Morphology control and phase transition of hexagonal sodium niobate particles

Hexagonal NaNbO₃ particles with an ilmenite structure and plate-like morphology were synthesized by a hydrothermal method. The morphological evolution of the solid products with the increasing mineralizer concentration was monitored via SEM during the hydrothermal reaction. By carefully controlling the mineralizer concentration, particles with a diameter of 10–60 µm and a thickness of 1–10 µm were obtained. The particles were transformed from the ilmenite structure into the perovskite structure during the thermal treatment at 600 °C. Their plate-like morphology was maintained with some cracking on the surface. The surface orientation of the perovskite particles was micro- and macroscopically characterized by EBSD and XRD analysis, respectively. The results indicate that thinner particles tend to be more oriented in the (00 l) crystal planes.     

Microwave sintering of fine grained HAP and HAP/TCP bioceramics

The effect of microwave sintering conditions on the microstructure, phase composition and mechanical properties of materials based on hydroxyapatite (HAP) and tricalcium phosphate (TCP) was investigated. Fine grained monophase HAP and biphasic HAP/TCP biomaterials were processed starting from stoichiometric and calcium deficient nanosized HAP powders. The HAP samples microwave (MW) sintered for 15 min at 900 °C, with average grain size of 130 nm, showed better densification, higher density and certainly higher hardness and fracture toughness than samples conventionally sintered for 2 h at the same temperature. By comparing MW sintered HAP and HAP/TCP samples, it was concluded that pure HAP ceramics have superior mechanical properties. For monophase MW sintered HAP samples, the decrease in the grain size from 1.59 μm to 130 nm led to an increase in the fracture toughness from 0.85 MPa m^1/2 to 1.3 MPa m^1/2.     

Sintering behavior and growth mechanism of β-TCP in nanocrystalline hydroxyapatite synthesized by mechanical alloying

Nanocrystalline carbonated HAp powder has been synthesized successfully within 2 h by mechanical alloying the stoichiometric mixture of CaCO₃, CaHPO₄·2H₂O at room temperature under open air. To observe the sintering behavior of HAp the as-milled sample is sintered at different temperatures. The amorphous HAp phase (~14 vol%) in as-synthesized sample transforms completely to crystalline HAp after sintering at 700 °C and after sintering the sample at 800 °C, the crystalline HAp partially transforms to β-TCP phase. Presence of low content of β-TCP phase in HAp powder could be useful in artificial hard tissue applications. Increase in sintering temperature up to 1000 °C results in enhancement of decomposition rate of HAp into β-TCP phase. Microstructure characterization in terms of lattice imperfections and relative phase abundances in non-sintered and all sintered samples are made both by analyzing the respective XRD patterns using Rietveld's structure refinement method as well as TEM images. The growth mechanism of β-TCP from crystalline HAp phase has been proposed based on structure and microstructure characterizations of sintered samples.     

Hydrothermal synthesis of single-crystal α-tristrontium phosphate particles

Anisotropic ceramic bodies can be fabricated by a reactive template grain growth method; however, template particles with suitable powder properties are required to create the ceramics with well controlled anisotropy. Therefore, we synthesized well-isolated α-tristrontium phosphate (α-TSP) particles with a hexagonal plate-like shape as template particles for anisotropic strontium apatite ceramics using α-strontium hydrogen phosphate (α-SrHPO₄) precursor particles. Three synthetic parameters were varied: (i) precursor particle size, (ii) stirring rate, and (iii) hydrothermal temperature. Well-isolated hexagonal plate-like α-TSP single-crystal particles were successfully synthesized by hydrothermal treatment at 150 °C for 3 h at a stirring rate of 150 rpm using fine α-SrHPO₄ precursor particles. The developed plane of the hexagonal plate-like α-TSP particles was determined to be the {00l} plane, and the side planes were revealed to be not {h00} planes, but inclined {h0l} planes. The resulting α-TSP particles may provide a promising template for the development of anisotropic apatite-based ceramics.     

In situ formation of biphasic calcium phosphates and their biological performance in vivo

The co-precipitation technique has been applied to synthesize biphasic calcium phosphate (BCP). After annealing at 900 °C for 24 h, hydroxyapatite (HAp) and β-tricalcium phosphate (β-TCP) were obtained as a single phase at 1.67 and 1.5 Ca/P ratios, respectively. Between these two extremes, a whole range of BCP preparations could be synthesized by using this technique with an accurate control of starting reactants. The biological performance of BCP granulates with a specific content of 62% HAp and 38% β-TCP was investigated. After immersion in Hanks’ balanced salt solution (HBSS) for 1 week, a precipitation started to be formed with individual small granules on the specimen surface. An MTT assay indicated that BCP granulates have no cytotoxic effects on MG-63 cells, and that they have good biocompatibility. An implantation experiment in mouse skulls revealed that BCP granulate provides a strong positive effect on bone formation in vivo in mice.     

Rapid synthesis of citrate-zinc substituted hydroxyapatite using the ultrasonication-microwave method

Bio-inspired citrate-hydroxyapatite (HAP) nanoparticles doped with zinc ions were prepared from mussel shells via a rapid method of ultrasonication and microwave irradiation. It was found that zinc ions can interact with citrate ions in the crystallization process of HAP. The growth of nanocrystals in citrate solution was slower than that in HCl solution. The addition of zinc ions reduced the residue of citrate in the products and increased the crystallinity of HAP. Furthermore, mineral platelets with the length of 29 ± 7 nm and the thickness of 3–5 nm were obtained for Zn/(Zn+Ca) = 5 mol%, which displayed similar morphology with HAP platelets in bone. Moreover, the obtained HAP nanoparticles are promising for use as bone graft materials in biomedical applications.     

Development of high strength hydroxyapatite by solid-state-sintering process

Hydroxyapatite (HAp) is a potential material for various biomedical applications. In the present study, an attempt has been made to synthesize this material using simpler and cheaper method of solid-state-reaction process. Samples were prepared by mixing the ingredients and then sintering the cold compacted pellets at various temperatures from 500 to 1250 °C. X-ray diffraction, thermo-gravitometric and differential thermal analysis and Fourier transform infrared (FTIR) spectroscopy techniques were used for structural characterization of the samples. It was found that Monetite phase of hydroxyapatite forms in the unsintered powder. Upon heating up to 1250 °C, samples undergo several structural transformations with final structure being α-tri calcium phosphate (TCP) after sintering at 1250 °C. Presence of various chemical groups in the samples was analyzed using Fourier transform infrared spectrometry and the results are in accordance with the literature. Mechanical tests showed that increasing compaction pressure during cold pressing improves mechanical strength of sintered product by reducing overall porosity. Compressive, tensile and bending strength, bulk modulus (in compression), and microhardness values were found to improve after resintering the pellets at 1250 °C, which were previously sintered at the same temperature. It was also found that the mechanical properties of synthesized HAp were better as compared to the natural products. In vitro biological studies in a simulated body fluid showed around 15–20% change in the surface roughness of the samples albeit with negligible weight gain in dry state.     

Reaction sintering of β-tricalcium phosphates and their mechanical properties

Various kinds of calcium oxides, carbonates and phosphates were used as the raw materials, and β-TCP ceramics was fabricated by reaction sintering at 1100 °C, and the sinterability, the reaction sintering behavior and mechanical properties of reaction-sintered β-TCP were investigated. Reaction-sintered bodies using CaHPO₄ + HAp consisted of single β-TCP phase, and bulk density and bending strength increased with extending sintering time. On the contrary, normal-sintered β-TCP synthesized using CaHPO₄ + HAp did not change in bulk density and bending strength with extending sintering time. Reaction-sintered body using CaHPO₄ + HAp as the raw materials showed higher bulk density and bending strength than normal sintered β-TCP.     

Influence of Tiron concentration on dispersability and sintering behaviors of hydroxyapatite in an aqueous system

Rheological and sintering behaviors of hydroxyapatite slurries with different Tiron concentrations were investigated. It was shown that HAp slurries could be stabilized at pH 11 with 2.25 wt% Tiron concentrations. Results confirmed that well dispersed slurries could be obtained with solid content as high as 50 wt%. Zeta potential measurements were conducted on HAp powders evaluated the influence of dispersant on surface charge properties of the particles. X-ray diffraction technique was used to study the crystalline phase evolution; scanning electron microscopy was used to estimate the particle size of the powder and fracture surfaces of bodies sintered at various temperatures. After sintering process at 1200 and 1350 °C, relative density and bending strength of HAp samples reached 76.67% and 92.18% and 57.77 and 97.36 MPa, respectively.     

Type-A zeolites with hydroxyapatite surface layers formed by an ion exchange reaction

To enhance adsorption of harmful ions on type-A zeolites (LTA), hydroxyapatite (HAp) thin layers were synthesized on the LTA surface by an ion exchange reaction of Ca²⁺ for NH₄⁺ under hydrothermal treatment. The temperatures and durations in the reactions were varied ranging from 25 to 200 °C and from 1 to 168 h. The samples synthesized were characterized by X-ray diffraction method (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer–Emmet–Teller method (BET). The structure of LTA was not destroyed by the hydrothermal treatments at 25 to 160 °C for 8 h and also at 120 °C for 1 to 72 h. The yield of HAp grown on the LTA surface, synthesized at 120 °C for 8 h, showed a maximum value of 0.82. The morphologies of HAp were dependent mainly on the temperatures. The specific surface area remained unchanged in the treatments at 25 to 40 °C for 8 h, as compared to the specific surface area of Ca-LTA, however up to 80 °C, the value decreased with an increase of exchange temperature.     

Preparation and properties of bimodal porous apatite ceramics through slip casting using different hydroxyapatite powders

A bimodal porous hydroxyapatite (HAp) body with high flexural strength was prepared through slip casting. The effect of different particle sizes on the flexural strength and microstructure of three different types of hydroxyapatite (HAp) powders was studied. The powder characteristic of laboratory-synthesized HAp powder (L-HAp) was obtained through a wet-milling method, drying and heating of a mixture of calcium hydrogen phosphate di-hydrate and calcium carbonate. The median particle size of L-HAp was 0.34 μm, and the specific surface area was 38.01 m²/g. The commercial HAp had median particle sizes for the K-HAp (Kishida chemical Co. Ltd., K-HAp) and T-HAp (Taihei chemical Co. Ltd., T-HAp) of 1.13 and 3.65 μm, and specific surface areas of 11.62 and 6.23 m²/g, respectively. The different powder characteristics affected the slip characteristics, and the flexural strength and microstructure of the sintered porous HAp bodies were also different. The flexural strengths of the porous HAp ceramics prepared by heating at 1200 °C for 3 h in air were 17.59 MPa for L-HAp with a porosity of 60.48%, 3.92 MPa for commercial K-HAp with a porosity of 79.37%, and 4.55 MPa for commercial T-HAp with a porosity of 76.46%.     

Evaluation of biphasic calcium phosphate/nanosized 3YSZ composites as toughened materials for bone substitution

In this research, biphasic calcium phosphate (BCP), comprising 70 wt% of beta tricalcium phosphate and 30 wt% of hydroxyapatite, was mixed with different amounts of 3 mol% yttria-stabilized zirconia (3YSZ) and sintered at 1200 °C to produce toughened bone substitutes. The fracture toughness (K_Ic) of the obtained bodies was determined using the indentation-strength fracture method. Scanning electron microscopy and energy dispersive X-ray spectroscopy analysis were utilized to study the microstructure of the samples. The phase composition of the samples was also determined using X-ray diffraction technique. In order to investigate the cell supporting ability of the samples, G-292 cells were cultured on them and cell morphology was evaluated after 48 h. Based on the results, the maximum fracture toughness and compressive strength values (i.e., 2.11 MPa m^0.5 and 150 MPa, respectively) were obtained for the sample containing 3 vol% of 3YSZ. The obtained fracture toughness value was approximately two times higher than that of the original BCP (1.07 MPa m^0.5) and also was comparable with that of the cortical human bone. The following mechanisms for the improved K_Ic of the β-tricalcium phosphate were determined: Grain bridging of 3YSZ particles during crack growth resistance, formation of microcracks on the tip of the larger cracks, absorbing crack extension energy due to the volume expansion during 3YSZ tetragonal-monoclinic transformation and crack deflection by the presence of 3YSZ particles. Also, 3YSZ additive encourages transformation of HA phase into β-TCP during sintering BCP. Finally, based on the cell studies, the samples exhibited an adequate cell attachment and a good cell spreading condition.     

Characterization and in vitro-bioactivity of natural hydroxyapatite based bio-glass–ceramics synthesized by thermal plasma processing

Natural bovine hydroxyapatite/SiO₂–CaO–MgO glass–ceramics were produced using the transferred arc plasma (TAP) processing method. Homogeneous mixtures of HA/25 wt% SiO₂–CaO–MgO and HA/50 wt% SiO₂–CaO–MgO batches obtained by dry mixing the respective compositions in a ball mill were processed in argon plasma using the TAP torch at 5 kW for 1, 2 and 3 min, respectively. The synthesized glass–ceramic samples were studied for phase composition, microstructure and bioactivity. The phase study of the synthesized glass–ceramics revealed the formation of calcium phosphate silicate with traces of calcium silicate. The structural study by SEM revealed that the prepared samples possessed smooth glassy surface morphology. The in vitro-bioactivity of the TAP synthesized glass–ceramics was examined in simulated body fluid (SBF). The SBF test results confirmed the development of crystalline carbonated apatite phase after 12 days of immersion. The cytocompatibility was evaluated through human fibroblast cell proliferation. The fibroblasts culture results showed that the sample was non-toxic and promoted cell growth.     

Characteristic reaction processes in the system brushite–NaOH solution

The reaction of brushite (CaHPO₄·2H₂O, DCPD) with NaOH solutions ranging in concentration from 0 to 40 mass% were investigated at 25 °C. At low NaOH concentrations below 20 mass%, hydroxyapatite (HAp) formed directly through the reaction (1) DCPD → HAp. At middle concentrations of 20–27 mass%, DCPD changed once into Ca(OH)₂ and then into HAp, i.e., through the consecutive reaction (2) DCPD → Ca(OH)₂ → HAp. At high concentrations above 27 mass%, the consecutive reaction (3) DCPD → HAp → Ca(OH)₂ was concluded. The boundary concentrations, i.e., singular points, between the first/second and the second/third reactions were estimated to be ca. 20 and 27 mass%, respectively. HAp particles obtained were platelet aggregates of very fine HAp microcrystals. The platelet form was compatible to the original platelet DCPD form. HAp samples prepared in this reaction system were structurally low crystalline and compositionally stoichiometric, and had a feature of large heating weight losses below 400 °C.     

Studies on a novel bioactive glass and composite coating with hydroxyapatite on titanium based alloys: Effect of γ-sterilization on coating

A novel silicate based bioactive glass coating composition containing B₂O₃ and TiO₂ having matching thermal properties with that of Ti₆Al₄ V implants was developed and characterized. A conventional vitreous enamelling technique was used for coating small flat surface and curved surface of small rods. Hydroxyapatite (HAp) micro and nano-crystalline particles were used to prepare bioactive glass-HAp composite coating. Scratch testing was used to study the coating adhesion and its fracture behaviour under simulated conditions. As observed from scratch testing results, adhesion strength of the coating improved from 21 N normal load to 27 N and 32 N on addition of micro-HAp and nano HAp powder, respectively, to bioactive glass matrix. Further, sterilization of the coated samples with 25 kGy gamma irradiation substantially enhanced the adhesion of glass coating and HAp-composite coating.     

Biomimetic chitosan-hydroxyapatite hybrid biocoatings for enamel remineralization

Development of biomimetic ceramic-based materials is currently a challenge in dental tissue engineering. Synthetic hybrid chitosan (CS)-hydroxyapatite (HAP) layers are regarded as candidates for teeth remineralization, protection against further demineralization ensuring also antibacterial activity. Thus, the aim of this work was to obtain new biomimetic CS-HAP layers for restoration of damaged mature enamels and to pursue morphological, compositional, structural and hardness modifications of the grown layers by immersion for 4, 7 and 10 days into artificial saliva (AS) under CS-Emdogain (EMD) hydrogel action. SEM-EDX, HRTEM-SAED, FTIR and micro-Raman findings indicated formation of carbonate-substituted HAP, B-type, with c-axis orientation in the newly formed CS-HAP coatings. Prolonged immersion span of 10 days caused increasing CS content in the superficial grown layer while carbonate content diminished. Optimum Ca/P ratio (1.85 at%) and hardness of 2.48 GPa were recorded for seven days growth using CS-EMD hydrogel. Subtle changes in HAP lattice parameters were recorded for 10-day grown layer while c-axis orientation of HAP crystals at mesoscale was preserved. Mechanism of CS interaction during in situ biomimetic synthesis and self-assembly of HAP crystals under CS-EMD hydrogel presence is also discussed.     

Application of hydrophilic ionic liquid treatment to the morphological observations of hydrated porous ceramic green bodies

In this study, a simple and convenient method for observing the surface morphology of hydrated porous ceramic green bodies is proposed. The porous hyrdoxyapatite (HAp) green body was prepared by a gelcasting process and was dried in a humid chamber from 90 to 50% relative humidity at 25 °C before subsequent treatment with a hydrophilic ionic liquid (IL). The surface morphology of the IL-treated porous HAp green body was observed using FE-SEM. The results showed that the pore morphology and microstructure of the HAp green body was readily observable without evidence of charging. The as-prepared sample showed pores approximately 300–600 μm in diameter, which gradually contracted to approximately 200–400 μm upon drying in the humid chamber. Following sintering at 1000 °C, the pores had further contracted to approximately 100–300 μm. The IL binds with the surrounding water to prevent the sample from drying in vacuum and acts as a conductive media, allowing the HAp ceramics to be observed in the electron microscope. In comparison to the micro-focused X-ray CT analysis, the fine pore structure (less than 100 μm) could only be observed using FE-SEM when the porous body had also been subjected to the IL treatment.     

Biomimetic fabrication of mulberry-like nano-hydroxyapatite with high specific surface area templated by dual-hydrophilic block copolymer

Novel porous and mulberry-like hydroxyapatite (HAp) nanoparticles with three-dimensionally hierarchical microstructures were developed by using the dual-hydrophilic block copolymer poly(methacrylate acid)-b-poly[N-(2-methacryloylxyethyl) pyrrolidone] (PMAA-b-PNMP) as the template. It was found that the morphology and Ca/P ratio of synthesized HAp was highly related to the concentration of block copolymer and solution pH, respectively. The morphological evolution of HAp nanoparticles in different conditions was investigated systematically by scanning electron microscopy (SEM), transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM), powder X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The possible mechanism of PMAA-b-PNMP assisted mulberry-like HAp formation was also proposed based on the time-dependent TEM results. Attributing to the high specific surface area (SSA) of 119 m² g⁻¹, these mulberry-like HAp nanoparticles exhibited excellent adsorption ability for Congo Red (CR). The maximum adsorption capacity was 467 mg g⁻¹ according to the Langmuir monolayer adsorption model.     

Preferential occupancy of metal ions in the hydroxyapatite solid solutions synthesized by hydrothermal method

The solid solutions in the systems of Ca-Cd HAp [Ca_10−xCd_xHAp (x = 0–10)], Ca-Sr HAp [Ca_10−xSr_xHAp (x = 0–10)] and Ca-Pb HAp [Ca_10−xPb_xHAp (x = 0–10)], were successfully synthesized at 200 °C for 12 h under hydrothermal conditions. The site of the metal ions in the solid solutions was analyzed by the Rietveld method. The results of the Rietveld analysis indicated that the metal ions of Pb²⁺, Sr²⁺, and Cd²⁺ all preferentially occupied M (2) sites in the apatite structure. The preferential occupancy of the metal ions in M (2) sites were explained mainly by their ionic radius and electronegativity.     

Adsorption and release of gemcitabine hydrochloride and oxaliplatin by hydroxyapatite

The aim of this study was to investigate the adsorption and the release profile of two anticancer drugs, gemcitabine hydrochloride (dFdU.HCl) and oxaliplatin (DACH-Pt), from hydroxyapatite (HAP) in order to evaluate HAP as local drug delivery system (DDS). Various initial concentrations of drug aqueous solutions were used in order to determine the maximum adsorption capacity of HAP after 48 h shaking. The maximum adsorption capacity of dFdU.HCl (400 mg/g HAP) was achieved after 40 h while the maximum adsorption capacity of DACH-Pt (49.1 mg/g HAP) was accomplished after 20 h. Adsorption processes for both drugs were found to fit the Freundlich equation. The release processes were studied by soaking the samples of loaded HAP in simulation body fluids (SBF). After only 1 h 65% of dFdU.HCl was released while the release of DACH-Pt from the HAP was more gradual since 55% of DACH-Pt was released in the first 24 h. Finally, in an attempt to understand the molecular basis of the drug action, the chemical interactions involved in the complex processes of drug delivery were studied theoretically.