Phase relationships in the Na<Subscript>2</Subscript>ZnP<Subscript>2</Subscript>O<Subscript>7</Subscript>–LiKZnP<Subscript>2</Subscript>O<Subscript>7</Subscript> system

The phase relationships in the Na₂ZnP₂O₇–LiKZnP₂O₇ system are studied. They are represented by a mixture of the starting components in the subsolidus region. The eutectic was found at a temperature of 640°C and composition of 0.5LiKZnP₂O₇. The phase formation of this system is compared with the previously studied NaKZnP₂O₇–LiKZnP₂O₇ system. It is shown that a structural factor affects the geometry of the state diagrams.     

Exploring the Redox Behavior of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Mn<Subscript>1−x</Subscript>Al<Subscript>x</Subscript>O<Subscript>3</Subscript> Perovskites for CO<Subscript>2</Subscript>-Splitting in Thermochemical Cycles

Mixed oxides with perovskite structure have been proposed as promising alternative for the solar fuel production via thermochemical redox cycles. For this work, the system La_0.6Sr_0.4Mn_1?xAl_xO₃ (x?=?0 to 0.8) was selected according to its high thermal stability and rapid oxidation kinetics, and the influence of the Al/Mn ratio on the redox properties was investigated. The characterization of the five oxides samples with different Al content confirmed the high redox capacity and the favorable behavior of these materials in consecutive cycles, as analyzed thermogravimetrically. The results show that following reduction at 1300?°C in inert atmosphere up to 0.32 mmol g^?1 of O₂ are released, while a 10-cycle reaction test confirms the feasibility of long term operation with these perovskites. It was observed that the reduction extent was enhanced with increasing the Al-content, but the oxidation degree is maximum for compositions near x?=?0.5, corresponding to an O₂ release of 0.318 mmol g^?1 (δ?=?0.132). After selecting the compositions with more promising redox properties, additional reactions were performed in a lab-scale fixed bed reactor with injection of CO₂ in the oxidation step at 900?°C in order to generate CO. In these tests, the most interesting results were obtained for the perovskite La_0.6Sr_0.4Mn_0.6Al_0.4O_3, with reduction extent of 0.266 mmol?g^?1, but the production of CO is in comparison significantly lower (0.114 mmol?g^?1). Further studies are required to determine the best operation conditions for thermochemical cycles using those materials.     

Photon interaction parameters for some ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Some photon interaction parameters such as mass attenuation coefficient, effective atomic number, half value layer, mean free path and electron density for 15ZnO–(17.5–x)Al₂O₃–xFe₂O₃–67.5P₂O₅ glass system (x = 0, 7.5, 12.5, 17.5) and 15ZnO–(25–x)Al₂O₃–xFe₂O₃–60P₂O₅ glass system (x = 0, 25) have been investigated in the photon energy range of 1 keV to 100 GeV. It has been observed that all the photon interaction parameters for the selected glass systems vary with the photon energy. Among the selected glass systems, the sample 15ZnO–25Fe₂O₃–60P₂O₅ glass system shows maximum values for mass attenuation coefficients, effective atomic numbers, electron densities and minimum values for mean free path and half value layer in the entire energy grid.     

Structural heterogeneity of SiO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> glass

It is shown that the phase heterogeneity of SiO₂–Na₂O–Al₂O₃ glass has a liquation and crystallization nature, the balance between which is determined by the conditions of their synthesis. An increase in the aluminum oxide content decreases the number of liquation and crystallization sites, and also the linear sizes of the crystalline formations without eliminating the phase separation due to the liquation. The area of metastable immiscibility in the SiO₂–Na₂O–Al₂O₃ system, which is determined by scanning electron microscopy, is probably wider than the area detected by the optical methods.     

Hydroisomerization of Benzene-Containing Gasoline Fraction on Pt/B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pt/WO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

The effect of the hydroisomerization conditions of the benzene-containing fraction of catalytic reforming gasoline on the yield and composition of products is studied on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts. These catalysts allow benzene to be completely removed from the raw material. At the same time, the greatest yields of liquid products are obtained with minimal losses of the octane number at 2 MPa, a mass feedstock hourly space velocity (MFHSV) of 2 h^?1, and 325°C: 96.3 and 95.4 wt % on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts, respectively. The activity of the catalysts is maintained for 100 h during their operation.     

Magneto Optical Properties of FeB<Subscript>x</Subscript>Fe<Subscript>2−x</Subscript>O<Subscript>4</Subscript> Nanoparticles

In this study, FeB_xFe_2?xO₄ nanoparticles (NPs) were synthesized by the polyol method. The M–H hysteresis curves exhibit superparamagnetic characteristics that are both coercivity and remanent magnetization values are negligible. The particle size dependent Langevin function was applied to calculate the magnetic particle dimensions around 9 nm. The measured magnetic moments of NPs are in range of (1.52–2.2) µ_B and almost half or less with respect to 4 µ_B of bulk Fe ferrite. Magnetic anisotropy was specified as uniaxial and calculated effective anisotropy constants (K _eff ) are between 43.3 × 10⁴ and 19.4 × 10⁴ emu/g. The UV–Vis diffuse reflectance spectroscopy and Kubelka–Munk theory were used to determine the optical properties. The estimated optical band gap values (2.15–2.48 eV) of FeB_xFe_2?xO₄ NPs are bigger with respect to reported values (1.88–2.12 eV) for Fe₃O₄ NPs in the literature. The bigger E _g values are mainly attributed to B concentration and partly to quantum confinement effect.     

Fe-doping effects on the structural and electrochemical properties of 0.5Li<Subscript>2</Subscript>MnO<Subscript>3</Subscript>·0.5LiMn<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>2</Subscript> electrode material

With the aim of achieving a high-performance 0.5Li₂MnO₃·0.5LiMn_0.5Ni_0.5O₂ material, a series of 0.5Li₂MnO₃·0.5LiMn _x Ni _y Fe_(1−x−y)O₂ (0.3 ≤ x ≤ 0.5, 0.4 ≤ y ≤ 0.5) samples with low Fe content was synthesized via coprecipitation of carbonates. Its crystal structure and electrochemical performance were characterized by means of powder X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, galvanostatic charge/discharge testing, cyclic voltammetry, and electrochemical impedance spectra. Rietveld refinements with a model integrating R [`3] \overline{3} m and Fm [`3] \overline{3} m indicate that a low concentration of Fe incorporated in 0.5Li₂MnO₃·0.5LiMn_0.5Ni_0.5O₂ decrease a disordered cubic domain of the composite structure. The preferential distribution of Fe in cubic rock-salt contributes to an unimaginable decrease of c-axis parameter of the predominant layered structure as the Fe content increases. Moreover, including Fe as a dopant can kinetically improve crystallization and also change the ratio of Mn³⁺/Mn⁴⁺ and Ni³⁺/Ni²⁺. As a result, 0.5Li₂MnO₃·0.5LiMn_0.4Ni_0.5Fe_0.1O₂ exhibits lower Warburg impedance and higher reversible capacity than the undoped material.     

Effects of ZnO–B<Subscript>2</Subscript>O<Subscript>3</Subscript> addition on sintering behaviors and microwave dielectric properties of Ba<Subscript>4</Subscript>Sm<Subscript>9.33</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript> ceramics

Effects of ZnO–B₂O₃ (ZB) addition on the densification, phase evolution and microwaves dielectric properties of Ba₄Sm_9.33Ti₁₈O₅₄ (BST) ceramics for low-temperature fired applications have been investigated. The sintering temperature of BST ceramics can be effectively lowered to about 1000°C with introduction of ZB. Tungsten bronze like single phase is observed in the BST ceramics with 0.5 and 1.0% ZB. However, Sm₂Ti₂O₇ secondary phase appears when ZB addition reaches 2%, and Sm₂Ti₂O₇ phase gradually increases with the increase ZB addition. Microwave dielectric properties of the present ceramics are strongly dependent on phase constitution and density. Optimal microwave dielectric properties of ε = 63.4, Qf = 2830 GHz, τ _f =–8.8 ppm/°C is obtained for BST ceramics with 1% ZB addition.     

Magnetic Properties of FeMn<Subscript>y</Subscript>Co<Subscript>y</Subscript>Fe<Subscript>2−2y</Subscript>O<Subscript>4</Subscript>@Oleylamine Nanocomposite with Cation Distribution

In this study, oleylamine (OAm) capped FeMn_yCo_yFe_2?2yO₄ (0.0?≤?y?≤?0.4) nanocomposites (NCs) were prepared via the polyol route and the impact of bimetallic Co³⁺ and Mn³⁺ ions on the structural and magnetic properties of Fe₃O₄ was investigated. The complete characterization of FeMn_yCo_yFe_2?2yO₄@OAm NCs were done by different techniques such as XRD, SEM, TGA, FT-IR, TEM, and VSM. XRD analyses proved the successful formation of mono-phase MnFe₂O₄ spinel cubic products free from any impurity. The average crystallite sizes were calculated in the range of 9.4–26.4 nm using Sherrer’s formula. Both SEM and TEM results confirmed that products are nanoparticles like structures having spherical morphology with small agglomeration. Ms continued to decrease up to Co³⁺ and Mn³⁺ content of y?=?0.4. Although Mössbauer analysis reveals that the nanocomposites consist three magnetic sextets and superparamagnetic particles are also formed for Fe₃O₄, Co_0.2Mn_0.2Fe_2.6O₄ and Co_0.4Mn_0.4Fe_2.2O₄. Cation distributions calculation was reported that Co³⁺ ions prefer to replace Fe²⁺ ions on tetrahedral side up to all the concentration while Mn³⁺ ions prefer to replace Fe³⁺ ions on the octahedral.     

Vapor–Liquid Equilibrium of Binary Components of the BrCF<Subscript>2</Subscript>COOCH<Subscript>3</Subscript>–CF<Subscript>3</Subscript>COOH–BrCF<Subscript>2</Subscript>COOH–CF<Subscript>3</Subscript>COOCH<Subscript>3</Subscript> Quaternary System

Vapor–liquid equilibria of binary components of the BrCF₂COOCH₃–CF₃COOH–BrCF₂COOH–CF₃COOCH₃ quaternary system have been studied experimentally at constant pressure. The experiments have been carried out on a modified Sventoslavskii ebulliometer. Using the Aspen Plus software package, the appropriate models have been selected and the vapor–liquid equilibria for six binary systems have been simulated.     

Mechanical,Structural and Thermal Properties of Transparent Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–TeO<Subscript>2</Subscript> Glass System

Oxide based optical glass materials has important potential material in many applications from fiber optic to sensor due to the high transparency and amourphous structures. The objective of this study is to synthesize the novel optical glass materials based on the bismuth and aluminum contents to be able to determine the physical, chemical and mechanical properties by considering the systematic experimental steps. In this study, Bi₂O₃–Al₂O₃ based tellurite optical glasses have been prepared by using conventional melt quenching method as a function of the both Bi₂O₃ and Al₂O₃ compositions. There is a strong interactions between the glass former and modifier ions that might effect on the structure and mechanical properties. During the experimental steps, thermal, structural and mechanical properties of the prepared glass materials have been determined considering the DTA/DSC, FT-IR spectroscopy, SEM and Vicker’s hardness techniques, respectively. Thermal parameters, like glass transition, T_g, onset, T_x, crystallization, T_p, and melting, T_m, temperatures were obtained by using DTA scan.     

Synthesis of the study of solid solutions based on the ZrO<Subscript>2</Subscript>–HfO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript>(CeO<Subscript>2</Subscript>) system

The results of the studies of the conditions of the liquid-phase synthesis of highly dispersed xerogels with a low degree of agglomeration and precursor nanopowders (~10–12 nm) based on zirconium dioxide in the ZrO₂–HfO₂–Y₂O₃(CeO₂) system are presented. The thermal decomposition of xerogels and formation of crystalline solid solutions with the structure of fluorite are investigated. The optimal conditions for the solidification of nanodispersed powders for fabricating compact ceramics based on solid solutions of ZrO₂ and the physical–chemical properties of these ceramics are studied.     

Porous ceramics based on the ZrO<Subscript>2</Subscript>(Y<Subscript>2</Subscript>O<Subscript>3</Subscript>)–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system for filtration membranes

The results of the studies of the process of fabricating ceramic filtration membranes in the system ZrO₂(Y₂O₃)–Al₂O₃ are presented. The phase compositions of the precursor powders and sintered ceramics have been investigated and their porous structures have been determined. Two stages of the implementation of the technology were demonstrated: fabrication of substrates with an open porosity ranging from 20 to 47% and pore sizes in the 100–300 nm range, as well as the deposition of nanocrystalline aluminum oxide layers on them. It has been established that the pore size distribution in the membrane layer of α-Al₂O₃ is unimodal (from 30 to 100 nm).     

Ultrafast Spectroscopy and Red Emission from β-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>/β-Ga<Subscript>2</Subscript>S<Subscript>3</Subscript> Nanowires

Ultrafast pump-probe and transient photoluminescence spectroscopy were used to investigate carrier dynamics in β-Ga₂O₃ nanowires converted to β-Ga₂O₃/Ga₂S₃ under H₂S between 400 to 600 °C. The β-Ga₂O₃ nanowires exhibited broad blue emission with a lifetime of 2.4 ns which was strongly suppressed after processing at 500–600 °C giving rise to red emission centered at 680 nm with a lifetime of 19 μs. Differential absorption spectroscopy reveals that state filling occurs in states located below the conduction band edge before sulfurization, but free carrier absorption is dominant in the β-Ga₂O₃/Ga₂S₃ nanowires processed at 500 to 600 °C for probing wavelengths >500 nm related to secondary excitation of the photo-generated carriers from the mid-gap states into the conduction band of Ga₂S₃.     

Vitreous region and properties of glasses of the Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>–GeS<Subscript>2</Subscript>–PbF<Subscript>2</Subscript> system

Vitrification in the Ga₂S₃–GeS₂–PbF₂ system is considered. The physicochemical properties of glasses, such as density, microhardness, electroconductivity, refraction index, and transmission percentage of specimens in visible and IR ranges of spectrum are studied; differential thermal analysis is carried out; and Raman and electron paramagnetic resonance spectra are investigated.     

Physicomechanical properties of refractory Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–C materials with ACPC

A study has been made on the effects of the amount of silicon nitride and graphite on the physicomechanical properties of Al₂O₃–Si₃N₄–C composites for lining purposes. Adding 2.5–5.0 wt.% silicon nitride and 0.5 wt.% reactive alumina improves the properties, raises their apparent density, and increases the mechanical strength, while reducing the open porosity. Optimized compositions have been determined for refractory materials of Al₂O₃–Si₃N₄–C composition, and it has been found that to attain the higher values of physicomechanical properties the amount of graphite should constitute 5–10 wt.%.     

Thermal investigation of ammonioborite (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>[B<Subscript>15</Subscript>O<Subscript>20</Subscript>(OH)<Subscript>8</Subscript>] · 4H<Subscript>2</Subscript>O

The thermal behavior of ammonioborite (NH₄)₃[B₁₅O₂₀(OH)₈] · 4H₂O is investigated using thermal X-ray diffraction, differential thermal analysis (DTA) in air and vacuum, and thermogravimetry. It is shown that the decomposition of the mineral (dehydration, dehydroxylation, deammoniation) proceeds in several stages, and the dehydration is accompanied by the amorphization. The thermal expansion of ammonioborite is sharply anisotropic. As in the case of other hydrous pentaborates, the thermal expansion is maximum in the direction in which pentaborate groups alternate with ammonium cations.     

Role of CeO<Subscript>2</Subscript> in Rh/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for CO<Subscript>2</Subscript> Reforming of Methane

Abstract  

The Rh/α-Al₂O₃ catalyst was modified by CeO₂ in order to improve the thermal stability and the carbon deposition resistance during the CO₂ reforming of methane The carbon formation was determined by TPO, TEM and Raman spectroscopy. Characterization results showed that the incorporation of Ce in the support inhibits the carbon deposition, increasing the useful life and the stability of the Rh base catalysts.