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.     

Characterization of sol-gel surfaces for biomedical applications

The aim of the present study was to characterize sol-gel derived titania coatings prepared by dipping. The surface characterization was carried out using X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF SIMS), combined with X-ray diffraction (XRD) and thermal analysis. Sol-gel derived titania surfaces mimicked the surface chemistry of the natural oxide layer found on commercial titanium implants. These surfaces could be used to develop an in vitro model of the osseointegration process. Similar analytical techniques were applied to apatite-like coatings and preliminary results suggest that hydroxyapatite coatings can be produced from a sol-gel route.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials, Oporto, Portugal, 10–13 September.     

Tetragonal to monoclinic transformation and microstructural evolution in ZrO2–9.7 mol% MgO during cyclic heating and cooling

The tetragonal (t) to monoclinic (m) transformation behaviour and its relationship to microstructural evolution were investigated by means of dilatometry and transmission electron microscopy for ZrO2–9.7 mol% MgO during cyclic heating and cooling between room temperature and 1490 K. In the as-sintered specimens, fine oblate ellipsoidal t-phase precipitates, 20–50 nm in diameter and 100–200 nm long, were distributed in the cubic (c)-phase matrix. They were below a critical size for transformation and exhibited no transformation in the first three cycles. In the fourth and further cycles, transformation occurred in two distinct stages. A low-temperature stage appeared at 850–1000 K on heating and at 400–700 K on cooling, while a high-temperature stage appeared at 1350–1400 K on heating and at 1000–1200 K on cooling. With the increasing number of cycles, at first the size of low-temperature stages increased and then decreased above ten cycles accompanying the development of the high-temperature stage. During cyclic heating and cooling, coarsening of ellipsoidal precipitates and decomposition of c- and t-phases occurred. As a result of the decomposition, MgO particles and a new m-phase containing a very low concentration of MgO were produced. The coarsened ellipsoidal t-phase precipitates were responsible for the low-temperature stage. The new m- or t-phase containing very low MgO produced by the decomposition was responsible for the high-temperature stage.     

Fabrication of novel sol-gel silica coatings reinforced with multi-walled carbon nanotubes

Novel sol-gel silica coatings reinforced with multi-walled carbon nanotubes (MWCNTs) have been prepared using the organic sol-gel route and the dip-coating technique on magnesium alloy substrates. Homogeneous and dense composite coatings with good reinforcement dispersion were fabricated using low temperature and atmospheric pressure fabrication conditions. The presence of nanotubes caused a substantial enhancement of silica coating fracture toughness on coatings deposited on grounded substrates but it was not as effective on polished substrates because of the low adhesion of the coating to the substrate. Bridging phenomena caused by the MWCNTs was observed, indicating that an effective load transfer between the silica matrix and the nanotube reinforcement was also achieved.     

Characterization of TiO2 and ZrO2 coatings on silica slabs and fibres

Titanium and zirconium dioxide coatings were deposited on optical fibres by the sol-gel procedure. The thickness of the layers on fibres was established by measurement of the intensity of characteristic X-rays by an electron microprobe analyser. The accuracy of the measurements was verified on broken layers by scanning electron microscopy. Also determined were the thicknesses of similar layers deposited on flat silica substrates with an ellipsometer and stylus surfometer as well as from reflectivity spectra and from specular total reflection of X-rays. The densities of TiO₂ and ZrO₂ layers on silica glass slabs were determined by X-ray total reflection. Values of 3.16 ± 0.02 and 4.69 ± 0.03 gm cm^–2 were found for titania and zirconia, respectively. The crystallinity of layers on silica plates was investigated by Raman spectroscopy. The thicknesses of coatings prepared by the dipping technique were related to the withdrawal speed. Equations for Newtonian and non-Newtonian fluids were tested and compared. A pseudo-plastic behaviour was suggested for all the solutions used in the experiments.     

Combined Langmuir-Blodgett and sol-gel coatings

Optical properties and in-depth structure of double-layer coatings on glass substrates were investigated. One of the layers was prepared by dip coating either from silica or titania sol, the other layer was made from ca. 130 nm Stöber silica particles by the Langmuir-Blodgett (LB) technique. Two different types of combined coatings were prepared: (1) nanoparticulate LB films coated with sol-gel (SG) films and (2) nanoparticulate LB films drawn onto SG films.Scanning electron microscopy and optical methods, i.e. UV-vis spectroscopy and scanning angle reflectometry were applied for analyzing the structure and thickness of coatings. These measurements revealed that the precursor sols could not penetrate into the particulate LB film completely in case of coating type (1). For coating type (2) very little overlap between the SG and LB layers was found resulting in significant improvement of light transmittance of combined coatings compared to single SG films.To show some possible advantages of the combination of these techniques additional studies were carried out. Surface morphology of combined coatings (1) was studied by atomic force microscopy. Surfaces with different roughness were developed depending on the thickness of the sol-gel film (titania: ca. 70 nm; silica: ca. 210 nm). The adhesive peel off test revealed improved mechanical stability of combined coatings (2), in comparison to LB films which makes them good candidates for further applications.     

Interfacial study of magnesium-containing fluoridated hydroxyapatite coatings

Magnesium-containing fluoridated hydroxyapatite (Mg_xFHA) coatings have been developed to improve the biological performances of fluoridated hydroxyapatite (FHA) coatings. The coatings are deposited on Ti6Al4V substrates via a sol-gel process. The interface between the coating and substrate is characterized by scanning electron microscopy, glow discharge optical emission spectroscopy and X-ray photoelectron spectroscopy for coating thickness, elemental distribution and chemical states. Pull-off test is used to evaluate the adhesion strength. The results show that the interdiffusion of elements happens at the coating/substrate interface. The incorporation of Mg ions into FHA coatings enhances the pull-off adhesion strength between the coating and the substrate, but no significant difference is observed with different Mg concentrations.     

HAp/Ti<Subscript>2</Subscript>Ni coatings of high bonding strength on Ti–6Al–4V prepared by the eutectic melting bonding method

Eutectic melting bonding (EMB) method is a useful technique for fabricating bioactive coatings with relatively high crystallinity and bonding strength with substrate on titanium substrates. Using the EMB method, hydroxyapatite/Ti₂Ni coatings were prepared on the surface of Ti–6Al–4V at a relatively low temperature (1,050 °C) in a vacuum furnace. The coatings were then characterized in terms of phase components, microstructure, bonding strength and cytotoxicity. The results showed that the coatings were mainly composed of HAp and Ti₂Ni, and the thickness of the coatings was approximately 300 μm. X-ray diffraction analysis showed that the coatings exhibited relatively high crystallinity. The tensile bonding strength between the coatings and the substrates was 69.68 ± 5.15 MPa. The coatings had a porous and rough surface which is suitable for cell attachment and filopodia growth. The cell culture study showed that the number of MG-63 cells increased, and the cell morphology changed with the incubation time. This study showed that the EMB method can be utilized as a potentially powerful method to obtain high quality hydroxyapatite coatings with desired mechanical and biocompatibility properties on Ti-alloy substrates.     

Sol-Gel Derived Hydroxylapatite Coatings for Biomedical Applications

This paper presents the preliminary findings of a novel coating technique for the deposition of hydroxylapatite coatings on ceramic substrates. Through the use of sol-gel methods crystalline coatings of hydroxylapatite on substrates of vycor glass, polycrystal line alumina and single crystal magnesia have been successfully produced. The production of sol-gel solutions, coatings and their analysis was examined by X-ray diffraction, scanning electron microscopy and atomic force microscopy. Results thus far indicate that high quality hydroxylapatite coatings can be produced on ceramic substrates, with coatings deposited in this manner offering a number of benefits over other coating methods.     

Composite calcium phosphate coatings with sustained Zn release

Zinc-substituted tricalcium phosphate/fluoridated hydroxyapatite (ZnTCP/FHA) biphasic composite coatings and Zinc containing fluoridated hydroxyapatite (ZnFHA) coating were prepared on Ti6Al4V substrates through a modified sol-gel method. The release of zinc ions from these coatings was characterized through a designed cycled immersion test: the coatings were soaked in the TRIS solution with pH of 7.25 at 37 °C for 96 h (one cycle). This process was repeated twice with the solution refreshed at the end of the each cycle. The Zn concentrations were measured at a 24-hour interval during the first cycle and at the end of each cycle. The results indicated that ZnTCP/FHA coatings released Zn at a rather slow and sustained rate while ZnFHA coatings released Zn at a rapid and therefore unsustained rate. This Zn release behavior difference is attributed to the different chemical states of Zn in the coatings. The current results demonstrated that the designed biphasic composite approach could potentially be a good way to tailor the release of Zn through combinations of different Zn chemical states, with the durability of the coatings not impaired.     

Novel sol-gel derived calcium phosphate coatings on Mg4Y alloy

Calcium phosphates (CaPs) and silicon containing calcium phosphates (Si-CaPs) coatings on a biodegradable magnesium yttrium alloy (Mg4Y) were prepared by a sol-gel technique to improve the bioactivity of the alloy surface. The experimental results show that thick porous coatings comprised of nano-sized calcium phosphate particles can be prepared by heating the as dip coated substrates at 450 °C. The in vitro degradation results show that the coatings do not alter the degradation kinetics of the substrates significantly and the release of magnesium and yttrium ions at initial time points was very similar for both the coated and bare substrates. The cyto-compatibility studies using MC3T3-E1 osteoblasts show that the coated substrates were more bioactive than the uncoated substrates as the cells begin to grow and form a matrix on the coated substrates more easily than on the bare metal. These preliminary results collectively show the potential of use of sol-gel derived calcium phosphate coatings on magnesium based degradable scaffolds to improve their surface bioactivity.     

A simple chemical method for preparation of hydroxyapatite coatings on Ti6Al4V substrate

A novel, simple and economical chemical bath method for deposition of calcium hydroxyapatite coating has been developed. The coatings were prepared from EDTA solutions in alkaline media on Ti6Al4V substrates. The method is based on thermal dissociation of the Ca(EDTA)^2- complex at 65–95 °C. Two chemical baths with and without presence of Na⁺ and Cl^- were used for the deposition. The Rutherford back scattering study shows that the coating material from bath which contained sodium and chlorine ions have their presence in the coated material. The bath which has been prepared with potassium substituting sodium and nitrate substituting chlorine produced coatings with better stoichiometry, with Ca/P=1,67. The X-ray analysis revealed that the calcium hydroxyapatite coatings have preferred crystal orientation in the 002 direction. © 2001 Kluwer Academic Publishers     

A dewetting process to nano-pattern collagen on hydroxyapatite

Nano-patterned collagen layers on the sintered hydroxyapatite (HAp) disk with a mirror surface were fabricated by the dewetting methods. The surface wettability, energy and tension were of great importance for the formation of nanostructured collagen layers. The maximum adsorption amount and binding affinity of collagen onto the sintered HAp particle were analyzed by the adsorption isotherm curve to elucidate the formation mechanism of nano-patterned collagen layers. The slow evaporation of solvent from the adsorbed collagen layers can produce netlike structures of collagen with an average pore diameter of 80–90 nm, and its height of rims was 2–3 nm from atomic force microscopy.     

Electrospray deposition of nanohydroxyapatite coatings: A strategy to mimic bone apatite mineral

The biological performance of orthopaedic and oral metallic implants can be enhanced significantly by the application of bioactive coatings. In this work, a cost-efficient alternative to the traditional technique to produce a hydroxyapatite (HA) coating with a nanostructured feature onto a metallic implant surface at room temperature via electrospray deposition, is presented. To evaluate the bioactive capacity of these nanoHA (nHA) coatings in vitro, an acellular simulated body fluid soaking experiment and a human osteoblast (HOB) cell culture work were conducted. Under these physiological conditions, the accelerated apatite precipitation process occurred on the nHA-coated titanium surfaces as compared to the uncoated titanium surfaces. HOB cells developed mature cytoskeletons with distinct evidence of actin stress fibres and vinculin adhesion plaques, on these nHA coatings. Hence, this deposition technique holds great potential in producing high quality nHA coatings for biomedical applications.     

Room-temperature synthesis of tin oxide nano-electrodes in aqueous solutions

Tin oxide nano-electrodes were fabricated on fluorine doped tin oxide (FTO) substrates at room temperature. SnO₂ was crystallized from ions in aqueous solutions to cover the substrates uniformly. They were single phase of SnO₂ nano-crystals and about 5–10 nm in size. The surface coatings changed the surface morphology of FTO substrates to increase roughness and surface area. FTO substrates covered with tin oxide had the same transparency as bare FTO substrates in the range from 200 nm to 850 nm.     

含碳纳米管有机无机复合涂层的制备与防护性能

为了改善铝合金材料的耐腐蚀性能, 研究了以正硅酸乙酯（TEOS）为主要原料, 加入一定量的KH-550, 并引入部分羟基化的多壁碳纳米管（MWCNTs-OH）进行复合, 以冰乙酸为催化剂, 采用溶胶---凝胶法在铝合金基体表面形成复合涂层。腐蚀电化学测试和扫描电镜分析结果表明, MWCNTs-OH的引入能够明显提高涂层的防护性能, 并有效防止涂层开裂。考察了MWCNTs-OH含量和热处理温度对涂层性能的影响。结果表明: MWCNTs-OH质量分数为0.04%、 热处理温度为130℃时制备的涂层性能最佳, 相应的试样在3.5wt%NaCl溶液中的腐蚀电流密度约为3.056×10-8A/cm2, 而同等实验条件下铝合金基体腐蚀电流密度为7.216×10-5A/cm2, 涂层的存在使腐蚀速率降低了3个数量级, 涂层对铝合金基体具有显著的防护效果。      

Electrophoretic deposition of composite hydroxyapatite-chitosan coatings

Cathodic electrophoretic deposition has been utilized for the fabrication of composite hydroxyapatite-chitosan coatings on 316L stainless steel substrates. The addition of chitosan to the hydroxyapatite suspensions promoted the electrophoretic deposition of the hydroxyapatite nanoparticles and resulted in the formation of composite coatings. The obtained coatings were investigated by X-ray diffraction, thermogravimetric and differential thermal analysis, scanning and transmission electron microscopy, potentiodynamic polarization measurements, and electrochemical impedance spectroscopy. It was shown that the deposit composition can be changed by a variation of the chitosan or hydroxyapatite concentration in the solutions. Experimental conditions were developed for the fabrication of hydroxyapatite-chitosan nanocomposites containing 40.9–89.8 wt.% hydroxyapatite. The method enabled the formation of adherent and uniform coatings of thicknesses up to 60 μm. X-ray studies revealed that the preferred orientation of the hydroxyapatite nanoparticles in the chitosan matrix increases with decreasing hydroxyapatite content in the composite coatings. The obtained coatings provided the corrosion protection for the 316L stainless steel substrates.     

Thermal barrier coatings from sol-gel-derived spray-grade Y2O3-ZrO2 microspheres

For the development of ceramic thermal barrier coatings, spray-grade yttria-stabilized zirconia microspheres were prepared by the sol-gel technique. Oxide microspheres were obtained by calcination of the corresponding gel spheres at 1000 °C. Scanning electron microscopic and optical microscopic observations revealed the material thus obtained to have a predominantly spherical morphology and the requisite size distribution (5–50 m). The dense, calcined microspheres showed good flowability. X-ray diffraction studies indicated the presence of the tetragonal polymorph of ZrO₂ as the major phase, in addition to about 14% monoclinic ZrO₂. The plasma-sprayed YSZ coatings made from the sol-gel-derived microspheres showed a further decrease in the monoclinic ZrO₂ content (6%). The coatings survived 40–50 thermal cycles (30 min at 1200 °C followed by a water quench), indicating good thermal shock resistance.     

Mechanical properties of nanocomposite organosilicate films

Nanocomposite coatings have been deposited on plastic substrates by the dipping–drawing technique. The coatings were constituted by a matrice of a hybrid organomineral gel and a reinforcement made of amorphous silica. Two methods by which increase the silica content were investigated: silica was added via a silicon alkoxide compound or via dense silica particles of 10 nm size. Young's modulus and the hardness of the coating were measured using home-built equipment, and results compared to literature models. It is shown that the agreement between models and experimental values depends on the method of preparation of the nanocomposite coating. On the other hand, deviations appear when the volume fraction of reinforcement surpasses the three-dimensional percolation threshold.     

Control of phase composition in hydroxyapatite/tetracalcium phosphate biphasic thin coatings for biomedical applications

Biphasic calcium phosphates comprising well-controlled mixtures of nonresorbable hydroxyapatite and other resorbable calcium phosphate phases often exhibit a combination of enhanced bioactivity and mechanical stability that is difficult to achieve in single-phase materials. This makes these biphasic bioceramics promising substrate materials for applications in bone tissue regeneration and repair. In this paper we report the synthesis of highly crystalline, biphasic coatings of hydroxyapatite/tetracalcium phosphate with control over the weight fraction of the constituent phases. The coatings were produced by pulsed laser deposition using ablation targets of pure crystalline hydroxyapatite. The fraction of tetracalcium phosphate phase in the coatings was controlled by varying the substrate temperature and the partial pressure of water vapor in the deposition chamber. A systematic study of phase composition in the hydroxyapatite/tetracalcium phosphate biphasic coatings was performed with X-ray diffraction. Tetracalcium phosphate in the coatings obtained at high substrate temperature is not formed by partial conversion of previously deposited hydroxyapatite. Instead, it is produced by nucleation and growth of tetracalcium phosphate itself from the ablation products of the hydroxyapatite target or by accretion of tetracalcium phosphate grains formed during ablation. This finding was confirmed by formation of calcium oxide, not tetracalcium phosphate, after annealing of pure hydroxyapatite coatings at high temperatures of 700–850∘C.