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 nanocrystalline sol-gel hydroxyapatite coatings

Sol-gel technology offers an alternative technique for producing bioactive surfaces for improved bone attachment. Previous work indicated that monophasic hydroxyapatite coatings were difficult to produce. In the present work hydroxyapatite was synthesized using the sol-gel technique with alkoxide precursors and the solution was allowed to age up to seven days prior to coating. It was found that, similar to the wet-chemical method of hydroxyapatite powder synthesis, an aging time is required to produce a pure hydroxyapatite phase. A methodology that has been successfully used to produce nanocrystalline hydroxyapatite thin film coatings via the sol-gel route on various substrates including alumina, Vycor glass, partially stabilized zirconia, Ti–6Al–4V alloy and single crystal MgO is described. Coatings produced on MgO substrates were characterized by X-ray diffraction and atomic force microscopy, while the analogous gels were examined with thermogravimetric and differential thermal analyses. The coatings were crack free and the surface was covered with small grains, of approximately 200 nm in size for samples fired to 1000 °C. Coating thickness varied between 70 and 1000 nm depending on the number of applied layers.     

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.     

Preparation and characterization of hydroxyapatite/collagen nanocomposite gel

The self-organized hydroxyapatite/colagen (HAp/Col) nanocomposite fiber (79.6/20.4 weight ratio) was synthesized by a co-precipitation method using Ca(OH)2, H3PO4, and Col as starting substances. The gelation of the nanocomposite is essential in the application of the scaffold for bone tissue engineering. We successfully prepared HAp/Col nanocomposite gels by a facile novel method using a sodium phosphate buffer at pH 6.8. The water-insoluble nanocomposite was homogeneously dispersed in the buffer to form a viscous mixture, and gels were obtained after incubating of the mixture at 37 degrees C. The mechanical strength of the gels was analyzed against the incubation time. The demineralized gel with EDTA had the typical nanostructure of native type I Col fibers from the results of scanning electron microscopy (SEM) and atomic force microscopy (AFM); the dense network of type I Col nano-fibers below 100 nm in diameter, and the periodic pattern of 68.8+/-4.4 nm (mean +/- SD) along the fibers were observed. The gelation of the HAp/Col nanocomposite in the buffer is attributed to the physical cross-linking through entanglement of the reconstituted Col fibrils.     

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.     

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.     

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.     

Electrochemical study of hydroxyapatite coatings on stainless steel substrates

Hydroxyapatite coatings were synthesized electrochemically onto stainless steel. In this study, the composition and morphology of the coatings changed with the deposition and sintering conditions. The electrolyte was kept close to the composition of simulated body fluid with an adjusted pH of 8.0. Deposition temperature affected the purity of the deposits with higher temperatures (65 °C) giving better coatings. The sintering techniques were also shown to affect the deposits, with x-ray diffraction patterns showing well-defined peaks for hydroxyapatite when sintering under vacuum conditions. Coating density and corrosion resistance was improved when applying a double-layer coating technique versus a single-layer. Grain sizes were 30 to 40 nm even after sintering of these coatings in air. The formed coatings were characterized by powder x-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and x-ray photoelectron spectroscopy.     

Bioactive borate glass coatings for titanium alloys

Bioactive borate glass coatings have been developed for titanium and titanium alloys. Glasses from the Na(2)O-CaO-B(2)O(3) system, modified by additions of SiO(2), Al(2)O(3), and P(2)O(5), were characterized and compositions with thermal expansion matches to titanium were identified. Infrared and X-ray diffraction analyses indicate that a hydroxyapatite surface layer forms on the borate glasses after exposure to a simulated body fluid for 2 weeks at 37 degrees C; similar layers form on 45S5 Bioglass((R)) exposed to the same conditions. Assays with MC3T3-E1 pre-osteoblastic cells show the borate glasses exhibit in vitro biocompatibility similar to that of the 45S5 Bioglass((R)). An enameling technique was developed to form adherent borate glass coatings on Ti6Al4V alloy, with adhesive strengths of 36 +/- 2 MPa on polished substrates. The results show these new borate glasses to be promising candidates for forming bioactive coatings on titanium substrates.     

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.     

Bioactive composite gradient coatings of nano-hydroxyapatite/polyamide66 fabricated on polyamide66 substrates

Tightly bonding of bioactive coating is the first crucial need for orthopaedic implants. This study describes a novel and convenient technique to prepare bioactive coating with high adhesion on orthopaedic substitutes made of polymeric matrix. Here, a chemical corrosion method has been adopted to fabricate a coating on the surface of injection-moulded polyamide66 (PA66) substrates by corrosive nano-hydroxyapatite/polyamide66 (n-HA/PA66) composite slurry. Scanning electron microscopy observation shows that a porous chemical corrosion region presents between the coating and dense PA66 substrate. Energy-dispersive X-ray spectroscopy analysis indicates that the chemical corrosion region is mainly composed of PA66 matrix, and the coating layer is an n-HA-rich layer. Both the pore size and n-HA composition increase gradually from the polymeric substrate towards the coating surface. Mechanical testing shows the bonding strength can reach 13.7 ± 0.2 MPa, which is much higher than that fabricated on polymeric matrix by other coating methods. The gradual transition in coating structure and composition benefits for the interface bonding and for the surface bone-bonding bioactivity. Subsequent cell experiments corroborate n-HA-rich coating and a porous structure is benefitting for cell attachment and proliferation. The convenient coating method could be popularized and applied on similar polymer implants to produce a tightly and porous bioactive coating for bone tissue regeneration.     

Preparation of layered bioceramic hydroxyapatite/sodium titanate coatings on titanium substrates using a hybrid technique of alkali-heat treatment and electrochemical deposition

Bioceramic hydroxyapatite/sodium titanate coating on sandblasted titanium substrate was fabricated by a three-step process. At first, the sandblasted titanium substrate was coated with a flake-like sodium titanate layer by alkali-heat treatment. In the second step, the alkali-heat treated titanium substrate was hydrothermal treated at 180 °C for 4 h with calcium solutions. In the third step, the hydroxyapatite (HA) coating was deposited onto the hydrothermal treated layer via electrochemical deposition method. The surface topography and roughness of the coatings were determined by field emission scanning electron microscope (FESEM) and a mechanical contact profilometer, respectively. The surface compositions were evaluated by X-ray diffraction (XRD), energy-dispersive X-ray spectrum (EDS), and X-ray photoelectron spectroscopy (XPS). The EDS, XPS, and XRD analysis confirm the presence of element Ca, Ca²⁺, and CaTiO₃ on sodium titanate layer after hydrothermal treatment with Ca(NO₃)₂ solution, respectively. FESEM micrograph shows the rod/needle-shaped crystallites are highly densely packed on the calcium-ion-containing layer with an average size of ~50 nm in diameter. The results indicate that the sodium titanate layer containing Ca²⁺ ions possesses higher ability to induce HA formation compared with the pure sodium titanate layer. It is revealed that surface composition plays an important role in the electrochemical deposition of HA. The calcium-ion-containing layer probably makes the nucleation of HA easy and effectively promotes orientated growth of HA on flake-like sodium titanate surface. The sodium titanate layer possesses a lower corrosion current density and a higher corrosion potential than sandblasted-Ti substrate. The sodium titanate layer should act as a barrier to the release of metal ions from metallic substrate to physiological solutions and thus reducing the electrochemical reaction rate.     

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.     

Laser engineered multilayer coating of biphasic calcium phosphate/titanium nanocomposite on metal substrates

In this work, laser coating of biphasic calcium phosphate/titanium (BCP/Ti) nanocomposite on Ti-6Al-4 V substrates was developed. A continuous wave neodymium-doped yttrium aluminium garnet (Nd:YAG) laser was used to form a robust multilayer of BCP/Ti nanocomposite starting from hydroxyapatite and titanium nanoparticles. In this process, low power coating is realized because of the strong laser-nanoparticle interaction and good sinterability of nanosized titanium. To guide the optimization of laser processing conditions for the coating process, a multiphysics model coupling electromagnetic module with heat transfer module was developed. This model was validated by laser coating experiments. Important features of the coated samples, including microstructures, chemical compositions, and interfacial bonding strength, were characterized. We found that a multilayer of BCP, consisting of 72% hydroxyapatite (HA) and 28% beta-tricalcium phosphate (β-TCP), and titanium nanocomposite was formed on Ti-6Al-4 V substrates. Significantly, the coating/substrate interfacial bonding strength was found to be two times higher than that of the commercial plasma sprayed coatings. Preliminary cell culture studies showed that the resultant BCP/Ti nanocomposite coating supported the adhesion and proliferation of osteoblast-like UMR-106 cells.     

Fluoridated hydroxyapatite/titanium dioxide nanocomposite coating fabricated by a modified electrochemical deposition

Fluoridated hydroxyapatite/titanium dioxide nanocomposite coating was successfully fabricated by a modified electrochemical deposition technique. F⁻ ions, nanoscaled TiO₂ particles and 6% H₂O₂ was added into the electrolyte, and ultrasonication was also performed to prepare this nanocomposite coating. The microstructure, phase composition, dissolution rate, bonding strength and in vitro cellular responses of the composite coating were investigated. The results show that the composite coating was uniform and dense owing to the effects of H₂O₂ and ultrasonication. The thickness of the composite coating was ~5 μm and scanning electron microscopy revealed that nanoscaled TiO₂ particles were imbedded uniformly between FHA crystals. The addition of F⁻ and TiO₂ reduced the crystallite size and increased the crystallinity of HA in FHA/TiO₂ composite coating. In addition, the composite coating shows higher bonding strength and lower dissolution rate than pure HA coating, and the in vitro bioactivity of FHA/TiO₂ composite coating was not affected as compared with pure HA coating.     

Bioactive coatings obtained at room temperature with hydroxyapatite and polysiloxanes

Low temperature Hydroxylapatite (HA) coatings were obtained on metal substrates by depositing HA particles suspended in a ormosil polymer gel made of an equimolar mixture of amino and epoxy substituted silanes. The new coatings were analysed by thermal analysis, infrared and solid state NMR, as well as X-ray diffraction and SEM observations. Results show the HA powder conserves its characteristic physicochemical properties during the coating process. Furthermore, the coatings induce the formation of a biomimetic HA layer when soaked in simulated body fluids. This room temperature process may lead to novel calcium phosphate coatings with better control of crystallinity and porosity and with the possible incorporation of biofunctional organic molecules.     

A novel method for the fabrication of homogeneous hydroxyapatite/collagen nanocomposite and nanocomposite scaffold with hierarchical porosity

Homogeneous nanocomposites composed of hydroxyapatite (HAp) and collagen were synthesized using a novel in situ precipitation method through dual template-driven. The morphological and componential properties of nanocomposites were investigated. The HAp particulates, in sizes of about 50–100 nm, were distributed homogeneously in the organic collagen hydrogel. Highly magnified TEM observation showed that HAp inorganic particles were composed of fine sub-particles (2–5 nm) without regular crystallographic orientation. Based on these homogeneous nanocomposites, a novel HAp/collagen nanocomposite scaffold with hierarchical porosity was prepared by multilevel freeze-drying technique. Compared to other conventional scaffolds for tissue engineering, this novel in situ method endows synthesized composite scaffolds with unique morphology—ultrafine HAp particles dispersed homogenously in collagen at nano level and the foam scaffold with hierarchical pore structures. The mechanical performance increased obviously compared with neat collagen. These results provided an efficient approach toward new biomimetic tissue scaffold for the biomedical applications with enhanced intensity/bioactivity and controlled resorption rates. This novel method, we expect, will lead to a wide application in many other hydrogel systems and may be useful for fabrication of various homogeneous inorganic/organic nanocomposites.     

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.