MgO–Na2O–P2O5-Based Sintering Additives for Tricalcium Phosphate Bioceramics

Effects of MgO–Na₂O–P₂O₅-based sintering additives on densification, microstructure, hardness, compression strength, and biodegradability of β-tricalcium phosphate (β-TCP) ceramics were studied. Three additive compositions were prepared and introduced into β-TCP. Uniaxially compacted ceramic structures, sintered at 1250°C in air, were characterized. Scanning electron microscopy was used to study the microstructure. The X-ray diffraction technique was used for phase analysis. Results showed that these additives modified the microstructure and improved the sintered density and mechanical properties. An increase of 9% in density, 40% in hardness and 38% in compression strength were achieved. Biodegradation analysis revealed that these additives could tailor the rate of resorption and hardness degradation of β-TCP.     

Reverse Micelle-Mediated Synthesis and Characterization of Tricalcium Phosphate Nanopowder for Bone Graft Applications

Nanocrystalline β-tricalcium phosphate (β-TCP) powder was synthesized using reverse micelle as a template system. Cyclohexane was used as the oil phase, aqueous solutions of calcium nitrate and phosphoric acid as the aqueous phase, and poly(oxyethylene)₅ nonylphenol ether (NP-5) and/or poly(oxyethylene)₁₂ nonylphenol ether (NP-12) as the surfactants. The powder were synthesized at a fixed Ca/P molar ratio of 1.5 at a pH of 10. The synthesized powder were calcined at 800°C to obtain monophasic β-TCP. Particle size, morphology, and surface area of the synthesized powder were dependent on the chemistry of the surfactant and composition of the microemulsion. The powder were characterized using a BET surface area analyzer, powder X-ray diffraction, dynamic light scattering technique, and transmission electron microscopy. TCP nanoparticles had a particle size between 32 and 135 nm, and a BET-specific average surface area between 57 and 103 m²/g with controlled morphology. The powder were consolidated and sintered at 1250°C in a 3 kW microwave furnace in the form of a compact disk. Human osteoprecursor cells (osteoblastic precursor cell line 1 [OPC1]) were used to assess the biocompatibility of TCP disks after 1, 5, and 11 days in culture using scanning electron microscopy, MTT assay, and alkaline phosphatase expressions. Disk samples were biocompatible and showed excellent OPC1 cell adhesion, growth, and proliferation. Biocompatible β-TCP nanopowder were synthesized with controlled particle size, morphology, and surface area using a reverse micelle-mediated template system.     

Preparation of Porous Ca10(PO4)6(OH)2 and β-Ca3(PO4)2 Bioceramics

Submicrometer-sized, pure calcium hydroxyapatite (HA, (Ca₁₀(PO₄)₆(OH)₂)) and β-tricalcium phosphate (β-TCP, Ca₃(PO₄)₂) bioceramic powders, that have been synthesized via chemical precipitation techniques, were used in the preparation of aqueous slurries that contained methyl cellulose to manufacture porous (70%–95% porosity) HA or β-TCP ceramics. The pore sizes in HA bioceramics of this study were 200–400 μm, whereas those of β-TCP bioceramics were 100–300 μm. The pore morphology and total porosity of the HA and β-TCP samples were investigated via scanning electron microscopy, water absorption, and computerized tomography.     

Effect of the HA/β-TCP Ratio on the Biological Performance of Calcium Phosphate Ceramic Coatings Fabricated by a Room-Temperature Powder Spray in Vacuum

Four calcium phosphate ceramic coatings, the less soluble hydroxyapatite (HA) coating, the more soluble β-tricalcium phosphate (β-TCP) coating, and two biphasic calcium phosphate (BCP) coatings with HA/β-TCP ratios of 70/30 and 30/70 were fabricated by spraying each corresponding powder onto a titanium substrate at room temperature (RT) in a vacuum, in order to investigate the effect of the HA/β-TCP ratio on the dissolution behavior and the cellular responses of the coating. No secondary phases, except for HA and β-TCP, were observed for the coatings in the X-ray diffraction results. The coating compositions were almost the same as those of the starting powders because the coating was conducted at RT. Microscopic examination of the coatings revealed crack-free and dense microstructures. The BCP coatings exhibited dissolution rates intermediate between those of the pure HA and β-TCP coatings. The dissolution rate of the coatings was largely dependent on their HA/β-TCP ratio. The cell proliferation and differentiation results indicated that the cellular responses of the coatings were not proportional to their dissolution rates. The 3HA–7TCP (HA/β-TCP ratio of 30/70) coating exhibited an optimal dissolution rate for excellent biological performance.     

Formation of Strontium-Stabilized β-Tricalcium Phosphate from Calcium-Deficient Apatite

A series of strontium-stabilized β-tricalcium phosphate (β-TCP) was prepared via the aqueous precipitation method, and characterized by X-ray diffraction and infrared fourier spectrometer techniques. The general principle of preparing calcium-deficient apatite and thereby heat-treating the resultant apatite above 700°C to form single-phase β-TCP was attempted to create strontium-substituted β-TCP. The results have proved that single phase β-TCP could be formed with the substituted strontium with only an influence on the increase in lattice constants with an increase in the concentration of strontium. Further, it is also stated from the present findings that strontium has a specific role in the crystallinity of the resultant β-TCP.     

Preparation of Fibrous, Porous Hydroxyapatite Ceramics from Hydroxyapatite Whiskers

Hydroxyapatite (HAp) whiskers have been used to prepare fibrous, porous HAp ceramics. The fibrous microstructure was retained in all cases after hot-pressing the HAp whiskers at 800-900°C (1 h, 30 MPa). The fracture path in the fibrous, porous HAp ceramics was partially intergranular, indicating the occurrence of crack deflection, bridging, and pull-out effects. When the whiskers were hot-pressed at 1000-1100°C (1 h, 30 MPa), only large equiaxed grains were present in the HAp ceramics; thus no toughening occurred. When nonstoichiometric HAp whiskers were used to fabricate a porous body, β-TCP precipitated on the whisker surface without destroying the fibrous microstructure. Sintering the HAp whiskers is thus an easy way for in situ fabrication of HAp/β-TCP fibrous, porous materials with a controlled biodegradation rate.     

Characterization and Mechanical Performance of the Mg-Stabilized β-Ca3(PO4)2 Prepared from Mg-Substituted Ca-Deficient Apatite

The preparation of Mg-stabilized β-tricalcium phosphate (β-TCP) was carried out by an aqueous precipitation method and the characterization of the powders was performed by powder X-ray diffraction, FT-IR spectra, Raman spectroscopy, and elemental analysis. The transformation of calcium-deficient apatite into β-TCP has occurred in the range of 700°–800°C. The calculated values for lattice parameters confirm the stabilization role played by Mg. The thermal stability of the Mg-stabilized β-TCP powders was evident until 1400°C, thus broadening the sintering temperature range without transformation into the undesirable α-TCP. Accordingly, the mechanical properties of the Mg-stabilized β-TCP were improved in comparison with those of pure β-TCP.     

A Novel Biphasic Bone Scaffold: β-Calcium Phosphate and Amorphous Calcium Polyphosphate

Calcium polyphosphate (CPP) was added to hydroxyapatite (HA) to develop a novel biphasic calcium phosphate (BCP). The effects of varying CPP dosage on the sintering property, the mechanical strength, and the phase compositions of HA were investigated. Results showed that CPP reacted with HA and produced β-calcium phosphate (β-TCP) and H₂O and that an excessive dosage of CPP (>10 wt%) obtained a novel BCP of β-TCP/amorphous-CPP, while a lesser dosage of CPP (<10 wt%) obtained a traditional BCP (HA/β-TCP). The porous β-TCP/amorphous-CPP scaffolds (porosity of 66.7%, pore diameter of 150–450 μm, and compressive strength of 6.70±1.5 MPa) were fabricated and their in vitro degradation results showed a significant improvement of degradation with the addition of CPP.     

Improvements in phase stability and densification of β-tricalcium phosphate bioceramics by strontium-containing phosphate-based glass additive

β-tricalcium phosphate (β-TCP), which transforms to α-TCP at around 1125?°C, is characterized by poor sinterability. In this study, for the first time strontium-containing phosphate-based glass (SPG) was used as a sintering additive for β-TCP, which was sintered at 1250?°C. The results indicated that the SPG additive allowed for liquid-state sintering of β-TCP, thereby noticeably promoting the densification of β-TCP bioceramics. In the sintering process SPG reacted with β-TCP, and the metal ions from SPG were substituted for the calcium ions of β-TCP. The SPG additive effectively inhibited the phase transformation of β-TCP to α-TCP in the bioceramics. The compressive strength of porous β-TCP bioceramics was markedly increased by introducing 10?wt% SPG. The SPG is considered as an effective sintering additive to improve the phase stability and mechanical strength of porous β-TCP bioceramics.     

Determination of Precise Unit-Cell Parameters of the α-Tricalcium Phosphate Ca3(PO4)2 Through High-Resolution Synchrotron Powder Diffraction

Unit-cell parameters of the α-tricalcium phosphate [TCP; Ca₃(PO₄)₂] were investigated using high-resolution synchrotron powder diffraction and the Rietveld method. The diffraction experiment was conducted at 29°C at the BL-15XU experimental station of SPring-8, Japan. Precise unit-cell parameters of the α-TCP were obtained; a =12.87271 (9), b =27.28034(8), c =15.21275(12) Å, α=γ=90°, and β=126.2078(4)°. The calculated density of α-TCP (2.8677 g/cm³) is smaller than that of β-TCP, indicating the "looser" structure of α-TCP.     

Porous Photocatalytic TiO2 Thin Films by Aerosol Deposition

Porous photocatalytic TiO₂ thin films were fabricated by the leaching technique, followed by aerosol deposition. Mixed powders of TiO₂ and β-tricalcium phosphate (TCP) were aerosol deposited at room temperature for the initial fabrication of composite films. After the β-TCP phases were leached out from the composite films in a diluted HCl aqueous solution for 24 h, porous TiO₂ films remained on the substrate. To fabricate these porous films, the β-TCP content was varied from 10 to 45 wt% and submicrometer-sized pores were formed after leaching. The porous TiO₂ films showed strong initial photocatalytic activities due to the adsorption effect of the pores and the enlarged surface area.     

Fabrication of HAp-Coated Micro-Channelled t-ZrO2 Bodies by the Multi-Pass Extrusion Process

HAp-coated micro-channelled t -ZrO₂ bodies were fabricated using a multi-pass extrusion process in which carbon powders were used to facilitate the formation of pores and ethylene vinyl acetate was used as a binder. The unidirectional pores and HAp coating layers can be obtained easily, using the extrusion process. The micro-channelled bodies were 180 μm in diameter, and the HAp layer was uniformly coated on the pore walls. However, after being sintered above 1200°C, the HAp decomposed and was transformed into β-TCP, in which a large number of pores were observed. The maximum values of bending strength of HAp-coated and uncoated porous t -ZrO₂ bodies sintered at 1500°C were about 116 and 173 MPa, respectively, and their relative densities were about 57% and 63%, respectively.     

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.     

Effect of Substitutional Monovalent and Divalent Metal Ions on Mechanical Properties of β-Tricalcium Phosphate

β-tricalcium phosphate (β-TCP) powder doped with monovalent or divalent metal ions was hot pressed at 1100°C, and the effect of substitutional monovalent and divalent metal ions on mechanical properties of β-TCP was investigated. The sinterability of β-TCP would be enhanced by the substitution of monovalent and divalent metal ions for β-TCP. Sintered β-TCP doped with 7.6 mol% of Mg²⁺ ion showed a bending strength of 160 MPa. It was found that the substituition of Mg²⁺ ion up to 9.6 mol% and a small amount of monovalent metal ions for β-TCP is effective to improve the mechanical strength of β-TCP.     

Effects of Mn-doping on the structure and in vitro degradation of β-tricalcium phosphate

β-tricalcium phosphate (β-TCP) is an ideal biomaterial for the bone repair because of its biocompatibility and biodegradability. In this study, 0 mol%, 5 mol%, 15 mol% and 30%mol bivalent manganese ion (Mn²⁺) doped β-TCP (Mn-TCP) powders were synthesized by a sol-gel method. The amount of the dopants significantly influences the crystallinity and the parameters related with structure of β-TCP, such as the lattice parameters and crystallite dimensions. The particle size and the particle distribution of doped β-TCP powers were evaluated as well. Meanwhile, the as-synthesized powders were consolidated by sintering at 1000 °C in muffle furnace for 5 h to get Mn-TCP porous material and the degradation experiment was carried out in Simulated Body Fluid (SBF) solution for 28 days. Then, Mn-TCP porous material were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and scanning electron microscope (SEM). Significantly, there were bone-like apatite materials deposited on the surface of bone-like porous materials. With the increasing doping amount of Mn²⁺, the newly formed apatite-like materials decreased, while the crystallinity increased significantly. Besides, pH results showed that alkaline environment was more favorable for the formation of sedimentary materials.     

Mechanosynthesis of complex oxides and preparation of mixed conducting nanocomposites for catalytic membrane reactors

Nanopowders of LaGaO₃- and LaMnO₃-based complex perovskites (P) and ceria-based fluorites (F) were prepared by mechanosynthesis. Compatible nanocomposites F + P and P + P with mixed ion and electron conducting (MIEC) properties were prepared and sintered at moderate temperatures up to dense ceramics. The obtained materials were studied by means of XRD, SEM, TEM, electrical conductivity measurements, temperature programmed (TP) reduction/oxidation and preliminary estimations of permeability were obtained. A new strategy based on the advantages of the mechanochemical ceramic approach is proposed to design multilayer ceramic membranes for CMR. Casting technology and one-step sintering were used for the production of thin film membranes with MIEC properties on porous substrates. The coarse fraction of as-milled powders from agglomerates with density 70% was used for the porous substrate, and fine fractions of aggregates with sizes <1 μm were used in preparation of composites for thin dense films. Ceria-based composites prepared by the Pechini route and/or mechanochemical method are proposed as materials for protecting thin films.     

Synthesis and characterization of β-TCP/CNT nanocomposite: Morphology,microstructure and in vitro bioactivity

In this study, β-TCP/CNT nanocomposite has been synthesized by solution precipitation method. Then, the effects of the different percentage of CNT (CNT1β-TCP, CNT3β-TCP, CNT5β-TCP) and surfactant (CNT1β-TCP1SDBS, CNT1β-TCP2SDBS, CNT1β-TCP3SDBS) on β-TCP/CNT nanocomposite powder were studied. The X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) analyses were used to characterize the samples. The observations revealed that the microstructure of 1 wt% CNT could provide dispersion without agglomeration in nanocomposite powder; however, a higher concentration of CNT powder in the nanocomposite resulted in the formation of Ca₂PO₇ phase. Implementing 2 wt% of SDBS as a surfactant modified the shape, size, and distribution of CNT particles on nanocomposites. Finally, the nanocomposite sample was immersed in simulated body fluid (SBF) to evaluate the in vitro bioactivity. It obviously showed an apatite layer on the surface after 7 days of immersion in SBF. Taken together, this nanocomposite might be potentially to be used as bone repair biomaterial.     

Non-equilibrium microstructure of bone china

Abstract

Commercial bone china microstructures are far from equilibrium consisting of distinct regions of lath-like (0·4–10 μm) anorthite and spheroidal (1–3 μm) β-tricalcium phosphate (β-TCP) nodules embedded in a heterogeneous composition glass along with isolated irregular (≤30 μm) α-quartz crystals. The composition and morphology of the phases formed on firing suggest that anorthite crystallised in clay relicts by the reaction of metakaolin with CaO, β-TCP crystallised from decomposition of bone ash, and that the liquid formed on vitrification has variable composition depending on the composition of adjacent phases. P₂ O₅was never detected in the glass suggesting that any P₂ O₅ that dissolves in the liquid on firing is transient. The cracks sometimes observed in and around β-TCP clusters arise from thermal expansion mismatch between β-TCP and the surrounding glass and anorthite.     

Fabrication of bioceramic scaffolds with pre-designed internal architecture by gel casting and indirect stereolithography techniques

A new technique of combining the gel casting and indirect rapid prototyping methods was utilized to fabricate macroporous β-tricalcium phosphate (β-TCP) scaffolds, which provided an excellent control over the internal architecture of scaffolds and enhanced their mechanical properties. A stereolithography apparatus was used to produce resin molds for ceramic gel casting. These molds were filled with a water based thermosetting ceramic slurry which solidifies inside the mold. After burning the resin mold and sintering, the β-TCP scaffolds with designed pore architecture were obtained. The pore morphology, size, and distribution of the resulting scaffolds were characterized using a scanning electron microscope. X-ray diffraction was used to determine the crystal structure and chemical composition of scaffolds. The mechanical measurements showed that the average compressive strength was 16.1 ± 0.8 MPa.     

Transmission Electron Microscopy of Annealed ZrO2+8 Mol% Sc2O3

The influence of heat treatment (800°C for 200 h) on the micro-structure of 8 mol% Sc₂O₃-ZrO₂ was investigated by XRD and TEM. The starting material was initially characterized and found to contain predominantly cubic-fluorite phase grains, with <5% of the grain containing the rhombohedral β phase. The β phase was positively identified by the analysis of electron diffraction pattern and by quantitative energy dispersive X-ray analysis. On aging, the relative amount of β phase was found to increase to about 15 to 20% by XRD measurement; this was confirmed by TEM observation. The orientation relation between the different variants of the β phase within a grain was determined to be (100)_r||(010)_r, and the geometrical arrangement of these variants within the grain was deduced using a 2¹/₂D imaging electron microscopy technique.