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WO2014030293A1 - Matériau à dilatation thermique négative - Google Patents

Matériau à dilatation thermique négative Download PDF

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Publication number
WO2014030293A1
WO2014030293A1 PCT/JP2013/004479 JP2013004479W WO2014030293A1 WO 2014030293 A1 WO2014030293 A1 WO 2014030293A1 JP 2013004479 W JP2013004479 W JP 2013004479W WO 2014030293 A1 WO2014030293 A1 WO 2014030293A1
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Prior art keywords
thermal expansion
negative thermal
negative
expansion material
metal element
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English (en)
Japanese (ja)
Inventor
東　正樹
研吾 岡
智可 坂口
光一郎 奈部谷
裕也 村松
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Tokyo Institute of Technology NUC
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Tokyo Institute of Technology NUC
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Priority to JP2014531487A priority Critical patent/JP6143197B2/ja
Publication of WO2014030293A1 publication Critical patent/WO2014030293A1/fr
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Definitions

  • the present invention relates to a material having negative thermal expansibility.
  • La which is an expensive rare earth element
  • La is used to replace a part of Bi, and thus there is a problem that the manufacturing cost is increased.
  • supply of rare earth elements is unstable.
  • a negative thermal expansion material in which a part of Bi is replaced with La has a large temperature hysteresis, it is necessary to select a resin material according to the temperature hysteresis of the negative thermal expansion material when forming a zero expansion material. There was a problem.
  • the present invention has been made in view of these problems, and an object of the present invention is to provide a negatively thermally expandable material with a lower manufacturing cost and less concern about the supply of raw materials. Another object of the present invention is to provide a negative thermal expansion material with suppressed temperature hysteresis.
  • One embodiment of the present invention is a negative thermal expansion material having negative thermal expansion, and includes a compound represented by the following general formula (1).
  • BiNi 1-x M x O 3 (1)
  • M is a metal element that can be a trivalent ion.
  • X satisfies 0.02 ⁇ x ⁇ 0.50.
  • M may be selected from the group consisting of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ga, Nb, Ru, Rh, and In.
  • a compound represented by the following general formula (2) in which a part of Bi is further substituted with R may be included.
  • Bi 1-y R y Ni 1-x M x O 3 (2)
  • R is a metal element that can only be a trivalent ion. Further, y satisfies 0 ⁇ y ⁇ 0.50. In this case, R may be selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.
  • a negative thermal expansible material that is less expensive to manufacture, has less worries about raw material supply, and suppresses temperature hysteresis.
  • Example 6 is a graph showing the temperature dependence of the average volume of each negatively heat-expandable material of Examples 1 to 9. It is a graph which shows the temperature dependence of the average volume of each negative thermal expansible material of Example 3, Example 10, and Comparative Example 1. It is a graph which shows the temperature dependence of the thermal expansion coefficient of the resin composite material of Example 11.
  • the negative thermal expansion material according to Embodiment 1 is a compound in which a part of Ni is substituted with a metal element M having a stable trivalence in BiNiO 3 as a base material.
  • the negative thermal expansion material according to Embodiment 1 includes a compound represented by the following general formula (1).
  • M is a metal element that can be a trivalent ion, and preferably, a trivalent is a metal element that is more stable than other valences.
  • M is selected from the group consisting of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ga, Nb, Ru, Rh, and In.
  • x satisfies 0.02 ⁇ x ⁇ 0.50.
  • the negative thermal expansion material according to the present embodiment exhibits negative thermal expansion of ⁇ 40 ppm / ° C. or more in a predetermined temperature range (for example, 300-390 K). If x is less than 0.02, sufficient negative thermal expansion cannot be obtained.
  • BiNiO 3 which is a base material of the compound represented by the general formula (1) is a perovskite oxide having a characteristic valence state of Bi 3+ 0.5 Bi 5+ 0.5 Ni 2+ O 3 .
  • Ni—O bonds form the structure skeleton, and Bi fills the gap.
  • the valence state of Bi 3+ 0.5 Bi 5+ 0.5 Ni 2+ O 3 becomes unstable.
  • a change to a valence state of Bi 3+ (Ni, M) 3+ O 3 occurs due to temperature rise, and when Ni—O contracts with a valence change from Ni 2+ to Ni 3+ , the entire volume becomes Shrink. That is, negative thermal expansion is realized by the negative thermal expansion material according to the present embodiment.
  • the negative thermal expansion material of the present embodiment it is possible to reduce the manufacturing cost of the negative thermal expansion material by using a metal element that is cheaper and less likely to be supplied without using an expensive rare earth element. it can. Furthermore, in the negative thermal expansion material of the present embodiment, it is possible to suppress the temperature hysteresis that occurs in the negative thermal expansion material represented by Bi 1-y La y NiO 3 in which a part of Bi is substituted with La. it can.
  • the negative thermal expansion material of the present embodiment is dispersed in a resin material such as engineering plastic, and the selection of materials and each component are made so that the thermal expansion of the resin material is offset by the negative thermal expansion of the negative thermal expansion material. By setting the content, a zero thermal expansion material can be obtained.
  • the method for producing the compound represented by the general formula (1) is not particularly limited, but it is preferably a method in which a composite metal oxide in which each metal element is uniformly dissolved can be synthesized and formed into an arbitrary shape.
  • a composite metal oxide in which each metal element is uniformly dissolved can be synthesized and formed into an arbitrary shape.
  • a high pressure eg, 2 GPa or more
  • a composite metal oxide in which each metal element is uniformly dissolved is obtained. can get.
  • the obtained oxide is pulverized, then molded and baked at a temperature equal to or lower than the sintering temperature, a thermal expansion suppressing member made of the compound represented by the general formula (1) is obtained.
  • the negative thermal expansion material according to the present embodiment is not limited to the above-described manufacturing method, and can also be manufactured by growing a thin film on a single crystal substrate by a sputtering method, a chemical solution method, a laser ablation method, or the like. Can do.
  • the negative thermal expansion material according to Embodiment 2 includes a compound represented by the following general formula (2).
  • M is a metal element that can be a trivalent ion, and preferably, a trivalent is a metal element that is more stable than other valences.
  • M is selected from the group consisting of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ga, Nb, Ru, Rh, and In.
  • x satisfies 0.02 ⁇ x ⁇ 0.50.
  • R is a metal element that can only be a trivalent ion.
  • R is selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.
  • y satisfies 0 ⁇ y ⁇ 0.05.
  • the negative thermal expansion material according to the present embodiment exhibits negative thermal expansion as in the first embodiment while reducing the content of the metal element R.
  • the temperature range showing negative thermal expansion is changed between when only a part of Bi is replaced and when only a part of Ni is replaced. Temperature range. Moreover, in this Embodiment, the temperature range which shows negative thermal expansion can be expanded compared with the case where only a part of Bi is substituted, and the case where only a part of Ni is substituted. For this reason, when producing a zero thermal expansion material, there exists an effect that the selection range of a resin material is expanded, and zero expansion can be realized in a wider temperature range.
  • the negative thermal expansion composite according to Embodiment 3 is a composite obtained by mixing the negative thermal expansion material of any of the above-described embodiments and a resin material.
  • the resin material is not particularly limited, and examples thereof include an epoxy resin, a phenol resin, and a polycarbonate.
  • the mixing ratio (volume ratio) between the negative thermal expansion material and the resin material is, for example, 5:95 to 80:20, although it depends on the thermal expansion coefficient of the negative thermal expansion material and the resin material used.
  • the positive thermal expansion of the resin material is offset by the negative thermal expansion of the negative thermal expansion material, thereby providing a material with a small ratio of dimensional change to temperature change.
  • Ni Ni with 0.8169g of using 0.6278g of Al (NO 3) 3 ⁇ 9H 2 O, except that the 0.10 ratio x of Al, the negative in the same manner as in Example 1 Procedure A thermally expandable material was obtained.
  • Example 1 except that 0.9068 g of Ni was used, 0.1596 g of Ga 2 O 3 was used instead of Al (NO 3 ) 3 ⁇ 9H 2 O, and the Ga ratio x was 0.10.
  • a negative thermal expansile material was obtained in the same procedure.
  • a negative thermal expansion material was obtained by a simple procedure.
  • Using 0.9068g of Ni using 0.6538g of Fe (NO 3) 3 ⁇ 9H 2 O in place of Al (NO 3) 3 ⁇ 9H 2 O, except that the 0.10 ratio x of Fe
  • a negative thermal expansion material was obtained in the same procedure as in Example 1.
  • Fe (NO 3) 3 ⁇ 9H 2 O 0.9807g
  • Al (NO 3) 3 ⁇ 9H 2 O 0.15 ratio x of Fe
  • FIG. 1 shows the temperature dependence of the average volume of each negatively thermally expandable material of Examples 1 to 9.
  • FIG. 2 shows the temperature dependence of the average volume of each negatively thermally expandable material of Example 3, Example 10, and Comparative Example 1.
  • Table 1 shows the linear thermal expansion coefficients of the negative thermal expansion materials of Examples 1 to 10 and Comparative Example 1.
  • Example 10 in which a part of Bi and Ni were simultaneously replaced, Comparative Example 1 in which only a part of Bi was replaced with La in a temperature region showing negative thermal expansion, and only a part of Ni was replaced with Ga It was confirmed that it was located between the temperature regions showing negative thermal expansion in Example 3. It was suggested that by substituting Bi and Ni together and adjusting the ratio of M and R, a temperature region showing negative thermal expansion can be set to a desired region. In Comparative Example 1, it was confirmed that the temperature hysteresis of negative thermal expansion was 30K, whereas in Example 9, the temperature hysteresis of negative thermal expansion was reduced to 15K.
  • Example 11 The negative thermal expansion material of Example 8 and a bisphenol type epoxy resin (manufactured by NAMICS) were mixed at a volume ratio of 20:80 to prepare a resin composite.
  • the temperature dependence of the coefficient of thermal expansion of this resin composite was measured using a strain gauge.
  • FIG. 3 the temperature dependence of the thermal expansion coefficient of the resin composite material of Example 11 is shown.
  • the thermal expansion coefficient of the epoxy resin alone is 80 ppm / K.
  • the coefficient of thermal expansion near room temperature was -8.4 ppm / K, and it was confirmed that the resin composite showed a negative value. From this, it is presumed that the thermal expansion becomes zero if the addition amount of the negative thermal expansion material is 17% by volume.
  • the present invention can be used for a material having negative thermal expansibility.

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PCT/JP2013/004479 2012-08-21 2013-07-23 Matériau à dilatation thermique négative Ceased WO2014030293A1 (fr)

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JP2015221749A (ja) * 2010-08-12 2015-12-10 キヤノン株式会社 熱膨張抑制部材および対熱膨張性部材
JP2017048071A (ja) * 2015-08-31 2017-03-09 国立大学法人東京工業大学 負熱膨張性材料、及び複合体
JP2017048072A (ja) * 2015-08-31 2017-03-09 公益財団法人神奈川科学技術アカデミー 負熱膨張性材料の製造方法
JP2018031063A (ja) * 2016-08-26 2018-03-01 地方独立行政法人神奈川県立産業技術総合研究所 負熱膨張性薄膜の形成方法
WO2018123897A1 (fr) * 2016-12-27 2018-07-05 国立大学法人名古屋大学 Matériau composite
US10124558B2 (en) 2010-08-12 2018-11-13 Kyoto University Thermal expansion suppressing member and anti-thermally-expansive member
JP2019210201A (ja) * 2018-06-08 2019-12-12 地方独立行政法人神奈川県立産業技術総合研究所 負熱膨張性材料、複合体、及び使用方法
JP2021017514A (ja) * 2019-07-23 2021-02-15 国立大学法人東京工業大学 樹脂組成物およびその樹脂成形体
JPWO2021172525A1 (fr) * 2020-02-27 2021-09-02
CN118497582A (zh) * 2024-07-16 2024-08-16 吉林大学 一种低温负热膨胀金属导电材料及其制备方法
EP4270558A4 (fr) * 2021-02-17 2025-01-08 Kolon Industries, Inc. Humidificateur à membrane de pile à combustible

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WO2010101153A1 (fr) * 2009-03-04 2010-09-10 国立大学法人京都大学 Oxyde de type perovskite ordonnée sur le site a
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JP2007194429A (ja) * 2006-01-19 2007-08-02 Fujitsu Ltd 強磁性・強誘電性材料及び半導体装置
JP2010029990A (ja) * 2008-07-29 2010-02-12 National Institute Of Advanced Industrial & Technology 負熱膨張率材料および該負熱膨張率材料を含む複合材料
WO2010101153A1 (fr) * 2009-03-04 2010-09-10 国立大学法人京都大学 Oxyde de type perovskite ordonnée sur le site a
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JP2015221749A (ja) * 2010-08-12 2015-12-10 キヤノン株式会社 熱膨張抑制部材および対熱膨張性部材
US10124558B2 (en) 2010-08-12 2018-11-13 Kyoto University Thermal expansion suppressing member and anti-thermally-expansive member
JP2017048071A (ja) * 2015-08-31 2017-03-09 国立大学法人東京工業大学 負熱膨張性材料、及び複合体
JP2017048072A (ja) * 2015-08-31 2017-03-09 公益財団法人神奈川科学技術アカデミー 負熱膨張性材料の製造方法
JP2018031063A (ja) * 2016-08-26 2018-03-01 地方独立行政法人神奈川県立産業技術総合研究所 負熱膨張性薄膜の形成方法
WO2018123897A1 (fr) * 2016-12-27 2018-07-05 国立大学法人名古屋大学 Matériau composite
JP6998051B2 (ja) 2018-06-08 2022-01-18 地方独立行政法人神奈川県立産業技術総合研究所 負熱膨張性材料、複合体、及び使用方法
JP2019210201A (ja) * 2018-06-08 2019-12-12 地方独立行政法人神奈川県立産業技術総合研究所 負熱膨張性材料、複合体、及び使用方法
EP4006096A4 (fr) * 2019-07-23 2023-08-23 Tokyo Institute of Technology Composition de résine et produit moulé la comprenant
CN114423820A (zh) * 2019-07-23 2022-04-29 国立大学法人东京工业大学 树脂组合物及其树脂成型体
US20220135764A1 (en) * 2019-07-23 2022-05-05 Tokyo Institute Of Technology Resin composition and resin molded body thereof
JP2021017514A (ja) * 2019-07-23 2021-02-15 国立大学法人東京工業大学 樹脂組成物およびその樹脂成形体
JP7351477B2 (ja) 2019-07-23 2023-09-27 国立大学法人東京工業大学 樹脂組成物およびその樹脂成形体
CN114423820B (zh) * 2019-07-23 2024-03-12 国立大学法人东京工业大学 树脂组合物及其树脂成型体
US12479972B2 (en) * 2019-07-23 2025-11-25 Institute Of Science Tokyo Resin composition and resin molded body thereof
WO2021172525A1 (fr) * 2020-02-27 2021-09-02 国立大学法人東京工業大学 Procédé de production de matériau à dilatation thermique négative, procédé de production de précurseur de réaction de matériau à dilatation thermique négative, précurseur de réaction de matériau à dilatation thermique négative, et matériau à dilatation thermique négative
JPWO2021172525A1 (fr) * 2020-02-27 2021-09-02
JP7745852B2 (ja) 2020-02-27 2025-09-30 国立大学法人東京科学大学 負熱膨張性材料の製造方法、負熱膨張性材料の反応前駆体の製造方法、および負熱膨張性材料の反応前駆体
EP4270558A4 (fr) * 2021-02-17 2025-01-08 Kolon Industries, Inc. Humidificateur à membrane de pile à combustible
CN118497582A (zh) * 2024-07-16 2024-08-16 吉林大学 一种低温负热膨胀金属导电材料及其制备方法

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