Phase equilibrium in systems based on oxides of zirconium,lanthanum and samarium

According to the results of the samples studied by X-ray diffraction and microstructural analyzes the phase equilibria in the binary La₂O₃ – Sm₂O₃ and ternary ZrO₂ – La₂O₃ – Sm₂O₃ systems were studied. The boundaries of the phase fields of the binary system are specified and an isothermal cross section of the ternary state diagram of the ZrO₂ – La₂O₃ – Sm₂O₃ system at a temperature of 1500 °C is constructed. No new phases have been identified in the studied systems. It is established that in the ternary system ZrO₂ – La₂O₃ – Sm₂O₃ at 1500 °C fields of solid solutions on the basis of cubic (F) modification with structure of fluorite type, tetragonal (T) modification of ZrO₂, monoclinic (B) modifications of Sm₂O₃, hexagonal (A) are formed. La₂O₃, as well as an ordered phase with a structure of the type of pyrochlore Ln₂Zr₂O₇ (Py). The boundaries of the phase fields and the parameters of the unit cells of the formed phases are determined. A characteristic feature of this isothermal cross section is the formation of a continuous series of solid solutions based on the phase of the pyrochlore type La₂Zr₂O₇ (Sm₂Zr₂O₇). The limiting solubility of Sm₂O₃ in the ordered phase La₂Zr₂O₇ is 16 mol. % along the section Sm₂O₃- (67 mol.% ZrO₂ - 33 mol.% La₂O₃). The solubility of La₂O₃ in the solid solution Sm₂Zr₂O₇ is slightly less and is 11 mol. % along the section La₂O₃- (67 mol.% ZrO₂ - 33 mol.% Sm₂O₃). The isothermal cross-section of the state diagram of the ZrO₂ – La₂O₃ – Sm₂O₃ system at 1500 °C is characterized by the presence of three three-phase (Py + T + F), (A + Py + B), (Py + F + B) and eight two-phase (A + Py), (B + A), (B + Py), (F + B), (T + F), (Py + T), (F + Py-two) areas.     

Phase relationships,important working properties,and classification of ceramic and other bonding systems

Conclusions A range of volume phase characteristics is proposed for suspensions, semifinished articles, and materials based on them, which will facilitate the determination and objective assessment of a variety of materials.A direct link is demonstrated between the chemical nature of the oxide solid phase, typical ionic potential, and the phase composition of the suspension, and the state of the disperse medium, and also the nature of rheological behavior.A number of principles are formulated for obtaining heat-resistant cements, and their classification is proposed, based on the volume proportion of liquid chemically bonded during the setting of the system.A new principle is proposed for obtaining heat-resistant cements based on incorporating in the composition of low-active (with high ionic potential values) materials, small additions of highly active materials. Castings of corundum composition were obtained with _bend after drying in the range 5–15 MPa.Translated from Ogneupory, No. 6, pp. 49–60, June, 1982.     

Phase relationships of rigid rod polymer/flexible coil polymer/solvent ternary systems

Phase diagrams of two types of rigid rod polymer/flexible coil polymer/methanesulfonic acid (MSA) ternary systems were determined by polarized optical microscopy at ambient conditions. The rigid rod polymer is a wholly aromatic high temperature resistant (no measurable T_g) poly (p-phenylenebenzobisthiazole) (PPBT). One of the flexible coil polymers is a wholly aromatic high temperature resistant poly (2,5′(6′) benzimidazole) (ABPBI), the other is a thermoplastic poly[2,2′ -(1–4-phenylene)-6,6′ -bis (3-phenyl-quinoxaline)] (PPQ) with T_g of 359°C. The solvent is methane-sulfonic acid (MSA). The experimentally determined critical concentration points, C_cr, are in excellent agreement with Flory's recent theory. Total phase segregation between the polymer pair in ternary solution was predicted and observed at C > C_cr. Different decomposition mechanisms of phase separation were observed as a function of concentration.     

Phase formation and magnetic properties of M-type lanthanum substituted strontium ferrites

Rare earth ion substitution is one of the most important methods for adjusting the magnetic properties of M-type hexagonal ferrites; however, the regularity of these phase formations has rarely been studied. In this work, La substituted Sr hexaferrite La_xSr_1-xO·nFe₂O₃ (La-SrM, 4.9 ≤ n ≤ 6.0, 0 ≤ x ≤ 0.6) was prepared using the traditional ceramic method. The effects of the Fe/Sr molar ratio (n), calcining temperature, and La³⁺ substitution (x) on SrM phase formation, the crystalline structure, and magnetic properties were investigated. With an increase of x up to a maximum value of 0.5–0.6, a higher calcining temperature is required to form the single M-phase of La-SrM samples. However, the optimal n values of single-phase La-SrM samples differ as the La substitution varies: when x = 0.1, n = 5.5–6.0; x = 0.2, n = 5.5–5.9; x = 0.3, 0.4 and 0.5, n = 5.7–5.8. The magnetic measurements show that La_0.2Sr_0.8O·5.8Fe₂O₃ has the highest specific saturation magnetization (σ_s), which is 2.2% higher than that of unsubstituted SrM (SrO·6Fe₂O₃), while the anisotropic field (H_A), the anisotropic constant (K₁), and Neel point (T_N) of La³⁺ substituted SrM decreased. Detailed structure analyses were conducted to explain the changes in magnetic properties. Fe³⁺ in the spin-up 2a sublattice of La_xSr_1-xO·5.8Fe₂O₃ decreased by approximately 5% from 98.5% (x = 0) to 93.85% (x = 0.4) with an increase in x. Additionally, a small amount of Fe³⁺ was reduced to Fe²⁺ in the spin-down 4f₂ sublattice with the maximum reduction amount of 4.13% reached at x = 0.2, thereby improving σ_s. The decrease in the bond angle of (4f₁) Fe3–O2–Fe5 (12k), (2a) Fe1–O4–Fe3 (4f₁), and (4f₁) Fe3–O4–Fe5 (12k) lead to the weakening of Fe–O–Fe superexchange of La-SrM so that H_A, K_1, and T_n decreased with increasing values of x. This work lays a solid foundation for the study of process regulation and ion substitution of permanent magnet ferrite.     

Collapse of structure in sepiolite and other layered silicate systems

Collapse of structure due to removal of water from sepiolite and other layered silicates was studied. Data from three systems - sepiolite, hydrated C₃S, and hydrated portland cement - are presented. Changes in mechanical properties and helium flow characteristics were correlated with collapse processes in sepiolite. Similarities in helium flow characteristics of the three systems are discussed to elucidate the role of decomposition processes in microstructural collapse. The sepiolite system appears to have potential as a model for the study of collapse processes in other cementitious systems.     

Eu3+-doped transparent potassium lanthanum silicate (KLaSiO4) glass-ceramic nanocomposites: Synthesis,properties and application

The preparation of Eu³⁺-doped novel K₂O-La₂O₃-Al₂O₃-SiO₂ (KLAS)-based glass and transparent KLS (KLaSiO₄) glass–ceramic (GC) nanocomposites is reported. Nanostructures of the transparent GCs were analyzed by FE-SEM, H(R)-TEM and SAED techniques. The average size of the crystallites is calculated using XRD data and found to be in the range 13–19?nm which is matched well with the average particle size observed from TEM images in the range 5–18?nm. Photoluminescence spectra of Eu³⁺ ions exhibit emission transitions of ⁵D₀?→?⁷F_j (j?=?0 and 1–4) under the excitation at 394?nm. The emission spectra reveals up to 3-fold enhancement of luminescence performance of the KLS GC nanocomposites compared to as-prepared glass. This enhancement is caused due to entering of Eu³⁺ ions into the KLS crystal sites by replacing the La³⁺ ions. Such luminescence properties of KLS glass-ceramic nanocomposites could be a promising candidate as laser host for many laser devices.     

A new family of Cu-doped lanthanum silicate apatites as electrolyte materials for SOFCs: Synthesis,structural and electrical properties

La_9.67Si_6-xCu_xO_26.5-x (LSC, x = 0, 0.1, 0.3 and 0.5) are synthesized by a citric-nitrate method. Substitution Si with Cu promotes the densification process of silicate apatite. Unit cell parameters and volume increase linearly with Cu content. The Rietveld refinement reveals a much more distorted (Si,Cu)O₄ tetrahedra in the oxygen stoichiometric La_9.67Si_5.5Cu_0.5O₂₆ sample. The structural observation from high temperature XRD implies a second-order phase transition in La_9.67Si_5.5Cu_0.5O₂₆. Cu-doping decreases the activation energy of oxygen ion conduction and increases the conductivity of LSC materials in the temperature range of 550–800 °C. La_9.67Si_5.5Cu_0.5O₂₆ shows the conductivity values of 29.3 and 12.3 mS cm⁻¹ at 800 °C and 650 °C, respectively. The oxygen ion transference number of La_9.67Si_5.5Cu_0.5O₂₆ is higher than 0.99. These attractive properties make the La_9.67Si_5.5Cu_0.5O₂₆ a promising oxygen ion conducting electrolyte for applications of solid oxide fuel cells, oxygen sensors, oxygen separation membranes, etc.     

Phase transformations in sodium zinc silicate glasses containing PbS nanocrystals

The phase composition and the kinetics of formation of the lead sulfide crystalline phase at the late stages of heat treatments of sodium zinc silicate glasses have been investigated using small-angle X-ray scattering and X-ray powder diffraction. It has been established that, after the completion of the precipitation of the PbS crystalline phase, the reaction PbS + ZnO = PbO + ZnS begins to proceed on the surface of nanocrystals. This reaction results in a decrease in the volume of the PbS phase and the precipitation of ZnS nanocrystals. The size effect has been revealed: PbS nanocrystals with a radius larger than approximately Å are stable, whereas nanocrystals with smaller sizes initiate the reaction PbS + ZnO = PbO + ZnS.     

微化工系统内多相流动及其传递反应性能研究进展

微化工系统是化学工程学科的研究热点之一,鉴于其良好的传递和反应特性,在多相反应和分离过程中受到了广泛的关注。目前关于微化工系统的研究主要集中在新型微分散技术、微介观尺度混合、多相传递性能以及反应过程调控等方面,近年来取得了显著的进展。本文主要针对微化工系统研究中的关键科学问题进行综述,探讨微化工系统的研究进展,并对其未来的发展方向进行了展望。     

Phase formation of Mn-doped zinc silicate in water at high-temperatures and high-pressures

Phase formation of Mn-doped zinc silicate (Zn₂SiO₄:Mn²⁺, ZSM) in high-temperature and high-pressure water was studied by in situ observations with a hydrothermal diamond anvil cell (HDAC). Precursor was prepared with zinc oxalate dihydrate, manganese oxalate, and silica, where the Zn/Mn/Si molar ratio was 192/8/120 to 199/1/120. Conditions of particle formation were at temperatures up to 650 °C and at pressures up to 1250 MPa. Precursors dissolved at temperatures of 145–203 °C and needle-like particles formed through homogeneous nucleation at temperatures from 357 to 374 °C, close to the critical point of water. The needle-like particles grew at growth rates of 0.5–3.8 μm/s and were identified to be ZSM as evident from their green luminescence. ZSM synthesized in supercritical water (400 °C for 180 min) by batch reactions had comparable luminescence with that of ZSM produced by solid-state reaction (1200 °C for 240 min) using the same precursor. The key finding in this work is that the precursors can be made to dissolve in near-critical water and that this allows ZSM to form via a homogeneous nucleation process.     

Preparation of V doped lanthanum silicate electrolyte ceramics by combustion method and study on conductance mechanism

Vanadium doped La_9.33Si_6−xV_xO_26+0.5x (x = 0.5, 1.0, 1.5) (LSVO) electrolyte powder was prepared by combustion method at 600°C for 5-7 min. The powder was sintered at 1500°C for 3 hours to prepare LSVO ceramics. XPS, IR, XRD, and EIS analysis show that V⁵⁺ doping replaces Si⁴⁺ in [SiO₄] to form [Si(V)O₄] tetrahedron. With the increase in x, the lattice volume increase. When x = 2.0, the LaVO₄ phase was formed, indicating that the limit doping amount of V⁵⁺ replacing Si⁴⁺ is x ≤ 1.5. The conductivity of LSVO increases significantly with the increase in x (x ≤ 1.0), which attributed to the defect reaction caused by V⁵⁺ doping. The addition of the interstitial oxygen Oi* in 6₃ channels and the increase of lattice volume leads to increased conductivity. When x = 1.0, the highest conductivity is 1.46 × 10⁻² S·cm⁻¹ (800°C). The doping enhancement conductivity mechanism is the Interstitial oxygen defect-Lattice volume composite enhancement mechanism.     

Structure-property relationships in elastomer-modified terpolymer systems

A number of terpolymers, incorporating as the elastomer phase polybutadiene, polyisoprene, poly-2,3-dimethylbutadiene, poly(butadiene-co-styrene), and poly(butadiene-co-2-methyl-5-vinypyridine), were studied. Matrices were composed of poly(styrene-co-acrylonitrile) (SAN), poly(α-methylstyrene-co-acrylonitrile), and poly(styrene-co-acenaphthylene). At constant elastomer content and elastomer molecular weight in systems employing a SAN matrix, Izod impact resistance was found to vary inversely with rising elastomer-glass transition temperature. In systems of various matrix composition, using a polybutadiene elastomer, heat deflection temperatures were found to very directly and impact resistance inversely with rising matrix-glass transition temperature. In acrylonitrile–butadiene–styrene (ABS), systems of constant matrix composition and elastomer content, varying the elastomer molecular weight from 0.6 to 2.6 × 10⁵ resulted in increasing the Izod impact resistance from 0.67 to 12.8 ft-lb/in. of notch.     

Fabrication of apatite-type lanthanum silicate films and anode supported solid oxide fuel cells using nano-sized printable paste

Apatite-type lanthanum silicate based films have attracted significant interests to use as an electrolyte of solid oxide fuel cells (SOFCs) working at intermediate temperature. We have prepared Mg doped lanthanum silicate (MDLS) films on NiO–MDLS cermet substrates by spin coating and sintering of nano-sized printable paste made by beads milling. Changes in crystal structure and microstructure of the paste films with the sintering temperature have been investigated to show that porous network structure with a grain growth evolves up to 1300 °C, whereas densification occurred above 1400 °C. Anode supported SOFCs using the pasted MDLS films were successfully fabricated: an open circuit voltage of 0.91 V and a maximum power density of 150 mW cm⁻² measured at 800 °C were obtained with the electrolyte film sintered at 1500 °C.     

Phase and microstructural evolution in lithium silicate glass-ceramics with externally added nucleating agent

Development of lithium disilicate-based glass-ceramics critically depends on use of nucleating agent in the glass matrix. The present study reports the effect of externally added nucleating agent Li₃PO₄ in Li₂O–K₂O–MgO–ZnO–ZrO₂–Al₂O₃–SiO₂ system which is compared with a reference composition (GC1) (SiO₂:Li₂O = 2.16:1) prepared with in situ formed Li₃PO₄. For externally added Li₃PO₄, two compositions were studied. In one case (GC2) before addition of Li₃PO₄, SiO₂:Li₂O ratio in glass was maintained as 2.87:1 and in another case (GC3) SiO₂:Li₂O ratio in glass was maintained same as reference GC1 that is, 2.16:1. The glasses were characterized by using MAS-NMR spectroscopy. Sintering and crystallization behavior of the glass-ceramics was characterized by using XRD, SEM, DTA. Due to in situ formation of Li₃PO₄, GC1 resulted in a dense sample with finer crystals of lithium disilicate. In GC2 and GC3, externally added lithium phosphate, which was in the form of ultrafine aggregated particles, formed flower-like colonies of radially outward crystals. Higher SiO₂:Li₂O ratio in GC2 resulted in lithium disilicate crystals and high viscous glass causing large air entrapment and so less densification. GC3 with higher lithia in glass showed higher densification than GC2 but only lithium metasilicate crystals were formed.     

Structure‐property relationships in copolyester elastomer‐layered silicate nanocomposites

While the field of polymer–clay nanocomposites is reaching maturity, some parts of the studied systems still present researchers with possibilities for the improvement of material properties. This study entails the understanding of the relationships in copolyester elastomer/organically modified layered silicate nanocomposite and the structure–property relationships within the system of the nanocomposite. A series of these nanocomposites was prepared via twin‐screw extrusion melt compounding. The experiments included the following three types of synthetic organosilicates: high aspect ratio Somasif (ME100) fluoromica and two lower aspect ratio Laponite synthetic hectorites, (WXFN) and (WXFP). These organosilicates were modified with quaternary octadecyltrimethylammonium bromide (ODTMA) and were used to prepare the nanocomposites. The nanocomposite structure on a micro‐ and nanometre scales was evaluated by two techniques, such as X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The mechanical properties of the nanocomposites were examined to determine the impact aspect ratio of the nanofiller and wt % loading have on performance. The addition of the 2 wt % high aspect ratio of ME100‐ODTMA, in particular, showed statistically improved tensile strength, tear resistance, creep resistance, and water vapor permeation barrier enhancement. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41742.     

Diffusion mechanisms between La2SiO5 and SiO2 during formation of textured lanthanum silicate oxyapatite crystals

Lanthanum silicate oxyapatite (LSO) is a promising alternative electrolyte for solid oxide fuel cell (SOFC) applications. They exhibit anisotropic oxide-ionic conduction; therefore, a preferential crystal orientation along the c-axis is necessary to achieve optimal conductivity. This study is performed to understand the reaction mechanisms involved in the formation of an LSO layer at the interface of the La₂SiO₅/SiO₂ diffusion pair during reactive sintering at high temperatures. Different La₂SiO₅/SiO₂ bilayers were fabricated in sandwich-type structures using silica-type quartz or La₂SiO₅ supports obtained via electrophoresis and uniaxial pressing, respectively. These supports were pre-sintered and then coated with a suspension of the opposite component. The diffusion pairs were isothermally heated at 1500 °C at different holding times (10, 20, and 40 h) and at 1600 °C for 10 h. Their surfaces and cross-sections were investigated via X-ray diffraction, scanning electron microscopy (SEM) observations, energy-dispersive X-ray spectroscopy (EDS), and Raman spectroscopy.Experimental results show that two different driving forces were involved in the nucleation and growth of apatite crystals. The first is the chemical potential gradient in lanthanum between the components of the layers, and the second is the electric field created to preserve the electroneutrality of the system. The predominant diffusing species in this bilayer system were La^+III and O^-II, and their diffusion is enhanced by the formation of a glassy phase on the silica grains through the transformation of silica-type quartz into cristobalite. The formation of a La₂Si₂O₇ intermediate phase was detected, which is vital to the interdiffusion of species and the nucleation and growth of oriented apatite crystals. The porosity gradient observed in the cross-section after reactive diffusion suggests the possibility of achieving an SOFC half-cell device via this process.     

Phase interaction and oxygen transport in oxide composite materials

Abstract

The oxygen permeability of oxide composite membranes containing similar volume fractions of the components, including (La_0.9 Sr_0.1)_0.98 Ga_0.8 Mg_0.2 O_3-δ(LSGM)–La_0.8 Sr_0.2Fe_0.8Co_0.2O_3-δ (LSFC), LSGM–La₂Ni_0.8Cu_0.2O_4+δ (LNC), SrCoO_3-δ–Sr₂Fe₃O_{6.5 ±δ}, Ce_0.8Gd_0.2O_2-δ (CGO)–LSFC and CGO–La_0.7Sr_0.3MnO_3-δ (LSM), was studied at 973–1223 K. In most cases, oxygen transport is substantially affected by component interaction, decreasing ionic conductivity due to cation interdiffusion, and formation of intermediate phases and/or blocking layers at grain boundaries. This interaction is maximised in systems where the phase components have similar structure and thus may form continuous solid solutions, for example LSGM–LSFC, or intermediate compounds such as Roddlesden–Popper phases in LSGM–LNC composites. The results show that, in addition to knowledge of the transport properties and volume fractions of percolating phases, analysis of ionic conduction in oxide composite materials requires assessment of phase interaction and grain boundary processes.     

Synthesis and densification of lanthanum silicate apatite electrolyte for intermediate temperature solid oxide fuel cell via co-precipitation method

Lanthanum silicate apatite (LSA, La_9.33+xSi₆O_26+1.5x, x = 0–0.67) has been widely investigated as a promising electrolyte material for intermediate temperature solid oxide fuel cell (SOFC). In this work, a facile and low-cost co-precipitation method is used to synthesize LSA precursor powders. The well dispersed nanopowders (ca. 70 nm) with pure hexagonal LSA phase are obtained by calcining the precursor at 900 °C. Impurity of La₂SiO₅, caused by the different precipitation productivities of La(NO₃)₃ and TEOS, can be eliminated through lowering the La/Si ratio in the starting mixtures. The dispersant (PEG200) plays a crucial role in co-precipitation processes, which can effectively mitigate the agglomeration and therefore significantly improve the sinterability of the nanoparticles. Dense LSA ceramic with relative density of 98% is obtained after sintering at 1550 °C, which exhibits a conductivity of 0.13 mS cm⁻¹ at 500 °C.