mg and alloy AZ31 in vivo in a rabbit mandible. First, Mg and AZ31 screws were compared to stainless steel screws in an in vitro pull-out test and determined to have a similar holding strength (∼40 N). A finite-element model of the screw was created using the pull-out test data, and this model can be used for future Mg alloy screw design. Then, Mg and AZ31 screws were implanted for 4, 8 and 12 weeks, with two controls of an osteotomy site (hole) with no implant and a stainless steel screw implanted for 12 weeks. Microcomputed tomography was used to assess bone remodeling and Mg/AZ31 degradation, both visually and qualitatively through volume fraction measurements for all time points. Histological analysis was also completed for the Mg and AZ31 at 12 weeks. The results showed that craniofacial bone remodeling occurred around both Mg and AZ31 screws. Pure Mg had a different degradation profile than AZ31; however, bone growth occurred around both screw types. The degradation rate of both Mg and AZ31 screws in the bone marrow space and the muscle were faster than in the cortical bone space at 12 weeks. Furthermore, it was shown that by alloying Mg, the degradation profile could be changed. These results indicate the promise of using Mg alloys for craniofacial applications.     

Synergistic effect of surface modification and scaffold design of bioplotted 3-D poly-ε-caprolactone scaffolds in osteogenic tissue engineering

The hydrophobic nature and the regular scaffold architecture of bioplotted poly(ε-caprolactone) (PCL) scaffolds present some hurdles for homogeneous tissue formation and differentiation. The current hypothesis is that a synergistic effect of applied surface modification and scaffold design enhances colonization and osteogenic differentiation. First, PCL scaffolds with a 0/90° lay-down pattern (0/90) were plotted and subjected to an oxygen plasma (O₂) or multistep surface modification, including post-argon 2-amino-ethylmethacrylate grafting (AEMA), followed by immobilization of gelatin type B (gelB) and physisorption of fibronectin (gelB Fn). Secondly, scaffolds of different designs were plotted (0/90° shift (0/90 S), 0/45° and 0/90° with narrow pores (0/90 NP)) and subjected to the double protein coating. Preosteoblasts were cultured on the scaffolds and the seeding efficiency, colonization and differentiation were studied. The data revealed that a biomimetic surface modification improved colonization (gelB Fn > gelB > AEMA > O₂). Compact scaffold architectures (0/90 NP, 0/45, 0/90 S > 0/90) positively influenced the seeding efficiency and differentiation. Interestingly, the applied surface modification had a greater impact on colonization than the scaffold design. In conclusion, the combination of a double protein coating with a compact design enhances tissue formation in the plotted PCL scaffolds.     

Modulating rheological and degradation properties of temperature-responsive gelling systems composed of blends of PCLA–PEG–PCLA triblock copolymers and their fully hexanoyl-capped derivatives

In this study, the ability to modulate rheological and degradation properties of temperature-responsive gelling systems composed of aqueous blends of poly(ε-caprolactone-co-lactide)-b-poly(ethylene glycol)-b-poly(ε-caprolactone-co-lactide) (PCLA–PEG–PCLA) triblock copolymers (i.e. uncapped) and their fully capped derivatives was investigated. Uncapped and capped PCLA–PEG–PCLA triblock copolymers, abbreviated as degree of modification 0 and 2 (DM0 and DM2, respectively), were composed of identical PCLA and PEG blocks but different end groups: namely hydroxyl and hexanoyl end groups. DM0 was synthesized by ring opening polymerization of l-lactide and ε-caprolactone in toluene using PEG as initiator and tin(II) 2-ethylhexanoate as the catalyst. A portion of DM0 was subsequently reacted with an excess of hexanoyl chloride in solution to yield DM2. The cloud point and phase behaviour of DM0 and DM2 in buffer as well as that of their blends were determined by light scattering in a diluted state and by vial tilting and rheological measurements in a concentrated state. Degradation/dissolution properties of temperature-responsive gelling systems were studied in vitro at pH 7.4 and 37 °C. The cloud points of DM0/DM2 blends were ratio-dependent and could be tailored from 15 to 40 °C for blends containing 15 to 100 wt.% DM0. Vial tilting and rheological experiments showed that, with solid contents between 20 and 30 wt.%, DM0/DM2 blends (15/85 to 25/75 w/w) had a sol-to-gel transition temperature at 10–20 °C, whereas blends with less than 15 wt.% DM0 formed gels below 4 °C and the ones with more than 25 wt.% DM0 did not show a sol-to-gel transition up to 50 °C. Complete degradation of temperature-responsive gelling systems took ～100 days, independent of the DM0 fraction and the initial solid content. Analysis of residual gels in time by GPC and ¹H-NMR showed no chemical polymer degradation, but indicated gel degradation by dissolution. Preferential dissolution of lactoyl-rich polymers induced enrichment of the residual gels in caproyl-rich polymers. To the best of our knowledge, degradation of temperature-responsive gelling systems by dissolution has not been reported or hypothesized as being the consequence of acylation of polymers. In conclusion, blending of PCLA–PEG–PCLA triblock polymers composed of identical backbones but different end groups provides for a straightforward preparation of temperature-responsive gelling systems with well-characterized rheological properties and potential in drug delivery. Furthermore, acylation of triblock copolymers may allow for the design of bioerodible systems with control over degradation by polymer dissolution.     

The processing of ultrafine-grained Mg tubes for biodegradable stents

An investigation was carried out on equal-channel angular pressing (ECAP) and extrusion processing of a ZM21 Mg alloy to obtain an improved candidate material for the manufacturing of biodegradable Mg stents. Ultrafine-grain size billets of the ZM21 alloy were obtained by two-stage ECAP aimed at achieving an initial refining of the structure at 200 °C and then reaching the submicrometer grain size range by lowering the processing temperature down to 150 °C. The investigation revealed a significant improvement in the properties of the ECAP-treated samples compared with the starting coarse-grained ZM21 alloy. The 0.2% yield strength rose from 180 to 340 MPa after 150 °C ECAP processing, while maintaining a fairly high tensile ductility. The ultrafine ZM21 alloy billets were then used for the extrusion of stent precursors having the form of small-size tubes. The grain size after extrusion remained in the submicrometer range while the hardness was revealed to be significantly higher than that of the coarse-grained ZM21 Mg alloy. It was demonstrated that processing of biodegradable Mg stent having an ultrafine-grained microstructure by ECAP and low-temperature extrusion is feasible and that the obtained products feature promising properties.     

Single-step electrochemical deposition of antimicrobial orthopaedic coatings based on a bioactive glass/chitosan/nano-silver composite system

Composite orthopaedic coatings with antibacterial capability containing chitosan, Bioglass® particles (9.8 μm) and silver nanoparticles (Ag-np) were fabricated using a single-step electrophoretic deposition (EPD) technique, and their structural and preliminary in vitro bactericidal and cellular properties were investigated. Stainless steel 316 was used as a standard metallic orthopaedic substrate. The coatings were compared with EPD coatings of chitosan and chitosan/Bioglass®. The ability of chitosan as both a complexing and stabilizing agent was utilized to form uniformly deposited Ag-np. Due to the presence of Bioglass® particles, the coatings were bioactive in terms of forming carbonated hydroxyapatite in simulated body fluid (SBF). Less than 7 wt.% of the incorporated silver was released over the course of 28 days in SBF and the possibility of manipulating the release rate by varying the deposition order of coating layers was shown. The low released concentration of Ag ions (<2.5 ppm) was efficiently antibacterial against Staphyloccocus aureus up to 10 days. Although chitosan and chitosan/Bioglass® coating supported proliferation of MG-63 osteoblast-like cells up to 7 days of culture, chitosan/Bioglass®/Ag-np coatings containing 342 μg of Ag-np showed cytotoxic effects. This was attributed to the relatively high concentration of Ag-np incorporated in the coatings.     

Biocompatibility and biodegradability of Mg–Sr alloys: The formation of Sr-substituted hydroxyapatite

Magnesium is an attractive material for use in biodegradable implants due to its low density, non-toxicity and mechanical properties similar to those of human tissue such as bone. Its biocompatibility makes it amenable for use in a wide range of applications from bone to cardiovascular implants. Here we investigated the corrosion rate in simulated body fluid (SBF) of a series of Mg–Sr alloys, with Sr in the range of 0.3–2.5%, and found that the Mg–0.5 Sr alloy showed the slowest corrosion rate. The degradation rate from this alloy indicated that the daily Sr intake from a typical stent would be 0.01–0.02 mg day^?1, which is well below the maximum daily Sr intake levels of 4 mg day^?1. Indirect cytotoxicity assays using human umbilical vascular endothelial cells indicated that Mg–0.5 Sr extraction medium did not cause any toxicity or detrimental effect on the viability of the cells. Finally, a tubular Mg–0.5 Sr stent sample, along with a WE43 control stent, was implanted into the right and left dog femoral artery. No thrombosis effect was observed in the Mg–0.5 Sr stent after 3 weeks of implantation while the WE43 stent thrombosed. X-ray diffraction demonstrated the formation of hydroxyapatite and Mg(OH)₂ as a result of the degradation of Mg–0.5 Sr alloy after 3 days in SBF. X-ray photoelectron spectroscopy further showed the possibility of the formation of a hydroxyapatite Sr-substituted layer that presents as a thin layer at the interface between the Mg–0.5 Sr alloy and the corrosion products. We believe that this interfacial layer stabilizes the surface of the Mg–0.5 Sr alloy, and slows down its degradation rate over time.     

In vitro and in vivo evaluation of the surface bioactivity of a calcium phosphate coated magnesium alloy

Magnesium has shown potential application as a bio-absorbable biomaterial, such as for bone screws and plates. In order to improve the surface bioactivity, a calcium phosphate was coated on a magnesium alloy by a phosphating process (Ca–P coating). The surface characterization showed that a porous and netlike CaHPO₄·2H₂O layer with small amounts of Mg²⁺ and Zn²⁺ was formed on the surface of the Mg alloy. Cells L929 showed significantly good adherence and significantly high growth rate and proliferation characteristics on the Ca–P coated magnesium alloy (p < 0.05) in in-vitro cell experiments, demonstrating that the surface cytocompatibility of magnesium was significantly improved by the Ca–P coating. In vivo implantations of the Ca–P coated and the naked alloy rods were carried out to investigate the bone response at the early stage. Both routine pathological examination and immunohistochemical analysis demonstrated that the Ca–P coating provided magnesium with a significantly good surface bioactivity (p < 0.05) and promoted early bone growth at the implant/bone interface. It was suggested that the Ca–P coating might be an effective method to improve the surface bioactivity of magnesium alloy.     

Microstructure,mechanical and corrosion properties of Mg–Dy–Gd–Zr alloys for medical applications

In previous investigations, a Mg–10Dy (wt.%) alloy with a good combination of corrosion resistance and cytocompatibility showed great potential for use as a biodegradable implant material. However, the mechanical properties of Mg–10Dy alloy are not satisfactory. In order to allow the tailoring of mechanical properties required for various medical applications, four Mg–10(Dy + Gd)–0.2Zr (wt.%) alloys were investigated with respect to microstructure, mechanical and corrosion properties. With the increase in Gd content, the number of second-phase particles increased in the as-cast alloys, and the age-hardening response increased at 200 °C. The yield strength increased, while the ductility reduced, especially for peak-aged alloys with the addition of Gd. Additionally, with increasing Gd content, the corrosion rate increased in the as-cast condition owing to the galvanic effect, but all the alloys had a similar corrosion rate (～0.5 mm year^?1) in solution-treated and aged condition.     

Influence of hydrothermal and mechanical conditions on the strength of zirconia

Low temperature degradation and mechanical and thermal cycling may decrease the strength of zirconia and jeopardize the long-term success of dental restorations made of this material. The objective of this study was to reveal the influence of different environmental and loading conditions on the strength of 3 mol.% yttria-stabilized polycrystalline tetragonal zirconia (3Y-TZP). A total of 144 disk specimens were produced from each of two 3Y-TZP materials, and subjected to one of the following conditions: (A) no further treatment (control); (B and C) 10⁶ and 5 × 10⁶ mechanical cycles, respectively, with an upper load limit of 100 N; (D) 10⁴ thermal cycles between 5 and 55 °C; (E) 200 days storage in water at 36 °C; (F) a successive combination of conditions B, D and E; (G) storage in water at 80 °C for 64 days; (H) storage in an autoclave at 134 °C for 8 h. Monoclinic phase content was evaluated by X-ray diffraction (XRD) analysis. Specimen strength was determined in a biaxial bending test. The two ceramics exhibited average strengths of 995 and 1239 MPa, respectively. No statistically significant influence of any treatment on strength was demonstrated for either material. However, XRD measurements revealed a substantial increase in monoclinic phase content, from an initial 2% (control) to up to 10%, according to storage conditions. As a consequence of hydrothermal loading a tetragonal to monoclinic phase transformation took place at the surface of the 3Y-TZP materials investigated, but, like thermal and mechanical cycling, this did not lead to significant changes in bulk strength.     

Effect of a plasmaelectrolytic coating on the strength retention of in vivo and in vitro degraded magnesium implants

The strength decrease in magnesium implants was studied in vitro and in vivo, with and without a protective plasmaelectrolytic coating. In vivo, degradation was examined by implanting rectangular plates on top of the nasal bone of miniature pigs. The presence of gas pockets in the soft tissue surrounding the implants was evaluated with intermediate X-rays and computed X-ray tomography scans before euthanasia. After 12 and 24 weeks of in vivo degradation, the large rectangular plates were removed and mechanically tested in three-point bending. In vitro, identical plates were immersed in simulated body fluid for 4, 8 and 12 weeks. In vitro and in vivo results showed that onset of gas release can be delayed by the plasmaelectrolytic coating. Mass loss and strength retention during in vivo degradation is about four times slower than during in vitro degradation for the chosen test conditions. Despite the slow degradation of the investigated WE43 alloy, the occurrence of gas pockets could not be completely avoided. Nevertheless, uniformity of degradation and reliable strength retention make this alloy a prime candidate for the use of magnesium in cranio-maxillofacial surgery.