Barium aluminate hydrates: Part V. 2BaO·Al2O3·2H2O and 2BaO·Al2O3

A new compound of formula 2BaO·Al₂O₃·2H₂O has been synthesised and studied by infra-red, X-ray and thermal analytical techniques. This hydrate yielded another crystalline product, 2BaO·Al₂O₃, during dehydration.     

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.     

Cation grain‐boundary diffusivity in SiO2‐ and MgO‐doped Al2O3

Cation grain‐boundary diffusion in undoped and aliovalent‐doped Al₂O₃ is characterized using Cr₂O₃ as a chemical tracer. The compositional depth profiles measured by secondary ion mass spectrometry are fitted to the Whipple‐LeClaire model. The results indicate that cation grain‐boundary diffusivity is insensitive to MgO and SiO₂ dopants between 1100°C and 1300°C.     

Quaternary System Al2O3–CaO–MgO–SiO2: I, Study of the Crystallization Volume of Al2O3

Compatibility relations of Al₂O₃ in the quaternary system Al₂O₃–CaO–MgO–SiO₂ were studied by firing and quenching followed by microstructural and energy-dispersive X-ray examination. A projection of the liquidus surface of the primary phase volume of Al₂O₃ was constructed in terms of the CaO, SiO₂, and MgO contents of the mixtures recalculated to 100 wt%. Two invariant points, where four solids coexist with a liquid phase, were defined, and the positions of the isotherms were tentatively established. The effect of SiO₂, MgO, and CaO impurities on Al₂O₃ growth also was studied.     

Controllable Preparation of Al2O3‐MgO·Al2O3‐CaO·6Al2O3 (AMC) Composite with Improved Slag Penetration Resistance

Compact Al₂O₃‐MgO·Al₂O₃‐CaO·6Al₂O₃ (AMC) composite was obtained by melting technology using industrial alumina, light‐burned magnesia, and quick lime as raw materials based on the Al₂O₃‐MgO‐CaO ternary phase diagram. The results show that the phases of MgO·Al₂O₃ and Al₂O₃ are formed as the main framework with plate‐like CaO·6Al₂O₃ crystals mainly discontinuously embedded in MgO·Al₂O₃. The bulk density of AMC composite is up to 3.42 g/cm³, equivalent to 90.5% of the theoretical density. The synthesized compact AMC composite in the work also exhibits better slag penetration resistance than the castable based on tabular corundum due to the formation of liquid phase.     

Improved Crack Healing and High‐Temperature Oxidation Resistance of Ni/Al2O3 by Y or Si Doping

Recovery of mechanical strength was investigated for 5 vol% Ni/α‐Al₂O₃ nanocomposites that had improved resistance to high‐temperature oxidation by doping with Y or Si (Ni/Al₂O₃‐Y and Ni/Al₂O₃‐Si). Surface cracks disappeared completely because of the oxidation product, NiAl₂O₄. The fraction of crack disappearance was comparable between Ni/Al₂O₃‐Y and Ni/Al₂O₃‐Si. The apparent activation energy of crack healing is similar to the grain‐boundary diffusion of Ni ions in an Al₂O₃ matrix. The rate‐controlling process of crack healing is the grain‐boundary diffusion of cations in an internally oxidized zone (IOZ) of the Ni/Al₂O₃ system. The bending strengths of the as‐sintered and as‐cracked Ni/Al₂O₃‐Y samples were 561 and 232 MPa, respectively. Heat treatment at 1200°C for 6 h resulted in a recovery of the bending strength up to 662 MPa for Ni/Al₂O₃‐Y as well as 606 MPa for Ni/Al₂O₃‐Si. Y and Si dopants were segregated into the Al site at the Al₂O₃ grain boundaries, and then, enhanced covalent bonding occurred with neighboring oxygen. While the flux of Ni ions was retarded slightly by doping with Y and Si, a shorter IOZ provided enough Ni ions to form NiAl₂O₄ on the surface. Ni/Al₂O₃‐Y and Ni/Al₂O₃‐Si have the desirable properties of crack healing and resistance to high‐temperature oxidation.     

Preparation, Structure, and Properties of Thermally and Mechanically Improved Aluminum Titanate Ceramics Doped with Alkali Feldspar

Aluminum titanate (AT) ceramic materials doped with alkali feldspar ((Na_0.6K_0.4)AlSi₃O₈) have been prepared. These ceramics exhibited high sinterability, large resistance to thermal decomposition, and large flexure strength. The existence of liquid-phase feldspar at sintering temperatures promoted the formation of AT ceramics as the sintering agent. It was considered that silicon ions substituting for aluminum ions at the surface of AT crystal grains lowered the surface energy and hindered the diffusion of Ti⁴⁺ and Al³⁺, giving rise to the large resistance to thermal decomposition. As a result, doping with alkali feldspar was found to effectively improve the mechanical and thermal properties of AT ceramics.     

Barium aluminate hydrates—VI. 2BaO.Al2O3.5H2O and 2BaO.Al2O3.H2O

The compound 2BaO.Al₂O₃.5H₂O has been synthesised and studied by infra-red, X-ray and thermal analytical techniques. The compound of approximate formula 2BaO.Al₂O₃.H₂O forms as a dehydration product. The results are interpreted in terms of the known structure.     

Synergistically optimizing electrical and thermal transport properties of Bi2O2Se ceramics by Te‐substitution

Bi₂O₂Se oxyselenides, characterized with intrinsically low lattice thermal conductivity and large Seebeck coefficient, are potential n‐type thermoelectric material in the mediate temperature range. Given the low carrier concentration of ~10¹⁵ cm^?3 at 300 K, the intrinsically low electrical conductivity actually hinders further enhancement of their thermoelectric performance. In this work, the isovalent Te‐substitution of Se plays an effective role in narrowing the band gap, which notably increases the carrier concentration to ~10¹⁸ cm^?3 at 300 K and the electron conduction activation energy has been lowered significantly from 0.33 to 0.14 eV. As a consequence, the power factor has been improved from 104 μW·K^?2·m^?1 for pristine Bi₂O₂Se to 297 μW·K^?2·m^?1 for Bi₂O₂Se_0.96Te_0.04 at 823 K. Meanwhile, the suppressed lattice thermal conductivity derives from the introduced point defects by heavier Te atoms. The gradually decreased phonon mean free path reflects the increasingly intense phonon scattering. Ultimately, the ZT value attains 0.28 for Bi₂O₂Se_0.96Te_0.04 at 823 K, an enhancement by a factor of ~2 as compared to that of pristine Bi₂O₂Se. This study has demonstrated that Te‐substitution of Se could synergistically optimize the electrical and thermal properties thus effectively enhancing the thermoelectric performance of Bi₂O₂Se.     

Electro‐Optic Property of Mg2+/Er3+‐Codoped LiNbO3 Crystal: Mg2+ Concentration Threshold Effect

A series of Mg²⁺/Er³⁺‐codoped congruent LiNbO₃ crystals were grown by Czochralski method from the growth melts containing 0.5 mol% Er₂O₃ while varied MgO content from 0.0 to 7.0 mol%. The unclamped electro‐optic coefficients γ₁₃ and γ₃₃ of these crystals were measured by Mach–Zehnder interferometry. Two different voltage‐applying schemes were adopted: one is the DC voltage applied to the crystal via Al films coated onto crystal surfaces and another is via a pair of external Cu slab electrodes. The coefficients measured by the two schemes show similar strong dependence on Mg²⁺ concentration. The dependence is non‐monotonous, dramatic, and unusual, and reveals the features of two Mg²⁺ concentration thresholds of optical damage: one in the Mg²⁺ concentration range of 1.2–2.0 mol% (in crystal) and another in 4.5–5.0 mol%. Around the threshold the electro‐optic coefficient decreases abruptly at first and then recovers quickly, and the coefficient drops by >20% (12%) at the first (second) threshold, which exceeds the error 3% considerably. The dramatic behavior is qualitatively explained on the basis of the EO coefficient model of LiNbO₃ and the defect structure model for Mg²⁺‐doped LiNbO₃.     

Al2O3含量对燃烧合成铝酸钙粉体物相组成的影响

本文以CaO、Al和Al2O3为原料,在氧气气氛下,采用燃烧合成法(CS)制备铝酸钙粉体,计算了CaO-Al-Al2O3-O2体系的绝热温度,结合物质自由能函数的相关理论、X衍射法(XRD),研究了Al2O3含量对燃烧合成铝酸钙粉体物相组成的影响.热力学计算及XRD物相分析结果表明:体系绝热温度随Al2O3含量的增多而降低,但均大于1800 K,说明体系反应可自持;当Al2O3/(Al2O3+ CaO) (mole)分别为0.3,0.47和0.55时,物相组成分别为C3A和C12A7,C12A7和CA,CA和CA2;热力学数据显示C12A7-C3A、C12A7-CA和CA-CA2之间物相可实现转化,但由于燃烧合成反应速度过快及不可控性导致物相之间尚未完成转化,致使燃烧合成铝酸钙的物相生成量与理论量有较大差异.     

Boosting the thermoelectric performance of Bi2O2Se by isovalent doping

N‐type Bi₂O₂Se has a bright prospect for mid‐temperature thermoelectric applications on account of the intrinsically low thermal conductivity. However, the low carrier concentration of Bi₂O₂Se (~10¹⁵ cm^?3) severely limits its thermoelectric performance. Herein, the boosting of the carrier concentration to ~10¹⁹ cm^?3 can be realized in our La‐doped Bi₂O₂Se ceramic samples, which could be ascribed to the formation of isoelectronic traps and the narrowing of band gap, and contribute to a marked increase in the electrical conductivity (from 0.03 S cm^?1 to 182 S cm^?1). Our X‐ray absorption near‐edge structure spectra results reveal that a local disordering of oxygen atoms could be an important reason for the intrinsically low thermal conductivity of Bi₂O₂Se, and the point defects can also suppress the lattice thermal conductivity in La‐doped Bi₂O₂Se. The ZT value can be enhanced by a factor of ~4.5 to 0.35 at 823 K for Bi_1.98La_0.02O₂Se as compared to the pristine Bi₂O₂Se. The coordinated optimization of electrical and thermal properties demonstrates an effective method for the rational design of high‐performance thermoelectric materials.     

High quality factor microwave dielectric ceramics in the (Mg1/3Nb2/3)O2–ZrO2–TiO2 ternary system

Novel high quality factor microwave dielectric ceramics (1?x)ZrTiO₄?x(Mg_1/3Nb_2/3)TiO₄ (0.325≤x≤0.4) and (ZrTi)_1?y(Mg_1/3Nb_2/3)_yO₄ (0.2≤y≤0.5) with the addition of 0.5 wt% MnCO₃ in the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system were prepared, using solid‐state reaction method. The relationship between the structure and microwave dielectric properties of the ceramics was studied. The XRD patterns of the sintered samples reveal the main phase belonged to α‐PbO₂‐type structure. Raman spectroscopy and infrared reflectivity (IR) spectra were employed to evaluate phonon modes of ceramics. The 0.65ZrTiO₄?0.35(Mg_1/3Nb_2/3)TiO₄?0.5 wt% MnCO₃ ceramic can be well densified at 1240°C for 2 hours and exhibits good microwave dielectric properties with a relative permittivity (ε_r) of 42.5, a quality factor (Q×f) value of 43 520 GHz (at 5.9 Ghz) and temperature coefficient of resonant frequency (τ_f) value of ?5ppm/°C. Furthermore, the (ZrTi)_0.7(Mg_1/3Nb_2/3)_0.3O₄?0.5 wt% MnCO₃ ceramic sintered at 1260°C for 2 hours possesses a ε_r of 31.8, a Q×f value of 35 640 GHz (at 6.3 GHz) and a near zero τ_f value of ?5.9 ppm/°C. The results demonstrated that the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system with excellent properties was a promising material for microwave electronic device applications.     

Preparation,microstructures, and mechanical properties of directionally solidified Al2O3/Lu3Al5O12 eutectic ceramics

Al₂O₃/Lu₃Al₅O₁₂ (LuAG) directionally solidified eutectic (DSE) ceramics with two solidification rates were prepared utilizing optical floating zone (OFZ) technique. The microstructures (eutectic morphology, preferred growth direction and interface orientation) of Al₂O₃/LuAG were characterized, and the mechanical properties (Vickers hardness and fracture toughness) were compared with those of Al₂O₃/REAG (RE = Y, Er, and Yb). Results show that Al₂O₃/LuAG with solidification rate of 30 mm/h has established preferred growth direction in both Al₂O₃ and LuAG phases with cellular eutectic structures. While Al₂O₃/LuAG with solidification rate of 10 mm/h only shows preferred growth direction in Al₂O₃ phase and presents degenerate irregular eutectic microstructures. Besides, Al₂O₃/LuAG exhibits higher hardness compared with Al₂O₃/REAG (RE = Y, Er, and Yb). In addition, a special attention is focused on the relations among rare earth ionic radius, eutectic microstructures, and mechanical properties of these DSE ceramics. It is demonstrated that a smaller rare earth ionic radius could lead to larger eutectic interspacing as well as higher Vickers hardness of DSE Al₂O₃/REAG, revealing the possibility and feasibility of microstructure control and mechanical properties optimization for DSE Al₂O₃/REAG ceramics by tailoring the rare earth elements.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

BaO−B2O3 system and its mysterious member Ba3B2O6

The first systematic study of the BaO–B₂O₃ system and barium orthoborate Ba₃B₂O₆ (3BaO·B₂O₃) was reported in 1949. Thereafter, the system was repeatedly refined but the structure of Ba₃B₂O₆ compound has not been adequately studied yet. In our study we have, for the first time, obtained the crystalline samples of Ba₃B₂O₆. The solved structure (Pbam, a = 13.5923(4) Å, b = 13.6702(4) Å, c = 14.8894(3) Å) belongs to the class of ‘anti‐zeolite’ borates with a pseudotetragonal [Ba₁₂(BO₃)₆]⁶⁺ cation pattern which contains channels along the c axis filled with anionic clusters. The Ba₃B₂O₆ compound may be regarded as a fluorine‐free end‐member of the Ba₃(BO₃)_2–xF_3x solid solution. The BaO–B₂O₃ phase diagram presented in our study is based on our research and literature data.     

Preparation of porous Al2O3 ceramics by starch consolidation casting method

Porous alumina ceramics were fabricated by starch consolidation casting using corn starch as a curing agent while their microstructure, mechanical properties, pore size distribution, and corrosion resistance were examined. Results showed that the porous alumina ceramics with the flexural strength of about 44.31MPa, apparent porosity of about 47.67% and pore size distribution in the range of 1‐4 μm could be obtained with 3wt% SiO₂ and 3wt% MgO additives. Corrosion resistance results showed mass losses: hot H₂SO₄ solution and NaOH solution for 10 hours were 0.77% and 2.19%, which showed that these porous alumina ceramics may offer better corrosion resistance in acidic conditions.     

Microstructure evolution,mechanical and tribological properties of Ti3(Al,Sn)C2/Al2O3 composites

In this paper, in situ formed Ti₃(Al,Sn)C₂/Al₂O₃ composites were fabricated by sintering the mixture of Ti₃AlC₂ and SnO₂. The Al atoms could diffuse out of the Ti₃AlC₂ layered structure to react with SnO₂, resulting in the formation of Ti₃(Al,Sn)C₂ solid solution and Al₂O₃. When the SnO₂ content was 20?wt.%, the sintered Ti₃(Al,Sn)C₂/Al₂O₃ composite exhibited the best overall mechanical properties, because of the optimized cooperative strengthening effect of solution strengthening and Al₂O₃ enhancement. When the SnO₂ content increased up to 30?wt.%, the flexural strength and fracture toughness of Ti₃(Al,Sn)C₂/Al₂O₃ composite dramatically decreased on account of the large accumulation of generated Al₂O₃. Moreover, according to the SiC ball-on-flat wear tests, it was found that the wear resistance of Ti₃(Al,Sn)C₂/Al₂O₃ composites was significantly improved as the SnO₂ content increased.     

Er3+ cross-section spectra of Er3+/Pr3+:Gd3Ga5O12 single-crystal: Pr3+-codoping effect

Fluorescence and absorption spectra at 530 nm (²H_11/2→⁴I_15/2), 560 nm (⁴S_3/2→⁴I_15/2), 660 nm (⁴F_9/2→⁴I_15/2), 980 nm (⁴I_11/2→⁴I_15/2), 1530 nm (⁴I_13/2→⁴I_15/2), and 2710 nm (⁴I_11/2→⁴I_13/2) of Er³⁺ in Gd₃Ga₅O₁₂ single-crystal codoped with Pr³⁺ have been measured. Judd-Ofelt analysis yields the intensity parameters Ω₂ = (0.68 ± 0.03) × 10⁻²⁰ cm², Ω₄ = (0.60 ± 0.07) × 10⁻²⁰ cm², and Ω₆ = (0.90 ± 0.17) × 10⁻²⁰ cm². A comparison with previously reported values of Er³⁺-only doping case shows that Pr³⁺-codoping causes slight change of both Ω₂ and Ω₄, while onefold increase of Ω₆. From calculated radiative rates and measured fluorescence spectra, Er³⁺ emission cross-section spectra were calibrated at first. Then, the absorption cross-section spectra were calculated using McCumber relation. In parallel, the absorption cross-section spectra were also obtained from the measured absorption spectrum, and compared with those obtained from the McCumber relation. The comparison shows that both methods give consistent result of absorption cross-section spectrum. Further comparison with Er³⁺-only doping case shows that Pr³⁺-codoping causes considerable change of Er³⁺ cross-section value. In spectrally mixing regions of Er³⁺ and Pr³⁺, Pr³⁺ emission affects little the determination of Er³⁺ emission cross-section as Pr³⁺ fluorescence is much weaker than Er³⁺ fluorescence due to low Pr³⁺ concentration.     

Microstructure of mayenite 12CaO·7Al2O3 and electron emission characteristics

Electron emission characteristic, electrical conductivity of polycrystalline mayenite (12CaO·7Al₂O₃) electride, formation of [Ca₂₄Al₂₈O₆₄]⁴⁺(e⁻)₄ framework as a function of phase content, and microstructure have been investigated. The mayenite microstructure was investigated using high-resolution transmission microscopy which revealed the type cage structure of 12CaO·7Al₂O₃ partially filled by extra-framework oxygen ions. Incorporation of electrons by means of carbon ion template 12CaO·7Al₂O₃ produces complex structure, and an incomplete ion template 12CaO·7Al₂O₃ structure consisting of mixture of a [Ca₂₄Al₂₈O₆₄]⁴⁺(e⁻)₄ and [Ca₂₄Al₂₈O₆₄]⁴⁺(O²⁻)₂ framework had a direct effect on the electron emission. Surface chemistry and stability of the 12CaO·7Al₂O₃ electride have been studied using x-ray photoelectron spectroscopy. The work function of phase pure 12CaO·7Al₂O₃ electride was determined from direct thermionic emission data and compared to the measurement from ultraviolet photoelectron spectroscopy (UPS). Depending on the extent of ion template of 12CaO·7Al₂O₃ structure, a work function of 0.9–1.2 eV and 2.1–2.4 eV has been measured and thermionic emission initiating at 600°C.