WO2014030293A1 - 負熱膨張性材料 - Google Patents

負熱膨張性材料 Download PDF

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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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thermal expansion
negative thermal
negative
expansion material
metal element
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French (fr)
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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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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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Description

負熱膨張性材料
　本発明は、負の熱膨張性を有する材料に関する。
　近年、ＬＳＩ製造などのナノテクノロジーの発展に伴い、熱膨張による位置決めの狂いが問題になっている。この問題に対処するため、温めると縮む性質、すなわち負の熱膨張性を有する材料が樹脂に分散されたゼロ膨張材料の開発が進められている。
　従来、負の熱膨張性を有する材料としては、ペロブスカイト構造を有するＢｉＮｉＯ３のうち、Ｂｉの一部をＬａで置換したＢｉ１－ｙＬａｙＮｉＯ３で表される負熱膨張性材料が既存材料の３倍もの負の熱膨張を示し、多くの樹脂の熱膨張係数（たとえば、数１０～１００ｐｐｍ／℃）に見合った負の熱膨張係数を有することが発見されている。
ＳＰｒｉｎｇ－８　利用者情報／２０１１年１１月　Ｐ．２６１
　上述した負熱膨張性材料では、Ｂｉの一部を置換するために、高価な希土類元素であるＬａが用いられているため、製造コストが高くなるという課題があった。希土類元素には供給が不安定であるという問題もある。また、Ｂｉの一部をＬａで置換した負熱膨張性材料は温度ヒステリシスが大きいため、ゼロ膨張材料を形成する際に負熱膨張性材料の温度ヒステリシスに応じた樹脂の材料選択が必要となるという課題があった。
　本発明はこうした課題に鑑みてなされたものであり、その目的は、製造コストがより安価で原料供給の不安が少ない負熱膨張性材料の提供にある。また、本発明の他の目的は、温度ヒステリシスが抑制された負熱膨張性材料の提供にある。
　本発明のある態様は、負の熱膨張性を有する負熱膨張性材料であって、下記一般式（１）で表される化合物を含むことを特徴とする。
ＢｉＮｉ１－ｘＭｘＯ３・・・（１）
（１）式中、Ｍは３価イオンとなり得る金属元素である。また、ｘは０．０２≦ｘ≦０．５０を満たす。
　上記態様の負熱膨張性材料において、ＭがＡｌ，Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ、Ｇａ，Ｎｂ、Ｒｕ，Ｒｈ，Ｉｎからなる群より選ばれてもよい。
　また、Ｂｉの一部がＲでさらに置換された下記一般式（２）で表される化合物を含んでもよい。
Ｂｉ１－ｙＲｙＮｉ１－ｘＭｘＯ３・・・（２）
（２）式中、Ｒは３価イオンにのみなり得る金属元素である。また、ｙは０＜ｙ＜０．５０を満たす。この場合、ＲがＬａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｙなる群より選ばれてもよい。
　本発明によれば、製造コストがより安価で原料供給の不安が少なく、温度ヒステリシスが抑制された負熱膨張性材料が提供される。
実施例１～９の各負熱膨張性材料の平均体積の温度依存性を示すグラフである。 実施例３、実施例１０および比較例１の各負熱膨張性材料の平均体積の温度依存性を示すグラフである。 実施例１１の樹脂複合材の熱膨張率の温度依存性を示すグラフである。
（実施形態１）
　実施形態１に係る負熱膨張性材料は、母物質のＢｉＮｉＯ３において、Ｎｉの一部が３価が安定な金属元素Ｍで置換された化合物である。具体的には、実施形態１に係る負熱膨張性材料は、下記一般式（１）で表される化合物を含む。
ＢｉＮｉ１－ｘＭｘＯ３・・・（１）
（１）式中、Ｍは３価イオンとなり得る金属元素であり、好ましくは、３価が他の価数よりも安定な金属元素である。具体的には、ＭはＡｌ，Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ、Ｇａ，Ｎｂ、Ｒｕ，Ｒｈ，Ｉｎからなる群より選ばれる。また、（１）式中、ｘは０．０２≦ｘ≦０．５０を満たす。本実施形態に係る負熱膨張性材料は、所定の温度範囲（たとえば、３００-３９０Ｋ）において－４０ｐｐｍ／℃以上の負の熱膨張を示す。なお、ｘが０．０２より小さいと、十分な負の熱膨張性を得ることができない。
　上記一般式（１）で表される化合物の母物質であるＢｉＮｉＯ３は、Ｂｉ３＋ ０．５Ｂｉ５＋ ０．５Ｎｉ２＋Ｏ３という特徴的な価数状態を持つペロブスカイト酸化物である。ペロブスカイト構造では、Ｎｉ－Ｏ結合が構造の骨格を作っており、Ｂｉはその隙間を埋めている。Ｎｉの一部を３価が安定な金属元素で置換することにより、Ｂｉ３＋ ０．５Ｂｉ５＋ ０．５Ｎｉ２＋Ｏ３という価数状態が不安定化する。この結果、昇温によってＢｉ３＋（Ｎｉ，Ｍ）３＋Ｏ３という価数状態への変化が生じ、Ｎｉ２＋からＮｉ３＋への価数変化に伴ってＮｉ－Ｏが収縮すると、全体の体積が収縮する。すなわち、本実施形態に係る負熱膨張性材料によって負の熱膨張が実現される。
　本実施形態の負熱膨張性材料によれば、高価な希土類元素を用いることなく、より安価で供給の不安が少ない金属元素を用いることにより、負熱膨張性材料の製造コストを低減することができる。さらに、本実施形態の負熱膨張性材料では、Ｂｉの一部をＬａで置換したＢｉ１－ｙＬａｙＮｉＯ３で表される負熱膨張性材料で生じるような温度ヒステリシスを抑制することができる。
　本実施の形態の負熱膨張性材料をエンジニアリングプラスチックなどの樹脂材料中に分散させ、樹脂材料の熱膨張が負熱膨張性材料の負の熱膨張で相殺するように材料の選択や各成分の含有量を設定することにより、ゼロ熱膨張材料を得ることができる。
（負熱膨張性材料の作製方法）
　上記一般式（１）で表される化合物の作製方法は特に限定されないが、各金属元素が均一に固溶した複合金属酸化物を合成して任意の形状に成形できる方法であると好ましい。例えば、Ｂｉ、Ｍ、Ｎｉの各酸化物を目的物と同じモル比で混合して高圧（例えば２ＧＰａ以上）を付与しながら焼結すると、各金属元素が均一に固溶した複合金属酸化物が得られる。得られた酸化物を粉砕してから、成形して前記焼結の温度以下で焼き固めると、上記一般式（１）で表される化合物からなる熱膨張抑制部材が得られる。この他、本実施の形態に係る負熱膨張性材料は、上述した作製方法に限られず、スパッタ法、化学溶液法、レーザアブレ－ション法などによる、単結晶基板上の薄膜育成によっても作製することができる。
（実施形態２）
　実施形態２に係る負熱膨張性材料は、母物質のＢｉＮｉＯ３において、実施形態１と同様にＮｉの一部が３価イオンとなり得る金属元素Ｍで置換され、かつ、Ｂｉの一部が３価のみを取り得る金属元素Ｒで置換された化合物である。具体的には、実施形態２に係る負熱膨張性材料は、下記一般式（２）で表される化合物を含む。
Ｂｉ１－ｙＲｙＮｉ１－ｘＭｘＯ３・・・（２）
（２）式中、Ｍは３価イオンとなり得る金属元素であり、好ましくは、３価が他の価数よりも安定な金属元素である。具体的には、ＭはＡｌ，Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ、Ｇａ，Ｎｂ、Ｒｕ，Ｒｈ，Ｉｎからなる群より選ばれる。ｘは０．０２≦ｘ≦０．５０を満たす。Ｒは３価イオンにのみなり得る金属元素である。ＲはＬａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｙなる群より選ばれる。また、ｙは０＜ｙ＜０．０５を満たす。本実施形態に係る負熱膨張性材料は、金属元素Ｒの含有量を低減しつつ、実施形態１と同様に負の熱膨張を示す。さらに、本実施形態では、ＭおよびＲの比率を調節することにより、負の熱膨張を示す温度領域をＢｉの一部のみを置換した場合と、Ｎｉの一部のみを置換した場合との間の温度領域に設定することができる。また、本実施の形態では、負の熱膨張を示す温度領域を、Ｂｉの一部のみを置換した場合と、Ｎｉの一部のみを置換した場合に比べて、広げることができる。このため、ゼロ熱膨張材料を作製する際に、樹脂材料の選択の幅を広げたり、より幅広い温度範囲でゼロ膨張を実現できるといった効果を奏する。
（実施形態３）
　実施形態３に係る負熱膨張性複合体は、上述したいずれかの実施形態の負熱膨張性材料と樹脂材料とを混合した複合体である。樹脂材料は特に限定されないが、たとえば、エポキシ樹脂、フェノール樹脂、ポリカーボネートなどが挙げられる。負熱膨張性材料と樹脂材料との混合比（体積比）は、使用する負熱膨張性材料および樹脂材料の熱膨張係数にもよるが、たとえば、５：９５～８０：２０である。本実施形態によれば、樹脂材料の正の熱膨張が負熱膨張性材料の負の熱膨張によって相殺されることにより、温度変化に対する寸法変化の割合が小さい材料が提供される。
　以下、本発明の実施例を説明するが、これら実施例は、本発明を好適に説明するための例示に過ぎず、なんら本発明を限定するものではない。
（実施例１：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ａｌ、ｘ＝０．０５））
Ｂｉ２Ｏ３（３．７０４０ｇ）、Ｎｉ（０．９８２２ｇ）、Ａｌ（ＮＯ３）３・９Ｈ２Ｏ（０．３１３９ｇ）を３５％硝酸溶液５０ｍｌに溶解し、スターラーで撹拌しながら蒸発乾固させた。得られた粉体を空気中で７５０℃で熱処理し、酸化物の混合粉とした後、酸化剤として働く過塩素酸カリウムを２０質量％混ぜ込み、金カプセルに封入した。このカプセルを高圧合成装置を用いて、６万気圧、１０００℃の条件下で３０分間処理した。得られた試料を水洗して塩化カリウムを除去して負熱膨張性材料を得た。
（実施例２：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ａｌ、ｘ＝０．１０））
　Ｎｉを０．８１６９ｇを用い、Ａｌ（ＮＯ３）３・９Ｈ２Ｏを０．６２７８ｇ用いて、Ａｌの比率ｘを０．１０としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例３：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ｇａ、ｘ＝０．０５））
　Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＧａ２Ｏ３を０．０７９８ｇ用いて、Ｇａの比率ｘを０．０５としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例４：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ｇａ、ｘ＝０．１０））
　Ｎｉを０．９０６８ｇを用い、Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＧａ２Ｏ３を０．１５９６ｇ用いて、Ｇａの比率ｘを０．１０としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例５：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ｃｒ、ｘ＝０．０５））
　Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＣｒ２Ｏ３を０．０６４９０ｇ用いて、Ｃｒの比率ｘを０．０５としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例６：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ｆｅ、ｘ＝０．０５））
　Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＦｅ（ＮＯ３）３・９Ｈ２Ｏを０．３２６９ｇ用いて、Ｆｅの比率ｘを０．０５としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例７：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ｆｅ、ｘ＝０．１０））
　Ｎｉを０．９０６８ｇ用い、Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＦｅ（ＮＯ３）３・９Ｈ２Ｏを０．６５３８ｇ用いて、Ｆｅの比率ｘを０．１０としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例８：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ｆｅ、ｘ＝０．１５））
　Ｎｉを０．８７８８ｇ用い、Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＦｅ（ＮＯ３）３・９Ｈ２Ｏを０．９８０７ｇ用いて、Ｆｅの比率ｘを０．１５としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例９：ＢｉＮｉ１－ｘＭｘＯ３（Ｍ＝Ｃｏ、ｘ＝０．０５））
　Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＣｏ（ＮＯ３）２・６Ｈ２Ｏを０．２３９９ｇ用いて、Ｃｏの比率ｘを０．０５としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（実施例１０：Ｂｉ１－ｙＲｙＮｉ１－ｘＭｘＯ３（Ｒ＝Ｌａ、ｙ＝０．０５、Ｍ＝Ｇａ、ｘ＝０．０５））
　Ａｌ（ＮＯ３）３・９Ｈ２Ｏに代えてＧａ２Ｏ３を０．０８０８ｇ用いて、Ｇａの比率ｘを０．０５とし、さらに、Ｂｉ２Ｏ３を３．８１７０ｇとし、Ｌａ２Ｏ３（０．１４０５ｇ）を用いて、Ｌａの比率ｙを０．０５としたことを除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
（比較例１：Ｂｉ１－ｙＲｙＮｉＯ３（Ｒ＝Ｌａ、ｙ＝０．０５））
　Ｂｉ２Ｏ３を３．８４０２ｇとし、Ｌａ２Ｏ３（０．１４１３ｇ）を用いてＬａの比率ｙを０．０５し、かつ、Ｎｉ（１．０１８５ｇ）を用いて、Ｍを用いない点を除いて、実施例１と同様な手順にて負熱膨張性材料を得た。
　実施例１～１０、比較例１の各負熱膨張性材料について、粉末Ｘ線回折装置（ブルカー社製Ｄ８　ＡＤＶＡＮＣＥ）により温度を変えながら格子定数を見積もり、単位胞当たりの平均体積を算出した。図１に、実施例１～９の各負熱膨張性材料の平均体積の温度依存性を示す。また、図２に、実施例３、実施例１０および比較例１の各負熱膨張性材料の平均体積の温度依存性を示す。表１に実施例１～１０、比較例１の各負熱膨張性材料の線熱膨張係数を示す。
Figure JPOXMLDOC01-appb-T000001
　図１および図２に示すように、実施例１～１０では、Ｎｉの一部を３価イオンとなり得る金属元素Ｍで置換することにより、比較例１のように希土類元素であるＬａを用いずに、あるいはＬａの量を減らした状態で、比較例１と同様に負の熱膨張を起こすことを確認した。さらに、実施例７、９では、比較例１と比べて温度ヒステリシスが小さくなることが確認された。
　また、ＢｉおよびＮｉの一部を同時置換した実施例１０では、負の熱膨張を示す温度領域がＢｉの一部のみをＬａで置換した比較例１と、Ｎｉの一部のみをＧａで置換した実施例３の負の熱膨張を示す温度領域の間に位置することが確認された。ＢｉおよびＮｉをともに置換し、ＭおよびＲの比率を調節することにより、負の熱膨張を示す温度領域を所望の領域に設定できることが示唆された。また、比較例１では、負の熱膨張の温度ヒステリシスが３０Ｋであるのに対して、実施例９では、負の熱膨張の温度ヒステリシスが１５Ｋに減少すること確認された。
（実施例１１）
　実施例８の負熱膨張性材料と、ビスフェノール型のエポキシ樹脂（ナミックス社製）とを体積比２０：８０にて混合し、樹脂複合体を作製した。この樹脂複合体の熱膨張率の温度依存性を歪みゲージを用いて計測した。図３に、実施例１１の樹脂複合材の熱膨張率の温度依存性を示す。エポキシ樹脂単体の熱膨張係数は８０ｐｐｍ／Ｋである。これに対して、実施例１１の樹脂複合材では、室温近傍での熱膨張係数は－８．４ｐｐｍ／Ｋであり、負の値を示すことが確認された。このことから、負熱膨張性材料の添加量を１７体積％にすれば、熱膨張がゼロになると推察される。
　本発明は、負の熱膨張性を有する材料に利用可能である。

Claims (5)

  1. 　負の熱膨張性を有する負熱膨張性材料であって、
    　下記一般式（１）で表される化合物を含むことを特徴とする負熱膨張性材料。
    ＢｉＮｉ１－ｘＭｘＯ３・・・（１）
    （１）式中、Ｍは３価イオンとなり得る金属元素である。また、ｘは０．０２≦ｘ≦０．５０を満たす。
  2. 　ＭがＡｌ，Ｆｅ，Ｃｒ，Ｇａからなる群より選ばれる請求項１に記載の負熱膨張性材料。
  3. 　Ｂｉの一部がＲでさらに置換された下記一般式（２）で表される化合物を含む請求項１または２に記載の負熱膨張性材料。
    Ｂｉ１－ｙＲｙＮｉ１－ｘＭｘＯ３・・・（２）
    （２）式中、Ｒは３価イオンにのみなり得る金属元素である。また、ｙは０＜ｙ＜０．０５を満たす。
  4. 　ＲがＬａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｙからなる群より選ばれる請求項３に記載の負熱膨張性材料。
  5. 　請求項１乃至４のいずれか１項に記載の負熱膨張性材料と樹脂材料とを混合した複合体。
PCT/JP2013/004479 2012-08-21 2013-07-23 負熱膨張性材料 Ceased WO2014030293A1 (ja)

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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 (ja) * 2020-02-27 2021-09-02
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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
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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
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