Calcium Phosphate Coatings Research Articles

Toward osteomimetic formation of calcium phosphate coatings with carbonated hydroxyapatite

Biomimetic production of coatings on various types of scaffolds is based mainly on simulated body fluid precipitation (SBF) of apatites, or, if the HCO3− is present, carbonated apatites. Recently, we proposed formation of calcium phosphates (CaP) precipitates by alkaline phosphatase (ALP) hydrolysing glycerophosphate in presence of calcium ions as an alternative to SBF. Since apatites synthesized in bone by the ALP activity contain carbonate anions, it was tempting to investigate whether the phosphatase method could be advanced into osteomimetic one. Therefore, taking example from the SBF studies, phosphatase incubation medium was enriched with carbonate ions at 4.2 and 27 mM concentration. X-ray diffraction of the precipitates disclosed peaks typical for hydroxyapatite (HAP). FTIR analysis showed that at both concentration of carbonate ions, apatites underwent both B and A substitution, more extensive at higher concentration. Thus, osteomimetic approach produced carbonated hydroxyapatites of the type encountered in bone tissue even at HCO3− concentration as low as 4.2 mM. Composite plates made of poly(ε-caprolactone) and mixture of β-tricalcium phosphate and hydroxyapatite at mass ratio of 1:0.5:0.5, respectively, were covered by CaP coatings, i.e., CaP-0, CaP-4.2, CaP-27, by incubation in phosphatase medium containing 0, 4.2 or 27 mM of NaHCO3, respectively. Pristine or coated PCL50 plates were used to study release of calcium and adsorption/desorption of proteins, or seeded with human bone marrow mesenchymal stem cells (hMSC) for study of cell adhesion, spreading and osteogenic differentiation. Introduction of carbonate into the CaP coatings significantly increased release of Ca2+ in a carbonate concentration-dependent manner; the release was up to 4 times higher, when compared to CaP-0 coating, and reached 0.41 ± 0.01 mM for CaP-27 after first 24 h. Coating CaP-4.2 yielded significantly higher adsorption of bovine serum albumin and cytochrome C than CaP-0. All of the CaP coatings improved significantly hMSC adhesion, however, only CaP-4.2 provided 2 times higher cell number than PCL50 after 2 weeks of culture. Interestingly, ALP activity calculated per cell number was the highest on pristine plates, presumably because hMSC differentiate preferentially into osteoblasts at lower seeding densities. It appears, therefore, that the osteomimetic approach may be useful for production of carbonated hydroxyapatite coatings, but requires further studies and replacing intestinal phosphatase used in this work with one originating from bone.

Properties of Coatings Based on Calcium Phosphate and Their Effect on Cytocompatibility and Bioactivity of Titanium Nickelide

Coatings based on calcium phosphate with thicknesses of 0.5 and 2 μm were obtained by high-frequency magnetron sputtering on NiTi substrates in an argon atmosphere. The coating was characterized using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and in vitro cytocompatibility and bioactivity studies. A biphasic coating of tricalcium phosphate (Ca3(PO4)2) and hydroxyapatite (Ca10(PO4)6(OH)2) with a 100% degree of crystallinity was formed on the surface. The layer enriched in calcium, phosphorus, and oxygen was observed using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Scanning electron microscopy showed that the surface structure is homogeneous without visible defects. The 2 µm thick coating obtained by sputtering with a deposition time of 4 h and a deposition rate of 0.43 µm/h is uniform, contains the highest amount of the calcium phosphate phase, and is most suitable for the faster growth of cells and accelerated formation of apatite layers. Samples with calcium phosphate coatings do not cause hemolysis and have a low cytotoxicity index. The results of immersion in a solution simulating body fluid show that NiTi with the biphasic coating promotes apatite growth, which is beneficial for biological activity.

A Tunable Calcium Phosphate Coating to Drive in vivo Osseointegration of Composite Engineered Tissues

Varying degrees of hydroxyapatite (HA) surface functionalization have been implicated as the primary driver of differential osteogenesis observed in infiltrating cells. The ability to reliably create spatially controlled areas of mineralization in composite engineered tissues is of growing interest in the field, and the use of HA-functionalized biomaterials may provide a robust solution to this challenge. In this study, we successfully fabricated polycaprolactone salt-leached scaffolds with two levels of a biomimetic calcium phosphate coating to examine their effects on MSC osteogenesis. Longer duration coating in simulated body fluid (SBF) led to increased HA crystal nucleation within scaffold interiors as well as more robust HA crystal formation on scaffold surfaces. Ultimately, the increased surface stiffness of scaffolds coated in SBF for 7 days in comparison to scaffolds coated in SBF for 1 day led to more robust osteogenesis of MSCs in vitro without the assistance of osteogenic signaling molecules. This study also demonstrated that the use of SBF-based HA coatings can promote higher levels of osteogenesis in vivo. Finally, when incorporated as the endplate region of a larger tissue-engineered intervertebral disc replacement, HA coating did not induce mineralization in or promote cell migration out of neighboring biomaterials. Overall, these results verified tunable biomimetic HA coatings as a promising biomaterial modification to promote discrete regions of mineralization within composite engineered tissues.

BTAINING OF CALCIUM-PHOSPHATE COATINGS ON THE TITANIUM SURFACE BY MICRO-ARC OXIDATION

The results of experiments on obtaining calcium-phosphate coatings on substrates of titanium grade VT1-0 by micro-arc oxidation (MAO) are presented. The coatings were obtained by adding different amounts of titanium oxide nanoparticles to the electrolyte. The microstructure and tribological properties of calcium phosphate coatings were investigated. In conducted research results have been established and determined optimal modes and parameters for obtaining calcium phosphate coatings. It is shown that the addition of titanium oxide nanoparticles to the electrolyte can affect the structure also the strength of the obtained coatings. The research results led to conclude that such treatment of MAO from titanium alloys is promising to improve their splices with bone tissue.

Titanium Implant Alloy Modified by Electrochemically Deposited Functional Bioactive Calcium Phosphate Coatings

Calcium phosphate-based (CaP) bioceramic materials are widely used in the field of bone regeneration, both in orthopaedics and in dentistry, due to their good biocompatibility, osseointegration and osteoconduction. The formation of CaP coatings on high-strength implant materials such as titanium alloys combines the superior mechanical properties of metals with the osteoconductive properties of CaP materials. In this work, the electrochemically assisted deposition of CaP coatings on the titanium alloy, TiAlNb, which is commonly used commercially as an implant material in orthopaedic devices, was examined. The barrier properties (electronic properties) of unmodified and CaP-modified titanium alloy were tested in situ in a simulated physiological solution, Hanks’ solution, under in vitro conditions of real implant applications using electrochemical impedance spectroscopy (EIS). The morphology and microstructure of the obtained CaP deposit were characterised by scanning electron microscopy (SEM) and chemical composition was assessed by energy dispersive X-ray spectroscopy (EDS) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The aim was to investigate the effect of calcium phosphate CaP coating on the corrosion resistance of the titanium TiAlNb alloy and to understand better the deposition process in the production of bioactive functional coatings on metallic implant materials.

In vitro cellular biocompatibility and in vivo degradation behavior of calcium phosphate-coated ZK60 magnesium alloy

Calcium phosphate (Ca-P) surface coating is a simple but effective way to enhance both corrosion resistance and biocompatibility of ZK60 magnesium alloy. However, cell compatibility on different Ca-P layers coated on ZK60 alloy has seldom been investigated. In this study, the effects of type, morphology and corrosion protection of several Ca-P coatings formed at pH 6.5, 7.8 and 10.2 on cell behavior were examined by using an osteoblastic cell line MC3T3-E1. Furthermore, in vivo behavior in rabbits of the alloy coated with the optimum Ca-P layer was also studied. It was found that the surface factors governed the cell morphology and density. The coating morphology plays a dominant role in these surface factors. The sample coated at pH 7.8 showed the best cellular biocompatibility, suggesting that the hydroxyapatite (HAp) layer formed at pH 7.8 was the optimum coating. In rabbits, this optimum coating enhanced remarkably the corrosion resistance of the alloy. During implantation, the outermost crystals of the HAp coating were shortened and thinned due to the dissolution of HAp caused by the body fluid of the rabbits. It is indicated that ZK60 alloy coated at pH 7.8 can be applied as a biodegradable implant.

A Tribological Investigation of the Titanium Oxide and Calcium Phosphate Coating Electrochemical Deposited on Titanium

Titanium (Ti) and its alloys are widely used in biomedical applications due to their excellent mechanical properties and biocompatibility. However, they are a concern due to the possibility of cytotoxic effects coming from the degradation products. This degradation occurs by the combined action of corrosion and mechanical wear of these materials, which are released in the biological environment by the biomaterial implanted. The present article aims to investigate a new route to improve electrochemical and tribological performance with surface modification. Regarding the deposition of a protective layer on the surface, it consists of titanium oxide (TiO2) and calcium phosphate (CaP). Both coatings were performed by chronoamperometric methods with titanium oxidation at 1 V and calcium phosphate reduction at −1.5 V. The corrosion and tribocorrosion tests demonstrated the effective combination of TiO2 and CaP layer to protect the Ti substrate. Furthermore, this coating combination reduced corrosion degradation and mechanical wear in PBS, simulating a physiological environment. Additionally, it was observed that this combination of coating decreased the dissipated energy, and consequently, the wear decreased during sliding tests. All these findings indicate the protective behavior of the TiO2 and CaP layer during the tribocorrosion tests.

A comparative study of apatite growth and adhesion on a laser-functionalized titanium surface

The laser processing of titanium has been proven to improve biological responses of the surface. In this paper, the Direct Laser Interference Patterning (DLIP) method has been proposed as a single-step functionalization of pre-modified titanium surfaces for biomedical applications. Immersion in Hank’s solution for the deposition of calcium phosphate coatings was applied to evaluate the biomedical potential of modified Ti substrates. The bioactive effect and adhesion force of the Ca-P coating were investigated by X-ray photoelectron spectroscopy and scratch tests with subsequent scanning electron microscopy observations and energy dispersive spectroscopy measurements. In general, the results confirmed that laser treatment positively influences bone-like apatite formation and has an impact on the surface wear resistance.

Creation of Bioactive Ceramic Composite Coatings on Zn–Mn–Mg Alloy via Micro-arc Oxidation and Hydrothermal Treatment for Orthopedic Implant Applications

Zinc alloys have emerged as promising biodegradable metals thanks to their critical physiological roles and encouraging degradation behavior. In this study, calcium phosphate (CaP) coatings were made on micro-arc oxidized Zn alloy using hydrothermal treatment (HT), which was motivated by the CaP-based minerals in natural bone tissue. The coating morphology was optimized by controlling the HT time, resulting in a homogeneous micro-CaP coating structure. The CaP coating significantly increased the cell viability and adhesion of MC3T3-E1 preosteoblasts and L-929 cells. Compared with the control group, the cell toxicity of the samples after MAO-HT was less, the number of cells was more, and the morphology was complete. Cell adhesion showed that the distribution of cells increased with the increase of HT time. In addition, the CaP coating significantly reduced the Zn ion release from the bulk material during the degradation process, resulting in a much lower Zn concentration and pH change in the surrounding environment. The micro-CaP coating structure and the regulated release of zinc ions are primarily responsible for the enhanced cytocompatibility and biomineralization of CaP-coated Zn biomaterials. In summary, the CaP coating on Zn-based biomaterial appears to be a viable approach to enhance its biocompatibility and to control its degradation rate. After that, the biocompatibility of the material can be improved by controlling the surface morphology of the material to adapt to the complex human environment.

In vitro degradation and corrosion evaluations of plasma electrolytic oxidized Mg–Zn–Ca–Si alloys for biomedical applications

Biodegradable calcium phosphate (CaP) ceramic coatings were prepared on self-designed Mg-2.0Zn-0.6Ca-xSi alloys by plasma electrolytic oxidation (PEO). The effect of calcium (Ca) and silicon (Si) on alloy microstructure and coating formation and biomineralization mechanisms were discussed. The in vitro bioactivity and degradability of CaP coatings were evaluated by immersion tests in simulated body fluid (SBF) solutions and trishydroxymethyl-aminomethane hydrochloric acid (Tris-HCl) buffer, respectively. The microstructure and chemical composition of the coatings, depositions and corrosion products were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), X-ray photoelectron spectrometer (XPS) and fourier transform infrared spectrometer (FT-IR). The electrochemical corrosion behavior of alloys and coatings was investigated using the electrochemical workstation. Results showed that the shape, quantity, size and distribution of second phases can be changed by the simultaneously addition of Ca and Si in Mg–Zn–Ca–Si alloys. The Si content in Mg-2.0Zn-0.6Ca-xSi alloy should not be higher than 0.8 wt%. The microstructure of Mg-2.0Zn-0.6Ca-xSi alloys can influence the formation and growth of PEO coating by altering the spark discharge characteristics. The plasma electrolytic oxidized Mg-2.0Zn-0.6Ca-0.8Si has potential to be served as biodegradable bone implant and cardiovascular stent.

Surface modification of Ti6Al7Nb alloy by Al2O3 nanofilms and calcium phosphate coatings

Here we have modified Ti6Al7Nb alloy by Al2O3 using Atomic Layer Deposition (ALD) and apatite coating electrodeposited and by Simulated Body Fluid method. X-Ray Fluorescence (FRX), Energy Scattering X-Ray Spectroscopy (EDS), Scanning Electron Microscopy (SEM), X-Ray Diffraction Spectroscopy (XRD), Raman Spectroscopy and Force Microscopy Atomic (AFM) revealed the chemical and crystallographic composition of Ti6Al7Nb before and after surface modifications. A laminar apatite crystal in the form of plates and irregular crystals, with the appearance of flakes growing from the center to the edge and resembling flowers were produced closed to synthetic apatite's. In vitro biological tests showed that surface modifications in the titanium alloy Ti6Al7Nb improved the bioactivity attributed to the formation of microporosity favorable to the greater production of total proteins and, also, influenced the nucleation of apatite's at the nanoscale. The results presented here confirmed the non-cytotoxicity, strongly supporting the application of these nanofilms in tissue engineering.

Macrophage Polarization Related to Biomimetic Calcium Phosphate Coatings: A Preliminary Study

Biomimetic calcium phosphate (BioCaP) coatings were used to deliver bone morphogenetic protein 2 (BMP2), and enhance osteogenesis. However, the mechanism for BioCaP coatings interacting with the immune response during bone regeneration remains unclear. In this preliminary study, the effect of BioCaP coatings on macrophage polarization without (BioCaP group) or with BMP2 (BioCaP+Inc.BMP2 group) was investigated. RAW 264.7 cells were cultured on the rough and platelike surfaces of coatings in BioCaP and BioCaP+Inc.BMP2 groups, while cultured on smooth surfaces in the group without material for 5 days. The BioCaP coatings per se modulated the switch of M1 to M2 phenotype from day 3, which promoted the expressions of Arg1 and CD 206 but reduced the expression of TNF-α compared with No material group. To detect the microenvironmental changes, the concentrations of calcium ion (Ca2+) and inorganic phosphate (Pi), pH values, as well as calcium phosphate crystal pattern were examined. The trends of ionic environmental changes were closely related with macrophage phenotype switch. These results suggest that BioCaP coating itself may affect the macrophage polarization through surface topography, surrounding ionic environment and calcium phosphate crystal pattern.

Dual-functional coatings on magnesium alloys: Enhancing corrosion behavior under stress and osteogenic effect in osteoporotic rats

Magnesium-based implants are subjected to complicated stresses during implantation in the human body. In this case, they undergo stress-induced corrosion and usually lead to early breakage or disintegration of implants. Calcium phosphate compounds have been used as coatings, bone cement and drug carrier in orthopedic application. Their success has been expanded to Mg alloys. Calcium phosphate-based coatings succeeded in corrosion control and osteointegration of Mg alloys in a big extent. However, their protective effect under stress condition is questionable considering the brittle nature. With the assistance of high pH microenvironment near Mg alloy surface, calcium phosphate coatings have the self-repair potential via the dissolution-precipitation mechanism. Inspired by this phenomenon, strontium doped hydroxyapatite (Sr-HA) coatings with higher solubility have been prepared on the surface of Mg alloys. Sr-HA coatings served as not only a physical barrier effect to postpone pitting formation, but also provide ion supplement to seal the cracks initiated during tensile deformation. The results obtained in slow strain rate tensile test (SSRT) demonstrated improved corrosion and mechanical behaviors of Sr-HA coated Mg alloys. Specifically, the elongation of Sr-HA coated alloy increased by 56.7 and 35.2% as compared to the bare and HA coated one in DMEM. In ovariectomized rats, the implants exhibited only 2.7–5.6% reduction of implant volume after 12 weeks implantation. Sr-HA coating further increased early new bone formation than HA coated implants. 12 weeks post-implantation, a large amount of bony tissue with higher trabecular thickness and hardness was formed adjacent to the Sr-HA coated implants. This study demonstrated the efficiency of a rapid dissolved Sr-HA coating on the corrosion behavior of Mg alloys under mechanical loading and the osteogenesis in ovariectomized rats. It therefore holds a promising practical significance for the future coating design strategy for Mg alloys when trying to expand their application range to locations with higher loading conditions.

Structure and electrical potential of calcium phosphate coatings modified with aluminum oxyhydroxide nanoparticles

The effect of the introduction of charged aluminum oxyhydroxide (AO) nanoparticles into the porous coatings from calcium phosphate formed by micro-arc oxidation on their electrical potential and structure was studied. The modification resulted in changes in the morphology and elemental composition of the coatings. The selection of coating functionalization parameters resulted in obtaining homogeneously distributed aluminum oxyhydroxide nanoparticles in the form of agglomerates, providing the maximum change in the electrical potential of the coatings. An increase in the duration of ultrasonic dispersion (USD) of initial AlN powder suspension from 10 to 60 min and an increase in the surface roughness of the coatings, parameter Ra, from 3.5 to 5.5 µm led to an increase in the surface electrical potential from −85 to −35 mV. At the same time, the aluminum content in the coating decreased from 3 to 1 at.% with an increase in the duration of USD of the AlN powder suspension from 10 to 60 minutes. The introduction of aluminum oxyhydroxide nanoparticles into the coating contributed to an improvement in corrosion properties, namely, an increase in the corrosion potential from 0.1 to 0.2 mV and a decrease in the corrosion current from 2.5 ∙10−9 to 1.1·10−9 A ∙ cm2.

Dual pulsed laser deposition of Ag nanoparticles on calcium phosphate coatings for biomedical applications

Pulsed laser deposition (PLD) represents a promising bottom-up methodology for the synthesis and transference of nanoparticles to the surface of a biomedical device. Silver (Ag) nanoparticles directly incorporated on the metallic implant emerge as an alternative strategy for local action against prosthetic joint-associated infections. In the present research, a dual sequential PLD process is proposed to obtain a bilayer coating with (1) a bio-derived calcium phosphate (CaP) layer, to provide osteointegrative properties and (2) the controlled growth of the Ag nanoparticles over it, ranging the number of laser pulses from 100 to 500. The characterization by SEM, EDS, TEM, XPS and AFM revealed the uniform deposit of Ag rounded nanoparticles, with a narrow mean size distribution, in the original non-oxidized metallic state. Moreover, given the evidences from XPS and AFM techniques, the occurrence of a coalescence phenomenon from 400 pulses onwards was proposed together with the expected positive linear relation between the number of pulses and Ag contribution with a deposition rate of 0.05 at. % of Ag per pulse. Conversely, the decrease in roughness as the Ag content increased was also verified. Finally, the expected bacteriostatic activity for these PLD deposited metallic state Ag nanoparticles against the bacterial strain Staphylococcus aureus was confirmed. Moreover, the evaluation of the osteoblast-like MG-63 cells viability on the Ag(100–500)-CaP coatings revealed a significant increased proliferation (p > 0.05) on the Ag100-CaP coating compared to the control (Ag0-CaP). When same coating was evaluated against S. aureus the effect was not significant. The possibility of modulating the amount of nanoparticles in the bilayer coating to obtain a greater or lesser effect in combination with CaP was revealed.

Influence of a Calcium Phosphate Coating (BONIT®) on the Proliferation and Differentiation Potential of Human Mesenchymal Stroma Cells in the Early Phase of Bone Healing.

When implanting osteosynthetic materials or orthopedic implants, the surface condition plays a decisive role for mid- to long-term osseointegration. BONIT®, an electrochemically produced calcium phosphate (CaP) coating, has been used in the surface refinement of implants since 1995. More than 3.5 million coated implants have been successfully placed so far. BONIT® has thus been able to demonstrate clinical success. However, due to its surface properties and solubility, and the resulting difficulty in culturing cells, there are no in vitro studies investigating its influence at the molecular level, particularly on bone metabolism. In a first step, the cells from a total of ten donors were seeded separately on four different surfaces: 1. a pure corundum-blasted titanium surface (CELLTex®, CT), 2. CT with additional BONIT® coating (CT + B), 3. a hydroxyapatite-blasted titanium surface (DUOTex®, DT), 4. DT with additional BONIT® coating (DT + B). In a second step, the cells were grown for 48 h. The proliferation behavior and differentiation potential of hMSCs were investigated at three consecutive time points (12 h, 24 h and 48 h) by quantifying the mRNA expression of ten important differentiation markers using quantitative real-time polymerase chain reaction (qRT-PCR). We were able to show that BONIT® has an influence on the early proliferation and differentiation behavior of hMSCs in patients of all age groups. The additional BONIT® coating on CELLTex® or DUOTex® led to a defined mRNA expression pattern for the investigated factors: a tendency towards a higher expression rate with coating present could be found for bone morphogenetic protein 2 (BMP2), osteopontin (OPN), osteocalcin (OC), receptor activator of NF-κB ligand (RANKL) and osteoprotegerin (OPG). A similar or lower expression rate was detected for runt-related transcription factor 2 (RUNX2), alpha-1 type I collagen (COL1A1), alkaline phosphatase (AP), osteonectin (ON) and insulin-like growth factor I (IGF1). We have developed a new method that allows the cultivation of human mesenchymal stromal cells (hMSCs) on the soluble coating BONIT® for gene expression analysis. BONIT® has a significant influence on the proliferation and differentiation behavior of human mesenchymal stroma cells. This study describes a defined gene expression pattern of bone metabolism that may help to understand the influence of this CaP coating on the early phase of implant osseointegration.

Composition and morphology of calcium phosphate coatings formed on resorbable substrates based on pure Mg and Mg-HAp composite

Composition and morphology of calcium phosphate coatings formed on resorbable substrates based on pure Mg and Mg-HAp composite

RF Magnetron Sputtering of Substituted Hydroxyapatite for Deposition of Biocoatings.

Functionalization of titanium (Ti)-based alloy implant surfaces by deposition of calcium phosphates (CaP) has been widely recognized. Substituted hydroxyapatites (HA) allow the coating properties to be tailored based on the use of different Ca substitutes. The formation of antibacterial CaP coatings with the incorporation of Zn or Cu by an RF magnetron sputtering is proposed. The influence of RF magnetron targets elemental composition and structure in the case of Zn-HA and Cu-HA, and the influence of substrate’s grain size, the substrate’s temperature during the deposition, and post-deposition heat treatment (HT) on the resulting coatings are represented. Sintering the targets at 1150 °C resulted in a noticeable structural change with an increase in cell volume and lattice parameters for substituted HA. The deposition rate of Cu-HA and Zn-HA was notably higher compared to stochiometric HA (10.5 and 10) nm/min vs. 9 ± 0.5 nm/min, respectively. At the substrate temperature below 100 °C, all deposited coatings were found to be amorphous with an atomic short-range order corresponding to the {300} plane of crystalline HA. All deposited coatings were found to be hyper-stochiometric with Ca/P ratios varying from 1.9 to 2.5. An increase in the substrate temperature to 200 °C resulted in the formation of equiaxed grain structure on both coarse-grained (CG) and nanostructured (NS) Ti. The use of NS Ti notably increased the scratch resistance of the deposited coatings from18 ± 1 N to 22 ± 2 N. Influence of HT in air or Ar atmosphere is also discussed. Thus, the deposition of Zn- or Cu-containing CaP is a complex process that could be fine-tuned using the obtained research results.

In situ growth of Ca-Zn-P coatings on the Zn-pretreated WE43 Mg alloy to mitigate corrosion and enhance cytocompatibility

Magnesium (Mg) alloys are potential materials for orthopedic fixation devices but rapid degradation of the materials restricts wider clinical applications. Herein, zinc-incorporated calcium phosphate (Ca-Zn-P) coatings are prepared on the Zn-pretreated WE43 Mg alloy by a hydrothermal technique under relatively stable and favorable conditions. The hydrothermal coating consists of a compact bottom layer of CaZn2(PO4)2∙2 H2O and ZnO granular crystals and a jagged upper layer of CaHPO4. The Zn coating reduces the corrosion current density of WE43 to (3.49 ± 1.60) × 10−5 A cm−2, whereas the Ca-Zn-P/Zn composite coating further reduces it by 3 orders of magnitude in the simulated body fluid (SBF). The charge transfer resistances of the Zn-coated and Ca-Zn-P/Zn-coated alloys increase by 49 and 7176 times to 835 and 1.22 × 105 Ω cm2, respectively. The 7-day immersion results reveal that the Zn coating cannot provide long-term protection to WE43 in SBF because of the formation of galvanic couples between the Zn coating and WE43. In contrast, Ca-Zn-P/Zn-coated WE43 remains intact after soaking for 7 days and furthermore, the Ca-Zn-P coating self-repairs and continues to grow despite dissolution. The compact and adherent Ca-Zn-P bottom layer plays a major role in mitigating corrosion of WE43 by hindering penetration of the aggressive medium and charge transfer of the corrosion reactions resulting in only slight corrosion of the Zn layer. Biologically, the Zn coating reduces attachment and proliferation of MC3T3-E1 pre-osteoblasts on WE43, but the composite coating fosters cell adhesion and proliferation which stems from the good biocompatibility of the hydrothermal layer and relatively stable surface conditions avoiding severe corrosion.

Investigation of hexamethylenetetramine effects on formation and corrosion resistance of anodic coatings developed on AZ31B alloys

To fabricate calcium-phosphate (CaP) coatings with good corrosion resistance on AZ31B alloys via micro-arc oxidation (MAO) treatment, hexamethylenetetramine (HMTA) was selected as an effective MAO additive of magnesium alloys. The influences of HMTA concentrations on formation mechanism and coating property were systematically investigated in a near-neutral base solution composed of NH4HF2, EDTA-CaNa2, phytic acid and phosphoric acid. The results show that HMTA can increase the solubility of calcium salts and significantly promote the formation of MAO coatings on AZ31B alloys. In a base solution with 360 g/L HMTA, the fabricated MAO sample achieves the best corrosion resistance in Hank's solution and the corrosion current density (icorr) is significantly decreased by two orders of magnitude than that treated in solution without HMTA. During MAO treatment, acting as an effective corrosion inhibitor of magnesium alloys, HMTA is helpful for coating formation via protecting the magnesium sample from corrosion. In 3.5 % NaCl solution with different HMTA concentrations, the maximum inhibition efficiency is 94.57 % at a HMTA concentration of 360 g/L. Moreover, HMTA molecules are absorbed on the surface of AZ31B alloys following the Langmuir absorption isotherm in the range of 120 to 360 g/L, however, excessively high concentrations fail to conform with the equation, which may be attributed to steric hindrance.