WO2010101153A1 - A-site ordered perovskite-type oxide - Google Patents

A-site ordered perovskite-type oxide Download PDF

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WO2010101153A1
WO2010101153A1 PCT/JP2010/053350 JP2010053350W WO2010101153A1 WO 2010101153 A1 WO2010101153 A1 WO 2010101153A1 JP 2010053350 W JP2010053350 W JP 2010053350W WO 2010101153 A1 WO2010101153 A1 WO 2010101153A1
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oxide
perovskite oxide
perovskite
site
present
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Japanese (ja)
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有文 龍
島川　祐一
直顕 林
高志 齊藤
東　正樹
重利 村中
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国立大学法人京都大学
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Definitions

  • the present invention relates to a novel A-site ordered perovskite oxide.
  • Optical parts, precision parts, composite / stacked parts, etc. that constitute various devices are required not to thermally expand during use.
  • Patent Document 1 discloses La 0.95 Sr 0.05 Fe 0.80 Co 0.20 O 3 , LaFe 0.75 Co as a raw material powder constituting an air electrode of a solid oxide fuel cell (SOFC).
  • SOFC solid oxide fuel cell
  • Perovskite oxides such as 0.20 Ni 0.05 O 3 have been reported ([Table 1] in Patent Document 1).
  • Patent Document 2 reports a lanthanum chromite oxide such as La 0.8 Sr 0.2 CrO 3 as a bonding material used for electrically bonding SOFC structural members to each other (Patent Document 2). 2 [Table 2] etc.).
  • Patent Document 3 reports a lead zirconate titanate (PZT) piezoelectric film doped with Nb as a piezoelectric body having a ferroelectric layer (Example 1 of Patent Document 3).
  • PZT lead zirconate titanate
  • Patent Documents 1 to 3 are suppressed in thermal expansion to some extent, in consideration of the recent increase in density and capacity of optical components and the like, further thermal expansion is possible. Prevention or suppression is required.
  • the main object of the present invention is to provide a metal oxide material whose volume decreases in a practical temperature range.
  • the present invention relates to the following perovskite oxide and a method for producing the same.
  • General formula (1) A'A 3 B 4 O 12 (1) (In the formula, A ′ and A are elements occupying the A site of the perovskite oxide, and A ′ is La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Pb, Na and K represent at least one metal element selected from the group consisting of Cu, Mn, Fe and Ni, and A represents at least one transition selected from the group consisting of Cu, Mn, Fe and Ni Represents a metal element, and B is an element occupying the B site of the perovskite oxide, and is selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Co, Ni, Ge, Sn, Zr, and Ru Indicates at least one transition metal element.) Perovskite oxide represented by 2.
  • a ′ represents at least one metal element selected from the group consisting of La, Bi and Y, A represents at least one transition metal element of Cu and Mn, and B represents Fe.
  • the perovskite oxide according to item 1. 3.
  • Item 3 The perovskite oxide according to Item 1 or 2 used as a thermal expansion buffer material. 4).
  • 3. The perovskite oxide according to item 1 or 2, wherein a mixture of the oxide of A ′, the oxide of A and the oxide of B is heat-treated under conditions of a pressure of 6 GPa or more and a temperature of 800 ° C. or more. Manufacturing method.
  • the perovskite oxide of the present invention has a structure in which 1/4 of the A site of the perovskite structure is occupied by the metal element A ′ and 3/4 of the transition metal element A is occupied.
  • This is an oxide in which the sites are ordered (A-site ordered perovskite oxide).
  • the perovskite oxide of the present invention since the A site is ordered in this manner, in a practical temperature range (about 25 to 450 ° C. (298 to 723 K)) such as a temperature during use of various devices. Volume decreases. That is, the perovskite oxide of the present invention undergoes thermal shrinkage (negative thermal expansion occurs) in the temperature range. For example, in the case of a perovskite oxide (LaCu 3 Fe 4 O 12 ) in which A ′ is La, A is Cu, and B is Fe in the general formula (1), as shown in FIG. ) Volume decreases dramatically in the vicinity.
  • a magnetic transition and an insulator-metal transition occur in the temperature range. This is because charge transfer occurs between the A site and the B site in the temperature range.
  • the temperature of the LaCu 3 Fe 4 O 12 is increased, the LaCu 3 Fe 4 O 12 changes from antiferromagnetic to paramagnetic at around 120 ° C. (393 K) as shown in FIG.
  • the transition from the insulator to the metal occurs around the same temperature. Therefore, the perovskite oxide of the present invention can suitably control the increase / decrease in volume by an external magnetic field or current.
  • the perovskite oxide of the present invention can be used as a constituent material for parts for various devices to produce parts or the like in which thermal expansion is prevented or suppressed.
  • the conventional metal oxide material undergoes anisotropic volume fluctuation
  • the perovskite oxide of the present invention undergoes isotropic volume fluctuation (said thermal shrinkage). Therefore, the parts made of the perovskite oxide of the present invention can be position-controlled with high accuracy on various devices.
  • the perovskite oxide of the present invention has the general formula (1) A'A 3 B 4 O 12 (1) (In the formula, A ′ and A are elements occupying the A site of the perovskite oxide, and A ′ is La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Pb, Na and K represent at least one metal element selected from the group consisting of Cu, Mn, Fe and Ni, and A represents at least one transition selected from the group consisting of Cu, Mn, Fe and Ni Represents a metal element, and B is an element occupying the B site of the perovskite oxide, and is selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Co, Ni, Ge, Sn, Zr, and Ru Indicates at least one transition metal element.) It is represented by
  • At least one metal element selected from the group consisting of La, Bi and Y is particularly preferable, and La is more preferable.
  • A is particularly preferably at least one transition metal element of Cu and Mn, and more preferably Cu.
  • B is particularly preferably Fe.
  • LaCu 3 Fe 4 O 12 , BiCu 3 Fe 4 O 12 and (La, Ca) Cu 3 Fe 4 O 12 are particularly preferable, and LaCu 3 Fe 4 O 12 is more preferable.
  • the shape, size, and the like of the perovskite oxide of the present invention are not particularly limited, and may be set as appropriate according to the target component, but are preferably in the form of particles from the standpoint of ease of processing of the component.
  • the average particle size is preferably about 1 to 1000 ⁇ m.
  • a known method may be adopted as a method for measuring the average particle diameter. For example, transmission electron microscopy may be used.
  • the crystal structure of the perovskite oxide of the present invention can be confirmed by, for example, X-ray diffraction method, Mossbauer spectroscopy or the like.
  • each constituent element is in a special ionic state.
  • the special ionic state of Cu 3+ in the A site occurs at room temperature.
  • Fe 3+ at the B site becomes Fe 3.75+ ions in a highly oxidized state called an abnormally high valence, and at the same time Cu 3+ at the A site becomes Cu 2+. Changes to ions.
  • the antiferromagnetic state at room temperature changes to paramagnetic from a temperature above 393 K (120 ° C.) as the ionic state changes. Moreover, what is in an insulator state at room temperature changes to a metal state in which current flows at a temperature above 393 K (120 ° C.).
  • the perovskite oxide of the present invention can be used as a material for parts constituting various devices.
  • the perovskite oxide of the present invention has no problem of thermal expansion during use, highly integrated and high power electronics components (for example, integrated circuits), precision optical components (for example, mirrors, lenses, etc.), It can be suitably used as a constituent material for precision machine parts (for example, machine tool parts).
  • precision machine parts for example, machine tool parts.
  • it can be suitably used as a material for a pickup device such as a DVD that requires submicron size position control.
  • the perovskite type oxide and a material exhibiting a thermal expansion action are mixed and sintered, so that the volume change with temperature is substantially zero.
  • the perovskite oxide of the present invention can also be used as a thermal expansion buffer material. What is necessary is just to adjust suitably the mixture ratio of the said perovskite type oxide and the said material according to the thermal expansion coefficient etc. of this material. Further, the perovskite oxides may be used alone or in combination of two or more.
  • the thermal expansion coefficient of various components can be adjusted with high accuracy. For example, there is a problem that a composite / stack component used in a high temperature and temperature history environment is peeled off between members due to a difference in thermal expansion coefficient of each member. According to the perovskite oxide of the present invention, since the coefficient of thermal expansion of various components can be adjusted with high accuracy, the above problem can be suitably avoided. Therefore, the perovskite oxide of the present invention is also useful as a material in, for example, a fuel cell stack member, an electronic substrate and the like.
  • the perovskite oxide of the present invention is, for example, mixed with an A ′ oxide, an A oxide and a B oxide, and then heat-treated (fired) under high temperature and high pressure. Can be manufactured.
  • the mixing ratio of the oxide of A ′, the oxide of A, and the oxide of B is not particularly limited, and a perovskite oxide represented by the general formula (1) (A′A 3 B 4 O 12 ) is obtained. What is necessary is just to set suitably.
  • the perovskite oxide of the present invention is used by using La 2 O 3 , CuO and Fe 2 O 3 in a molar ratio of 1: 6: 4. An oxide is suitably obtained.
  • the heat treatment can be performed according to a known method. For example, after filling a platinum capsule with a mixture of an oxide of A ′, an oxide of A and an oxide of B, the obtained capsule is pressurized and heated using a known apparatus.
  • known devices include a cubic anvil type high pressure generator.
  • the pressure when heat-treating the mixture of A ′ oxide, A oxide and B oxide is preferably about 6 GPa or more, more preferably about 10 to 15 GPa.
  • the heat treatment temperature is preferably about 800 ° C. or higher, and more preferably about 1000 to 1200 ° C.
  • the perovskite oxide of the present invention is suitably obtained by performing the heat treatment at a pressure of about 10 GPa or more and a temperature of 1000 ° C. or more.
  • the heat treatment time may be appropriately adjusted according to the heat treatment conditions such as the heat treatment temperature so that the raw materials sufficiently react, but is usually about 30 minutes to 2 hours.
  • the mixture Prior to the heat treatment, the mixture may contain known additives.
  • known additives include oxidizing agents such as KClO 4 .
  • the perovskite type oxide of the present invention is thermally contracted in a practical temperature range (about 25 to 450 ° C. (about 298 to 723 K)) such as the temperature when using various devices because the A site is ordered. To do.
  • the perovskite oxide of the present invention can be suitably controlled in volume increase / decrease by an external magnetic field or current.
  • the volume change occurs isotropically.
  • the perovskite oxide of the present invention exhibiting such characteristics can be suitably used as a constituent material for highly integrated / high output electronics parts, precision optical parts, precision machine parts and the like.
  • the perovskite oxide of the present invention as a thermal expansion buffer material, it is possible to manufacture highly integrated and high output electronic components that have substantially no volume change due to temperature.
  • FIG. 1 shows a crystal structure (cubic crystal structure, space group: Im-3) of an A-site ordered perovskite oxide.
  • FIG. 2 shows a change in volume of the perovskite oxide obtained in Example 1 due to heat.
  • FIG. 3 is a graph showing the magnetic transition and insulator-metal transition of the perovskite oxide obtained in Example 1 due to heat.
  • FIG. 4 is a schematic diagram of the cubic anvil type high-pressure generator used in Examples 1 and 2.
  • FIG. 5 shows the X-ray diffraction spectrum of LaCu 3 Fe 4 O 12 obtained in Example 1.
  • 6 shows the X-ray diffraction spectrum of BiCu 3 Fe 4 O 12 obtained in Example 2.
  • Example 1 A perovskite oxide of LaCu 3 Fe 4 O 12 was produced.
  • the obtained capsules were heated for about 1 hour under conditions of a pressure of 10 GPa and a temperature of 1400 K using a cubic anvil type high pressure generator as shown in FIG.
  • the perovskite oxide of LaCu 3 Fe 4 O 12 was obtained by the above method.
  • Example 2 A perovskite oxide of BiCu 3 Fe 4 O 12 was produced.
  • the obtained capsules were heated for about 1 hour under conditions of a pressure of 10 GPa and a temperature of 1300 K using a cubic anvil type high pressure generator as shown in FIG.
  • Test example 1 The volume change rate due to heat of the perovskite oxide obtained in Example 1 and Example 2 was confirmed.
  • FIG. 2 shows the volume change of the perovskite oxide obtained in Example 1 due to heat.
  • the volume change rate of the perovskite oxide of Example 1 when the heating temperature was 393 K was determined by the following formula. ⁇ (Volume when the heating temperature is 423K ⁇ Volume when the heating temperature is 373K) / Volume when the heating temperature is 373K ⁇ ⁇ 100 (%)
  • the volume change rate of the perovskite oxide of Example 2 when the heating temperature was 450 K was obtained by the following formula. ⁇ (Volume when the heating temperature is 473K ⁇ Volume when the heating temperature is 423K) / Volume when the heating temperature is 423K ⁇ ⁇ 100 (%) The results are shown in Table 1.
  • Test example 2 The perovskite oxide obtained in Example 1 was confirmed to have a magnetic transition due to heat and an insulator-metal transition.
  • the magnetic transition was confirmed using a magnetometer (“MPMS” manufactured by Quantum Design).
  • MPMS magnetometer
  • PPMS physical property measuring apparatus manufactured by Quantum Design Co., Ltd.
  • FIG. 3 shows a graph showing the magnetic transition and the insulator-metal transition of the perovskite oxide obtained in Example 1 due to heat.
  • the perovskite oxide of Example 1 undergoes a magnetic transition from antiferromagnetism to paramagnetism at the temperature at which the volume decreased in Test Example 1 above, and further from the insulator. It can be seen that the transition to metal occurs. From these results, it can be seen that the perovskite oxide of the present invention can control the increase or decrease in volume by an external magnetic field or current.

Abstract

Disclosed is a metal oxide material of which the volume is decreased in a practically effective temperature range. Specifically disclosed is a perovskite-type oxide represented by general formula (1). A'A3B4O12 (1) (In the formula, A' and A are elements occupying the A-site in a perovskite-type oxide, wherein A' represents at least one metal element selected from a group consisting of La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Pb, Na and K, and A represents at least one transition metal element selected from a group consisting of Cu, Mn, Fe and Ni; and B is an element occupying the B-site in a perovskite-type oxide and represents at least one transition metal element selected from a group consisting of Fe, Ti, V, Cr, Cu, Mn, Co, Ni, Ge, Sn, Zr and Ru.)

Description

Ａサイト秩序型ペロブスカイト酸化物A-site ordered perovskite oxide
　本発明は、新規Ａサイト秩序型ペロブスカイト酸化物に関する。 The present invention relates to a novel A-site ordered perovskite oxide.
　各種デバイスを構成する光学部品、精密部品、複合・スタック部品等は、使用時において熱膨張しないことが求められている。 Optical parts, precision parts, composite / stacked parts, etc. that constitute various devices are required not to thermally expand during use.
　そのため、前記構成部材の材料として、従来より、熱膨張が抑制された金属酸化物材料が注目されている。特に、近年における光学部品等の高密度大容量化に伴い、熱膨張がより一層抑制された金属酸化物材料が求められている。 Therefore, conventionally, a metal oxide material in which thermal expansion is suppressed has attracted attention as a material of the constituent member. In particular, with the recent increase in density and capacity of optical components and the like, there has been a demand for metal oxide materials in which thermal expansion is further suppressed.
　例えば、特許文献１には、固体電解質型燃料電池（ＳＯＦＣ）の空気極を構成する原料粉末として、Ｌａ０．９５Ｓｒ０．０５Ｆｅ０．８０Ｃｏ０．２０Ｏ３、ＬａＦｅ０．７５Ｃｏ０．２０Ｎｉ０．０５Ｏ３等のペロブスカイト型酸化物が報告されている（特許文献１の［表１］等）。 For example, Patent Document 1 discloses La 0.95 Sr 0.05 Fe 0.80 Co 0.20 O 3 , LaFe 0.75 Co as a raw material powder constituting an air electrode of a solid oxide fuel cell (SOFC). Perovskite oxides such as 0.20 Ni 0.05 O 3 have been reported ([Table 1] in Patent Document 1).
　特許文献２には、ＳＯＦＣの構造部材同士を電気的に接合する場合に用いられる接合材料として、Ｌａ０．８Ｓｒ０．２ＣｒＯ３等のランタンクロマイト系酸化物が報告されている（特許文献２の［表２］等）。 Patent Document 2 reports a lanthanum chromite oxide such as La 0.8 Sr 0.2 CrO 3 as a bonding material used for electrically bonding SOFC structural members to each other (Patent Document 2). 2 [Table 2] etc.).
　特許文献３には、強誘電体層を有する圧電体として、Ｎｂがドープされたチタン酸ジルコン酸鉛（ＰＺＴ）圧電体膜が報告されている（特許文献３の実施例１等）。 Patent Document 3 reports a lead zirconate titanate (PZT) piezoelectric film doped with Nb as a piezoelectric body having a ferroelectric layer (Example 1 of Patent Document 3).
　しかしながら、特許文献１～３において具体的に報告されている金属酸化物材料は、熱膨張がある程度抑制されているものの、近年における光学部品等の高密度大容量化を考慮した場合、さらなる熱膨張の防止又は抑制が求められる。 However, although the metal oxide materials specifically reported in Patent Documents 1 to 3 are suppressed in thermal expansion to some extent, in consideration of the recent increase in density and capacity of optical components and the like, further thermal expansion is possible. Prevention or suppression is required.
特開２００８－３０５６６９号公報JP 2008-305669 A 特開２００８－２０７１８８号公報JP 2008-207188 A 特開２００８－３０６１６４号公報JP 2008-306164 A
　本発明は、実用的な温度領域で体積が減少する金属酸化物材料を提供することを主な目的とする。 The main object of the present invention is to provide a metal oxide material whose volume decreases in a practical temperature range.
　本発明者は、鋭意研究を重ねた結果、特定のペロブスカイト型酸化物が上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of extensive research, the present inventor has found that a specific perovskite oxide can achieve the above object, and has completed the present invention.
　即ち、本発明は、下記のペロブスカイト型酸化物及びその製造方法に係る。
１．　一般式（１）
Ａ’Ａ３Ｂ４Ｏ１２　　　（１）
（式中、Ａ’及びＡはペロブスカイト型酸化物のＡサイトを占める元素であって、Ａ’はＬａ、Ｂｉ、Ｙ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、Ｎａ及びＫからなる群から選ばれる少なくとも一種の金属元素を示し、ＡはＣｕ、Ｍｎ、Ｆｅ及びＮｉからなる群から選ばれる少なくとも一種の遷移金属元素を示し、Ｂはペロブスカイト型酸化物のＢサイトを占める元素であって、Ｆｅ、Ｔｉ、Ｖ、Ｃｒ、Ｃｕ、Ｍｎ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｎ、Ｚｒ及びＲｕからなる群から選ばれる少なくとも一種の遷移金属元素を示す。）
で表されるペロブスカイト型酸化物。
２．　一般式（１）中、Ａ’はＬａ、Ｂｉ及びＹからなる群から選ばれる少なくとも一種の金属元素を示し、ＡはＣｕ及びＭｎの少なくとも一種の遷移金属元素を示し、ＢはＦｅを示す、上記項１に記載のペロブスカイト型酸化物。
３．　熱膨張緩衝材として用いる上記項１又は２に記載のペロブスカイト型酸化物。
４．　Ａ’の酸化物、Ａの酸化物及びＢの酸化物の混合物を、圧力６ＧＰａ以上及び温度８００℃以上の条件下で熱処理することを特徴とする上記項１又は２に記載のペロブスカイト型酸化物の製造方法。 That is, the present invention relates to the following perovskite oxide and a method for producing the same.
1. General formula (1)
A'A 3 B 4 O 12 (1)
(In the formula, A ′ and A are elements occupying the A site of the perovskite oxide, and A ′ is La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Pb, Na and K represent at least one metal element selected from the group consisting of Cu, Mn, Fe and Ni, and A represents at least one transition selected from the group consisting of Cu, Mn, Fe and Ni Represents a metal element, and B is an element occupying the B site of the perovskite oxide, and is selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Co, Ni, Ge, Sn, Zr, and Ru Indicates at least one transition metal element.)
Perovskite oxide represented by
2. In general formula (1), A ′ represents at least one metal element selected from the group consisting of La, Bi and Y, A represents at least one transition metal element of Cu and Mn, and B represents Fe. 2. The perovskite oxide according to item 1.
3. Item 3. The perovskite oxide according to Item 1 or 2 used as a thermal expansion buffer material.
4). 3. The perovskite oxide according to item 1 or 2, wherein a mixture of the oxide of A ′, the oxide of A and the oxide of B is heat-treated under conditions of a pressure of 6 GPa or more and a temperature of 800 ° C. or more. Manufacturing method.
　本発明のペロブスカイト型酸化物は、図１に示すように、ペロブスカイト構造のＡサイトの１／４を上記金属元素Ａ’が占有し、３／４を上記遷移金属元素Ａが占有することによりＡサイトが秩序化された酸化物（Ａサイト秩序型ペロブスカイト酸化物）である。 As shown in FIG. 1, the perovskite oxide of the present invention has a structure in which 1/4 of the A site of the perovskite structure is occupied by the metal element A ′ and 3/4 of the transition metal element A is occupied. This is an oxide in which the sites are ordered (A-site ordered perovskite oxide).
　本発明のペロブスカイト型酸化物は、このようにＡサイトが秩序化されていることにより、各種デバイスの使用時の温度等の実用的な温度領域（２５～４５０℃（２９８～７２３Ｋ）程度）において体積が減少する。すなわち、本発明のペロブスカイト型酸化物は、前記温度領域で熱収縮する（負の熱膨張が起こる）。例えば、一般式（１）中の上記Ａ’がＬａ、ＡがＣｕ、ＢがＦｅであるペロブスカイト型酸化物（ＬａＣｕ３Ｆｅ４Ｏ１２）の場合、図２に示すように、１２０℃（３９３Ｋ）付近で体積が劇的に減少する。 In the perovskite oxide of the present invention, since the A site is ordered in this manner, in a practical temperature range (about 25 to 450 ° C. (298 to 723 K)) such as a temperature during use of various devices. Volume decreases. That is, the perovskite oxide of the present invention undergoes thermal shrinkage (negative thermal expansion occurs) in the temperature range. For example, in the case of a perovskite oxide (LaCu 3 Fe 4 O 12 ) in which A ′ is La, A is Cu, and B is Fe in the general formula (1), as shown in FIG. ) Volume decreases dramatically in the vicinity.
　また、本発明のペロブスカイト型酸化物は、前記温度領域において、磁気転移及び絶縁体－金属転移が起こる。これは、前記温度領域においてＡサイト－Ｂサイト間で電荷移動が起こるためである。例えば、前記ＬａＣｕ３Ｆｅ４Ｏ１２の温度を上昇させた場合、図３に示すように、１２０℃（３９３Ｋ）付近で、前記ＬａＣｕ３Ｆｅ４Ｏ１２は反強磁性から常磁性へと転移し、さらに、同温度付近で、絶縁体から金属へと転移する。従って、本発明のペロブスカイト型酸化物は、外部磁場や電流によって体積の増減を好適に制御できる。 In the perovskite oxide of the present invention, a magnetic transition and an insulator-metal transition occur in the temperature range. This is because charge transfer occurs between the A site and the B site in the temperature range. For example, when the temperature of the LaCu 3 Fe 4 O 12 is increased, the LaCu 3 Fe 4 O 12 changes from antiferromagnetic to paramagnetic at around 120 ° C. (393 K) as shown in FIG. Furthermore, the transition from the insulator to the metal occurs around the same temperature. Therefore, the perovskite oxide of the present invention can suitably control the increase / decrease in volume by an external magnetic field or current.
　本発明のペロブスカイト型酸化物は、各種デバイス用の部品等の構成材料として用いることにより、熱膨張が防止又は抑制された部品等を製造できる。 The perovskite oxide of the present invention can be used as a constituent material for parts for various devices to produce parts or the like in which thermal expansion is prevented or suppressed.
　しかも、従来の金属酸化物材料は、体積の変動が異方的に起こるのに対し、本発明のペロブスカイト型酸化物は、体積の変動（前記熱収縮）が等方的に起こる。そのため、本発明のペロブスカイト型酸化物を材料とした部品は、各種デバイス上で高精度での位置制御が可能になる。 In addition, the conventional metal oxide material undergoes anisotropic volume fluctuation, whereas the perovskite oxide of the present invention undergoes isotropic volume fluctuation (said thermal shrinkage). Therefore, the parts made of the perovskite oxide of the present invention can be position-controlled with high accuracy on various devices.
　Ａサイト秩序型ペロブスカイト酸化物
本発明のペロブスカイト型酸化物は、一般式（１）
Ａ’Ａ３Ｂ４Ｏ１２　　　（１）
（式中、Ａ’及びＡはペロブスカイト型酸化物のＡサイトを占める元素であって、Ａ’はＬａ、Ｂｉ、Ｙ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、Ｎａ及びＫからなる群から選ばれる少なくとも一種の金属元素を示し、ＡはＣｕ、Ｍｎ、Ｆｅ及びＮｉからなる群から選ばれる少なくとも一種の遷移金属元素を示し、Ｂはペロブスカイト型酸化物のＢサイトを占める元素であって、Ｆｅ、Ｔｉ、Ｖ、Ｃｒ、Ｃｕ、Ｍｎ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｎ、Ｚｒ及びＲｕからなる群から選ばれる少なくとも一種の遷移金属元素を示す。）
で表される。 A-site ordered perovskite oxide The perovskite oxide of the present invention has the general formula (1)
A'A 3 B 4 O 12 (1)
(In the formula, A ′ and A are elements occupying the A site of the perovskite oxide, and A ′ is La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Pb, Na and K represent at least one metal element selected from the group consisting of Cu, Mn, Fe and Ni, and A represents at least one transition selected from the group consisting of Cu, Mn, Fe and Ni Represents a metal element, and B is an element occupying the B site of the perovskite oxide, and is selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Co, Ni, Ge, Sn, Zr, and Ru Indicates at least one transition metal element.)
It is represented by
　Ａ’としては、特に、Ｌａ、Ｂｉ及びＹからなる群から選ばれる少なくとも一種の金属元素が好ましく、Ｌａがより好ましい。 As A ′, at least one metal element selected from the group consisting of La, Bi and Y is particularly preferable, and La is more preferable.
　Ａとしては、特に、Ｃｕ及びＭｎの少なくとも一種の遷移金属元素が好ましく、Ｃｕがより好ましい。 A is particularly preferably at least one transition metal element of Cu and Mn, and more preferably Cu.
　Ｂとしては、特に、Ｆｅが好ましい。 B is particularly preferably Fe.
　本発明のペロブスカイト型酸化物としては、特に、ＬａＣｕ３Ｆｅ４Ｏ１２、ＢｉＣｕ３Ｆｅ４Ｏ１２及び（Ｌａ、Ｃａ）Ｃｕ３Ｆｅ４Ｏ１２が好ましく、ＬａＣｕ３Ｆｅ４Ｏ１２がより好ましい。 As the perovskite oxide of the present invention, LaCu 3 Fe 4 O 12 , BiCu 3 Fe 4 O 12 and (La, Ca) Cu 3 Fe 4 O 12 are particularly preferable, and LaCu 3 Fe 4 O 12 is more preferable.
　本発明のペロブスカイト型酸化物の形状、大きさ等は特に限定されず、目的の部品等に応じて適宜設定すればよいが、部品の加工容易性等の観点から粒子状であることが好ましい。前記ペロブスカイト型酸化物が粒子状である場合、平均粒径は、１～１０００μｍ程度が好ましい。平均粒径の測定方法には、公知の方法を採用すればよい。例えば、透過型電子顕微鏡法等が挙げられる。 The shape, size, and the like of the perovskite oxide of the present invention are not particularly limited, and may be set as appropriate according to the target component, but are preferably in the form of particles from the standpoint of ease of processing of the component. When the perovskite oxide is in the form of particles, the average particle size is preferably about 1 to 1000 μm. A known method may be adopted as a method for measuring the average particle diameter. For example, transmission electron microscopy may be used.
　本発明のペロブスカイト型酸化物の結晶構造は、例えば、Ｘ線回折法、メスバウアー分光法等によって確認できる。 The crystal structure of the perovskite oxide of the present invention can be confirmed by, for example, X-ray diffraction method, Mossbauer spectroscopy or the like.
　本発明のペロブスカイト型酸化物は、構成する各元素が特殊なイオン状態にある。例えば、ＬａＣｕ３Ｆｅ４Ｏ１２を例にとると、室温下でＬａ３＋Ｃｕ３＋ ３Ｆｅ３＋ ４Ｏ２－ １２となり、ＡサイトでＣｕ３＋という特殊なイオン状態が生じている。さらに、３９３Ｋ（１２０℃）より上の温度では、ＢサイトのＦｅ３＋が異常高原子価と称される高い酸化状態のＦｅ３．７５＋イオンになるのと同時に、ＡサイトのＣｕ３＋がＣｕ２＋イオンへと変化する。 In the perovskite oxide of the present invention, each constituent element is in a special ionic state. For example, taking the LaCu 3 Fe 4 O 12 as an example, and La 3+ Cu 3+ 3 Fe 3+ 4 O 2- 12 , and the special ionic state of Cu 3+ in the A site occurs at room temperature. Furthermore, at temperatures above 393 K (120 ° C.), Fe 3+ at the B site becomes Fe 3.75+ ions in a highly oxidized state called an abnormally high valence, and at the same time Cu 3+ at the A site becomes Cu 2+. Changes to ions.
  本発明のペロブスカイト型酸化物は、前記イオン状態の変化に伴い、室温下で反強磁性状態であるものが３９３Ｋ（１２０℃）より上の温度ではから常磁性へと変化する。また、室温下で絶縁体状態であるものが、３９３Ｋ（１２０℃）より上の温度では電流が流れる金属状態へと変化する。 In the perovskite oxide of the present invention, the antiferromagnetic state at room temperature changes to paramagnetic from a temperature above 393 K (120 ° C.) as the ionic state changes. Moreover, what is in an insulator state at room temperature changes to a metal state in which current flows at a temperature above 393 K (120 ° C.).
　本発明のペロブスカイト型酸化物は、各種デバイスを構成する部品の材料として使用できる。特に、本発明のペロブスカイト型酸化物は、使用時における熱膨張の問題がないので、高集積・高出力のエレクトロニクス部品（例えば、集積回路等）、精密光学部品（例えば、ミラー、レンズ等）、精密機械部品（例えば、工作機械部品等）等の構成材料として好適に使用できる。例えば、サブミクロンサイズの位置制御を必要とするＤＶＤ等のピックアップ装置の材料として好適に用いることができる。 The perovskite oxide of the present invention can be used as a material for parts constituting various devices. In particular, since the perovskite oxide of the present invention has no problem of thermal expansion during use, highly integrated and high power electronics components (for example, integrated circuits), precision optical components (for example, mirrors, lenses, etc.), It can be suitably used as a constituent material for precision machine parts (for example, machine tool parts). For example, it can be suitably used as a material for a pickup device such as a DVD that requires submicron size position control.
　本発明のペロブスカイト型酸化物を用いて各種部品を製造する際、該ペロブスカイト型酸化物と熱膨張作用を示す材料とを混合し、焼結させることにより、温度による体積変化が実質ゼロである部品を製造することが可能になる。すなわち、本発明のペロブスカイト型酸化物は、熱膨張緩衝材としても使用できる。前記ペロブスカイト型酸化物と前記材料との配合割合は、該材料の熱膨張率等に応じて適宜調整すればよい。また、前記ペロブスカイト型酸化物は一種単独で使用してもよいし、二種以上を組み合わせて使用してもよい。 When manufacturing various parts using the perovskite type oxide of the present invention, the perovskite type oxide and a material exhibiting a thermal expansion action are mixed and sintered, so that the volume change with temperature is substantially zero. Can be manufactured. That is, the perovskite oxide of the present invention can also be used as a thermal expansion buffer material. What is necessary is just to adjust suitably the mixture ratio of the said perovskite type oxide and the said material according to the thermal expansion coefficient etc. of this material. Further, the perovskite oxides may be used alone or in combination of two or more.
　本発明のペロブスカイト型酸化物を熱膨張緩衝材として用いることにより、各種部品の熱膨張率を高精度で調節することができる。例えば、高温、温度履歴環境下で用いる複合・スタック部品は、各部材の熱膨張率の違いによって各部材間で剥離してしまうという問題がある。本発明のペロブスカイト型酸化物によれば、各種部品の熱膨張率を高精度で調節できるため、前記問題を好適に回避できる。従って、本発明のペロブスカイト型酸化物は、例えば、燃料電池用スタック部材、エレクトロニクス基板等における材料としても有用である。 By using the perovskite oxide of the present invention as a thermal expansion buffer material, the thermal expansion coefficient of various components can be adjusted with high accuracy. For example, there is a problem that a composite / stack component used in a high temperature and temperature history environment is peeled off between members due to a difference in thermal expansion coefficient of each member. According to the perovskite oxide of the present invention, since the coefficient of thermal expansion of various components can be adjusted with high accuracy, the above problem can be suitably avoided. Therefore, the perovskite oxide of the present invention is also useful as a material in, for example, a fuel cell stack member, an electronic substrate and the like.
　Ａサイト秩序型ペロブスカイト酸化物の製造方法
　本発明のペロブスカイト型酸化物は、例えば、Ａ’の酸化物、Ａの酸化物及びＢの酸化物を混合後、高温高圧下で、熱処理（焼成）することにより製造できる。 Method for Producing A-Site Ordered Perovskite Oxide The perovskite oxide of the present invention is, for example, mixed with an A ′ oxide, an A oxide and a B oxide, and then heat-treated (fired) under high temperature and high pressure. Can be manufactured.
　Ａ’の酸化物、Ａの酸化物及びＢの酸化物の配合割合は、特に限定されず、一般式（１）（Ａ’Ａ３Ｂ４Ｏ１２）で示されるペロブスカイト型酸化物が得られるよう適宜設定すればよい。例えば、ＬａＣｕ３Ｆｅ４Ｏ１２のペロブスカイト型酸化物を製造する場合、Ｌａ２Ｏ３、ＣｕＯ及びＦｅ２Ｏ３をモル比で１：６：４の割合で用いることにより、本発明のペロブスカイト型酸化物が好適に得られる。 The mixing ratio of the oxide of A ′, the oxide of A, and the oxide of B is not particularly limited, and a perovskite oxide represented by the general formula (1) (A′A 3 B 4 O 12 ) is obtained. What is necessary is just to set suitably. For example, when producing a perovskite oxide of LaCu 3 Fe 4 O 12 , the perovskite oxide of the present invention is used by using La 2 O 3 , CuO and Fe 2 O 3 in a molar ratio of 1: 6: 4. An oxide is suitably obtained.
　前記熱処理は、公知の方法に従って行うことができる。例えば、白金カプセルに、Ａ’の酸化物、Ａの酸化物及びＢの酸化物の混合物を充填後、得られたカプセルを公知の装置を用いて加圧及び加熱する方法が挙げられる。公知の装置としては、例えば、立方体アンビル型高圧発生装置等が挙げられる。 The heat treatment can be performed according to a known method. For example, after filling a platinum capsule with a mixture of an oxide of A ′, an oxide of A and an oxide of B, the obtained capsule is pressurized and heated using a known apparatus. Examples of known devices include a cubic anvil type high pressure generator.
　Ａ’の酸化物、Ａの酸化物及びＢの酸化物の混合物を熱処理する際の圧力は、６ＧＰａ程度以上が好ましく、１０～１５ＧＰａ程度がより好ましい。 The pressure when heat-treating the mixture of A ′ oxide, A oxide and B oxide is preferably about 6 GPa or more, more preferably about 10 to 15 GPa.
　熱処理温度は、８００℃以上程度が好ましく、１０００～１２００℃程度がより好ましい。 The heat treatment temperature is preferably about 800 ° C. or higher, and more preferably about 1000 to 1200 ° C.
　特に、前記熱処理が、１０ＧＰａ程度以上の圧力及び１０００℃以上の温度で行われることにより、本発明のペロブスカイト型酸化物が好適に得られる。 In particular, the perovskite oxide of the present invention is suitably obtained by performing the heat treatment at a pressure of about 10 GPa or more and a temperature of 1000 ° C. or more.
　熱処理時間は、原料が十分に反応するよう熱処理温度等の熱処理条件に応じて適宜調整すればよいが、通常３０分～２時間程度である。 The heat treatment time may be appropriately adjusted according to the heat treatment conditions such as the heat treatment temperature so that the raw materials sufficiently react, but is usually about 30 minutes to 2 hours.
　前記熱処理に先だって、前記混合物には公知の添加剤を含有させてもよい。公知の添加剤としては、例えばＫＣｌＯ４等の酸化剤が挙げられる。 Prior to the heat treatment, the mixture may contain known additives. Examples of known additives include oxidizing agents such as KClO 4 .
　本発明のペロブスカイト型酸化物は、Ａサイトが秩序化されていることにより、各種デバイスの使用時の温度等の実用的な温度領域（２５～４５０℃程度（２９８～７２３Ｋ程度））で熱収縮する。また、本発明のペロブスカイト型酸化物は、外部磁場や電流によって体積の増減を好適に制御できる。 The perovskite type oxide of the present invention is thermally contracted in a practical temperature range (about 25 to 450 ° C. (about 298 to 723 K)) such as the temperature when using various devices because the A site is ordered. To do. The perovskite oxide of the present invention can be suitably controlled in volume increase / decrease by an external magnetic field or current.
　さらに、本発明のペロブスカイト型酸化物は、体積の変動（前記熱収縮）が等方的に起こる。 Furthermore, in the perovskite oxide of the present invention, the volume change (the heat shrinkage) occurs isotropically.
　このような特性を示す本発明のペロブスカイト型酸化物は、高集積・高出力のエレクトロニクス部品、精密光学部品、精密機械部品等の構成材料として好適に使用できる。例えば、本発明のペロブスカイト型酸化物を熱膨張緩衝材として用いることにより、温度による体積変化が実質ゼロである高集積・高出力エレクトロニクス部品等を製造できる。また、高温、温度履歴環境下で用いた場合に各部材間での剥離が防止又は抑制された、複合・スタック部品を製造できる。 The perovskite oxide of the present invention exhibiting such characteristics can be suitably used as a constituent material for highly integrated / high output electronics parts, precision optical parts, precision machine parts and the like. For example, by using the perovskite oxide of the present invention as a thermal expansion buffer material, it is possible to manufacture highly integrated and high output electronic components that have substantially no volume change due to temperature. Moreover, when used in a high temperature and temperature history environment, it is possible to manufacture a composite / stacked component in which separation between members is prevented or suppressed.
図１は、Ａサイト秩序型ペロブスカイト型酸化物の結晶構造（立方晶結晶構造、空間群：Ｉｍ－３）を示す。FIG. 1 shows a crystal structure (cubic crystal structure, space group: Im-3) of an A-site ordered perovskite oxide. 図２は、実施例１で得られたペロブスカイト型酸化物の熱による体積変化を示す。FIG. 2 shows a change in volume of the perovskite oxide obtained in Example 1 due to heat. 図３は、実施例１で得られたペロブスカイト型酸化物の熱による磁気転移及び絶縁体－金属転移を示すグラフである。FIG. 3 is a graph showing the magnetic transition and insulator-metal transition of the perovskite oxide obtained in Example 1 due to heat. 図４は、実施例１及び２で用いた立方体アンビル型高圧発生装置の模式図を示す。FIG. 4 is a schematic diagram of the cubic anvil type high-pressure generator used in Examples 1 and 2. 図５は、実施例１で得られたＬａＣｕ３Ｆｅ４Ｏ１２のＸ線回折スペクトルを示す。FIG. 5 shows the X-ray diffraction spectrum of LaCu 3 Fe 4 O 12 obtained in Example 1. 図６は、実施例２で得られたＢｉＣｕ３Ｆｅ４Ｏ１２のＸ線回折スペクトルを示す。6 shows the X-ray diffraction spectrum of BiCu 3 Fe 4 O 12 obtained in Example 2. FIG.
以下に実施例を示し、本発明をより具体的に説明する。但し、本発明は実施例に限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
　実施例１
　ＬａＣｕ３Ｆｅ４Ｏ１２のペロブスカイト型酸化物を製造した。 Example 1
A perovskite oxide of LaCu 3 Fe 4 O 12 was produced.
　まず、市販のＬａ２Ｏ３、ＣｕＯ及びＦｅ２Ｏ３をモル比で１：６：４の割合で混合した後、ＫＣｌＯ４を添加し、混合物を得た。なお、ＫＣｌＯ４は、前記混合物中における含有量が２０重量％となるように添加した。 First, commercially available La 2 O 3 , CuO and Fe 2 O 3 were mixed at a molar ratio of 1: 6: 4, and then KClO 4 was added to obtain a mixture. KClO 4 was added so that the content in the mixture was 20% by weight.
　得られた混合物を白金カプセルに充填後、得られたカプセルを図４に示すような立方体アンビル型高圧発生装置を用いて、圧力１０ＧＰａ、温度１４００Ｋの条件下、約１時間加熱した。 After filling the obtained mixture into platinum capsules, the obtained capsules were heated for about 1 hour under conditions of a pressure of 10 GPa and a temperature of 1400 K using a cubic anvil type high pressure generator as shown in FIG.
　加熱後、希酸を用いてＫＣｌ及び少量の未反応原料を除去した。 After heating, KCl and a small amount of unreacted raw material were removed using dilute acid.
　以上の方法により、ＬａＣｕ３Ｆｅ４Ｏ１２のペロブスカイト型酸化物を得た。 The perovskite oxide of LaCu 3 Fe 4 O 12 was obtained by the above method.
　得られたＬａＣｕ３Ｆｅ４Ｏ１２のＸ線回折スペクトルを図５に示す。 The X-ray diffraction spectrum of the obtained LaCu 3 Fe 4 O 12 is shown in FIG.
　実施例２
　ＢｉＣｕ３Ｆｅ４Ｏ１２のペロブスカイト型酸化物を製造した。 Example 2
A perovskite oxide of BiCu 3 Fe 4 O 12 was produced.
　まず、市販のＢｉ２Ｏ３、ＣｕＯ及びＦｅ２Ｏ３をモル比で１：６：４の割合で混合した後、ＫＣｌＯ４を添加し、混合物を得た。なお、ＫＣｌＯ４は、前記混合物中における含有量が２０重量％となるように添加した。 First, commercially available Bi 2 O 3 , CuO and Fe 2 O 3 were mixed at a molar ratio of 1: 6: 4, and then KClO 4 was added to obtain a mixture. KClO 4 was added so that the content in the mixture was 20% by weight.
　得られた混合物を白金カプセルに充填後、得られたカプセルを図４に示すような立方体アンビル型高圧発生装置を用いて、圧力１０ＧＰａ、温度１３００Ｋの条件下、約１時間加熱した。 After filling the obtained mixture into platinum capsules, the obtained capsules were heated for about 1 hour under conditions of a pressure of 10 GPa and a temperature of 1300 K using a cubic anvil type high pressure generator as shown in FIG.
　加熱後、希酸を用いてＫＣｌ及び少量の未反応原料を除去した。 After heating, KCl and a small amount of unreacted raw material were removed using dilute acid.
　以上の方法により、ＢｉＣｕ３Ｆｅ４Ｏ１２のペロブスカイト型酸化物を得た。 By the above method, a perovskite oxide of BiCu 3 Fe 4 O 12 was obtained.
　得られたＢｉＣｕ３Ｆｅ４Ｏ１２のＸ線回折スペクトルを図６に示す。 The X-ray diffraction spectrum of the obtained BiCu 3 Fe 4 O 12 is shown in FIG.
　試験例１
　実施例１及び実施例２で得られたペロブスカイト型酸化物の熱による体積変化率を確認した。 Test example 1
The volume change rate due to heat of the perovskite oxide obtained in Example 1 and Example 2 was confirmed.
　具体的には、Ｘ線回折装置（リガク社製ＲＩＮＴ２５００）を用いて、実施例１及び実施例２で得られたペロブスカイト型酸化物の温度を除々に上げながら、各温度下での結晶の格子定数を測定し体積を計算した。 Specifically, using an X-ray diffractometer (RINT2500 manufactured by Rigaku Corporation), while gradually raising the temperature of the perovskite oxide obtained in Example 1 and Example 2, the crystal lattice at each temperature The constant was measured and the volume was calculated.
　実施例１で得られたペロブスカイト型酸化物の熱による体積変化を図２に示す。 FIG. 2 shows the volume change of the perovskite oxide obtained in Example 1 due to heat.
　加熱温度が３９３Ｋのときの実施例１のペロブスカイト型酸化物の体積変化率を下記式により求めた。
｛（加熱温度が４２３Ｋのときの体積－加熱温度が３７３Ｋときの体積）／加熱温度が３７３Ｋときの体積｝×１００（％） The volume change rate of the perovskite oxide of Example 1 when the heating temperature was 393 K was determined by the following formula.
{(Volume when the heating temperature is 423K−Volume when the heating temperature is 373K) / Volume when the heating temperature is 373K} × 100 (%)
　また、加熱温度が４５０Ｋのときの実施例２のペロブスカイト型酸化物の体積変化率を下記式により求めた。
｛（加熱温度が４７３Ｋのときの体積－加熱温度が４２３Ｋときの体積）／加熱温度が４２３Ｋときの体積｝×１００（％）
　結果を表１に示す。 Further, the volume change rate of the perovskite oxide of Example 2 when the heating temperature was 450 K was obtained by the following formula.
{(Volume when the heating temperature is 473K−Volume when the heating temperature is 423K) / Volume when the heating temperature is 423K} × 100 (%)
The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、実施例１及び実施例２で得られたペロブスカイト型酸化物は、１２０℃（３９３Ｋ）、１７７℃（４５０Ｋ）という実用的な温度で加熱された際、体積が減少することがわかる。 As is clear from Table 1, the perovskite oxides obtained in Examples 1 and 2 decreased in volume when heated at practical temperatures of 120 ° C. (393 K) and 177 ° C. (450 K). I understand that
　試験例２
　実施例１で得られたペロブスカイト型酸化物の熱による磁気転移及び絶縁体－金属転移を確認した。 Test example 2
The perovskite oxide obtained in Example 1 was confirmed to have a magnetic transition due to heat and an insulator-metal transition.
　磁気転移については、磁力計（クウォンタムデザイン社製「ＭＰＭＳ」）を用いて確認した。また、絶縁体－金属転移については、物理特性測定装置（クウォンタムデザイン社製「ＰＰＭＳ」）を用いて確認した。 The magnetic transition was confirmed using a magnetometer (“MPMS” manufactured by Quantum Design). The insulator-metal transition was confirmed by using a physical property measuring apparatus (“PPMS” manufactured by Quantum Design Co., Ltd.).
　実施例１で得られたペロブスカイト型酸化物の熱による磁気転移及び絶縁体－金属転移を示すグラフを図３に示す。 FIG. 3 shows a graph showing the magnetic transition and the insulator-metal transition of the perovskite oxide obtained in Example 1 due to heat.
　図３から明らかなように、実施例１のペロブスカイト型酸化物は、上記試験例１で体積が減少した温度を境に、反強磁性から常磁性への磁気転移が起こり、さらに、絶縁体から金属への転移が起こることがわかる。かかる結果から、本発明のペロブスカイト型酸化物は、外部磁場や電流によって体積の増減を制御できることがわかる。 As is clear from FIG. 3, the perovskite oxide of Example 1 undergoes a magnetic transition from antiferromagnetism to paramagnetism at the temperature at which the volume decreased in Test Example 1 above, and further from the insulator. It can be seen that the transition to metal occurs. From these results, it can be seen that the perovskite oxide of the present invention can control the increase or decrease in volume by an external magnetic field or current.

Claims (4)

  1. 一般式（１）
    Ａ’Ａ３Ｂ４Ｏ１２　　　（１）
    （式中、Ａ’及びＡはペロブスカイト型酸化物のＡサイトを占める元素であって、Ａ’はＬａ、Ｂｉ、Ｙ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、Ｎａ及びＫからなる群から選ばれる少なくとも一種の金属元素を示し、ＡはＣｕ、Ｍｎ、Ｆｅ及びＮｉからなる群から選ばれる少なくとも一種の遷移金属元素を示し、Ｂはペロブスカイト型酸化物のＢサイトを占める元素であって、Ｆｅ、Ｔｉ、Ｖ、Ｃｒ、Ｃｕ、Ｍｎ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｎ、Ｚｒ及びＲｕからなる群から選ばれる少なくとも一種の遷移金属元素を示す。）
    で表されるペロブスカイト型酸化物。     General formula (1)
    A'A 3 B 4 O 12 (1)
    (In the formula, A ′ and A are elements occupying the A site of the perovskite oxide, and A ′ is La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Pb, Na and K represent at least one metal element selected from the group consisting of Cu, Mn, Fe and Ni, and A represents at least one transition selected from the group consisting of Cu, Mn, Fe and Ni Represents a metal element, and B is an element occupying the B site of the perovskite oxide, and is selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Co, Ni, Ge, Sn, Zr, and Ru Indicates at least one transition metal element.)
    Perovskite oxide represented by
  2. 一般式（１）中、Ａ’はＬａ、Ｂｉ及びＹからなる群から選ばれる少なくとも一種の金属元素を示し、ＡはＣｕ及びＭｎの少なくとも一種の遷移金属元素を示し、ＢはＦｅを示す、請求項１に記載のペロブスカイト型酸化物。 In general formula (1), A ′ represents at least one metal element selected from the group consisting of La, Bi and Y, A represents at least one transition metal element of Cu and Mn, and B represents Fe. The perovskite oxide according to claim 1.
  3. 熱膨張緩衝材として用いる請求項１又は２に記載のペロブスカイト型酸化物。 The perovskite oxide according to claim 1 or 2, which is used as a thermal expansion buffer material.
  4. Ａ’の酸化物、Ａの酸化物及びＢの酸化物の混合物を、圧力６ＧＰａ以上及び温度８００℃以上の条件下で熱処理することを特徴とする請求項１又は２に記載のペロブスカイト型酸化物の製造方法。 The perovskite oxide according to claim 1 or 2, wherein a mixture of the oxide of A ', the oxide of A and the oxide of B is heat-treated under conditions of a pressure of 6 GPa or more and a temperature of 800 ° C or more. Manufacturing method.
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CN110902725A (en) * 2019-11-11 2020-03-24 北京科技大学 Fluxing agent synthesis method of metastable-phase rare earth copper-iron-based perovskite oxide
JP2021082598A (en) * 2021-02-18 2021-05-27 国立研究開発法人産業技術総合研究所 Conductive material, conductive ceramics, conductive paste, conductive material film, production method of composite oxide, production method of conductive paste, and production method of conductive material film
JP7039075B2 (en) 2021-02-18 2022-03-22 国立研究開発法人産業技術総合研究所 Conductive material, conductive ceramics, conductive paste, conductive material film, composite oxide manufacturing method, conductive paste manufacturing method and conductive material film manufacturing method
CN113398909A (en) * 2021-06-08 2021-09-17 中国科学院物理研究所 Perovskite material and preparation method and application thereof
CN113398909B (en) * 2021-06-08 2022-05-24 中国科学院物理研究所 Perovskite material and preparation method and application thereof
WO2023163057A1 (en) * 2022-02-25 2023-08-31 日本化学工業株式会社 Negative thermal expansion material and composite material
JP7408721B2 (en) 2022-02-25 2024-01-05 日本化学工業株式会社 Negative thermal expansion materials and composite materials

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