Synthesis of characterization of ZnxTiyS and its photocatalytic activity for hydrogen production from methanol/water photo-splitting

In order to enhance the production of hydrogen, a new system based on a Zn_xTi_yS photocatalyst is investigated. Zn_xTi_yS (x = 1, 0.95, 0.9, 0.85, 0.8 mol and y = 0, 0.05, 0.1, 0.15, 0.2 mol, respectively) is prepared using thiourea (H₂NCSNH₂). The formed Zn_xTi_yS particles are globular, ～6 μm in diameter, and composed of small spherical particles about 600 nm in diameter. The Zn_xTi_yS particles absorb at wavelengths above 380 nm in the UV-region like TiO₂. The evolution of H₂ by methanol/water (1:1) photo-splitting over Zn_xTi_yS in a methanol/water system is dramatically enhanced versus pure ZnS. In particular, 4.0 mmol of H₂ gas is produced in 10 h when 1.0 g of Zn_0.9Ti_0.1S was used, and its performance increases in KOH solutions. Based on cyclic voltammetry (CV) and UV–vis spectroscopy measurements, the high photo-activity of Zn_0.9Ti_0.1S is attributed to the existence of a band-gap that includes the redox potential of water.     

Synthesis,structure and oxygen thermally programmed desorption spectra of La1−xCaxAlyFe1−yO3−δ perovskites

Perovskites La_1−xCa_xAl_yFe_1−yO_3−δ (x, y = 0 to 1) were prepared by high-temperature solid-state synthesis based on mixtures of oxides produced by colloidal milling. The XRD analysis showed that perovskites La_0.5Ca_0.5Al_yFe_1−yO_3−δ with a high Fe content (1 − y = 0.8–1.0) were of orthorhombic structure, perovskites with a medium Fe content (1 − y = 0.8–0.5) were of rhombohedral structure, and perovskite with the lowest Fe content (1 − y = 0.2) were of cubic structure. Thermally programmed desorption (TPD) of oxygen revealed that chemical desorption of oxygen in the temperature range from 200 to 1000 °C had proceeded in the two desorption peaks. The low-temperature α-peak (in the 200–550 °C temperature range) was brought about by oxygen liberated from oxygen vacancies; the high-temperature β-peak (in the 550–1000 °C temperature range) corresponded to the reduction of Fe⁴⁺ to Fe³⁺. The chemidesorption oxygen capacity increased with increasing Ca content and decreased with increasing Al content in the perovskites. The Al³⁺ ions restricted, probably for kinetic reasons, the reduction of Fe⁴⁺ and the high-temperature oxygen desorption associated with it.     

Microwave dielectric properties of (Ba1−xSrx)(Mg0.5W0.5)O3 ceramics

The densification, microstructural evolution and microwave dielectric properties of (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics with x=0, 0.25, 0.5 and 0.75 are investigated in this study. The sintering temperature of the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ is significantly reduced from 1575 °C to 1400 °C as the x value increases from 0 to 0.25 and 0.50; this result is accompanied by the formation of the (Ba_1−ySr_y)WO₄ phase and a small quantity of second phase surrounding the grains. The grain size of the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics is increased by raising the Sr²⁺ content, which significantly lowers the sintering temperature. The microstructure of the (Ba_0.75Sr_0.25)(Mg_0.5W_0.5)O₃ ceramic displays the smallest average grain size of approximately 0.8 μm, with a narrow grain size distribution. Without long annealing time, very high Q×f values are obtained for the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics sintered at 1400–1575 °C for a duration of only 2 h. The (Ba_0.75Sr_0.25)(Mg_0.5W_0.5)O₃ ceramic sintered at 1400 °C results in the best microwave dielectric properties, including ε_r of 20.6, Q×f of 152,600 GHz and τ_f of +24.0 ppm/°C.     

Oxygen ionic transport in SrFe1−yAlyO3−δ and Sr1−xCaxFe0.5Al0.5O3−δ ceramics

The oxygen permeability of mixed-conducting Sr_1−xCa_xFe_1−yAl_yO_3−δ (x=0–1.0; y=0.3–0.5) ceramics at 850–1000 °C, with an apparent activation energy of 120–206 kJ/mol, is mainly limited by the bulk ionic conduction. When the membrane thickness is 1.0 mm, the oxygen permeation fluxes under pO₂ gradient of 0.21/0.021 atm vary from 3.7×10⁻¹⁰ mol s⁻¹ cm⁻² to 1.5×10⁻⁷ mol s⁻¹ cm⁻² at 950 °C. The maximum solubility of Al³⁺ cations in the perovskite lattice of SrFe_1−yAl_yO_3−δ is approximately 40%, whilst the brownmillerite-type solid solution formation range in Sr_1−xCa_xFe_0.5Al_0.5O_3−δ system corresponds to x>0.75. The oxygen ionic conductivity of SrFeO₃-based perovskites decreases moderately on Al doping, but is 100–300 times higher than that of brownmillerites derived from CaFe_0.5Al_0.5O_2.5+δ. Temperature-activated character and relatively low values of hole mobility in SrFe_0.7Al_0.3O_3−δ, estimated from the total conductivity and Seebeck coefficient data, suggest a small-polaron mechanism of p-type electronic conduction under oxidising conditions. Reducing oxygen partial pressure results in increasing ionic conductivity and in the transition from dominant p- to n-type electronic transport, followed by decomposition. The low-pO₂ stability limits of Sr_1−xCa_xFe_1−yAl_yO_3−δ seem essentially independent of composition, varying between that of LaFeO_3−δ and the Fe/Fe_1−γO boundary. Thermal expansion coefficients of Sr_1−xCa_xFe_1−yAl_yO_3−δ ceramics in air are 9×10⁻⁶ K⁻¹ to 16×10⁻⁶ K⁻¹ at 100–650 °C and 12×10⁻⁶ K⁻¹ to 24×10⁻⁶ K⁻¹ at 650–950 °C. Doping of SrFe_1−yAl_yO_3−δ with aluminum decreases thermal expansion due to decreasing oxygen nonstoichiometry variations.     

Production and properties of substituted LaFeO3-perovskite tubular membranes for partial oxidation of methane to syngas

Tubular membranes of La_0.6Ca_0.4Fe_0.75Co_0.25O_3−δ and La_0.5Sr_0.5Fe_1−yTi_yO_3−δ (y = 0, 0.2) for the application of partial oxidation of methane to syngas were produced by thermoplastic extrusion and investigated by oxygen permeation measurements. The optimum ceramic content in the feedstock for extrusion was found to be 51 vol% as a result of rheology measurements. Tubes with an outer diameter of 4.8–5.5 mm and thickness of 0.25–0.47 mm were produced with densities higher than 95% of the theoretical density. The oxygen permeation flux of the tubular membranes was measured with air on one side and Ar or Ar + CH₄ mixture on the other side. The oxygen permeation rate decreased with Ti-substitution while it was considerably increased by introduction of 5% methane into the system. The normalized oxygen fluxes in air/Ar gradient at 900 °C were measured to be 0.06, 0.051, and 0.012 μmol cm⁻² s⁻¹ for LCFC, LSF, and LSFT2, respectively, and 0.18 μmol cm⁻² s⁻¹ for LSFT2 with 5% methane.     

Dielectric and Magnetic properties of (1 − x)BiFeO3–xBa0.8Sr0.2TiO3 ceramics

The polycrystalline samples of (1 ? x)BiFeO₃–xBa_0.8Sr_0.2TiO₃ (x = 0, 0.1, 0.2, 0.25, 0.3, 0.4 and x = 1) were prepared by the conventional solid state reaction method. The effect of substitution in BiFeO₃ by Ba_0.8Sr_0.2TiO₃ on the structural, dielectric and magnetic properties was investigated. X-ray diffraction study showed that these compounds crystallized at room temperature in the rhombohedral distorted perovskite structure for x ≤ 0.3 and in cubic one for x = 0.4. As Ba_0.8Sr_0.2TiO₃ content increases, the dielectric permittivity increases. This work suggests also that the Ba_0.8Sr_0.2TiO₃ substitution can enhance the magnetic response at room temperature. A remanent magnetization M_r and a coercive magnetic field H_C of about 0.971 emu/g and 2.616 kOe, respectively were obtained in specimen with composition x = 0.1 at room temperature.     

Continuous hydrothermal synthesis of Ca1−xSrxTiO3 solid-solution nanoparticles using a T-type micromixer

In this work, a continuous hydrothermal synthesis method in supercritical water was applied to environmentally benign production of Ca_1−xSr_xTiO₃ (x = 0.0–1.0) solid-solution nanoparticles as key materials in conducting, electric, magnetic, and photocatalytic fields. A T-type micromixer (330 μm id) was introduced for rapid heating of stating solutions of Ca(NO₃)₂, Sr(NO₃)₂, and TiO₂ sol using turbulent flow mixing with preheated NaOH aqueous solution and also for exact control of reaction temperature. At 673 K and 30 MPa for 5.0 s mean residence time, Ca_1−xSr_xTiO₃ solid-solution nanoparticles having crystallite diameters of around 20 nm with monomodal diameter distributions were obtained without byproducts and production of CaTiO₃ and SrTiO₃ separately over the whole composition range. Effects of NaOH molality, Ca and Sr compositions in the starting solutions, and mean residence time on the reaction were examined. The results showed that TiO₂ sol dissolution and Ca_1−xSr_xTiO₃ precipitation were almost finished within 0.25 s mean residence time, and after that Ostwald ripening proceeded.     

Optimized piezoelectric and structural properties of (Bi,Na)TiO3–(Bi,K)TiO3 ceramics for energy harvester applications

We investigated (1−x)(Bi,Na)TiO₃–x(Bi,K)TiO₃ (x=0, 0.14, 0.16, 0.18, 0.20, and 0.22) compositions of lead-free piezoelectric ceramics for potential energy harvester applications. Composition and sintering temperature of (1−x)(Bi,Na)TiO₃–x(Bi,K)TiO₃ were varied to extract the optimized processing temperature with each composition. We compared and analyzed sintering temperature-dependent surface morphologies and electrical properties. Maximum piezoelectric charge constant of 180 pC/N were obtained from the 0.8(Bi,Na)TiO₃–0.2(Bi,K)TiO₃composition at the sintering temperature of 1180 °C. Temperature dependent dielectric permittivity was measured to know the phase transition. We corresponded two different anomaly peaks, observed at 84 and 290 °C, as the rhombohedral-tetragonal and tetragonal-cubic phase transitions, respectively. Due to these phase transitions, different shapes of polarization-electric field loops (P-E loops) were measured and compared. Finally, output power of 42.39 nW/cm² were obtained for the (1−x)(Bi,Na)TiO₃–x(Bi,K)TiO₃ lead free piezoelectric ceramics.     

Effects of microwave sintering on the properties of 0.87(Mg0.7Zn0.3)TiO3–0.13(Ca0.61La0.26)TiO3 ceramics

0.87(Mg_0.7Zn_0.3)TiO₃–0.13(Ca_0.61La_0.26)TiO₃ (referred to as 87MZCLT) ceramics were prepared by microwave sintering and conventional sintering. The experimental results demonstrated that the sintering cycle of 87MZCLT ceramics was greatly shortened and the impurity phase (Mg_0.7Zn_0.3)Ti₂O₅ was eliminated by microwave sintering. Moreover, the 87MZCLT ceramics prepared by microwave sintering show more uniform, fine-grained microstructure as well as much less Zn evaporation. As a result, the quality factor was increased by 40% compared with conventional sintering. All samples were sintered at 1275 °C for 20 min with heating and cooling rate of 15 °C/min and gave excellent microwave dielectric properties: ?_r = 26.21, Q × f = 120,000 GHz, τ_f = ?3 ppm/°C.     

Effect of Zn2+ substitution on the microwave dielectric properties of LiMgPO4 and the development of a new temperature stable glass free LTCC

The LiMg_(1?x)Zn_xPO₄ ceramics have been prepared by the solid state ceramic route. The LiMg_(1?x)Zn_xPO₄ ceramic retains the orthorhombic structure up to x = 0.2. The compositions with 0.3 ≤ x ≤ 0.8 exist as a mixture of orthorhombic and monoclinic phases. When Mg²⁺ is fully replaced with Zn²⁺ (x = 1.0) complete transition to monoclinic phase occurs. The ceramic with x = 0.1 (LiMg_0.9Zn_0.1PO₄) sintered at 925 °C exhibits low relative permittivity (?_r) of 6.7, high quality factor (Q_u × f) of 99,700 GHz with a temperature coefficient of resonant frequency (τ_f) of ?62 ppm/°C. The slightly large τ_f is adjusted nearly to zero with the addition of TiO₂. LiMg_0.9Zn_0.1PO₄–TiO₂ composite with 0.12 volume fraction TiO₂ sintered at 950 °C shows good microwave dielectric properties: ?_r = 10.1, Q_u × f = 52,900 GHz and τ_f = ?5 ppm/°C. The ceramic is found to be chemically compatible with silver.     

Catalytic activity of nanometer La1−xSrxCoO3 (x = 0, 0.2) perovskites towards VOCs combustion

Combustive oxidation of volatile organic compounds (VOCs), such as propyl alcohol, toluene and cyclohexane, were studied. The combustion was catalyzed by nanoparticles of La_1−xSr_xCoO₃ (x = 0, 0.2) perovskites prepared by a co-precipitation method. The results showed high activities of the perovskite catalysts. Compared to LaCoO₃, in particular, La_0.8Sr_0.2CoO₃ was much higher in catalytic ability. The total oxidation of VOCs followed the increasing order: cyclohexane < toluene < propyl alcohol. The T_99% of cyclohexane was 40 °C lower than that of toluene, which appeared to be determined by the bond strengths of the weakest C–H and C–C bonds. The 100-h stability experiments showed that La_1−xSr_xCoO₃ (x = 0, 0.2) perovskite was highly stable.     

High-temperature thermoelectric properties of polycrystalline Zn1−x−yAlxTiyO ceramics

The as-sintered Zn_1−xAl_xO (0 ≤ x ≤ 0.05) samples crystallized in the ZnO with a wurtzite structure, along with a small amount of the cubic spinel ZnAl₂O₄. The addition of Al₂O₃ to ZnO gave rise to a decrease in grain size, ranging from 7.3 to 2.7 μm and in relative density, ranging from 99.2 to 90.1% of the theoretical density. In the Zn_0.97Al_0.03−yTi_yO samples, as the amount of TiO₂ increased, the grain size of ZnO grains and second phases, such as Zn₂TiO₄ and ZnAl₂O₄, as well as density increased. The co-doping of Al and Ti led to a significant increase in both the electrical conductivity and the absolute value of the Seebeck coefficient, resulting in an increase in the power factor. The highest value of power factor (3.8 × 10⁻⁴ W m⁻¹ K⁻²) was attained for Zn_0.97Al_0.02Ti_0.01O at 800 °C. It is demonstrated that the Al and Ti co-doping is fairly effective for enhancing thermoelectric properties.     

Combustion synthesis and EIS characterization of TiO2–SnO2 system

TiO₂ is an insulator, but using specific dopants, can modify sharply its electronic structure towards semiconducting behavior. This type of response is widely applied in many electrochemical and electrocatalytical devices, namely chlorine production, hydrocarbon oxidation, CO and CO₂ hydrogenation and as electroactive substrata for biological cell growth.Combustion synthesis is a very simple, rapid and clean method for material preparation, which will be used in the preparation of the (1 − x)TiO₂–xSnO₂, x = 0.05–0.3. Tin oxalate and titanium isopropoxide are used as precursors for the synthesis. The as-prepared powders are fine and homogeneous, the average particle size is in the range of 5–10 nm, powders and ceramic compact bodies are characterized by DRX, SEM–TEM–EDX, DTA–TG and EIS. The impedance spectroscopy of the sample 10 mol% of SnO₂ indicates the presence of several phases which promote a matrix composite based in an electrical TiO₂ insulator compatible with an electronic conducting phase tin rich. This could be attributed to the spinodal decomposition effect observed in TiO₂–SnO₂ system.     

Microstructure and microwave-frequency electromagnetic properties of Ni0.4Zn0.6Fe2O4/Ba0.6Sr0.4TiO3 composites

(x)Ni_0.4Zn_0.6Fe₂O₄+(1−x)Ba_0.6Sr_0.4TiO₃ composite ceramics with x=0.6, 0.7, 0.8, 0.9 and 1 were synthesized by solid state reaction method. The high dense composites have only two phases, i.e., Ni_0.4Zn_0.6Fe₂O₄ and Ba_0.6Sr_0.4TiO₃. The permittivity ε′ of the composites decreases slightly with the frequency increasing from 3 MHz to 1 GHz. The permittivity ε′′ of the composites also shows a little increase with frequency in the 3 MHz–1 GHz range. The permeability displays a relaxation resonance within the 3 MHz–1 GHz frequency range. The permeability μ′ increases while the cut-off frequency decreases with the Ni_0.4Zn_0.6Fe₂O₄ concentration, obeying the Snoek's law μ_if_r=constant. The permittivity ε′ of the composites decreases with Ni_0.4Zn_0.6Fe₂O₄ concentration. The composites have a relatively higher ε′ than the pure Ni_0.4Zn_0.6Fe₂O₄ at 1–10 GHz. In the frequency range of 1–10 GHz, the magnetic permeability μ′ reaches its maximum and μ′′ shows a minimum for the composite with x=0.6 in all ceramics. The permeability μ′ of the composites decreases with dc magnetic field at 1–10 GHz. The permeability shows a domain wall resonance, and the resonance frequency shifts to high frequency with the dc magnetic field. The permittivity was also influenced by the dc magnetic field due to a magnetodielectric effect.     

Crystal structure,thermal expansion and electrical conductivity of perovskite oxides BaxSr1−xCo0.8Fe0.2O3−δ (0.3 ≤ x ≤ 0.7)

Ba_xSr_1−xCo_0.8Fe_0.2O_3−δ (0.3 ≤ x ≤ 0.7) composite oxides were prepared and characterized. The crystal structure, thermal expansion and electrical conductivity were studied by X-ray diffraction, dilatometer and four-point DC, respectively. For x ≤ 0.6 compositions, cubic perovskite structure was obtained and the lattice constant increased with increasing Ba content. Large amount of lattice oxygen was lost below 550 °C, which had significant effects on thermal and electrical properties. All the dilatometric curves had an inflection at about 350–500 °C, and thermal expansion coefficients were very high between 50 and 1000 °C with the value larger than 20 × 10⁻⁶ °C⁻¹. The conductivity were larger than 30 S cm⁻¹ above 500 °C except for x > 0.5 compositions. Furthermore, conductivity relaxation behaviors were also investigated at temperature 400–550 °C. Generally, Ba_0.4Sr_0.6Co_0.8Fe_0‘2O_3−δ and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ are potential cathode materials.     

Rapid synthesis of low thermal expansion materials of Ca1−xSrxZr4P6O24

A rapid synthesis method is introduced for the synthesis of low thermal expansion materials of Ca_1?xSr_xZr₄P₆O₂₄ (x = 0, 0.5 and 1) and optimum synthesizing conditions are obtained. It is shown that these materials can be synthesized by one-step sintering by putting the preheated mixture of CaCO₃, SrCO₃ and NH₄H₂PO₄ directly into a pipe furnace at the sintering temperature (1673–1873 K). With this method, the sintering procedure is much simplified and sintering time and energy exhausts are considerably reduced with respect to the conventional solid state reactions which usually require multiple-step and longer time sintering at different temperatures with intermediate grindings for the synthesis of these materials. By putting the samples directly at the sintering temperature, the formation of the secondary phase ZrP₂O₇ can be largely avoided. This insures the rapid synthesis of Ca_1?xSr_xZr₄P₆O₂₄. MgO is introduced to increase the density of Ca_0.5Sr_0.5Zr₄P₆O₂₄ ceramics. A sintered density of 3.10 g cm^?3, relative density of 96.2% for Ca_0.5Sr_0.5Zr₄P₆O₂₄ is obtained with 1.0 wt.% MgO. The coefficients of thermal expansion are about 0.27 × 10^?6 K^?1. Raman spectroscopic and differential scanning calorimetry (DSC) analyses reveal that there are no phase transitions of all the samples from 113 K to 1423 K.     

Low temperature sintering of ZnTiO3/TiO2 based dielectric with controlled temperature coefficient

Structure, microstructure and dielectric properties of ZnTiO₃ and rutile TiO₂ mixtures (ZnTiO₃ + xTiO₂ with x = 0, 0.02, 0.05, 0.1, 0.15 and 0.2) sintered using ZnO–B₂O₃ glass phase (5 wt.% added) as sintering aid have been investigated. For all compounds, the sintering temperature achieves 900 °C. The X-ray diffraction patterns indicate for x = 0.1 that the material is composed by three phases identified as ZnTiO₃ hexagonal, TiO₂ rutile and ZnO. The presence of ZnO is explained by the introduction of Ti into Zn site to form the (Zn_1−xTi_x)TiO_3+x solid solution in resulting the departure of ZnO from the ZnTiO₃ structure. The ZnTiO₃ + 0.15TiO₂ composition sintered at 900 °C with glass addition exhibits attractive dielectrics properties (ɛ_r = 23, tan(δ) < 10⁻³ and a temperature coefficient of the dielectric constant near zero (τ_ɛ = 0 ppm/°C)) at 1 MHz. It is also shown that the introduction of TiO₂ allows to tune the temperature coefficient of the permittivity. All these properties lead this system compatible to manufacture silver based electrodes multilayer dielectrics devices.     

Characteristics of Cu and Mo-doped Ca3Co4O9−δ cathode materials for use in solid oxide fuel cells

In this study, Cu and Mo ions were doped in Ca₃Co₄O_9−δ to improve the electrical conductivity and electrochemical behavior of Ca₃Co₄O_9−δ ceramic and the performance of a solid oxide fuel cell (SOFC) single cell based on NiO-SDC/SDC/doped Ca₃Co₄O_9−δ-SDC were examined. Cu substitution in the monoclinic Ca₃Co₄O_9−δ ceramic effectively enhanced the densification, slightly increased the grain size, and triggered the formation of some Ca₃Co₂O₆; however, no second phase was found in porous Mo-doped Ca₃Co₄O_9−δ ceramics even when the sintering temperature reached 1050 °C. Substitution of Cu ions caused slight increase in the Co³⁺ and Co⁴⁺ contents and decrease in the Co²⁺ content; however, doping with Mo ions showed the opposite trend. Doping the Ca₃Co₄O_9−δ ceramic with a small amount of Cu or Mo increased its electrical conductivity. The maximum electrical conductivity measured was 218.8 S cm⁻¹ for the Ca₃Co_3.9Cu_0.1O_9−δ ceramic at 800 °C. The Ca₃Co_3.9Cu_0.1O_9−δ ceramic with a coefficient of thermal expansion coefficient of 12.1×10⁻⁶ K⁻¹ was chosen as the cathode to build SOFC single cells consisting of a 20 μm SDC electrolyte layer. Without optimizing the microstructure of the cathode or hermetically sealing the cell against the gas, a power density of 0.367 Wcm⁻² at 750 °C was achieved, demonstrating that Cu-doped Ca₃Co₄O_9−δ can be used as a potential cathode material for IT-SOFCs.     

Effects of Sr-doping on the giant magnetocaloric effect of EuTiO3

The magnetic properties and magnetocaloric effect of Eu_1−xSr_xTiO₃ (x=0–0.1) compounds are investigated. With slight Sr-doping, the ferromagnetic (FM) coupling significantly increased and FM exchange is dominant in the delicate balance. A giant reversible magnetocaloric effect (MCE) and large refrigerant capacity (RC) for Eu_1−xSr_xTiO₃ compounds were observed. The values of −ΔS_M^max are evaluated to be around 10 J/kg K under a magnetic field change of 1 T and 21 J/kg K under a magnetic field change of 2 T, respectively. But, the values of RC are increased with the more Eu in EuTiO₃ to be substituted by Sr. Therefore, the giant reversible MCE and large RC make the Eu_1−xSr_xTiO₃ compound a good candidate for magnetic refrigerant working at low-temperature and low-field.     

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.