Sol–gel synthesis of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte

The effect of calcination on Li ion conductivity of Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) solid electrolyte prepared by a sol–gel method is examined. The Li ion conductivity of LAGP increases with calcination temperature. After reaching maximum conductivity at 850 °C, the conductivity decreases with increase of the calcination temperature. The calcination holding time also strongly affects Li ion conductivity of LAGP. The conductivity increases with holding time until 12 h and then decreases. It is found that the control of crystallization rate is critical to obtain bulk LAGP with high Li ion conductivity. The highest bulk and total conductivities at 30 °C are 9.5×10⁻⁴ and 1.8×10⁻⁴ S cm⁻¹, respectively, obtained for the bulk LAGP calcined at 850 °C for 12 h.     

Influence of calcination temperature on the piezoelectric properties of Ag2O doped 0.94(K0.5Na0.5)NbO3–0.06LiNbO3 ceramics

The effects of calcination temperature on the bulk density, piezoelectric, and ferroelectric properties were investigated for the Ag₂O doped 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ ceramics. The calcination temperatures were varied from 750 to 950 °C by 50 °C differences. An tetragonal XRD pattern, consistent with single-phase 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ was obtained after calcination at 850 °C for 2 h. And the experimental results showed that Ag₂O doped 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ ceramics calcined at 850 °C had a remnant polarization P_r=24.5 μC/cm², bulk density=4.32 g/cm³, piezoelectric constant d₃₃=282 pC/N and electromechanical coefficient k_p=37.8%.     

Charge–discharge curves and discharge capacities of LiNi1−yCoyO2 synthesized from lithium carbonate and nickel and cobalt oxides

LiNi_1?yCo_yO₂ (y=0.1, 0.3, and 0.5) were synthesized by a solid-state reaction method at 800 °C and 850 °C using Li₂CO₃, NiO, and Co₃O₄ as the starting materials. The electrochemical properties of the synthesized LiNi_1?yCo_yO₂ were then investigated. For samples with the same composition, the particles synthesized at 850 °C were larger than those synthesized at 800 °C. The particles of all the samples synthesized at 850 °C were larger than those synthesized at 800 °C. LiNi_0.5Co_0.5O₂ synthesized at 850 °C had the largest first discharge capacity (159 mA h/g), followed in order by LiNi_0.7Co_0.3O₂ synthesized at 800 °C (158 mA h/g) and LiNi_0.9Co_0.1O₂ synthesized at 850 °C (151 mA h/g). LiNi_0.9Co_0.1O₂ synthesized at 850 °C had the best cycling performance with discharge capacities of 151 mA h/g at n=1 and 156 mA h/g at n=5.     

Structural,thermal and electrical studies of a novel rubidium phosphite tellurate compound

Structural, thermal and electrical properties studies of rubidium phosphite tellurate, RbH(PO₃H)·Te(OH)₆, were performed. An endothermic peak, which reached a completion at about 315 °C accompanied with a weight loss of 4.6 wt.%, was attributed to dehydration. Four types of pellets were produced, namely pellets A, B, C and D. Pellet A was tested with platinum–carbon paper electrode, and pellets B, C and D were tested with gold electrodes. Both pellets A and B were studied from 113 °C to 317 °C for 135 h. Pellet C was first investigated from room temperature to 176 °C for 360 h. After cooling down to room temperature, a second measurement with pellet C was carried out under the same conditions as used for pellets A and B. Pellet D, on the other hand, was heated up to 450 °C, kept at that temperature for 2 h and then cooled down to room temperature prior to the conductivity measurements. It was observed that the conductivities of pellets A and B decreased to values of 5.2 × 10^?8 S cm^?1 and 6.6 × 10^?7 S cm^?1 at 317 °C, respectively, and an unexpected rise in the conductivity (9.89 × 10^?6 S cm^?1 at 317 °C) was seen with pellet C. Dehydration of RbH(PO₃H)·Te(OH)₆ might be responsible for this unexpected rise in the conductivity of pellet C. The monoprotic part RbH(PO₃H) of RbH(PO₃H)·Te(OH)₆ apparently became diprotic (Rb₂H₂P₂O₅) part of Rb₂H₂P₂O₅·[Te(OH)₆]₂ after dehydration. The measured conductivity of pellet D, which was dehydrated prior to the measurement, reached a value of 5.41 × 10^?5 S cm^?1 at 317 °C and showed a good stability over-each-run time and temperatures measurement up to 317 °C. The dehydrated compound, Rb₂H₂P₂O₅·[Te(OH)₆]₂, has also a higher hydrogen density relative to the starting compound, RbH(PO₃H)·Te(OH)₆. It is deduced that completion of the dehydration can be responsible for the unexpected rise in the conductivity of RbH(PO₃H)·Te(OH)₆. This unusual case is important for studies in solid acid proton conductors.     

Dielectric properties of nano-sized Ba0.7Sr0.3TiO3 powders prepared by spray pyrolysis

Nano-sized Ba_0.7Sr_0.3TiO₃ powders are prepared by post-treatment of the precursor powders with hollow and thin wall structure at temperatures between 900 and 1100 °C. Ethylenediaminetetraacetic acid and citric acid improve the hollowness of the precursor powders prepared by spray pyrolysis. The mean sizes of the powders post-treated at temperatures of 900, 1000 and 1100 °C are 42, 51 and 66 nm, respectively. The densities of the Ba_0.7Sr_0.3TiO₃ pellets obtained from the powders post-treated at 900, 1000 and 1100 °C are each 5.36, 5.55 and 5.38 g cm^?3 at a sintering temperature of 1300 °C. The pellet obtained from the powders post-treated at 1000 °C has higher maximum dielectric constant than those obtained from the powders post-treated at 900 and 1100 °C.     

Annealing effect on dielectric property of AlN ceramics

Effects of slow-cooling at high temperatures and annealing at intermediate temperatures on dielectric loss tangent of AlN ceramics were explored. Y₂O₃ was added as a sintering additive to AlN powders, and the powders were pressureless-sintered at 1900 °C for 2 h in a nitrogen flow atmosphere. In succession to the sintering, AlN samples were slow-cooled at a rate of 1 °C/min from 1900 to 1750 °C and/or annealed at 970 °C for 4 h. Al₅Y₃O₁₂ was detected in the AlN ceramics obtained by the slow-cooling and AlYO₃ was found in the ceramics cooled at a rate of 30 °C/min. AlN ceramics with a relative density of 0.986 were obtained by the slow-cooling method. On the other hand, very low tan δ values between 2.6 and 4.6 × 10⁻⁴ were obtained when the AlN ceramics were annealed at 970 °C for 4 h.     

Transparent Lu3NbO7 bodies prepared by reactive spark plasma sintering and their optical and mechanical properties

Transparent lutetium niobate (Lu₃NbO₇) bodies were prepared by reactive spark plasma sintering using Lu₂O₃ and Nb₂O₅ powders. Fully dense Lu₃NbO₇ bodies with density greater than 99.5% of the theoretical were obtained at 1300–1650 °C. The grains steadily grew from 0.1 to 0.6 μm with increasing sintering temperature from 1200 to 1450 °C and significant grain growth from 2.2 to 9.2 μm occurred at 1550–1650 °C. The Lu₃NbO₇ body sintered at 1450 °C showed the highest transmittance of 63% at 550 nm after heat treatment at 850 °C in air for 6 h. Fully dense, submicron-size transparent Lu₃NbO₇ exhibited Vickers hardness of ～13.0 GPa and indentation fracture toughness of 1.0 MPa m^1/2.     

SPS processing of bismuth-layer structured ferroelectric ceramics yielding highly textured microstructures

The spark plasma sintering (SPS) behaviour of nano-sized Bi₄Ti₃O₁₂ (BIT) and micron-sized CaBi₂Nb₂O₉ (CBNO) powders is described. The densification process of both powders is very rapid, i.e. the densification occurs within a very narrow time interval (2–3 min using a heating rate of 100 °C min⁻¹ and a pressure of 50 MPa). The BIT powder exhibits a lower densification onset temperature (∼650 °C) and higher maximum shrinkage rate (8.9 × 10⁻³ s⁻¹ at 780 °C) than that of the CBNO powder (∼825 °C and 4.5 × 10⁻³ s⁻¹ at 950 °C). Isothermal compaction studies revealed that fully dense nano-sized BIT compacts could be obtained within the temperature region 750 °C < T_iso < 850 °C while for T_iso > 850 °C compacts containing elongated platelet grains are formed. A new preparation route to produce highly textured compacts is described in detail. Appropriate pre-forms are prepared by spark plasma sintering (SPS) and these fully dense compacts are subject to superplastic deformation in the SPS unit to achieve a total compressive strain of ∼60%. This strain was achieved within a period of 1.5 min and with a maximum strain rates of 1.1 × 10⁻² s⁻¹ achieved at ∼840 °C and 1.3 × 10⁻² s⁻¹ at 1020 °C for the BIT and CBNO compacts, respectively. The X-ray studies showed that the Lotgering orientation factors of grains in the deformed BIT and CBNO compacts are 99% and 70%. The formation of highly textured compacts is suggested to be governed by a superplastic deformation-induced directional dynamic ripening mechanism.     

Preparation and characterization of La and Cr co-doped SrTiO3 materials for SOFC anode

Using citric acid–nitrate process, La and Cr co-doped A-site deficient SrTiO₃ (LSTC) materials were synthesized. The single-phase perovskite structure of LSTC materials can be obtained in airy atmosphere when the dopant content of chromium does not exceed 20 mol%. The LSTC material has excellent chemical compatibility with yttria-stabilized zirconia (YSZ) at 1400 °C. The particle diameters of LSTC powders calcined at 800 °C are all less than 60 nm. The LSTC pellet sintered in air at 1400 °C for 5 h shows a highly densified microstructure composed of polyhedral grains on a micron scale. At 800 °C, the conductivity of LSTC20 pellet is 1.96×10^?3 S/cm in static air. The conduction activation energy of LSTC20 pellet is calculated to be 0.33 eV in the temperature range of 550–800 °C. The LSTC can be considered as a potential candidate anode material for SOFC with YSZ as electrolyte, but its conductivity needs to be further improved.     

Effects of La doping on electrical conductivity,thermal expansion and electrochemical performance in LaxSr1–xCo0.9Sb0.1O3–δ cathodes for IT–SOFCs

Perovskite oxides La_xSr_1–xCo_0.9Sb_0.1O_3–δ (LSCSbx, x=0.0–0.8) are investigated as IT–SOFC cathodes supported with La_0.9Sr_0.1Ga_0.8Mg_0.2O_3–δ (LSGM) electrolyte. All LSCSbx oxides have a tetragonal distorted perovskite structure with s.g. P4/mmm, while a La₂Co₂O₅ impurity phase was observed within La doping levels at x=0.6–0.8. The LSCSb0.4 has a good chemical compatibility with LSGM electrolyte for temperatures up to 1050 °C. XPS examinations indicate the existence of Co³⁺/Co⁴⁺ mixed valence states in LSCSbx. The conductivity increases with La doping and the LSCSbx with x=0.4 exhibits the highest electrical conductivity (e.g., 673–1637 S cm⁻¹ at 300–850 °C). The thermal expansion coefficient (TEC) decreases from 25.89×10^–6 K^–1 for x=0.0 to 18.5×10^–6 K^–1 for x=0.6 at 30–900 °C. Among the LSCSbx compositions, the LSCSb0.2 exhibits the lowest polarization resistance (R_p), which is merely 0.069 Ω cm² at 700 °C. The maximum power density of the cell with LSCSb0.2 cathode on 300 µm thick LSGM electrolyte attains 564 mW cm^–2 at 850 °C, which is higher than that of SrCo_0.9Sb_0.1O_3–δ (SCSb) cathode. All of the results indicate that LSCSb0.2 is a promising material for application in IT–SOFCs cathodes.     

Effects of B2O3 on microstructure and ionic conductivity of Li6.5La3Zr1.5Nb0.5O12 solid electrolyte

Li_6.5La₃Zr_1.5Nb_0.5O₁₂ (LLZN) garnet-type structure was synthesized at low temperature with B₂O₃ addition by solid state reaction method. The effects of B₂O₃ content on the formation, microstructure, ionic conductivity and activation energy of the LLZN solid electrolytes have been investigated by X-Ray diffraction (XRD), scanning electron microscopy (SEM) and alternate current (AC) impedance spectroscopy. The cubic LLZN phase was obtained after calcining at 850 °C for 6 h and no phase evolution was observed after sintering at 1100 °C for 6 h. The relative density and lithium ion conductivity increased first and then decreased with increasing B₂O₃ content, reaching the maximum value of 92.4% and 1.86×10⁻⁴ S cm⁻¹ respectively in the sample with 1.4 wt% B₂O₃. By contrast, the activation energy reached a minimum value of ~31.5 kJ mol⁻¹.     

Synthesis and characterization of nanometric gadolinia powders by room temperature solid-state displacement reaction and low temperature calcination

Nanometric-sized gadolinia (Gd₂O₃) powders were obtained by applying solid-state displacement reaction at room temperature and low temperature calcination. The XRD analysis revealed that the room temperature product was gadolinium hydroxide, Gd(OH)₃. In order to induce crystallization of Gd₂O₃, the subsequent calcination at 600 ∼ 1200 °C of the room temperature reaction products was studied. Calculation of average crystallite size (D) as well as separation of the effect of crystallite size and strain of nanocrystals was performed on the basic of Williamson-Hall plots. The morphologies of powders calcined at different temperatures were followed by scanning electron microscopy. The pure cubic Gd₂O₃ phase was made at 600 °C which converted to monoclinic Gd₂O₃ phase between 1400° and 1600 °C. High-density (96% of theoretical density) ceramic pellet free of any additives was obtained after pressureless sintering at 1600 °C for 4 h in air, using calcined powder at 600 °C.     

Ni4Nb2O9 ceramics prepared by the reaction-sintering process

Fabrication of Ni₄Nb₂O₉ ceramics via a reaction-sintering process was investigated. A mixture of raw materials was sintered into ceramics by bypassing calcination and subsequent pulverization stages. Ni₄Nb₂O₉ phase appeared at 1300 °C and increased with increasing soak time. Ni₄Nb₂O₉ content was found >96% in 1350 °C/2 h sintering pellets. A density of 5.71 g/cm³ was obtained for pellets sintered at 1350 °C for 2 h. This reaches 96.5% of the theoretical density. As the sintering temperature increased to 1350 °C, an abnormal grain growth occurred and grains >100 μm could be found. ?_r of 15.4–16.9 are found in pellets sintered at 1200–1300 °C. Q × f increased from 9380 GHz in pellets sintered at 1200 °C to 14,650 GHz in pellets sintered at 1250 °C.     

Microstructure and dielectric properties of amorphous BaSm2Ti4O12 thin films for MIM capacitor

BaSm₂Ti₄O₁₂ (BST) film grown at room temperature was amorphous, while the film grown at 300 °C was also amorphous but contained a small amount of crystalline Sm₂Ti₂O₇ (ST). The crystalline BST phase was formed when the film was grown at 700 °C and subjected to rapid thermal annealing (RTA) at 900 °C. On the other hand, the ST phase was formed in the film grown at 300 °C and subjected to RTA at 900 °C. A high capacitance density of 2.12 fF/μm² and a low leakage current density of 1.15 fA/pF V were obtained from the 150 nm-thick BST film grown at 300 °C. Its capacitance density could conceivably be further increased by decreasing the thickness of the film. It had linear and quadratic coefficients of capacitance of −785 ppm/V and 5.8 ppm/V² at 100 kHz, respectively. Its temperature coefficient of capacitance was also low, being approximately 255 ppm/°C at 100 kHz.     

Mechanical behavior of zirconium diboride–silicon carbide ceramics at elevated temperature in air

The mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics were characterized from room temperature up to 1600 °C in air. ZrB₂ containing nominally 30 vol% SiC was hot pressed to full density at 1950 °C using B₄C as a sintering aid. After hot pressing, the composition was determined to be 68.5 vol% ZrB₂, 29.5 vol% SiC, and 2.0 vol% B₄C using image analysis. The average ZrB₂ grain size was 1.9 μm. The average SiC particles size was 1.2 μm, but the SiC particles formed larger clusters. The room temperature flexural strength was 680 MPa and strength increased to 750 MPa at 800 °C. Strength decreased to ～360 MPa at 1500 °C and 1600 °C. The elastic modulus at room temperature was 510 GPa. Modulus decreased nearly linearly with temperature to 210 GPa at 1500 °C, with a more rapid decrease to 110 GPa at 1600 °C. The fracture toughness was 3.6 MPa·m^½ at room temperature, increased to 4.8 MPa·m^½ at 800 °C, and then decreased linearly to 3.3 MPa·m^½ at 1600 °C. The strength was controlled by the SiC cluster size up to 1000 °C, and oxidation damage above 1200 °C.     

Aluminum titanate based ceramics from aluminum sludge waste

This work aims at obtaining aluminum titanate-based ceramics (Al₂TiO₅: AT) composites from industrial wastes. Al-sludge waste and rutile ore were used as rich sources of alumina and titania instead of pure materials. Sludge-(0–40 wt%) rutile mixtures were mixed, formed and fired at 1350 °C for various times. Phase composition, microstructure, densification, mechanical and thermal behaviors of the obtained AT composites have been investigated. Complete conversion of the starting materials to AT with bulk density of 3.199 g/cm³, compressive strength and modulus of rupture of 326.425 MPa and 30.84 MPa, respectively and very low CTE (−0.927*10⁻⁶ K⁻¹) were achieved by firing the sludge-(30 wt%) rutile at 1350 °C for 4 h. These results suggest that the obtained AT-ceramics from Al-sludge waste-rutile ore are a promising and an ecofriendly route.     

Synthesis,sintering and electrical properties of yttria–calcia-doped ceria

Crystalline yttria and calcia doped ceria powder, with a composition of Ce_0.8Y_0.18Ca_0.02O_2?δ has been prepared by a coprecipitation procedure from the corresponding nitrates of component cations. Nanopowder was obtained after thermal treatment at 700 °C 2 h of the coprecipitated mixtures. Specific surface area was 45 m²/g. Isostatically and uniaxially pressed pellets were prepared from the powder. Sintering behaviour was followed by CHR dilatometer. Isothermal sintering was carried out between 1100 and 1300 °C. Apparent density as high as 98% D_th was attained by firing isostatically pressed pellets at 1150 °C 4 h. Uniaxially pressed pellets attained the same apparent density at 1275 °C 2 h, being in both cases very low the densification temperatures. Microstructure was observed by scanning electron microscopy (SEM). Ionic conductivity was determined by complex impedance spectroscopy. Bulk and grain boundary conductivities have similar values, and the total conductivity attains good value compatible with the use as electrolyte in solid oxide fuel cell (SOFC).     

Pressureless sintering of titanium carbide doped with boron or boron carbide

Titanium carbide ceramics with different contents of boron or B₄C were pressureless sintered at temperatures from 2100 °C to 2300 °C. Due to the removal of oxide impurities, the onset temperature for TiC grain growth was lowered to 2100 °C and near fully dense (>98%) TiC ceramics were obtained at 2200 °C. TiB₂ platelets and graphite flakes were formed during sintering process. They retard TiC grains from fast growth and reduced the entrapped pores in TiC grains. Therefore, TiC doped with boron or B₄C could achieve higher relative density (>99.5%) than pure TiC (96.67%) at 2300 °C. Mechanical properties including Vickers’ hardness, fracture toughness and flexural strength were investigated. Highest fracture toughness (4.79 ± 0.50 MPa m^1/2) and flexural strength (552.6 ± 23.1 MPa) have been obtained when TiC mixed with B₄C by the mass ratio of 100:5.11. The main toughening mechanisms include crack deflection and pull-out of TiB₂ platelets.     

Synthesis and characterization of LTCC compositions with middle permittivity based on CaO-B2O3-SiO2 glass/CaTiO3 system

CaTiO₃ ceramics with the addition of CaO-B₂O₃-SiO₂ (CBS) glass (45–55 wt%) composites were sintered at 830 °C, 850 °C, 875 °C and 900 °C. To illustrate influence mechanism of the different glass contents and sintering temperatures on the properties of the composites, we focused on the multiple performances of the composites by employing different qualitative and quantitative instruments. Composites with 50 wt% glass sintered at 875 °C presented fairly ideal performance: the bulk density was 3.20 g/cm³, the dielectric constant was 25.7 and the dielectric loss was 0.0009 at 7 GHz. Micro-Structure analysis of the composites showed a dense and pore-less microstructure except for few pores with size around 1 μm. In addition, the composite could meet the shrinkage requirement of Ag electrodes and could not possibly react with Ag electrodes any more. This makes them suitable for various dielectric applications at low sintering temperature.     

Electric field-assisted flash sintering of tin dioxide

SnO₂ green pellets were submitted to ac electric fields at temperatures below 1350 °C. Electric current pulses occurred and a substantial modification was found in the microstructure of the pellets after application of 80 V cm⁻¹ at 900, 1100 and 1300 °C. Similar experiments were carried out in SnO₂ mixed to 2 wt.% MnO₂. The linear shrinkage of the pellets was monitored with a dilatometer during the application of the electric field. Scanning electron microscopy micrographs of the pellets show the grain structure evolution after the electric current pulses. The larger is the electric current flow through the SnO₂ pellet, the larger are the shrinkage and the average grain size. Even though sintering occurs without significant densification in SnO₂, the welding of the grains is evident. The apparent density of green pellets of SnO₂ with MnO₂ addition sintered at 1100 °C increased 110% with the application of 80 V cm⁻¹, 5 A.