Pulsed laser deposition of hydroxyapatite on nanostructured titanium towards drug eluting implants

Titania nanotubes grown on titanium substrates by electrochemical anodization in glycerol–ammonium fluoride–water system were used to develop efficient drug carrying implants upon coating hydroxyapatite (HA) ceramic. The nanostructured surfaces achieved by anodization were caped with HA crystallites by pulsed laser deposition. The implant substrates were studied for their drug carrying capacity using gentamicin as a model. The nano-tubular surface with HA coating had better drug loading capacity of about 800 μg/cm² gentamicin while the bare anodized substrate carried less than 660 μg/cm². The HA coating alone stored as low as 68 μg/cm² and released the drug within the initial burst period itself. The ceramic coated anodized substrates were found to be more efficient in controlled delivery for longer than 160 h with a drug release of 0.5 μg/cm² even towards the end. The substrate with nanostructuring alone delivered the whole drug within 140 h. This study proposes the application of laser deposition of HA over nanostructured titanium, which proves to be promising towards controlled drug eluting bioceramic coated metallic prostheses.     

Pulsed laser deposition of titania on rutile nanorod arrays

Oriented rutile nanorod arrays are precipitated on metallic Ti plates from a precursor derived by interactions between Ti and aqueous hydrogen peroxide. Pulsed laser deposition (PLD) is then carried out to deposit titania on the nanorod arrays, in comparison with bare Ti substrates, utilizing a high-temperature sintered rutile target in oxygen atmosphere. It is found that dense and homogeneous titania thin films are obtained on Ti substrates; while growth on the rutile nanorod arrays is epitaxial, resulting in enlarged nanorods conformally covered with titania. Titania grown on both Ti substrates and rutile nanorod arrays is either pure rutile or a mixture of anatase and rutile, with the formation of anatase favored by an increasing oxygen pressure during the PLD procedure. The surface roughness and the particle size of the dense titania films on Ti substrates increase as a result of increasing oxygen pressure and prolonged deposition time. The PLD-induced epitaxial growth of titania is inhibited by increasing substrate temperatures. The photocatalytic experiments reveal a significantly enhanced activity for the rutile nanorod arrays after a subsequent PLD treatment.     

Pulsed laser deposition of hydroxyapatite thin films

Hydroxyapatite is a bioactive ceramic material that mimics the mineral composition of natural bone. This material does not possess acceptable mechanical properties for use as a bulk biomaterial; however, it does demonstrate significant potential for use as a coating on metallic orthopaedic and dental prostheses. This paper reviews recent developments involving pulsed laser deposition of hydroxyapatite thin films for medical and dental applications. The structural, mechanical, and biological properties of hydroxyapatite thin films are described. In addition, future directions in pulsed laser deposition of hydroxyapatite thin films are discussed.     

Pulsed laser deposition of silicon-substituted hydroxyapatite coatings

Thin films of Si-substituted hydroxyapatite (Si-HA) were deposited on Si and Ti substrates by pulsed laser deposition (PLD), in the presence of a water vapour atmosphere. The PLD ablation targets were made with different mixtures of commercial carbonated HA and Si powder, in order to produce the Si-HA thin films. The physicochemical properties of the coatings and the incorporation of the Si into the HA structure was studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Si atoms were successfully incorporated into the HA structure, and were found to be in the form of SiO₄⁴⁻ groups, principally displacing carbonate groups off the HA structure.     

Bioceramic coating of hydroxyapatite on titanium substrate with Nd-YAG laser

The ability to bond to bone tissue is a unique property of bioactive ceramics. Hydroxyapatite (HAp) is one of the potential bioceramics candidates due to its superior bio-compatibility. Significant effort has been devoted to coat HAp ceramics on metallic substrates. Most of these processes, such as ion-beam sputter coating, thermal spraying, and flame spraying, are high temperature line of sight processes, which suffer from undesirable phase formation and weak metal/HAP bonding strength. This paper presents a unique process to coat HAp powders on titanium substrates at low temperature and enhance the coating/substrate interface by laser surface engineering. Nd-YAG laser transmits HAp powders and the laser power is absorbed by titanium substrate to produce a thin layer of molten region. During coating process, HAp powders are kept at low temperature before they are entrapped in metallic layer. Scanning electron microscope (SEM) was used to investigate the microstructure of coating; the chemical composition of the coating is determined by energy dispersive spectrometry (EDS). Mechanical properties of the interface between coating and Ti substrate were investigated by nanoindentation.     

Electrolytic deposition of magnesium-substituted hydroxyapatite crystals on titanium substrate

Electrolytic deposition of magnesium-substituted hydroxyapatite (Mg-HAp) coatings on titanium was investigated and Mg-HAp crystals with up to 2 wt.% Mg²⁺ were deposited in electrolytes with various Mg²⁺ concentration. The incorporation of Mg substantially changed the morphology of the HAp crystals and decreased the crystal size and crystallinity of the HAp. The similarity with natural dentin and bone in composition and the increased specific surface of the Mg-HAp coatings on the Ti substrates were believed to benefit the bioactivity and the drug-carrying properties of the coatings.     

Sol–gel derived hydroxyapatite/titania biocoatings on titanium substrate

A simple sol–gel method was successfully developed for a hydroxyapatite (HA)/TiO₂ double layer deposition on a pure titanium substrate. Phase formation, surface morphology, and interfacial microstructure were investigated by differential scanning calorimetry analysis (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The TiO₂ layer was coated by a spin coating method at a speed of 1500 rpm for 15 s, followed by a heat treatment at 560 °C for 20 min. The HA film was subsequently spin coated on the outer surface at the same speed and then heat-treated at difference temperatures. Results indicated that the HA phase began to crystallize after a heat treatment at 580 °C; and the crystallinity increased obviously at a temperature of 780 °C. The HA film showed a porous structure and a thickness of 5–7 μm after the heat treatment at 780 °C. SEM observations revealed no delamination and crack at the interfaces of HA/TiO₂ and TiO₂/Ti. The HA film with a porous structure is expected to be more susceptible to the natural remodeling processes when it is implanted in a living body.     

Colloidal characterization and electrophoretic deposition of hydroxyapatite on titanium substrate

Hydroxyapatite (HA) powders were prepared by a modified chemical co-precipitation method and electrophoretically deposited onto a titanium tubular substrate. The zeta potential, electromobility and the particle size of the HA suspension was characterized at various pH values and the most stable and dispersed suspension condition was identified. Electrophoretic deposition of the HA particles on the titanium substrate was then carried out at this optimum suspension condition. Studies on deposition rate and examination on the microstructure of the sintered deposit were performed. The stoichiometry of the HA before and after sintering were also confirmed. The deposition experimental data obtained in the present work was also compared with theoretical model proposed in the literature. Lastly, the adhesion strength of the coating was also quantified using shear strength tests.     

Laser surface modification of titanium substrate for pulsed laser deposition of highly adherent hydroxyapatite

Biomedical implant devices made out of titanium and its alloys are benefited by a modified surface or a bioactive coating to enhance bone bonding ability and to function effectively in vivo for the intended period of time. In this respect hydroxyapatite coating developed through pulsed laser deposition is a promising approach. Since the success of the bioactive ceramic coated implant depends mainly on the substrate-coating strength; an attempt has been made to produce micro patterned surface structure on titanium substrate for adherent hydroxyapatite coating. A pulsed Nd-YAG laser beam (355 nm) with 10 Hz repetition rate was used for surface treatment of titanium as well as hydroxyapatite deposition. The unfocussed laser beam was used to modify the substrate surface with 500–18,000 laser pulses while keeping the polished substrate in water. Hydroxyapatite deposition was done in a vacuum deposition chamber at 400°C with the focused laser beam under 1 × 10⁻³ mbar oxygen pressure. Deposits were analyzed to understand the physico-chemical, morphological and mechanical characteristics. The obtained substrate and coating surface morphology indicates that laser treatment method can provide controlled micro-topography. Scratch test analysis and microindentation hardness values of coating on laser treated substrate indicate higher mechanical adhesion with respect to coatings on untreated substrates.     

Synthesized silicon-substituted hydroxyapatite coating on titanium substrate by electrochemical deposition

Silicon-substituted hydroxyapaptite (Si-HA) coatings were prepared on titanium substrates by electrolytic deposition technique in electrolytes containing Ca²⁺, PO₄ ³⁻ and SiO₃ ²⁻ ions with various SiO₃ ²⁻/(PO₄ ³⁻ + SiO₃ ²⁻) molar ratios(η_si). The deposition was all conducted at a constant voltage of 3.0 V, with titanium substrate as cathode and platinum as anode, for 1 h at 85°C. The coatings thus prepared were characterized with inductively coupled plasma (ICP), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), field-emission-type scanning electron microscope (FSEM). The results show that the silicon amount in the coatings increases linearly to about 0.48 wt% at first with increasing η_si between 0 and 0.03, then increases slowly to about 0.55 wt% between 0.03 and 0.10 and finally maintains almost at a level around 0.55 wt% between 0.10 and 0.30. The tree-like Si-HA crystals are observed in the coatings prepared in the electrolyte of η_si = 0.20. And the presence of silicon in electrolytes decreases the thickness of the coatings, with effect being more significant as η_si increased. Additionally, the substitution of Si causes some OH⁻ loss and changes the lattice parameters of hydroxyapatite (HA).     

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.     

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.     

Preparation of hydroxyapatite-containing titania coating on titanium substrate by micro-arc oxidation

Hydroxyapatite-containing titania coatings on titanium substrates were formed by micro-arc oxidation (MAO) in electrolyte containing calcium acetate monohydrate (CH₃COO)₂Ca·H₂O) and sodium phosphate monobasic dihydrate (NaH₂PO₄·2H₂O) using a pulse power supply. Scanning electron microscopy (SEM) with Energy dispersive X-ray spectrometer (EDX) and X-ray diffraction (XRD) were employed to characterize the microstructure, elemental composition and phase components of the coatings. The coatings were rough and porous, without apparent interface to the titanium substrates. All the oxidized coatings contained Ca and P as well as Ti and O, and the porous coatings were made up of anatase, rutile and hydroxyapatite. Such MAO films are expected to have significant applications as artificial bone joints and dental implants.     

Pulsed laser deposition of indium antimonide

Single crystalline oriented films of indium antimonide have been grown on cadmium telluride substrates by the pulsed laser deposition technique. The films were (111) oriented which is the substrate orientation. The composition of the grown films were found to deviate from that of the target owing to loss of antimony during evaporation. This deviation from stoichiometry led to film-substrate reaction, resulting in mixed interface. The antimony deficiency in the films were controlled by correcting the stoichiometry, which led to avoiding mixed interfaces. The stoichiometric films showed good surface morphology and well defined sharp interfaces. The IR transmission spectrum showed sharp band to band absorption and effective detection in the MWIR. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Effect of titanium and titania on chemical characteristics of hydroxyapatite plasma-sprayed into water

HA and its composite particles (HA/Ti, HA/TiO₂) were plasma-sprayed into water as well as on the Ti substrate, respectively. The microstructure and phase compositions of the sprayed HA and its composite particles before and after impinging on the substrate were studied by using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. The results showed that the HA in the composite particles sprayed into water had a higher crystallinity than that in the composite coating. The addition of Ti or TiO₂ could both influence the decomposition of HA, but no chemical reacting product between them was formed before and after impinging on the substrate. However, EDS analyses showed the occurrence of interdiffusion of elements between HA and TiO₂, which was favorable to enhance the cohesive strength of particles in the composite coating. The post heat treatment at 650 °C for 2 h can effectively improve the crystallinity of coating by transforming amorphous phases into HA.     

Interfacial titanium oxide between hydroxyapatite and TiAlFe substrate

The interface between nano-crystalline hydroxyapatite (HA) thin films and a titanium alloy (Ti5Al2.5Fe) has been studied by means of Fourier transform infrared spectrophotometry and X-ray diffraction at grazing incidence. The HA thin films were deposited by radio-frequency magnetron sputtering in low pressure dry argon on substrates kept at low temperature or heated at 550 °C. The effect of film treatment by sputtering and annealing in humid air, as a simple, effective way of restoring the crystallinity and stoichiometry of the HA bulk, was studied in correlation with the development of a titanium oxide layer at the film-substrate interface. An interfacial TiO₂ film grew at the interface during annealing in moist air, while a TiO₂ layer diffused into the HA films when directly sputtered at 550 °C. The formation of an interfacial titanium oxide layer was inhibited by the insertion of a crystalline TiN buffer interlayer between the substrate and the HA film. Separately, the mechanical characteristics of the different HA films were monitored by nanoindentation to find out how they had been affected.     

ZrO2/hydroxyapatite coating on titanium by electrolytic deposition

In this study, hydroxyapatite (HA) was coated on a titanium (Ti) substrate over a ZrO(2) layer by the electrolytic deposition method, this double layer coating was then compared with a single layer coating of HA. The HA layer was used to increase the bioactivity and osteoconductivity of the Ti substrate, and the ZrO(2) layer was intended to improve the bonding strength between the HA layer and Ti substrate, and to prevent the corrosion of the Ti substrate. The electrolytic deposition formed an HA layer with a thicknesses of approximately 20 mum, which adhered tightly to the Ti substrate. The bonding strength of the HA/ZrO(2) double layer coating on Ti was markedly improved when compared to that of the HA single coating on Ti. The improvement in bonding strength with the use of a ZrO(2) base layer was attributed to the resulting increase in chemical affinity of the ZrO(2) to the HA layer and to the Ti substrate. The osteoblast-like cells cultured on the HA/ZrO(2) coating surface, proliferated in a similar manner to those on the HA single coating and on the pure Ti surfaces. At the same time, the corrosion resistance of Ti was improved by the presence of the ZrO(2) coating, as shown by a potentiodynamic polarization test.     

Characterization of the chemically deposited hydroxyapatite coating on a titanium substrate

Bioactive hydroxyapatite (HA) coating on titanium (Ti) implant can be used as a drug delivery device. A controlled release of drug around the implant requires the incorporation of drug into the coating material during the coating process. HA coating was prepared using a two-step procedure in conditions suitable for simultaneous incorporation of the protein-based drug into the coating material. Monetite coating was deposited on Ti substrate in acidic condition followed by the transformation of the monetite coating to HA. X-ray diffraction (XRD) confirmed the formation of the monetite phase at the first step of the coating preparation, which was transformed into HA at the second step. Fourier transform infrared spectroscopy demonstrated typical bands of a crystallized carbonated HA with A- and B-type substitution, which was confirmed by the XRD refinement of the structural parameters. Scanning electron microscope was used to observe the morphology of monetite and HA coatings. Adhesion of the coatings was measured using a scratch tester. The critical shearing stress was found to be 84.20 ± 1.27 MPa for the monetite coating, and 44.40 ± 2.39 MPa for the HA coating.     

沉积温度对多孔钛表面仿生制备羟基磷灰石的影响

为研究沉积温度对羟基磷灰石涂层生长的影响,制备了不同温度条件下成分恒定的仿生沉积液,并采用纯钛和不同孔径的多孔钛做基体,在其表面仿生沉积羟基磷灰石涂层,再将得到的涂层试样浸泡在标准模拟体液中检测其生物活性.通过X射线衍射仪(XRD)分析涂层物相结构,用金相显微镜、环境扫描电子显微镜(ESEM)表征涂层形貌,利用能谱分析仪(EDS)计算钙磷比.研究表明:基体孔径增大,有利于沉积液进入到孔隙且表面粗糙度相对增大,从而使得HA涂层变得均匀致密;沉积温度由30℃升高至37℃,会加快HA涂层致密均匀的生长,但温度升高到44℃时,HA晶粒变粗大,涂层变得疏松化;模拟体液浸泡后,Ti/HA涂层试样表面有新的HA生成,且Ca/P比接近标准的1.67,表明该Ti/HA涂层试样具有良好的生物活性.适当增大钛基体孔径,提高沉积液温度,可以得到均匀致密的HA生物活性涂层.     

Properties of pulsed laser deposited fluorinated hydroxyapatite films on titanium

Fluorinated hydroxyapatite coated titanium was investigated for application as implant coating for bone substitute materials in orthopaedics and dentistry. Pulsed laser deposition technique was used for films preparation. Fluorinated hydroxyapatite target composition, Ca₁₀(PO₄)₆F_1.37(OH)_0.63, was maintained at 2 J/cm² of laser fluence and 500-600 °C of the substrate temperature. Prepared films had a compact microstructure, composed of spherical micrometric-size aggregates. The average surface roughness resulted to be of 3 nm for the film grown at 500 °C and of 10 nm for that grown at 600 °C, showing that the temperature increase did not favour the growth of a more fine granulated surface. The films were polycrystalline with no preferential growth orientation. The films grown at 500-600 °C were about 8 μm thick and possessed a hardness of 12-13 GPa. Lower or higher substrate temperature provides the possibility to obtain coatings with different fine texture and roughness, thus tayloring them for various applications.