Reversible Reaction with CO2 and Control of CO2 Absorption/Desorption Properties of Ba2(Fe1−xInx)2O5 Solid Solutions

Ba₂(Fe_1?xIn_x)₂O₅ was prepared by a solid‐state reaction under a N₂ flow. It was revealed that the solid solutions had a cubic perovskite structure with disordered oxygen vacancies at room temperature. Thermogravimetry and X‐ray diffraction measurements revealed that Ba₂(Fe_1?xIn_x)₂O₅ can reversibly react with CO_2. It was found that the equilibrium temperature of the reaction could be controlled by preparing solid solution.     

High‐pressure synthesis of a 12CaO·7Al2O3–12SrO·7Al2O3 solid solution

Solid solutions of 12CaO·7Al₂O₃ (C12A7) and 12SrO·7Al₂O₃ (S12A7) crystals were synthesized under high pressure. X‐ray diffraction patterns revealed that the lattice constants of the synthesized samples depend linearly on the compositional ratio of C12A7 and S12A7. Electron‐probe X‐ray microanalyses show that the chemical compositions of the crystals are represented by xC12A7·(1?x)S12A7 (0<x<1). These results indicate that the variation in the lattice constants is originated from a difference in the ionic radii of Ca²⁺ and Sr²⁺ ions. From impedance measurements, it was found that S12A7 has the highest conductivity (~1 × 10^?3 Scm^?1 at 550°C) among the solid solutions in the C12A7–S12A7 system.     

Elucidating the Effect of Iron Speciation (Fe2+/Fe3+) on Crystallization Kinetics of Sodium Aluminosilicate Glasses

We report on the influence of Fe₂O₃ on the crystallization kinetics of nepheline (Na₂O·Al₂O₃·2SiO₂)‐based sodium aluminosilicate glasses. A series of glasses with varying Al₂O₃/Fe₂O₃ content were synthesized in the system 25Na₂O–(25–x) Al₂O₃–xFe₂O₃–50SiO₂ (x varies between 0 and 5 mol%) through melt‐quench technique. A systematic set of experiments were performed to elucidate the influence of iron speciation (Fe²⁺/Fe³⁺) on the crystallization kinetics of these glasses including: (1) obtaining the details of nonisothermal crystallization kinetics by differential scanning calorimetry, (2) determining the influence of heat treatment on the structure and iron coordination in glasses by X‐ray photoelectron spectroscopy and wet chemistry, and (3) following the crystalline phase evolution in glasses in air and inert environments by X‐ray diffraction and scanning electron microscopy. The crystallization of two polymorphs of NaAlSiO₄—carnegieite (orthorhombic) and nepheline (hexagonal)—was observed in all the glasses, wherein the incorporation of iron promotes the formation of nepheline over carnegieite while shifting the crystallization mechanism from surface to volume. The influence of environment (air versus inert) and iron content on the crystallization kinetics of these glasses is contextualized from the perspective of the devitrification problem usually observed in sodium‐ and alumina‐rich high level nuclear waste glasses.     

The Synthesis of Ba‐ and Fe‐ Substituted CsAlSi2O6 Pollucites

Barium‐substituted CsAlSi₂O₆ pollucites, Cs_xBa_(1?x)/2AlSi₂O₆, and barium‐ and iron‐substituted pollucites, Cs_xBa_(1?x)/2Al_xFe_1?xSi₂O₆ and Cs_xBa_1?xAl_xFe_1?xSi₂O₆ were synthesized with 1 ≥ x≥ 0.7 using a hydrothermal synthesis procedure. Rietveld analysis of X‐ray diffraction data confirmed the substitution of Ba for Cs and Fe for Al, respectively. The crystallographic analysis also describes the effects of three different types of pollucite substitutions on the pollucite unit cell: Ba²⁺ for Cs¹⁺ cation results in little effect on cell dimensions, intermediate concentrations of Ba²⁺ and Fe³⁺ substitution result in net minor expansion due to Fe³⁺ addition, and large Ba and Fe substitutions result in overall framework contraction. Elemental analysis combined with microscopy further supports the phase purity of these new phases. These materials can be used to study the stability of CsAlSi₂O₆ as a durable ceramic waste form, which could accommodate with time Cs and its decay product, Ba. Furthermore, success in iron substitution for aluminum into the pollucite lattice predicts that redox charge compensation for Cs cation decay is possible.     

Crystal Structure and Optical Performance of Al3+ and Ce3+ Codoped Ca3Sc2Si3O12 Green Phosphors for White LEDs

Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSS:Ce) green phosphors used for white light‐emitting diodes (LEDs) are synthesized and codoped with Al³⁺ via a solid‐state reaction method. The crystal structure and vibrational modes are analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, and Raman scattering spectroscopy. The energy transfer behavior and optical performance are characterized by photoluminescence and excitation spectra, quantum efficiency, and time‐resolved photoluminescence. The incorporation of Al³⁺ into CSS:Ce can inhibit the formation of the impurity phases Sc₂O₃ and CeO₂, improve crystallinity, and enhance the photoluminescence intensity as well as quantum efficiency. The substitution of Sc³⁺ with Al³⁺ increased the crystal field splitting of Ce³⁺ and resulted in the red shift of photoluminescence. The results show that Ca₃Sc_2?xAl_xSi₃O₁₂:Ce³⁺ has high quantum efficiency, making it a promising green phosphor that can be collocated with a commercial 450 nm blue LED and a red phosphor for solid‐state lighting applications.     

Statistical Optimization of the Biodiesel Production Process Using a Magnetic Core‐Mesoporous Shell KOH/Fe3O4@γ‐Al2O3 Nanocatalyst

A magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was synthesized using the Fe₃O₄@γ‐Al₂O₃ core‐shell structure as support and KOH as active component. The prepared samples were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDS), Fourier transform infrared (FTIR), Brunauer‐Emmett‐Teller (BET), and vibrating sample magnetometry (VSM) techniques. Transesterification of canola oil to methyl esters (biodiesel) in the presence of the magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was investigated. Response surface methodology (RSM) based on the Box‐Behnken design (BBD) was employed to optimize the influence of important operating variables on the yield of biodiesel. A biodiesel yield of 97.4 % was achieved under optimum reaction conditions. There was an excellent agreement between experimental and predicted results.     

Structure Evolution and Enhanced Microwave Dielectric Characteristics of (Sr1−xCax)La2Al2O7 Ceramics

(Sr_1?xCa_x)La₂Al₂O₇ (0.1 ≤ x ≤ 0.5) ceramics were prepared by a standard solid‐state reaction method. Their densification behavior and microwave dielectric properties were investigated together with the structural evolution. X‐ray diffraction analysis indicated that the major phase of Ruddlesden–Popper structure with n = 2 was obtained for all the compositions investigated here. Partial Ca substitution improved the sintering behavior of SrLa₂Al₂O₇ ceramics. More importantly, microwave dielectric characteristics were enhanced in (Sr_1?xCa_x)La₂Al₂O₇ ceramics with compositions of x = 0.1~0.3. The stacking fault was confirmed by TEM observation in the present ceramics, and the microwave dielectric loss was influenced by it. The best combination of microwave dielectric characteristics was achieved for the composition of x = 0.1: ε_r = 19.9, Qf = 135 400 GHz and τ_f = ?18.5 ppm/°C.     

Effect of Ca2+ Substitution on the Structure,Microstructure, and Microwave Dielectric Properties of Sr2Al2SiO7 Ceramic

The effect of Ca²⁺ substitution on the structure, microstructure, and microwave dielectric properties of Sr–gehlenite (Sr₂Al₂SiO₇) ceramic has been investigated. The structure and microstructure of Sr_2?xCa_xAl₂SiO₇ ceramics were analyzed via X‐ray diffraction (XRD) as well as scanning and transmission electron microscopic techniques. While the end‐members (x = 0 and 2) form isostructural compounds, a highly defective, nonstoichiometric, Ca‐rich secondary phase was observed via bright‐field transmission electron microscopy and energy dispersive X‐ray spectroscopy in compositions corresponding to x = 0.75 and 1.5. The concentration of secondary phase in x = 0.75 is too low to be detected via XRD or scanning electron microscopy. Identical selected‐area electron‐diffraction patterns of the compounds (x = 0, 1, and 2) confirmed that they belong to the space group P2₁m (no. 113) with tetragonal crystal symmetry. The porosity‐corrected relative permittivity at microwave frequencies showed a gradual increase with Ca²⁺ content; however, Ca²⁺ substitution made only marginal changes to the microwave dielectric properties except in the case of x = 1.5, in which the secondary phase reduced the quality factor considerably. Thermal conductivity decreased with increasing Ca²⁺ content, and the compounds with defective structures showed the lowest thermal conductivity. All the compounds exhibited low coefficients of linear thermal expansion, with values varying in the range 2.3–3.6 ppm/°C.     

Light‐induced electrons suppressed by Eu3+ ions doped in Ca11.94−xSrxAl14O33 caged phosphors for LED and FEDs

Control of light‐induced electron generation is of vital importance for the application of caged phosphors. For Eu‐doped Ca_11.94?xSr_xAl₁₄O₃₃ caged phosphors, the suppressed effect of strontium doping on the light‐induced electrons is observed compared to the europium‐free Ca_11.94?xSr_xAl₁₄O₃₃ phosphors. In the presence of europium ions, Sr doping will promote the reduction of Eu³⁺ to Eu²⁺. The Rietveld refinement suggests that unit cell volumes of the Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 samples are expanded when Ca²⁺ ions are replaced by Sr²⁺ ions. The absorption and FTIR transmittance spectra confirm that the competitive reaction of encaged O^2? anions with H₂ is suppressed. For the sample (x=0.48), the higher thermal activation energy (~0.40 eV) for luminescence quenching can be attributed to the more rigid framework structure after Sr doping. For Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 phosphors, their emission colours are tuned from red to purple upon 254 nm excitation and from pink to blue under electron beam excitation through Sr substitution. The insight gained from this work may have a significant guiding to design new phosphors for LED and FEDs and novel nanocaged mutifunctional materials.     

Structural elucidation and iron oxidation states in situ formed β‐Ca3(PO4)2/α‐Fe2O3 composites

A detailed structural analysis on the in situ synthesized β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites is demonstrated. Compositional ratios, the influence and occupancy of iron at the β‐Ca₃(PO₄)₂ lattice, oxidation state of iron in the composites are derived from analytical techniques involving XRD, FT‐IR, Raman, refinement of the powder X‐ray diffraction and X‐ray photoelectron spectroscopy. Iron exists in the Fe³⁺ state throughout the investigated systems and favors its occupancy at the Ca²⁺(5) site of β‐Ca₃(PO₄)₂ until critical limit, and thereafter crystallizes as α‐Fe₂O₃ at ambient conditions. Fe³⁺ occupancy at the β‐Ca₃(PO₄)₂ lattice yields a Ca₉Fe(PO₄)₇ structure that is isostructural with its counterpart. A strong rise in the soft ferromagnetic behavior of β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites is obvious that depends on the content of α‐Fe₂O₃ in the composites. Overall, the diverse level of iron inclusions at the calcium phosphate system with a Ca/P ratio of 1.5 yields a structurally stable β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites with assorted compositional ratios.     

Effect of Nonmagnetic Zn2+ Cations on Initial Permeability of Microwave‐Treated NiMg Ferrites

Magnesium is replaced systematically by zinc in Ni_0.2Mg_0.8‐xZn_xFe₂O₄ (x = 0.2–0.8) prepared by microwave‐assisted solid‐state reaction route. The structure is confirmed by X‐ray diffractograms. An improvement in initial permeability is observed with substituent in Ni_0.2Mg_0.8‐xZn_xFe₂O₄ due to increase in average grain size. The obtained permeability values are varying between 106 and 687 at 1 MHz. The permeability plots revealed that Curie‐transition temperature (T_c) is decreasing with increase in zinc. Both x = 0.2 and 0.4 compositions show low relative loss factor of order 10^?5 to 10^?4, which are exhibiting required magnetic properties for transformer and inductor core applications.     

Subsolidus Phase Relationship in the CaO–CuO–TiO2 Ternary System at 950°C in Air

The subsolidus phase relationship in the CaO–CuO–TiO₂ ternary system at 950°C in air was investigated. Total 26 samples having various nominal compositions were prepared by the solid‐state reaction at 950°C in air, and their equilibrium phases were analyzed by powder X‐ray diffraction (XRD). The CaCu₃Ti₄O₁₂ phase exhibits variable stoichiometry and forms as the Ca_1?xCu_3+xTi₄O₁₂‐type (?0.019 ≤x ≤0.048) solid solution at 950°C in air. On the basis of our results and previous reports on the binary phase diagrams, the subsolidus phase diagram of the CaO–CuO–TiO₂ ternary system could be constructed at 950°C in air.     

Atomic Scale Mechanisms of the Reduction of Nickel–Magnesium Aluminate Spinels

The dynamics of the reduction reaction of Ni_xMg_1?xAl₂O₄ to form nickel metal and a remnant oxide was quantified to understand spinel behavior in catalysis applications. X‐ray diffraction, thermogravimetry, and pycnometry were employed to track the evolution of high‐Ni spinels to metastable nonstiochiometric spinels during reduction, but before the phase transformation to theta alumina. Rietveld refinements of X‐ray diffraction data were used to quantify structural changes in the spinel and the phase fraction, crystallite size, and microstrain of all phases during H₂ reduction. During reduction, one O^2? is lost for each Ni²⁺ reduced to Ni metal. Ni_0.25Mg_0.75Al₂O₄ and Ni_0.5Mg_0.5Al₂O₄ were shown to form Ni metal and a non‐stoichiometric spinel of the same Mg‐Al ratio as the starting composition. NiAl₂O₄ and Ni_0.75Mg_0.25Al₂O₄ were found to become unstable as full reduction was approached, and metastable spinel, Θ‐Al₂O₃, and α‐Al₂O₃ formed sequentially given sufficient time at temperature.     

Variation of Band Gap and Lattice Parameters of β−(AlxGa1−x)2O3 Powder Produced by Solution Combustion Synthesis

Single‐phase monoclinic aluminum–gallium oxide powders, β?(Al_xGa_1?x)₂O₃, have been produced by solution combustion synthesis for Al fraction 0 ≤ x < 0.8. α?(Al_xGa_1?x)₂O₃ is observed for x = 1, with mixed α + β for x = 0.8. The contraction in lattice parameters and increase in band gap with increasing Al concentration were characterized by X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS), respectively, and are compared with a first‐principles density‐functional theory calculation. A novel filtering procedure is described to reduce the uncertainty involved in measuring band gap using photoemission, and to remove asymmetry in XPS line shapes caused by differential charging of loose powder. The lattice parameters vary linearly with Al fraction, but exhibit a change in slope at x = 0.5 that is attributed to the difference between aluminum occupying tetrahedral and octahedral sites in the monoclinic lattice. The band gap changes linearly with local stoichiometry, including increasing when aluminum content at the surface is enriched relative to the interior, with a range of over 1.8 eV.     

Phase Evolution and Microstructural Studies in CaZrTi2O7–Nd2Ti2O7 System

A series of compositions with general stoichiometry Ca_1?xZr_1?xNd_2xTi₂O₇ has been prepared by high‐temperature solid‐state reaction of component oxides and characterized by powder X‐ray diffraction and electron probe for microanalyses (EPMA). The phase fields in CaZrTi₂O₇–Nd₂Ti₂O₇ system and distribution of ions in different phases have been determined. Four different phase fields, namely monoclinic zirconolite, cubic perovskite, cubic pyrochlore, and monoclinic Nd₂Ti₂O₇ structure types are observed in this system. The 4M‐polytype of zirconolite structure is stabilized by substitution of Nd³⁺ ion. The addition of Nd³⁺ ions form a cubic perovskite structure‐type phase and thus observed in all the compositions with 0.05 ≤ x ≤ 0.80. Cubic pyrochlore structure‐type phase is observed as a coexisting phase in the nominal composition with 0.20 ≤ x ≤ 0.90. Only a subtle amounts of Ca²⁺ and Zr⁴⁺ are incorporated into the perovskite‐type Nd₂Ti₂O₇ structure. EPMA analyses on different coexisting phases revealed that the pyrochlore and perovskite phases have Nd³⁺‐rich compositions.     

Photoluminescence Properties of Heavily Eu3+‐Doped BaCa2In6O12 Phosphor for White‐Light‐Emitting Diodes

Heavily Eu³⁺‐doped BaCa₂In₆O₁₂ phosphors were prepared by conventional solid‐state reaction, and its structural properties were investigated by means of Rietveld refinement method using an X‐ray source. XRD patterns confirm the hexagonal phase of BaCa₂In₆O₁₂: Eu³⁺ phosphors. The obtained spectrum data indicate that the emission spectra of Ba_1?xEu_xCa₂In₆O₁₂ samples excited at 393 nm exhibit a series of shaped peaks assigned to the ⁵D_0,1,2,3 →⁷F_J (J = 0,1,2,3,4) transitions. Luminescence from the higher excited states, such as ⁵D₁, ⁵D₂, and ⁵D₃, were also observed even though the Eu³⁺ concentration was up to x = 0.4. More importantly, the Ba_1?xEu_xCa₂In₆O₁₂ phosphor still emits white luminescence, when the Eu³⁺ ion concentration is up to x = 0.07 before concentration quenching is observed, which shows that the phosphor is a promising single‐phase phosphor for near ultraviolet (NUV) light‐emitting diodes (LED). Furthermore, the temperature's impact on white luminescent properties was studied. Finally, a white‐light‐emitting diodes (W‐LEDs) fabricated with the Ba_0.95Eu_0.05Ca₂In₆O₁₂ phosphor incorporated with an encapsulant in ultraviolet LEDs (λ_max = 395 nm) is discussed.     

Chemical zoning of calcium aluminoferrite formed during melt crystallization in CaO-SiO2-Al2O3-Fe2O3 pseudoquaternary system

In the CaO-SiO₂-Al₂O₃-Fe₂O₃ pseudoquaternary system, the solid solutions of Ca₂(Al_xFe_1−x)₂O₅, with x<0.7 (ferrite), Ca₂SiO₄ (belite), Ca₃Al₂O₆ (C₃A) and Ca₁₂Al₁₄O₃₃ (C₁₂A₇), were crystallized out of a complete melt during cooling at 8.3 °C/min. Upon cooling to 1370 °C, both the crystals of ferrite with x=0.41 and belite would start to nucleate from the melt. During further cooling, the x value of the precipitating ferrite would progressively increase and eventually approach 0.7. At ambient temperature, the ferrite crystals had a zonal structure, the x value of which successively increased from the cores toward the rims. The value of 0.45 was confirmed for the cores by EPMA. The chemical formula of the rims was determined to be Ca_2.03[Al_1.27Fe_0.68Si_0.02]_Σ1.97O₅ (x=0.65). As the crystallization of ferrite and belite proceeded, the coexisting melt would become progressively enriched in the aluminate components. After the termination of the ferrite crystallization, the C₃A and belite would immediately crystallize out of the melt, followed by the nucleation of C₁₂A₇. The C₁₂A₇ accommodated about 2.1 mass% Fe₂O₃ in the chemical formula Ca_12.03[Al_13.61Fe_0.37]_Σ13.98O₃₃, being free from the other foreign oxides (SiO₂ and P₂O₅).     

Zn‐Cr Co‐Substitution Effect on Structural and Electromagnetic Properties of CuFe2O4 via Oxalate Decomposition Route

Zn‐Cr‐co‐substituted Cu_1‐xZn_xFe_2‐2xCr_2xO₄ ferrites (where x = 0.0–0.5) were prepared via thermal decomposition of oxalate precursors. The thermal decomposition up to ferrites formation was followed by differential thermal analysis–thermogravimetry measurements. Mössbauer technique was used to predict the possible cation distribution of the entire system, and X‐ray diffraction, Fourier transform infrared, and electromagnetic measurements were used for confirmation. The superparamagnetic characteristics estimated via Mössbauer studies, for samples with higher substitution, agreed well with vibrating sample magnetometer, magnetic susceptibility, and conductivity results. All the samples showed semiconducting properties in which conductivity decreases by increasing substitution. The effect of cationic substitution on the entire system was investigated and discussed.     

Investigation of luminescence properties of Pb2+‐doped Sr2B2O5 phosphor

A near‐UV emitting phosphor, Pb²⁺‐doped Sr₂B₂O₅ was synthesized by the solid‐state reaction method at 900°C for 3 hours in air. The structure of the phosphor was verified by X‐ray diffraction study which shows monoclinic phase. Fourier transform infrared (FTIR) analysis confirmed the formation of Sr₂B₂O₅. The excitation and emission spectra of the synthesized phosphors were investigated at room temperature with photoluminescence spectrophotometer. The emission and excitation bands of Pb²⁺‐doped Sr₂B₂O₅ were observed at 370 and 289 nm, respectively. The dependence of the PL intensities on the Pb²⁺ concentration for the Sr_2?xPb_xB₂O₅ (0.01 ≤ x ≤ 0.03) phosphors was studied and it was observed that the concentration quenching of Pb²⁺ in Sr₂B₂O₅ is 0.025 mol.     

Comparative Study of Silver Nanoparticles Coated and Uncoated NiO–Fe2O3–CaO–SiO2–P2O5 Ferromagnetic Bioactive Ceramics

Bioactive ferromagnetic ceramics of system xNiO–(3?x)Fe₂O₃–52CaO–30SiO₂–15P₂O₅, (x = 0, 3 mol%) have been prepared in the laboratory using sol–gel technique. Silver nanoparticles coating has been undertaken on the surface of synthesized samples. Comparative study of silver nanoparticles coated and uncoated samples has been undertaken with the help of transmission electron microscopy, X‐ray diffraction (XRD), degradation, drug delivery, hemolysis, antimicrobial, and cell culture studies. XRD patterns indicate the growth of hydroxyl apatite layer on the surface of coated as well as uncoated samples. Ferromagnetic properties of samples have been investigated with the help of vibrating sample magnetometer technique. Samples have shown good response as drug carriers under normal conditions as well as under the influence of magnetic field. Drug release mechanism and mesoporus nature of samples have been investigated with the help of Brunauer–Emmett–Teller technique. Nonreactivity of samples (coated and uncoated) with red blood cells and white blood cells show nontoxic nature of the samples. Coated samples have shown better antimicrobial properties against six different microorganisms, including some resistive strain like methicillin‐resistant Staphylococcus aureus with minimum inhibitory concentration of 0.05 mg/ml as compared to uncoated samples. It has been observed that samples also provide a healthy environment for the growth of MG 63 cell lines. It has been noticed that presence of silver nanoparticles on the surface of samples improve degradation and antimicrobial properties.