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.     

Preparation and characterization of multi-walled carbon nanotube/hydroxyapatite nanocomposite film dip coated on Ti–6Al–4V by sol–gel method for biomedical applications: An in vitro study

In the present research, the introduction of multi-walled carbon nanotubes (MWCNTs) into the hydroxyapatite (HA) matrix and dip coating of nanocomposite on titanium alloy (Ti–6Al–4V) plate was conducted in order to improve the performance of the HA-coated implant via the sol–gel method. The structural characterization and electron microscopy results confirmed well crystallized HA–MWCNT coating and homogenous dispersion of carbon nanotubes in the ceramic matrix at temperatures as low as 500 °C. The evaluation of the mechanical properties of HA and HA/MWCNT composite coatings with different weight percentages of MWCNTs showed that the addition of low concentrations of MWCNTs (0.5 and 1 wt.%) had improved effect on the mechanical properties of nanocomposite coatings. Moreover, this in vitro study ascertained the biocompatibility of the prepared sol–gel-derived HA/MWCNT composite coatings.     

Nano-structural bioactive gradient coating fabricated by computer controlled plasma-spraying technology

The poor mechanical property of hydroxyapatite was the major problem for load bearing and implant coating in clinical applications. To overcome this weakness, a bioactive gradient coating with a special design composition of hydroxyapatite (HA), ZrO₂, Ti, bioglass was developed. This 120 μm coating with an upper layer of 30–50 μm porous HA produced by computer controlled plasma spraying which maintained energy level of the plasma which ensure proper melting of powder. The crystal size of the coating was 18.6–26.2 nm. Transformation of t-ZrO₂ to m-ZrO₂ reduced the thermal stress that weakened the coating and lowered down interfacial strength of the coating and metal substrate. Thermal stress of sprayed coating was 16.4 MPa which was much smaller than the sample without thermal treatment of 67.1 MPa. Interfacial strength between the coating and metal substrate was 53 MPa which is much higher than conventional Hydroxyapatite coating. Based on XRD analysis crystallinity of HA approached 98%. Therefore, high temperature treatment improved long term stability of the coating through improved crystallinity of hydroxyapatite and reduced other impure calcium phosphate phase.     

Synthesis and bioactivity of porous Ti alloy prepared by foaming with TiH2

A novel porous Ti–6Al–4V with an open cell structure was fabricated by powder metallurgy process with the addition of TiH₂ as the pore forming and active agent. Control of porosity of porous Ti alloy made it possible to obtain the porous Ti with the Young's modulus value of 5.8–9.5 GPa, which was similar to that of human cancellous bone. This kind of porous Ti alloy with good biomechanical properties is potential to alleviate the problem of mechanical mismatch between the bone and the Ti implant. The porous Ti alloy prepared by the addition of TiH₂ as foaming agent had a uniform distribution of pores with pore size of 90–190 μm and porosity of 43–59%. In order to improve the biological properties, the duplex titania/apatite coatings were applied onto the surface of porous Ti alloy. The titania coating was deposited by chemical treatment and the apatite coating was subsequently applied by immersing the samples in a simulated body fluid. Results showed that a homogeneous nanocrystallite titania coating with a thickness of 0.8 μm was formed on the surface of the Ti alloy after chemical treatment. The carbonate-containing apatite coating with a thickness of 1 μm was deposited on the surface of titania coating after immersion in simulated body fluid for 7 days. The nucleation of the carbonate-containing apatite can be induced from the electrostatic interaction between the OH-containing groups on the surface of titania coating and the calcium and phosphate ions in the metastable simulated body fluid on those specific superficial sites. The growth kinetics of the coatings was also discussed. Cell culture test showed the well stretched and proliferated cells on the surface of the sample, indicating the good biocompatibility of porous Ti alloy.     

The influence of residual stress on the shear strength between the bone and plasma-sprayed hydroxyapatite coating

Plasma-sprayed HA coating (HAC) 50 and 200 μm thick on Ti6Al4V cylinders was transcortically implanted in the femora of canines. Push-out testing of implant-bone interfaces showed that the HAC coating exhibited higher shear strength at 50 μm coating than 200 μm one. The plasma-sprayed HACs were exhibited compressive residual stresses and the thicker HAC exhibited higher residual stress than that of the thinner HAC. Due to the structure for 50 and 200 μm implants were the same, meaning similar cohesive strength of the lamellar splats. And, there was no difference in the physiological environment; hence the difference of the shear strength for the 50 and 200 μm-HAC implants could best be attributed to the compressive residual stress existed in the HA coating.     

Topographical characterization and microstructural interface analysis of vacuum-plasma-sprayed titanium and hydroxyapatite coatings on carbon fibre-reinforced poly(etheretherketone)

In the present study, topographical characterization and microstructural interface analysis of vacuum-plasma-sprayed titanium and hydroxyapatite (HA) coatings on carbon fibre-reinforced polyetheretherketone (CF/PEEK) was performed. VPS-Ti coatings with high roughness values (Ra=28.29±3.07 m, Rz=145.35±9.88 m) were obtained. On this titanium, intermediate layer HA coatings of various thicknesses were produced. With increasing coating thickness, roughness values of the HA coatings decreased. A high increase of profile length ratio, Lr, of the VPS-Ti coatings (Lr=1.45) compared to the grit-blasted CF/PEEK substrate (Lr=1.08) was observed. Increasing the HA coating thickness resulted in a reduction of the Lr values similar to the roughness values. Fractal analysis of the obtained roughness profiles revealed that the VPS-Ti coatings showed the highest fractal dimension of D=1.34±0.02. Fractal dimension dropped to a value of 1.23–1.25 for all HA coatings. No physical deterioration of the CF/PEEK substrate was observed, indicating that substrate drying and the used VPS process parameter led to the desired coatings on the composite material. Cross-section analysis revealed a good interlocking between the titanium intermediate layer and the PEEK substrate. It is therefore assumed that this interlocking results in suitable mechanical adhesive strength. From the results obtained in this study it is concluded that VPS is a suitable method for manufacturing HA coatings on carbon fibre-reinforced PEEK implant materials.     

Mechanical and histological evaluations of cobalt-chromium alloy and hydroxyapatite plasma-sprayed coatings in bone

This study evaluated the mechanical and histological behavior of cobalt-chromium (CoCr) alloy and hydroxyapatite (HA) plasma-sprayed coatings in canine cortical bone after 6 and 12 weeks of implantation, using CoCr alloy as the substrate. the substrate was bond-coated with microtextured CoCr alloy coating to ensure adherence between the substrate and top coats. A macrotextured CoCr alloy top coat with surface roughness R _a=34.25±5.50 m was produced to create suitable pores ranging from 25 m to 200 m for bone ingrowth. For HA top coat, a relatively smooth surface (R _a=15.14±3.21 m) was prepared for bone apposition. Shear testing of bone/implant interfaces showed that the CoCr alloy top coat exhibited significantly lower (p<0.01) mean shear strength than the HA top coat at each time interval. The maximum shear strength was 10.88±0.38 MPa for HA-coated implants 12 weeks post-implantation. After histological evaluations, substantial differences in the extent of new bone formation and the types of implant/bone contact were found between two kinds of implants. Direct bone-to-HA coating contact was consistently observed, while a layer of fibrous tissue intervening at the bone-CoCr alloy coating interface was found. Occasionally, partial dissolution of HA coating was seen after 12 weeks of implantation. The results of this study suggested that plasma-sprayed macrotextured CoCr coatings may not be an effective alternative for biological fixation.     

Porous Titanium Coatings Through Electrophoretic Deposition of TiH2 Suspensions

In the biomedical field, modification of titanium surfaces to improve the osteoinductive and antibacterial behavior is widely investigated. This functionalization can be further ameliorated by providing a porous coating with high loading capacity for bioactive materials and drug delivery carriers at the implant surface. In this work, a new powder metallurgical processing route used to deposit such porous pure titanium coatings on Ti based substrates is presented. The coatings were prepared by electrophoretic deposition (EPD) of TiH₂ powder suspensions followed by dehydrogenation and sintering in vacuum. The use of hydrides allowed to lower the sintering temperature below that of the α–β transition of the Ti6Al4V substrate. Measurement of the tensile bond strength confirmed a strong adhesion of the porous coating. Deposition of powders with different grain sizes resulted in porous titanium coatings with varying thickness, pore morphology, and surface roughness. The possibility to extend this coating technique to complex shaped implants is highlighted.     

Silicon-substituted hydroxyapatite composite coating by using vacuum-plasma spraying and its interaction with human serum albumin

The incorporation of silicon can improve the bioactivity of hydroxyapatite (HA). Silicon-substituted HA (Ca₁₀(PO₄)_6−x (SiO₄) _x (OH)_2−x , Si-HA) composite coatings on a bioactive titanium substrate were prepared by using a vacuum-plasma spraying method. The surface structure was characterized by using XRD, SEM, XRF, EDS and FTIR. The bond strength of the coating was investigated and XRD patterns showed that Ti/Si-HA coatings were similar to patterns seen for HA. The only different XRD pattern was a slight trend toward a smaller angle direction with an increase in the molar ratio of silicon. FTIR spectra showed that the most notable effect of silicon substitution was that –OH group decreased as the silicon content increased. XRD and EDS elemental analysis indicated that the content of silicon in the coating was consistent with the silicon-substituted hydroxyapatite used in spraying. A bioactive TiO₂ coating was formed on an etched surface of Ti, and the etching might improve the bond strength of the coatings. The interaction of the Ti/Si-HA coating with human serum albumin (HSA) was much greater than that of the Ti/HA coating. This might suggest that the incorporation of silicon in HA can lead to significant improvements in the bioactive performance of HA.     

Hydroxyapatite-anatase-carbon nanotube nanocomposite coatings fabricated by electrophoretic codeposition for biomedical applications

In order to eliminate micro-cracks in the monolithic hydroxyapatite (HA) and composite hydroxyapatite/carbon nanotube (HA/CNT) coatings, novel HA/TiO₂/CNT nanocomposite coatings on Ti6Al4V were attempted to fabricate by a single-step electrophoretic codeposition process for biomedical applications. The electrophoretically deposited layers with difference contents of HA, TiO₂ (anatase) and CNT nanoparticles were sintered at 800°C for densification with thickness of about 7–10 μm. A dense and crack-free coating was achieved with constituents of 85 wt% HA, 10 wt% TiO₂ and 5 wt% CNT. Open-circuit potential measurements and cyclic potentiodynamic polarization tests were used to investigate the electrochemical corrosion behavior of the coatings in vitro conditions (Hanks’ solution at 37°C). The HA/TiO₂/CNT coatings possess higher corrosion resistance than that of the Ti6Al4V substrate as reflected by nobler open circuit potential and lower corrosion current density. In addition, the surface hardness and adhesion strength of the HA/TiO₂/CNT coatings are higher than that of the monolithic HA and HA/CNT coatings without compromising their apatite forming ability. The enhanced properties were attributed to the nanostructure of the coatings with the appropriate TiO₂ and CNT contents for eliminating micro-cracks and micro-pores.     

Hydrothermal preparation of tailored hydroxyapatite

Hydrothermal vapor treatment method was applied for preparation of ceramic biomaterials. Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂; HA) ceramics prepared by sintering with random crystal surface have already been used as bone-repairing materials which can directly bond to natural bones. If materials of HA could have the tailored specific crystal surface, they should have the advantage of adsorptive activity and osteoconductivity in comparison with the sintered HA. In the present study, porous HA sheets of about 50 μm to 1 mm in thickness and porous HA granules of about 50 μm to 1 mm in size with tailored crystal surface were prepared by the hydrothermal vapor exposure method at temperatures below 200°C. Porous sheets and porous granules of HA with controlled crystal surface should be suitable for scaffold of cultured bone, for bone graft material and for drug delivery system (DDS).     

Structure and properties of hydroxyapatite-bioactive glass composites plasma sprayed on Ti6Al4V

Hydroxyapatite (HA)-coated Ti6Al4V has recently been used as a bone substitute in orthopaedic and dental applications because of its favourable bioactivity and mechanical properties. Studies in the literature have shown that the bioactivity of calcium phosphate bioactive glass (BG) is higher than that of HA. In an attempt to increase the bioactivity of Ha-coated Ti6Al4V and enhance the bonding strength between coating and substrate, in the present study, HA/BG composites are applied onto Ti6Al4V using a plasma spraying technique. Microstructure and phase changes of the composite coating after plasma spraying are studied. The coating-substrate bonding strength is evaluated using an Instron, following the ASTM C633 method. Results indicate that the average bonding strengths of BG, HA/BG and HA coatings are 33.0±4.3, 39.1±5.0, and 52.0±11.7 MPa, respectively. Open pores with sizes up to 50 m are found in both BG and HA/BG coatings, which are probably advantageous in including mechanical interlocking with the surrounding bone structure, once implanted. These HA/BG composites could provide a coating system with sufficient bonding strength, higher bioactivity, and a significant reduction in cost in raw materials. The future of this HA/BG composite coating system seems pretty bright.     

Morphology and immersion behavior of plasma-sprayed hydroxyapatite/bioactive glass coatings

A series of hydroxyapatite/bioactive glass (HA/BG) coatings have been plasma-sprayed on Ti6Al-4V substrate using HA/BG powders that were prepared by both sinter-granulation and direct mixing methods. The morphology and immersion behavior of these coatings in a simulated body fluid (SBF) were investigated. The results showed that in-house fabricated BG and sinter-granulated HA powders were irregularly shaped and dense. When 5 wt % or more BG was added in HA, the powder became rough and porous. X-ray diffraction (XRD) patterns showed that the presence of BG enhanced the decomposition of HA structure during fabrication of the powders. Reasonably high bond strengths were obtained from all coatings. The granulated type HA/BG coatings showed no significant differences in bond strength from the mixed type HA/BG coatings. The plasma spray process itself and the presence of BG enhanced the decomposition of apatite. Surface morphology of all sinter-granulated type coatings was similar to that of monolithic HA coating, that was comprised of patches of smooth and shiny glassy film and irregularly-shaped particles on its surface. The dissolution depth of plasma-sprayed coatings immersed in SBF was largely dependent on the type and composition of the coating. Granulated type HA/BG coatings were much less dissolvable than monolithic HA or mixed type HA/BG coatings. It seems that the presently used granulation method for the preparation of HA/BG powders plays a predominant role in determining the dissolution behavior of the plasma-sprayed coatings. ©©2000 Kluwer Academic Publishers     

Comparison of Tantalum and Hydroxyapatite Coatings on Titanium for Applications in Load Bearing Implants

Over the years hydroxyapatite (HA) coatings have been used to improve biologic properties of Ti‐based load bearing metal implants. However, applicability of HA coated implants is subjected to physical stability of the HA phase and mechanical integrity of the coating‐substrate interface. In this study, we have compared the microstructure and in vitro cell–materials interactions of newly developed laser deposited Ta coatings and radio frequency (RF) induction plasma sprayed HA coatings on Ti substrate. In vitro biocompatibility study, using human osteoblast cell line hFOB, showed equally excellent cellular adherence and growth on Ta and HA coatings. Quantitative assay of cell survivability on these coatings showed that the Ta coatings provide comparable initial cell attachment to that of HA coatings. Microstructural analysis of the coatings showed strong metallurgical bonding without sharp interface between the Ta coating and the Ti substrate, while the interface between HA coating and the Ti substrate was sharp. The interface microstructural features and in vitro cell–materials interactions of Ta coatings on Ti clearly demonstrate their potential to replace HA based coatings for enhanced/early biologic fixation. Other significant benefits of these dense Ta coatings include high toughness, strong bonding with the substrate, and long‐term stability of the interface.     

Ti-HA-BaTiO_3生物复合材料的制备与性能

为进一步提高骨修复材料的骨诱导性能,引入了BaTiO_3压电涂层。首先,通过等离子喷涂法在Ti基体上制备羟基磷灰石(HA)、Ti-HA和Ti-HA-BaTiO_3这3种生物涂层;然后,采用正交试验设计优化了喷涂工艺参数,用SEM/EDS对涂层的形貌和成分进行了表征,并通过划痕试验测试了涂层与基体的结合强度;最后,进行了细胞培养试验,用CCK-8法对细胞毒性进行了评价,并在SEM下观察了细胞的粘附形态。结果显示:细胞带有伪足,呈梭形和不规则多边形,且粘附在Ti-HA-BaTiO_3复合涂层表面;细胞伸展形态良好,涂层的细胞毒性等级不高于1级。可见,Ti-HA-BaTiO_3复合材料可以作为临床植入材料应用。     

Bioactive glass–ceramic coated titanium implants prepared by electrophoretic deposition

Surface modification of Ti alloys towards an improved osteoinductive behaviour is one of the major challenges in orthopaedic implant technology nowadays. One way to achieve this is by applying a bioactive coating which can increase the rate of osseointegration and chemical bonding of surrounding bone to the implant. In the present work, the production of a bioactive glass–ceramic coating on flat Ti alloys by electrophoretic deposition is demonstrated. The coatings are applied by cathodic deposition from non-aqueous suspensions followed by sintering in vacuum, avoiding uncontrolled oxidation of the Ti substrates. The use of non-aqueous suspensions both allowed to reduce the deposition time and yielded homogeneous coatings with a uniform thickness of 8 μm. Evaluation of the coating adhesion confirmed the good mechanical performance of the coatings with a tensile bond strength of 41.0 ± 11.1 MPa. Additionally, a feasibility study demonstrated the potential of electrophoretic deposition as a coating technique for commercial complex implants.     

Improvement in crystallinity of apatite coating on titanium with the insertion of CaF2 buffer layer

In the apatite coatings on Ti the heat treatment process is necessary to crystallize the apatite structure for improved chemical stability and biological properties. However, the heat treatment normally degrades the mechanical strength of the coating layer associated with thermally induced stress. In this study, we aimed to improve the crystallization of apatite coating by using calcium fluoride (CaF₂) as a buffer layer. The insertion of a thin layer of CaF₂ (0.2–1 μm) between apatite and Ti significantly improved the crystallization behavior of apatite. Moreover, this crystallization was more enhanced as the thickness of CaF₂ was increased. When a 1 μm-thick CaF₂ was inserted, the crystallization of apatite initiated at a temperature as low as 320 °C, being a dramatic improvement in the crystallization when considering the crystallization initiation temperature of a bare apatite coating on Ti was ∼450 °C. As a result of this crystallization enhancement, the dissolution behavior of CaF₂-inserted apatite coatings was more stable than that of the bare apatite coating, showing much reduced initial-burst effect. Preliminary cellular assay showed the CaF₂-inserted apatite coating provided a substrate for cells to spread and grow favorably, as being similar to the bare apatite coating. This novel way of apatite coating on Ti using CaF₂ buffer layer may be useful in the coating systems particularly requiring low temperature processing and increased crystallinity with high chemical stability.     

Fabrication of nano-structured HA/CNT coatings on Ti6Al4V by electrophoretic deposition for biomedical applications

In order to improve the bone bioactivity and osteointegration of metallic implants, hydroxyapatite (HA) is often coated on their surface so that a real bond with the surrounding bone tissue can be formed. In the present study, cathodic electrophoretic deposition (EPD) has been attempted for depositing nanostructured HA coatings on titanium alloy Ti6Al4V followed by sintering at 800 degrees C. Nano-sized HA powder was used in the EPD process to produce dense coatings. Moreover, multiwalled carbon nanotubes (CNTs) were also used to reinforce the HA coating for enhancing its mechanical strength. The surface morphology, compositions and microstructure of the monolithic coating of HA and nanocomposite coatings of HA with different CNT contents (4 to 25%) on Ti6Al4V were investigated by scanning-electron microscopy, energy-dispersive X-ray spectroscopy and Xray diffractometry, respectively. Electrochemical corrosion behavior of the various coatings in Hanks' solution at 37 degrees C was investigated by means of open-circuit potential measurement and cyclic potentiodynamic polarization tests. Surface hardness, adhesion strength and bone bioactivity of the coatings were also studied. The HA and HA/CNT coatings had a thickness of about 10 microm, with corrosion resistance higher than that of the substrate and adhesion strength higher than that of plasma sprayed HA coating. The properties of the composite coatings were optimized by varying the CNT contents. The enhanced properties could be attributed to the use of nano-sized HA particles and CNTs. Compared with the monolithic HA coating, the CNT-reinforced HA coating markedly increased the coating hardness without deteriorating the corrosion resistance or adhesion strength.     

Electrophoretic bilayer deposition of zirconia and reinforced bioglass system on Ti6Al4V for implant applications: An in vitro investigation

The physical, chemical and biological properties of the bioglass reinforced yttria-stabilized composite layer on Ti6Al4V titanium substrates were investigated. The Ti6Al4V substrate was deposited with yttria stabilized zirconia — YSZ as the base layer of thickness ≈ 4–5 μm, to inhibit metal ion leach out from the substrate and bioglass zirconia reinforced composite as the second layer of thickness ≈ 15 μm, which would react with surrounding bone tissue to enhance bone formation and implant fixation. The deposition of these two layers on the substrate was carried out using the most viable electrophoretic deposition (EPD) technique. Biocompatible yttria-stabilized zirconia (YSZ) in the form of nano-particles and sol gel derived bioglass in the form of micro-particles were chosen as precursors for coating. The coatings were vacuum sintered at 900 °C for 3 h. The biocompatibility and corrosion resistance property were studied in osteoblast cell culture and in simulated body fluid (SBF) respectively. Analysis showed that the zirconia reinforced bioglass bilayer system promoted significant bioactivity, and it exhibited a better corrosion resistance property and elevated mechanical strength under load bearing conditions in comparison with the monolayer YSZ coating on Ti6Al4V implant surface.