Inversion of quartz solid solutions at cryogenic temperatures

Quartz solid solution crystals of six different compositions were obtained from crystallization of glass powders belonging to the Li₂O–Al₂O₃-SiO₂ (LAS) system. They were analyzed in situ by laboratory-based X-ray diffraction down to cryogenic temperatures (−190°C). Temperature-resolved analysis of their lattice parameters allowed determination of the critical inversion temperature T_c in these materials, marking the displacive phase transition from a high-quartz- to a low-quartz-like lattice. Integrating available data from other literature sources, an updated phase diagram for the occurrence of high and low quartz solid solution phases is provided for the LAS system; these data are expected to support future development of functional materials relying on these crystalline phases.     

Towards new zero-thermal-expansion materials: Li-free quartz solid solutions stuffed with transition metal cations

Stuffed aluminosilicate quartz solid solutions (Qss) represent the main functional component of state-of-the-art zero-thermal-expansion glass-ceramics. For the first time, we present the synthesis of Li-, Mg- and Zn-free Qss solely stuffed with transition metal cations (Fe²⁺, Ni²⁺, Co²⁺); partial Li⁺ co-doping enables also significant Mn²⁺ incorporation. They were obtained by glass powder crystallization; Qss crystals exhibit compositionally tunable coefficients of thermal expansion (CTEs), from ? 2 × 10^?6 K^?1 to ～10 × 10^?6 K^?1 in the range 30–300 °C. Co²⁺-bearing crystals exhibit the closest-to-zero CTE value (0.2 ×10^?6 K^?1) and the most isotropic behavior in the whole Qss family, opening up new perspectives for the development of Li-free low-expansion materials. From a structural point of view, we identified the unit cell volume (and not the pseudo-hexagonality of the aluminosilicate framework) as the key structural parameter leading to low or negative CTEs in Qss, with a linear correlation extending to non-stuffed non-silicate quartz-like phases.     

XRD, EDX and IR analysis of solid solutions between thaumasite and ettringite

Solid solutions between thaumasite and ettringite were prepared by methods analogous to those well established for the preparation of thaumasite and ettringite. The extent of immiscibility in this system is investigated by varying the Al:Si and SO₄²⁻:CO₃²⁻ ratios in reactant mixtures. The solids produced were analysed by quantitative X-ray diffraction, with Rietveld refinement also providing accurate unit cell dimensions, energy-dispersive X-ray analysis and infrared spectroscopy. The compositional and unit cell variations in the solid solution are discussed. A wide variety of solid solution compositions were produced with both the thaumasite and ettringite structures, but all preparations were considerably diluted by secondary amorphous products.     

Thermodynamic and structural analyses of the solid phases in multi-alkane mixtures similar to petroleum cuts at ambient temperature

Structural analyses were carried out by X-ray diffraction, at ambient temperature, on multi-alkane samples whose mole fraction distribution shows a shape of the ‘exponential decreasing’ type, as observed in petroleum cuts. Nine samples, whose normal-alkane number varies from 15 to 23, have been studied with mole fraction continuous distributions of normal-alkanes going from C₂₂-C₃₆ to C₁₄-C₃₆: each mixture differs from the previous sample by the addition of a lighter n-alkane. At the solid state, the multi-alkane solid samples C₂₂-C₃₆ and C₂₁-C₃₆ are two-phase, C₂₀-C₃₆ to C₁₅-C₃₆, three-phase, and the broader distribution C₁₄-C₃₆, four-phase. In these polyphase solid systems, whose heaviest n-alkane is always C₃₆, the average composition of the heavy and middle phases are constant and their structure are isostructural to the β′ ordered intermediate solid solution, observed in n-alkane binary or ternary molecular alloys; the mean carbon atom number of the light phase decreases as the global average carbon atom number of the synthetic mixtures in relation to the addition of light n-alkanes and its structure simultaneously evolves from the β′ ordered intermediate solid solution towards the β-RI(Fmmm) and the disordered solid solutions, observed in pure n-alkanes: the light n-alkane added between each distribution intercalates itself into the structure whose molecule stacking period (thickness) is compatible with its own carbon chain length, in order to reduce the molecular gaps.     

Formation of high entropy metal diborides using arc-melting and combinatorial approach to study quinary and quaternary solid solutions

High entropy metal diborides (HEBs) represent a radically new approach to extend the chemical composition window of ultra-high temperature ceramics (UHTCs). In this work, arc-melting was used to produce dense HEBs starting from UHTC powders. In order to understand the influence of each individual diboride within the quinary system (HfB₂, ZrB₂, TiB₂, TaB₂ and CrB₂), we investigated five quaternary equimolar solid solutions e.g. Hf-Zr-Ti-Ta, Hf-Zr-Ti-Cr, Hf-Zr-Ta-Cr, Hf-Ti-Ta-Cr, Zr-Ti-Ta-Cr and the overall quinary equimolar combination. Arc-melting allowed a rapid screening of favorable and unfavorable combinations. The produced HEBs were free from undesired oxides and characterized by linear variation of lattice parameters typical of diborides and binary solid solutions. Because of evaporation during arc melting, CrB₂ was hardly found in the solid solution, suggesting that vapor pressure should be taken into account when designing HEB compositions especially for operating temperatures exceeding 2000 °C. Finally, Vickers microhardness ranged between the typical values of starting diborides.     

The rheological and structural behavior of silylcellulosics derivatives

The trimethylsilylcellulose (TMSC) samples were characterized in solution by osmometry, viscometry, and gel permeation chromatography. The Mark-Houwink-Sakurada (M-H-S) equation coefficients were determined in chloroform, 1,1,1-trichloroethane, and o-xylene, in all cases the exponent “a” being higher than unit, this indicating a great stiffness of the macromolecules in solution. Also, the temperature dependence of the limiting viscosity number and M-H-S coefficients respectively for TMSC in o-xylene were studied. The exponent from M-H-S equation is also higher than unit, and increases linearly with the temperature. The GPC studies indicates a relative high polydispersity of the studied samples; the polydispersity index being situated between 2 and 3. The change of the crystalline structure as the result of silylation reaction was evidenced, the crystallinity of silyl derivatives depending on the substitution degree (DS), and the molecular weight. The viscous flow parameters for dilute solutions of trimethylsilylcellulose in o-xylene were determined in the temperature range 30–70°C. The temperature dependence of the dynamic viscosity of the solutions obeys an Arrhenius-type equation in which the apparent activation energy is linearly dependent on both the solution's concentration and molecular weight. For preexponential factor no significant dependence on concentration and molecular weight was found. This behavior was attributed to the very great stiffness of the macromolecular chains. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2277–2285, 2001     

Methanol decomposition to synthesis gas at low temperature over palladium supported on ceria–zirconia solid solutions

The Ce_xZr_1−xO₂ solid solution was used as a support of a palladium catalyst for methanol decomposition to synthesis gas at low temperature. All Pd-containing catalysts tested in this study showed high selectivity to synthesis gas (over 96%). The Pd supported on the composite oxide with a Ce/Zr molar ratio of 4/1 exhibited the highest activity. Pd/Ce_0.8Zr_0.2O₂ (17 wt.%) (cop) (prepared by coprecipitation method) showed a conversion of 51.2% for the methanol decomposition at 473 K, which was higher than those over 17 wt.% Pd/CeO₂ (cop) (40.7%) and 17 wt.% Pd/ZrO₂ (cop) (24.3%) at 473 K. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a higher BET surface area and smaller Pd particles than those of 17 wt.% Pd/CeO₂ (cop). Moreover, a more active Pd^σ+ state could be maintained by Zr⁴⁺ ion modification due to promotion of the oxygen mobility and enhancement of the reductibility and increase in the acid sites of the CeO₂ support. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a much higher conversion (51.2%) than that over 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (imp) (prepared by impregnation method) (17.2%) at 473 K. This is due to the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) possessing many small Pd particles. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed an initial conversion of 51.2% at 473 K but the conversion decreased to 43.1% after 24 h on stream. This deactivation was attributed to carbonaceous deposit on the catalyst surface. The amounts of coke on the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst were 0.9 wt.% after 24 h on stream at 473 K and 2.1 wt.% after 1 h on stream at 523 K.     

Temperature-related changes in the structure of YSAG:Yb garnet solid solutions with high Sc3+ concentration

The paper presents the results of the Sc³⁺ solubility limits estimation in dodecahedral and octahedral garnet sites for 1100–1700 °C temperature range. The region of existence of solid solutions with the garnet structure in the Y₂O₃-Al₂O₃-Sc₂O₃ and Yb₂O₃-Al₂O₃-Sc₂O₃ systems narrows with increasing synthesis temperature. The Sc³⁺ solubility in the dodecahedral site of the YbSAG and YSAG garnets decreases with increasing temperature, and at 1700 °C it is about 64 at. %. In the octahedral site of YbSAG garnet, the Sc³⁺solubility decreases from 89.5 to 66.5 at. % with increasing temperature, and in the YSAG system it is about 97.5 at.%. The overall Sc³⁺ solubility with the simultaneous introduction into both garnet sites is lower than with doping on one of the sites and also decreases with increasing temperature. The thermal stability of the compositions belonging to single-phase regions was confirmed by vacuum sintering up to 1850 °C.     

Three-phase borate solid solution with low sintering temperature,high-quality factor,and low dielectric constant

The sintering and microwave dielectric properties of a ceramic material based on the mixing of Mg₃B₂O₆ and Zn₃B₂O₆ have been widely studied using first-principles calculations and experimental solid-state reactions. Characterization methods include the Network Analyzer, X-ray, Raman diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and differential-thermal and thermo-mechanical analyzer. The increasing amount of Mg²⁺ results in the appearance of Mg₂B₂O₅ and ZnO, and the mutual substitution (Mg²⁺ and Zn²⁺) phenomenon has emerged in Zn₃B₂O₆ and Mg₂B₂O₅. The mechanisms have been explained with the help of DFT calculations. The bond parameters and electron distributions of the ZnO₄ tetrahedron and MgO₆ octahedron have been modified due to substitution. The sintering, substitution, and phase formation properties have been analyzed quantitatively through the energy parameters. The best dielectric properties were obtained for x = 0.20 sintered at 950°C, ε_r = 6.47, Q × f = 89 600 GHz (15.2 GHz), τ_f = −48.6 ppm/°C, relative density = 96.7%. The mixing of Zn₃B₂O₆ and Mg₃B₂O₆ ceramics is a feasible method to obtain a ceramic with low sintering temperature and excellent dielectric properties.     

Properties of solid solutions of poly(ethylene oxide)/epoxidized natural rubber blends and LiClO4

Solid solutions of blends of poly(ethylene oxide) (PEO) and epoxidized natural rubber (ENR) comprising 12 wt % of LiClO₄ were studied. Two glass transition temperatures, corresponding to the T_gs of the constituents, confirm immiscibility of the polymers over the entire composition range. It turns out that the T_gs of both polymers slightly increase after addition of salt to the blends. This shift is approximately constant over the whole range of blend composition. Accordingly, T_g measurements reveal that the salt dissolves to approximately equal relative amounts in the two phases. The degree of crystallinity of PEO in blends with ENR descends only to a minor extent with ENR content. However, addition of salt leads first to decreasing crystallinity and second this decrease becomes more pronounced with the addition of ENR. It shows that under these experimental conditions the salt content in PEO increases as compared to ENR. As one expects, the rate of isothermal crystallization does not change in blends as long as PEO is in excess. The situation changes again when salt is added. The rate decreases in a certain range of crystallization temperatures when ENR is added, demonstrating that salt is favorably dissolved in PEO. Conductivity was measured in polymers comprising different salt concentrations. A power‐law dependence of conductivity on salt concentration was found. It results that the mobility of charge carriers in PEO exceeds that of ENR by five orders of magnitude. Therefore, the conductivity in blends is primarily governed by PEO as long as PEO is in excess. Conductivity measurements reveal again that salt is preferably dissolved in PEO. The distribution coefficient is estimated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Aluminum-doped ceria-zirconia solid solutions with enhanced thermal stability and high oxygen storage capacity

A facile solvothermal method to synthesize aluminum-doped ceria-zirconia (Ce_0.5Zr_0.5-xAl_xO_2-x/2, x = 0.1 to 0.4) solid solutions was carried out using Ce(NH₄)₂(NO₃)₆, Zr(NO₃)₃·2H₂O Al(NO₃)₃·9H₂O, and NH₄OH as the starting materials at 200°C for 24 h. The obtained solid solutions from the solvothermal reaction were calcined at 1,000°C for 20 h in air atmosphere to evaluate the thermal stability. The synthesized Ce_0.5Zr_0.3Al_0.2O_1.9 particle was characterized for the oxygen storage capacity (OSC) in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy, and the Brunauer-Emmet-Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce_0.5Zr_0.3Al_0.2O_1.9 solid solutions calcined at 1,000°C for 20 h with a BET surface area of 18 m² g⁻¹ exhibited a considerably high OSC of 427 μmol-O g⁻¹ and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO₂ and Ce_0.5Zr_0.5O₂. The incorporation of aluminum ion in the lattice of ceria-based catalyst greatly enhanced the thermal stability and OSC.     

Catalytic decomposition of nitrous oxide over perovskite type solid oxide solutions and supported noble metal catalysts

The catalytic decomposition of nitrous oxide to nitrogen and oxygen has been investigated over various solid oxide solutions (SOS), La_0.8Sr_0.2MO_3– (M=Cr, Fe, Mn, Co or Y), La_1.8Sr_0.2CuO_4– and supported Pd, Pt catalysts. The reaction was carried out in a gradientless recycle reactor at 1 atm pressure with a feed gas containing about 0.5% N₂O (in helium). Among the various solid solutions, La_0.8Sr_0.2CoO_3– showed a maximum N₂O conversion of 90% at 600C. The order of activity observed for N₂O decomposition was La_0.8Sr_0.2CoO_3–>La_0.8Sr_0.2FeO_3–>La_1.8Sr_0.2CuO_4–> La_0.8Sr_0.2MnO_3–La_0.8Sr_0.2CrO_3–La_0.8Sr_0.2YO_3–. The activity of La_0.8Sr_0.2CoO_3– was compared with supported Pd, Pt and also with unsubstituted LaCoO₃ catalysts under similar reaction conditions. Among all the catalysts tested in this study, Pd/Al₂O₃ showed the lowest light-off temperature for N₂O decomposition. The activity of La_0.8Sr_0.2CoO_3– was found to be comparable to Pd/Al₂O₃ catalyst at temperatures above 500 C. The influence of added oxygen (about 4%) in the feed was examined over La_0.8Sr_0.2CoO_3– and Pd/Al₂O₃ catalysts and only in the case of cobalt catalyst was the conversion of N₂O decreased by 13%. By choosing varied sintering conditions, La_0.8Sr_0.2CoO_3– of different BET surface areas were prepared and the light-off temperature was found to decrease with increase in surface area. The results obtained over solid solutions are discussed on the basis of the cation mixed valency and oxygen properties of the catalyst.     

Correlation between B value deviation and sintering temperature of perovskite solid solution materials

The effects of different sintering temperatures on the system of Ba_0.5Sr_0.5TiO₃–La_0.8Ca_0.2MnO₃ (BST-LCM) material were investigated by means of scanning electron microscopy, X-ray, resistance-temperature measurements, and X-ray photoelectron spectroscopy. X-ray diffraction and X-ray photoelectron spectroscopy confirm that BST-LCM is completely miscible and BST is the main phase, which under the premise of following the theory of small polaron conduction, titanium ions interact with manganese ions, which affects the electrical properties of the system of BST-LCM material. For the electrical properties of related, the LCM content is inversely proportional to the activation energy. Through the linear fitting of the experimental data, the empirical formula between the sintering temperature B value and the content of solid solution is obtained, and the approximate B value within a certain range can be preliminarily calculated.     

低温合成高钙固硫粉煤灰水泥的研究

试验采用低温合成方法将高钙固硫粉煤灰制成低温合成粉煤灰水泥熟料，采用XRD分析，力学性能测定等测试方法研究其物相及性能，试验表明高钙固硫粉煤灰低温合成熟料的胶凝矿物主要为C12A7、β-C2S、CA，将其与硅酸盐熟料，二水石膏复合，可制得具有良好性能的高铝水泥-硅酸盐水泥-石膏系统的复合水泥。     

Solid Solutions of Lindbergite–Glushinskite Series: Synthesis,Ionic Substitutions,Phase Transformation and Crystal Morphology

To clarify the crystal chemical features of natural and synthetic oxalates Me²⁺(C₂O₄)∙2H₂O (Me²⁺ = Fe, Mn, Mg, Zn), including minerals of the humboldtine group, solid solutions of lindbergite Mn(C₂O₄)∙2H₂O–glushinskite Mg(C₂O₄)∙2H₂O were precipitated under various conditions, close to those characteristic of mineralization in biofilms: at the stoichiometric ratios ((Mn + Mg)/C₂O₄ = 1) and non-stochiometric ratios ((Mn + Mg)/C₂O₄ < 1), in the presence and absence of citrate ions. Investigation of precipitates was carried out by powder X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Thermodynamic modelling was performed in order to evaluate the lindbergite–glushinskite equilibrium. It was shown that glushinskite belongs to the orthorhombic β-modification (sp. Gr. Fddd), while lindbergite has a monoclinic α-modification (sp. gr. C2/c). Mg ions incorporate lindbergite in much higher quantities than Mn ions incorporate glushinskite; moreover, Mn glushinskites are characterized by violations of long-range order in their crystal structure. Lindbergite–glushinskite transition occurs abruptly and can be classified as a first-order isodimorphic transition. The Me²⁺/C₂O₄ ratio and the presence of citric acid in the solution affect the isomorphic capacity of lindbergite and glushinskite, the width of the transition and the equilibrium Mg/Mn ratio. The transition is accompanied by continuous morphological changes in crystals and crystal intergrowths. Given the obtained results, it is necessary to take into account in biotechnologies aimed at the bioremediation/bioleaching of metals from media containing mixtures of cations (Mg, Mn, Fe, Zn).     

Influence of high energy ball milling on structural,microstructural and optical properties of TiO2 nanoparticles

The influence of high-energy ball milling on structural, microstructural, and optical properties of TiO₂ by modifying the nanoparticle size was studied. Five samples were extracted at different milling times (0, 2, 4, 8, and 13 h). The average particle sizes estimated by dynamic light scattering (DLS) were 205, 155.8, 116.8, 82.9, and 82.7 nm at 0, 2, 4, 8, and 13 h, respectively. X-ray diffraction analysis confirmed progressive broadening of the peaks as the milling time elapsed. Besides, a correlation was found between d spacing and the average crystal size. The UV–Vis diffuse reflectance spectra of TiO₂ revealed a decrease in reflectance due to particle size reduction. Similarly, an alteration of the bandgap transition energy was presented, whose values gradually decreased from 2.966 eV to 2.861 eV for the sample without and with the maximum duration milling performed (13 h), respectively. Likewise, the SEM analysis showed a distribution in nanoparticle size that became more homogeneous and smaller average grain size as the milling duration was longer.     

High strengthening effects and excellent wear resistance of Ti3Al(Si)C2 solid solutions

The Ti₃Al_1.2−xSi_xC₂ (x = 0, 0.2, 0.4) powders were synthesized from Ti, Al, Si, and TiC powders, and nearly pure Ti₃Al_1.2−xSi_xC₂ bulks were fabricated by the means of two-time hot-pressing method. Significant strengthening effect in bulks was found after the addition of 0.2 Si and 0.4 Si to form Ti₃Al(Si)C₂ solid solutions. The flexural strengths of Ti₃AlSi_0.2C₂ and Ti₃Al_0.8Si_0.4C₂ were 485 and 554 MPa, 14% and 30% larger than the strength of Ti₃AlC₂, respectively. The Vickers hardness of these compounds were separately, 6.95 and 7.57 GPa, representing the enhancements of 37% and 49% over those of Ti₃AlC₂. The tribological behavior was studied by dry-sliding method with a S45C steel at the sliding speed of 30 m/s and the normal load of 20-80 N. The results showed that after incorporating different contents of Si, the friction coefficient was between 0.22 and 0.30, correspondingly lower wear rate was 3.19-2.61 × 10⁻⁶ mm³/Nm. These excellent tribological performances were attributed to the presence of continuous self-generated oxidized films during tribological examination. Finally, the phase compositions and microhardness of the oxidized films were analyzed and characterized.     

复合可聚合乳化剂制备高固含量低黏度聚丙烯酸酯乳液

以DNS-86和F-6为复合可聚合乳化剂APS为引发剂,MMA、BA为单体采用半连续法制备20%固含量种子乳液,以种子乳液为介质,选用4种不同类型乳化剂:非离子可聚合乳化剂F-6,阴离子可聚合乳化剂DNS-86、常规非离子乳化剂OP-10、常规阴离子乳化剂SDS进行不同组合,同时滴加预乳化液、引发剂、缓冲剂直接二次成核制备62%固含量二元粒径分布乳液。重点研究了乳化剂复合方式、用量及配比、反应温度等对聚合稳定性、乳液流变性等的影响。,     

An unusual promotion of the redox behaviour of CeO2-ZrO2 solid solutions upon sintering at high temperatures

The reduction behaviour of a high surface area CeO₂-ZrO₂ solid solution is compared with that of a high surface area CeO₂. It is shown that, upon sintering induced by repetitive reduction/oxidation processes, the temperature of reduction of the solid solution decreases from 900 to 700 K. In contrast, the reduction at low temperatures of the CeO₂ sample is strongly retarded after such treatments. The role of ZrO₂ in promoting the reduction at low temperatures is discussed.