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1.
Tae-Jin Park Mark J. Davis Paula Vullo Tina M. Nenoff James L. Krumhansl Alexandra Navrotsky 《Journal of the American Ceramic Society》2009,92(9):2053-2058
Barium titanosilicates are possible oxide forms for the immobilization of short-lived fission products in radioactive waste. Ba2 TiSi2 O8 (fresnoite) and BaTiSiO5 (Ba-titanite) samples were prepared by a solid-state synthesis. The enthalpies of formation of Ba2 TiSi2 O8 crystal and glass at 25°C and of BaTiSiO5 glass were obtained from drop solution calorimetry in a molten lead borate (2PbO–B2 O3 ) solvent at 701°C. The enthalpy of formation for fresnoite composition samples from constituent oxides was exothermic and became more exothermic with increasing crystallinity. Differential scanning calorimetry revealed that the crystallization rate of the fresnoite glasses increased with increasing devitrification. A modified Product Consistency Test-Procedure B (PCT-B) was used to collect solubility data on the fresnoite and titanate phases. The tests suggest that both glassy and crystalline fresnoite exhibit favorable aqueous stability and should be explored further as radioactive waste forms for long-term storage. 相似文献
2.
Yong Ding Yoshinari Miura Akiyoshi Osaka 《Journal of the American Ceramic Society》1994,77(11):2905-2910
Improved polar ( c -axis) oriented growth of fresnoite (Ba2 TiSi2 O8 ) was observed for surface crystallization of a glass 33.3BaO· 16.7TiO2 · 50SiO2 (in mol%) due to ultrasonic surface treatment with an aqueous suspension of Ba2 TiSi2 O8 , and an oriented film more than 50 μm in thickness was prepared. The effect of ultrasonic treatment on the polar orientation depends on the suspending particles; of these, foreign particles of a phase other than the crystallizing Ba2 TiSi2 O8 give poorer efficiency than the Ba2 TiSi2 O8 particles. It is assumed that fresnoite has a tendency toward preferred polar growth on the glass, and seeding of a large number of fine particles through ultrasonic bombardment realizes the tendency. The polar-oriented growth kinetics of Ba2 TiSi2 O8 were also discussed. 相似文献
3.
Stephan Senz reas Graff Werner Blum Dietrich Hesse Hans-Peter Abicht 《Journal of the American Ceramic Society》1998,81(5):1317-1321
Fresnoite grows at 700° and 800°C, and Ba6 Ti7 O40 grows at 1200°C with definite orientations, which are determined by X-ray diffraction pole figure analysis. Partially textured fresnoite is formed at higher temperatures. The SiO2 films react with the BaTiO3 crystals, forming the phases Ba2 TiSi2 O8 (fresnoite) and Ba6 Ti17 O40 . At 700° and 800°C, both phases grow with definite orientations, which are determined by X-ray diffraction pole figure analysis. Partially textured polycrystalline phases are formed at higher temperatures. 相似文献
4.
Raman spectra were measured on B2 O3 -SiO2 glasses heat-treated at different temperatures and for different periods of time. It was found that the intensity ratio of the 810- and 475-cm−1 bands depended on the thermal history and composition of glass. The intensity vs heat-treatment temperature curve exhibited a maximum in the glass-transition temperature range. High-temperature Raman spectra were measured on 0.5B2 O3 -0.5SiO2 glass, both with increasing and decreasing temperature, between room temperature and 600°C. Above 300°C with increasing temperature, the intensity of the 810-cm−1 band decreased, whereas the intensity of the 475-cm−1 band increased. The changes reversed with decreasing temperature. The reversible change of the intensity of the two bands was interpreted as a reversible formation and decomposition of boroxy rings with temperature. The reaction becomes very sluggish below the glass transition so that the intensity ratio stayed constant below 300°C. 相似文献
5.
BH. V. JANAKIRAMA-RAO 《Journal of the American Ceramic Society》1966,49(11):605-609
Infrared spectra of binary and ternary compositions in the glassy state and in the devitrified crystalline state in the system GeO2 -P4 O10 -V2 O5 were studied and compared with infrared spectra of crystalline spinels, which are known to contain V5+ ions in sixfold coordination. Results indicated that the fundamental vibration frequency of the V—O bond occurred at wave number 1015 cm−1 . The spectra also provided evidence that the V5+ ion existed in sixfold coordination in the glassy state, as well as in the devitrified crystalline state, and that the VO6 octahedron retained its identity even at low concentrations and melting temperatures of 1450°C. Conductivity measurements indicated that, as the concentration of V2 O5 decreased below the critical range of 5 to 10 mole %, there was an abrupt loss in the electronic conductivity of the glasses; the conductivity decreased with increasing concentration of the lower valence states of vanadium. A mechanism of conduction compatible with the structure of glasses in the system is suggested to explain these observations. 相似文献
6.
Hong-Wen Wang 《Journal of the American Ceramic Society》1995,78(4):1134-1135
in a recent article of the Journal , Yu et al .1 reported their experimental results on the effect of Al2 O3 and Bi2 O3 on the formation mechanism of Sn-doped Ba2 Ti9 O20 . They claimed that both Al2 O3 and Bi2 O3 can dramatically assist the formation of Sn-doped Ba2 Ti9 O20 but are based on different mechanisms. They concluded that first, Bi2 O3 melts above 830°C and accelerates the migration of the involved reactants to form Ba2 Ti9 O20 ; second, Al2 O3 can reduce the height of the potential energy barrier of the formation of Ba2 Ti9 O20 due to the intergrowth of BaAl2 Ti6 O16 phase. They explained their results from a point of view that the formation of Ba2 Ti9 O20 is controlled by (1) the migration of reactants to the interfaces and (2) the height of the potential-energy barrier of the reaction at the interfaces. However, based on their results, we feel their conclusions are incautious and may be misleading, as will be discussed later. 相似文献
7.
Yaping Zhang Yunxia Yang Yuwen Ou Wei Hua Jiahua Zheng Guorong Chen 《Journal of the American Ceramic Society》2009,92(8):1881-1883
Glasses with compositions 50Bi2 O3 – x Sb2 O3 –10B2 O3 –(40– x ) SiO2 ( x =0, 1, 3, 5, 8, 10) have been prepared by conventional melt quench technique. Substitution of Sb2 O3 for SiO2 exerted an obvious effect on properties of glasses, especially, increased glass transition temperature ( T g ) and crystalline temperature ( T c ) greatly. Results of infrared transmission spectra attributed the effect to the formation of new bridging bonds of Sb–O–B and Sb–O–Si in glass network. 相似文献
8.
E. F. RIEBLING 《Journal of the American Ceramic Society》1973,56(6):303-309
Binary Sb2 O3 -GeO2 glasses containing 45 mol% Sb2 O3 and ternary Sb2 O3 -B2 O3 -GeO2 glasses containing 50 mol% GeO2 were prepared. Their densities (volumes), refractive indices, and infrared spectra were determined, and their colors and high-temperature viscosities were estimated visually. Small amounts of Sb2 O3 (∼10 mol%) appear to perturb neither the Ge-O-Ge network nor those B-O-Ge networks with small B/Ge ratios (∼0.2). The B-O-Ge networks with larger B/Ge ratios (∼1.0) depolymerize in the presence of even less Sb2 O3 . Amounts of Sb2 O3 >10 mol% appear to depolymerize the Ge-O-Ge and Ge-O-B networks progressively, possibly with the formation of chains. A structurally sensitive ir isofrequency contour technique developed for ternary glass systems was applied successfully to these Sb2 O3 -B2 O3 -GeO2 glasses. These contours can thus readily detect significant network depolymerization in the absence of the usual network modifiers. 相似文献
9.
Sea-Fue Wang Chiang-Chuang Chung Chai-Hui Wang Jinn P. Chu 《Journal of the American Ceramic Society》2002,85(6):1619-1621
Preparation of dense and phase-pure Ba2 Ti9 O20 is generally difficult using solid-state reaction, since there are several thermodynamically stable compounds in the vicinity of the desired composition and a curvature of Ba2 Ti9 O20 equilibrium phase boundary in the BaO–TiO2 system at high temperatures. In this study, the effects of B2 O3 on the densification, microstructural evolution, and phase stability of Ba2 Ti9 O20 were investigated. It was found that the densification of Ba2 Ti9 O20 sintered with B2 O3 was promoted by the transient liquid phase formed at 840°C. At sintering temperatures higher than 1100°C, the solid-state sintering became dominant because of the evaporation of B2 O3 . With the addition of 5 wt% B2 O3 , the ceramic yielded a pure Ba2 Ti9 O20 phase at sintering temperatures as low as 900°C, without any solid solution additive such as SnO2 or ZrO2 . The facilities of B2 O3 addition to the stability of Ba2 Ti9 O20 are apparently due to the eutectic liquid phase which accelerates the migration of reactant species. 相似文献
10.
The phase development sequence based on a composition equivalent to Ba2 Ti9 O20 during heating is found to be in the following order: BaTi5 O11 > BaTi4 O9 > Ba2 Ti9 O20 . The lowest rate of formation of Ba2 Ti9 O20 is caused by its high surface energy and interface energy, which result in a low nucleation rate. The existence of BaTi5 O11 in calcined powder helps to form Ba2 Ti9 O20 in sintered compacts. The effect of BaTi5 O11 on Ba2 Ti9 O20 formation can be explained by their similar oxygen packing and by reduced volume change during transformation. The amount of BaTi5 O11 formed during heating depends greatly on the compositional homogeneity of powders. The addition of SnO2 aids the formation of Ba2 Ti9 O20 by reduced strain energy at transformation and reduced surface energy. 相似文献
11.
The hexagonal perovskite, Ba8 ZnTa6 O24 , was prepared in single-phase form and was found to be a stable secondary phase, formed as a result of the loss of ZnO from Ba(Zn1/3 Ta2/3 )O3 microwave dielectrics. The experimental and calculated X-ray patterns of Ba8 ZnTa6 O24 indicate it is isostructural with Ba8 Ta6 NiO24 with an 8H (cchc)2 close-packed BaO3 stacking sequence and the lattice parameters, a =10.0825(14), c =19.0587(38)Å. High-density ceramics of Ba8 ZnTa6 O24 could be prepared at temperatures considerably lower (1400°C) than those used to sinter pure Ba(Zn1/3 Ta2/3 )O3 , and exhibit very good microwave dielectric properties with ɛ=30.5, Q f =62 300, and τf =+36 ppm/°C at 8.9 GHz. 相似文献
12.
Terry J. Garino Tina M. Nenoff Tae-Jin Park Alexandra Navrotsky 《Journal of the American Ceramic Society》2009,92(9):2144-2146
Barium (Ba)-substituted CsTiSi2 O6.5 materials of two types, Cs x Ba1− x TiSi2 O(7− x /2) and Cs x Ba(1− x )/2 TiSi2 O6.5 were synthesized with the pollucite structure with 1≥ x ≥0.6. When the Ba-substituted precursor materials were heat treated to 850°C for 4 h, a mixture of amorphous and unidentifiable phases formed. However, with the addition of 10 wt% of crystalline CsTiSi2 O6.5 to the Ba-containing precursors, nearly single-phase pollucite was obtained after 20 h at 750°C for x ≥0.6. The added crystalline CsTiSi2 O6.5 particles act as nuclei that allow the Ba-containing materials to crystallize into the pollucite phase and to avoid the formation of unwanted phases that would otherwise nucleate and grow. These new materials can be used to study the stability of CsTiSi2 O6.5 as a durable ceramic waste form, which could accommodate with time both Cs and its decay product, Ba. 相似文献
13.
Jiaqing Yu Hangwei Zhao Jiasheng Wang Fei Xia 《Journal of the American Ceramic Society》1994,77(4):1052-1056
High-performance Ba2 Ti9 O20 ceramics are attracting great attention, but their formation mechanism still is somewhat unclear. The present investigation shows that the formation of Ba2 Ti9 O20 can be promoted strikingly by the participation of Bi2 O3 and Al2 O3 . The effect of Bi2 O3 on the formation of Ba2 Ti9 O20 is attributed to the fact that migration of the involved reactants is accelerated by liquid which forms from the melting of Bi2 O3 above 830°C. This migration, however, is not the only rate-limiting factor. A high potential-energy barrier, resulting from stress that arises along the crystal-structured layers, also heavily restricts the formation of Ba2 Ti9 O20 . The participation of Al2 O3 , on the other hand, can reduce the height of this potential-energy barrier and effectively improve the kinetics of the formation of Ba2 Ti9 O20 by causing the formation of BaAI2 Ti6 O16 crystals; these crystals intergrow with Ba2 Ti9 O20 crystals and result in decreased stress. 相似文献
14.
The heterogeneous phase distribution found in Ba2 Ti9 O20 ceramic resonators results from a temperature-dependent phase boundary and slow reaction kinetics. When sintered at 1350°C or higher in oxygen the Ba2 Ti9 O20 phase becomes slightly reduced and barium-rich. Thus a stoichiometric composition forms rutile and "Ba2 Ti9 O20 'phase. On slow cooling the excess barium diffuses to the oxygen-rich surface where it reacts to form an envelope of rutile-free material surrounding a core containing a small amount of rutile. 相似文献
15.
Dong-Wan Kim Do-Kyun Kwon Kug Sun Hong Deug Joong Kim 《Journal of the American Ceramic Society》2003,86(5):795-799
Samples of 1/6Ba5 Nb4 O15 ·5/6BaNb2 O6 along with the pure end members, Ba5 Nb4 O15 and BaNb2 O6 , were sintered under low oxygen partial pressure. The degradation mechanisms of dielectric loss in this reducing atmosphere have been studied. We found that the degradation occurred primarily due to the formation of oxygen vacancies caused by the reduction of Nb5+ . This was determined by measuring the electrical conductivity, and through X-ray photoelectron spectroscopy. More importantly, the dielectric loss of 1/6Ba5 Nb4 O15 ·5/6BaNb2 O6 samples with higher temperature stability was further decreased on sintering in a reducing atmosphere. This observation has been explained by considering the increased porosity and formation of a reduced second phase, Ba0.65 NbO3 . 相似文献
16.
Bing Zhang Qi Chen Li Song Huiping Li Fengzhen Hou 《Journal of the American Ceramic Society》2008,91(6):2036-2038
The influence of 0–16 mol% Sb2 O3 substitution for P2 O5 on the properties of ZnO–P2 O5 glasses has been investigated. It was shown that Sb2 O3 could participate in the glass network and thermal stability of the glasses decreased with increasing Sb2 O3 content. Glass transition temperature T g , softening temperature T s , and water durability all decreased firstly (up to 6 mol% Sb2 O3 added) and then increased. Substitution of 12 mol% Sb2 O3 led to a 16°C decrease in T g and 30°C decrease in T s , and weight loss of the glass was only 0.42 mg/cm2 , which is ∼11 times lower than that of the glass without Sb2 O3 after immersion in deionized water at 90°C for 1 day. The glass containing 12 mol% Sb2 O3 might be a substitute for Pb-based glasses in some applications. 相似文献
17.
Hsin-chun Lu Lawrence E. Burkhart Glenn L. Schrader 《Journal of the American Ceramic Society》1991,74(5):968-972
Barium titanate precursors with Ba/Ti ratio 2:9 and 1:5 were prepared by first hydrolyzing titanium alkoxide and then mixing the resulting titania sol with a barium alkoxide-methanol solution. After drying, the xerogels of the precursors of barium titanates were sintered at temperatures from 700°C (4 h) to 1200°C (110 h or longer). Characterization of the product was performed using X-ray diffraction and laser Raman spectroscopy. At 700°C, BaTi5 O11 was formed from the 1:5 precursor and a two-phase mixture of BaTi2 O5 and BaTi5 O11 was formed from the 2:9 precursor. After prolonged heating at 1200°C, the latter mixture converted to a single-phase material, Ba2 Ti9 O20 . 相似文献
18.
A. HALLIYAL A. SAFARI A. S. BHALLA R. E. NEWNHAM L. E. CROSS 《Journal of the American Ceramic Society》1984,67(5):331-335
Grain-oriented glass-ceramics of Li2 Si2 o5 , fresnoite (Ba2 TiSi2 O8 ), and its isomorphs Sr2 TiSi2 O8 , and Ba2 TiGe2 O8 , were prepared by recrystallizing glasses in a temperature gradient. Electromechanical and hydrostatic piezoelectric properties of these glass-ceramics were measured. Piezoelectric voltage coefficients g33 and hydrostatic voltage coefficient gh of these glass-ceramics are comparable to those of polyvinylidene fluoride and an order of magnitude higher than the corresponding values of lead zirconate-titanate. These glass-ceramics seem to be attractive candidate materials for hydrophones and several piezoelectric devices. Hydrostatic piezoelectric properties of Ba2 TiSi2 O8 and Ba2 TiGe2 O8 single crystals were also measured. The unusually high values of gh in fresnoite single crystals and glass-ceramics are supposed to be due to positive d31 in these materials. A composite model is proposed to explain the positive sign of d31 in fresnoite based on its crystal structure and internal Poisson's ratio stress. 相似文献
19.
Dong-Wan Kim Jeong-Ryeol Kim Sung-Hun Yoon Kug Sun Hong Chang Kyung Kim 《Journal of the American Ceramic Society》2002,85(11):2759-2762
The effect of B2 O3 on the sintering temperature and microwave dielectric properties of Ba5 Nb4 O15 has been investigated using X-ray powder diffraction, scanning electron microscopy, and a network analyzer. Interactions between Ba5 Nb4 O15 and B2 O3 led to formation of second phases, BaNb2 O6 and BaB2 O4 . The addition of B2 O3 to Ba5 Nb4 O15 resulted in lowering the sintering temperature from 1400° to 925°C. Low-fired Ba5 Nb4 O15 could be interpreted by measuring changes in the quality factor ( Q × f ), the relative dielectric constant (ɛr ), and the temperature coefficient of resonant frequency (τf ) as a function of B2 O3 additions. More importantly, the formation of BaNb2 O6 provided temperature compensation. The microwave dielectric properties of low-fired Ba5 Nb4 O15 had good dielectric properties: Q × f = 18700 GHz, ɛr = 39, and τf = 0 ppm/°C. 相似文献
20.
Hiroaki Takeda Masataka Ohgaki Takashi Kizuki Kazuaki Hashimoto Yoshitomo Toda Shigekazu Udagawa Kimihiro Yamashita 《Journal of the American Ceramic Society》2000,83(11):2884-2886
The formation process of Ba2 La8 (SiO4 )6 O2 was clarified using thermogravimetry–differential thermal analysis (TG-DTA) and a high-temperature powder X-ray diffraction (HT-XRD) method. Phase changes identified from the HT-XRD data surprisingly corresponded to the weight loss and/or endothermic peaks observed in the TG-DTA curves. Raw material with the composition Ba2 La8 (SiO4 )6 O2 was completely reacted at 1400°C and produced only an apatite-type compound without a secondary phase. Moreover, the synthesis of Ba2+ x La8− x (SiO4 )6 O2−δ crystals with x = 0–2 was attempted using a solid-state reaction. 相似文献