Modeling of the Hydrolysis of α-Tricalcium Phosphate

Some of the formulations of apatitic calcium phosphate bone cements are based on the hydrolysis of α-tricalcium phosphate (α-Ca₃(PO₄)₂, α-TCP). In this work the hydrolysis kinetics of α-TCP are studied, taking into account the particle-size distribution of the initial powder, to identify the mechanisms that control the reaction in its successive stages. The temporal evolution of the depth of reaction is calculated from the degree of reaction data, measured by X-ray diffractometry. A kinetic model is proposed, which suggests the existence of two rate-limiting mechanisms: initially, the surface area of the reactants and, subsequently, the diffusion through the hydrated layer formed around the reactants. For the specific particle size and preparation used, the controlling mechanism changeover takes place after 16 h of reaction.     

Phase Evolution during the Formation of α-Tricalcium Phosphate

The formation of α-tricalcium phosphate from monobasic ammonium phosphate and calcium carbonate was investigated using a number of complementary techniques. Differential thermal analysis showed five distinct thermal events attributed to melting of the ammonium phosphate, decomposition of acidic calcium orthophosphate into an amorphous calcium metaphosphate, crystallization of β-calcium metaphosphate, crystallization of β-calcium pyrophosphate, and calcination of calcium carbonate. X-ray diffraction analyses as a function of temperature supported the evolution of these events and phases and also showed the formation of other intermediates, including an amorphous phase, apatite, lime, and β-tricalcium phosphate. Thermal gravimetric analysis (TGA) showed a large weight loss occurring between 150° and 250°C due to reaction between the acidic phosphate liquid and the calcium carbonate. This resulted in an amorphous intermediate with a Ca/P ratio between 0.5 and 1.0 from which both β-calcium metaphosphate and β-calcium pyrophosphate crystallized. Mass spectroscopy indicated that the ammonia and carbon dioxide were evolved in four different steps, while water was evolved in at least five steps. These decomposition steps correlated with those observed by TGA. Scanning electron microscopy indicated the formation of an intermediate phase that coated the calcium carbonate by 250°C. The proposed mechanistic reaction path to alpha-tricalcium phosphate involves the formation and consumption of the following sequence of intermediates: an acidic amorphous condensed phosphate; β-calcium metaphosphate and β-calcium pyrophosphate; lime, apatite, and β-tricalcium phosphate.     

Amorphous α-Tricalcium Phosphate: Preparation and Aqueous Setting Reaction

The mechanical and setting properties of calcium phosphate cements are considerably determined by the pretreatment of the constituents. In this report we show for the first time that prolonged high-energy ball milling of α-tricalcium phosphate (α-TCP) led to mechanically induced phase transformation from the crystalline to the amorphous state. The amorphous material demonstrated a high reactivity such that the time for substantially complete conversion of α-TCP to calcium-deficient hydroxyapatite in 2.5% Na₂HPO₄ solution decreased from about 20 h (1 h of grinding in ethanol, 85% relative crystallinity) to 4–6 h for a material with a crystallinity of 8% (24 h of grinding). This reactivity could be attributed to an increased thermodynamic and kinetic solubility of the ground materials. Mechanically activated α-TCP cements were produced with compressive strengths of up to 80 MPa and setting times of 5–16 min. The effect of reactant preparation and cement mixing parameters on the physical and chemical properties of mechanically activated α-TCP cement was investigated. By comparing cements of similar porosity and degree of conversion it was demonstrated that apatite specific surface area has a strong influence on cement mechanical performance, which highlights the importance of this previously overlooked parameter in improving strength.     

Kinetic Model for α–Tricalcium Phosphate Hydrolysis

A mechanistic model for the kinetics of hydrolysis of α-tricalcium phosphate (α–Ca₃(PO₄)₂ or α-TCP) to hydroxyapatite (Ca_{10− x} (HPO₄) _x (PO₄)_{6− x} (OH)_{2− x} or HAp) has been developed. The model is based on experimental hydrolysis rate data obtained using isothermal calorimetry. Analysis of the kinetic data according to the general kinetics models in terms of the fractional degree of reaction and time suggests the hydrolysis to be controlled by different rate-limiting mechanisms as reaction proceeds. Initially, the hydrolysis kinetics depend on the surface area of the anhydrous α-TCP. Subsequently, they change to a dependence on the rate of HAp product formation controlled by a nucleation and growth mechanism. The model predicts that HAp nuclei form at essentially one time and growth occurs in two dimensions, leading to a platelike morphology. The change in the reaction mechanism occurs at a fractional degree of hydrolysis, which does not change significantly with temperature in the range of 37°–56°C.     

模拟体液中电沉积制备磷酸钙盐涂层的研究

采用电沉积方法在模拟体液中制备磷酸钙盐涂层,研究了电流密度、电解液浓度、电沉积时间以及后处理对涂层表面形貌、组分和结构的影响。研究表明：在1～10mA／cm^2电流密度下沉积60～75min可以在模拟体液中制备结晶度较低的磷酸钙盐类涂层,涂层分别经模拟体液、碱液和水热处理后前驱体都转变为羟基磷灰石。     

Lath-like Structure of β-Tricalcium Phosphate in Orthopedic Implants

The lath-like β-tricalcium phosphate (β-TCP) in the sintered porous β-TCP implants was revealed by transmission electron microscope (TEM). Samples of sintered porous β-TCP implants were extracted from rabbit tibia after implanted for 1–6 months. Although the majority of sintered β-TCP particles are in a granular shape, the lath-like structures of implants are observed occasionally. The length of laths is on the order of 1 μm, while the thickness of laths is on the order of 10 nm. The X-ray energy dispersive spectroscopy and the electron diffraction indicate that the lath-like material is β-TCP with its rhombohedral (     ) plane parallel to the longitudinal direction of laths. High resolution TEM imaging also confirms the finding of electron diffraction. This abnormal morphology of β-TCP have raised our attention, even though its formation mechanism and effects on osseointegration is not yet certain.     

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.     

Synthesis and Structure Refinement of Zinc-Doped β-Tricalcium Phosphate Powders

Zinc substituted β-tricalcium phosphate [β-Ca₃(PO₄)₂] was formed by substituting a zinc precursor in calcium-deficient apatite through aqueous precipitation technique. Heat treatment at 1000°C led to the formation of well crystalline β-Ca₃(PO₄). Refinement technique was used to determine the influence of incorporated zinc in the β-Ca₃(PO₄) structure. The structural data for all the four different zinc substituted β-Ca₃(PO₄) ranging from 0–9 mol% of zinc investigated in the present study confirmed the rhombohedral structure of β-Ca₃(PO₄) in the hexagonal setting (space group R 3 c ). The incorporation of lower sized Zn²⁺ (0.745 Å for sixfold coordination with O) at the higher sized Ca²⁺ (1.00 Å for sixfold coordination with O) site in the β-Ca₃(PO₄) structure led to the contraction of unit cell parameters. The added zinc prefers to occupy the Ca(5) site of β-Ca₃(PO₄) structure.     

Apatite Formation on Calcium Phosphate Invert Glasses in Simulated Body Fluid

Calcium phosphate invert glasses, which contain P₂O₇²⁻ and PO₄³⁻ ions, have been prepared via the addition of a small amount of TiO₂. The formation of bonelike calcium phosphate apatite on the surface of the phosphate invert glasses was examined in simulated body fluid (SBF) at a temperature of 37°C. Soaking for 20 d resulted in the deposition of leaflike apatite particles on 6CaO·3P₂O₅·TiO₂ invert glass (based on molar ratio). The glass had much-greater chemical durability against SBF, in comparison with a metaphosphate glass; P ions were not dissolved excessively from the 6CaO·3P₂O₅·TiO₂ glass, so the apatite formation was not suppressed.     

Mesoporous Calcium Phosphate Via Post-Treatment of α-TCP

α-Tricalcium phosphate (α-TCP) macroporous ceramic scaffold was chemically treated with a buffered solution at pH=4. Mesopores were formed in the scaffold after the treatment to result in a remarkable increase in surface area of the scaffold. The increase in the surface area is caused by precipitation of octacalcium phosphate (OCP). Bimodal pore size distribution consisting of mesopores and macropores obtained by the treatment of α-TCP scaffold having higher initial porosity brought about high adsorption of bovine serum albumin (BSA) than monomodal pore size distribution of mesopores. Adsorption of BSA, acidic protein, was suggested to result from crystallographic characters of OCP.     

Ionic Substitutions in Biphasic Hydroxyapatite and β-Tricalcium Phosphate Mixtures: Structural Analysis by Rietveld Refinement

The structural information on the influence of ionic additions in biphasic (hydroxyapatite (HAP) and β-tricalciumphosphate (β-TCP)) mixtures ranging from single ionic substitutions to combined ionic substitutions of most of the essential ions embedded in biological apatite was analyzed through the Rietveld refinement technique. The results have proved that the determined quantitative phase composition of HAP and β-TCP in biphasic mixtures was dependent on the initial calcium (Ca) deficiency of the precursor powders precipitated from the different molar concentrations used in the synthesis. The substitution of cations (Na⁺, Mg²⁺, and K⁺) improved the stabilization of the β-TCP structure whereas anions (F⁻ and Cl⁻) were found incorporated at the OH⁻ site of the HAP phase. Rietveld analysis of X-ray powder diffraction data from the present study proved to be a powerful technique to describe the position and occupancy of certain ions like Mg²⁺ and Cl⁻ in the biphasic mixtures. However, it has also shown limitations in tracking back other ions like Na⁺, K⁺, and F⁻, which require the use of other complementary characterization methods.     

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.     

Forming and Sintering Behavior of B- and C-Doped α and β-SiC

The effects of forming pressure and sintering temperature on shrinkuge, density, and phase composition of α- and β-SiC were determined. Alpha SiC developed the 4H phase at the expense of the 6H phase at >2150°C. The beta form converted to the 6H phuse at >2000°C, with intermediate development of the 15R and 4H phases     

Precipitation of Carbonated Calcium Phosphate Powders from a Highly Supersaturated Simulated Body Fluid Solution

Carbonated hydroxy apatite (CHA) powders were prepared by precipitation from a modified simulated body fluid (5 × M-SBF). The ionic concentrations were five times higher than in human blood plasma with the exception of Mg²⁺ and HCO₃⁻ concentrations that were reduced in order to accelerate crystal growth. Spheroaggregates of CHA platelets with molar (Ca+Mg)/P ratios ranging from 1.44 to 1.56 were obtained after precipitation at 50°C. The crystallite size in the c direction was approximately 31 nm and depending on the precipitation time, a CO₃²⁻ content of 1.8–5.2 wt% was determined. Using this low-temperature precipitation method, CHA powders with a high specific surface area of 83 m²/g and a composition and crystallite size close to those of the mineral phase of human bone were obtained.     

Boron Redistribution in Sintered α-SiC During Thermal Oxidation

The redistribution of the boron impurity in sintered α-SiC during thermal oxidation was investigated over the temperature range 1200· to 1400,°C using sputter-induced photon spectrometry (SIPS). The process was modeled with the Stanford University Processing Engineering Models Program (SUPREM) which permitted the estimation of diffusivities of boron in the growing oxide and the substrate. The process is characterized by segregation of the boron in the oxide near the interface and a corresponding depletion of boron in the substrate. The apparent diffusivities in the oxide were about three orders of magnitude higher than the published values for boron in pure SiO₂, presumably because the film is much less pure than pure SiO₂. The apparent diffusivities of the boron in the polycrystalline silicon carbide were almost five orders of magnitude higher than the published values for boron in single-crystal silicon carbide. The diffusivities in the silicon carbide represent boron transport via the grain boundaries which were partially oxidized during the thermal treatment.     

New Approach to the β→α Polymorphic Transformation in Magnesium-Substituted Tricalcium Phosphate and its Practical Implications

The transformation β→α in Mg-substituted Ca₃(PO₄)₂ was studied. The results obtained showed that, contrary to common belief, there is, in the system Mg₃(PO₄)₂–Ca₃(PO₄)₂, a binary phase field where β+α-Ca₃(PO₄)₂ solid solutions coexist. This binary field lies between the single-phase fields of β- and α-Ca₃(PO₄)₂ solid solution in the Ca₃(PO₄)₂-rich zone of the mentioned system. In the light of the results and the Palatnik–Landau's Contact Rule of Phase Regions, a corrected phase equilibrium diagram has been proposed. The practical implications of these findings with regard to the synthesis of pure α- and β- Mg-substituted Ca₃(PO₄)₂ powders and to the sintering of related bioceramics with improved mechanical properties are pointed out.     

不同干燥方式对凝胶注模成形陶瓷坯体干燥过程的影响

本文通过凝胶注模成形得到氧化铝陶瓷坯体,采用直接干燥、高湿干燥、液相介质干燥等方式对坯体进行干燥,研究了不同的干燥方式对坯体干燥速率及干燥效果的影响。结果表明：凝胶注模成形坯体对环境温度、湿度的变化非常敏感,高湿干燥、液相介质干燥可有效减缓干燥速率,避免干燥过程中出现的开裂现象。     

Microstructural Development During Gas-Pressure Sintering of α-Silicon Nitride

Gas-pressure sintering of α-Si₃N₄ was carried out at 1850 ° to 2000°C in 980-kPa N₂. The diameters and aspect ratios of hexagonal grains in the sintered materials were measured on polished and etched surfaces. The materials have a bimodal distribution of grain diameters. The average aspect ratio in the materials from α-Si₃N₄ powder was similar to that in the materials from β-Si₃N₄ powder. The aspect ratio of large and elongated grains was larger than that of the average for all grains. The development of elongated grains was related to the formation of large nuclei during the α-to-β phase transformation. The fracture toughness of gaspressure-sintered materials was not related to the α content in the starting powder or the aspect ratio of the grains, but to the diameter of the large grains. Crack bridging was the main toughening mechanism in gas-pressure-sintered Si₃N₄ ceramics.     

Size Control of α-Alumina Particles Synthesized in 1,4-Butanediol Solution by α-Alumina and α-Hematite Seeding

The effects of seed particles and shear rate on the size and shape of α-Al₂O₃ particles synthesized in glycothermal conditions are described. It is proposed that seed particles provide a low-energy, epitaxial surface in solution to lower the overall surface energy contribution to the nucleation barrier, thus increasing nucleation frequency and subsequently reducing the particle size of hexagonal α-Al₂O₃ platelets or polyhedra, depending on synthesis conditions, in 1,4-butanediol solution. Seeds have a significant effect on the size of hexagonal α-Al₂O₃ platelets in samples with high seed concentration. The particle size of α-Al₂O₃ platelets decreases from 3 to 4 µm to 100 to 200 nm by increasing the number concentration of seeds. In the case of α-Fe₂O₃ seeding, the effect of seeding on the size of α-Al₂O₃ particles closely resembles the effects obtained with α-Al₂O₃ seeding. Regardless of seed concentration, high stirring rate promotes the formation of hexagonal platelets with high aspect ratio, whereas medium and low stirring rates promote the formation of elongated platelets and polyhedra with 14 faces, respectively.     

R-Curve Behavior of In Situ Toughened α-SiAlON Ceramics

R -curves of single-phase Y- and Ca-containing α-SiAlON ceramics have been measured. They range from flat ones for fine-grain ceramics to pronounced rising ones when large elongated grains are present. The highest toughness measured reached 11.5 MPa·m^1/2 over a crack extension of about 1000 μm.