高圧力の科学と技術

スクッテルダイト化合物の高圧合成と物性

新重希土類スクッテルダイトリン化物, LnT₄P₁₂(Ln = heavy lanthanide, Y; T = Fe, Ru, Os) の高圧合成と電気的, 磁気的性質

城谷一民

2006 年 16 巻 4 号 p. 308-312
発行日: 2006年
公開日: 2007/01/15

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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高圧合成によるPrFe₄Sb₁₂の純良結晶作成とその特異な物性

田中謙弥, 青木英和

2006 年 16 巻 4 号 p. 313-321
発行日: 2006年
公開日: 2007/01/15

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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CoSb₃を母体とした充填スクッテルダイト化合物の高圧合成と熱電特性

滝沢博胤

2006 年 16 巻 4 号 p. 322-328
発行日: 2006年
公開日: 2007/01/15

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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川井式高圧装置を用いたスクッテルダイト化合物の高圧合成と物性

福岡宏

2006 年 16 巻 4 号 p. 329-335
発行日: 2006年
公開日: 2007/01/15

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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スクッテルダイト化合物の高圧下における結晶成長

関根ちひろ

2006 年 16 巻 4 号 p. 336-341
発行日: 2006年
公開日: 2007/01/15

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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充填スクッテルダイト化合物の多彩な物性

松平和之

2006 年 16 巻 4 号 p. 342-349
発行日: 2006年
公開日: 2007/01/15

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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充填スクッテルダイト化合物の圧力誘起超伝導

三宅厚志, 清水克哉

2006 年 16 巻 4 号 p. 350-356
発行日: 2006年
公開日: 2007/01/15

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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充填スクッテルダイト化合物の高圧下超音波測定

中西良樹, 孫培傑, 藤野拓也, 中村光輝, 吉澤正人

2006 年 16 巻 4 号 p. 357-364
発行日: 2006年
公開日: 2007/01/15

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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高圧下極低温におけるPrOs₄Sb₁₂の磁化測定

田山孝

2006 年 16 巻 4 号 p. 365-373
発行日: 2006年
公開日: 2007/01/15

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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論文

ひずみゲージ式圧力変換器ベルセロ法により測定されたアセトンの負の高圧力

廣和樹, 大出義仁, 和田任弘

2006 年 16 巻 4 号 p. 374-378
発行日: 2006年
公開日: 2007/01/15

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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実験ワンポイント

広い密度・圧力領域における超臨界流体に対する精密密度測定の新しい方法

吉田健, 松林伸幸, 中原勝

2006 年 16 巻 4 号 p. 379-380
発行日: 2006年
公開日: 2007/01/15

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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ノート

動物プランクトンおよび卵の孵化に対する圧力の影響測定用高圧システム

清水昭夫, 吉木朝子, 戸田龍樹

2006 年 16 巻 4 号 p. 381-383
発行日: 2006年
公開日: 2007/01/15

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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