[신간의 별자리x] 우리/미술, 그리고 ‘슬픔의 박물관’

Fast Lithium Ion Conduction in Garnet‐Type Li7La3Zr2O12

Electroceramics are advanced materials whose properties and applications depend on the close control of structure, composition, ceramic texture, dopants and dopant (or defect) distribution. Impedance spectroscopy is a powerful technique for unravelling the complexities of such materials, which functions by utilizing the different frequency dependences of the constituent components for their separation. Thus, electrical inhomogeneities in ceramic electrolytes, electrode/electrolyte interfaces, surface layers on glasses, ferroelectricity, positive temperature coefficient of resistance behavior and even ferrimagnetism can all be probed, successfully, using this technique.

Electroceramics: Characterization by Impedance Spectroscopy

The use of electric current to activate the consolidation and reaction-sintering of materials is reviewed with special emphasis of the spark plasma sintering method. The method has been used extensively over the past decade with results showing clear benefits over conventional methods. The review critically examines the important features of this method and their individual roles in the observed enhancement of the consolidation process and the properties of the resulting materials.

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1000 at 1000: The effect of electric field and pressure on the synthesis and consolidation of materials: a review of the spark plasma sintering method.

There has been much recent interest in a so-called “giant-dielectric phenomenon” displayed by an unusual cubic perovskite-type material, CaCu3Ti4O12; however, the origin of the high permittivity has been unclear [M. A. Subramanian, L. Dong, N. Duan, B. A. Reisner, and A. W. Sleight, J. Solid State Chem. 151, 323 (2000); C. C. Homes, T. Vogt, S. M. Shapiro, S. Wakimoto, and A. P. Ramirez, Science 293, 673 (2001); A. P. Ramirez, M. A. Subramanian, M. Gardel, G. Blumberg, D. Li, T. Vogt, and S. M. Shapiro, Solid State Commun. 115, 217 (2000)]. Impedance spectroscopy on CaCu3Ti4O12 ceramics demonstrates that they are electrically heterogeneous and consist of semiconducting grains with insulating grain boundaries. The giant-dielectric phenomenon is therefore attributed to a grain boundary (internal) barrier layer capacitance (IBLC) instead of an intrinsic property associated with the crystal structure. This barrier layer electrical microstructure with effective permittivity values in excess of 10 000 can be fa...

CaCu3Ti4O12: One-step internal barrier layer capacitor

Polycrystalline barium titanate that has been doped to give a positive temperature coefficient of resistance (PTCR) effect is an inhomogeneous material electrically. Analysis of ac impedance data using the complex impedance plane representation gives the dc resistance of PTCR ceramics. By additional use of the complex electric modulus formalism to analyze the same data, the inhomogeneous nature of the ceramics may be probed. This reveals the presence of two, sometimes three elements in the equivalent circuit. Grain‐boundary and bulk effects may be distinguished from capacitance data: grain‐boundary effects have temperature‐independent capacitances, whereas bulk effects show a capacitance maximum at the Curie point and Curie–Weiss behavior above the Curie point. Both grain‐boundary and bulk effects appear to contribute to the PTCR effect. These results reveal limitations in current theories of the PTCR effect.

Impedance and modulus spectroscopy of semiconducting BaTiO3 showing positive temperature coefficient of resistance

Giant Barrier Layer Capacitance Effects in CaCu3Ti4O12 Ceramics

Oxide ion conductors find important technical applications in electrochemical devices such as solid-oxide fuel cells (SOFCs), oxygen separation membranes and sensors. Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material; however, it is often reported to possess high leakage conductivity that is problematic for its piezo- and ferroelectric applications. Here we report this high leakage to be oxide ion conduction due to Bi-deficiency and oxygen vacancies induced during materials processing. Mg-doping on the Ti-site increases the ionic conductivity to ~0.01 S cm(-1) at 600 °C, improves the electrolyte stability in reducing atmospheres and lowers the sintering temperature. This study not only demonstrates how to adjust the nominal NBT composition for dielectric-based applications, but also, more importantly, gives NBT-based materials an unexpected role as a completely new family of oxide ion conductors with potential applications in intermediate-temperature SOFCs and opens up a new direction to design oxide ion conductors in perovskite oxides.

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Derek C. Sinclair

Papers

Electroceramics: Characterization by Impedance Spectroscopy

CaCu3Ti4O12: One-step internal barrier layer capacitor

Impedance and modulus spectroscopy of semiconducting BaTiO3 showing positive temperature coefficient of resistance

Giant Barrier Layer Capacitance Effects in CaCu3Ti4O12 Ceramics

A family of oxide ion conductors based on the ferroelectric perovskite Na0.5Bi0.5TiO3