Hydroxyapatite Thin Films Research Articles

Biomedical properties of laser prepared silver-doped hydroxyapatite

Thin films of hydroxyapatite (HA) and silver-doped HA were synthesized using KrF excimer laser deposition. Material was ablated from one target composed from silver and HA segments. Layers properties as silver content, structure, color, FTIR spectra and antibacterial properties (Gram-positive Bacillus subtilis) were measured. Silver concentration in HA layers of 0.06, 0.3, 1.2, 4.4, 8.3, and 13.7 at % was detected. The antibacterial efficacy changed with silver dopation from 71.0 to 99.9%. The focus is on investigation of minimum Ag concentration needed to reach a high antibacterial efficacy.

Enhanced osteoblast and osteoclast responses to a thin film sputtered hydroxyapatite coating

A sputtering technique followed by a low temperature hydrothermal treatment has been demonstrated to produce a dense-and-bioactive hydroxyapatite thin film coating. The purpose of the present study was to investigate osteoblast and osteoclast responses to the hydroxyapatite coated plates and titanium plates with similar roughness. Rat bone marrow stromal cells were cultured on these plates to induce osteoblasts. The cells showed a significantly enhanced proliferation on the hydroxyapatite surface, accompanied by increase of osteoblastic phenotypes. The co-cultured osteoclasts exhibited the significantly different cell number and morphology between the hydroxyapatite and the titanium surfaces. A series of osteoclast marker genes were more stimulated on the hydroxyapatite and thirty two percent of the hydroxyapatite surface area could be resorbed by osteoclasts. The thin film sputtered hydroxyapatite could provide a favorable surface for both osteoblast and osteoclast formation and their function, indicating its good osteoconductivity and biodegradability.

Hydroxyapatite coating on the Ti–35Nb–xZr alloy by electron beam-physical vapor deposition

The aim of this study was to investigate the hydroxyapatite coating on the Ti–35Nb–xZr alloy by electron beam-physical vapor deposition. The Ti–35Nb–xZr ternary alloys contained from 3 wt.% to 10 wt.% Zr content were manufactured by arc melting furnace. Hydroxyapatite (HA) coatings were prepared by electron-beam physical vapor deposition (EB-PVD) method, and crystallization treatment was performed in Ar atmosphere at 300 and 500 °C for 1 h. The coated surface morphology of Ti–35Nb–xZr alloy was examined by FE-SEM, EDX and XRD, respectively. In order to evaluate the corrosion behavior, the tests were performed by potentiodynamic, cyclic polarization and AC impedance test. All the electrochemical data were obtained using a potentiostat. The Ti–35Nb–xZr alloys exhibited equiaxed structure with β phase, the peak of β phase increased with Zr contents. The hardness and elastic modulus of Ti–35Nb–xZr alloys decreased as Zr content increased. The HA coated layer was approximately 150 nm and Ca/P ratio of HA coated surface after heat treatment at 500 °C was around 1.67. The HA thin film consisted of small droplets with spherical shape by crystallization. From the anodic polarization curves, HA coated and heat treated Ti–35Nb–10Zr alloy showed higher corrosion potential than other samples. HA coated film on the Ti–35Nb–10Zr alloy can be shown high polarization resistance by crystallization.

Pyroelectric, piezoelectric, and photoeffects in hydroxyapatite thin films on silicon

Hydroxyapatite (HA) is the major component of bone and is used in artificial form in many biomedical applications. It was once believed to have a centrosymmetric crystal structure. In theoretical and experimental studies published in 2005, it was shown to have a monoclinic P21 structure. In the work reported here, 500 nm films of HA were spin-coated on silicon wafers. The materials were not poled. They had a nonuniform polarization distribution and exhibited pyroelectricity, piezoelectricity, and photoeffects. Structures of this type may have a number of technological applications.

755 ゾル-ゲル法によるハイドロキシアパタイト薄膜形成及び密着強度評価(材料力学III)

755 ゾル-ゲル法によるハイドロキシアパタイト薄膜形成及び密着強度評価(材料力学III)

Surface modification of magnetron-sputtered hydroxyapatite thin films via silicon substitution for orthopaedic and dental applications

There have been a significant advances made in the field of bioceramics, particularly hydroxyapatite (HA) during the past 10years. Emphasis has now shifted towards designing HA with enhanced bioactivity for bone tissue repair. The aim of this study was to assess whether surface wettability can be correlated with cellular interactions with silicon-substituted hydroxyapatite (SiHA)-coated titanium (Ti) substrates. SiHA thin coatings of varying Si compositions were deposited on Ti substrates via a magnetron co-sputtering technique. These coatings were then subjected to an in vitro study using primary human ostoeblast (HOB) cells, to evaluate their biological property. HOB cells showed initial poor adhesion and spreading on hydrophobic Ti surface. The application of HA or SiHA thin coatings on Ti substrates by magnetron co-sputtering technique renders the surface more hydrophilic, with water contact angles between 30 and 40°. HOB cells attached, spread and proliferated well on these coatings. Enhanced calcification (formation of calcium phosphate nodules across the collagenous matrices) was observed on SiHA coatings with increasing Si content. This interdisciplinary paper highlighted that enhanced bioactivity was associated with surface wettability. Producing a nanostructured HA coating on a Ti substrate by magnetron sputtering resulted in the promotion of cell proliferation and calcification, and the latter was further enhanced with Si substitution. Hence, SiHA thin coating holds great potential as an alternative dental material.

Nucleation of calcium hydroxyapatite thin films from simulated body fluid

Calcium hydroxyapatite (CHA) formation was produced by biomimetic deposition on the surfaces of silica layers of the steel bands, using slightly modified simulated body fluid (SBF). The used SBF had a pH value of 7·4 and a similar ionic composition like human plasma. Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) method was used to analyse obtained phases on the surfaces of silica films after various times of sample soaking in SBF. Atomic force microscopy (AFM) investigations pointed out the mechanism of CHA nucleation. Mass changes investigations of the CHA thin films showed that the depth of CHA films was dependent on the aging time of silica substrate in SBF.

Studies of bacterial adhesion on TiN, SiO 2–TiO 2 and hydroxyapatite thin layers deposited on titanium and Ti6Al4V alloy for medical applications

The Staphylococcus epidermidis biofilm formation on titanium or titanium alloy, coated with TiN, SiO 2–TiO 2 and electrodeposited hydroxyapatite, was tested. Surfaces of titanium, Ti6Al4V alloy or TiN, modified with SiO 2–TiO 2 layer, were found to be highly resistant to bacterial adhesion. Only small amounts of bacterial cells were observed on matrices coated by thin hydroxyapatite films, deposited on both SiO 2–TiO 2 and TiN + SiO 2–TiO 2 interlayers. Biological tests showed that the biofilm formed massively on polished and ground titanium and titanium alloy surfaces, also those covered with TiN, but not on those modified with SiO 2–TiO 2 nanofilm.

The biocompatibility of HA thin films deposition on anodized titanium alloys

A thin hydroxyapatite (HA) film was deposited on anodized titanium for the biocompatibility by RF sputtering method. The anodized titanium has improved its bioactivity further by the HA deposition on the anodized titanium surface. TiO 2 layer with 0.2 ~ 0.5 μm diameter pore size was formed on the Ti surface by anodization. HA film deposited surface showed that the pore size and number decreased compared with non-HA deposited surface. The corrosion resistance of HA deposited/anodized Ti was higher than that of the non-treatment Ti alloy in Hank's solution, indicating better protective effect. From the results of cell culture using MTT assays, the best cell proliferation showed in HA deposited surface after anodization of Ti surfaces compared with another surface treatment.

Crystallisation kinetics of hydroxyapatite thin films prepared by sol-gel process

In this study, the crystallisation of nano hydroxyapatite (HA) films on stainless steel 316L was studied. The film was prepared by sol-gel technique. The process was started with preparation of an HA sol. After aging of the sol at room temperature, a stainless steel 316L substrate was dip coated and then was heat treated from 350 to 450°C at different periods of time in air. The crystallisation behaviour and the transformation-temperature-time diagram of HA films were achieved and analysed using the avrami equation. The results showed that the crystallisation of HA began at 250°C and was increased up to 450°C. The obtained HA film showed a nanostructure character with a suitable crystalinity after heat treatment.

Improved biocompatibility of hydroxyapatite thin film prepared by aerosol deposition

Technical development for an efficient coating of bioactive materials improves the characteristics of a fully functional implant. The aim of this study was to investigate the osteoinductive effect of a newly developed hydroxyapatite (HA)-coating technique using aerosol deposition without post-heat treatment [room temperature (RT) group] on the titanium (Ti) dental implant in vitro and in vivo, compared with that of HA coating with post-heat treatment (HT-400 group) or machined surface (control group). Cell proliferation or attachment on the HA-coated Ti surface was assessed using tetrazolium salt, WST-8 or scanning electron microscopy (SEM). Human osteoblasts (HOB) on RT group were well attached and grew alike in the control or HT-400 group. The alkaline phosphatase activity of HOB cultured on RT and HT-400 group was significantly higher than the control group (p < 0.05). Evaluation by SEM, TEM, and XRD demonstrated that aerosol deposition facilitated HA particles to form a dense and uniform HA layer in the RT group despite no post-heating. In a rabbit tibia model (n = 3), the ratios of bone implant contact and bone area in the RT group (49.88%, 86.05%) were greater than in the HT-400 group (38.82%, 77.34%) or the control (28.31%, 73.86%). The finding of this study showed that the HA coating using aerosol deposition without post-heat treatment has a good biocompatibility, and provide a promoting strategy to enhance osseointegration in the application of the dental implant.

Formation of Hydroxyapatite on Titanium Oxides in Simulated Body Fluid under UV Irradiation

Hydroxyapatite (HAp), Ca10(PO4)6(OH)2, is known to precipitate on bioactive materials by soaking in simulated body fluid (SBF). The formation of HAp on TiO2 and CaTiO3 surfaces under continuous ultraviolet (UV) irradiation was investigated in this study. Pure Ti substrates were chemically treated with H2O2/ HNO3 solution at 353 K for 20 min to form a TiO2 gel layer. The samples were then hydrothermally treated with an aqueous NH3 or an aqueous Ca(OH)2 solution in an autoclave at 453 K for 12 h. An adhesive and sufficiently crystallized anatase-type TiO2 film or perovskite-type CaTiO3 film could be synthesized on the Ti surface, respectively. The samples were immersed in SBF in darkness or under UV irradiation. The UV irradiation promoted the formation of HAp, which may be due to the generation of functional Ti-OH or Ti-O groups on both surfaces. On the other hand, the UV light also produces electron-hole pairs in the product films. In TiO2, much photogenerated holes migrated to the surface and repelled the Ca2+ ions in the solution. As a consequence, the UV irradiation suppressed the formation of HAp thin film on the surface of TiO2.

In vitro dissolution and mechanical behavior of c-axis preferentially oriented hydroxyapatite thin films fabricated by pulsed laser deposition

Owing to its resemblance to the major inorganic constituent of bone and tooth, hydroxyapatite is recognized as one of the most biocompatible materials and is widely used in systems for bone replacement and regeneration. In this study the pulsed laser deposition technique was chosen to produce hydroxyapatite with different crystallographic orientations in order to investigate some of the material properties, including its in vitro dissolution behavior, as well as mechanical properties. The crystallographic orientations of hydroxyapatite coatings can be carefully controlled, mainly by varying the energy density of the KrF excimer laser (248 nm) used for deposition. Nanoindentation results showed that highly c-axis oriented hydroxyapatite coatings have higher hardness and Young's modulus values compared with the values of randomly oriented coatings. After 24h immersion in simulated physiological solution the overall surface morphology of the highly oriented coatings was dramatically altered. The porosity was drastically increased and sub-micron pores were formed throughout the coatings, whereas the average size of the grains in the coatings was not significantly changed. The composition of the textured hydroxyapatite coatings remained essentially unchanged. Their c-axis texture, on the other hand, was rather enhanced with an increase in immersion time. The c-axis oriented hydroxyapatite surfaces are likely to promote preferentially oriented growth through a cyclic process of dissolution and reprecipitation, followed by homoepitaxial growth. The remarkable morphological and microstructural changes after dissolution suggest a capability of highly textured hydroxyapatite as a tissue engineering scaffold with an interconnecting porous network that may be beneficial for cellular activity.

Hydroxyapatite thin films synthesized by pulsed laser deposition and magnetron sputtering on PMMA substrates for medical applications

Functionalized implants represent an advanced approaching in implantology, aiming to improve the biointegration and the long-term success of surgical procedures. We report on the synthesis of hydroxyapatite (HA) thin films on polymethylmetacrylate (PMMA) substrates – used as cranio-spinal implant-type structures – by two alternative methods: pulsed laser deposition (PLD) and radio-frequency magnetron sputtering (MS). The deposition parameters were optimized in order to avoid the substrate overheating. Stoichiometric HA structures were obtained by PLD with incident laser fluences of 1.4–2.75 J/cm 2 , pressures of 30–46.66 Pa and 10 Hz pulses repetition rate. The MS depositions were performed at constant pressure of 0.3 Pa in inert and reactive atmospheres. SEM-EDS, XRD, FTIR and pull-out measurements were performed assessing the apatitic-type structure of the prepared films along with their satisfactory mechanical adhesion. Cell viability, proliferation and adhesion tests in osteosarcoma SaOs2 cell cultures were performed to validate the bioactive behaviour of the structures and to select the most favourable deposition regimes. For PLD, this requires a low fluence of 1.4 J/cm 2 , reduced pressure of water vapours and a 100 °C/4 h thermal treatment. For MS, the best results were obtained for 80% Ar + 20% O 2 reactive atmosphere at low RF power (∼75 W). Cells grown on these coatings exhibit behaviour similar to those grown on the standard borosilicate glass control: increased viability, good proliferation, and optimal cell adhesion. In vitro tests proved that HA/PMMA neurosurgical structures prepared by PLD and MS are compatible for the interaction with human bone cells.

Synthesis and Characterizations of Strontium Substituted Hydroxyapatite Thin Films

Strontium substituted hydroxyapatite(SrHAp) were fabricated both in the form of powder as reference and thin film by using inorganic precursor reaction. The sol-gel process has been used for the deposition of SrHAp layer on stainless steal 316L substrate by spin coating technique, after that the films were annealed in air at various temperatures. The chemical composition of SrHAp is represented (SrxCa1-x)5(PO4)3OH, where x is equal to 0, 0.5 and 1.0. Investigations of the phase structure of SrHAp were carried out by using X-ray diffraction technique (XRD). The results showed that strontium is incorporated into hydroxyapatite where its substitution for calcium increases in the lattice parameters, and Sr3(PO4)2 can be detected at 900°C. The SEM micrographs showed that SrHAp films exhibited porous structure before develop to a cross-linking structure.

Oriented hydroxyapatite single crystals produced by the electrodeposition method

We propose here the use of cathodic electrodeposition as tool to fabricate implant coatings consisting in nano/micro single crystals of hydroxyapatite (HA), preferentially orientated along the c-axis. Coating characterization is the base of this work, where we discuss the mechanisms related to the deposition of oriented hydroxyapatite thin films. It is shown that when deposited on titanium alloys, the HA coating is constituted by two distinct regions with different morphologies: at a distance of few microns from the substrate, large HA single crystals are oriented along the c-axis and appear to grow up from a base material, consisting in an amorphous HA. This organized system has a great importance for cell investigation once the variables involved in the cell/surface interaction are reduced. The use of such systems could give a new insight on the effect of particular HA orientation on the osteoblast cells.

Polycrystalline coating of hydroxyapatite on TiAl6V4 implant material grown at lower substrate temperatures by hydrothermal annealing after pulsed laser deposition

Hydroxyapatite (HA) 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. Pulsed laser deposition (PLD) of thin films of HA on TiAl6V4 have shown crystalline coatings to be obtained at temperatures of the order of 350-500 degrees C. This condition of high substrate temperature promoted the oxidation of the substrate surface prior to the growth of the HA layer and the oxidation layer degraded the adhesion of the coating to the substrate. In this study, thin films of HA were deposited on TiAl6V4 alloy at a lower temperature of 200 degrees C by PLD and crystallized by a hydrothermal treatment at 100 degrees C. The film was subjected to mechanical as well as cell viability tests in vitro. The thickness, roughness, crystallanity, composition ratio, adhesive strength, and cell adhesion of the film suggest the application of this technique for producing bioactive implants.

Biofunctional alendronate–Hydroxyapatite thin films deposited by Matrix Assisted Pulsed Laser Evaporation

We applied Matrix Assisted Pulsed Laser Evaporation (MAPLE) in order to synthesize alendronate-hydroxyapatite thin films on titanium substrates. Alendronate-hydroxyapatite composite nanocrystals with increasing bisphosphonate content (0, 3.9, 7.1% wt) were synthesized in aqueous medium. Then, they were suspended in deionised water, frozen at liquid nitrogen temperature and used as targets for MAPLE experiments. The depositions were conducted with a KrF* excimer laser source (l = 248 nm, t FWHM = 25 ns) in mild conditions of temperature and pressure. The obtained thin films had a good crystallinity, which slightly decreases with the increase of alendronate content, and exhibited a porous-like structure. Osteoblast-like MG63 cells and human osteoclasts were cultured on the thin films up to 14 days. In the presence of alendronate, MG63 cells displayed a normal morphology, increased proliferation and higher values of differentiation parameters, namely type I collagen, osteocalcin, and osteoprotegerin/TNF-related activation-induced cytokine receptor ratio. In contrast, osteoclasts showed significantly reduced proliferation, and increased level of Caspase 3. Moreover, the coatings synthesized from hydroxyapatite at relatively high bisphosphonate content (7.1% wt) displayed a reduced production of Tumour Necrosis Factor alpha (TNF- α) and Interleukin 6 (IL-6), suggesting a down-regulatory role of alendronate on the inflammatory reaction. The successful deposition of alendronate modified hydroxyapatite thin films yields coatings with enhanced bioactivity, able to promote osteoblast differentiation and to inhibit osteoclast proliferation.

Microstructural Study of Mn and Si Co‐substituted Hydroxyapatite Thin Films Produced by a Sol–Gel Method

Microstructural changes in sol-gel derived hydroxyapatite thin films associated with Mn and Si co-substitution are investigated. The apatite-forming ability of fabricated thin films in simulated body fluid are found to be affected by changes in the crystallinity and formation of a more dissolvable calcium phosphate phase.

Effects of Mg doping on sol–gel derived nanocrystalline hydroxyapatite thin films

Both pure and Mg doped thin films were fabricated by sol–gel dip coating. The films were sintered either at 800 or 1000°C. The average grain size of the films was significantly affected by Mg substitution in the hydroxyapatite (HA) structure and change in the sintering temperature. The grains were considerably larger in the films sintered at higher temperatures. In addition, Mg doped films contained significantly larger grains compared to undoped HA films. Mg doping also caused rodlike grains at 800°C, and led to whitlockite (β-TCP) formation at 1000°C. The ratio of the existing phases was estimated as β-TCP/HA=27 : 73. All the films had rough surfaces with high porosity. It was also observed that undoped films had higher surface roughness than Mg doped ones.