Effects of structure and composition of the CaP composite coatings on apatite formation and bioactivity in simulated body fluid

The surface properties of biomaterials determine the interactions between biomedical devices and the surrounding biological environment. The surface modification of biomaterials is extensively recognized as a key strategy in the design of the next generation of bone implants and tissue engineering. In this study, the highly ordered octacalcium phosphate (OCP) coating and OCP/protein coating with hierarchically porous structure in nano-micro scale were constructed on titanium substrate by electrochemically-induced deposition (ED). The formation behavior of apatite on OCP and OCP/protein coatings immersed in simulated body fluid (SBF) was investigated in physicochemical aspects. It is indicated that soaked in SBF, the OCP and OCP/protein coatings are possible to induce relevant apatite formation on their surface, and the apatite-forming behavior in body environment is depended on the chemical composition and structure of the coatings. The apatite formed on OCP/protein composite coating possesses carbonated structure, needle-like crystals in nano scale, lower Ca/P ratio and higher degree of the preferred c-axis orientation, which are similar to the mineral composition and structure in natural bone, and hence called as bone-like apatite.     

Biological and physical properties of pulsed-Laser-deposited zirconia/hydroxyapatite on titanium: In vitro study

Coating dental implants with hydroxyapatite (HA) may give certain advantages such as active encouragement of new bone growth, a lower rejection rate, and an improved long-term prosthesis fixation. This study examined the mechanical and biological properties of titanium alloy implant cores with an interlayer of zirconia and a coating of HA created using pulsed Laser deposition (PLD). The thickness of the zirconia layer was 50–100 nm, and the HA layer was ～600 nm. The crystallinity, morphology, wettability, and Ca/P ratio of the HA layer were investigated by electron microscopy, X-ray diffraction, goniometric measurement of contact angle, and wavelength dispersive X-ray analysis. The physical tests indicated adequate mechanical properties and a satisfactory adhesion to a titanium core modified with zirconia and HA. Cell proliferation and metabolic activity of human embryonal lung fibroblasts were determined using counting of harvested cells and providing an MTT assay. it was demonstrated that none of the samples were cytotoxic and their surfaces promoted cell colonization. PLD was found to be a promising method of applying coatings to a metal core for dental implants, and the in vitro biological tests suggest that the crystalline HA coating can improve the biological properties of titanium covered with zirconia.     

Surface modification of titanium by nano-TiO2/HA bioceramic coating

A nano-TiO₂/hydroxyapatite composite bioceramic coating was developed and applied to the surfaces of pure titanium discs by the sol-gel method. A TiO₂ anatase bioceramic coating was utilized in the inner layer, which could adhere tightly to the titanium substrate. A porous hydroxyapatite (HA) bioceramic coating was utilized in the outer layer, which has higher solubility and better short-term bioactivity. Conventional HA coatings and commercially pure titanium were used as controls. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed to characterize the crystallization, surface morphology, and thickness of the coatings. The bioactivities of the coatings were evaluated by in vitro osteoblast cultures. Results showed that the nano-TiO₂/HA composite bioceramic coating exhibited good crystallization and homogeneous, nano-scale surface morphology. In addition, the nano-TiO₂/HA coating adhered tightly to the substrate, and the in vitro osteoblast cultures exhibited satisfactory bioactivity.     

X-ray photoelectron spectroscopy study of the growth kinetics of biomimetically grown hydroxyapatite thin-film coatings

Hydroxyapatite (HA) thin-film coatings grown biomimetically using simulated body fluid (SBF) are desirable for a range of applications such as improved fixation of fine- and complex-shaped orthopedic and dental implants, tissue engineering scaffolds and localized and sustained drug delivery. There is a dearth of knowledge on two key aspects of SBF-grown HA coatings: (i) the growth kinetics over short deposition periods, hours rather than weeks; and (ii) possible difference between the coatings deposited with and without periodic SBF replenishment. A study centred on these aspects is reported. X-ray photoelectron spectroscopy (XPS) has been used to study the growth kinetics of SBF-grown HA coatings for deposition periods ranging from 0.5 h to 21 days. The coatings were deposited with and without periodic replenishment of SBF. The XPS studies revealed that: (i) a continuous, stable HA coating fully covered the titanium substrate after a growth period of 13 h without SBF replenishment; (ii) thicker HA coatings about 1 μm in thickness resulted after a growth period of 21 days, both with and without SBF replenishment; and (iii) the Ca/P ratio at the surface of the HA coating was significantly lower than that in its bulk. No significant difference between HA grown with and without periodic replenishment of SBF was found. The coatings were determined to be carbonated, a characteristic desirable for improved implant fixation. The atomic force and scanning electron microscopies results suggested that heterogeneous nucleation and growth are the primary deposition mode for these coatings. Primary osteoblast cell studies demonstrated the biocompatibility of these coatings, i.e., osteoblast colony coverage of approximately 80%, similar to the control substrate (tissue culture polystyrene).     

Calcium phosphate coatings deposited by laser ablation at 355 nm under different substrate temperatures and water vapour pressures

Calcium phosphate coatings were deposited on Ti-6Al-4V by laser ablation with a 355 nm Nd:YAG laser at different substrate temperatures. Two series of coatings were deposited at water vapour pressures of 10 and 45 Pa by varying the substrate temperature from 20 to 600 °C. Characterisation of their structure and adhesion has been carried out in order to study the effect of the deposition temperature and the water vapour pressure on the coating properties. It has been found that a high temperature favours the synthesis of crystalline phases. Ca rich phases are synthesised at 10 Pa while hydroxyapatite is obtained at 45 Pa with some alfa tricalcium phosphate. Scratch test measurements have shown, that the coating-substrate adhesion for coatings deposited at 45 Pa is remarkably increased at substrate temperatures higher than 400 °C, but the highest adhesion has been found for amorphous coatings obtained at 10 Pa and 200 °C.     

Characterization of calcium phosphate coatings doped with Mg, deposited by pulsed laser deposition technique using ArF excimer laser

Calcium phosphate layers were deposited on Ti6Al4V substrates with TiN buffer layers by use of pulsed laser deposition method. With this technique three pressed pellets consisted of tricalcium phosphate (TCP, Ca(3)(PO(4))(2)), hydroxyapatite (HA, Ca(10)(PO(4))(6)(OH)(2)) and hydroxyapatite-doped with magnesium (HA with 4% of Mg and trace amount of (Ca,Mg)(3)(PO(4))(2)) were ablated using ArF excimer laser (lambda=193 nm). The using of different targets enabled to determine the influence of target composition on the nature of deposited layers. The obtained deposits were characterized by means of Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction method (XRD). The obtained Fourier spectras revealed differences in terms of intensity of spectral bands of different layers. The analysis from XRD showed that Mg-doped HA layer has crystalline structure and TCP and HA layers composition is characterized by amorphous nature.     

在金属基带上用激光脉冲沉积法制备帽子层CeO_2的研究

利用脉冲激光沉积法在带有Y2O3、YSZ隔离层的金属基带上制备了CeO2帽子层。主要讨论了温度、激光脉冲频率对CeO2隔离层的影响,用X射线θ~2θ扫描、Φ扫描对薄膜的取向和织构进行表征。结果表明在温度为610℃、激光频率为10Hz、1Pa氧压下制备的CeO2隔离层能有效地继承衬底的织构,平均平面内Φ扫描半高宽度为6.9°。扫描电镜可以观察到薄膜表面致密且无裂纹,原子力显微镜观测表面平均粗糙度在10nm以下。     

Effect of two-step functionalization of Ti by chemical processes on protein adsorption

Titanium and its alloys are widely used for orthopedic and dental implants because of their superior mechanical properties, low modulus, excellent corrosion resistance and good biocompatibility. However, it takes several months for titanium implants and bone tissue to reach integration. Hence, there is growing interest in shortening the process of osseointegration and thereby reducing surgical restrictions. Various surface modifications have been applied to form a bioactive titanium oxide layer on the metal surface, which is known to accelerate osseointegration.The present work shows that titanium dioxide (TiO₂) layers formed on titanium substrates by etching in a solution of sodium hydroxide (NaOH) or hydrogen peroxide/phosphoric acid (H₃PO₄/H₂O₂, with a volume ratio of 1:1) are highly suitable pre-treatments for apatite-like coating deposition. Using a two-step procedure (etching in an alkaline or acidic solution followed by soaking in Hanks’ medium), biomimetic calcium phosphate coatings were deposited on porous TiO₂ layers. The combined effects of surface topography and chemistry on the formation of the calcium phosphate layer are presented. The topography of the TiO₂ layers was characterized using HR-SEM and AFM techniques. The nucleation and growth of calcium phosphate (Ca-P) coatings deposited on TiO₂ porous layers from Hanks’ solution was investigated using HR-SEM microscopy. AES, XPS and FTIR surface analytical techniques were used to characterize the titanium dioxide layers before and after deposition of the calcium phosphate coatings, as well as after the process of protein adsorption. To evaluate the potential use of such materials for biomedical applications, the adsorption of serum albumin, the most abundant protein in the blood, was studied on such surfaces.     

Pulsed laser deposition and its current research status in preparing hydroxyapatite thin films

Pulsed laser deposition (PLD) is a conceptually and experimentally simple yet highly versatile tool for thin films and multi-layer film research. The mechanisms, advantages and disadvantages of pulsed laser deposition were reviewed. The process and some methods to resolve the drawbacks of PLD were discussed. Pulsed laser deposition of hydroxyapatite thin films was reviewed. Simple adjustment of PLD parameters can deposit hydroxyapatite in situ in crystalline form, amorphous films or HA with other calcium phosphate phases. Compared with plasma sprayed HA coatings the pulsed laser deposition HA thin films have higher coating/substrate adhesion and have minor undesirable phases under optimal conditions. Finally, we suggested some new researches should be done.     

Calcium Phosphate-Based Composite Coating by Micro-Arc Oxidation (MAO) for Biomedical Application: A Review

Calcium phosphate (Ca-P) based composites have attracted great attention in the scientific community over the last decade for the development of biomedical applications. Among such Ca-P-based structures, carbonate apatite (CA) and hydroxyapatite (HA) materials have received much attention in the clinical and biomedical fields, mainly because of their unique biological characteristics. These characteristics can promote the biocompatibility of implant materials and osseointegration between the implant and host bone. Various studies have been carried out on the fabrication of Ca-P coatings on orthopedic and dental implants using the micro-arc oxidation (MAO) process; however, there has not been a comprehensive review of the control of MAO parameters to achieve an optimal coating structure. This article presents a critical analysis of the synthesis techniques that have been adopted for the fabrication of Ca-P-based coatings on both commercially pure titanium (CP-Ti) and biomedical grade Ti alloys. Moreover, this work elucidates the influence of MAO processing parameters such as electrolyte concentration, pH value, voltage, and time on the crystal structure and surface morphology of Ca-P coatings. It is shown that the surface thickness, crystal structure, and surface morphology of Ca-P coatings directly influence their biocompatibility.     

Synthesis and characterization of laser ablated TiNi films

TiNi thin films with BaTiO₃ and PbZr_0.52Ti_0.48O₃ (PZT) as buffer layers were deposited on Si(100) substrates by the pulsed laser deposition (PLD) method. Buffer layers (BaTiO₃ and PZT) were deposited at 600 °C in oxygen (O₂) environment and TiNi films were deposited on the top of the buffer layer in presence of 15 mTorr nitrogen (N₂) at various deposition temperatures (50, 300, and 500 °C). Synthesis and characterization of TiNi films were investigated from the crystallographic point of view by using X-ray diffractometer (XRD) and atomic force microscope (AFM) techniques. It is found that buffer layer of BaTiO₃ and PZT have improved the crystallinity of TiNi films deposited at higher temperatures. The TiNi/PZT film was uniform compared to TiNi/BaTiO3 film with the exception of agglomerates that appeared throughout the layer.     

Pulsed laser deposition of silicon substituted hydroxyapatite coatings from synthetical and biological sources

Silicon substituted hydroxyapatite (Si-HA) is a new material with an enhanced bioactibity and it can be produced by chemical synthesis. Nevertheless, the coating of metallic substrates with a bioactive material is a common method nowadays to improve its integration with the receptor bone.Si-HA films were deposited by pulsed laser deposition (PLD), using targets composed of mixtures of HA with different Si containing sources such as SiO₂ and diatomaceous earth. The Si-HA films were characterized in terms of structure and chemical composition by spectroscopic techniques (FTIR, XPS), and several ion beam techniques (RBS, PIXE). The analysis revealed that the Si is successfully incorporated into the HA structure, as well as traces of other elements such as Na, Fe or K.     

Hydroxyapatite/titania composite bioactivity coating processed by sol-gel method

Hydroxyapatite/titania composite material was coated onto a titanium (pure Ti) substrate by sol-gel method. The hydroxyapatite (HA) and titania (TiO₂) sol were made from precursor and mixed together. The insertion of TiO₂ enhanced the chemical affinity and the physical consistency between HA and Ti substrate. The HA/TiO₂ composite coating adhered tightly to the Ti substrate. Owing to the insertion of TiO₂, the crystallinity of HA has been delayed. The specimens with HA/TiO₂ composite coatings were soaked into SBF, and displayed good bone-like apatite forming ability. The bioactivity of the composite HA coatings were tested in vitro by cell culture.     

Analysis of the interface between a pulsed laser deposited calcium phosphate coating and a titanium alloy substrate

Calcium phosphate coatings deposited on titanium alloy are intended to add a bioactive surface to medical implants. This work presents the characterisation of the interface between Ti-6Al-4V and a crystalline calcium phosphate coating obtained by pulsed laser deposition, with a KrF excimer laser, at 575 °C and under a 45 Pa water-vapour atmosphere. The coating–substrate system was studied by secondary-ion mass spectrometry, scanning electron microscopy, X-ray diffractometry, Raman spectroscopy and X-ray photoelectron spectroscopy. The results show that the deposition process promotes the interdiffusion of substrate elements into the coating and coating elements into the substrate oxide layer. Thus, a graded layer of mixed calcium phosphate and amorphous titanium oxide is formed. For the substrate, a hydroxyapatite coating acts more as a barrier for oxygen incoming from a gas than as an oxygen source during deposition. Moreover, oxygen diffusion into the substrate occurs. Thus, the content of oxygen of this oxide layer diminishes with depth. When the oxygen concentration is low enough it is incorporated in solid solution in the titanium alloy . PACS 81.15.Fg; 68.55.-a; 87.68.+z     

SEM and EDX studies of bioactive hydroxyapatite coatings on titanium implants

This work presents a study on an alternative coating method based on biomimetic techniques which are designed to form a crystalline hydroxyapatite layer very similar to the process corresponding to the formation of natural bone. The HA formation on the surface of titanium alloy pretreated with NaOH solution is investigated. Two types of solutions such as supersaturated calcification solution (SCS) and modified SCS (M-SCS) were used to investigate bone-like apatite formation on alkali-treated titanium. The hydroxyapatite deposits are investigated by means of scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The data suggest that the method utilized in this work can be successfully applied to obtain deposition of uniform coatings of crystalline hydroxyapatite on titanium substrates.     

Process and performance of hot dip zinc coatings containing ZnO and Ni-P under layers as barrier protection

A new coating system of under layer for hot dip zinc coating was explored as an effective coating for steel especially for application in relatively high aggressive environments. The influence of different barrier layers formed prior to hot dip galvanization was investigated to optimize high performance protective galvanic coatings. The deposition of ZnO and Ni-P inner layers and characteristics of hotdip zinc coatings were explored in this study. The coating morphology was characterized by scanning electron microscope (SEM) analysis. The hot dip zinc coatings containing under layer showed substantial improvement in their properties such as good adhesion, and high hardness. In addition, a decrease in the thickness of the coating layer and an enhancement of the corrosion resistance were found. Open circuit potential (OCP) of different galvanized layers in different corrosive media viz. 5% NaCl and 0.5 M H₂SO₄ solutions at 25 ± 1 °C was measured as a function of time. A nobler OCP was exhibited for samples treated with ZnO and Ni than sample of pure Zn; this indicates a dissolution process followed by passivation due to the surface oxide formation. The high negative OCP can be attributed to the better alloying reaction between Zn and Fe and to the sacrificial nature of the top pure zinc layer.     

Inhomogeneity of calcium phosphate coatings deposited by laser ablation at high deposition rate

Calcium phosphate coatings were deposited with a KrF excimer laser onto titanium alloy to study their homogeneity. Deposition was performed at a high deposition rate under a water vapour atmosphere of 45 Pa and at a substrate temperature of 575 °C. Samples were also submitted to annealing under the same conditions of deposition for different times just after deposition. The effects of the annealing were also investigated. The morphology of the coatings was studied by scanning electron microscopy. Their structure and phase distribution was analysed by X-ray diffractometry and infrared and micro-Raman spectroscopies. Besides the non-uniform thickness, the results reveal an inhomogeneity in the spatial distribution of calcium phosphate phases in the coatings. The phase distribution can be almost completely correlated with the deposition rate. High deposition rates (0.5 nm/pulse) occurring in the centre of deposition results in the formation of amorphous calcium phosphate, while lower deposition rates favour the presence of hydroxyapatite and alpha tricalcium phosphate. At intermediate deposition rates, beta tricalcium phosphate is found, probably because the superimposed effect of energetic particles bombardment. The annealing process promotes the crystallisation of the amorphous material. The importance of the deposition rate in the phases obtained is stated after comparing these results with a previous work where homogeneous hydroxyapatite coatings were obtained under the same conditions of laser fluence, temperature and pressure, but at lower deposition rates. Received: 22 November 2001 / Accepted: 12 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +34-93/402-1138, E-mail: jmfernandez@fao.ub.es     

Synthesis of functionally graded bioactive glass-apatite multistructures on Ti substrates by pulsed laser deposition

Functionally graded glass-apatite multistructures were synthesized by pulsed laser deposition on Ti substrates. We used sintered targets of hydroxyapatite Ca₁₀(PO₄)₆(OH)₂, or bioglasses in the system SiO₂-Na₂O-K₂O-CaO-MgO-P₂O₅ with SiO₂ content of either 57 wt.% (6P57) or 61 wt.% (6P61). A UV KrF* (λ = 248 nm, τ > 7 ns) excimer laser source was used for the multipulse laser ablation of the targets. The hydroxyapatite thin films were obtained in H₂O vapors, while the bioglass layers were deposited in O₂. Thin films of 6P61 were deposited in direct contact with Ti, because Ti and this glass have similar thermal expansion behaviors, which ensure good bioglass adhesion to the substrate. This glass, however, is not bioactive, so yet more depositions of 6P57 bioglass and/or hydroxyapatite thin films were performed. All structures with hydroxyapatite overcoating were post-treated in a flux of water vapors. The obtained multistructures were characterized by various techniques. X-ray investigations of the coatings found small amounts of crystalline hydroxyapatite in the outer layers. The scanning electron microscopy analyses revealed homogeneous coatings with good adhesion to the Ti substrate. Our studies showed that the multistructures we had obtained were compatible with further use in biomimetic metallic implants with glass-apatite coating applications.     

Surface analysis of biocompatible coatings on titanium

The coatings of hydroxyapatite, which is widely used for orthopaedic and dental prothesis, were deposited by using the dip-coating method. The layers of hydroxyapatite were grown on commercial Ti substrates. In order to improve the adhesion of hydroxyapatite, the substrate was a priori covered with titania or calcium titanate by using the sol-gel technique. For comparison, commercial samples of hydroxyapatite coating (manufactured by means of plasma-spray apparatus) were analysed. The chemical composition and the structure of the coatings (TiO₂, CaTiO₃ and hydroxyapatite) were studied by using X-ray photoelectron spectroscopy (XPS), scanning Auger microscopy (SAM), X-ray diffraction (XRD) and secondary electron microscopy (SEM) techniques. The data of quantitative XPS analysis and the surface images (SAM and SEM) displayed the superior quality (cleanness, homogeneity, etc.) of hydroxyapatite deposited by sol-gel in comparison with commercial samples investigated.     

Effect of employing ultrasonic waves during pulse electrochemical deposition on the characteristics and biocompatibility of calcium phosphate coatings

In the present work, we investigated the effect of employing ultrasonic waves during pulse electrochemical deposition on surface topography, chemical composition and biocompatibility of calcium phosphate (Ca-P) coatings. The SEM and 3D AFM images showed that the anodized titanium surface was covered with the uniform and refined size of plate-like Ca-P crystals, when the ultrasonic treatment of the electrolyte with power of 60 W was carried out during deposition. In contrast, for the Ca-P; 0 W coating applied under only the magnetic stirring of the electrolyte, the microstructure was non-uniform and some Ca-P crystals with the larger size were randomly observed in different regions, causing a rougher surface. The FTIR results also revealed that employing the ultrasound increases the deposition of a coating involved in only the most stable Ca-P phase of carbonated hydroxyapatite (CHA). However, in the absence of ultrasound, besides the prominent phase of CHA, some less stable Ca-P phases like octa calcium phosphate (OCP) and brushite were also formed in the Ca-P; 0 W coating. The Ca-P; 60 W coating showed the higher ability for apatite biomineralization after a 7-day immersion in the simulated body fluid (SBF). This coating also provided a better surface for the cellular activity, as compared to the Ca-P; 0 W coating.