Effects of solution composition and electrophoretic deposition voltage on various properties of nanohydroxyapatite coatings on the Ti13Zr13Nb alloy

The purpose of the research was to establish the influence of the solution composition and the electrophoretic deposition voltage on the coating homogeneity and thickness, nanohardness, adhesion, corrosion resistance and wettability. The Ti13Zr13Nb alloy was coated by the electrophoretic technique with hydroxyapatite in a solution containing 0.1, 0.2 or 0.5?g nanoHAp in 100?mL of suspension and at voltage 15, 30 or 50?V. The scanning electron and atomic force microscopies, polarization curves technique for corrosion assessment, nanoindentation and nanoscratch tests, and measurements of contact angle in simulated body fluid were performed. The obtained results revealed the complex and interrelated effects of both process determinants on the structure and properties of hydroxyapatite coatings, which were attributed to the role of the size, shape and content in suspension of hydroxyapatite particles.     

Effects of electrophoretic deposition times and nanotubular oxide surfaces on properties of the nanohydroxyapatite/nanocopper coating on the Ti13Zr13Nb alloy

Load-bearing implants are developed with a particular emphasis placed on an application of ceramic hydroxyapatite coatings in order, to enhance the bioactivity of titanium implants and to shorten the healing time. Therefore, thin, fully crystalline coatings that are, highly adhesive, hydrophilic and demonstrating antibacterial properties are ly looked for. The aim of this research was to develop and characterize the properties of (nano)hydroxyapatite coatings implemented with nanocopper particles and obtained by the electrophoretic method. The deposition was carried out on the Ti13Zr13Nb alloy, either on a bare surface or a nanotubular oxide layer. The deposition was made for 1 or 2 min. The chemical composition, phase composition, coating structure, homogeneity, thickness, nanoindentation and nanomechanical properties, adhesion determined by a nanoscratch test, and wettability measured by a contact angle were investigated. The presence of nanotubular oxide layers caused no significant change in nanoindentation and nanomechanical propertie and an increase in adhesion strength and a decrease in the contact angle. The increase in deposition time resulted in an increased thickness, a decreased hardness, an increased adhesion strength and wettabilty. The observed effects in the composite (nano)HAp/Cu – (nano)TiO₂ coatings are attributed to the change in the structure of coatings following the increasing deposition time and coating thickness.     

Marine biological waste as a source of hydroxyapatite for bone tissue engineering applications

The demand for bone graft substitutes for orthopedics and dentistry is constantly growing due to the increase of ageing-related diseases. Synthetic hydroxyapatite (HA) is largely used as a bone graft material thanks to its biocompatibility, osteointegration, osteoconductive and osteoinductive properties and similarity to biological apatite, the main mineral component of bones and teeth. Biogenic apatite has gained attention due to its peculiar intrinsic characteristics: multi-doped ion composition and micro- and nano-scale architecture make natural-derived HA particularly promising for biomedical applications.At the same time, the growing interest in green materials is pushing towards the use of more sustainable biomaterials precursors, including re-use materials: marine waste, such as mollusk-shells, shellfish carapaces, cuttlefish bone, and fishbone have become widely studied sources of biogenic HA. Indeed, they are rich in calcium carbonate (CaCO₃), which can be converted into HA by environmentally sustainable processes. This allows the transformation of waste into valuable materials, while paying attention to the issues of sustainability and circular economy.In this review, we listed and discussed the methods to produce HA starting from shell-derived CaCO₃, describing all the steps and synthesis routes proposed for the conversion procedure, with a special focus on the different species of marine shells used. We discussed the use of HA alone or in combination with other materials (natural and synthetic polymers), used to enhance the mechanical and biological properties.We summarized the types of devices obtained by marine-derived HA, including nanorods, particulates and scaffolds and we described their in vitro and in vivo behavior.The up-to-date literature was summarized in tables with a special focus on the in vitro and in vivo biological evaluation of such materials.In conclusion, composite biomaterials based on marine-derived biogenic HA are reported as potential candidates for synthetic bone substitutes highlighting their potential, limitations and future perspectives.     

Tribological behaviour of RF-magnetron sputter deposited hydroxyapatite coatings in physiological solution

The aim of the paper is to explore the tribological performance of hydroxyapatite (HA) coatings deposited by radio frequency (RF) magnetron sputtering on AZ31 magnesium alloy (96% Mg, 3% Al, 0.7% Zn, 0.3% Mn) for biomedical applications. In this study, the position of the samples on a substrate holder, relative to a target erosion zone was taken into consideration in order to elucidate its impact on the coating characteristics, such as composition, morphology, surface topography and tribology. Substrate rotation and arc-movement were foreseen in the experimental set-up to increase the uniformity of thin film properties. The deposited HA thin films were revealed to exhibit an increase of the Ca/P ratio from 1.83 to 1.97, a decrease of (002) texture and thickness, as the samples were shifted towards the target erosion zone. By coatings, the roughness of Mg alloy was decreased (R_{a Mg alloy}=31.3 nm; R_{a coating}=29 nm and 21 nm). The coating placed in the centre of the substrate holder showed high hardness and Young's modulus (H =8.3±0.9 GPa; E=89±10 GPa) than the coating prepared under the target erosion zone (H =6.9±1.1 GPa; E=75±6 GPa). The coating deposited under target erosion zone exhibits superior friction behaviour in simulated body fluid environment, with the friction coefficient (μ) of 0.184, while the sample located in the centre of the substrate holder possesses the friction coefficient (0.306) comparable to the AZ31 substrate (0.307). The low wear rate was determined in the case of coating deposited under target erosion zone (4.83×10⁻⁵ mm³ N⁻¹ m⁻¹) than uncoated AZ31 substrate (0.00518 mm³ N⁻¹ m⁻¹) or than coating placed in the centre of the substrate holder (0.00294 mm³ N⁻¹ m⁻¹).     

Comparative study of the hydroxyapatite coatings prepared with/without substrate bias

The aim of this paper is to prepare the hydroxyapatite by Ion Beam Assisted Deposition and to investigate in terms of its elemental and phase composition, roughness and in vitro corrosion resistance. The coatings were prepared with and without applying bias on substrate, in order to find the effect of bias on the chemical, structural, morphological and anti-corrosive properties. The biased coatings exhibited Ca/P ratio closer to the value of the stoichiometric HAP (1.67). The phase composition is not affected by the bias evolution. The adhesion of both coatings is still satisfactory for biomedical applications, irrespective of the bias. Hydroxyapatite deposited without bias presented the best corrosion resistance in SBF at 37 °C, probably due to its smooth surface and low porosity. Moreover, this coating proved to have the highest protection ability at the SBF corrosive attack.     

Fabrication,characterization and cellular biocompatibility of porous biphasic calcium phosphate bioceramic scaffolds with different pore sizes

Facile wet-chemical methods are applied to synthesize hydroxyapatite and β-tricalcium phosphate nanoparticles, respectively. Porous biphasic calcium phosphate (BCP) bioceramic scaffolds are then fabricated using as-prepared HA and β-tricalcium phosphate nanoparticle powders. The macro pore diameter of BCP bioceramic scaffolds can be controlled by adjusting the amount of surfactants. The average diameter of the macro pores in BCP bioceramic scaffolds increases from 100 to 600 µm with the decrease amount of sodium dodecyl sulfate from 0.8 to 0.5 g, respectively. The BCP bioceramic scaffolds gradually degrade and the calcium-phosphate compounds fully deposit when soaking in simulated body fluid solution. Moreover, The BCP bioceramic scaffolds have outstanding biocompatibility to promote the cellular growth and proliferation of human dental pulp stem cells (hDPSCs). The hDPSCs also demonstrate favorable cellular adhering capacity on the pore surface of scaffolds, especially on the scaffolds with 100–200 µm pore diameter. The porous BCP bioceramic scaffold with inter-connected pore structure, outstanding in vitro cellular biocompatibility, favorable cell viability and adhesion ability will be a promising biomaterial for bone or dentin tissue regeneration.     

Structure of the hydroxyapatite plasma-sprayed coatings deposited on pre-heated titanium substrates

Plasma spraying is the most commonly used thermal spray method for the application of hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) coatings. In the present study, the HA coatings were plasma spraying deposited onto plates of titanium pre-heated to 20 °C, 300 °C and 550 °C. The obtained HA coatings were investigated by means of X-ray diffraction and scanning electron microscopy. It is found that the coatings, in addition to HA, contain the tetracalcium phosphate (TTCP, (Ca₄(PO₄)₂O) phase (~10%) and a small amount of CaO (<2%). Crystal structure of HA in the coatings is revealed to be distorted. The PO4 tetrahedrons are deformed (Baur distortion coefficient D1(TO) ~0.2). The distances Ca1-O1 and Ca1-O2 are changed as compared to these in stoichiometric hydroxyapatite. These distortions are considered as a result of internal stresses, which are demonstrated in the broadening of peaks on X-ray diffraction pattern of HA. Microstructure of coatings consisting of flattened splats was formed by fully molten particles. The axial base texture was developed in the coatings. Ultrastructure is columnar with a preferred orientation of c-axes of the crystals parallel to the normal of plane coating n. The heating of substrate has a marked effect on the ultrastructure of coatings: the domain size increases from 790 to 1100 Å, the strain Δ decreases from 1.6·10^-3 to 1,2·10^–3, TTCP content diminishes from 12% to 7%. These results show that the effects due to heating of the substrate may be associated with partial recovery of HA microstructure.     

Studies on novel bioactive glasses and bioactive glass-nano-HAp composites suitable for coating on metallic implants

A series of novel zinc oxide (ZnO) containing bioactive glass compositions in SiO₂-Na₂O-CaO-P₂O₅ system and composite with hydroxyapatite (HAp) nano-particles were developed and applied as coating on Ti-6Al-4V substrates. The bioactive glasses and their composites were also processed to yield dense scaffolds, porous scaffolds and porous bone filler materials. The coating materials and the coatings were characterized and evaluated by different in vitro techniques to establish their superior mechanical properties. The cytotoxicity test of the coating material, porous and dense scaffolds and coated specimens showed non-cytotoxicity, biocompatibility and promising in vitro bioactivity for all tested samples. The dissolution behaviour studies of the bioactive glasses and the composites in simulated body fluid showed promising in vitro release pattern and bioactivity for all tested samples. Addition of nanosized HAp improves mechanical properties of the bioactive glass coating without affecting the in vitro bioactivity.     

Polymer nanocomposites for bone tissue substitutes

Following the quest for new composite biomaterials for bone tissue engineering, this work presents the processing of new nanocomposite made of polycaprolactone matrix and wollastonite particles. Wollastonite nanopowder was obtained by thermal treatment of polymethyloxosilane resin mixed with silica and calcium hydroxide. Bioactive character of the ceramic nanopowder was verified in simulated body fluid (SBF). The apatite formation on wollastonite grain surface after immersion in SBF was observed. Basic mechanical properties of the samples containing various amount of ceramic nanoparticles have been examined. It was shown that the presence of small amount of wollastonite nanoparticles (0.5–1.0 wt%) improves significantly the Young's modulus, tensile strength, and work-of-fracture of polymer matrix composite. Increased content of ceramic nanoadditive (>2%) in nanocomposites resulted in degradation of their mechanical characteristics.     

Porous wollastonite-hydroxyapatite bioceramics from a preceramic polymer and micro- or nano-sized fillers

Wollastonite-hydroxyapatite ceramics have been successfully prepared by a novel method, corresponding to the thermal treatment in air of a silicone embedding micro- and nano-sized fillers. CaCO₃ nano-sized particles, providing CaO upon decomposition, acted as “active” filler, whereas different commercially available or synthesised hydroxyapatite particles were used as “passive” filler. The homogeneous distribution of CaO, at a quasi-molecular level, favoured the reaction with silica derived from the polymer, at only 900 °C, preventing extensive decomposition of hydroxyapatite. Open-celled porous ceramics suitable for scaffolds for bone-tissue engineering applications were easily prepared from filler-containing silicone resin mixed with sacrificial PMMA microbeads as templates. The pore size (in the range of 80-400 μm) and the open porosity percentage (40-50%) were evaluated by means of micro-computerized tomographic analysis. A preliminary assessment of the biocompatibility and cell activity of the produced ceramics was performed successfully by in vitro tests using human osteoblast cells.     

Comparative investigation of antibacterial yet biocompatible Ag-doped multicomponent coatings obtained by pulsed electrospark deposition and its combination with ion implantation

The aim of this work is to obtain antibacterial yet biocompatible coatings using pulsed electrospark deposition (PED). For this purpose new composite electrodes were fabricated from reaction mixtures Ti–C–20%Fe-10%Ca₃(PO₄)₂–3.4%Mg–X%Ag with different amount of antibacterial component (X = 0, 0.5, 1.0, 1.5 and 2.0 at% of Ag) using self-propagating high-temperature synthesis method. The electrodes consisted of TiC grains surrounded by TiFe₂ and TiFeP intermetallic matrix, CaO and MgO inclusions, and Ag-based phase. The influence of Ag content on the electrode mass transfer kinetics was studied by comparing the total substrate weight gain and electrode mass loss during PED. The structure, elemental composition, and surface roughness of coatings were studied by means of X-ray diffraction, scanning electron microscopy, and optical profilometry. The coatings were characterized in terms of Ag⁺ ion release, mechanical and electrochemical properties, as well as biocompatibility. The antibacterial characteristics of Ag-doped PED coatings were compared with those obtained by PED using Ag-free electrode and then implanted with Ag⁺ ions. The results indicated that an increase in the Ag content in electrode leads to a decrease in electrode erosion and substrate weight gain, but the efficiency of the PED process increases. Doping with a small amount of Ag (≤ 1 at%) resulted in 100% antibacterial effect against both gram-positive S. aureus and gram-negative E. сoli bacteria. In addition, the dynamics of МС3Т3-Е1 cell proliferation on the surface of PED coatings with 0.6–0.7 at% of Ag was similar to that in control samples, hereby indicating their biocompatibility. The coating biological characteristics were discussed based on the results of Ag⁺ ion release and electrochemical tests.     

Room temperature synthesis of chitosan/apatite powders and coatings

Bioactive chitosan/apatite powders and adherent coatings have been synthesized by a co-precipitation method and an alkaline transformation at room temperature. Powders with organic/inorganic ratios ranging from 42 to almost 90% can be prepared in substantial amounts. This method allows to coat Ti6Al4V substrates yielding films with thicknesses of approximately 1 μm that show an adhesion strength superior to 15 MPa. The coating procedure can be repeated to increase the thickness of the layer. The formation of apatite onto these materials after immersion in a simulated body fluid (SBF) indicates a potential bioactivity in vivo. The materials have been characterized by viscosimetry, XRD, FTIR, SEM, EDS and TG/ATD. The adhesion strength was determined by a pull-out test.     

Studies on plasma sprayed bi-layered ceramic coating on bio-medical Ti-13Nb-13Zr alloy

Biomedical Ti alloys are prone to undergo degradation due to the combined effect of wear and corrosion. To overcome these problems, surface modification techniques are being used. In this paper, the biomedical Ti alloy Ti-13Nb-13Zr was plasma sprayed with nanostructured Al₂O₃-13 wt%TiO₂, yttria stabilized zirconia powders and bilayer containing alternate layers of the two coatings to improve the corrosion resistance and microhardness of the substrate. The plasma sprayed coatings were characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The microstructure, microhardness and surface roughness of the coatings were investigated. The corrosion resistance of the coatings was studied in simulated body conditions. The results show improved corrosion resistance for the bilayered coating compared to the individual plasma sprayed coatings on biomedical Ti-13Nb-13Zr alloy substrate.     

Fabrication of corrosion resistant, bioactive and antibacterial silver substituted hydroxyapatite/titania composite coating on Cp Ti

The present work is aimed at developing a bioactive, corrosion resistant and anti bacterial nanostructured silver substituted hydroxyapatite/titania (AgHA/TiO₂) composite coating in a single step on commercially pure titanium (Cp Ti) by plasma electrolytic processing (PEP) technique. For this purpose 2.5 wt% silver substituted hydroxyapatite (AgHA) nanoparticles were prepared by microwave processing technique and were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM) methods. The as-synthesized AgHA particles with particle length ranging from 60 to 70 nm and width ranging from 15 to 20 nm were used for the subsequent development of coating on Cp Ti. The PEP treated Cp Ti showed both titania and AgHA in its coating and exhibited an improved corrosion resistance in 7.4 pH simulated body fluid (SBF) and 4.5 pH osteoclast bioresorbable conditions compared to untreated Cp Ti. The in vitro bioactivity test conducted under Kokubo SBF conditions indicated an enhanced apatite forming ability of PEP treated Cp Ti surface compared to that of the untreated Cp Ti. The Kirby-Bauer disc diffusion method or antibiotic sensitivity test conducted with the test organisms of Escherichia coli (E. coli) for 24 h showed a significant zone of inhibition for PEP treated Cp Ti compared to untreated Cp Ti.     

Influence of concentration of hydroxyapatite surface modifier agent on bioactive composite characteristics

The characterization of chitosan – hydroxyapatite (CH – HAp) composite sponges prepared via freeze-drying methodology is reported in this study. Stearic acid (SA), added as a surface modifier of the HAp nanoparticles, induced changes in the TG/DTG results, particle size distribution and particle morphology. Composite sponges prepared with SA coated HAp demonstrated enhanced biocompatibility and structural properties, as compared to the composites prepared with uncoated HAp. SA coating modified the morphology of the composite, promoting a better dispersion of HAp particles within the composite sponges, and better homogeneity of the polymeric cover with HAp particles. The viability of the composites for cell culture applications was analyzed, and the results suggest that the sponges are biocompatible. Therefore, SA proved to be a good candidate for surface coating of HAp nanoparticles prevent agglomerations, and could be used effectively in the preparation of biocompatible composite sponges with chitosan.     

Influence of gelatin coatings on compressive strength of porous hydroxyapatite ceramics

Porous ceramics prepared by the foam replication technique have a high porosity and low mechanical stability. It has been reported that coating such porous ceramics with gelatin allows for an improved compressive strength. Little details regarding the influence of important gelatin parameters such as concentration, temperature and drying conditions as well as bloom number which is a measure of the gel rigidity, on this toughening effect are available. This paper investigates the influence of these parameters on compressive strength of gelatin coated porous hydroxyapatite ceramics. It was found that concentration in the gelatin sols has a marked impact whereas sol temperature, bloom number and differing conditions during subsequent drying have only little influence on the compressive strength of the coated ceramics.     

Highly loaded hydroxyapatite microsphere/ PLA porous scaffolds obtained by fused deposition modelling

The goal of the work was the manufacturing of hydroxyapatite microsphere/polylactic acid (PLA) scaffolds by means of fused deposition modelling (FDM). Micrometer-sized hydroxyapatite spheres synthesized by spray drying (sdHA), were dispersed in PLA by extrusion compounding. Composite filaments were obtained from extrusion which were used in FDM 3D printing for the production of macroporous scaffolds. The sdHA microspheres were used in the composite in order to improve the biomimicry and the bioactivity of the 3D printed scaffold to increase the bone regeneration capacity. Morphological, thermal, physical and mechanical characterizations were performed on the 3D printed composites. Pure PLA scaffolds were 3D printed and used as a reference.Thermal analyses, TGA and DSC evidenced that the glass transition temperature and the degree of crystallinity of PLA were not influenced by the presence of sdHA. Morphological analysis showed a smooth surface of the printed samples when pure PLA was used. A rough surface was found on the PLA/sdHA composites, confirming, the homogeneous dispersion of the ceramic phase in the polymeric matrix. The higher porosity of the composite samples compared to PLA ones, most likely caused a decrease of the mechanical performances of the PLA/sdHA scaffolds. Composite scaffolds displayed stiffness values compatible with that of bone tissue.     

Sodium dodecyl sulfate mediated microwave synthesis of biocompatible superparamagnetic mesoporous hydroxyapatite nanoparticles using black Chlamys varia seashell as a calcium source for biomedical applications

Designing biocompatible superparamagnetic mesoporous nanoparticles for advanced healthcare applications has received much attention. In this research, we have synthesized intrinsic mesoporous superparamagnetic hydroxyapatite (HAp) nanoparticles using bio-waste of black Chlamys varia seashell as a calcium source by sodium dodecyl sulfate (SDS)–enabled microwave-assisted synthesis approach. The synthesized Fe-doped HAp nanoparticles were characterized using various characterization techniques to know the phase purity and morphological features. The incorporation of Fe greatly affected the morphology of HAp nanoparticles without affecting their crystalline phase. Superparamagnetic behavior was observed with the incorporation of Fe in the HAp nanoparticles. Further, saturation magnetization was enhanced with higher incorporation of Fe ions. The cytotoxicity studies of the synthesized pure and Fe-doped HAp samples conducted using a human osteoblasts cell line (MG63), which indicated that Fe-doped HAp nanoparticles are biocompatible. Further, antibacterial activity analysis also confirmed their excellent antibacterial performance against different pathogens. Hence, SDS-enabled microwave-assisted synthesis approach using seashell as a calcium source would be a better approach for the production of intrinsic mesoporous superparamagnetic HAp nanoparticles for various biomedical applications, such as drug targeting, hyperthermia cancer therapy, and magnetic resonance imaging.     

Size and morphology-controlled synthesis of mesoporous hydroxyapatite nanocrystals by microwave-assisted hydrothermal method

We report the rapid microwave-assisted hydrothermal synthesis of mesoporous hydroxyapatite (HAp) nanocrystals with controlled size, morphology, and surface area using various organic modifiers as regulators. The products were analyzed for their crystalline nature, phase purity, morphology, particle size and pore size distribution. Results indicated that ascorbic acid, cetyltrimethyl ammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) play an important role to obtain needle like, rod like and fiber like mesoporous HAp nanocrystals with different specific surface area by controlling growth habit of HAp along c-axis. In addition, the prepared samples were B-type carbonated HAp similar to bone minerals. Therefore, the present approach can be a promising way to obtain precursor for making tissue engineering scaffolds, drug/protein delivery carriers and bone fillers with tunable characteristics.