Warm with high color rendering index white light from hybridization of Ca2BO3Cl:Eu2+ yellow phosphor and CdSe/ZnS nanocrystals

Yellow emitting Ca₂BO₃Cl:Eu²⁺ phosphor was prepared by solid state reaction at 900 °C. The particle was monoclinic crystal structure, and showed broad band emission at around 540–590 nm due to the 5d–4f transition. Single Ca₂BO₃Cl:Eu²⁺ phosphor converted white LED exhibited the CIE coordinates of (0.3441, 0.2675) with low CRI of 67.4. Hybridization of Ca₂BO₃Cl:Eu²⁺ with 535 and 610 nm emitting CdSe/ZnS nanocrystals contributed to increasing white spectrum and generated the warm color temperature (4055 K) with high CRI (83.9) of white light. The acceptable color stability was also observed from (0.3687, 0.3051) at 20 mA to (0.3645, 0.3101) at 80 mA.     

Catalytic decomposition of CH2Cl2 over supported Ru catalysts

Ru/TiO₂ and Ru/Al₂O₃ were prepared by wet impregnation of TiO₂ and Al₂O₃, and tested in the catalytic decomposition of dichloromethane (DCM). Ru/TiO₂ catalyst presents the higher activity than Ru/Al₂O₃ catalyst, with 50% and 90% conversion occurring at 235 and 267 °C, respectively. Moreover, the higher stability on Ru/TiO₂ catalyst is observed, which can be related to ready removal of Cl species produced during DCM decomposition. The chlorine uptake on Ru/TiO₂ catalyst is estimated at 240 °C to be 0.36 mmol Cl/g_cat, while on Ru/Al₂O₃, the value is 1.46 mmol Cl/g_cat.     

Effect of B2O3 and CuO additives on the sintering temperature and microwave dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics

The B₂O₃ added Ba(Zn_1/3Nb_2/3)O₃ (BBZN) ceramic was sintered at 900 °C. BaB₄O₇, BaB₂O₄, and BaNb₂O₆ second phases were found in the BBZN ceramic. Since BaB₄O₇ and BaB₂O₄ second phases have an eutectic temperature around 900 °C, they might exist as the liquid phase during sintering at 900 °C and assist the densification of the BZN ceramics. Microwave dielectric properties of dielectric constant (ɛ_r) = 32, Q × f = 3500 GHz, and temperature coefficient of resonance frequency (τ_f) = 20 ppm/°C were obtained for the BZN with 5.0 mol% B₂O₃ sintered at 900 °C for 2 h. The BBZN ceramics were not sintered below 900 °C and the microwave dielectric properties of the BBZN ceramics sintered at 900 °C were very low. However, when CuO was added, BBZN ceramic was well sintered even at 875 °C. The liquid phase related to the BaCu(B₂O₅) second phase could be responsible for the decrease of sintering temperature. Good microwave dielectric properties of ɛ_r = 36, Q × f = 19,000 GHz and τ_f = 21 ppm/°C can be obtained for CuO doped BBZN ceramics sintered at 875 °C for 2 h.     

A comparative study of hydroxyapatites synthesized using various fuels through aqueous and alcohol mediated combustion routes

Nano-sized calcium hydroxyapatite, [Ca₁₀(PO₄)₆(OH)₂] has been synthesized by the sol–gel combustion method using calcium nitrate and di-ammonium hydrogen phosphate as precursors in the aqueous medium. Triethyl phosphite was used as a phosphate precursor for alcohol mediated combustion. The aqueous and alcohol media were employed for the investigation of combustion synthesis in the presence of various fuels such as urea, glycine, alanine, hydrazine and hexamine. The metal-to-fuel ratio in the synthesis was maintained at 1 to facilitate complete combustion and the Ca/P ratio was maintained at 1.67 to aid the stoichiometric formation of hydroxyapatite. The combustion products were calcined at 800 °C for 10 h and were characterized by powder XRD, FT-IR, HR-SEM and HR-TEM techniques. All the five fuels used under the alcohol mediated combustion, resulted in forming phase pure hydroxyapatite; whereas the aqueous mediated combustion method yielded biphasic calcium phosphate containing Ca₁₀(PO₄)₆(OH)₂ and β-TCP depending on the nature of the fuel.     

Photochemical reductive elimination of [PtIV(NH3)4(NH2)Cl]2 +: Photogeneration of hydrazine

When [Pt^IV(NH₃)₅Cl]^3 + is deprotonated the complex [Pt^IV(NH₃)₄(NH₂)Cl]^2 + is formed. Upon NH₂⁻ → Pt^IV LMCT excitation (λ_irr > 250 nm) a reductive elimination takes place: [Pt^IV(NH₃)₄(NH₂)Cl]^2 + → [Pt^II(NH₃)₃Cl]⁺ + N₂H₄ + H⁺. Since Pt(II) ammine complexes can be reoxidized to Pt(IV) by H₂O₂ it is suggested that in a cyclic process the overall reaction could proceed according to the equation: 2 NH₃ + H₂O₂ → N₂H₄ + 2 H₂O.     

Mechanosynthesis of hydroxyapatite–ferrite composite nanopowder

In the present work, an investigation of the mechanosynthesis of calcium hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) from a mixture of calcium oxide (СаО) and ammonium hydrophosphate ((NH₄)₂HPO₄) and mechanotreatment of HA in a planetary mill with the use of steel drums and milling body has been performed. The obtained results have shown that the mechanosynthesis of crystalline nanodisperse HA proceeds through the stage of formation of an amorphous material. The temperature treatment of HA powders at 1000 °C has enabled us to establish the influence of the treatment time on the phase composition of the powders and establish the following sequence of phase transformations: Ca₁₀(PO₄)₆(OH)₂→β-Ca₃(PO₄)₂ (t_milling~2 h), β-Ca₃(PO₄)₂→α-Ca₃(PO₄)₂ (t_milling~5 h), β-,α-Ca₃(PO₄)₂→Ca₁₀(PO₄)₆(OH)₂ (t_milling~7 h).The mechanosynthesis and mechanotreatment of hydroxyapatite in steel drums with steel balls is accompanied by the contamination of hydroxyapatite by their wear debris (iron + manganese). A large part of oxidized iron forms superparamagnetic inclusions distributed in HA powder. A small part of Fe³⁺ and Mn²⁺ ions from the steel wear debris enters into the hydroxyapatite lattice, substituting Ca²⁺ ions. As a result, a nanocomposite powder consisting of hydroxyapatite, alloyed by Fe³⁺ and Mn²⁺ ions and ferrite inclusions forms. The phase composition of HA powders, the degree of their alloying by Fe³⁺ and Mn²⁺ ions, and the content of ferrite inclusions can be controlled by changing the time of mechanotreatment.     

Phase and melting relationships of β, α and α′-Ca3(PO4)2 polymorphs in the Ca3(PO4)2-Zn3(PO4)2 system

In order to provide an exact knowledge of the phase transitions and melting relationships of Ca₃(PO₄)₂ (TCP) in the presence of zinc, a revisited version of the rich-Ca₃(PO₄)₂ region of the phase diagram of the system Ca₃(PO₄)₂-Zn₃(PO₄)₂ has been established in the present work. Experimental determination of this diagram was carried out by solid-state reactions of samples prepared from pure NH₄H₂PO₄, CaCO₃ and ZnO raw materials. X-ray Diffraction, Differential Thermal Analyses and Field Emission Scanning Electron Microscopy studies allowed to revise the α, β, α + β-TCP phase stability fields, delimitating for the first time the biphasic α + α′-TCP field and the melting relationships in the high temperature region of the system. The results allowed to determine two peritectic invariant points, at ≈1400 °C for 95 mol% Ca₃(PO₄)₂ and at ≈1490 °C for ≈99.5 mol% Ca₃(PO₄)₂.     

Structural,chemical and dielectric properties of ceramic injection moulded Ba(Zn1/3Ta2/3)O3 microwave dielectric ceramics

We report the development of a ceramic injection moulding (CIM) process to produce complex-shaped structures using high-performance microwave ceramic materials. In particular, we describe the synthesis methods and the structural, chemical and dielectric properties of Ba(Zn_1/3Ta_2/3)O₃ (BZT) doped with Ni and Zr ceramics produced using ceramic injection moulding. Sintering the ceramic injection moulded Ba(Zn_1/3Ta_2/3)O₃ to a relative density of ∼94% was possible at a temperature of 1680 °C and a time of 48 h. The best samples to date exhibit a dielectric constant, ɛ_r, of ∼30, a Q value, of ∼31,250 (i.e. tan δ < 3.2 × 10⁻⁵) at 2 GHz, and a temperature coefficient of resonance frequency, τ_f, of 0.1 ppm/°C.     

Effects of the sintering atmosphere on the BaZn1/3Ta2/3O3 based Cu multilayer ceramic capacitors

Recent papers report that BaZn_1/3Ta_2/3O₃ (BZT) ceramic can be sintered at a temperature as low as 1050 °C owing to the use of flux agents like B₂O₃ + LiF combined with a slight non-stoichiometry, whereas its usual sintering temperature is 1400 °C. This low sintering temperature (below the Cu's melting point = 1083 °C) opens the route to fabricate copper based multilayer ceramic capacitors, in condition that a reductive atmosphere is used during the sintering. This paper presents the effect of three various sintering atmospheres (air, H₂ (1%) in N₂ and H₂ (1%) in Ar) on the stability and the dielectric properties of BZT. It is researched a suitable sintering atmosphere to prevent Cu from oxidation and to preserve the dielectric properties of BZT. Using the appropriate atmosphere, copper based multilayer ceramic capacitors, with attractive dielectric properties, have been successfully processed.     

Wetting,densification and phase transformation of La2O3/A2O3/B2O3-based glass–ceramics

A lead-free, non-alkali La₂O₃–Al₂O₃–B₂O₃ (LAB) glass with Al₂O₃ filler had been investigated for low temperature co-firing ceramic (LTCC) application. The glass forming window and several physical properties of the LAB systems were investigated by ICP, TMA, XRD, DSC, and SEM/EDS. The results show that the densification and crystallization temperatures of LAB/Al₂O₃ were between 700 °C and 950 °C and depended greatly on the formulation. Crystalline phase LaBO₃ (LB) and LaAl₂B₃O₉ (L2A3B) crystallized starting at 825 °C and 925 °C, respectively. High degree of densification and crystallization of one glass–Al₂O₃ composition (L30A) was observed with the microstructure composed of tabular L2A3B grains interlocking with submicron Al₂O₃ and LB grains.     

Hot corrosion behaviors of SrZrO3 ceramic co-doped with Y2O3 and Yb2O3 in molten Na2SO4, V2O5, and Na2SO4 + V2O5 salts mixture

The hot corrosion behaviors of Sr(Y_0.05Yb_0.05Zr_0.9)O_2.95 (SYYZ) ceramic were investigated in Na₂SO₄, V₂O₅, and Na₂SO₄ + V₂O₅ salts mixture, respectively. Na₂SO₄ did not react with SYYZ ceramic at 900, 950 and 1000 °C. m-ZrO₂, YVO₄ and YbVO₄ were the main corrosion products on the SYYZ ceramic surface in V₂O₅ at 800 and 900 °C, whereas Sr₃V₂O₈ and t-ZrO₂ appeared at 1000 °C. In Na₂SO₄ + V₂O₅ salts mixture, the corrosion products were Sr₃V₂O₈ and t-ZrO₂ at 800 and 900 °C on the SYYZ ceramic surface, however, a new phase of SrZrO₃ developed at 1000 °C. The phase transformation and chemical interaction are the primary corrosion mechanisms for degradation of SYYZ ceramic.     

High temperature deformation of non-directionally solidified Al2O3/YAG/ZrO2 eutectic bulk ceramic

Excellent high temperature mechanical properties of melt-grown Al₂O₃-based eutectics have previously been demonstrated in samples prepared by directional solidification methods. In this study, the deformation behaviour of melt-grown Al₂O₃/YAG/ZrO₂ eutectic bulk prepared by a non-directional solidification method was investigated by means of compressive tests in a temperature range of 1200–1700 °C. The non-directionally solidified eutectic bulk ceramic has a colony structure and is polycrystalline. It begins to show ductility and has a compressive strength of 320 MPa at 1500 °C, which is much higher than that of the sintered ceramic with the same composition. However, its plastic deformability is insufficient, even at 1700 °C (just below the melting point of 1715 °C), and cracking occurs during compressive deformation.     

Synthesis,structure, and substitution reactivity of a new bi-oxo capped molybdenum cluster: [Mo3(μ3-O)2(μ-O2CCH2Cl)6(H2O)2(OH)]+

A new bi-oxo capped molybdenum carboxylate, [Mo₃(μ₃-O)₂(μ-O₂CCH₂Cl)₆(H₂O)₂(OH)]⁺, was synthesized by refluxing [Mo₃(μ₃-O)₂(μ-O₂CCH₃)₆(H₂O)₃]^2 + in chloroacetic acid for 20 h (T = 110 °C). Using ion-exchange chromatography (0.5 M NaClO₄ eluant), the trinuclear molybdenum ion was isolated and allowed to crystallize slowly (T = 4 °C) as the perchlorate salt (yield 23%). Upon dissolution of the compound in methanol-d₄, substitution of the terminal ligands for solvent occurs readily in which the observed exchange rate constant is k_obs^298K = 5.3 × 10^− 5 (± 0.3) s^− 1 and activation parameters equal to ΔH³ = 130 (± 10) kJ mol^− 1 and ΔS³ = 111 (± 33) J mol^− 1 K^− 1. From the kinetic data, we find that ligand substitution follows a dissociative pathway and that rates of substitution are faster than expected when compared to the molybdenum acetate analog. Herein, we report the synthesis, crystallographic study, and substitution reactivity of a new molybdenum bi-oxo capped cluster with bridging chloroacetate ligands.     

Synthesis of Nb2O5 and Ta2O5 nanopowders by means of an endo-templating method

Finding efficient templates for the nanostructuring of materials is a key point. Here, the niobium (V) - and tantalum (V) oxide ceramics nanopowders have been synthesized by a hard-templating approach by using the tricalcium phosphate biomaterial (Ca₃(PO₄)₂.xH₂O) as template agent. The oxide ceramics were investigated by X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, nitrogen physisorption and Scanning Electron Microscopy (SEM). It was observed that the surface properties (specific surface areas, pore volumes) of the Nb₂O₅ and Ta₂O₅ powders were strongly dependent of the amount of the Ca₃(PO₄)₂.xH₂O template previously used in the preparation of the [oxide ceramics/template] composites. For instance, with a Ca₃(PO₄)₂.xH₂O/ceramic salt weight ratio ranging from 0 to 1, the specific surface areas of Nb₂O₅ and Ta₂O₅ were gradually enhanced of 48–166 m²/g and 5–84 m²/g, respectively. The pore volumes were increased as well. The use of the eco-friendly tricalcium phosphate material (Ca₃(PO₄)₂.xH₂O) as template in the hard-templating approach may be suitable and efficient in the aim of synthesizing materials with enhanced surface properties.     

Kinetics of calcium sulfoaluminate formation from tricalcium aluminate,calcium sulfate and calcium oxide

The formation kinetics of tricalcium aluminate (C₃A) and calcium sulfate yielding calcium sulfoaluminate (C₄A₃$) and the decomposition kinetics of calcium sulfoaluminate were investigated by sintering a mixture of synthetic C₃A and gypsum. The quantitative analysis of the phase composition was performed by X-ray powder diffraction analysis using the Rietveld method. The results showed that the formation reaction 3Ca₃Al₂O₆ + CaSO₄ → Ca₄Al₆O₁₂(SO₄) + 6CaO was the primary reaction < 1350 °C with and activation energy of 231 ± 42 kJ/mol; while the decomposition reaction 2Ca₄Al₆O₁₂(SO₄) + 10CaO → 6Ca₃Al₂O₆ + 2SO₂ ↑ + O₂ ↑ primarily occurred beyond 1350 °C with an activation energy of 792 ± 64 kJ/mol. The optimal formation region for C₄A₃$ was from 1150 °C to 1350 °C and from 6 h to 1 h, which could provide useful information on the formation of C₄A₃$ containing clinkers. The Jander diffusion model was feasible for the formation and decomposition of calcium sulfoaluminate. Ca^2 + and SO₄^2 − were the diffusive species in both the formation and decomposition reactions.     

Blue-violet ceramic pigments based on Co and Mg Co2−xMgxP2O7 diphosphates

Solid solutions of Co and Mg diphosphates with compositions Co_2?xMg_xP₂O₇ (x = 0, 0.1, 0.2, 0.3, 0.5, 0.7, 1.0, 1.5 and 1.8) have been prepared and characterized for the first time as alternative low-toxicity blue ceramic pigments. The compositions were prepared through the conventional coprecipitation route and calcined up to 1000 °C/2 h. Samples were characterized by thermal analysis, XRD, SEM/EDX, UV–vis-NIR spectroscopy and colour measurements (CIE-L^*a^*b^*). Isostructural Co_2?xMg_xP₂O₇ diphosphate solid solutions (monoclinic system and P21/c spatial group) formed successfully within the studied range of compositions, accompanied only by a minor quantity of residual Co or Mg orthophosphates (M₃(PO₄)₂). Interestingly, the obtained solid solutions developed nice blue-violet colourations even with high Mg doping after enamelling within double-firing (x = 1.5–1.8) and single-firing (x = 1.0–1.5) ceramic glasses. These optimal compositions containing a minimized Co amount (measured values around 7–16 wt%) could be therefore less toxic alternatives to the conventional Co₃(PO₄)₂ blue ceramic pigment.     

Proton conductive YSZ-phosphate composite electrolyte for H2S SOFC

A new oxide-salt composite electrolyte, YSZ–K₃PO₄–Ca₃(PO₄)₂, shows proton conductivity in the order of 10^?2 S/cm at 700 °C. The proton transport number, determined using a hydrogen concentration cell, rises from more than 93% at 550 °C to 99% at 700 °C. The composite electrolyte is chemically stable in H₂S containing atmosphere, and so is a good candidate electrolyte material for H₂S solid oxide fuel cells applications.     

Microstructure and dielectric characteristics of Nb2O5 doped BaTiO3-Bi(Znl/2Til/2)O3 ceramics for capacitor applications

The effects of Nb₂O₅ addition on the dielectric properties and phase formation of 0.8BaTiO₃-0.2Bi(Zn_l/2Ti_l/2)O₃ (0.8BT-0.2BZT) ceramics were investigated. The desired perovskite phase was achieved with Nb₂O₅ doping levels being in the range of 0.5 wt.%–3.0 wt.%. The 0.8BT-0.2BZT ceramics doped with 1.5 wt.% Nb₂O₅ was found to possess a moderate dielectric constant (ε = 1170) and low dielectric loss (tanδ = 1%) at room temperature and 1 kHz frequency, showing a flat dielectric behavior over the temperature range of −55 °C–200 °C. Based on this composition, the X9R-MLCC (multilayer ceramic capacitor) with Ag0.7-Pd0.3 electrode was sintered at 1060 °C. The optimized capacitance of the MLCC is 26.5 nF, with dielectric loss tanδ of 0.9% and electrical resistance of 4.50 × 10¹¹ Ω at room temperature, leading to a high time constant of 11,900 s, decreasing to 175 s at 200 °C, being one order higher than those of commercial X7R MLCC. In addition, the equivalent series resistance (ESR) was found to be on the order of 0.2 mΩ at 2 MHz, much lower than that of the DC Bus Capacitor Bank for the automotive inverters (where the desired characteristic is <3 mΩ). All these characteristics of the newly developed MLCC will benefit the high temperature and high power capacitor applications.     

Effect of CaO addition on the structure and electrical conductivity of the pyrochlore-type GdSmZr2O7

Polycrystalline GdSm_1?xCa_xZr₂O_7?x/2 (0 ≤ x ≤ 0.20) ceramics have been prepared by the solid-state reaction method. The effects of CaO addition on the microstructure and electrical properties of the pyrochlore-type GdSmZr₂O₇ ceramic were investigated. GdSm_1?xCa_xZr₂O_7?x/2 (x ≤ 0.05) ceramics exhibit a pyrochlore-type structure; however, GdSm_1?xCa_xZr₂O_7?x/2 (0.10 ≤ x ≤ 0.20) ceramics consist of the pyrochlore-type structure and a small amount of CaZrO₃. The total conductivity of GdSm_1?xCa_xZr₂O_7?x/2 ceramics follows the Arrhenius relation, and gradually increases with increasing temperature from 723 to 1173 K. GdSm_1?xCa_xZr₂O_7?x/2 ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10^?4–1.0 atm at each test temperature. The highest total conductivity is about 1.20 × 10^?2 S cm^?1 at 1173 K for the GdSm_0.9Ca_0.1Zr₂O_6.95 ceramic.     

Microwave properties of Ba(Mg1/3Ta2/3)O3, Ba(Mg1/3Nb2/3)O3 and Ba(Co1/3Nb2/3)O3 ceramics revealed by Raman scattering

Five Ba(Co_1/3Nb_2/3)O₃ samples sintered at different temperatures (form 1350 to 1550 °C), one Ba(Mg_1/3Ta_2/3)O₃ and a Ba(Mg_1/3Nb_2/3)O₃ sample were examined by Raman scattering to reveal the correlation of the 1:2 ordered perovskite structure with the microwave properties, such as dielectric constant and Q factors. The Ba(Co_1/3Nb_2/3)O₃ sample sintered at 1400 °C, which possesses the highest microwave Q value and the lowest dielectric constant among five Ba(Co_1/3Nb_2/3)O₃ samples, has the narrowest width and the highest frequency of the stretch mode of oxygen octahedron (i.e. A_1g(O) near 800 cm⁻¹). We found that the dielectric constant is strongly correlated with the Raman shift of A_1g(O) stretch modes, and the width of A_1g(O) stretch mode reflects the quality factor Q × f value in the 1:2 ordered perovskite materials. This concludes that the oxygen octahedron play an important role of the material's microwave performance. Based on the results of Q × f values and the lineshapes of A_1g(O) stretch mode, we found that the propagation of microwave energy in Ba(Mg_1/3Ta_2/3)O₃ and Ba(Mg_1/3Nb_2/3)O₃ shows weak damping behavior, however, Ba(Co_1/3Nb_2/3)O₃ samples sintered at different temperature exhibit heavily damped behavior.