Hydroxyapatite Bioceramic Coatings Prepared by Hydrothermal-electrochemical Deposition Method

The hydroxyapatite（HA） ceramic coating was successfully prepared on Ti6A14V alloy by the hydrothermal-electrochemical deposition method with constant voltage model. The phases of deposits were analyzed by X-ray diffraction. The releationship between crystallinity and depositing temperature was discussed. The microstructures of hydroxyapatite coating were observed by scanning electron microscope. The experimental results showed that the phases, crystaUinity and morphologies of deposits were influenced by depositing temperature （100℃, 120℃, 140℃, 160℃, 180℃ and 200℃, respectively）. The special hydrothermal environment can lower the crystallization temperature of HA. The crystallinity of HA increases firstly and then decreases with the increase of temperature. There is little hydroxyapatite deposited on the Ti6A14V surface when the depositing temperature is 100℃. The HA deposition increases with the increase of the depositing temperature. And the HA morphologies are influenced by the depositing temperature.

Hydroxyapatite Coatings on Titanium Prepared by Electrodeposition in a Modified Simulated Body Fluid

Hydroxyapatite coatings were directly prepared on anodized titanium by electro-deposition method in a modified simulated body fluid.The configuration,structure and bioactivity of the coating were investigated with scanning electron microscopy(SEM),X-ray diffraction analyzer(XRD)and Fourier transform infrared spectros-copy(FTIR)techniques.The results demonstrated that pure and homogeneous hydroxyapatite coating can be obtained without any post-treatment.The prepared coating showed good bioactivity in simulated body fluid(SBF).The time required for a fully covered dense hydroxyapatite coatings was 4 days immersion in SBF.

Preparation and properties of a cerium-containing hydroxyapatite coating on commercially pure titanium by micro-arc oxidation

A porous cerium-containing hydroxyapatite coating on commercially pure titanium was prepared by micro-arc oxidation （MAO） in an electrolytic solution containing calcium acetate, p-glycerol phosphate disodium salt pentahydrate （β-GP）, and cerium nitrate. The thickness, phase, composition morphology, and biocompatibility of the oxide coating were characterized by X-ray diffraction （XRD）, electron probe microanalysis （EPMA）, scanning electron microscopy （SEM） with energy dispersive X-ray spectrometer （EDS）, and cell culture. The thickness of the MAO film is about 15-25 ~tm, and the coating is porous and uneven, without any apparent interface to the titanium substrates. The results of XRD and EDS show that the porous coating is made up of hydroxyapatite （HA） film containing Ce. The favorable osteoblast cell affinity makes the Ce-HA film have a good biocompatibility. The Ce-HA film is expected to have significant medical applications as dental implants and artificial bone joints.

Influence of processing parameters and heat treatment on phase composition and microstructure of plasma sprayed hydroxyapatite coatings

Air plasma spraying process was employed to fabricate various hydroxyapatite(HA)coatings on titanium substrates.The influence of processing parameters on the phase composition and the microstructure of the obtained coatings was investigated.The effect of heat treatment on as-sprayed coating in terms of the crystallinity and microstructure was also studied.The phase composition of coatings was analyzed by X-ray diffraction(XRD)and FTIR.The surface and cross-section morphologies and microstructure of coatings as well as the morphology of feedstock were evaluated using scanning electron microscope(SEM).The crystallization temperature of amorphous HA phase in as-sprayed coating was examined by using differential thermal analysis(DTA). The results suggest that phase composition and microstructure of as-sprayed HA coatings strongly depend on the spraying parameters,and heat treatment at 760 ℃for 2 h is one of effective means for increasing the crystallinity and improvement in microstructure of as-sprayed HA coatings.

Influence of Zirconia on Hydroxyapatite Coating on Ti-Alloy by Laser Cladding

Coating titanium alloy with the bioceramic material hydroxyapatite(HAP) has been used to improve the poor osteoinductive properties of pure titanium alloy. But in clinical applications, the mechanical failure of HAP-coated titanium alloy implant suffered at the interface of the HAP coatings and titanium alloy substrate will be a potential weakness in prosthesis. Yttria-stablized zirconia (YSZ) is expected to enhance the mechanical properties of the HAP coating and reduce the coefficient of thermal expansion difference between the coated layer and the substrate. These may reinforce the bonding strength between the coatings and the substrate. In this paper, HAP/YSZ composite coatings were cladded by laser. The effects of zirconia on the microstructure, mechanical properties and formation of tricalcium phosphate (TCP, Ca 3(PO 4) 2) of the HAP/YSZ composite coatings were evaluated. XRD, SEM and TEM were used to investigate the phase composition, microstructure and morphology of the coatings. The experimental results showed that adding YSZ in coatings was favorable to the composition and stability of HAP, and to the improvement of the adhesion strength, microhardness and microtoughness. A well uniform, crack-free coating of HAP/YSZ composites was formed on Ti-alloy substrate by laser cladding.

Influence of Different Chelating Agents on Corrosion Performance of Microstructured Hydroxyapatite Coatings on AZ91D Magnesium Alloy

To improve the bioactivity and corrosion resistance of AZ91 D magnesium alloy,hydroxyapatite（HAp） coatings with novel microstructured morphologies were prepared successfully on AZ91 D substrates via a facile hydrothermal method.Different chelating agents including polyaspartic acid（PASP） and ethylenediaminetetraacetic acid（EDTA） were introduced to investigate their effects on the morphology and corrosion resistance of the coated magnesium alloys.The results revealed that the coating prepared with PASP was composed of many uniform urchin-like microspheres,while the coating prepared with EDTA consisted of many flower-like particles.Moreover,the crystallinity of the coating prepared with EDTA was much higher than that of the coating prepared with PASP.Electrochemical tests revealed that the corrosion resistance of the substrate was significantly improved after being coated with each coating.Immersion test of the coated samples in simulated body fluid（SBF） demonstrated that the coatings could be biodegraded gradually and induce the formation of calcium phosphate particles.

Study on the subsonic speed flame spraying coating of hydroxyapatite

A new method of preparation of biomaterial composite coating by the techniqueof subsonic thermal spraying was discussed in this paper. Ti_6Al_4V and pure Ti were chosen assubstrate and sublayer material respectively and the working layer was sprayed with biomaterialhydroxyapatite (HAP), forming the composite coating. The experiments of heat shock and tensilestrength showed that the bonding strength between coating and substrate is almost as same as that ofspecimen in which Ni/Al powder was adopted as sublayer. The phases of TiN, TiO_2, and Ti_2O_3 wereformed in the sublayer, which are free of toxic and have no side effects. The powder of workinglayer HAP was decomposed partly during spraying, but it can be solved by later treatment.

HA coating on Mg alloys for biomedical applications:A review

Magnesium(Mg)alloys are receiving increasing attention as biodegradable implant materials in recent years.However,their low corrosion resistance and fast degradation in the physiological environment remain challenges for a widespread application.Hydroxyapatite(HA)coating on Mg alloys can enhance their corrosion resistance,biocompatibility,and bioactivity of the Mg alloy substrates since the compositions of HA are similar to those of the hard tissue of natural bone.This review analyzes the challenges of Mg alloys for biomedical applications,the fundamental requirements for biodegradable metals,and the corrosion mechanisms of Mg alloys in the physiological environment.The benefits of HA coatings on Mg alloys,the most commonly used surface coating techniques and their advantages and limitations,and the in vitro and in vivo performance of Mg alloys with and without surface coatings are comprehensively elucidated.Multistep processes such as alkali treatment and then HA coating by electrochemical deposition on Mg alloys appear to be necessary to achieve a satisfactory surface coating on Mg alloys,which has been demonstrated to have the potential to improve the degrading behavior,bioactivity and biocompatibility.Multifunctional coatings are most effective in achieving safe and bioactive Mg alloy surfaces for promising biodegradable implant applications.

In vitro biodegradability and biocompatibility of porous Mg-Zn scaffolds coated with nano hydroxyapatite via pulse electrodeposition

The biodegradability and biocompatibility of porous Mg-2Zn（mass fraction, %） scaffolds coated with nano hydroxyapatite（HAP） were investigated. The nano HAP coating on Mg-2Zn scaffolds was prepared by the pulse electrodeposition method. The as-deposited scaffolds were then post-treated with alkaline solution to improve the biodegradation behavior and biocompatibility for implant applications. The microstructure and composition of scaffold and nano HAP coating, as well as their degradation and cytotoxicity behavior in simulated body fluid（SBF） were investigated. The post-treated coating is composed of needle-like HAP with the diameter less than 100 nm developed almost perpendicularly to the substrate, which exhibits a similar composition to natural bone. It is found that the products of immersion in SBF are identified to be HAP,（Ca,Mg）3（PO4）2 and Mg（OH）2. The bioactivity, biocompatibility and cell viabilities for the as-coated and post-treated scaffold extracts are higher than those for the uncoated scaffold. MG63 cells are found to adhere and proliferate on the surface of the as-coated and post-treated scaffolds, making it a promising choice for medical application. The results show that the pulse electrodeposition of nano HAP coating and alkaline treatment is a useful approach to improve the biodegradability and bioactivity of porous Mg-Zn scaffolds.

Biomimetic hydroxyapatite coating on the 3D-printed bioactive porous composite ceramic scaffolds promoted osteogenic differentiation via PI3K/AKT/mTOR signaling pathways and facilitated bone regeneration in vivo

The architecture and surface modifications have been regarded as effective methods to enhance the bi-ological response of biomaterials in bone tissue engineering.The porous architecture of the implanta-tion was essential conditions for bone regeneration.Meanwhile,the design of biomimetic hydroxyap-atite(HAp)coating on porous scaffolds was demonstrated to strengthen the bioactivity and stimulate osteogenesis.However,bioactive bio-ceramics such asβ-tricalcium phosphate(β-TCP)and calcium sili-cate(CS)with superior apatite-forming ability were reported to present better osteogenic activity than that of HAp.Hence in this study,3D-printed interconnected porous bioactive ceramicsβ-TCP/CS scaf-fold was fabricated and the biomimetic HAp apatite coating were constructed in situ via hydrothermal reaction,and the effects of HAp apatite layer on the fate of mouse bone mesenchymal stem cells(mBM-SCs)and the potential mechanisms were explored.The results indicated that HAp apatite coating en-hanced cell proliferation,alkaline phosphatase(ALP)activity,and osteogenic gene expression.Further-more,PI3K/AKT/mTOR signaling pathway is proved to have an important impact on cellular functions.The present results demonstrated that the key molecules of phosphatidylinositol 3-kinase(PI3K),protein kinase B(AKT)and mammalian target of rapamycin(mTOR)were activated after the biomimetic hydrox-yapatite coating were constructed on the 3D-printed ceramic scaffolds.Besides,the activated influence on the protein expression of Runx2 and BMP2 could be suppressed after the treatment of inhibitor HY-10358.In vivo studies showed that the constructed HAp coating promoted bone formation and strengthen the bone quality.These results suggest that biomimetic HAp coating constructed on the 3D-printed bioac-tive composite scaffolds could strengthen the bioactivity and the obtained biomimetic multi-structured scaffolds might be a potential alternative bone graft for bone regeneration.

Effects of zinc-substituted nano-hydroxyapatite coatings on bone integration with implant surfaces

Objective:The purpose of this study was to investigate the effects of a zinc-substituted nano-hydroxyapatite(Zn-HA) coating,applied by an electrochemical process,on implant osseointegraton in a rabbit model.Methods:A Zn-HA coating or an HA coating was deposited using an electrochemical process.Surface morphology was examined using field-emission scanning electron microscopy.The crystal structure and chemical composition of the coatings were examined using an X-ray diffractometer(XRD) and Fourier transform infrared spectroscopy(FTIR).A total of 78 implants were inserted into femurs and tibias of rabbits.After two,four,and eight weeks,femurs and tibias were retrieved and prepared for histomorphometric evaluation and removal torque(RTQ) tests.Results:Rod-like HA crystals appeared on both implant surfaces.The dimensions of the Zn-HA crystals seemed to be smaller than those of HA.XRD patterns showed that the peaks of both coatings matched well with standard HA patterns.FTIR spectra showed that both coatings consisted of HA crystals.The Zn-HA coating significantly improved the bone area within all threads after four and eight weeks(P<0.05),the bone to implant contact(BIC) at four weeks(P<0.05),and RTQ values after four and eight weeks(P<0.05).Conclusions:The study showed that an electrochemically deposited Zn-HA coating has potential for improving bone integration with an implant surface.

Corrosion Behavior and Biocompatibility of Hydroxyapatite Coating on H_2SO_4 Passivated 316L SS for Human Body Implant

The aim of this studies at simultaneous improvement of the corrosion behavior and biocompatibility of metallic implant and bone Osseointegration simultaneously. Stainless steel 316L （SS） was used as metallic substrate and after surface treatment with 15 vol.% sulfuric acid, it was coated with hydroxyapatite coating employing plasma - spraying process. Structure characterization techniques including XRD, SEM and EDX were also utilized to investigate the microstructure, morphology, and crystallinity of the coating. Electrochemical potentiodynamic tests were performed in two types of physiological solutions in order to determine and compare the corrosion resistance behavior of the coated and uncoated specimens as an indication of biocompatibility. The results indicate that the surface treatment and hydroxyapatite coating improve the corrosion resistance behavior of SS. The corrosion current density of the surface treated and the hydroxyapatite coated SS also decrease. These also show that surface treated and hydroxyapatite coated SS can be used as human body implants with the goals of corrosion resistance improvement （biocompatibility） and bone osseointegration.

Determination of bisphosphonates anti-resorptive properties based on three forms of ceramic materials: Sorption and release process evaluation

There is a strong need to search for more effective compounds with bone anti-resorptive properties,which will cause fewer complications than commonly used bisphosphonates. To achieve this goal, it is necessary to search for new techniques to characterize the interactions between bone and drug. By studying their interaction with hydroxyapatite(HA), this study used three forms of ceramic materials,two of which are bone-stimulating materials, to assess the suitability of new active substances with antiresorptive properties. In this study, three methods based on HA in loose form, polycaprolactone/HA(a polymer-ceramic materials containing HA), and polymer-ceramic monolithic in-needle extraction(MINE) device(a polymer inert skeleton), respectively, were used. The affinity of risedronate(a standard compound) and sixteen aminomethylenebisphosphonates(new compounds with potential antiresorptive properties) to HA was defined according to the above-mentioned methods. Ten monolithic materials based on 2-hydroxyethyl methacrylate/ethylene dimethacrylate are prepared and studied, of which one was selected for more-detailed further research. Simulated body fluids containing bisphosphonates were passed through the MINE device. In this way, sorptionedesorption of bisphosphonates was evaluated using this MINE device. The paper presents the advantages and disadvantages of each technique and its suitability for assessing new active substances. All three methods allow for the selection of several compounds with potentially higher anti-resorptive properties than risedronate, in hope that it reflects their higher bone affinity and release ability.

RF magnetron-sputtered coatings deposited from biphasic calcium phosphate targets for biomedical implant applications

Bioactive calcium phosphate coatings were deposited by radio-frequency magnetron sputtering from biphasic targets of hydroxyapatite and tricalcium phosphate,sintered at different mass%ratios.According to Raman scattering and X-ray diffraction data,the deposited hydroxyapatite coatings have a disordered structure.High-temperature treatment of the coatings in air leads to a transformation of the quasi-amorphous structure into a crystalline one.A correlation has been observed between the increase in the Ca content in the coatings and a subsequent decrease in Ca in the biphasic targets after a series of deposition processes.It was proposed that the addition of tricalcium phosphate to the targets would led to a finer coating's surface topography with the average size of 78 nm for the structural elements.

Forsterite-hydroxyapatite composite scaffolds with photothermal antibacterial activity for bone repair

Bone engineering scaffolds with antibacterial activity satisfy the repair of bacterial infected bone defects,which is an expected issue in clinical.In this work,3D-printed polymer-derived forsterite scaffolds were proposed to be deposited with hydroxyapatite(HA)coating via a hydrothermal treatment,achieving the functions of photothermal-induced antibacterial ability and bioactivity.The results showed that polymer-derived forsterite scaffolds possessed the photothermal antibacterial ability to inhibit Staphylococcus aureus(S.aureus)and Escherichia coli(E.coli)in vitro,owing to the photothermal effect of free carbon embedded in the scaffolds.The morphology of HA coating on forsterite scaffolds could be controlled through changing the hydrothermal temperature and the pH value of the reaction solution during hydrothermal treatment.Furthermore,HA coating did not influence the mechanical strength and photothermal effect of the scaffolds,but facilitated the proliferation and osteogenic differentiation of rat bone mesenchymal stem cells(rBMSCs)on scaffolds.Hence,the HA-deposited forsterite scaffolds would be greatly promising for repairing bacterial infected bone defects.