Sinterability,Mechanical, Microstructural,and Electrical Properties of Gadolinium-Doped Ceria Electrolyte for Low-Temperature Solid Oxide Fuel Cells

In this study, we report key functional properties of gadolinium-doped ceria (Gd_0.1Ce_0.9O_1.95, GDC) sintered at low temperatures as well as single-cell electrochemical performance of a single-cell prepared there of. GDC solid solutions were sintered at various temperatures ranging 1100–1400^∘C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), density measurements, mechanical strength tests and electrical conductivity measurements. The dry-pressed GDC disc sample sintered at 1100^∘C was found to have 96% of the theoretical density and higher sintering temperatures led to higher densities. SEM micrographs of the fracture and plan surfaces of the sintered discs established the absence of any open pores. The sample sintered at 1100^∘C exhibited high electrical conductivity of 0.027 S/cm at 650^∘C. The mechanical strength of the sintered samples was determined to be in the range of 150–175 MPa. Greater than 96% of theoretical density, good mechanical strength, and high electrical conductivity of GDC disc samples sintered at 1100^∘C established the viability of low-temperature processing of GDC for its use as an SOFC electrolyte. Accordingly, a single-cell was prepared by co-sintering of GDC electrolyte and LSCF-GDC cathode at 1100^∘C and subsequent firing of CuO-GDC anode at 900^∘C. The electrochemical performance of the cell was evaluated in H₂ fuel at 650^∘C.     

Effect of attrition milling on the piezoelectric properties of Bi0.5Na0.5TiO3-based ceramics

Bismith sodium titanate (BNT)-based powders were prepared by conventionally mixed-oxide method using Bi₂O₃, Na₂CO₃ and TiO₂. The La₂O₃ was added as the modifier to the BNT composition for easily poling and reducing an abnormal dielectric loss at high temperatures. In this study, the investigated compositions were Bi_0.5Na_0.5TiO₃ and Bi_0.5Na_0.485La_0.005TiO₃. The powders were calcined at 900 °C for 2 h by slow heating rate at 100 °C/h. The calcined BNT-based powders were then attrition-milled for 3 h with a high speed at 350 rpm. After drying, the fine powders were uniaxially pressed and then cold-isostatically pressed (CIP) at 240 MPa for 10 min. All pressed pellets were sintered at 1000–1100 °C for 2 h in air atmosphere. The microstructure of sintered pellets was investigated by SEM. Results of dielectric and piezoelectric property measurement were also reported.     

PMN-PFN Relaxor Ferroelectric Ceramics by a Reaction-Sintering Process

Pb((Mg_1/3Nb_2/3)_0.6(Fe_1/2Nb_1/2)_0.4)O₃ (PMFN) perovskite relaxor ferroelectric ceramics produced by reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Mg(NO₃)₂, Fe(NO₃)₃ and Nb₂O₅ was pressed into pellets and sintered directly. PMFN ceramics of 100% perovskite phase were obtained. Density of 7.84 g/cm³ (95% of theoretical value) was obtained after sintered at 1250°C for 2 h. Grain sizes of 3–6 m were formed after 2 h sintering at 1150–1250°C. Dielectric constant at room temperature under 10 kHz reaches 22400 after sintered at 1250°C for 2 h.     

The Applicability of Sr-deficient <Emphasis Type="Italic">n</Emphasis>-type SrTiO<Subscript>3</Subscript> for SOFC Anodes

Here we discuss the effect of preparation conditions on structural stability and electrical properties of Sr-deficient n-type SrTiO₃. In particular, an explanation of a wide scatter of conductivity values in Y- and Nb-doped SrTiO₃. reported in the literature is proposed, based on the existing defect chemistry model of n-doped SrTiO₃. It was confirmed that when sintered in air, Sr-deficient SrTiO₃ doped with Nb and/or Y, remains single phase until the solubility limit (e.g., 30% for Nb or 4% for Y). However, when sintered at low po₂, the material transforms from a vacancy compensated to an electronically compensated compound with a strontium deficient second phase. Measured at 800°C in low po₂, the maximum conductivity of these multi-phase compounds was 340 S/cm and 100 S/cm for the Nb-doped and Y-doped sample, respectively. However, the conductivity dropped dramatically to less than 10 S/cm when samples of the same compositions were sintered in air, again measured in reducing atmosphere.     

Piezoelectric and Magnetoelectric Properties of Lead Zirconate Titanate/Ni-Ferrite Particulate Composites

Piezoelectric and magnetoelectric properties of magnetoelectric particulate composites with Lead Zirconate Titanate (PZT) and Ni-ferrite were investigated. The maximum magnetoelectric voltage coefficient, (dE/dH)_max, increased with higher sintering temperature up to 1250°C. Composites sintered at 1300°C, had dissolution of Fe ions into PZT, or interdiffusion between PZT and ferrite. Connectivity of the ferrite particles and sintering temperature were important factors for fabrication of this particulate composite. The composite added with 20 wt.% amount of Ni-ferrite, sintered at 1250°C for 2 hours, had the highest magnetoelectric voltage coefficient of 115 mV/cm · Oe at room temperature. This value is comparable to that of the BaTiO₃-CoFe₂O₄ based composites reported by Philips laboratory, and is 44% higher than other magnetoelectric particulate composites.     

The Effect of Sintering Processes on the Properties of Mn-F Doped PZT Ceramics

Fluoridated PZT ceramics were produced by solid-state and liquid-phase sintering methods, according to the formula Pb(Zr_0.52Ti_0.48)_1-xMn_xO_3-yF_y, where 0 < x < 0.015 and 0 < y < 0.1. The effects of sintering processes on the phase development and microstructure of Mn-F doped PZT ceramics have been investigated using XRD and FEGSEM. In solid-state sintering, the fluoride additive enhanced the densification of PZT ceramics, enabling densification to >95% relative density at a temperature as low as 1000°C. However, fluoride loss at high temperatures was found to be a significant problem. Alternatively, ceramics with a density >92% were prepared by sintering at a temperature of 850°C by incorporating a eutectic mixture of PbO and V₂O₅ as sintering aid. Problems associated with volatilization of fluoride compounds during sintering could be alleviated using this approach. EPMA was employed to analyze the distribution of the additives in the calcined powders and sintered ceramics. The nonlinear dielectric properties were determined by measuring P-E loops, using an AC electric field in the range 0.1 to 2.0 kV mm^?1.     

Characteristics of thick-film CO2 sensors based on NASICON with Na2CO3-CaCO3 auxiliary phases

Potentiometric CO₂ sensors were fabricated using a NASICON (Na_1+x Zr₂Si_xP_3−x O₁₂) thick film and auxiliary layers. The powder of a precursor of NASICON with high purity was synthesized using the sol-gel method. Using the NASICON paste, an electrolyte was prepared on the alumina substrate through screen printing and then sintered at 1000^∘C for 4 h. In the present study, as new auxiliary phases, a series of Na₂CO₃-CaCO₃ system was deposited on the Pt sensing electrode. The electromotive force (EMF) values were found to be linearly dependent on the logarithm of the CO₂ concentration in the range of 1000–10000 ppm. The device to which Na₂CO₃-CaCO₃ (1:2) was attached showed good sensing properties at low temperatures.     

Correlation between dielectric properties and sintering temperatures of polycrystalline CaCu/sub 3/Ti/sub 4/O/sub 12/

Dielectric properties of polycrystalline CaCu/sub 3/Ti/sub 4/O/sub 12/ (CCTO) pellets sintered in the temperature range 1000-1200/spl deg/C were evaluated with impedance spectroscopy at frequency range of 10/sup 2/ to 10/sup 7/ Hz from 90 K to 294 K. A correlation has been established between the pair values of low frequency limit dielectric constant and the total resistivity and the sintering temperature. For example, the sample sintered at 1100/spl deg/C demonstrates higher value of low frequency limit dielectric constant and lower value of total resistivity, while the sample sintered at 1000/spl deg/C demonstrates lower values of low frequency limit dielectric constant and higher value of total resistivity. This correlation has been successfully explained by relating with the difference in grain size and grain volume resistivities of these two polycrystalline CCTO samples. Further, it is suggested that donor doping of oxygen vacancies Vo' and Vo" may be the reason to cause the difference in the grain volume resistivities of these two samples.     

Thermoelectric properties of p-type Bi0.5Sb1.5Te3 compounds fabricated by spark plasma sintering

P-type thermoelectric Bi_0.5Sb_1.5Te₃ compounds were prepared by the spark plasma sintering method with temperature ranges of 300–420^∘C and powder sizes of ∼75 μm, 76–150 μm, 151–250 μm. As the sintering temperature increased, the electrical resistivity and thermal conductivity of the compound were greatly changed due to an increase in the relative density. The Seebeck coefficient and electrical resistivity were varied largely with decreasing the powder size. Subsequently, the compound sintered at 380^∘C with the powders of ∼75 μm showed the maximum figure-of-merit of 2.65 × 10⁻³K⁻¹ and the bending strength of 73 MPa.     

Influence of microstructure on oxide ionic conductivity in doped CeO2 electrolytes

Doped ceria (CeO₂) compounds are fluorite type oxides, which show oxide ionic conductivity higher than yttria stabilized zirconia, in oxidizing atmospheres. As a consequence of this, considerable interest has been shown in application of these materials for `low (500^∘–650^∘C)’ temperature operation of solid oxide fuel cells (SOFCs). In this study, some rare earth (eg. Gd, Sm, and Dy) doped CeO₂ nano-powders were synthesized via a carbonate co-precipitation method. Fluorite-type solid solution were able to be formed at low temperature, such as 400^∘C and dense sintered bodies were subsequently fabricated in the temperature ranging from 1000^∘ to 1450^∘C by conventional sintering (CS) method. To develop high quality solid electrolytes, the microstructure at the atomic level of these doped CeO₂ solid electrolytes were examined using transmission electron microscopy (TEM). The specimens obtained by CS had continuous and large micro-domains with a distorted pyrochlore structure or related structure, within each grain. We conclude that the conducting properties in these doped CeO₂ systems are strongly influenced by the micro-domain size in the grain. To minimize the micro-domain size, spark plasma sintering (SPS) was examined. SPS has not been used to fabricate dense sintered bodies of doped CeO₂ electrolytes, previously; carbon from the graphite dies penetrates the specimens and inhibits densification. To overcome this challenge, and to be able to produce dense sintered bodies of doped CeO₂ of a grain size that minimizes the microdomain growth, a combination of SPS and CS methods were examined. Using this combined method we report that we were able to produce fully dense specimens with improved conductivity. This is correlated with a reduction in the size of the micro-domains. Consequently we conclude that the control of micro-domain size within the grain structure is a key component in the successful design of electrolyte materials with improved conductivity.     

Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics

The effect of B₂O₃ and CuO on the sintering temperature and microwave dielectric properties of BaTi₄O₉ ceramics was investigated. The BaTi₄O₉ ceramics were able to be sintered at 975^∘C when B₂O₃ was added. This decrease in the sintering temperature of the BaTi₄O₉ ceramics upon the addition of B₂O₃ is attributed to the formation of BaB₂O₄ second phase whose melting temperature is around 900^∘C. The B₂O₃ added BaTi₄O₉ ceramics alone were not sintered below 975^∘C, but were sintered at 875^∘C when CuO was added. The formation of BaCu(B₂O₅) second phase could be responsible for the decrease in the sintering temperature of the CuO and B₂O₃ added BaTi₄O₉ ceramics. The BaTi₄O₉ ceramics containing 2.0 mol% B₂O₃ and 5.0 mol% CuO sintered at 900^∘C for 2 h have good microwave dielectric properties of ε_r = 36.3, Q× f = 30,500 GHz and τ_f = 28.1 ppm/^∘C     

Ni–Mn–Fe–Cr–O negative temperature coefficient thermistor compositions: Correlation between processing conditions and electrical characteristics

A study has been carried out to correlate the effect of sintering temperature on the microstructural, electrical and reliability aspects of Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ (x = 0 to 0.3 and y = 0 to 0.3) negative temperature coefficient thermistor compositions prepared by solid-state route. The calcined and sintered compositions were characterized by X-ray diffraction and Scanning Electron Microscopy. The existence of cubic spinel single-phase region was determined by sintering Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ samples in air at temperatures 1150 to 1250 °C. X-ray diffraction patterns of samples sintered above 1200 °C shows additional Bragg reflections of a rock salt structured NiO phase besides normal cubic spinel. A maximum B-value of 4044 K was obtained for Ni_0.75Mn_1.95Cr_0.25Fe_0.05O₄ composition at a sintering temperature 1250 °C/3 h. The reliability of the thermistor compositions were evaluated by performing accelerated ageing based on thermal cycling test. We found that chromium enhances the reliability of Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ (x = 0 to 0.3 and y = 0 to 0.3) based NTC thermistor compositions. A maximum reliability of +0.25% resistance drift was observed at sintering temperature 1200 °C for 0.25 mol% chromium content. Excellent reliability of Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ NTC thermistor compositions makes it ideal candidates for high-performance thermal sensor applications.     

The Effects of Lithium and Oxygen Contents Inducing Capacity Loss of the LiMn2O4 Obtained at High Synthetic Temperature

Well-crystallized LiMn₂O₄ has been synthesized at different calcination temperatures using the melt-impregnation method. The lattice constant of LiMn₂O₄ increased with increasing calcination temperatures. Li/LiMn₂O₄cells calcined at lower temperatures (700–800°C) showed excellent cycling performances at room temperature. However, those cells calcined at higher temperature (850–900°C) exhibited abrupt capacity loss in the early stage and very poor cycle retention rate (>65%) after 50 cycles. It was considered that poor cycle performance of the spinels obtained at high temperature resulted from the lithium sublimation and oxygen deficiency during synthetic process. We found that above two factors, lithium sublimation and oxygen deficiency, were the commonly important factors to induce capacity loss in the Li/LiMn₂O₄ system, especially obtained at high synthetic temperature.     

Influence of the processing rates and sintering temperatures on the dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

The stoichiometric CaCu₃Ti₄O₁₂ pellets were prepared by the solid state synthesis. X-ray diffraction data revealed the tenorite CuO and cuprite Cu₂O secondary phases on the unpolished CaCu₃Ti₄O₁₂ samples regardless of the heating rates. Also, the dielectric constant marked the highest for the CaCu₃Ti₄O₁₂ sample sintered at the lowest heating rate (1°C/min), which was explained by the increased grain conductivity due to the cation reactions. On the other hand, Cu₂O phase was found only on the unpolished CaCu₃Ti₄O₁₂ sample sintered over 1100°C and those are considered as the remains reduced from the CuO phase. The higher sintering temperature showed the increased dielectric constant and the loss tangent of the CaCu₃Ti₄O₁₂ samples, and this result could be interpreted by the impedance measurement data. The relationship between the processing condition and the dielectric properties was discussed in terms of the cation non-stoichiometry and the defect chemistry in CaCu₃Ti₄O₁₂.     

Microwave dielectric properties of B2O3-added Li2MgTiO4 ceramics for LTCC applications

Li₂MgTiO₄ (LMT) ceramics which are synthesized using a conventional solid-state reaction route. The LMT ceramic sintered at 1250°C for 4 h had good microwave dielectric properties. However, this sintering temperature is too high to meet the requirement of low-temperature co-fired ceramics (LTCC). In this study, the effects of B₂O₃ additives and sintering temperature on the microstructure and microwave dielectric properties of LMT ceramics were investigated. The B₂O₃ additive forms a liquid phase during sintering, which decreases the sintering temperature from 1250°C to 925°C. The LMT ceramic with 8 wt% B₂O₃ sintered at 925°C for 4 h was found to exhibit optimum microwave dielectric properties: dielectric constant 15.16, quality factor 64,164 GHz, and temperature coefficient of resonant frequency -28.07 ppm/°C. Moreover, co-firing of the LMT ceramic with 8 wt% B₂O₃ and 20 wt% Ag powder demonstrated good chemical compatibility. Therefore, the LMT ceramics with 8 wt% B₂O₃ sintered at 925°C for 4 h is suitable for LTCC applications.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

SrLnAlO4 (Ln=Nd and Sm) Microwave Dielectric Ceramics

SrLnAlO₄ (Ln=Nd and Sm) ceramics with K₂NiF₄ structure were prepared by a solid state reaction approach, and their microwave dielectric characteristics were evaluated together with the microstructures. The single phase dense SrNdAlO₄ and SrSmAlO₄ ceramics were obtained by sintering at 1450–1475°C and 1475–1500°C, respectively, and the good microwave dielectric characteristics were achieved: (1) = 17.8, Q · f = 25,700 GHz, _f = –9 ppm/°C for SrNdAlO₄; and (2) = 18.8, Q · f = 54,880 GHz, _f = 2 ppm/°C for SrSmAlO₄ dense ceramics. The Qf value significantly increased with increasing sintering temperature.     

Ni-Cu-Zn Ferrites for low temperature firing: II. Effects of powder morphology and Bi2O3 addition on microstructure and permeability

The morphology of Ni-Cu-Zn ferrite powders obtained by milling of a calcined raw materials mixture strongly effects the densification behavior during sintering at 900^∘C. In order to obtain dense samples sub-micron powders with enhanced reactivity are required. The addition of Bi₂O₃ as sintering additive is beneficial: the density of samples sintered at 900^∘C increases with the bismuth oxide concentration up to 0.75 wt.%. The process of liquid phase sintering was studied by dilatometry. The grain size of the sintered samples slightly increases for 0.25 wt.% Bi₂O₃ compared to bismuth-free samples, whereas for 0.3–0.5 wt.% Bi₂O₃ additions bimodal grain growth is observed with a significant fraction of very large grains. For > 0.5 wt.% Bi₂O₃ a homogeneous coarse-grained microstructure is obtained. The permeability increases for small bismuth oxide additions, but decreases for a Bi-oxide content of more than 0.5%. Maximum permeability of μ_i = 900 is observed for intermediate Bi₂O₃ concentrations. PACS codes: 75.50 Gg; 81.20 Ev; 81.40 Rs     

Structural, Thermal and Electrical Properties of Ce-Doped SrMnO3

The Sr_1-xCe_xMnO_1- system (0 x 0.5) was investigated with respect to its structural, thermal and electrical properties. Although un-doped SrMnO₃ has the perovskite structure above 1400°C, the structure is unstable at room temperature. However, partial substitution of Ce for Sr in SrMnO₃ stabilizes the perovskite structure down to room temperature. Single phase perovskite is obtained for 0.1 x 0.3 in Sr_1-xCe_xMnO_1-, and it remains stable even following heat treatment at 800°C for 100 h. The dependence of the electrical conductivity on temperature was measured from room temperature to 1000°C in air. Ce doping dramatically enhanced the electrical conductivity of SrMnO₃. Sr_0.7Ce_0.3MnO_1- exhibits a higher conductivity (290 S · cm^-1 at 1000°C) than that of La_0.8Sr_0.2MnO₃ (LSM, about 175 S · cm^-1) and remains n-type over the whole range of temperature examined. The thermal expansion coefficients in the system were nearly constant with values ranging between 1.24 × 10^-6 and 1.01 × 10^-6 cm/cm · K for temperatures of 50°C to 1000°C.     

High temperature electrical characterization of nano-crystalline BaTiO3 synthesized using Ba(NO3)2 and TiO2

The reaction of Ba(NO₃)₂ with TiO₂ was studied by thermogravimetric (TG) and differential scanning calorimetric (DSC) techniques up to 1000°C and in nitrogen atmosphere. It was found that the formation of BaTiO₃ takes place above 600°C. BaTiO₃ powder was prepared by calcination of Ba(NO₃)₂ and TiO₂ precursor mixture at 800°C for 8 h. X-ray diffraction analysis of the synthesized BaTiO₃ confirmed the formation of tetragonal phase. Average crystallite size was found to be 44 nm, For the electrical and morphological characterization pellets of the obtained powder were sintered at 1000 °C for 12 h. Scanning electron micrograph (SEM) exhibits spherical and rod shaped grains. The dielectric constant, dissipation factor, complex plane impedance and ac conductivity of the sintered pellet has been measured in the temperature range of 40–600°C and frequency range of 100 Hz–2 MHz. DC conductivity of the sample was obtained from the impedance data. The conductivities (both ac and dc) and relaxation time (τ) exhibit two regions of temperature dependence, namely region I, which represents (280–450°C) and region II, which governs (450-600°C). Conduction and relaxation in both the temperature regions are explained in terms of hopping of electrons and doubly ionized oxygen vacancies (V_O^??).