An effective growth method to improve the homogeneity of relaxor ferroelectric single crystal Pb(In1/2Nb1/2)O3‐ Pb(Mg1/3Nb2/3)O3‐PbTiO3

Compositional segregation usually has negative effects on the growth of solid solution ferroelectric single crystals of Pb(In_1/2Nb_1/2)O₃‐Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (abbr. PIN‐PMN‐PT or PIMNT). A modified Bridgman method was adopted in this work to control the segregation and improve the compositional homogeneity significantly. The characteristic of this work is to use multiround growths and gradient composition raw materials in order to keep the PbTiO₃ concentration constant during the crystal growth. As an example, the two‐round growth of ternary PIN‐PMN‐PT single crystal is conducted in the same Pt crucible with gradient raw materials, where the first‐round boule was used as the seed crystal for the second‐round growth. Our results show that the as‐grown (Ф80 mm × 270 mm) PIN‐PMN‐PT crystals exhibit higher phase transition temperatures (T_c∼180 °C, T_r/t∼110 °C) and larger coercive field (E_c∼5–5.5 kV/cm), which are much better than the performances of Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ crystals, and similar dielectric and piezoelectric performances (ε∼5000, tanδ∼1.25%, d₃₃∼1500 pC/N, k_t∼60%). And about 85 percent of the crystal boule grown by the two‐round growth technique could maintain its compositions around the morphotropic phase boundary.     

The precipitation of magnesium hydroxoaluminate hydrate powders from sodium hydroxoaluminate solutions: Precipitate phases and precipitation mechanisms

Magnesium hydroxoaluminate hydrates were precipitated from different sodium hydroxoaluminate and hydroxoaluminate-hydroxide solutions at ambient temperature, at C_Al = 0.1 M, OH/Al ratios = 4–9 and XS OH/Al ratios = 1–6. The precipitations were monitored by potentiometric (pH) measurements while the final precipitate compositions were examined by chemical analysis, infra-red spectrophotometry and thermal analysis. At solution OH/Al ratio = 4, the main precipitate phase at 20°C was Mg(H₂O)_n[Al(OH)₄]₂ admixed with some Al(OH)₃; at solution OH/Al ratio = 5, the main phase was Mg₂(H₂O)₄[Al₂(OH)₁₀]; at solution OH/Al ratio = 7, the main phase was Mg₄(H₂O)_n(OH)₄[Al₂(OH)₁₀] while at solution OH/Al ratio = 9, the main phase was Mg₆(H₂O)_n(OH)₈[Al₂(OH)₁₀] admixed with some Mg(OH)₂. These hydrates were dehydrated at 60–100°C probably to the compounds Mg₂[Al₂O₃(OH)₄], Mg₄(OH)₄[Al₂O₃(OH)₄] and Mg₆(OH)₈[Al₂O₃(OH)₄], respectively.     

Synthesis of Hydrotalcite using Magnesium from Seawater and Dolomite

Abstract

Three methods of synthesizing hydrotalcite(HT) have been developed using magnesium from seawater and dolomite(MgCa(CO₃)₂). In the first process, 1.0M Na₂CO₃solution was added to calcium ion free artificial seawater containing AlCl₃ with an initial Mg/Al molar ratio of 2.0～3.7 until a pH of 10 was obtained. The solution was then continuously stirred for Ih at 60°C. CO₃ ^2--HT was precipitated as a single phase, and the initial Mg/Al molar ratio, which each recovery of Mg²⁺and Al³⁺ from the solution was above 98%, was 2.0–2.3. In the second process, a Ca(OH)₂ slurry was added to artificial seawater containing AlCl₃ with an initial Mg/Al molar ratio of 1.0～5.0 until a pH of 10.5 was obtained, and then was stirred for Ih at 60°C. HT was also precipitated as a single phase with initial Mg/Al molar ratio 2.0～4.0. The initial Mg/Al molar ratio, which each recovery of Mg²⁺ and Al³⁺ from the solution was above 98%, was 2.2～3.3, but SO₄ ^2- and Cl^? were contained in the precipitated HT. When HT was produced using initial Mg/Al molar ratio of 3.0 at 25°C, SO₄ ^2- and Cl^?in the HT were ion-exchanged with CO₃ ^2- in a 0.05M Na₂CO₃solution for 24h at 25°C, and SO₄ ^2- and Cl^? content of the HT were decreased to 0.5 and 0.05wt%, respectively. In the third process, dolomite calcined at 1000°C was added to an AlCl₃ solution with an initial Mg/Al molar ratio of 1.0～2.0, and the solution was stirred for 1～4h at 25～90°C. HT was precipitated with the smallest amount of MgO and Mg(OH)₂ when the initial Mg/Al molar ratio was 1.5 and the solution was stirred for 4h at 90°C.     

On the effects of Ga3+ and La3+ ions in MgCu ferrite: Humidity‐sensitive electrical conduction

Pure and gallium or lanthanum substituted MgCu ferrites, Mg_0.5Cu_0.5Fe_2‐xM_xO₄ (with x = 0 or 0.2 and M = La or Ga) have been prepared by solid state reaction. Sintering experiments were carried out at different temperatures between 900 and 1100°C. The phase composition and lattice parameters were determined by XRD, while the effect of Ga and La substitutions on the granular structure was studied by SEM. Experimental results revealed that the densification behaviour and some physical properties are in close relation with the structural changes of pure ferrite caused by the presence of La and Ga substitutions. The gallium containing compound, Mg_0.5Cu_0.5Fe_1.8Ga_0.2O₄, is monophasic and contains a great number of pores, whereas the lanthanum containing compound, Mg_0.5Cu_0.5Fe_1.8La_0.2O₄, is biphasic and exhibits a high density. The humidity characteristics show that the gallium ion enhances the humidity sensitivity of the MgCu ferrite sintered at 1000°C. This interesting effect is promising for the future of the Ga‐substituted MgCu ferrite to be used as sensitive material for fabrication of ceramic humidity sensors. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Distribution of Cations and the Proton Location in Kaersutite

The crystal of Kaersutite, (Na_0.63K_0.37Ca_1.99) (Mg_3.10Fe_0.98Al_0.51Mn_0.01Ti₀₅₅) (Si_6.07Al_1.93) (O, OH)₂₄ from lecality Vlčí Hora – Bohemia was studied by powder neutron diffraction. The refinement of the crystal structure within space group C2/m gave cell dimensions a = 0.9863, b = 1.8040 and c = 0.5306 nm, β = 105° 28′, Z = 2. Protons were found to form bridges between two 03 ioxygens. (This location allows for the existence of proton per f.u. in maximum). The actual population was refined to 0.8. The occupation of the five eation sites was determined as follows: M 1 (0.60 Mg + 0.25 Ti + 0.10 Al + 0.05 Fe), M 2 (0.50 Mg + 0.35 Fe + 0.15 Al), M 3 (0.8 Mg + p.2 Fe), M 4 (Ca) and A (Na, K).     

Nanostructural and optical features of amorphous AlxSi0.45−xO0.55 (0 ⩽ x ⩽ 0.05) thin films prepared by RF-magnetron sputter techniques

The nanostructural, chemical, and optical features of Al_xSi_0.45−xO_0.55 (0 ⩽ x ⩽ 0.05) thin films were investigated in terms of Al concentration and post-deposition annealing conditions; the films were prepared by co-sputtering a Si main target and Al-chips, and the annealing was carried out at temperatures of 400–1100 °C. The a-Si_0.45O_0.55 films prepared without Al-chips and annealed at 800 °C contain ∼3.5 nm-sized Si nanocrystallites. The photoluminescence (PL) intensity as well as the volume fraction of Si nanocrystallites increased with increasing the concentration of Al to a certain level. In particular, the intensity of the PL spectra of the Al_0.025Si_0.425O_0.550 films which were annealed at 800 °C increased significantly at wavelengths of ∼580 nm. It is highly likely that the observed increase in the PL intensity is caused by the raise in the total volume of the ∼3.5 nm-sized nanocrystallites in the films. The addition of Al as well as the post-deposition annealing allow adjustment and control of the nanostructural and light-emission features of the a-SiO_x films.     

Application of Rietveld Method to the Structural Characteristics of Substituted Copper Ferrite Compounds

A series of ferrite samples of the chemical composition Cu_0.7 (Zn_0.3‐xMg_x)Al_0.3Fe_1.7O₄ [x=0.05, 0.1, 0.15 and 0.2], prepared by ceramic technique at 1000°C, were found to have cubic spinel structure. On applying the full pattern fitting of Rietveld method using FullProf program, the exact coordinates of atoms, the unit cell dimensions, the atom occupation factors, isotropic temperature factors, the profile shape parameters as well as the interatomic distances have been determined. It was found that the lattice parameter decreases with increasing the Mg content. Also the variation of the cation distribution has been discussed on the basis of site preference, size and valence of the substituting cations. The low isotropic microstrain values obtained during the refinement process may be attributed to the method of the preparation in which the samples after the last sintering were treated by annealing.     

The crystal structure of an iron-rich variety of zanazziite belonging to heteropolyhedral framework roscherite-group beryllophosphates

The iron-rich variety of zanazziite Ca₂[Mg_0.65Fe_0.35□_1.0][Mg_1.90Fe_1.25Al_0.5Mn_0.35]_Σ4Be₄(PO₄)₆(OH)₄(H₂O,OH)₂ · 4H₂O, which is a heteropolyhedral framework roscherite-group beryllophos-phate from the Sapucaia pegmatite (Minas Gerais, Brazil), was studied by X-ray diffraction. The refinement was carried out in the triclinic and monoclinic systems. It was found that the cation distribution on octahedral sites in the crystal structure is in better agreement with the monoclinic symmetry (a = 15.876 Å, b = 11.860 Å, c = 6.607 Å, β = 95.49°, sp. gr. C2/c). In the sample under study, no ordering of Mg or Fe atoms in octahedral sites is observed in sp. gr. P \(\bar 1\), unlike the more iron-rich member of the roscherite group (atencioite).     

Nd3+:Y3Al5O12 laser ceramics: Influence of the size of yttrium oxide particles on sintering

The influence of the size of Y₂O₃ powder particles on the structure formation and densification of Nd³⁺:Y₃Al₅O₁₂ laser ceramics has been studied. It is shown that the use of 50- and 100-nm yttrium oxide particles makes it possible to synthesize single-phase yttrium aluminum garnet at temperatures of 1200 and 1500°C, respectively, whereas in the case of 5000-nm yttrium oxide particles 2-h exposure at a temperature of 1500°C yields only 80 wt % of the Nd³⁺:Y₃Al₅O₁₂ phase. Bulk swelling of pressed samples during sintering of 2.94Y₂O₃-0.06Nd₂O₃-5Al₂O₃ powders with the size ratio of the initial particles R(Al₂O₃/Y₂O₃) ～ 5 is observed. The application of different-sized powders (R ～ 2.5) provides quantitative ratios between phases in the 3Y₂O₃-5Al₂O₃ system at which shrinkage in a temperature range of 20–1500°C is dominant. Laser ceramics 0–2 at % Nd³⁺:Y₃Al₅O₁₂ have been obtained by the solid-phase sintering of oxide powders (R ～ 2.5). The slope efficiency for 1 at % Nd³⁺:Y₃Al₅O₁₂ laser ceramics is found to be 33%.

     

Structure and optical properties of Mg‐doped ZnO nanoparticles by polyacrylamide method

Mg‐doped ZnO (Mg_xZn_1‐xO) nanoparticles with precise stoichiometry are synthesized through polyacrylamide polymer method. Calcination of the polymer precursor at 650 °C gives particles of the homogeneous solid solution of the (Mg_xZn_1‐xO) system in the composition range (x < 0.15). ZnO doping with Mg causes shrinkage of lattice parameter c. The synthesized Mg_xZn_1‐xO nanoparticles are typically with the diameter of 70–85 nm. Blue shift of band gap with the Mg‐content is demonstrated, and photoluminescence (PL) from ZnO has been found to be tunable in a wide range from green to blue through Mg doping. The blue‐related PL therefore appeared to be caused by energetic shifts of the valence band and/or the conduction band of ZnO. Mg_xZn_1‐xO nanoparticles synthesized by polyacrylamide‐gel method after modified by polyethylene glycol surfactant have a remarkable improvement of stability in the ethanol solvent, indicating that these MZO nanoparticles could be considered as the candidate for the application of solution–processed technologies for optoelectronics at ambient temperature conditions.     

High-quality silicon/insulator heteroepitaxial structures formed by molecular beam epitaxy using Al2O3 and Si

Heteroepitaxial growth of γ-Al₂O₃ films on a Si substrate and the growth of Si films on the γ-Al₂O₃/Si structures by molecular beam epitaxy have been investigated. It has been found from AFM and RHEED observations that, γ-Al₂O₃ films with an atomically smooth surface with an RMS values of ∼3 Å and high crystalline quality can be grown on Si (1 1 1) substrates at substrate temperatures of 650–750°C. Al₂O₃ films grown at higher temperatures above 800°C, did not show good surface morphology due to etching of a Si surface by N₂O gas in the initial growth stage. It has also been found that it is possible to grow high-quality Si layers by the predeposition of Al layer followed by thermal treatment prior to the Si molecular beam epitaxy. Cross-sectional TEM observations have shown that the epitaxial Si had significantly improved crystalline quality and surface morphology when the Al predeposition layer thickness was 10 Å and the thermal treatment temperature was 900°C. The resulting improved crystalline quality of Si films grown on Al₂O₃ is believed to be due to the Al₂O₃ surface modification.     

An X‐ray powder diffraction study of the microstructural evolution on heating 3:2 and 2:1 mullite single‐phase gels

Single‐phase gels with compositions 3Al₂O₃·2SiO₂ and 2Al₂O₃·SiO₂ were prepared by gelling mixtures of aluminium nitrate and tetraethylorthosilicate. Gels were fast heated at different temperatures between 900°C and 1600°C. The phase transformation and microstructural changes of both mullite precursor gels over the temperature range were followed by X‐ray powder diffraction (XRD), lattice parameter determination (LP), and scanning and transmission electron microscopies (SEM and TEM). The distribution of crystallite sizes and strains were determined by linewidth refinements of X‐ray diffraction patterns using the integral breadth method of Langford and the Warren‐Averbach analysis. XRD of both heated gels showed the formation of crystalline mullite single phase. Some amount of glassy phase coexisted with mullites at low temperatures, i. e. below 900°C. The compositional range of mullites formed on heating gels at temperatures between 900°C and 1600°C was dependent on the starting nominal composition of gels. SEM and TEM micrographs of both heated gels below 1200°C showed the formation of small, discrete, prismatic, well‐shaped nanocrystals in a very ordered arrangement. The size of these nanocrystals was dependant on the nominal composition of gels and increased on rising the heating temperature of gel precursors. The microstructural features obtained from linewidth refinement results of X‐ray diffraction patterns also allowed to suggest the formation of prismatic a little elongated nanocrystals at temperatures below 1200°C. Microstrain values were small and only displayed a relatively significant value for mullites processed at 900°C. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication of Cr4+,Nd3+:YAG transparent ceramics for self-Q-switched laser

Transparent 0.1 at.%Cr,1.0 at.%Nd:YAG (Y₃Al₅O₁₂) ceramics were fabricated by a solid-state reaction and vacuum sintering with CaO as a charge compensator and tetraethyl orthosilicate (TEOS) as a sintering aid using high-purity powders of Al₂O₃, Y₂O₃, Nd₂O₃ and Cr₂O₃. The mixed powder compacts were sintered at 1800 °C for 5 h and 30 h under vacuum. The optical transmittance of the Cr,Nd:YAG ceramics sintered at 1800 °C for 5 h and 30 h is ∼63% and ∼78% in the infrared wavelengths, respectively. The two samples exhibit pore-free structures and the average grain size is about 10 and 20 μm. For the sample sintered at 1800 °C for 5 h, the dominant fracture mechanism is the transgranular fracture. With increase of holding time up to 30 h, the ratio of intergranular fracture surfaces increase and more Cr³⁺ ions in the Cr,Nd:YAG ceramic transform to Cr⁴⁺. High-quality Cr⁴⁺,Nd³⁺:YAG transparent ceramics may be a potential self-Q-switched laser material.     

Crystal and Molecular Structure of 1-Ethyl-3-[tris(trimethylsiloxanyl)silyl]pyrrolinium Hydrochloride

The crystal and molecular structure of 1-Ethyl-3[tris(trimethylsiloxyl)silyl]pyrrolinium hydro-chloride (C₁₅H₃₈N⁺O₃Si₄ · C¹⁻) has been determined by direct methods. The title compound crystallizes in the monoclinic space group C2/c with a = 20.640(3), b = 19.494(2), c = 27.34(3) Å, β = 90.60(4)°, V = 11000(13) ų, Z = 16, D_x = 1.034 Mg m⁻³. There are two molecules with different conformations in the crystal. The pyrroline rings are non-planar.-The Si O Si angles range from 149(1)° to 163(1)°. Two of the SiMe₃ groups are disordered. All molecules are connected by C¹⁻ – N⁺ contacts and C¹⁻ - HN⁺ hydrogen bonds to form double chains.     

Phase Equilibrium of the Ga–Al–Sb system

Employing the method of liquid-phase epitaxy (LPE) solid-solutions of Ga_1–xAl_xAl_xSb (0 ≦ x ≦ 0.8) have been obtained. The dependence of Sb solubility on Al concentration in the liquid phase at 403°C, 452°C, 500°C has been established. The dependence of AlSb concentration in the solid phase on the composition of the liquid phase has been investigated at 452°C. Using the chemical constants equilibrium method, the phase equilibrium of the Ga–Al–Sb system in the region of liquid phase composition near the Ga-rich corner of the phase diagram has been calculated. The comparison of experimental and calculated data for the liquid and solid phases shows their agreement within the limits of experimental error.     

Thermal expansion and transition temperature of glasses in the systems BeO–Al2O3–B2O3 and MgO–Al2O3–B2O3

Researches were conducted for glasses in the systems BeO–Al₂O₃–B₂O₃ and MgO–Al₂O₃–B₂O. The following characteristics have been determined: thermal expansion coefficient within 20–300 °C, structural thermal expansion coefficient (STEC) and glass transition temperature. The discussed properties of Be-aluminoborate and Mg-aluminoborate glasses have been compared with those of Ca-, Sr- and Ba-aluminoborate glasses. TEC of studied glasses gets higher going from Be-aluminoborate glasses to Ba-aluminoborate ones, but T_g decreases under the same succession. The dependence of STEC on the nature of a given cation is more complicated. The pattern of dependence of the properties on composition is due to changing the boron coordination number with respect to oxygen, which is the main network-former, and to competition between the aluminium and boron for the oxygen brought by an ion-modifier. The difference between the effect of one ion-modifier and that of another is determined by decreasing the radius of an ion and increasing its electric field strength in the succession from Ba²⁺ to Be²⁺. The ions of Be and Mg can also act as network-former to some extent.     

Ferroelectric PbTiO3 Powders and Thin Films Derived from Sol-Gel Processing

Lead titanate powders and thin films were prepared by the sol-gel process of metal alkoxide solutions and solvents. From DSC measurements, phase transition temperature of crystallized PbTiO₃ powders was obtained at about 484 °C. From XRD investigation, it was confirmed that the tetragonal phase of polycrystalline PbTiO₃ thin films is formed by coating of concentrated solution on all of the substrates we used after heat treatment above 500 °C. It was found by SEM and ellipsometric analysis that the thin film coated with 0.25 M concentrated solutions once had an average thickness of about 720 Å. Surfaces of thin films were crack-free, uniform, and its average grain size investigated by SEM was 0.6–0.8 μm. Band gap energy of PbTiO₃ thin film coated on the Al₂O₃ (2243) substrate was 3.45 eV, which is assumed to be due to the direct band to band transition. Dielectric constant (ϵ) and dielectric loss (tan δ) of PbTiO₃ thin film amounted to 60–70 and 0.01–0.02 in the region of 10 kHz ∼ 1 MHz at room temperature, respectively, and transition temperature was 486 °C at 1 MHz. From the hysteresis loop of PbTiO₃ thin film, spontaneous polarization of 12 μC/cm² and coercive filed of 45 kV/cm were obtained.     

Mild hydrothermal synthesis and structures of mixed‐valence iron phosphates: SrFe3(PO4)3 and the interesting Mg2+‐doped AFe3 (PO4)3 (A = Ba,Pb) in Fe2+ site

Series of mixed valence monophosphates AFe_3‐xMg_x(PO₄)₃ [A = Sr(x = 0), Ba(x = 0.6), Pb(x = 0.6)] were synthesized by mild hydrothermal treatment at 210 °C. Refinements of single crystal X‐ray diffraction datas show all these compounds are isostructural. The attempts to make AFe₃(PO₄)₃ (A = Ba, Pb) hydrothermally in the experiment were unsuccessful. However, the Mg‐doped homologues AFe_2.4Mg_0.6(PO₄)₃ (A = Ba, Pb) were synthesized with the addition of MgCO₃ in the reactants as mineralizer. EDS and single crystal X‐ray data refinement indicated that the Mg²⁺ cations were doped in the Fe²⁺ sites of AFe_2.4Mg_0.6(PO₄)₃ (A = Ba, Pb). The influence of the Mg‐doping on the structure and the reason why the Mg doped in the Fe(II) site instead of A site was discussed from the point of view of the bond valence model.     

The Range of Metastable Formation and the Morphology of the Crystals in the System CaCO3–MnCO3

Both slow precipitation, hydrogen carbonate transport at room temperature as well as hydrothermal decomposition of oxalates were used to grow mixed crystals in the system CaCO₃–MnCO₃. The limits of the immiscibility gap below 400 °C and the range of metastable formation at low temperatures were investigated Changes of the morphology of the crystals dependent on the temperature of formation and their composition are described.     

Solar-blind 4.55 eV band gap Mg0.55Zn0.45O components fabricated using quasi-homo buffers

A route for synthesizing high Mg content single-phase wurtzite MgZnO films having band gaps in the solar-blind region is demonstrated by employing molecular beam epitaxy on Al₂O₃ substrates. Importantly, a low Mg content “quasi-homo” buffer, Mg_0.17Zn_0.83O, was applied to accommodate a host of structural discrepancies and therefore, avoiding phase separation in a high Mg content film, Mg_0.55Zn_0.45O, as proved by X-ray diffraction. The Mg fraction in the overgrown single-phase epilayer, Mg_0.55Zn_0.45O, was confirmed by Rutherford backscattering spectrometry.