The Review of High Pressure Science and Technology

Reviews - High Pressure Synthesis and Physical Properties of Skutterudite Compounds -

High-Pressure Synthesis, Electrical and Magnetic Properties of New Skutterudite Phosphides with Heavy Lanthanide (Including Y), LnT₄P₁₂ (Ln = Heavy Lanthanide and Y; T = Fe, Ru and Os)

Ichimin SHIROTANI

2006 Volume 16 Issue 4 Pages 308-312
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.308

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New filled skutterudite phosphides with heavy lanthanide (including Y), LnT₄P₁₂ (Ln = heavy lanthanide and Y; T = Fe, Ru and Os) have systematically been prepared at high temperatures and high pressures. The new relationship between lattice constants and atomic numbers of lanthanides was obtained for filled skutterudite phosphides. Electrical and magnetic properties of the skutterudites with heavy lanthanide have been studied at low temperatures. The superconductivity, the paramagnetic behavior, ferromagnetic and antiferromagnetic transitions were found for the new filled skutterudites prepared at high pressure. Thus, these compounds are classified to four groups by their magnetic properties. The physical properties of new filled skutterudite phosphides with heavy lanthanide (including Y) are discussed.

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High-Pressure Synthesis of High Quality Filled Skutterudite PrFe₄Sb₁₂ and Its Anomalous Physical Properties

Kenya TANAKA, Hidekazu AOKI

2006 Volume 16 Issue 4 Pages 313-321
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.313

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For the filled skutterudite compounds, high-pressure synthesis is thought to be a powerful technique, because it is possible to synthesize compounds that could not been grown by the flux method under ambient pressure and to improve the filling factor of rare-earth ions. In this article, we report the details of high-pressure synthesis of the filled skutterudite PrFe₄Sb₁₂ and the brief result of its physical properties. As a result, we have succeeded in synthesizing high-quality crystals of PrFe₄Sb₁₂ with higher Pr-filling factor and obtaining information about the crystalline electric field of PrFe₄Sb₁₂.

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High Pressure Synthesis and Thermoelectric Properties of CoSb₃-based Filled Skutterudites

Hirotsugu TAKIZAWA

2006 Volume 16 Issue 4 Pages 322-328
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.322

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Filled skutterudites exhibit thermoelectric properties that comply with the concept of a "phonon-glass and electron-crystal (PGEC)". The optimal filled skutterudite for PGEC would have filler atoms that exhibit large thermal vibration amplitudes in the voids of the host skutterudite lattice. It is desirable that these loosely bound filler atoms give rise to strong phonon scattering without affecting the essential part of the band structure. In this report, the use of high-pressure technique for the synthesis of CoSb₃-based filled skutterudites is reviewed. By using the high-pressure technique, new filled skutterudites, M_xCo₄Sb₁₂ (M=Ge, Sn, and Pb), have been successfully synthesized without charge compensation of the host lattice. The structural aspect and the thermoelectric properties of M_xCo₄Sb₁₂ are discussed.

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High-Pressure Synthesis and Properties of New Filled Skutterudite Compounds Using a Kawai-Type Cell

Hiroshi FUKUOKA

2006 Volume 16 Issue 4 Pages 329-335
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.329

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In the present article, high-pressure and high-temperature synthesis of new skutterudite compounds using a Kawai-type cell was reported. The structure and usage of the Kawai-type cell were explained. The first filled skutterudite compounds containing Ge atoms in the host network have been prepared at 7 GPa and 800°C in the Ln-Rh-Sb-Ge system, where Ln = La, Ce, Pr, and Nd. Some characteristic features of the Skutterudite structure were discussed.

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Crystal Growth of Skutterudite Compounds under High Pressure

Chihiro SEKINE

2006 Volume 16 Issue 4 Pages 336-341
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.336

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In this article, the experimental technique of synthesizing skutterudite compounds using multi-anvil-type high-pressure apparatus is described in detail. We also present the experimental technique of in situ observation for crystallization of the compounds under high temperatures and high pressures using synchrotron radiation. Using the technique for in situ X-ray diffraction, we determined the crystallization condition of some binary skutterudite compounds and filled skutterudite compounds under high pressure.

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Wide Variety of Physical Properties in the Filled Skutterudites

Kazuyuki MATSUHIRA

2006 Volume 16 Issue 4 Pages 342-349
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.342

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The attractive physical properties of filled skutterudites are reviewed in terms of strongly correlated electrons system. Furthermore, our recent results on the filled skutteduite phosphides synthesized under high-pressure and high-temperature conditions are reported. Sm-based filled skutterudites SmT₄P₁₂ (transition metal T = Fe, Ru, Os) show the variety of physical properties. We discuss the change of the characteristic behavior in SmT₄P₁₂ by the replacement of transition metal. We reveal that the heavy rare earth based filled skutteduite TbRu₄P₁₂ shows a multiple antiferromagnetic ordering. The anomalous phase diagram is discussed.

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Pressure-Induced Superconductivity of the Filled Skutterudite

Atsushi MIYAKE, Katsuya SHIMIZU

2006 Volume 16 Issue 4 Pages 350-356
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.350

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We found the first example of pressure-induced superconductivity in the filled skutterudite PrRu₄P₁₂ above 12 GPa, which shows a metal-insulator transition at 63 K and ambient pressure. In this article, we introduce our technical developments of measurements and results under high pressure using a diamond-anvil cell, such as electrical resistivity, powder X-ray diffraction and ac-calorimetry in the filled skutterudite.

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Ultrasonic Study of the Filled Skutterudite Compounds under Hydrostatic Pressure

Yoshiki NAKANISHI, Peijie SUN, Takuya FUJINO, Mitsuter NAKAMURA, Masah ...

2006 Volume 16 Issue 4 Pages 357-364
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.357

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We have developed a clamped piston-cylinder high pressure cell and performed ultrasonic measurements on the filled skutterudite compounds under hydrostatic pressures. Technical details and recent advances in the researches were reviewed by showing one of the compounds SmRu₄P₁₂ which exhibits a metal-insulator transition at T_MI = 16.5 K and an additional transition at T_N = 14 K. A pronounced elastic softening toward the additional temperature was induced in the application of pressure. Present results demonstrated that ultrasonic measurements on the filled skutterudite compounds under hydrostatic pressure are a powerful method to explore and elucidate a phase transition associated with a multipolar ordering.

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Magnetization Measurements in PrOs₄Sb₁₂ under High Pressure and Very Low Temperature

Takashi TAYAMA

2006 Volume 16 Issue 4 Pages 365-373
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.365

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We present here a setup for the dc magnetization measurements at high pressures and low temperatures using a Faraday-type capacitive magnetometer with a miniature BeCu piston-cylinder pressure cell, which allows us to pressurize sample up to 1.5 GPa at low temperatures. The magnetic force is measured capacitively by monitoring the displacement of parallel plate capacitor. The magnetometer can be used at temperatures down to 0.06 K and in high magnetic fields up to 15 T. The magnetometer with the pressure cell has a good sensitivity for magnetic moments of 10^-4emu. Its application to the filled skutterudite superconductor PrOs₄Sb₁₂ is presented.

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Articles

High Negative Pressures in Acetone Measured by the Berthelot Method Using Strain Gauge Pressure Transducer

Kazuki HIRO, Yoshihito OHDE, Tadahiro WADA

2006 Volume 16 Issue 4 Pages 374-378
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.374

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Liquids under negative pressures are in meta-stable and stretched states thermodynamically. So, the states transformed easily to coexisting states with vapors through heterogeneous nucleation processes. Therefore, it has been difficult even now to generate static negative pressures to measure liquids' properties under the pressures. In this paper, negative pressures were measured by the Berthelot method using a strain gauge pressure transducer. A sample liquid was acetone. Negative pressures increased with temperature cycles through two stages and attained a maximum value of ca.-20 MPa for acetone of ca.0.06 cm³.

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One Point of Experiment

New Method for Precise Measurement of Density of Supercritical Fluid over a Wide Range of Pressure

Ken YOSHIDA, Nobuyuki MATUBAYASI, Masaru NAKAHARA

2006 Volume 16 Issue 4 Pages 379-380
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.379

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We have developed two methods to determine the density of supercritical fluid sealed in a tube. One is the mass-volume method that is applicable to higher densities than 0.07 g cm^-3 at 400°C when the fluid is water. In this method, the mass of the sample and the bore volume of the tube are determined precisely. The other is the chemical shift method, which takes advantage of the temperature dependence of the chemical shift and the PVT data. The latter is especially powerful at lower densities.

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Notes

A New Hydrostatic Pressure Apparatus for the Study of Zooplankton throughout Its Life History

Akio SHIMIZU, Tomoko YOSHIKI, Tatuki TODA

2006 Volume 16 Issue 4 Pages 381-383
Published: 2006
Released on J-STAGE: January 15, 2007

DOIhttps://doi.org/10.4131/jshpreview.16.381

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A hydrostatic pressure apparatus for the study of zooplankton throughout its life history from egg to adult was developed. The feature of this apparatus is as follows. (1) Pressure increases gradually. (2) A maximum of nine zooplanktons or their eggs can be observed independently at once. (3) This apparatus is small and easy to carry. The influence of pressure on the egg-hatching of Calanus sinicus was investigated using this system. The egg-hatching success decreased significantly with increasing pressure. Eggs would not survive if they did not hatch with the depth of water of 100 m or less.

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