Growth and characterization of lead-free Ba(1−x)CaxTi(1−y)ZryO3 single crystal

A lead-free Ba_(1?x)Ca_xTi_(1?y)Zr_yO₃ (BCZT) single crystal (x=0.08, y=0.26) was grown by the Czochralski (CZ) method in a mixed flux of TiO₂ and ZrO₂. The composition of as-grown BCZT was analyzed by electron probe micro-analysis. The structure, dielectric properties and phase transition were investigated at different temperatures. The X-ray diffraction results confirmed that the structure of the as-grown BCZT crystal was cubic both at 25 °C and 500 °C. The temperature dependence of the dielectric constant and Raman spectra characterization revealed that there was a phase transition from cubic to tetragonal, which happened between 200 K and 250 K. With increasing frequency, the Curie temperature shifted towards high temperature.     

Relaxation of polaronic charge carriers in lithium manganese spinels

Lithium manganese spinels Li_1+xMn_2−xO₄, 0 ⩽ x ⩽ 0.33, were prepared by wet chemistry technique followed by heat-treatment at 750 °C or 800 °C. Differential scanning calorimetry was used to reveal phase transitions. Electrical properties were studied by impedance spectroscopy. LiMn₂O₄ exhibited phase transition below room temperature. The transition, seen as an exothermic event in DSC and a steep decrease of conductivity upon cooling, was sharp in sample sintered at 800 °C and broadened over a range of temperature in sample sintered at 750 °C. In the low temperature phase of LiMn₂O₄, two relaxations of similar strength were observed in the frequency dependent permittivity. The low frequency process was identified as relaxation of charge carriers since the relaxation frequency followed the same temperature dependence as the dc conductivity. The high frequency process exhibited milder temperature dependence and was attributed to dipolar relaxation in the charge-ordered structure. The dipolar relaxation was barely visible in Li substituted samples, x ⩾ 0.05, which did not undergo structural phases transition. Measurements extended to liquid nitrogen temperature showed gradual lowering of the activation energy of conductivity and relaxation frequencies, behavior typical for phonon-assisted hopping of small polarons.     

Crystal growth of ZrW2O8 and its optical and mechanical characterization

ZrW₂O₈ is known for its isotropic negative thermal expansion over a wide of range of temperature from ?272 to 777 °C. However, ZrW₂O₈ melts incongruently at 1257 °C and is stable only over a short temperature interval between 1105 and 1257 °C. This makes the growth of single crystals a formidable challenge. In order to study the intrinsic properties of this compound, a repeatable, viable single crystal growth strategy is required. Here we report a simple, self-seeding, self-fluxing single crystal growth process which resulted in single crystals of ZrW₂O₈ up to about 4 mm in size. Grown crystals were characterized by X-ray diffraction (XRD), Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Mechanical properties of the crystals were studied using nanoindentation.     

Crystallization of a niobium phosphate glass

Niobium phosphate glasses with composition 37P₂O₅ · 23K₂O · 40Nb₂O₅ are stable in relation to crystallization during the heating process, exhibit a low critical cooling rate, and are potentially good for nuclear wasteforms. The crystallization of these glasses was evaluated by optical microscopy after proper heat treatments, showing that surface crystallization is the main process occurring during the heat treatment. Two main crystalline phases were observed. These crystalline phases were KNb₃O₈ and K₃NbP₂O₉. Surface crystal growth rates were measured in the temperature range of 806–972 °C (T_g = 683 °C) for both crystalline phases. Apparent crystallization enthalpies were determined through the Arrhenius plots of lnU vs. 1/T. The enthalpies are 496 kJ/mol and 513 kJ/mol for each crystalline phase, respectively. The surface density of nucleation sites (N_s) on 3 μm diamond paste polished surfaces is (2.4 ± 0.7) × 10⁸ nuclei/m² for one crystalline phase and (9.8 ± 0.8) × 10⁹ nuclei/m² for the other crystalline phase, when revealed at 838 °C/17.5 h, and these values show a slight variation depending on the time and the temperature. At the tested temperatures, only one crystal phase appeared inside the volume, and a volume density of nucleation sites N_v = 5 × 10⁶ nuclei/m³ was measured.     

Crystal growth kinetics in cordierite and diopside glasses in wide temperature ranges

We measured and collected literature data for the crystal growth rate, u(T), of μ-cordierite (2MgO · 2Al₂O₃ · 5SiO₂) and diopside (CaO · MgO · 2SiO₂) in their isochemical glass forming melts. The data cover exceptionally wide temperature ranges, i.e. 800–1350 °C for cordierite and 750–1378 °C for diopside. The maximum of u(T) occurs at about 1250 °C for both systems. A smooth shoulder is observed around 970 °C for μ-cordierite. Based on measured and collected viscosity data, we fitted u(T) using standard crystal growth models. For diopside, the experimental u(T) fits well to the 2D surface nucleation model and also to the screw dislocation growth mechanism. However, the screw dislocation model yields parameters of more significant physical meaning. For cordierite, these two models also describe the experimental growth rates. However, the best fittings of u(T) including the observed shoulder, were attained for a combined mechanism, assuming that the melt/crystal interface growing from screw dislocations is additionally roughened by superimposed 2D surface nucleation at large undercoolings, starting at a temperature around the shoulder. The good fittings indicate that viscosity can be used to assess the transport mechanism that determines crystal growth in these two systems, from the melting point T_m down to about T_g, with no sign of a breakdown of the Stokes–Einstein/Eyring equation.     

Influence of europium ions on structure and crystallization properties of bismuth borate glasses and glass ceramics

Glasses of the xEu₂O₃ · (100?x)[2Bi₂O₃ · B₂O₃] system with 0 ? x ? 25 mol% have been characterized by X-ray diffraction and FTIR spectroscopy measurements. Melting at 1100 °C and the rapid cooling at room temperature permitted us to obtain glass samples. In order to improve the local order and to develop crystalline phases, the glass samples were kept at 625 °C for 24 h. After heat treatment two crystalline phases were put into evidence. One of the crystalline phases was observed for the host glass matrix, the x = 0 mol% sample, and belongs to the cubic system. The second one was observed for the x = 25 mol% sample and was find to be orthorhombic with two unit cell parameters very close to each other. For the samples with 0 < x < 25 mol% there is a mixture of the two mentioned phases. FTIR spectroscopy data suggest that both Bi₂O₃ and B₂O₃ play the glass network former role while the europium ions play the network modifier role in the studied glasses.     

The (Bi,Pb)4Sr3Ca3Cu4Ox glass–ceramics: Disordered metal and superconductor

The (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass, annealed under proper conditions, is transformed into a granular metal and superconductor. Oxide superconductors of the bismuth family crystallize as a result of annealing: (Bi,Pb)₂Sr₂CuO_x (2201, T_c = 10 K), (Bi,Pb)₂Sr₂CaCu₂O_x (2212, T_c = 85 K) and (Bi,Pb)₂Sr₂Ca₂Cu₃O_x (2223, T_c = 100 K). (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass–ceramic samples were obtained by annealing an amorphous solid at temperatures between 650 °C and 870 °C. The temperature dependence of resistivity in annealed samples was measured with the conventional four-terminal method in the temperature range from 3 K to 300 K. The (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass–ceramics may be considered as a disordered metal and superconductor. The material has high resistivity and a high, usually negative, temperature coefficient of resistivity (TCR). Its granular and disordered character is also reflected in its superconducting properties. The normal-state and superconducting properties are correlated.     

Growth and characteristic of Sr3Tb(BO3)3 crystal

A new borate single crystal of Sr₃Tb(BO₃)₃ with dimension Ф20×25 mm² has been grown by the Czochralski method. The grown crystal was characterized by DTA–TGA, FTIR and X-ray powder diffraction analysis. The results showed the crystal with [BO₃]^3? is congruently melting at 1351.35 °C which belongs to hexagonal structure. The hardness of Sr₃Tb(BO₃)₃ crystal is 422.5 VDH, and is equal to 5.0 moh. The thermal expansion coefficients were determined to be 2.08×10^?5/°C along (1 0 0) direction and 7.43×10^?6/°C along (0 0 1) direction and the transmission spectrum was measured in 320–1800 nm at room temperature. The magnetic properties of the single crystal were studied which showed its paramagnetism and magnetic anisotropy. The specific Faraday rotation of single crystal was measured at room temperature in 532, 633, and 1064 nm wavelength. The Verdet constants and magneto-optical figures of merit were investigated. The primary emphasis is laid to explore a new magneto-optical material, all the magneto-optical properties of Sr₃Tb(BO₃)₃ are comparing to the ones of TGG.     

Growth improvement and characterization of AgGaxIn1−xSe2 chalcopyrite crystals using the horizontal Bridgman technique

AgGa_xIn_1?xSe₂ single crystals with x=0.4 have been grown by the horizontal Bridgman technique for nonlinear optical application requires phase matching. High purity polycrystalline synthesis of AgGa_xIn_1?xSe₂ was carried out at 850 °C, which is a relatively lower temperature compared to those in earlier reports, thus reducing secondary phase formation. An average Ga:In ratio of 62:38 (±3%) was measured using energy dispersive spectroscopy (EDS). As grown, a single crystal shows very high IR transmission of ～65% in the spectral range of 4000–600 cm^?1. There was no significant change in its IR transmission after annealing it at 500 °C for 20 days in vacuum in the presence of AgGa_xIn_1?xSe₂ powder. This indicates a low concentration of defects in the crystal. The results demonstrate that the improved new synthesis method for crystal growth was promising and that the quality of the crystal was good.     

Thermal properties and glass formation in the SiO2–B2O3–Bi2O3–ZnO quaternary system

Lead-free glasses in the SiO₂–B₂O₃–Bi₂O₃–ZnO quaternary system were studied. The glass formation region, as determined by XRD patterns of bulk samples, was limited to glasses having more than 40 mol% of the glass-forming oxides SiO₂ and B₂O₃. Crystalline phases of Zn₂SiO₄ (willemite) were detected in compositions of 30SiO₂ · 10B₂O₃ · 20Bi₂O₃ · 40ZnO and 20SiO₂ · 10B₂O₃ · 25Bi₂O₃ · 45ZnO. Glass transition temperatures (T_g), dilatometric softening points (T_d) and linear coefficients of expansion in the temperatures range of 25–300 °C (α_25–300) were measured for subsystems along the B₂O₃ join of 10, 20 and 30 mol%. For these subsystems, T_g ranged from 411 to 522 °C, and T_d ranged from 453 to 563 °C, both decreasing with increasing Bi₂O₃ content. The measured α_25–300 ranged from 53 to 95 × 10⁻⁷ °C⁻¹, with values increasing with increasing Bi₂O₃ content. The ZnO content had the opposite effect to the Bi₂O₃ content. It appears that Bi³⁺ acts as a glass-modifier in this quaternary system.     

Characteristics of heteroepitaxial Cu2−xMnxO/Nb–SrTiO3 p–n junction

Mn-doped cuprous oxide Cu_2?xMn_xO (CMO), where x = 0.03, is a p-type diluted magnetic semiconductor (DMS) with Curie temperature above room temperature [M. Wei, N. Braddon, et al., Appl. Phys. Lett. 86 (2005) 0725141; Y.L. Liu, S. Harrington, et al., Appl. Phys. Lett. 87 (2005) 222108]. We have grown CMO (x = 0.03) thin films of about 200 nm thick on n-type semiconducting (0 0 1)Nb–SrTiO₃(NSTO) single crystal substrates by pulsed laser deposition. Cubic crystalline phases of CMO layers were obtained in a narrow deposition pressure window of about 20 mTorr at growth temperature of 650 °C. X-ray diffraction and TEM studies of these heterostructures reveal a cube-on-cube epitaxial relationship of [CMO]₀₀₁/[NSTO]₀₀₁. All the oxide p–n junctions with the size of 500 × 500 μm were fabricated by the shadow masking technique. These junctions show highly asymmetric I–V characteristics. The rectification ratio at room temperature is about 10³ at ±2 V. Leakage current density of 10^?4 A cm^?2 at ?1 V is observed. No apparent junction breakdown is recorded at reverse bias voltages down to ?5 V. From the 1/C²–V plots, the forward bias turn on voltage is ～1.4 V. Clear junction current rectifying property is maintained at up to 200 °C. Our results have demonstrated that epitaxial CMO films can be fabricated on lattice matched cubic substrates. They are suitable DMS for above room temperature spintronic junction applications.     

Incorporation of B2O3 in CaO-SiO2-P2O5 bioactive glass system for improving strength of low-temperature co-fired porous glass ceramics

Bioactive glass ceramics (BGCs) have different rates of biodegradation and mechanical properties depending on their chemical compositions and sintering temperatures. The present study was aimed to develop the boron-rich, phosphorus-low CaO–SiO₂–P₂O₅–B₂O₃ bioactive glasses (BG-B_x, X = 0, 10, 20) potentially for improving the mechanical properties of BGCs via low-temperature co-fired process. The B₂O₃-free BG-B₀ shrunk well at ~ 726 °C and melted at over 1050 °C, while the onset shrinking and melting temperatures of the 20 mol% B₂O₃-doped BG-B₂₀ was lowered to ~ 648 °C and ~ 952 °C, respectively. The BG-B₂₀ thermally treated at 850–950 °C was transformed into wollastonite and calcium borate, and crystallization decreased the kinetics but did not inhibit the development of hydroxyapatite on their powder and disc surface when immersed in simulated body fluid. The in vitro degradation in Tris buffer confirmed that the degradation rate markedly increased with increasing boron content in BG-B_x. The compressive strength and flexural strength of the 10% BG-B₂₀-reinforced 45S5 porous BGC sintered at 850 °C was nearly four times than that of 45S5 porous constructs. These studies suggest that the boron-rich, phosphorus-low CaO–SiO₂–P₂O₅–B₂O₃ system is a promising biomaterial and potential low temperature co-fired aid for improving the mechanical and biological properties of porous BGCs.     

Dilithium dialuminium trisilicate phase obtained using coal bottom ash

The Li₂Al₂Si₃O₁₀ glass-ceramics well crystallized and with a regular morphology was produced starting from a mixture of Li₂CO₃, TiO₂, Al₂O₃ and coal bottom ash, after reducing the magnetite phase content. Its measured thermal expansion coefficient in the temperatures range from 25 °C to 300 °C is α_(25–300) = −23.4 × 10⁻⁷ °C⁻¹. This value is ≈18% smaller than that for the commercial lithium glass-ceramics (−23.4 × 10⁻⁷ °C⁻¹ to 50 × 10⁻⁷ °C⁻¹).     

Magnetic and magnetostrictive behavior of Dy3+ doped CoFe2O4 single crystals grown by flux method

We studied the effect of Dy³⁺ content on the magnetic properties of cobalt ferrite single crystal. The single crystals of CoFe_1.9Dy_0.1O₄ were grown by the flux method using Na₂B₄O₇.10 H₂O (Borax) as a solvent (flux). The black and shiny single crystals were obtained as a product. The X-ray diffraction analysis at room temperature confirmed the spinel cubic structure with lattice constant a=8.42 Å of the single crystals. The compositional analysis endorses the presence of constituents Co, Fe and Dy elements after sintering at 1300 °C within the final structure. The magnetic hysteresis measurements at various temperatures viz. 10 K, 100 K, 200 K and 300 K reveal the soft ferrimagnetic nature of the single crystal than that of for pure CoFe₂O₄. The observed saturation magnetization (M_s) and coercivity (H_c) are found to be lower than that of pure CoFe₂O₄ single crystal. The magnetostriction (λ) measurement was carried out along the [001] direction. The magnetic measurements lead to conclude that the present single crystals can be used for magneto-optic recording media.     

Redox reactions during temperature change in soda-lime–silicate melts doped with copper and iron or copper and manganese

Glasses with the base composition 16Na₂O · 10CaO · 74SiO₂ doped with copper and iron or copper and manganese were studied by high temperature UV–vis–NIR spectroscopy. The spectra exhibited distinct absorption bands attributed to the respective transition metal ions present (Cu²⁺, Fe²⁺, Fe³⁺, Mn³⁺). In glasses doped with only one polyvalent element, the absorption decreases linearly with increasing temperature, the absorption bands are shifted to smaller wave numbers and get broader. In glasses doped with two types of transition metals, the situation is the same up to a temperature of around 550 °C. At larger temperature, the Cu²⁺-absorption in glasses also co-doped with iron increases again, while in glasses doped with both copper and manganese the absorption is approximately the same as in glasses solely doped with copper. It is shown that this is due to redox reactions between polyvalent species. These reactions are frozen in at temperatures <550 °C.     

Growth condition related orientation transition for YBa2Cu3O7−δ films on NdGaO3 substrate

For comprehensive understanding, the crystallographic out-of-plane axis transition for YBa₂Cu₃O_7?δ (YBCO or Y123) films grown on (110) NdGaO₃ (NGO) substrate, using liquid phase epitaxy (LPE), was systematically investigated via changing flux composition, processing temperature and oxygen partial pressure. It is found that LPE films could grow, remarkably, in a wide temperature range between 24 K above and 25 K below the peritectic temperature (T_p). The unpredicted c-oriented films formed at the temperatures above T_p, is deduced to be attributed to the etch-back behavior, i.e., Nd partially dissolved from the NGO substrate into solution, which leads to a locally high supersaturation for facilitating film growth. Even more distinctively, decreasing from the high temperature in this wide range, the YBCO films characteristically experienced the orientation transitions, the double transition of the c-axis oriented→a/c-axis mixed→c-axis oriented in air, and a single evolution of the c-axis→a-axis in the pure oxygen atmosphere. By combining supersaturation with the NGO etch-back, and solute diffusion, the transition origin of the film orientation in various temperature regions was clarified.     

Influence of thermal and thermoelectric treatments on structure and electric properties of B2O3–Li2O–Nb2O5 glasses

A transparent glass with the composition 60B₂O₃–30Li₂O–10Nb₂O₅ (mol%) was prepared by the melt quenching technique. The glass was heat-treated with and without the application of an external electric field. The as-prepared sample was heat-treated (HT) at 450, 500 and 550 °C and thermoelectric treated (TET) at 500 °C. The following electric fields were used: 50 kV/m and 100 kV/m. Differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman, dc and ac conductivity, as a function of temperature, were used to investigate the glass and glass-ceramics properties. LiNbO₃ crystals were detected, by XRD, in the 500 °C HT, 550 °C HT and 500 °C TET samples. The presence of an external electric field, during the heat-treatment process, improves the formation of LiNbO₃ nanocrystals at lower temperatures. However, in the 550 °C HT and in the TET samples, Li₂B₄O₇ was also detected. The value of the σ_dc decreases with the rise of the applied field, during the heat-treatment. This behavior can indicate an increase in the fraction of the LiNbO₃ crystallites present in these glass samples. The dc and ac conduction processes show dependence on the number of the ions inserted in the glass as network modifiers.The Raman analysis suggests that the niobium ions are, probably, inserted in the glass matrix as network formers.These results reflect the decisive effect of temperature and electric field applied during the thermoelectric treatment in the structure and electric properties of glass-ceramics.     

Thermal expansion of glass–ceramics in the system BaO/Al2O3/B2O3

Glasses in the system BaO/Al₂O₃/B₂O₃ with and without the addition of platinum were melted. In one sample series, the BaO-concentration was varied while the ratio [Al₂O₃]/[B₂O₃] was kept constant. In another sample series, the [BaO]/[Al₂O₃]-ratio (= 0.9) was kept constant and the B₂O₃ concentration was varied. The samples were thermally treated at 720 °C for 24 h and subsequently at 780 °C for 4 h. In most thermally treated samples, the crystalline phase BaO · Al₂O₃ · B₂O₃ occurred. At some compositions, the platinum-doped samples showed larger concentrations of the crystalline phases. The most remarkable property of the obtained glass–ceramics is their zero or negative thermal expansion coefficient. Here, notable differences were observed: samples with fine grained microstructures showed thermal expansion coefficients approximately zero up to temperatures of around 80 °C. By contrast, samples with coarser microstructures and large spheroidal crystals exhibit negative expansion coefficients up to temperatures of around 280–375 °C. The thermal expansions of these samples were close to those of the mean thermal expansion of the unit cell of the BaO · Al₂O₃ · B₂O₃ phase. The thermal expansion of the fine grained samples was approximately equal to that of the crystallographic a-axis of the BaO · Al₂O₃ · B₂O₃ phase.     

Crystallization of chicken egg white lysozyme from assorted sulfate salts

Chicken egg white lysozyme has been found to crystallize from ammonium, sodium, potassium, rubidium, magnesium, and manganese sulfates at acidic and basic pH, with protein concentrations from 60 to 190 mg/ml. Crystals have also been grown at 4°C in the absence of any other added salts using isoionic lysozyme which was titrated to pH 4.6 with dilute sulfuric acid. Four different crystal forms have been obtained, depending upon the temperature, protein concentration, and precipitating salt employed. Crystals grown at 15°C were generally tetragonal, with space group P4₃2₁2. Crystallization at 20°C typically resulted in the formation of orthorhombic crystals, space group P2₁2₁2₁. The tetragonal ↔ orthorhombic transition appeared to be a function of both the temperature and protein concentration, occurring between 15 and 20°C and between 100 and 125 mg/ml protein concentration. Crystallization from 1.2 M magnesium sulfate at pH 7.8 gave a trigonal crystal, space group P3₁2₁, a=b=87.4, c=73.7, γ=120°, which diffracted to 2.8 Å. Crystallization from ammonium sulfate at pH 4.6, generally at lower temperatures, was also found to result in a monoclinic form, space group C2, a=65.6, b=95.0, c=41.2, β=119.2°. A crystal of ∼0.2×0.2×0.5 mm grown from bulk solution diffracted to ∼3.5 Å.