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.     

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.     

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.     

Microstructural Tailoring and Characterization of a Calcium α-SiAlON Composition

Three calcium α-SiAlON microstructures—namely, fine-grained, bimodal, and large elongated—were developed using powders of the same composition and then characterized. The evolution of grain size and morphology was determined to be a process of nucleation and growth that could be controlled with a two-step sintering technique. The extent of texture was identified in the as-hot-pressed materials as a function of sintering conditions. Samples with different microstructures exhibited different hardness and fracture toughness. The true hardness was derived from the intrinsic relation between applied loads and indent sizes. The effect of microstructure on hardness and fracture toughness was analyzed.     

Electron Beam-Induced "Nanocalcination" of Boehmite Nanostrips to Mesoporous α-Alumina Phase

Phase transformation of boehmite (AlOOH) nanostrips to α-Al₂O₃ nanolaces was investigated under electron beam irradiation of a 200 keV transmission electron microscope (TEM). X-ray diffraction pattern showed that the powder consisted of boehmite phase before the electron exposure, while selected area electron diffraction patterns demonstrated the formation of stable α-alumina phase after bombardment with high-energy electrons. The in situ TEM observations revealed that the initial morphology remained unchanged while a lace-like mesostructure of α-alumina was developed.     

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.     

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.     

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.     

Joining of Calcium Phosphate Invert Glass-Ceramics on a β-Type Titanium Alloy

A bioactive calcium phosphate invert glass-ceramic containing β-Ca₃(PO₄)₂ crystals could be joined strongly with a Ti–29Nb–13Ta–4.6Zr alloy consisting of a β-titanium phase by heating the metal on which the mother glass powders with a composition 60CaO·30P₂O₅·7Na₂O·3TiO₂ (mol%) were placed, at 800°C for 1 h in air; the tensile joining strength was estimated to be ∼26 MPa on average. A compositionally gradient layer was developed on the metallic substrate during the heating. When the metal with glass powders on it was heated at 850°C in air, the phosphate glassy phase flowed viscously, permeating the oxide layer formed around the surface of the metal, which was thicker than that formed by heating at 800°C; a compositionally gradient layer was not developed, and a strong joining was not realized. The joining between the glass-ceramic and the metal is suggested to be controlled by viscous flow of the glassy phase in the glass-ceramic and by reaction of the glassy phase with the oxide phase formed around the surface layer of the metal.     

The β→αTransformation in Poly crystalline SiC: III, The Thickening of α Plates

The final stages of the β→α polymorphic phase transformation in conventionally sintered and hot-pressed SiC were studied by optical and transmission electron microscopy. The interface between the α and β regions of partially transformed grains invariably contains thin α lamellae adjacent and parallel to coherent β twins (or β stacking faults). These planar defects serve as nucleation sites for the transformation, with growth of α occurring by the motion of partial dislocations nucleated at the intersection of coherent and incoherent twin boundaries. Various structural phenomena in SiC, including faulting, mi-crosyntaxy, and long-period polytypism, are discussed in terms of this transformation mechanism.     

Topotactic Growth of β-Alumina on α-Alumina

Thin foils of polycrystalline α-alumina were reacted with a potassium-rich vapor at ≤900°C. Potassium β-alumina formed along α-alumina grain boundaries and protruded from holes in the foils. Conventional transmission electron microscopy was used to analyze the α-alumina/β-alumina phase boundary for possible orientation relations.     

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.     

Hydrolysis of α-Tricalcium Phosphate in Simulated Body Fluid and Dehydration Behavior During the Drying Process

The hydrolysis of α-tricalcium phosphate (α-TCP) in a simulated body fluid (SBF) at 37°C was investigated. The hydration rate was found to be slower in SBF than that in deionized water. The concentration of ions in SBF was monitored by ICP. The hydrolysis product, which was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infra red, and X-ray photoelectron spectroscopy, was determined to be carbonate-containing, calcium-deficient hydroxyapatite (CO₃−CDHAp) with Mg²⁺, Na⁺, and Cl⁻ impurities similar to the biological apatite. An amorphous layer on the α-TCP surface was found to be the precursor of the apatite phase, which may either form crystalline apatite or may decompose back to α-TCP at a lower temperature.     

Carbothermal Synthesis of α-SiC Micro-Ribbons

We report the synthesis of microscopic α-SiC ribbons (belts) on the surface of a graphite rod at 1800°–1900°C by a carbothermal process. The width of the ribbons produced ranged from 500 nm to 5 μm and the aspect ratio was up to 400. The ribbon thickness ranged from 50 to 800 nm. Their growth mechanism was explained by accelerated growth along the twin boundary. SiC whiskers grew on the rod along with the ribbons. Frequently, ribbons were growing from the tip of a whisker or whiskers were growing from the edge of a ribbon. SiC ribbons may find applications in high-temperature sensors, photo-electronic devices, or robust cantilevers in micro (or nano) electro mechanical systems. Alternatively, they can be used as reinforcements in composite materials, conferring anisotropic mechanical properties, such as unidirectional flexibility, to the composite.     

Autoclave-Free Formation of α-Hemihydrate Gypsum

Flue gas gypsum may be converted to α-hemihydrate by suspending the starting material in inorganic salt solutions of high concentration or in diluted sulfuric acid and maintaining the suspension at boiling, or near boiling temperature for a period of time. The crystal morphology of the produced α-hemihydrate gypsum and, thus, its quality depend significantly on the composition of the liquid phase. Additions of different carbonic acids may improve the quality of the product distinctly. Under optimal working conditions the quality of the formed α-hemihydrate gypsum is similar to that of a material produced in an autoclave.     

Photoluminescence of Cerium-Doped α-SiAlON Materials

Cerium-doped α-SiAlON (M _x Si_{12−( m + n )}Al _{m + n} O _n N_{16– n} ) materials have been prepared by gas-pressure sintering and post-hot-isostatic-press (HIP) annealing, using four powder mixtures of α-Si₃N₄, AlN, and either (i) CeO₂, (ii) CeO₂+ Y-α-SiAlON seed, (iii) CeO₂+ Y₂O₃, or (iv) CeO₂+ CaO. Cerium-containing CeAl(Si_{6– z} Al _z )(N_{10– z} O _z ) (JEM) phase, rather than Ce-α-SiAlON phase, forms in the sample with only CeO₂, whereas a single-phase α-SiAlON generates in samples with dual doping (CeO₂+ Y₂O₃ and CeO₂+ CaO). On ultraviolet-light excitation, JEM gives one broad emission band with maximum at 465 nm and a shoulder at 498 nm; α-SiAlON shows an intense and broad emission band that peaks at 500 nm. The unusual long-wavelength emissions in JEM and α-SiAlON are due to increases in the nephelauxetic effect and the ligand-field splitting of the 5 d band, because the coordination of Ce³⁺ in JEM and α-SiAlON is nitrogen enriched.     

Plasma Etching of α-Sialon Ceramics

Plasma etching of β-Si₃N₄, α-sialon/β-Si₃N₄ and α-sialon ceramics were performed with hydrogen glow plasma at 600°C for 10 h. The preferential etching of β-Si₃N₄ grains was observed. The etching rate of α-sialon grains and of the grain-boundary glassy phase was distinctly lower than that of β-Si₃N₄ grains. The size, shape, and distribution of β-Si₃N₄ grains in the α-sialon/β-Si₃N₄ composite ceramics were revealed by the present method.     

Normal-Pressure Hot-Pressing of α-Alumina-Diamond Composites

α-Alumina-diamond composites have been developed by normal hot-pressing procedures using a conventional pressure of 32 MPa and 1250°C. Heretofore this type of composite has required a pressure of 6 GPa (60 kbar) to prevent the transformation of diamond to graphite. The mechanical properties, density, and thermal expansion coefficient of these composites have been characterized. The fracture toughness ( K _Ic) of alumina shows a considerable increase with the addition of diamond particles. Diamond additions tend to decrease the thermal expansion coefficient of these composites. The composite properties are dependent on the volume fraction of diamond particles.     

Internal Reduction of Chromium-Doped α-Alumina

(Al,Cr)₂O₃ single crystals and polycrystals were internally reduced at 1873 K in an Al/Al₂O₃ buffer for periods of time ranging from 1 to 100 h. The growth kinetics of the reduction scale were measured. The microstructure of the reduction scale was investigated by SEM and TEM. As a result of the reduction, two types of discrete chromium precipitates developed inside the alumina matrix (inside the single crystal or the polycrystalline grains), each one being characterized by a particular morphology (needle or spheroid) and a low-energy orientation relationship with respect to the alumina matrix. In addition, larger precipitates without special orientation relationship developed along the grain boundaries and at the triple junctions of the polycrystais. In the first part of this paper, the precipitate morphology and size are described in terms of the crystallography of the interface between the two crystal structures in relation to the reduction mechanism. In the second part, the global reduction scale growth is analyzed in terms of point defect fluxes across the reduction scale.