Cellulose templating method for the preparation of La0.8Sr0.2Ga0.83Mg0.17O2.815 (LSGM) solid oxide electrolyte

La_0.8Sr_0.2Ga_0.83Mg_0.17O_2.815 (LSGM) materials are synthesized with a fast and facile cellulose templating method for the first time and characterized by XRD, EIS, Archimedes method and SEM–EDS. LSGM powders with a phase purity of 91.7 mol% are obtained after the calcination at 1300 °C for 12 h. SEM–EDS results indicate possible decomposition and reconstruction of the LSGM phase due to the diffusion of Sr-rich species to the grain boundaries for the sample sintered at 1500 °C for 6 h. Maximum conductivity value is found to be 4.2 × 10^?2 S cm^?1 at 800 °C for the sample calcined at 1300 °C for 12 h and sintered at 1400 °C for 6 h. Phase purity, stability and relative density are the important factors for obtaining high performance LSGM electrolytes. Therefore, cellulose templating method is a promising candidate for the preparation of LSGM electrolytes.     

Enhanced sintering behavior of LSGM electrolyte and its performance for solid oxide fuel cells deposited by vacuum cold spray

How to obtain dense La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ (LSGM) electrolyte at low sintering temperature (<1300 °C) is a challenge to improve solid oxide fuel cell (SOFC) performance at intermediate operation temperature. In this study, a double-layer design method for vacuum cold spray (VCS) prepared-LSGM electrolyte assisted with two-step sintering at a low temperature was proposed. The sintering behavior of VCS deposited LSGM layers at 1200 °C was investigated. The LSGM layers became denser in most regions except the appearance of some cracks. Subsequently, the effect of a second LSGM layer on the sintered top layer was studied to block cracks. Results showed that the co-sintered layer with a thickness of approximately 5 μm presented a maximum open circuit voltage of ∼0.956 V at 650 °C and a maximum power density of 592 mW/cm² at 750 °C. Result indicates that the sintering assisted VCS is a promising method to prepare the LSGM electrolyte applied in intermediate temperature SOFCs.     

Synthesis of La0.9Sr0.1Ga0.8Mg0.2O2.85 powder by gel combustion route with two-step doping strategy

A two-step doping strategy was applied to the synthesis of La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.85 (LSGM1020) powder by a gel combustion method. The Mg-doped LaGaO₃ powder was prepared in the first step, and Sr incorporation in the Mg-doped LaGaO₃ powder was done in the second step to obtain the final LSGM1020 powder. The two-step procedure is effective in preparing higher purity powders than the traditional one-step procedure. Rietveld refinement of X-ray powder diffraction (XRD) patterns shows that incorporation of Mg in LaGaO₃ in the first step enlarges the LaGaO₃ lattice: this facilitates the incorporation of Sr in the second doping step and thus high purity powder is obtained. Relatively phase pure LSGM1020 powder with only 3.1% of LaSrGaO₄ was obtained after calcination at 1300 °C for 5 h. Therefore, the two-step doping strategy is an effective procedure for the preparation of LSGM powders with high Sr- and Mg-doping levels.     

Study of strontium ferrites substituted by lanthanum on the structural and magnetic properties

M-type strontium ferrites, Sr_0.8La_0.2Fe₁₂O₁₉ have been synthesized by conventional ceramic process. The effects of lanthanum addition and sintering temperature on microstructures and magnetic properties of SrFe₁₂O₁₉ and Sr_0.8La_0.2Fe₁₂O₁₉ samples were investigated. Microstructural analysis of the SrFe₁₂O₁₉ and Sr_0.8La_0.2Fe₁₂O₁₉ specimens, sintered at different temperatures revealed that average grain sizes of SrFe₁₂O₁₉ ferrites were larger than that of Sr_0.8La_0.2Fe₁₂O₁₉ ferrite and increased with increasing sintering temperature. The X-ray diffraction (XRD) results confirmed the strontium hexagonal ferrite phase of SrFe₁₂O₁₉ and Sr_0.8La_0.2Fe₁₂O₁₉ compounds. A maximum coercivity value of 4850 Oe and maximum saturation magnetization value of 102 emu/g were obtained for the SrFe₁₂O₁₉ ferrite sintered at 1150 °C and for the SrFe₁₂O₁₉ and Sr_0.8La_0.2Fe₁₂O₁₉ ferrites sintered at 1300 °C, respectively. The remanence (Mr) of Sr_0.8La_0.2Fe₁₂O₁₉ sample sintered at 1200 °C possesses the maximum value of 60 emu/g.     

Limiting current oxygen sensor based on La0.8Sr0.2Ga0.8Mg0.2O3−δ as both dense diffusion barrier and solid electrolyte

La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ (LSGM) was synthesized by a high temperature solid-state reaction. The crystal structure, relative density and electrical conductivity were measured with XRD, Archimedes method, and Van Der Pauw DC four-probe method. A limiting current oxygen sensor based on LSGM as both solid electrolyte and dense diffusion barrier was prepared by a Pt paste bonding method. The results show that LSGM has pure perovskite structure (cubic symmetry with space group of Pm-3m (No.221)), high density (relative density is 97.6%) and electrical conductivity (0.18 S∙cm⁻¹ at 1073 K). The sensor works optimally over temperature range of 973‒1123 K and oxygen concentration of 1.92%‒21%. The operating voltage ranges from 0.67 to 0.98 V. The limiting current is in proportion to oxygen concentration. The sensor has the highest sensitivity at 1123 K and low measurement error of less than 4%.     

Synthesis of HfB2 powders by mechanically activated borothermal reduction of HfCl4

HfB₂ powders were synthesized via a borothermal reduction route from mechanically activated HfCl₄ and B powder blends. Mechanical activation of the powder blends was carried out for 1 h in a high-energy ball mill using hardened steel vial and balls. Mechanically activated powders were subsequently annealed at 1100 °C for 1 h under Ar atmosphere. Then, purification processes such as washing with distilled water and leaching in HCl solution were applied for the elimination of the undesired boron oxide (B₂O₃) phase and the probable Fe impurity. The effect of boron amount on the microstructure of the resultant powders was investigated. The boron amount in the starting blends plays an important role in the formation of the HfO₂ phase. HfB₂ powders without any detectable HfO₂ were prepared by adding 20 wt% excess amount of boron. Microstructural analyses of the mechanically activated, annealed and purified powders were performed using X-ray diffractometer (XRD), particle size analyzer (PSA), stereomicroscope (SM), scanning electron microscope/energy dispersive spectrometer (SEM/EDS) and transmission electron microscope (TEM).     

Lowering the sintering temperature of Gd-doped ceria by mechanochemical activation

Two kinds of Ce_0.8Gd_0.2O_2?δ pellets were synthesized by a solid-state reaction using two types of commercial CeO₂ and Gd₂O₃. In contrast to previous reports, pellets with a sintered density of 99% at 1300 °C were obtained regardless the powder used. Mechanochemical activation of the starting materials by 7 h of high energy milling, which resulted in particles several tens of nanometer in size, was effective in reducing the sintering temperature. Ce_0.8Gd_0.2O_2?δ pellets could be synthesized by direct sintering without calcination due to the homogeneous distribution of fine starting materials. The final phase was confirmed by the ionic conductivity, X-ray diffraction patterns and lattice parameters.     

Facile synthesis of Ti3SiC2 powder by high energy ball-milling and vacuum pressureless heat-treating process from Ti–TiC–SiC–Al powder mixtures

In this article, Ti/TiC/SiC/Al powder mixtures with molar ratios of 4:1:2:0.2 were high energy ball-milled, compacted, and heated in vacuum with various schedules, in order to reveal the effects of temperature, soaking time, thickness of the compacts, and carbon content on the purity of the sintered compacts. X-ray diffraction and scanning electron microscopy were employed to investigate the phase purity, particle size and morphology of the synthesized samples. It was found that the Ti₃SiC₂ content nearly reached 100 wt.% on the surface layer of the sintered compacts prepared in the temperature range from 1350 °C to 1400 °C for 1 h. Powder containing 91 wt.% Ti₃SiC₂ was successfully synthesized by heating 6 mm green compacts of 4Ti/1TiC/2SiC/0.2Al at 1380 °C for 1 h in vacuum. The excessive carbon content failed to improve the purity of Ti₃SiC₂ powder. TiC phase was the main impurity in the formation process of Ti₃SiC₂.     

Production of TiB2 by SHS and HCl leaching at different temperatures: Characterization and investigation of sintering behavior by SPS

Sub-micron sized TiB₂ ceramic powders were prepared via self-propagating high-temperature synthesis (SHS) followed by HCl leaching at different temperatures. Purified powders obtained using optimum process parameters were consolidated by field assisted sintering technology/spark plasma sintering (FAST/SPS) technique. Phase and microstructural analyses of both the powder and sintered samples were carried out by X-ray diffractometer (XRD) and scanning electron microscope (SEM). The chemical analyses and particle size measurements of the specimen were conducted by inductively coupled plasma-mass spectrometry (ICP-MS) and dynamic light scattering (DLS) techniques. The final properties of the sintered sample were determined in terms of density and microhardness. The effects of different HCl leaching temperatures on the formation, microstructure, particle size, purity and sintering behavior of the SHS-produced TiB₂ powders were investigated. The SHS reaction of TiO₂-B₂O₃-Mg powders as a starting mixture yielded MgO, Mg₃(BO₃)₂ and Mg beside the desired phase TiB₂. All three magnesium containing by-products were completely removed by performing hot HCl leaching. TiB₂ powders after SHS reaction and leaching with 9.3 M HCl for 30 min at 80 °C revealed a minimum purity of 98.4% and a homogenous particle size distribution with an average particle size of 536 nm. In the ultimate SPS experiment which was conducted at 1500 °C for 5 min under a pressure of 50 MPa, a relative density of 94.9% and a micro-hardness value of 24.56 GPa were achieved.     

Fabrication,microstructure and mechanical properties of novel bulk binderless (Ti0.8Zr0.2)C carbides prepared by mechanical alloying and spark plasma sintering

Nanocrystalline (Ti_0.8Zr_0.2)C powder consisting in grains of about 200 nm in diameter obtained by mechanical alloying was sintered by a spark plasma sintering (SPS) process without the addition of any binder phase. The microstructure, Vickers micro hardness and density in relation to the sintering time and temperature are carefully described. The most suitable sintering condition under pressure of 50 MPa is 1650 °C for 5 min. In this sintering condition, the hardness can reach 2760 Hv and the relative density can reach 98%.     

Preparation of ultra-fine Sm0.2Ce0.8O1.9 powder by a novel solid state reaction and fabrication of dense Sm0.2Ce0.8O1.9 electrolyte film

A novel solid state reaction was adopted to prepare Sm_0.2Ce_0.8O_1.9 (SDC) powder. A mixed oxalate Sm_0.2Ce_0.8(C₂O₄)_1.5·2H₂O was synthesized by milling a mixture of cerium acetate hydrate, samarium acetate hydrate, and oxalic acid for 5 h at room temperature. An ultra-fine SDC powder with the primary particle size of 5.5 nm was obtained at 300 °C. The ultra-low temperature for the formation of SDC phase was due to the atomic level mixture of the Sm³⁺ and Ce⁴⁺ ions. The crystal sizes of SDC powders at 300 °C, 550 °C, 800 °C, and 1050 °C were 5.5 nm, 11.4 nm, 24.1 nm and 37.5 nm, respectively. The sintering curves showed that the powder calcined at lower temperature was easier to be sintered owning to its smaller particle size. A solid oxide electrolytic cell (SOEC), comprising porous La_0.8Sr_0.2Cu_0.1Fe_0.9O_3−δ (LSCF) for substrate, LSCF–SDC for active electrode, SDC for electrolyte, and LSCF–SDC for symmetric electrode, was fabricated by dip-coating and co-sintering techniques. An extremely dense SDC film with the thickness of 20 μm was obtained at only 1200 °C, which was about 100–300 °C lower than the literatures׳ reports. The designed SOEC was proved to work effectively for decomposing NO (3500 ppm, balanced in N₂), 80% NO can be decomposed at 600 °C.     

Microwave sintering of CeO2 and Y2O3 co-stabilised ZrO2 from stabiliser-coated nanopowders

Tetragonal ZrO₂ polycrystalline (TZP) composites with 2 wt.% Al₂O₃ and co-stabilised with 1 mol% Y₂O₃ and (4, 6 or 8) mol% CeO₂ were sintered at 1450 °C for 20 min in a single mode 2.45 GHz microwave furnace. For comparison, conventional sintering was performed in air at 1450 °C for 20 min. The starting powder mixture was obtained by a suspension coating technique using yttrium nitrate, cerium nitrate and pure m-ZrO₂ nanopowder. Fully dense material grades were obtained by both sintering methods. The influence of the composition and the sintering methods on the final phase composition and microstructure were investigated by X-ray diffraction and scanning electron microscopy. Finer and more uniform microstructures were observed in the microwave sintered ceramics when compared to the conventionally sintered samples. The fracture toughness increases with decreasing stabiliser content, whereas a reverse relation was found for the Vickers hardness. Comparable toughness and hardness values were obtained for the microwave and conventionally sintered samples.     

Combustion synthesis and characterization of LSCF-based materials as cathode of intermediate temperature solid oxide fuel cells

Nanocrystalline SOFC cathode materials of perovskite family, La_1?xSr_xM_1?yCo_yO₃, where 0 < x ≤ 0.5, 0 < y ≤ 0.8 (M is transitional metal = Mn or Fe), have been synthesized at a relatively low temperature by combustion synthesis using alanine as a novel fuel. Detailed X-ray powder diffraction analyses show 47–96% phase purity in the as-synthesized powder and upon calcination at ～825 °C single-phase material is obtained wherein the nanocrystallinity (crystallite size ～19–24 nm) is retained. Densification studies of the materials are carried out within 900–1100 °C. The coefficient of thermal expansion (CTE) of these cathodes is measured. Electrical conductivity of the cathodes sintered at different temperatures are measured in the temperature range 700–900 °C and correlated with the density of the sintered materials. The electrochemical performances of Ni-YSZ anode-supported SOFC having YSZ electrolyte (～10 μm) with CGO interlayer (～15 μm) are studied with the developed cathodes in the temperature range 700–800 °C using H₂ as fuel and oxygen as oxidant. Highest current density of ～1.7 A/cm² is achieved during testing at 800 °C measured at 0.7 V with a cathode composition of La_0.5Sr_0.5Co_0.8Fe_0.2O₃. Precipitation of nanocrystalline grains over the core grains in porous microstructure of this cathode might be one of the reasons for such high cell performance.     

Conductivity of Co and Ni doped lanthanum-gallate synthesized by citrate sol–gel method

Solid solutions of Sr and Mg doped lanthanum-gallate (LSGM) with addition of 3 and 5 at% of cobalt and nickel at the B-site in ABO₃ perovskite structure were obtained using citrate sol–gel method. The synthesized powders were calcined at 900 °C and then finally sintered at 1450 °C for only 2 h, which resulted in approximately 95% density. Impedance spectroscopy was utilized for electrical characterization in the temperature range 200–600 °C. The activation energies calculated from impedance spectra for bulk and grain boundary conductivities were decreased by the addition of transition metals (Co and Ni) and subsequently the conductivity was increased. Two different regions were clearly distinguished in the plots ln(σT) vs. 10,000/T for grain boundary conductivities, indicating changes in the mechanism of charge transport with the temperature. It is concluded that addition of cobalt above 5 at% in the LSGM prepared by citrate sol–gel method does not enhance the electrolytic properties of LSGM. XRD results suggested possible coexistence of two perovskite crystalline phases in nickel doped samples. However, it is still more favorable for use in IT-SOFC applications than cobalt since it has less influence on the electrolytic domain of LSGM.     

Synthesis and characterization of La0.85Sr0.15Ga0.85Mg0.15O3−δ electrolyte by steric entrapment synthesis method

Strontium and magnesium doped lanthanum gallate La_0.85Sr_0.15Ga_0.85Mg_0.15O_3−δ (LSGM) oxygen ionic conducting ceramics were prepared by a steric entrapment synthesis (SES) method, which is a polymeric precursor synthesis method by using polyvinyl alcohol in aqueous solution. The perovskite LSGM phase formed essentially at a calcination temperature of 900 °C. Pure and single perovskite LSGM phase with high relative density of 97.1% was obtained after sintering at 1450 °C, while the relative density of the LSGM sample sintered at the same temperature by solid state reaction (SSR) method was 80.6% in present experiment. Comparing with SSR synthesis method, the sintering temperature by SES can be reduced at least 100 °C. Impedance spectra revealed that the grain-boundary resistivity of LSGM synthesized by SES was smaller than that by SSR method, and the conductivities of the samples by SES were higher than those by SSR method at all measuring temperatures.     

Effect of Bi2O3 addition on the sintering and microstructural development of gadolinia-doped ceria ceramics

The effect of small amounts (0.2–2.0 wt.%) of bismuth oxide on the sintering behavior and microstructural development of Ce_0.9Gd_0.1O_1.95 (GDC) submicronized powders has been studied using XRD for the lattice parameter measurements, the constant heating rate (CHR) method in air to monitor the shrinkage kinetics of powder compacts, and scanning electron microscopy (SEM) to study the microstructure of the sintered samples. Sintering of GDC compacts was significantly improved by adding small amounts of Bi₂O₃ (≤2.0 wt.%), and samples of doped-GDC sintered at 1200–1400 °C for 2–4 h were dense bodies (98–99.5% of theoretical density). Measurements showed that the addition of Bi₂O₃ could reduce the sintering temperature by about 250–300 °C lower than that for undoped-GDC samples. A liquid phase-assisting mechanism was assumed as the main cause for the enhancement of the densification process. The average grain size of doped-GDC sintered samples grew with the increasing of Bi₂O₃ addition up to 1.0 wt.%, and then decreased indicating a poor wetting properties of the formed liquid phase.     

Hydrothermal synthesis of nanocrystalline BaSnO3 using a SnO2·xH2O sol

A BaSnO₃ powder with a crystallite size of 27.6 nm has been prepared through a hydrothermal reaction of a peptised SnO₂·xH₂O and Ba(OH)₂ at 250 °C and the following crystallization of this hydrothermal product at 330 °C. The peptisation of the SnO₂·xH₂O gel is dependent on the pH value. Through peptisation the mean particle size of SnO₂·xH₂O in the aqueous solution has been decreased by a factor of 100 to 8 nm. A limited agglomeration in the sol-prepared powder has been observed under the microscope. The structure evolution and crystallisation behaviours of the sol-prepared powders were investigated by TG-DTA, IR and XRD. The BaSn(OH)₆ phase in the as-prepared powder transforms into an amorphous phase at 260 °C, from which the BaSnO₃ particles nucleate and grow with an increase in temperature. The single-phase BaSnO₃ powder has been obtained at a temperature as low as 330 °C. This sol-prepared powder is more sinter-reactive than the gel-prepared powder and can be sintered to a ceramic with 90.7% of the theoretic density.     

Crystallization processes,compressibility, sinterability and mechanical properties of La-monazite-type ceramics

Lanthanide orthophosphate ceramics with monazite structure gained broad interest for several industrial applications. The crystallization processes, compressibility and sinterability of monazite-type lanthanum orthophosphate powder hydrothermally synthesized at 200 °C as well as mechanical properties of the sintered compacts were investigated. Based on a combination of thermo- and surface area analyses, X-ray diffraction as well as scanning electron microscopy studies it was found that the crystallization process occurs at ∼500 °C and the final crystallization of LaPO₄ monoclinic phase takes place at 1400 °C. The sintered pellets are characterized by a density of 98% of theoretical density, a Vickers hardness of 5.7 ± 0.1 GPa and fracture toughness of 1.4 ± 0.1 MPa m^0.5.     

Physical properties of V-doped TiO2 nanoparticles synthesized by sonochemical-assisted process

V-doped TiO₂ nanoparticles were synthesized by sonochemical process using titanium isopropoxide as a titanium source, vanadyl acetylacetonate as a dopant source. Sonication was conducted using sonic horn operated at 20 kHz for 20 min until the completely precipitated product was reached. The as-synthesized precipitates with various vanadium dopant (1–5 mol %) were calcined at 500–1000 °C for 4 h. The relevant physical properties of the nanoparticles were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and transmission electron microscope (TEM). The anatase phase TiO₂ nanoparticles can be synthesized by sonochemical process. Post calcinations process results in the anatase-to-rutile phase transformation and the enhancement in crystallinity with increasing temperature. The results also indicate good incorporation of V ions in TiO₂ lattices and significant effect of V dopant on alternation of interplanar spacing of TiO₂.     

A comparative study of the properties of terbium aluminum garnet powder sintered in air,vacuum and by laser irradiation

The structural and optical properties of terbium aluminum garnet (TAG) powder sintered (～1100 °C) in air, vacuum (～10^?6 mbar) and with 70 W of unfocussed CW CO₂ laser radiation, have been studied using X-ray powder diffraction (XRD), scanning electron microscopy (SEM/TEM), FTIR, optical absorption and photoluminescence techniques. Structural properties of TAG are found to be independent of the sintering procedure except that the pure TAG crystalline phase (Tb₃Al₅O₁₂) is evolved in about 2 h in the case of laser sintering compared to 8 h needed in air sintering (by furnace) and 4 h needed in the case of vacuum furnace sintering. On the other hand, the absorption/emission intensity (300–600 nm region) of TAG samples sintered in vacuum is higher compared to that of laser/furnace sintering in air.