Interfacial bond strength of electrophoretically deposited hydroxyapatite coatings on metals

Hydroxyapatite (HAp) coatings were deposited onto substrates of metal biomaterials (Ti, Ti6Al4V, and 316L stainless steel) by electrophoretic deposition (EPD). Only ultra-high surface area HAp powder, prepared by the metathesis method 10Ca(NO₃)₂ + 6(NH₄)₂HPO₄ + 8NH₄OH), could produce dense coatings when sintered at 875–1000°C. Single EPD coatings cracked during sintering owing to the 15–18% sintering shrinkage, but the HAp did not decompose. The use of dual coatings (coat, sinter, coat, sinter) resolved the cracking problem. Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) inspection revealed that the second coating filled in the valleys in the cracks of the first coating. The interfacial shear strength of the dual coatings was found, by ASTM F1044-87, to be 12 MPa on a titanium substrate and 22 MPa on 316L stainless steel, comparing quite favorably with the 34 MPa benchmark (the shear strength of bovine cortical bone was found to be 34 MPa). Stainless steel gave the better result since -316L (20.5 m mK^-1) > -HAp (14 m mK^-1), resulting in residual compressive stresses in the coating, whereas -titanium (10.3 m mK^-1) < -HAp, resulting in residual tensile stresses in the coating. © 1999 Kluwer Academic Publishers     

Microstructures and bond strengths of plasma-sprayed hydroxyapatite coatings on porous titanium substrates

Hydroxyapatite (HA) coating was carried out by plasma spraying on bulk Ti substrates and porous Ti substrates having a Young’s modulus similar to that of human bone. The microstructures and bond strengths of HA coatings were investigated in this study. The HA coatings with thickness of 200–250 μ m were free from cracks at interfaces between the coating and Ti substrates. XRD analysis revealed that the HA powder used for plasma spraying had a highly crystallized apatite structure, while the HA coating contained several phases other than HA. The bond strength between the HA coating and the Ti substrates evaluated by standard bonding test (ASTM C633-01) were strongly affected by the failure behavior of the HA coating. A mechanism to explain the failure is discussed in terms of surface roughness of the plasma-sprayed HA coatings on the bulk and porous Ti substrates.     

Bioactive nanocomposite coatings of collagen/hydroxyapatite on titanium substrates

Collagen/hydroxyapatite (HA) nanocomposite thin films containing 10, 20, and 30 wt.% HA were prepared on commercially pure titanium substrates by the spin coating of their homogeneous sols. All of the nanocomposite coatings having a thickness of ∼7.5 μm exhibited a uniform and dense surface, without any obvious aggregation of the HA particles. A minimum contact angle of 36.5° was obtained at 20 wt.% HA, suggesting that these coatings would exhibit the best hydrophilicity. The in vitro cellular assays revealed that the coating treatment of the Ti substrates favored the adhesion of osteoblast-like cells and significantly enhanced the cell proliferation rate. The cells on the nanocomposite coatings expressed much higher alkaline phosphatase (ALP) levels than those on the uncoated Ti substrates. Increasing the amount of HA resulted in a gradual improvement in the ALP activity. The nanocomposite coatings on Ti substrates also exhibited much better cell proliferation behaviors and osteogenic potentials than the conventional composite coatings with equivalent compositions, demonstrating the greater potential of the former as implant materials for hard tissue engineering.     

Sol-gel derived hydroxyapatite coatings on titanium substrate

Biomaterials, in particular those used for orthopaedic prostheses, consist of a metallic substrate, exhibiting excellent mechanical properties, coated with a ceramic layer, which guarantees resistance to the corrosion and an elevated bioactivity. In this paper the preparation of sol-gel films of hydroxyapatite, HA (Ca₁₀(PO₄)₆(OH)₂), on titanium substrate is described. The samples were obtained through the dip-coating method, starting from a colloidal suspension of hydroxyapatite. In order to increase the adhesion between the HA film and the metallic substrate, the same substrate has been preliminarily coated either with titanium oxide, TiO₂ (in the anatase or rutile phase), or calcium titanate, CaTiO₃ (perovskite). Also these latter films have been deposited from a sol-gel solution. The characterization of the films through XRD, SEM, and AFM gave good results for the crystallinity of the deposited HA; for what concerns the sample morphology, the films turned out to be homogeneous and crack-free.     

Antibacterial hydroxyapatite coatings on titanium dental implants

Titanium and its alloys are often used as substrates for dental implants due to their excellent mechanical properties and good biocompatibility. However, their ability to bind to neighboring bone is limited due to the lack of biological activity. At the same time, they show poor antibacterial ability which can easily cause bacterial infection and chronic inflammation, eventually resulting in implant failure. The preparation of composite hydroxyapatite coatings with antibacterial ability can effectively figure out these concerns. In this review, the research status and development trends of antibacterial hydroxyapatite coatings constructed on titanium and its alloys are analyzed and reviewed. This review may provide valuable reference for the preparation and application of high-performance and multi-functional dental implant coatings in the future.     

Plasma sprayed graded titanium hydroxyapatite coatings

Abstract

A series of graded titanium-hydroxyapatite (HA) coatings have been produced by single gun plasma spray technology, and their performance was compared with that of pure HA coating. The results show that deformed HA and titanium particles exhibit an alternate distribution in respective networks formed within the coatings. In comparison with a pure HA coating, less cracks appeared on the surface of the graded coatings and the shear bond strength was increased by 50-80%. The graded coating with two interlayers and a thin outer HA layer contained crystalline HA, an amorphous phase, α-tricalcium phosphate (TCP), β-TCP, tetracalcium phosphate (TTCP), TiO₂ and TiN; while no Ti-HA compounds were formed. As compared with pure HA coating, the graded coating contained more decomposed phases TCP and TTCP, resulting from titanium catalysing HA decomposition.     

热处理对羟基磷灰石涂层相组成、表面形貌与结合强度的影响

羟基磷灰石(HA)涂层的喷涂及其后处理工艺对其组织结构和结合强度具有重要影响.比较了热处理对不同粒度HA涂层相组成、表面形貌与结合强度的影响,为该类涂层制备工艺的优化提供实验依据.采用等离子喷涂法在纯钛表面制备了不同粒度的HA涂层,对其进行650℃不同保温时间的后热处理.利用X射线衍射仪、扫描电子显微镜和电子拉伸机检测了涂层的相组成、表面与断口形貌及剪切结合强度等.结果表明,涂层经650℃保温0.5h热处理后,非晶相和分解相基本全部转变为结晶HA.经热处理晶化后,涂层表面生成300nm以下的微粒子,双重涂层BC表面更易形成.粗粉末涂层CC和BC热处理后的剪切强度提高,而细粉末涂层FC则相反;HA涂层的剪切断裂主要是发生在涂层与基体间的界面上.     

Nano-Ag-loaded hydroxyapatite coatings on titanium surfaces by electrochemical deposition

Hydroxyapatite (HA) coatings on titanium (Ti) substrates have attracted much attention owing to the combination of good mechanical properties of Ti and superior biocompatibility of HA. Incorporating silver (Ag) into HA coatings is an effective method to impart the coatings with antibacterial properties. However, the uniform distribution of Ag is still a challenge and Ag particles in the coatings are easy to agglomerate, which in turn affects the applications of the coatings. In this study, we employed pulsed electrochemical deposition to co-deposit HA and Ag simultaneously, which realized the uniform distribution of Ag particles in the coatings. This method was based on the use of a well-designed electrolyte containing Ag ions, calcium ions and l-cysteine, in which cysteine acted as the coordination agent to stabilize Ag ions. The antibacterial and cell culture tests were used to evaluate the antibacterial properties and biocompatibility of HA/Ag composite coatings, respectively. The results indicated the as-prepared coatings had good antibacterial properties and biocompatibility. However, an appropriate silver content should be chosen to balance the biocompatibility and antibacterial properties. Heat treatments promoted the adhesive strength and enhanced the biocompatibility without sacrificing the antibacterial properties of the HA/Ag coatings. In summary, this study provided an alternative method to prepare bioactive surfaces with bactericidal ability for biomedical devices.     

Biomechanical evaluation of different hydroxyapatite coatings on titanium for keratoprosthesis

Stable tissue integration is important to keratoprosthesis (KPro). The aim of this study was to evaluate the tissue bonding ability of hydroxyapatite (HAp)-coated titanium KPro. The samples were divided into three groups: test groups (IBAD group and AD group) and Ti control. The coated samples had a HAp layer created by ion beam assisted deposition (IBAD) or aerosol deposition (AD). The surface characteristics were analyzed with SEM, AFM, and XRD. The samples were surgically inserted into the muscles of rabbits. Eight weeks after healing, the attachment to the tissue was tested with a universal test device. The three samples exhibited distinctive surface morphology. The force to remove the HAp implants from the muscles was significantly greater than that of Ti group (P<0.01), with the AD samples requiring the greatest force (P<0.01). After removal, SEM showed that the tissue was firmly attached to the surface of AD samples. Photomicrographs of the peri-implant muscles showed a layer of aligned fibrous tissue without severe inflammation. The AD samples had more fibroblasts. Results indicate that because of enhanced mechanical adhesion of soft tissue to the implants, HAp-coated Ti by AD is a suitable KPro skirt material.     

Plasma spraying of zirconia-reinforced hydroxyapatite composite coatings on titanium: Part I Phase, microstructure and bonding strength

Plasma-sprayed hydroxyapatite (HA) coatings applied to metal substrates can induce a direct chemical bond with bone and hence achieve biological fixation of the implant. However, the poor bonding strength between HA and substrate has been of concern to orthopaedists. In this study, two submicrometre ZrO2 powders stabilized with both 3 and 8 mol% Y2O3 (TZ3Y and TZ8Y, respectively) were incorporated in a plasma-sprayed HA coating on Ti-6Al-4V substrate to investigate the change in phase, microstructure and bonding strength. The results show that ZrO2 composite coatings contain more unmelted particles and greater porosity. During plasma spraying, ZrO2 reacts with the CaO in HA to form CaZrO3 and accelerates HA decomposition to -TCP and Ca4P2O9. Nevertheless, bonding strength increases with increase of ZrO2 content in the range 0 to 10 wt% studied. The higher Y2O3-containing TZ8Y apparently exerts a greater strengthening effect than the lower Y2O3-containing TZ3Y.     

磁/电场约束下钛合金表面羟基磷灰石/TiO_2复合生物涂层的制备

用恒电位阳极氧化法分别以硫酸和磷酸为电解液,在钛合金基体上制备出具有不同孔径大小和不同晶型的TiO2涂层. 外加磁场条件下,在TiO2涂层上电沉积形成纳米羟基磷灰石涂层.当垂直电场方向施加1T磁场时,在洛伦兹力影响下生长成羟基磷灰石生长成长度大约为200nm,直径大约为50nm的棒状晶粒;在磁场平行于电场的条件下,生成直径为50-70nm的粒状晶粒.纳米羟基磷灰石与多孔TiO2涂层之间几何形貌的匹配程度,影响复合涂层与钛合金基体的结合强度.当TiO2涂层的孔径大约为100 nm时,棒状羟基磷灰石晶粒与钛合金基体间的锁合更牢固,结合力更强.     

Evaluation of adhesion strength and toughness of fluoridated hydroxyapatite coatings

Adhesion strength and fracture toughness are two crucial mechanical properties for bioceramic coatings on metal implants directly affecting successful implantation and long-term stability. In this study, the adhesion strength of sol-gel derived FHA coatings on Ti6Al4V substrates was measured by pull-out tensile test, and the toughness was assessed by energy release method. With increase of the degree of fluoridation, the adhesion strength increases up to about 40% and the fracture toughness increases about 200 to 300%. Contrary to the wide-spread belief, it is interesting to note that after soaking in the Tris-buffered physiological saline solution (for 21 days), the adhesion strength increases about 60% as compared with the as-deposited coating, instead of decreasing. The mechanism of the increase is discussed.     

Electrophoretic-deposited novel ternary silk fibroin/graphene oxide/hydroxyapatite nanocomposite coatings on titanium substrate for orthopedic applications

The combination of graphene oxide (GO) with robust mechanical property, silk fibroin (SF) with fascinating biological effects and hydroxyapatite (HA) with superior osteogenic activity is a competitive approach to make novel coatings for orthopedic applications. Herein, the feasibility of depositing ternary SF/GO/HA nanocomposite coatings on Ti substrate was firstly verified by exploiting electrophoretic nanotechnology, with SF being used as both a charging additive and a dispersion agent. The surface morphology, microstructure and composition, in vitro hemocompatibility and in vitro cytocompatibility of the resulting coatings were investigated by SEM, Raman, FTIR spectra and biocompatibility tests. Results demonstrated that GO, HA and SF could be co-deposited with a uniform, smooth thin-film morphology. The hemolysis rate analysis and the platelet adhesion test indicated good blood compatibility of the coatings. The human osteosarcoma MG63 cells displayed well adhesion and proliferation behaviors on the prepared coatings, with enhanced ALP activities. The present study suggested that SF/GO/HA nanocomposite coatings could be a promising candidate for the surface functionalization of biomaterials, especially as orthopedic implant coating.     

The process of electrochemical deposited hydroxyapatite coatings on biomedical titanium at room temperature

Calcium phosphate (CaP) ceramics, especially hydroxyapatite (HA), have received much attention and have been clinically applied in orthopaedics and dentistry due to their excellent biocompatibility. Among several methods for preparing HA coating, electrochemical deposition is a relatively new and possible process. However, documented electrochemical processes were conducted at elevated temperature. In this study, uniform HA coatings have been directly deposited on titanium at room temperature. X-ray diffractometry (XRD) results demonstrated that dicalcium phosphate dihydrate (CaHPO₄·2H₂O, DCPD) was the main component of the coating deposited at lower current densities (1 and 5 mA/cm²). HA structure was obtained at current density above 10 mA/cm² and remained stable after heat treatment at 100–600 °C for 1 h. Part of HA phase was transformed into β-TCP and became a biphasic calcium phosphate coating after annealing at 700 °C. Scratch tests showed that HA coating was not scraped off until a shear stress of 106.3 MPa. Coatings deposited at room temperature exhibited stronger adhesion than those at elevated temperature. HA coating revealed a dense inner layer and rough surface morphology which could fulfill the requisition of implant materials and be adequate to the attachment of bone tissue.     

Highly adhesive hydroxyapatite coatings on titanium alloy formed by ion beam assisted deposition

A compact crystalline hydroxyapatite coating on Ti–6Al–4V substrate with an atomic intermixed coating/substrate interface about 27 nm in width was synthesized by ion beam assisted deposition (IBAD) and a following post-treatment. The coating after post-treatment was identified by X-ray diffraction as crystalline hydroxyapatite. The interface between coatings and substrates was studied by Auger electron spectroscopy. The adhesive strength between coatings and substrates was measured by scratch tester. The results showed that the adhesive strength of IBAD coatings is nearly twice that of ion beam sputtered coatings. The study also showed that coatings prepared by IBAD eliminated the interfacial deficiencies existing in plasma-sprayed coatings.     

Nanoindentation study of magnetron-sputtered CrN and CrSiN coatings

CrN and CrSiN coatings were deposited on stainless steel substrate by reactive magnetron sputtering. The coatings were characterized for phases, chemical composition, microstructure, and mechanical properties by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM)/energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), and nanoindentation technique, respectively. The cubic phase was the only phase observed in both the coatings as observed in XRD results. A dense morphology was observed in these coatings deposited with high nitrogen and Si contents, 50:50 and 18.65 at.%, respectively. Nanoindentation measurement of CrN coatings, with Ar + N₂ proportions of 60:40, showed maximum hardness (H) and modulus (E) of 21 ± 0.85 GPa and 276 ± 13 GPa, respectively. The CrN coatings deposited in pure N₂ atmosphere showed H and E values of 27 ± 1.62 and 241 ± 10 GPa, respectively. The measured H and E values of CrSiN coatings were found to be 28 ± 1.40 GPa and 246 ± 10 GPa, respectively. The improved hardness in both the coatings was attributed mainly to a reduction in crystallite size, decrease in surface roughness, and dense morphology. The incorporation of Si into the CrN coatings has improved both hardness and Young’s modulus.     

In vitro cytocompatibility and corrosion resistance of zinc-doped hydroxyapatite coatings on a titanium substrate

To improve biocompatibility and corrosion resistance during the initial implantation stage, zinc-substituted hydroxyapatite (ZnHAp) coating was fabricated on pure titanium by the electrolytic deposition method. The morphology, microstructure and chemical composition of the coating were investigated by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis and Fourier transform infrared spectroscopy. The prepared ZnHAp crystals were calcium deficient and were carbonated owing to the incorporation of some Zn²⁺. This incorporation of Zn²⁺ into the HAp significantly reduced porosity and caused the coating to become noticeably denser. In addition, the Zn²⁺ ions were homogeneously distributed in the coating. The potentiodynamic polarisation test revealed that the ZnHAp-coated surface showed superior corrosion resistance over that of the HAp-coated surface and bare Ti. The in vitro bioactivity was evaluated in a simulated body fluid, which revealed that the ZnHAp coating can rapidly induce bone-like apatite formation of nuclear and growth features. In addition, the cell response tests showed that the MC3T3-E1 cells on the ZnHAp coating clearly enhanced the in vitro cytocompatibility of Ti compared with the same cells on HAp coating. ZnHAp coating was thus beneficial for improving biocompatibility.     

Effect of vacuum deposited coatings on the fatigue strength of commercial-grade titanium

A procedure is described and results are given for a study of the effect of coatings made of nitrides TiN and (CrTi)N on the fatigue strength σ_?1 of sheet titanium VT1-0 with high-frequency (～ 10 kHz) cyclic bending. Use of cantilever specimens of simple geometry consisting of two steps of constant cross section made it possible on one hand to improve their technological efficiency, and on the other hand to provide the maximum reliability for experimental results in view of accurate determination of the failure stresses by calculation. Due to high-frequency loading the test time is reduced including the time for the production and preparation of specimens due to shortening them with an increase in working frequency during resonance tests. Six batches of material are tested including uncoated specimens. It is shown that with a base thickness of 0.5 mm coatings on TiN and (CrTi)N with a thickness of 0.6 Μm increase σ_?1 by 11.3 and 7.5% respectively. Introduction beneath the TiN coating of intermediate layers of Ti and Cr with a thickness up to 0.25 Μm leads to a reduction in σ_?1 compared with this characteristic for a TiN coating without an interlayer. An interlayer of Cr promotes a reduction in σ_?1 to a level below that for uncoated material by ?3.8%, but a layer Ti increases it above this level by +3.8%. Analysis of the results obtained shows that introduction of the ‘worst’ Cr interlayer with a thickness of 0.5 Μm beneath the worst of the two comparable coatings, i.e., a (CrTi)N coating, increases the value of σ_?1 by 17% compared with σ_?1 for uncoated material. A practical possibility is noted for optimizing coatings and improving σ_?1 as a result varying production process parameters without reorganizing it. This makes it possible to solve the problem with the minimum expenditure of time and materials.     

Plasma-sprayed zirconia bond coat as an intermediate layer for hydroxyapatite coating on titanium alloy substrate

This study aims to strengthen the bonding at HA coating/Ti–6Al–4V interface by adding an intermediate ZrO₂ bond coat between them. The bonding strength of the HA/ZrO₂ coating was evaluated with the separately prepared HA coating as control. The phase, microstructure and chemistry, and surface roughness of the plasma-sprayed two-layer HA/ZrO₂ coating on Ti–6A1–4V substrate were investigated by X-ray diffractometry, scanning electron microscopy, and surfcorder, respectively. Experimental results indicate that the bonding strength increases from 28.6±3.22 MPa for HA coating to 36.2±3.02 MPa for HA/ZrO₂ composite coating. Elemental analysis employed on the surface of ZrO₂ bond coat, on which the HA top coat was first dissolved completely in HCl acid, reveals the sign of diffusion of calcium ions from HA to ZrO₂ bond coat. In addition, rougher surface morphology provided by ZrO₂ bond coat is also considered to aid in the bonding at HA/ZrO₂ interface. Similar coating system done by other researchers is compared and discussed.