Cation-Exchange Characteristics of Sintered Hydroxyapatite in the Strongly Acidic Region

The ion-exchange behavior of hydroxyapatite (Ca₁₀(PO₄)₆-OH)₂) (HAp), fired at high temperatures, has been investigated in the strongly acidic region (pH 2 and 3). According to the present study, HAp fired above 1000°C can exchange ions from Ca²⁺ to Pb²⁺, even at pH 2, without dissolution. The molar ratios of Pb²⁺/Ca²⁺ after ion exchange are approximately unity in all cases. Ion exchange occurs in a thin layer near the surface of HAp particles fired at 1300°C. After ion exchange, Pb-Cl-apatite crystals are created in the strongly acidic region (pH 2).     

Effect of CO32− Incorporation on the Mechanical Properties of Wet Chemically Synthesized β-Tricalcium Phosphate (TCP) Ceramics

Calcium-deficient hydroxyapatite (CDHA) powders were synthesized by a wet chemical precipitation method using Ca(OH)₂ and H₃PO₄ solutions. Single-phase β-tricalcium phosphate (β-TCP) powder with a molar (Ca+Mg)/P ratio of 1.5 was obtained after calcination of CDHA synthesized under vacuum. During synthesis in air, CO₂ can be adsorbed and HBO₄²⁻ is partly substituted by CO₃²⁻, resulting in a lower phosphorous content and consequently an increase of the molar (Ca+Mg)/P ratio to 1.53. A two-phase β-TCP powder containing 20 wt% hydroxyapatite (HA) was obtained after calcination. Samples prepared from β-TCP powders synthesized under vacuum achieved a compressive strength of 301±23 MPa at 99.6% fractional density, while TCP/HA samples prepared in air achieved a maximum compressive strength of 132±29 MPa at 91.7% fractional density. This decrease in strength can be correlated to the porosity retaining due to CO₂ release during sintering and residual tensile stresses in the TCP matrix caused by the thermal expansion mismatch of β-TCP and HA.     

Crystallization and Chemical Strengthening of Stuffed β-Quartz Glass-Ceramics

Metastable solid solutions with the β-quartz structure can be crystallized from most glasses in the system SiO₂-Mg(AlO₂)₂-LiAlO₂ as well as from many containing the additional components Zn(AlO₂)₂ Al(AlO₂)₃, Li₂ZnO₂, and Li₂BeO₂. Internal nucleation is afforded by additions of ZrO₂ or TiO₂. Either transparent or opaque crystalline materials can be formed from glasses containing about 70% SiO₂. The transparency is due to a combination of low birefringence in the major stuffed β-quartz phase and minute crystal size. Thermal expansions vary from -20 to +50 × 10⁻⁷/°C. Thermal stability is highly variable. Breakdown products include spinel, cordierite, β-spodumene, willemite, mullite, and cristobalite. Magnesian compositions can be strengthened by a 2Li⁺⇌ Mg²⁺ ionexchange reaction. Abraded flexural strengths range from 30,000 to 160,000 psi.     

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.     

Sinterability of β-Calcium Orthophosphate Powder Prepared by Spray-Pyrolysis

Mixed solutions of Ca(NO₃)₂ and (NH₄)₂HPO₄ with Ca/P = 1.50 were spray-pyrolyzed at 600°C to produce β-calcium orthophosphate (β-Ca₃(PO₄)₂) powder; the spray-pyrolyzed powder was ground and then calcined at 600°C for 1 h. The best crystalline β-Ca₃(PO₄)₂ powder was obtained from the solution with 1.80 mol.L^–1 Ca(NO₃)₂, 1.20 mol.L^–1 (NH₄)₂HPO₄. The resulting powder was composed of primary particles with sizes of <0.5 μm. Dense β-Ca₃(PO₄)₂ ceramics with a relative density of 96.1% could be fabricated by firing this compressed powder at 1070°C for 5 h.     

Low-Temperature Sintering and Piezoelectric Properties of (Na0.5K0.5)NbO3 Lead-Free Piezoelectric Ceramics

(Na_0.5K_0.5)NbO₃ (NKN) ceramic with 1.5 mol% CuO added (NKNC) was well sintered even at a low temperature of 900°C with the addition of ZnO. Most of the ZnO reacted with the CuO and formed the liquid phase that assisted the densification of the specimens at 900°C. A few Zn²⁺ ions entered the matrix of the specimens and increased the coercive field ( E _c) and Q _m values of the specimens. High-piezoelectric properties of k _p=0.37, Q _m=755, and ɛ₃ ^T /ɛ₀=327 were obtained from the NKNC ceramics containing 1.0 mol% ZnO sintered at 900°C for 2 h.     

Novel Preparation Method of Hydroxyapatite Fibers

A novel method for preparing calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂: HAp) fibers has been developed. HAp fibers can be prepared successfully by heating a compact consisting of calcium metaphosphate (ß-Ca(PO₃)₂) fibers with Ca(OH)₂ particles in air at 1000°C and subsequently treating the resultant compact with dilute aqueous HCl solution. The ß-Ca(PO₃)₂ fibers and the Ca(OH)₂ in the compact were converted into fibrous HAp and CaO phases by the heating, and the CaO phase was removed by acid-leaching. HAp fibers obtained in the present work were 40-150 µm in length and 2-10 µm in diameter. The fibers had almost the same dimensions as those of the ß-Ca(PO₃)₂ fibers.     

Effect of CuO on the Sintering Temperature and Piezoelectric Properties of (Na0.5K0.5)NbO3 Lead-Free Piezoelectric Ceramics

When a small amount of CuO was added to (Na_0.5K_0.5)NbO₃ (NKN) ceramics sintered at 960°C for 2 h, a dense microstructure with increased grains was developed, probably due to liquid-phase sintering. The Curie temperature slightly increased when CuO exceeded 1.5 mol%. The Cu²⁺ ion was considered to have replaced the Nb⁵⁺ ion and acted as a hardener, which increased the E _c and Q _m values of the NKN ceramics. High piezoelectric properties of k _p=0.37, Q _m=844, and ɛ₃ ^T /ɛ₀=229 were obtained from the specimen containing 1.5 mol% of CuO sintered at 960°C for 2 h.     

Synthesis of Compositionally Homogeneous Sr(CuxZn1−x)1/2W1/2O3

A complex perovskite of Sr(Cu _x Zn_{1- x} )_1/2 W_1/2O₃ (SCZW) is synthesized by a new combination of wet and dry processess. Mixed oxides containing Cu²⁺ and Zn²⁺ (CZ) are prepared by the wet process (coprecipitate method). SCZW is obtained by the dry process (mixed-oxide method) from a mixture of CZ, SrCO₃, and WO₃. SCZW has practically no compositional, unlike solid solutions prepared by the conventional dry method. The wet–dry process method is useful because the wet process is applied to only B-site cations having the same valence.     

Optical Properties of Dysprosium-Doped Low-Phonon-Energy Glasses for a Potential 1.3 μm Optical Amplifier

Dysprosium-doped glasses were prepared in the system of gallium-based sulfide, tellurite, zirconium-baed and indium-based fluorides and their optical properties were studied. From the absorption cross sections of five f-f bands, three Judd-Ofelt parameters, ω _t ( t = 2, 4, 6), of Dy³⁺ ion were determined. The compositional variaton of the ω₂value showed the order sulfide > tellurite > fluorozirconate > fluoroindate, whereas the ω₆ value showed the opposite tendency. Compositional variaton of the fluorescence intensity ratio of the (⁴F_9/2⁶H_13/2)/(⁴F_9/2)→⁶H_15/2) is explained by the ratio of ω₂/ω₆ of doped Dy³⁺. The emission probabilities A and the branching ratio β from ⁶H_9/2 and ⁶F_11/2 levels, which are the doublet initial level of the 1.3 μm luminescence, were calculated for the glasses, and it was found that both values showed a tendency similar to that of ω₂ against the glass composition. In the sulfide glass, A was 2.6 × 10³S^-1 and β was 93%, both the highest in all of the glasses investigated. By 1.06 μm pumping of a Nd: YAG laser, the sulfide glass showed strong 1.3 μm emission and the lifetime was 25 μs, resulting in a quantum efficiency of 7%. This value is higher than that of the Pr³⁺:¹G₄ level in ZBLAN glass with β= 60%.     

Introducing Compressive Surface Stresses into Brittle Materials

Sodium β-Al₂O₃ changes its molar volume upon ion exchange. This effect can be utilized to introduce surface compression into brittle matrices. Experiments are reported wherein spinel/20 vol% Na-β-Al₂O₃ and glass/20 vol% Na-β-Al₂O₃ composites containing constrained Na-β-Al₂O₃ particles underwent Na⁺ to K⁺ ion exchange in KNO₃ melts and thereafter exhibited shorter Vickers microindentation cracks.     

Anisotropic Thermal Expansion of β-Ca2SiO4 Monoclinic Crystal

Crystals of β-Ca₂SiO₄ (space group P 12₁/ n 1) were examined by high-temperature powder X-ray diffractometry to determine the change in unit-cell dimensions with temperature up to 645°C. The temperature dependence of the principal expansion coefficients (α_i) found from the matrix algebra analysis was as follows: α₁= 20.492 × 10⁻⁶+ 16.490 × 10⁻⁹ ( T - 25)°C⁻¹, α₂= 7.494 × 10⁻⁶+ 5.168 × 10⁻⁹( T - 25)°C⁻¹, α₃=−0.842 × 10⁻⁶− 1.497 × 10⁻⁹( T - 25)°C⁻¹. The expansion coefficient α₁, nearly along [302] was approximately 3 times α₂ along the b -axis. Very small contraction (α₃) occurred nearly along [     01]. The volume changes upon martensitic transformations of β↔α_L' were very small, and the strain accommodation would be almost complete. This is consistent with the thermoelasticity.     

Conduction and Dielectric Loss Mechanisms in β-Alumina and Glass: A Discussion Based on the Paired Interstitialcy Model

A paired interstitialcy model is used as a basis for qualitative comparisons of conductivity and dielectric phenomena in β-alumina crystals and in glass. Thus, the increase in the conductivity of sodium silicate glasses with increasing Na₂O activity can be explained if the concentration of (Na₂*)²⁺ interstitial pairs increases with increased polarizability of O^2- ions, expressed in terms of the optical basicity parameter, Δ. Similarly, the occurrence of the pronounced minima in conductivity isotherms (the mixed-alkali effect in glass) is attributed to disappearance of mobile interstitial pairs, e.g. (Li₂*)²⁺ or (K₂*)²⁺, and the stabilization (by polarization interactions) of apparently immobile mixed-alkali pairs, (LiK*)²⁺. The phenomenon of coionic conduction in certain β-alumina crystals is an interesting departure from this general pattern. The orientation dependence of the electrical modulus spectrum of monocrys-talline β-alumina highlights the presence of a bimodal distribution of relaxation times, in which the low-frequency component ( v ₀=10¹¹ Hz) may arise from the rearrangement of interstitial pairs and the high-frequency component ( v ₀=2×10¹² Hz) may arise from less hindered ionic motions. It is suggested that the motions of interstitial pairs and surrounding cations are mutually catalytic and that some form of combined motion is responsible for both the electrical and mechanical relaxations in β-alumina and glass.     

An Alternative Chemical Route for the Synthesis and Thermal Stability of Chemically Enriched Hydroxyapatite

Hydroxyapatite (HAp: Ca₁₀(PO₄)₆(OH)₂) was synthesized by aqueous precipitation using CaCl₂ and Na₃PO₄ with NaOH added to ensure completion of the reaction at room temperature. The HAp powder prepared using stoichiometric amounts of NaOH was stable even at 1200°C, but the HAp prepared with sub-stoichiometric amounts of NaOH resulted in its transformation into β-tricalcium phosphate at 600°C. The reaction pH, X-ray diffraction, thermal analysis, scanning electron microscopy, Fourier transform infrared analyses and inductively coupled plasma-optical emission spectroscopy were used to characterize the phase purity, thermal stability, morphology, and chemical composition of the synthesized HAp powder.     

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.     

Reinforcement of Hydroxyapatite Bioceramic by Addition of Ni3Al and Al2O3

The effects of Ni₃Al and Al₂O₃ additions on the mechanical properties of hydroxyapatite (HAp) were investigated. The addition of Ni₃Al particles increased the strength as well as the fracture toughness of HAp. However, the improvements in the properties were limited because of the formation of microcracks around the metal particles. The microcracks were formed because of the large difference in the coefficients of thermal expansion between HAp and Ni₃Al, and because of the relatively large size of Ni₃Al particles (∼20 µm). The addition of submicrometer Al₂O₃ powder was also effective in increasing the mechanical properties. The flexural strength and the fracture toughness were increased from about 100 MPa and 0.7 MPam^1/2, respectively, to 200 MPa and 1.5 MPam^1/2 by the addition of 20 vol% Al₂O₃. When Ni₃Al and Al₂O₃ were added together, the fracture toughness was further increased to 2.3 MPam^1/2. This increase in the fracture toughness was attributed to the synergistic effect of matrix strengthening and crack interactions with the metal particles.     

Studies in Lithium Oxide Systems: XIII, Li,O.Al2O3.2SiO2-Li2O.Al2O3.2GeO2

Complete solid solubility was demonstrated to occur between LiAlGeO₄ and the low temperature form of Li AlSiO₂ (a-eucryptite). Hydrother-mal preparation was necessary for the silicate-rich compositions. Under atmospheric pressure, about 65 mole % LiAlGeO₄ entered the β-eucryβ-tite phase at 1150°C, but solid solutions containing more than 25 mole % LiAlGeO4 exsolved if held at lower temperatures. Directional thermal expansion data were obtained by X-ray diffraction methods on both α- and β-eucryptite and their solid solutions. Substitution of Ge⁴⁺ for Si⁴⁺ produced no significant difference in the thermal expansion coefficients in the α and β phases. An increase in the lattice parameters in the a and c directions took place as expected when Ge⁴⁺ (0.53 A) was substituted for Si⁴⁺ (0.39 A).     

Structure Change in Strontium Oxide-Doped Dicalcium Silicates

A series of strontium-bearing dicalcium silicate (Ca₂Si0₄ solid solutions (C₂S( ss )), (Sr_χCa_1-χ)₂SiO₄ with 0.02 ≤χ≤ 0.10, was prepared and examined by powder X-ray diffrac-tometry. These crystals, heated in the stable-temperature region of the α phase and then quenched in water, were composed of the β phase, with χ≤ 0.08, and the α'_L and β phases, with χ= 0.10. With increasing x, the unit-cell axes of the β phase expanded and the β angle became small with eventual increase in the unit-cell volume. The Rietveld analysis of the β-C₂S( ss ) with χ= 0.08 showed that the Sr²⁺ ions preferentially occupied the seven-coordinated site rather than the eight-coordinated site. This site preference, which was originally established in the parent α-phase structure, seemed to cause the systematic change in the cell dimensions.     

Chemical Strengthening of Glass-Ceramics in the System Li2O-Al2O3-SiO2

Fine-grained glass-ceramics containing a large proportion of β-spodumene solid-solution crystals were strengthened by immersion in molten sodium and potassium salt baths. An ion-exchange reaction placed sodium or potassium ions in lithium ion sites in the β-spodumene structure. The resultant "crowding" of the structure produced a surface compressive layer. In this system, strengths (modulus of rupture on abraded specimens) in excess of 100,000 psi were realized. In a similar manner, stuffed β-quartz solid-solution glass-ceramics derived from the crystallization of Li₂O-Al₂O₃-SiO₂ glasses containing an appropriate amount of nucleating agent were strengthened by K⁺-for-Li⁺ exchange. Stable β-quartz solid-solution glass-ceramics were strengthened by Na⁺-for-Li⁺ exchange, but no significant increase in strength was obtained in the metastable β-quartz materials.     

Pr3+/Er3+ Codoped Ge-As-Ga-S Glasses as Dual-Wavelength Fiber-optic Amplifiers for 1.31 and 1.55 μm Windows

Fluorescence emissions at both 1.31 and 1.55 μm communication windows were observed from Pr³⁺/Er³⁺ codoped Ge-As-Ga-S glasses with a single wavelength pumping at 986 nm. The lifetime of the Er³⁺:⁴ I _11/2 level decreased as the Pr³⁺ concentration increased, and that of the Pr³⁺:¹ G ₄ level increased as the Er³⁺ concentration increased. Energy transfer from the Er³⁺:⁴ I _11/2 level to the Pr³⁺:¹ G ₄ level was responsible for emission of the 1.31 μm fluorescence from the Pr³⁺:¹ G ₄ level. Ge-As-Ga-S glasses that have been doped with Pr³⁺ and Er³⁺ cations are promising amplifier materials for both 1.31 and 1.55 μm communication windows.