In vitro degradation resistance of glucose and L-cysteine-bioinspired Schiff-base anodic Ca−P coating on AZ31 magnesium alloy

A Schiff base(a compound containing a C=N bond)induced anodic Ca−P coating was prepared on AZ31 Mg alloy in a mixed solution of CaCl_(2) and KH_(2)PO_(4) at 60℃ in the presence of glucose and L-cysteine.The microstructure and chemical composition of the coatings were characterized using FE-SEM,FT-IR,XRD,and XPS.The in vitro degradation resistance of the coated samples was evaluated via potentiodynamic polarization(PDP),electrochemical impedance spectroscopy(EIS),and hydrogen evolution test.The experimental results show that the Ca−PSchiff base coating is composed of CaHPO_(4)(DCPA)and hydroxyapatite(HA),whereas HA is not present in the Ca−P coating.The Ca−P_(Schiff base) coating thickness is about 2 times that of Ca−P coating(Ca−P coating:(9.13±4.20)μm and Ca−P_(Schiff base):(18.13±5.78)μm).The corrosion current density of the Ca−P_(Schiff base) coating is two orders of magnitude lower than that of the Ca−P coating.The formation mechanism of the Ca−P_(Schiff base) is proposed.

In vitro degradation and cytocompatibility of a low temperature in-situ grown self-healing Mg-Al LDH coating on MAO-coated magnesium alloy AZ31

Basically,Mg–Al layered double hydroxide(LDH)coatings are prepared on the surface of micro-arc oxidation(MAO)coated magnesium(Mg)alloys at a high temperature or a low pH value.This scenario leads to the growth rate of LDH coating inferior to the dissolution rate of the MAO coating.This in turn results in limited corrosion resistance of the composite coating.In this study,a Mg–Al LDH coating on MAO-coated Mg alloy AZ31 is prepared through a water bath with a higher pH(13.76)at a lower temperature(60℃).FE-SEM,EDS,XRD,XPS,and FT-IR are applied to analyze the surface morphology,chemical compositions,and growth process.Electrochemical polarization,electrochemical impedance spectroscopy(EIS)and hydrogen evolution tests are employed to evaluate the corrosion resistance of the samples.The results disclose that the MAO coating is completely covered by the nanosheet-structured LDH coating with a thickness of approximately 3.8μm.The corrosion current density of the MAO-LDH composite coating is decreased four orders of magnitude in comparison to its substrate;the presence of a wide passivation region in anodic polarization branch demonstrates its strong self-healing ability,indicating the hybrid coating possesses excellent corrosion resistance.The formation mechanism of the LDH coating on the MAO-coated Mg alloy is proposed.Furthermore,the cytocompatibility is assessed via an indirect extraction test for MC3T3-E1 pre-osteoblasts,which indicates an acceptable cytocompatibility of osteoblasts for the composite coating.

Corrosion resistance of in-situ growth of nano-sized Mg（OH）2 on micro-arc oxidized magnesium alloy AZ31—Influence of EDTA

One of the major obstacles for the clinical use of biodegradable magnesium(Mg)-based materials is their high corrosion rate. Micro-arc oxidation(MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)2 film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium(EDTA-2 Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)2 hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)2 coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating.The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)2 film. The current density of Mg(OH)2-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)2-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.

Corrosion resistance of nanostructured magnesium hydroxide coating on magnesium alloy AZ31: influence of EDTA

A hexagonal nanosheet Mg(OH)2 coating was prepared through a one-step hydrothermal method using LiOH solution as mineralizer and then modified by ethylenediaminetetraacetic acid(EDTA) to minimize the rapid corrosion of AZ31 Mg alloy.The performance of the coating was evaluated using electrochemical technique,hydrogen evolution measurements, nanoscratch test,Fourier-transform infrared spectroscopy(FTIR), X-ray diffraction(XRD) patterns and field-emission scanning electron microscopy(FESEM).The results suggested that the corrosion rate of bare AZ31 Mg alloys was significantly reduced by one and two orders of magnitude through the protection from Mg(OH)2 coating and modification with EDTA(i.e., EDTA-Mg(OH)2 coating), respectively.FESEM micrographs indicated that the modification in EDTA elicits to the formation of an EDTA-Mg(OH)2 composite with a thickness as twice as that of as-prepared Mg(OH)2 coating.Nanoscratch tests revealed strong adhesion between the composite or Mg(OH)2 coating and the substrate.The study of formation and corrosion mechanisms of the coatings manifested that Mg(OH)2 was first formed near the intermetallic compound AlMn particles and gradually covered the entire surface, wherein the AlMn particles played an important role in the coating growth process.And it also proved that EDTA accelerated the formation of Mg(OH)2.

Corrosion resistance of an amino acid-bioinspired calcium phosphate coating on magnesium alloy AZ31

An L-cysteine-bioinspired calcium phosphate(Ca-P)coating is prepared upon magnesium alloy AZ31 in a water bath at 60℃.FE–SEM,FTIR,XRD,electrochemical characterization,hydrogen evolution tests and XPS were used to evaluate the microstructure,chemistry and corrosion performance of the samples.Results indicate that L-cysteine promotes the nucleation process of the coating and significantly increases its thickness.This can be attributed to the complexation of the carboxyl group and mercapto group of L-cysteine with calcium ions.Indeed,the obtained Ca-P coating possesses higher corrosion resistance than that prepared in L-cysteine-free bath.

In vitro corrosion resistance of a Ta2O5 nanofilm on MAO coated magnesium alloy AZ31 by atomic layer deposition

Micro-arc oxidation(MAO)coating with outstanding adhesion strength to Mg alloys has attracted more and more attention.However,owing to the porous structure,aggressive ions easily invaded the MAO/substrate interface through the through pores,limiting long-term corrosion resistance.Therefore,a dense and biocompatible tantalum oxide(Ta2O5)nanofilm was deposited on MAO coated Mg alloy AZ31 through atomic layer deposition(ALD)technique to seal the micropores and regulate the degradation rate.Surface micrography,chemical compositions and crystallographic structure were characterized using FE-SEM,EDS,XPS and XRD.The corrosion resistance of all samples was evaluated through electrochemical and hydrogen evolution tests.Results revealed that the Ta2O5 film mainly existed in the form of amorphousness.Moreover,uniform deposition of Ta2O5 film and effective sealing of micropores and microcracks in MAO coating were achieved.The current density(icorr)of the composite coating decreased three orders of magnitude than that of the substrate and MAO coating,improving corrosion resistance.Besides,the formation and corrosion resistance mechanisms of the composite coating were proposed.