Influence of Crystallization on the Conversion of Sm3+→Sm2+ in SrO–Bi2O3–K2O–B2O3 Glass‐Ceramics

Sm³⁺‐doped glass 13SrO–2Bi₂O₃–5K₂O–80B₂O₃ was fabricated by the conventional melt‐quenching technique. The glass‐ceramics were obtained by heating the as‐prepared glasses in air atmosphere at selected temperatures 550°C, 600°C, 615°C, and 650°C, respectively. The luminescence spectra of both Sm³⁺ and Sm²⁺ were detected in the ceramic heated at 650°C where crystalline phase is formed. The as‐prepared glass and the ceramics heated at 550°C, 600°C, and 615°C show only the emission due to Sm³⁺. In the sample heated at 650°C in air atmosphere, however, part of Sm³⁺ ions was converted to Sm²⁺, giving rise to sharp emission lines which are characteristic of Sm²⁺ in crystalline state. It is suggested that Sm²⁺ ions are located at Sr²⁺ site in the ceramic while Sm³⁺ ions are located at Bi³⁺ sites. The Sm²⁺‐doped glass‐ceramic has a high optical stability because the fluorescence intensity decreases by only about 8% of its initial value upon excitation at 488 nm Ar⁺ laser.     

White‐Light and Yellow/Blue Photoluminescence Emission Based on Dy3+‐Doped SiO2–Gd2O3 Composites

This work attempts to obtain Dy³⁺‐doped SiO₂–Gd₂O₃ by sol–gel process_, with a molar ratio of 70Si⁴⁺–30Gd³⁺ and Dy³⁺ concentrations of 0.1, 0.3, 0.5, and 1 mol%. Heat treatment at temperatures of 1000°C, 1100°C, 1200°C, and 1300°C have been performed. From XRD, the Gd₂O₃ cubic phase was observed at 1000°C and 1100°C, at 1200°C also were observed Gd₂O₃ monoclinic phase, predominant at 1300°C. The band‐gap values vary between 4.4 and 5.3 eV, showing dependence on the crystalline phase. Under UV excitation, emission spectra show bands assigned to the Dy³⁺ transitions: ⁴F_9/2→⁶H_15/2 (484 nm), ⁴F_9/2→⁶H_13/2 (572 nm), and ⁴F_9/2→⁶H_11/2 (668 nm). The excitation at 275 nm has shown more effective. The ratio between the most intense emission bands (yellow/blue) show values around 0.84 and 1.63. CIE chromaticity diagrams show color coordinates at blue, yellow, and white regions, as a function of Dy³⁺ concentration and heat treatment. The lifetime values of excited state ⁴F_9/2 were around 0.20 and 0.69 ms. The morphology of particles changed from spherical to coral‐like shape as a function of heat treatment are observed. The sol–gel process showed to be an interesting route to obtain Dy³⁺‐doped binary system materials.     

Enhanced thermoelectric properties of 2H–MoS2 thin film by tuning post sulfurization temperature

Two-dimensional transition metal dichalcogenide semiconductors (TMDCs) like MoS₂ are becoming more popular as thermoelectric materials because they are abundant, nontoxic, and have good performance. In the study, the MoS₂ thin films have prepared by the sputtering and post-sulfurization process at various temperatures 450 °C, 550 °C, 650 °C, and 750 °C. The XRD data exhibits the formation of the 2H phase of MoS₂ thin film with (002), (004), and (006) planes. The Raman spectroscopy has confirmed the 2H–MoS₂ thin films with 2LA (M), A_1g, E_2g, and E_g vibrational modes. The SEM images have shown the thin MoS₂ flakes. The Seebeck and electrical conductivity data indicated an enhancement in Seebeck coefficient and electrical conductivity from 20 to 31 μV/^°C and 26–53 S/m, respectively, as the post sulfurization temperature increased from 450 °C to 750 °C. The enhancement of the Seebeck coefficient and electrical conductivity have been linked to the perfection of the 2H phase of MoS₂ film. The improved crystal structure has increased carrier mobility, leading to a high power factor of the 5.09 μWm^?1C^?2.     

Influence of processing conditions on the ionic conductivity of holmium zirconate (Ho2Zr2O7)

Nanopowders of holmium zirconate (Ho₂Zr₂O₇) synthesised through carbon neutral sol-gel method were pressed into pellets and individually sintered for 2 h in a single step sintering (SSS) process from 1100 °C to 1500 °C at 100 °C interval and in a two step sintering (TSS) process at (I) −1500 °C for 5 min followed by (II) - 1300 °C for 96 h. Relative density of each of the sintered pellet was determined using the Archimedes’ technique and the theoretical density was calculated from crystal structure data. Grain size was obtained from SEM micrographs using ImageJ. Pellets processed by TSS have been found to be denser (98 %) with less grain growth (1.29 μm) as compared to the pellets processed using SSS process. Ionic conductivity of Ho₂Zr₂O₇ pellets sintered by two different processes was measured using ac impedance spectroscopy technique over the temperature range of 350 °C–750 °C in the frequency range of 100 mHz–100 MHz for both heating and cooling cycles. The temperature dependence of bulk (2.67⨯10⁻³ Scm⁻¹) and grain boundary (2.50⨯10⁻³ Scm⁻¹) conductivities of Ho₂Zr₂O₇ prepared by TSS process are greater than those processed by SSS process suggesting the strong influence of processing conditions and grain size. Results of this study, indicates that the TSS is the preferable route for processing the holmium zirconate as it can be sintered to exceptionally high densities at lower temperature, exhibits less grain growth and enhanced ionic conductivity compared with the samples processed by SSS process. Hence, holmium zirconate can be considered as a promising new oxide ion conducting solid electrolyte for intermediate temperature SOFC applications between 350 °C and 750 °C temperature range.     

Preparation of highly porous Al2O3 aerogel by one-step solvent-exchange and ambient-pressure drying

This work presents the preparation of alumina aerogel via sol-gel route utilizing ambient-pressure drying. A novel and efficient solvent-exchange process has been utilized as an alternative to conventional solvent-exchange processes by directly boiling the hydro-gel in solvent. High emphasis has been given in the selection of solvent based on polarity, boiling point, and specific gravity compared with water to facilitate efficient solvent-exchange and reuse of the solvent. The ambient-pressure-dried alumina aerogel was thermally treated at temperature from 300°C-1200°C to study the change in density, porosity, specific surface area, and microstructure along with crystalline properties. The ambient-pressure-dried alumina aerogel showed lower tapped density 0.108 g/cm³, specific surface area 519 m²/g, and total weight loss of 36.94% at 900°C. The degree of crystalline structure from amorphous was observed to increase with increase in thermal treatment temperature above 300°C, dominant above 700°C, whereas the transformation of bayerite γ-Al(OH)₃ to boehmite γ-AlO₂H was observed at 150°C-300°C and to γ-Al₂O₃ phase was observed at temperature of 300°C-1200°C.     

Fabrication and properties of macro-porous SiC using Al2O3–Y2O3–SiO2 as bonding additives

Macro-porous SiC was fabricated without using pore-forming agents by an in situ reaction bonding process. A bonding additive, Al₂O₃–Y₂O₃–SiO₂, with a low melting temperature was mixed with SiC particles and sintered at 1500 °C and 1600 °C for 1 h in Ar. Macro-porous SiC with a porosity of 32.7–45.9%, a pore size of 3.4–4.2 μm, and a relatively narrow and uniform pore size distribution was fabricated by varying the amount of bonding additive. The flexural strength of macro-porous SiC prepared at 1500 °C increased from 47.2 MPa to 71.2 MPa while the porosity decreased from 45.9% to 42.8%, respectively. When the sintering temperature of the macro-porous SiC was increased to 1600 °C, the flexural strengths were significantly reduced to 32.6–35.6 MPa, along with a reduction in porosity and pore size. The permeability of macro-porous SiC prepared at 1500 °C varied from 1.59 × 10^?12 m² to 1.26 × 10^?12 m², depending on the porosity. As the sintering temperature increased from 1500 °C to 1600 °C, the permeability decreased to less than 1.00 × 10^?12 m² because of the reduced porosity and average pore size. The electrical resistivity of macro-porous SiC prepared at 1500 °C and 1600 °C varied from 2.7 × 10⁸ Ω-cm to 1.4 × 10⁹ Ω-cm and from 1.3 × 10⁸ Ω-cm to 1.7 × 10⁹ Ω-cm, respectively, with increasing volume percent of bonding additives. The relatively high electrical resistivity was apparently due to neck bonding phase between SiC particles formed by phases consisting of Y₂Si₂O₇, YAG, and residual Al₂O₃.     

Oxygen transport,thermal and electrochemical properties of NdBa0.5Sr0.5Co2O5+δ cathode for SOFCs

In this study, the crystal structure, thermal, oxygen transport, electrical conductivity and electrochemical properties of the perovskite NdBa_0.5Sr_0.5Co₂O_5+δ (NBSC55) are investigated. In the temperature range of 250 °C–350 °C, the weight loss upon heating was due to a partial loss of lattice oxygen and along with a reduction of Co⁴⁺ to Co³⁺. The tend of weight-loss slows down as temperature increased above 350 °C indicating a reduction of Co³⁺ to Co²⁺ during this stage. The oxygen migration is dominated by surface exchange process at high temperature range (650-800 °C); however, the bulk diffusion process prevails at low temperature range (500–600 °C). For long-term testing, the polarization resistance of NBSC55 increases gradually form 3.13 Ω cm² for 2 h to 3.34 Ω cm² for 96 h at 600 °C and an increasing-rate for polarization resistance is around 0.22% h^?1. The power density of the single cell with NBSC55 cathode reached 341 mW cm^?2 at 800 °C.     

Low‐Temperature Sintering of β‐Spodumene Ceramics Using Li2O–GeO2 as a Sintering Additive

Low‐temperature sintering of β‐spodumene ceramics with low coefficient of thermal expansion (CTE) was attained using Li₂O–GeO₂ sintering additive. Single‐phase β‐spodumene ceramics could be synthesized by heat treatment at 1000°C using highly pure and fine amorphous silica, α‐alumina, and lithium carbonate powders mixture via the solid‐state reaction route. The mixture was calcined at 950°C, finely pulverized, compacted, and finally sintered with or without the sintering additive at 800°C–1400°C for 2 h. The relative density reached 98% for the sample sintered with 3 mass% Li₂O–GeO₂ additive at 1000°C. Its Young's modulus was 167 GPa and flexural strength was 115 MPa. Its CTE (from R.T. to 800°C) was 0.7 × 10^?6 K^?1 and dielectric constant was 6.8 with loss tangent of 0.9% at 5 MHz. These properties were excellent or comparative compared with those previously reported for the samples sintered at around 1300°C–1400°C via melt‐quenching routes. As a result, β‐spodumene ceramics with single phase and sufficient properties were obtained at about 300°C lower sintering temperature by adding Li₂O–GeO₂ sintering additive via the conventional solid‐state reaction route. These results suggest that β‐spodumene ceramics sintered with Li₂O–GeO₂ sintering additive has a potential use as LTCC for multichip modules.     

Preparation of CeO2-ZrO2 mixed oxide with high surface area and high thermal stability

Ceria-zirconia solid particles have been recognized as a key material of the automotive exhaust catalysts since they can release and uptake oxygen owing to the rapid reversible oxidation states of cerium between Ce³⁺ and Ce⁴⁺. Several methods have recently been described to prepare the CeO₂-ZrO₂ solid particles used in the catalysts. In this paper, a new coprecipitation method is used to prepare the CeO₂-ZrO₂ solid particles. The Ce-Zr alcogel is dried and calcined in flowing N₂ not in flowing air under atmospheric pressure. The results show that the ceria-zirconia sample calcined at 650 °C has high surface area over 90 m²g⁻¹, which drops to 40 m²g⁻¹ following treatment at 900°C.     

Insights into High‐Temperature Uniaxial Compression Deformation Behavior of Ti3AlC2

We report on strain‐rate‐dependent compression deformation behavior of Ti₃AlC₂ at 1000°C–1200°C. At 1000°C and high strain rate (10^?2 or 10^?3 s^?1), Ti₃AlC₂ deforms in a nonplastic manner. Upon increasing temperature and reducing strain rate, Ti₃AlC₂ exhibits a limited plasticity. For instance, the true plastic strain at 1200°C and 10^?4 s^?1 is only 3%, beyond which strain softening following a short hardening regime occurs. The softening results from the formation of localized microvoids and microcracks. Decreasing the strain rate further to 10^?5 s^?1 at 1200°C, strain hardening instead of softening is identified. Under such conditions, the plastic strain remarkably increases, reaching a value as high as 27%. Postdeformation microstructural analyses of the dislocation configurations explicitly evidence the dislocation reactions, formation of hexagonal dislocation networks and dislocation entanglements. These account for the strain hardening. The extraordinary plasticity at 1200°C and 10^?5 s^?1 benefits from the initiation of nonbasal slip systems. Finally, a complete high‐temperature deformation scenario for nanolaminated Ti₃AlC₂ is elaborated.     

The technology of the Li/Cl2 in SO2Cl2 cell system IV. high temperature performance,storability, and safety characteristics

Tests were conducted to determine the performance, storability, and safety characteristics for specially designed Li/Cl₂ in SO₂Cl₂ (Li/CSC) cells at temperatures as high as 150° C. Discharge tests at 150° C showed that practical Li/CSC D cells yield energy densities of 0.75 to 0.91 Wh cm^?3 for constant resistive loads of 3.0 to 75.0 ohms, respectively. Further, the performance results obtained for cells stored at 150° C and either discharged at 25° C or discharged at 150° C showed little loss in realized capacity but exhibited a noted loss in rate capability. These cells have been subjected to abusive conditions such as short circuit, forced overdischarge, incineration, puncture, and shock sensitivity testing following prolonged discharge at both ambient and elevated temperatures. Safety/hazard testing has also included specific combinations of the above abusive conditions. The results relative to the safe, efficient use of the cells at elevated as well as room temperatures will be discussed.     

Effect of Annealing Temperature on TiO2 Nanorod Films Prepared by dc Reactive Magnetron Sputtering for Dye-Sensitized Solar Cells

Anatase TiO₂ nanorod films have been prepared on ITO coated glass substrates at room temperature by dc reactive magnetron sputtering technique. The nanorods are highly ordered and are perpendicular to the substrate. XRD measurements show that the anatase nanorods have a preferred orientation along the [110] direction. The prepared nanorods were annealed at different temperatures (200?C500 °C) in air for 1 h. The dye-sensitized solar cells (DSSC) have been made using the as-deposited and annealed TiO₂ nanorods as working electrodes. It has been found that annealing improves the efficiency of the DSSC. An optimum conversion efficiency of 2.13%, at 100 mW/cm² light intensity has been achieved with TiO₂ nanorods annealed at 300 °C.     

Effects of calcination temperature on structure and magnetic properties of pure FeCo2O4 powders

A series of FeCo₂O₄ powders was initially synthesized using a hydrothermal method and subsequently calcined at various temperatures to produce the final product. Pure phase FeCo₂O₄ powders can only be formed in the temperature range of 950–1050 °C. In this work, we study the cation occupation, cation valence, bond length and bond angle changes of the pure phase FeCo₂O₄ powders formed in such a narrow temperature range. Octahedral lattice distortion in the pure phase FeCo₂O₄ samples has been observed. More tetrahedral Fe³⁺ and octahedral Co²⁺ are excited and exchanged their sites as the calcination temperature increases from 950 °C to 1000 °C, and part of Co³⁺ ions are reduced to Co²⁺ in the sample calcined at 1050 °C. The structure of the sample calcined at 1000 °C is close to that of the ideal FeCo₂O₄ spinel. Magnetic measurements show that ferrimagnetism and anti-ferromagnetism coexist in the pure phase FeCo₂O₄ samples. Interaction changes between ferrimagnetism and antiferromagnetism caused by the structural changes of the samples have been studied. Due to the pinning of the local anti-ferromagnetism to ferrimagnetism in the sample, the sample shows a Barkhausen jump below 150 K. As the measurement temperature increases further, the system enters into a reentrant spin glass state.     

Reaction,densification, and mechanical properties of Ti2AlCx ceramics at low applied pressure and temperature

Ti₂AlC_x ceramic was produced by reactive hot pressing (RHP) of Ti:Al:C powder mixtures with a molar ratio of 2:1:1–.5 at 10–20 MPa, 1200–1300°C for 60 min. X-ray diffraction analysis confirmed the Ti₂AlC with TiC, Ti₃Al as minor phases in samples produced at 10–20 MPa, 1200°C. The samples RHPed at 10 MPa, 1300°C exhibited ≥95 vol.% Ti₂AlC with TiC as a minor phase. The density of samples increased from 3.69 to 4.04 g/cm³ at 10 MPa, 1200°C, whereas an increase of pressure to 20 MPa resulted from 3.84 to 4.07 g/cm³ (2:1:1 to 2:1:.5). The samples made at 10 MPa, 1300°C exhibited a density from 3.95 to 4.07 g/cm³. Reaction and densification were studied for 2Ti–Al–.67C composition at 10 MPa, 700–1300°C for 5 min showed the formation of Ti–Al intermetallic and TiC phases up to 900°C with Ti, Al, and carbon. The appearance of the Ti₂AlC phase was ≥1000°C; further, as the temperature increased, Ti₂AlC peak intensity was raised, and other phase intensities were reduced. The sample made at 700°C showed a density of 2.87 g/cm³, whereas at 1300°C it exhibited 3.98 g/cm³; further, soaking for 60 min resulted in a density of 4.07 g/cm³. Microhardness and flexural strength of Ti₂AlC_0.8 sample were 5.81 ± .21 GPa and 445 ± 35 MPa.     

The System Bi2O,—B2O3

The phase diagram for the system Bi₂O₃-B₂O₃ has been determined experimentally. The melting point of Bi₂O₃ has been redetermined as 825° C with an estimated overall uncertainty of about ±3°C, and the molal heat of fusion of Bi₂O₃, calculated from the slope of the liquidus curve, is 2050 cal per mole. The system contains a body-centered cubic phase of approximate composition 12Bi₂O₃·B₂O₃, which melts incongruently at 632°C. Four congruently melting compounds exist in the system: 2Bi₂O₃· B₂O₃·5B₂O₃, Bi₂O₃·3B₂O₃, and Bi₂O₃·4B₂O₃, with melting points, respectively, of 675°, 722°, 708°, and 715°C. The Bi₂O₃·4B₂O₃ compound exhibits a sluggish transformation at 696°C. Compositions containing up to 97.5 wt% (85 mole %) Bi₂O₃ can be partly or totally quenched to glass. Indices of the quenched glasses are greater than 1.74. A region of liquid immiscibility extends at 709°C from almost pure B₂O₃ to 19.0 mole % Bi₂O₃. The extent of immiscibility theoretically calculated agrees with the experimentally determined value when 1.20 A is used for the ionic radius of Bi³⁺.     

Influence of operating temperature on CO<Subscript>2</Subscript>-NH<Subscript>3</Subscript> reaction in an aqueous solution

Although aqueous ammonia solution has been focused on the removal of CO₂ from flue gas, there have been very few reports regarding the underlying analysis of the reaction between CO₂ and NH₃. In this work, we explored the reaction of CO₂-NH₃-H₂O system at various operating temperatures: 40 °C, 20 °C, and 5 °C. The CO₂ removal efficiency and the loss of ammonia were influenced by the operating temperatures. Also, infrared spectroscopy measurement was used in order to understand the formation mechanism of ion species in absorbent, such as NH₂COO⁻, HCO₃⁻, CO₃²⁻, and NH₄⁺, during CO₂, NH₃, and H₂O reaction. The reactions of CO₂-NH₃-H₂O system at 20 °C and 40 °C have similar reaction routes. However, a different reaction route was observed at 5 °C compared to the other operating temperatures, showing the solid products of ammonium bicarbonates, relatively. The CO₂ removal efficiency and the formation of carbamate and bicarbonate were strongly influenced by the operating temperatures. In particular, the analysis of the formation carbamate and bicarbonate by infrared spectroscopy measurement provides useful information on the reaction mechanism of CO₂ in an aqueous ammonia solution.     

Structural modifications of nanostructured ceria CeO2,xH2O during dehydration process

Hydrated nanostructured cerium dioxide CeO₂, xH₂O (hydrated nanoceria) has been synthesized in room conditions via a precipitation route. This hydrated nanoceria phase has been subjected to thermal decomposition in the temperature range from 25 °C to 800 °C. At least three decomposition steps have been observed in thermal and thermogravimetric analyses. Three different samples of cubic nanoceria respectively obtained at room temperature (RT-nanoceria), 80 °C (80-nanoceria) and 600 °C (600-nanoceria) have been studied by X-Ray diffraction, Raman spectroscopy and scanning electron microscopy analyses. The analyses of X-ray diffraction profiles and Raman vibrational bands have clearly shown that dehydration is accompanied by increasing crystallite size, lattice parameter contraction. The cubic structure of hydrated RT-nanoceria might be associated with a complex chemical formula unit involving Ce⁴⁺, Ce³⁺ mixed valences, oxygen vacancies, lattice and surface water and OH^? proton species.     

Phase and microstructure evolution of Sc2O3–CeO2 –ZrO2ceramics in Na2SO4 + V2O5 molten salts

In this study, the destabilization resistance of Sc₂O₃ and CeO₂ co-stabilized ZrO₂ (SCZ) ceramics was tested in Na₂SO₄ + V₂O₅ molten salts at 750°C–1100 °C. The phase structure and microstructure evolution of the samples during the hot corrosion testing were analyzed with X-ray diffraction (XRD), Raman spectra, scanning electron microscopy (SEM), energy dispersive X-ray spectrum (EDS), and X-ray photoelectron spectroscopy (XPS). Results showed that the destabilization of SCZ ceramics at 750 °C was the result of the chemical reaction with V₂O₅ to produce m-ZrO₂ and CeVO₄, and little ScVO₄ was detected in the Sc₂O₃-rich SCZ ceramics. The primary corrosion products at 900 °C and 1100 °C were CeO₂ and m-ZrO₂ due to the mineralization effect. The Sc₂O₃-rich SCZ ceramics exhibited excellent degradation resistance and phase stability owing to the enhanced bond strength and the decreased size misfit between Zr⁴⁺ and Sc³⁺. The destabilization mechanism of SCZ ceramic under hot corrosion was also discussed.     

Reactive hot pressing route for dense ZrB2-SiC and ZrB2-SiC-CNT ultra-high temperature ceramics

The in-situ exothermic reactions between ZrC_0.8, B₄C and Si have assisted densification and allowed to obtain fully dense ZrB₂-31 wt.%SiC ultra-high temperature ceramics within 6 min at 1750 °C. The use of zirconium carbide instead of metallic zirconium in the green body obviated the possibility of in-situ SHS process and allowed to apply the pressure at low temperatures. The latter provided a first densification stage just above 1050 °C. A slight carbon excess was created in the green body to preserve the carbon nanotubes. The developed reactive hot pressing route (1830 °C, 3 min, 30 MPa) has been successfully used to obtain ZrB₂-SiC ceramics containing 8 vol.% of multi-wall carbon nanotubes (MW-CNT). The carbon nanotubes survived the thermal cycle and could be clearly observed in the sintered ceramics. The CNT addition improved the fracture toughness of the composite from 4.3 MPa m^1/2 for ZrB₂-31 wt.%SiC to 6.8 MPa m^1/2 for ZrB₂-29 wt.%SiC-CNT.