JP7408721B2 - Negative thermal expansion materials and composite materials - Google Patents
Negative thermal expansion materials and composite materials Download PDFInfo
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- JP7408721B2 JP7408721B2 JP2022080386A JP2022080386A JP7408721B2 JP 7408721 B2 JP7408721 B2 JP 7408721B2 JP 2022080386 A JP2022080386 A JP 2022080386A JP 2022080386 A JP2022080386 A JP 2022080386A JP 7408721 B2 JP7408721 B2 JP 7408721B2
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、温度上昇に対して収縮する負熱膨張材及び該負熱膨張材を含む複合材料に関するものである。 TECHNICAL FIELD The present invention relates to a negative thermal expansion material that contracts with increasing temperature and a composite material containing the negative thermal expansion material.
多くの物質は温度が上昇すると、熱膨張によって長さや体積が増大する。これに対して 、温めると逆に体積が小さくなる負の熱膨張を示す材料（以下「負熱膨張材」ということがある）も知られている。 When the temperature of many materials increases, their length and volume increase due to thermal expansion. On the other hand, there are also known materials that exhibit negative thermal expansion (hereinafter sometimes referred to as "negative thermal expansion materials") whose volume conversely decreases when heated.
負の熱膨張を示す材料は、他の材料とともに用いて、温度変化による材料の熱膨張の変化を抑制することができることが知られている。 It is known that materials exhibiting negative thermal expansion can be used in conjunction with other materials to suppress changes in the material's thermal expansion due to temperature changes.
負の熱膨張を示す材料としては、例えば、β－ユークリプタイト、タングステン酸ジルコニウム（ＺｒＷ２Ｏ８）、リン酸タングステン酸ジルコニウム（Ｚｒ２ＷＯ４（ＰＯ４）２）、ＺｎｘＣｄ１－ｘ（ＣＮ）２、マンガン窒化物、ビスマス・ニッケル・鉄酸化物等が知られている。 Examples of materials exhibiting negative thermal expansion include β-eucryptite, zirconium tungstate (ZrW 2 O 8 ), zirconium phosphotungstate (Zr 2 WO 4 (PO 4 ) 2 ), and Zn x Cd 1- x (CN) 2 , manganese nitride, bismuth nickel iron oxide, etc. are known.
リン酸タングステン酸ジルコニウムの線膨張係数は、０～４００℃の温度範囲で－３．４～－３．０ｐｐｍ／℃であり、負熱膨張性が大きいことが知られている。このリン酸タングステン酸ジルコニウムと、正の熱膨張を示す材料（以下「正熱膨張材」ということがある。）とを併用することで、低熱膨張の材料を製造することができる（特許文献１～２等参照）。また、正熱膨張材である樹脂等の高分子化合物と負熱膨張材とを併用することも提案されている（特許文献３等参照）。 The coefficient of linear expansion of zirconium tungstate phosphate is -3.4 to -3.0 ppm/°C in the temperature range of 0 to 400°C, and it is known that it has a large negative thermal expansion property. By using this zirconium tungstate phosphate in combination with a material exhibiting positive thermal expansion (hereinafter sometimes referred to as a "positive thermal expansion material"), a material with low thermal expansion can be manufactured (Patent Document 1). ~2nd place). It has also been proposed to use a polymer compound such as a resin as a positive thermal expansion material in combination with a negative thermal expansion material (see Patent Document 3, etc.).
また、下記非特許文献１には、α－Ｃｕ２Ｖ２Ｏ７の銅バナジウム複合酸化物は、室温から２００℃の温度域で－５～－６ｐｐｍ／℃の線膨張係数を有することが開示されている。また、該銅バナジウム複合酸化物のＣｕの一部をＺｎ、Ｇａ、Ｆｅから選ばれる少なくとも１種の元素で置換したり、或いはＶの一部をＰで置換することにより、更に負熱膨張特性を向上させる方法も提案されている（特許文献４～５）。 Furthermore, Non-Patent Document 1 below discloses that the copper vanadium composite oxide of α-Cu 2 V 2 O 7 has a linear expansion coefficient of -5 to -6 ppm/°C in the temperature range from room temperature to 200°C. has been done. In addition, by substituting a part of Cu in the copper-vanadium composite oxide with at least one element selected from Zn, Ga, and Fe, or by substituting a part of V with P, negative thermal expansion characteristics can be further improved. Methods for improving this have also been proposed (Patent Documents 4 to 5).
しかしながら、非特許文献１や、特許文献４及び５の銅バナジウム複合酸化物は、リン酸タングステン酸ジルコニウムに比べ、線膨張係数が小さくなるが、より安価な原料系で製造でき、工業的に有利に製造することができること及び耐水性に優れる観点から、非特許文献１の銅バナジウム複合酸化物に比べて更に、負熱膨張特性を向上させることが要求されている。 However, although the copper-vanadium composite oxides of Non-Patent Document 1 and Patent Documents 4 and 5 have a smaller linear expansion coefficient than zirconium tungstate phosphate, they can be manufactured using cheaper raw materials and are industrially advantageous. In view of the fact that it can be produced in a similar manner and has excellent water resistance, it is required to further improve the negative thermal expansion characteristics compared to the copper vanadium composite oxide of Non-Patent Document 1.
従って、本発明は、優れた負熱膨張特性を有する負熱膨張材を提供することを目的とする。 Therefore, an object of the present invention is to provide a negative thermal expansion material having excellent negative thermal expansion characteristics.
本発明者らは、Ｃｕ２Ｖ２Ｏ７の銅バナジウム複合酸化物の負熱膨張特性を更に向上させる方法を検討する中で、該銅バナジウム複合酸化物にＣａを固溶させて含有させることにより、負熱膨張特性が向上することを見出し、本発明を完成するに至った。 The present inventors, while considering a method for further improving the negative thermal expansion characteristics of a copper vanadium composite oxide of Cu 2 V 2 O 7 , found that the copper vanadium composite oxide contains Ca as a solid solution. It was discovered that the negative thermal expansion characteristics were improved by this method, and the present invention was completed.
すなわち、本発明（１）は、下記一般式（１）：
ＣｕｘＣａｙＶｚＯｔ （１）
（式中、ｘは１．５０≦ｘ≦２．２０、ｙは０＜ｙ≦０．４０、ｚは１．７０≦ｚ≦２．３０、ｔは６．００≦ｔ≦９．００を示す。但し、１．５０＜ｘ＋ｙ≦２．６０である。）
で表される銅バナジウム複合酸化物からなり、該銅バナジウム複合酸化物はＣｕ２Ｖ２Ｏ７に起因するＺｉｅｓｉｔｅ相（β相）の単相又はＺｉｅｓｉｔｅ相（β相）とＢｌｏｓｓｉｔｅ相（α相）との混相の結晶構造を有することを特徴とする負熱膨張材を提供するものである。
That is, the present invention (1) has the following general formula (1):
Cu x Ca y V z O t (1)
(In the formula, x is 1.50≦x≦2.20, y is 0<y≦0.40, z is 1.70≦z≦2.30, and t is 6.00≦t≦9.00. (However, 1.50 < x+y≦ 2.60 .)
The copper-vanadium composite oxide consists of a single Ziesite phase (β phase) or a Ziesite phase (β phase) and a Blossite phase (α phase) caused by Cu 2 V 2 O 7 . ) A negative thermal expansion material is provided which is characterized by having a crystal structure of a mixed phase.
また、本発明（２）は、熱膨張係数が、－１０．０×１０－６／Ｋ以下であることを特徴とする（１）の負熱膨張材を提供するものである。 Furthermore, the present invention (2) provides the negative thermal expansion material of (1), which has a thermal expansion coefficient of -10.0×10 −6 /K or less.
また、本発明（３）は、平均粒子径が、０．１～１００μｍであることを特徴とする（１）又は（２）の負熱膨張材を提供するものである。 In addition, the present invention (3) provides the negative thermal expansion material of (1) or (2), which has an average particle diameter of 0.1 to 100 μm.
また、本発明（４）は、ＢＥＴ比表面積が、０．０５～５０ｍ２／ｇであることを特徴とする（１）～（３）いずれかの負熱膨張材を提供するものである。 Further, the present invention (4) provides the negative thermal expansion material according to any one of (1) to (3), characterized in that the BET specific surface area is 0.05 to 50 m 2 /g.
また、本発明（５）は、球形度が０．７以上１．０以下の球状粒子の含有率が、個数基準で７５％以上であることを特徴とする（１）～（４）いずれかの負熱膨張材を提供するものである。 Further, the present invention (5) is characterized in that the content of spherical particles having a sphericity of 0.7 or more and 1.0 or less is 75% or more based on the number of particles. The present invention provides a negative thermal expansion material.
また、本発明（６）は、更に、リンを固溶させて含有することを特徴とする（１）～（５）いずれかの負熱膨張材を提供するものである。 The present invention (6) further provides the negative thermal expansion material according to any one of (1) to (5), which further contains phosphorus as a solid solution.
また、本発明（７）は、本発明（１）～（６）いずれかの負熱膨張材と正熱膨張材とを含むことを特徴とする複合材料を提供するものである。 Furthermore, the present invention (7) provides a composite material characterized by containing the negative thermal expansion material and the positive thermal expansion material according to any one of the present inventions (1) to (6).
また、本発明（８）は、前記正熱膨張材が、金属、合金、ガラス、セラミックス、ゴム及び樹脂から選ばれる少なくとも１種であることを特徴とする（７）の複合材料を提供するものである。 Further, the present invention (8) provides the composite material according to (7), wherein the positive thermal expansion material is at least one selected from metals, alloys, glass, ceramics, rubber, and resins. It is.
本発明によれば、優れた負熱膨張特性を有する負熱膨張材を提供することができる。 According to the present invention, a negative thermal expansion material having excellent negative thermal expansion characteristics can be provided.
以下、本発明をその好ましい実施形態に基づいて説明する。
本発明の負熱膨張材は、下記一般式（１）：
ＣｕｘＣａｙＶｚＯｔ （１）
（式中、ｘは０＜ｘ＜２．５０、ｙは０＜ｙ＜２．００、ｚは１．７０≦ｚ≦２．３０、ｔは６．００≦ｔ≦９．００を示す。但し、１．００≦ｘ＋ｙ≦３．００である。）
で表される銅バナジウム複合酸化物からなることを特徴とする。
Hereinafter, the present invention will be explained based on its preferred embodiments.
The negative thermal expansion material of the present invention has the following general formula (1):
Cu x Ca y V z O t (1)
(In the formula, x is 0<x<2.50, y is 0<y<2.00, z is 1.70≦z≦2.30, and t is 6.00≦t≦9.00. However, 1.00≦x+y≦3.00.)
It is characterized by being made of a copper-vanadium composite oxide represented by
一般式（１）中、ｘは、０＜ｘ＜２．５０である。ｘは、負熱膨張特性がより高くなる点で、好ましくは１．００≦ｘ≦２．３０、特に好ましくは１．５０≦ｘ≦２．２０である。
一般式（１）中、ｙは、０＜ｙ＜２．００である。ｙは、負熱膨張特性がより高くなる点で、好ましくは０．００５≦ｙ≦１．００、特に好ましくは０．０１≦ｙ≦０．５０、一層好ましくは０．０２≦ｙ≦０．４０である。
一般式（１）中、ｚは、１．７０≦ｚ≦２．３０である。ｚは、負熱膨張特性がより高くなる点で、好ましくは１．８０≦ｚ≦２．２０である。
一般式（１）中、ｔは、６．００≦ｔ≦９．００である。ｔは、負熱膨張特性がより高くなる点で、好ましくは６．００≦ｔ≦８．００である。
但し、一般式（１）中のｘ＋ｙは、１．００≦ｘ＋ｙ≦３．００である。ｘ＋ｙは、負熱膨張特性がより高くなる点で、好ましくは１．５０≦ｘ＋ｙ≦２．５０である。
In general formula (1), x satisfies 0<x<2.50. x is preferably 1.00≦x≦2.30, particularly preferably 1.50≦x≦2.20, in that the negative thermal expansion property becomes higher.
In general formula (1), y is 0<y<2.00. y is preferably 0.005≦y≦1.00, particularly preferably 0.01≦y≦0.50, and even more preferably 0.02≦y≦0. It is 40.
In general formula (1), z is 1.70≦z≦2.30. z is preferably 1.80≦z≦2.20 in that the negative thermal expansion property becomes higher.
In general formula (1), t is 6.00≦t≦9.00. t is preferably 6.00≦t≦8.00 in that the negative thermal expansion property becomes higher.
However, x+y in general formula (1) is 1.00≦x+y≦3.00. x+y is preferably 1.50≦x+y≦2.50 in that the negative thermal expansion property becomes higher.
本発明の負熱膨張材のＢＥＴ比表面積は、特に制限されないが、好ましくは０．０５～５０ｍ２／ｇ、特に好ましくは０．１０～１０ｍ２／ｇ、一層好ましくは０．２０～８ｍ２／ｇである。負熱膨張材のＢＥＴ比表面積が、上記範囲にあることにより、負熱膨張材を樹脂やガラス等のフィラーとして用いる際に、取扱いが容易になる。なお、本発明において、負熱膨張材のＢＥＴ比表面積は、全自動比表面積測定装置Ｍａｃｓｏｒｂ（マウンテック社製）を用いてＢＥＴ１点法により測定された値である。 The BET specific surface area of the negative thermal expansion material of the present invention is not particularly limited, but is preferably 0.05 to 50 m 2 /g, particularly preferably 0.10 to 10 m 2 /g, and even more preferably 0.20 to 8 m 2 /g. When the BET specific surface area of the negative thermal expansion material is within the above range, handling becomes easy when the negative thermal expansion material is used as a filler for resin, glass, etc. In the present invention, the BET specific surface area of the negative thermal expansion material is a value measured by the BET one-point method using a fully automatic specific surface area measuring device Macsorb (manufactured by Mountech Co., Ltd.).
本発明の負熱膨張材の平均粒子径は、特に制限されないが、走査型電子顕微鏡観察法により求められる平均粒子径で、好ましくは０．１～１００μｍ、特に好ましくは０．２～８０μｍである。負熱膨張材の平均粒子径が上記範囲にあることにより、負熱膨張材を樹脂やガラス等のフィラーとして用いる際に、取扱いが容易になる。なお、本発明において、負熱膨張材の平均粒子径については、走査型電子顕微鏡観察において、倍率１０００倍で任意に抽出した粒子２０個の粒子径の算術平均値を、平均粒子径として求めた。このとき、各粒子の粒子径とは、粒子の二次元投影像を横断する線分のうち最も大きい長さ（最大長）をいう。 The average particle diameter of the negative thermal expansion material of the present invention is not particularly limited, but is an average particle diameter determined by scanning electron microscopy, and is preferably 0.1 to 100 μm, particularly preferably 0.2 to 80 μm. . When the average particle diameter of the negative thermal expansion material is within the above range, handling becomes easy when the negative thermal expansion material is used as a filler for resin, glass, etc. In addition, in the present invention, the average particle diameter of the negative thermal expansion material was determined by the arithmetic mean value of the particle diameters of 20 particles arbitrarily extracted at a magnification of 1000 times in scanning electron microscopy observation. . At this time, the particle diameter of each particle refers to the largest length (maximum length) of the line segments that intersect the two-dimensional projected image of the particle.
本発明の負熱膨張材の粒子形状は、特に制限されず、例えば、球状、粒状、板状、鱗片 状、ウィスカー状、棒状、フィラメント状、破砕状であってもよいが、正熱膨張材との混合時にチッピング等による微粒分等の発生を抑制し、より均一混合できる観点から粒子形状は球状のものを多く含むものが一層好ましい。 The particle shape of the negative thermal expansion material of the present invention is not particularly limited, and may be, for example, spherical, granular, plate-like, scale-like, whisker-like, rod-like, filament-like, or crushed, but the positive thermal expansion material It is more preferable for the particle shape to contain many spherical particles from the viewpoint of suppressing the generation of fine particles due to chipping and the like and allowing more uniform mixing.
なお、本発明において、粒子形状が球状とは、必ずしも真球状のものである必要はない。本発明において球状とは球形度が０．７０以上１．００以下のものであることを示す。
本発明において、球形度とは、サンプルを倍率１００～１０００で電子顕微鏡観察し画像解析処理を行い、得られたパラメーターから下記計算式（１）で求められる。
球形度＝等面積円相当径／外接円径 （１）
（式（１）中、等面積円相当径とは、粒子の周長に円周が相当する円の直径を指す。外接円径とは、粒子の最長径を指す。）
In addition, in the present invention, the particle shape does not necessarily have to be perfectly spherical. In the present invention, spherical means that the sphericity is 0.70 or more and 1.00 or less.
In the present invention, sphericity is determined by observing a sample with an electron microscope at a magnification of 100 to 1000, performing image analysis processing, and using the following calculation formula (1) from the obtained parameters.
Sphericity = Equal area circle equivalent diameter / Circumscribed circle diameter (1)
(In formula (1), the equivalent area circle diameter refers to the diameter of a circle whose circumference corresponds to the circumference of the particle. The circumscribed circle diameter refers to the longest diameter of the particle.)
本発明の負熱膨張材において、球形度が０．７０以上１．００以下である球状粒子の含有率は、個数基準で、好ましくは７５％以上、特に好ましくは８０％以上である。負熱膨張材中の球形度が０．７０以上１．００以下である球状粒子の含有率が上記範囲にあることにより、正熱膨張材との混合時にチッピング等による微粒分等の発生を抑制し、正熱膨張材にする分散性及び充填特性が優れる。
本発明において、球形度が０．７０以上１．００以下である球状粒子の含有率は、サンプルを倍率１００～１０００で電子顕微鏡観察し、任意に抽出した粒子５０個について画像解析処理を行い、抽出した粒子に占める、上記計算式（１）から求められる球形度が０．７０以上１．００以下である粒子の個数基準の含有割合（百分率）を示す。
In the negative thermal expansion material of the present invention, the content of spherical particles having a sphericity of 0.70 or more and 1.00 or less is preferably 75% or more, particularly preferably 80% or more, based on the number of particles. By having the content of spherical particles with a sphericity of 0.70 or more and 1.00 or less in the negative thermal expansion material within the above range, the generation of fine particles due to chipping etc. is suppressed when mixed with the positive thermal expansion material. It has excellent dispersibility and filling properties as a positive thermal expansion material.
In the present invention, the content of spherical particles with a sphericity of 0.70 to 1.00 is determined by observing a sample with an electron microscope at a magnification of 100 to 1000, and performing image analysis processing on 50 arbitrarily extracted particles. The number-based content ratio (percentage) of particles having a sphericity of 0.70 or more and 1.00 or less as determined from the above calculation formula (1) in the extracted particles is shown.
前記画像解析処理に用いられる画像解析装置としては、例えば、ルーゼックス（ニレコ社製）、ＰＩＴＡ－０４（セイシン企業社製）等が挙げられる。球形度の値は１に近づくほど真球状に近くなる。 Examples of the image analysis device used in the image analysis process include Luzex (manufactured by Nireco), PITA-04 (manufactured by Seishin Enterprise Co., Ltd.), and the like. The closer the sphericity value is to 1, the closer to a perfect sphere.
本発明の負熱膨張材は、α－Ｃｕ２Ｖ２Ｏ７の銅バナジウム複合酸化物に比べて、負熱膨張特性が高くなる。すなわち、本発明の負熱膨張材の熱膨張係数は、α－Ｃｕ２Ｖ２Ｏ７の銅バナジウム複合酸化物に比べて、小さい。 The negative thermal expansion material of the present invention has higher negative thermal expansion characteristics than the α-Cu 2 V 2 O 7 copper vanadium composite oxide. That is, the thermal expansion coefficient of the negative thermal expansion material of the present invention is smaller than that of the α-Cu 2 V 2 O 7 copper vanadium composite oxide.
なお、本発明において、熱膨張係数は、以下の手順により求められる。先ず、試料１．００ｇにプロピレンカーボネート０．０５ｇを加えて乳鉢で３分間粉砕混合した後、０．１５ｇを計量し、φ６ｍｍの金型に全量充填する。次いで、ハンドプレスを用いて、０．５ｔの圧力で成型して粉末成型体を作製する。得られた粉末成型体を電気炉にて７００℃まで３時間で昇温し、４時間保持してセラミック成型体を作製する。次いで、作製したセラミック成形体について、熱機械測定装置（例えば、ＮＥＴＺＳＣＨ ＪＡＰＡＮ製 ＴＭＡ４０００ＳＥ）を用いて熱膨張係数を測定する。測定条件を、窒素雰囲気、荷重１０ｇ、温度範囲５０℃～４２５℃とし、温度範囲５０℃～４２５℃にて繰り返し２回測定し、２回目の測定の５０～４００℃間の熱膨張係数を、負熱膨張材の熱膨張係数とする。 In addition, in this invention, a thermal expansion coefficient is calculated|required by the following procedure. First, 0.05 g of propylene carbonate was added to 1.00 g of a sample, and the mixture was pulverized and mixed in a mortar for 3 minutes, and then 0.15 g was weighed and the entire amount was filled into a mold with a diameter of 6 mm. Next, a powder molded body is produced by molding using a hand press at a pressure of 0.5 t. The temperature of the obtained powder molded body is raised to 700° C. over 3 hours in an electric furnace and held for 4 hours to produce a ceramic molded body. Next, the coefficient of thermal expansion of the produced ceramic molded body is measured using a thermomechanical measuring device (for example, TMA4000SE manufactured by NETZSCH JAPAN). The measurement conditions were a nitrogen atmosphere, a load of 10 g, and a temperature range of 50°C to 425°C. Measurements were repeated twice in the temperature range of 50°C to 425°C, and the coefficient of thermal expansion between 50 and 400°C in the second measurement was This is the thermal expansion coefficient of the negative thermal expansion material.
本発明の負熱膨張材の熱膨張係数は、α－Ｃｕ２Ｖ２Ｏ７の銅バナジウム複合酸化物に比べて、熱膨張係数が小さくなる限りは、制限されるものではないが、本発明の負熱膨張材の熱膨張係数は、－１０．０×１０－６／Ｋ以下、好ましくは－１２．０×１０－６／Ｋ以下であり、下限値についても特に制限されるものではないが、概ね－５０．０×１０－６／Ｋ以上、好ましくは－４０．０×１０－６／Ｋ以上である。本発明の負熱膨張材において、正熱膨張材と複合させたときに熱膨張係数が正の膨張を相殺させ易くなる点で、特に好ましくは－５０．０×１０－６～－１０．０×１０－６／Ｋである。 The coefficient of thermal expansion of the negative thermal expansion material of the present invention is not limited as long as the coefficient of thermal expansion is smaller than that of the α-Cu 2 V 2 O 7 copper vanadium composite oxide. The coefficient of thermal expansion of the negative thermal expansion material is -10.0 x 10 -6 /K or less, preferably -12.0 x 10 -6 /K or less, and there is no particular restriction on the lower limit value. is approximately −50.0×10 −6 /K or more, preferably −40.0×10 −6 /K or more. In the negative thermal expansion material of the present invention, the thermal expansion coefficient is particularly preferably −50.0×10 −6 to −10.0 because when combined with a positive thermal expansion material, the positive expansion can be easily offset. ×10 −6 /K.
また、一般式（１）で表される銅バナジウム複合酸化物には、基本的にはＺｉｅｓｉｔｅ相（β相）とＢｌｏｓｓｉｔｅ相（α相）が存在し、また、これらの混相のものも存在する。本発明の負熱膨張材は、Ｚｉｅｓｉｔｅ相（β相）、Ｂｌｏｓｓｉｔｅ相（α相）、あるいは、Ｚｉｅｓｉｔｅ相（β相）とＢｌｏｓｓｉｔｅ相（α相）の混相のものであってもよいが、得られた銅バナジウム複合酸化物をＸ線回折分析したときに、Ｚｉｅｓｉｔｅ相（β相）の単相、或いはＺｉｅｓｉｔｅ相（β相）に起因する２θ＝２５°付近のメインピークがＢｌｏｓｓｉｔｅ相（α相）に起因する２θ＝２７°付近のメインピークに比べてピークの高さが高いＺｉｅｓｉｔｅ相（β相）をより多く含む混相のものが、負熱膨張性に優れたものになる観点から好ましい。 In addition, the copper-vanadium composite oxide represented by the general formula (1) basically has a Ziesite phase (β phase) and a Blossite phase (α phase), and a mixed phase of these also exists. . The negative thermal expansion material of the present invention may be a Ziesite phase (β phase), a Blossite phase (α phase), or a mixed phase of a Ziesite phase (β phase) and a Blossite phase (α phase). When the copper-vanadium composite oxide was subjected to X-ray diffraction analysis, the main peak around 2θ = 25° caused by a single Ziesite phase (β phase) or a Blossite phase (α phase) was observed. ) A mixed phase containing more Ziesite phase (β phase) with a higher peak height than the main peak near 2θ=27° caused by ) is preferable from the viewpoint of having excellent negative thermal expansion properties.
本発明において、２θ＝２５°付近とは、２θ＝２３．５～２６．５°を示す。また、２θ＝２７°付近とは、２θ＝２６．８～２７．８°を示す。
本発明の負熱膨張材では、線源としてＣｕＫα線を用いて、負熱膨張材をＸ線回折分析したときに、２θ＝２５°付近の回折ピークは、Ｚｉｅｓｉｔｅ相（β相）に由来するものであり、２θ＝２７°付近の回折ピークは、Ｂｌｏｓｓｉｔｅ相（α相）に由来するものである。
In the present invention, around 2θ=25° means 2θ=23.5 to 26.5°. Further, the vicinity of 2θ=27° indicates 2θ=26.8 to 27.8°.
In the negative thermal expansion material of the present invention, when the negative thermal expansion material is analyzed by X-ray diffraction using CuKα rays as a radiation source, the diffraction peak near 2θ=25° is derived from the Ziesite phase (β phase). The diffraction peak near 2θ=27° is derived from the Blossite phase (α phase).
また、本発明において、負熱膨張性を調整したり正熱膨張材への分散性を改良することを目的として、必要により、前記一般式（１）で表される銅バナジウム複合酸化物に、更にリンを固溶させて含有させることができる。つまり、本発明の負熱膨張材としては、リンが固溶している前記一般式（１）で表される銅バナジウム複合酸化物からなるものが挙げられる。
固溶させて含有させるリンの量が多くなるに従って、熱膨張係数は大きくなるが、前記一般式（１）で表される銅バナジウム複合酸化物のＶ原子に対するＰ原子のモル比（Ｐ／Ｖ）で０．０より大きく０．３以下、好ましくは０．０より大きく０．２以下とすることにより、本発明の負熱膨張材の熱膨張係数が－１０．０×１０－６／Ｋ以下、好ましくは－１２．０×１０－６／Ｋ以下のものが得られる観点から好ましい。
In addition, in the present invention, for the purpose of adjusting the negative thermal expansion property or improving the dispersibility in the positive thermal expansion material, if necessary, the copper vanadium composite oxide represented by the general formula (1) may be added to the copper vanadium composite oxide represented by the general formula (1). Furthermore, phosphorus can be contained as a solid solution. That is, examples of the negative thermal expansion material of the present invention include those made of a copper-vanadium composite oxide represented by the general formula (1) in which phosphorus is dissolved in solid solution.
As the amount of phosphorus contained in solid solution increases, the coefficient of thermal expansion increases, but the molar ratio of P atoms to V atoms (P/V ) is greater than 0.0 and less than or equal to 0.3, preferably greater than 0.0 and less than or equal to 0.2, so that the coefficient of thermal expansion of the negative thermal expansion material of the present invention is -10.0×10 -6 /K The following is preferred from the viewpoint of obtaining -12.0×10 -6 /K or less.
本発明の負熱膨張材の製造方法は、特に制限されないが、下記の第１工程及び第２工程を行うことにより工業的に有利に製造される。 Although the method for producing the negative thermal expansion material of the present invention is not particularly limited, it can be industrially advantageously produced by performing the following first and second steps.
本発明の負熱膨張材の製造方法は、Ｃｕ源、Ｃａ源、及びＶ源を混合し原料混合物を調製する第１工程と、
該原料混合物を焼成し、負熱膨張材を得る第２工程と、
を有することを特徴とする。
The method for producing a negative thermal expansion material of the present invention includes a first step of mixing a Cu source, a Ca source, and a V source to prepare a raw material mixture;
a second step of firing the raw material mixture to obtain a negative thermal expansion material;
It is characterized by having the following.
第１工程は、Ｃｕ源、Ｃａ源及びＶ源を混合し原料混合物を調製する工程である。 The first step is a step of mixing a Cu source, a Ca source, and a V source to prepare a raw material mixture.
第１工程に係るＣｕ源としては、例えば、グルコン酸銅、クエン酸銅、酢酸銅、乳酸銅等の有機カルボン酸の銅塩、鉱酸の銅塩、銅の酸化物、銅の水酸化物等が挙げられる。 Examples of the Cu source in the first step include copper salts of organic carboxylic acids such as copper gluconate, copper citrate, copper acetate, and copper lactate, copper salts of mineral acids, copper oxides, and copper hydroxides. etc.
第１工程に係るＣａ源としては、例えば、カルシウムの炭酸塩、酸化物、水酸化物、ハロゲン化物、カルボン酸塩等が挙げられる。カルシウムのカルボン酸塩としては、グルコン酸塩、クエン酸塩、シュウ酸塩、酢酸塩、乳酸塩等が挙げられる。 Examples of the Ca source in the first step include calcium carbonates, oxides, hydroxides, halides, and carboxylates. Examples of calcium carboxylates include gluconate, citrate, oxalate, acetate, and lactate.
第１工程に係るＶ源としては、例えば、バナジウム酸及びそのナトリウム塩、カリウム塩、アンモニウム塩、カルボン酸塩、五酸化バナジウム等のバナジウムの酸化物等が挙げられる。カルボン酸のバナジウム塩としては、ギ酸、酢酸、グリコール酸、乳酸、グルコン酸等のモノカルボン酸塩、シュウ酸、マレイン酸、マロン酸、リンゴ酸、酒石酸、コハク酸等のジカルボン酸、カルボキシル基の数が３であるクエン酸等のカルボン酸塩が挙がられる。 Examples of the V source in the first step include vanadic acid and its sodium salt, potassium salt, ammonium salt, carboxylic acid salt, vanadium oxide such as vanadium pentoxide, and the like. Vanadium salts of carboxylic acids include monocarboxylic acid salts such as formic acid, acetic acid, glycolic acid, lactic acid, and gluconic acid; dicarboxylic acids such as oxalic acid, maleic acid, malonic acid, malic acid, tartaric acid, and succinic acid; Examples include carboxylic acid salts having a number of 3, such as citric acid.
第１工程では、原料混合物中のＣｕ、Ｃａ及びＶの各原子モル比が、前記一般式（１）で表される銅バナジウム複合酸化物の組成となるように適宜、Ｃｕ源、Ｃａ源及びＶ源の混合量を調製することが好ましい。 In the first step, the Cu source, Ca source and It is preferable to adjust the mixing amount of the V source.
第１工程では、Ｃｕ源、Ｃａ源及びＶ源の混合処理を、湿式又は乾式で行うことができるが、均一な原料混合物を容易に得ることができるという点で、湿式で混合処理を行うことが好ましい。湿式混合処理を行う方法としては、Ｃｕ源、Ｃａ源及びＶ源が不溶性又は難溶性の溶媒を用いて行うことが、原料混合物として均一に分散させたものが得られ易く、このためＸ線回折的に単相の一般式（１）で表される銅バナジウム複合酸化物が得られ易い点で、好ましい。湿式混合処理に用いられる溶媒としては、Ｃｕ源、Ｃａ源及びＶ源の種類によっても異なるが、水、メタノール、エタノール等が挙げられる。また、Ｃｕ源
、Ｃａ源、Ｖ源の平均粒子径は、反応性が高くなる点で、レーザー回折法により求められる平均粒子径（Ｄ５０）で、５０μｍ以下が好ましく、０．１～４０μｍが特に好ましい。
In the first step, the Cu source, Ca source, and V source can be mixed in a wet or dry manner, but it is preferable to perform the mixing treatment in a wet manner because a uniform raw material mixture can be easily obtained. is preferred. As for the wet mixing treatment, it is best to use a solvent in which the Cu source, Ca source, and V source are insoluble or poorly soluble, because it is easier to obtain a uniformly dispersed raw material mixture, and therefore X-ray diffraction This method is preferable in that it is easy to obtain a single-phase copper-vanadium composite oxide represented by the general formula (1). Examples of the solvent used in the wet mixing process include water, methanol, ethanol, etc., although they differ depending on the types of Cu source, Ca source, and V source. In addition, the average particle diameter of the Cu source, Ca source, and V source is preferably 50 μm or less, particularly 0.1 to 40 μm, in terms of the average particle diameter (D50) determined by laser diffraction method, since the reactivity becomes high. preferable.
また、湿式混合処理を行う装置としては、各原料が均一に分散したスラリーが得られれば、特に制限はない。また、スラリーの調製において、必要により、スラリーをメディアミルで湿式粉砕処理することができる。メディアミルとしては、ビーズミル、ボールミル、ペイントシェーカー、アトライタ、サンドミル等のメディアミルが挙げられる。また、実験室レベルの少量の場合は、乳鉢等を用いて湿式混合処理を行ってもよい。
また、湿式混合処理を一層効率的に行う観点から、スラリーに、分散剤を混合してもよい。スラリーに混合させる分散剤としては、各種の界面活性剤、ポリカルボン酸アンモニウム塩等が挙げられる。スラリー中の分散剤の濃度は、分散効果が高くなる点で、好ましくは０．０１～１０質量％、特に好ましくは０．１～５質量％である。
Further, there is no particular restriction on the equipment for performing the wet mixing process as long as a slurry in which each raw material is uniformly dispersed can be obtained. Further, in preparing the slurry, the slurry can be wet-pulverized using a media mill, if necessary. Examples of the media mill include a bead mill, a ball mill, a paint shaker, an attritor, and a sand mill. In addition, in the case of a small amount at a laboratory level, a wet mixing process may be performed using a mortar or the like.
Further, from the viewpoint of performing wet mixing treatment more efficiently, a dispersant may be mixed into the slurry. Examples of the dispersant to be mixed into the slurry include various surfactants, polycarboxylic acid ammonium salts, and the like. The concentration of the dispersant in the slurry is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 5% by mass, from the viewpoint of increasing the dispersion effect.
湿式混合処理後に全量乾燥して溶媒を除去することにより、原料混合物を得ることができる。 A raw material mixture can be obtained by drying the entire amount after the wet mixing treatment to remove the solvent.
また、第１工程では、Ｃｕ源、Ｃａ源及びＶ源を水溶媒に溶解させた後に、水溶媒を除去することにより、原料混合物を得ることもできる。この場合、Ｃｕ源、Ｃａ源及びＶ源として、水溶媒に溶解するものを用いればよい。水溶媒に溶解するＣｕ源としては、例えば、有機カルボン酸の銅塩、鉱酸の銅塩等が挙げられる。また、水溶媒に溶解するＣａ源としては、例えば、有機カルボン酸のカルシウム塩、炭酸塩、水酸化物等が挙げられる。
水溶媒に溶解するＶ源としては、バナジウム酸及びそのナトリウム塩、カリウム塩、アンモニウム塩、カルボン酸塩等が挙げられる。
Moreover, in the first step, a raw material mixture can also be obtained by dissolving the Cu source, Ca source, and V source in a water solvent and then removing the water solvent. In this case, as the Cu source, Ca source, and V source, those soluble in the water solvent may be used. Examples of the Cu source that dissolves in the water solvent include copper salts of organic carboxylic acids, copper salts of mineral acids, and the like. Furthermore, examples of the Ca source that dissolves in the water solvent include calcium salts, carbonates, and hydroxides of organic carboxylic acids.
Examples of the V source that dissolves in an aqueous solvent include vanadate and its sodium salt, potassium salt, ammonium salt, carboxylate salt, and the like.
第１工程において、Ｖ源としてカルボン酸のバナジウム塩を用いる場合、水溶媒に五酸化バナジウム、還元剤及びカルボン酸を添加し、６０～１００℃で加熱処理してカルボン酸のバナジウム塩を生成させ、この反応液をそのまま用いて、Ｃｕ源及びＣａ源を混合して、Ｃｕ源、Ｃａ源及びＶ源を含有する原料混合液を得、次いで、該原料混合液から水溶媒を除去して、原料混合物を調製してもよい。 In the first step, when a vanadium salt of a carboxylic acid is used as a V source, vanadium pentoxide, a reducing agent, and a carboxylic acid are added to an aqueous solvent, and the vanadium salt of a carboxylic acid is generated by heat treatment at 60 to 100°C. Using this reaction solution as it is, mix a Cu source and a Ca source to obtain a raw material mixture containing a Cu source, a Ca source, and a V source, and then remove the water solvent from the raw material mixture, A raw material mixture may also be prepared.
還元剤としては、還元糖が好ましく、還元糖としては、例えば、グルコース、フルクトース、ラクトース、マルトース、スクロース等が挙げられ、このうち、ラクトース、スクロースが、優れた反応性を有するという観点から特に好ましい。還元糖の添加量は、五酸化バナジウム中のＶに対する還元糖中のＣのモル比（Ｃ／Ｖ）で、好ましくは０．７～３．０であり、効率的に還元反応を行うことができる点で、より好ましくは０．８～２．０である。カルボン酸の添加量は、五酸化バナジウムに対するモル比で、好ましくは０．１～４．０であり、効率的に透明なバナジウム溶解液を得ることができる点で、より好ましくは０．２～３．０である。 As the reducing agent, reducing sugars are preferable, and examples of the reducing sugars include glucose, fructose, lactose, maltose, sucrose, etc. Among these, lactose and sucrose are particularly preferable from the viewpoint of having excellent reactivity. . The amount of reducing sugar added is the molar ratio (C/V) of C in the reducing sugar to V in vanadium pentoxide, which is preferably 0.7 to 3.0, so that the reduction reaction can be carried out efficiently. More preferably, it is 0.8 to 2.0. The amount of carboxylic acid added is preferably 0.1 to 4.0 in terms of molar ratio to vanadium pentoxide, and more preferably 0.2 to 4.0 in terms of efficiently obtaining a transparent vanadium solution. It is 3.0.
なお、第１工程において、湿式混合処理後に全量乾燥して溶媒を除去して得られる前記一般式（１）で表される銅バナジウム複合酸化物の組成は、各原料仕込み時のＣｕ源、Ｃａ源及びＶ源中のＣｕ、Ｃａ及びＶの原子モル比とほぼ一致する。 In addition, in the first step, the composition of the copper vanadium composite oxide represented by the general formula (1) obtained by drying the entire amount after wet mixing treatment and removing the solvent is based on the Cu source, Ca The atomic molar ratios of Cu, Ca and V in the source and the V source almost match.
第２工程は、第１工程で調製した原料混合物を焼成して、本発明の負熱膨張材を得る工程である。 The second step is a step of firing the raw material mixture prepared in the first step to obtain the negative thermal expansion material of the present invention.
第２工程における焼成温度は、好ましくは５８０～７８０℃、より好ましくは６００～７５０℃である。一方、第２工程における焼成温度が、上記範囲未満だと、前記一般式（１）で表される銅バナジウム複合酸化物の生成が不十分となる傾向があり、また、上記範囲を超えると、坩堝等への融着により生成物の回収が困難になる傾向がある。第２工程における焼成時間は、特に制限されず、本発明の負熱膨張材が生成するまで十分な時間焼成を行う。 The firing temperature in the second step is preferably 580 to 780°C, more preferably 600 to 750°C. On the other hand, if the firing temperature in the second step is less than the above range, the production of the copper vanadium composite oxide represented by the general formula (1) tends to be insufficient, and if it exceeds the above range, Recovery of the product tends to be difficult due to fusion to the crucible or the like. The firing time in the second step is not particularly limited, and firing is performed for a sufficient time until the negative thermal expansion material of the present invention is produced.
本発明の負熱膨張材の生成については、例えば、Ｘ線回折分析で単相の一般式（１）で表される銅バナジウム複合酸化物が得られているかどうかで、本発明の負熱膨張材の生成を確認することができる。なお、本発明において単相であるとは、一般式（１）で表される銅バナジウム複合酸化物のＺｉｅｓｉｔｅ相（β相）が単独で存在すること、Ｂｌｏｓｓｉｔｅ相（α相）が単独で存在すること、あるいは、Ｚｉｅｓｉｔｅ相（β相）とＢｌｏｓｓｉｔｅ相（α相）の混相で存在していることを指し、Ｘ線回析的に、一般式（１）で表される銅バナジウム複合酸化物以外の回析ピークが検出されないことを意味する。 Regarding the production of the negative thermal expansion material of the present invention, for example, whether or not a single-phase copper vanadium composite oxide represented by the general formula (1) is obtained by X-ray diffraction analysis is determined. You can check the production of materials. In addition, in the present invention, being a single phase means that the Ziesite phase (β phase) of the copper vanadium composite oxide represented by the general formula (1) exists alone, and the Blossite phase (α phase) exists alone. or exists as a mixed phase of Ziesite phase (β phase) and Blossite phase (α phase). This means that no other diffraction peaks are detected.
第２工程では、多くの場合、焼成時間が１時間以上、好ましくは２～２０時間で、原料混合物のほぼ全てが、前記一般式（１）で表される銅バナジウム複合酸化物からなる負熱膨張材となる。 In the second step, the firing time is often 1 hour or more, preferably 2 to 20 hours, and almost all of the raw material mixture is made of the copper-vanadium composite oxide represented by the above general formula (1) using negative heat. Becomes an expanding material.
第２工程における焼成雰囲気は、特に制限されず、不活性ガス雰囲気下、真空雰囲気下、酸化性ガス雰囲気下、大気中のいずれであってもよい。 The firing atmosphere in the second step is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and the air.
第２工程では、焼成を１回行ってもよいし、所望により複数回行ってもよい。例えば、粉体特性を均一にする目的で、一度焼成したものを粉砕し、粉砕物について更に焼成を行ってもよい。 In the second step, firing may be performed once or multiple times as desired. For example, in order to make the powder properties uniform, the fired product may be ground, and the ground material may be further fired.
焼成後、適宜冷却し、必要に応じ粉砕、解砕、分級等を行い、目的とする負熱膨張材を得る。 After firing, it is appropriately cooled, and if necessary, pulverization, crushing, classification, etc. are performed to obtain the desired negative thermal expansion material.
また、前記一般式（１）で表される銅バナジウム複合酸化物に、更にリンを固溶させて含有させた負熱膨張材を製造するには、前記第１工程において、Ｃｕ源、Ｃａ源及びＶ源に加えてＰ源を添加して混合し原料混合物を調製し、次いで前記第２工程を行うことにより製造することができる。
Ｐ源としては、リン酸が好ましい。
第１工程におけるＰ源の添加量は、Ｖ源中のＶ原子に対するＰ源中のＰ原子のモル比（Ｐ／Ｖ）で０．０より大きく０．３以下、好ましくは０．０より大きく０．２以下である。
In addition, in order to produce a negative thermal expansion material in which the copper vanadium composite oxide represented by the general formula (1) further contains phosphorus as a solid solution, in the first step, a Cu source, a Ca source, It can be produced by adding and mixing a P source in addition to a V source to prepare a raw material mixture, and then performing the second step.
As the P source, phosphoric acid is preferred.
The amount of P source added in the first step is the molar ratio (P/V) of P atoms in the P source to V atoms in the V source, which is greater than 0.0 and less than or equal to 0.3, preferably greater than 0.0. It is 0.2 or less.
粒子形状が球状である負熱膨張材を製造する方法としては、前記第１工程において湿式混合処理後の全量乾燥を、スプレードライヤーによる噴霧乾燥法を用いて行うことにより、湿式混合処理後のスラリーを乾燥処理し、次いで前記第２工程を行うことにより、球形度が０．７０以上１．００以下の球状粒子の含有率が、個数基準で７５％以上、好ましくは８０％以上である負熱膨張材を製造する方法が挙げられる。
噴霧乾燥法において、霧化された液滴の大きさは特に限定されないが、１～４０μｍが好ましく、５～３０μｍが特に好ましい。スプレードライヤーへのスラリーの供給量は、この観点を考慮して決定することが好ましい。
なお、スプレードライヤーにおいて乾燥のために用いる熱風の温度は、１００～２７０℃、好ましくは１５０～２３０℃であることが、粉体の吸湿を防ぎ粉体の回収が容易になることから好ましい。
As a method for producing a negative thermal expansion material having a spherical particle shape, in the first step, the entire amount after the wet mixing treatment is dried using a spray drying method using a spray dryer, so that the slurry after the wet mixing treatment is dried. by drying and then performing the second step, the content of spherical particles with a sphericity of 0.70 or more and 1.00 or less is 75% or more, preferably 80% or more based on the number of particles. Examples include methods for manufacturing an intumescent material.
In the spray drying method, the size of the atomized droplets is not particularly limited, but is preferably 1 to 40 μm, particularly preferably 5 to 30 μm. The amount of slurry supplied to the spray dryer is preferably determined in consideration of this point of view.
The temperature of the hot air used for drying in the spray dryer is preferably 100 to 270°C, preferably 150 to 230°C, since this prevents moisture absorption of the powder and facilitates recovery of the powder.
本発明の負熱膨張材の製造方法により得られる一般式（１）で表される銅バナジウム複合酸化物からなる負熱膨張材の平均粒子径は、好ましくは０．１～１００μｍ、特に好ましくは０．２～８０μｍであり、また、ＢＥＴ比表面積は、０．０５～５０ｍ２／ｇ、特に好ましくは０．１０～１０ｍ２／ｇである。負熱膨張材の平均粒子径及び／又はＢＥＴ比表面積が、上記範囲にあることが、負熱膨張材を樹脂やガラス等へのフィラー用として用いる際に、取扱いが容易になる点で好ましい。 The average particle diameter of the negative thermal expansion material made of a copper vanadium composite oxide represented by the general formula (1) obtained by the method for producing a negative thermal expansion material of the present invention is preferably 0.1 to 100 μm, particularly preferably 0.2 to 80 μm, and the BET specific surface area is 0.05 to 50 m 2 /g, particularly preferably 0.10 to 10 m 2 /g. It is preferable that the average particle diameter and/or BET specific surface area of the negative thermal expansion material be within the above ranges because handling becomes easy when the negative thermal expansion material is used as a filler for resin, glass, etc.
また、本発明に係る負熱膨張材は、樹脂分散性や負熱膨張材の耐湿性を向上させることを目的として、必要により粒子表面が、表面処理が施されていてもよい。また、本発明に係る負熱膨張材の製造方法は、樹脂分散性や負熱膨張材の耐湿性を向上させることを目的として、必要により、第２工程を行い得られる負熱膨張材に対し、表面処理を施してもよい。 Further, the negative thermal expansion material according to the present invention may be subjected to surface treatment on the particle surface, if necessary, for the purpose of improving resin dispersibility and moisture resistance of the negative thermal expansion material. In addition, in the method for producing a negative thermal expansion material according to the present invention, for the purpose of improving the resin dispersibility and the moisture resistance of the negative thermal expansion material, the negative thermal expansion material obtained by performing a second step, if necessary, is provided. , surface treatment may be performed.
表面処理としては、例えば、シランカップリング剤、チタネート系カップリング剤、脂肪酸又はその誘導体、Ｚｎ、Ｓｉ、Ａｌ、Ｂａ、Ｃａ、Ｍｇ、Ｔｉ、Ｖ、Ｓｎ、Ｃｏ、Ｆｅ及びＺｒから選ばれる元素を１種又は２種以上含有する無機化合物等で粒子表面を被覆処理する方法等が挙げられる（例えば、ＷＯ２０２０／０９５８３７号パンフレット。ＷＯ２０２０／２６１９７６号パンフレット、ＷＯ２０１９／０８７７２２号パンフレット、特開２０２０―１４７４８６号公報参照）。また、これらを適宜組み合わせて表面処理を行ってもよい。 As surface treatment, for example, a silane coupling agent, a titanate coupling agent, a fatty acid or a derivative thereof, an element selected from Zn, Si, Al, Ba, Ca, Mg, Ti, V, Sn, Co, Fe, and Zr. (For example, WO2020/095837 pamphlet. WO2020/261976 pamphlet, WO2019/087722 pamphlet. (see publication). Further, the surface treatment may be performed by appropriately combining these.
本発明の負熱膨張材の製造方法を行い得られる負熱膨張材の熱膨張係数は、－１０．０×１０－６／Ｋ以下、好ましくは－１２．０×１０－６／Ｋ以下であり、下限値については概ね－５０．０×１０－６／Ｋ以上、好ましくは－４０．０×１０－６／Ｋ以上である。本発明の負熱膨張材の製造方法を行い得られる負熱膨張材の熱膨張係数、正熱膨張材と複合させたときに熱膨張係数が正の膨張を相殺させ易くなる点で、特に好ましくは－５０．０×１０－６～－１０．０×１０－６／Ｋである。 The thermal expansion coefficient of the negative thermal expansion material obtained by the method for producing a negative thermal expansion material of the present invention is -10.0×10 -6 /K or less, preferably -12.0×10 -6 /K or less. The lower limit is approximately −50.0×10 −6 /K or more, preferably −40.0×10 −6 /K or more. The thermal expansion coefficient of the negative thermal expansion material obtained by the method for producing a negative thermal expansion material of the present invention is particularly preferable in that the thermal expansion coefficient easily offsets the positive expansion when combined with a positive thermal expansion material. is −50.0×10 −6 to −10.0×10 −6 /K.
本発明の負熱膨張材は、粉体又はペーストとして用いられる。本発明の負熱膨張材をペーストとして用いる場合には、本発明の負熱膨張材を、溶媒及び／又は粘性の低い液状樹脂に混合及び分散させ、ペーストの状態で用いる。また、本発明の負熱膨張材を、溶媒及び／又は粘性の低い液状樹脂に分散させ、更に必要により、バインダー、フラックス材及び分散剤等を含有させて、ペーストの状態で用いてもよい。 The negative thermal expansion material of the present invention is used in the form of powder or paste. When using the negative thermal expansion material of the present invention as a paste, the negative thermal expansion material of the present invention is mixed and dispersed in a solvent and/or a liquid resin with low viscosity, and used in the form of a paste. Further, the negative thermal expansion material of the present invention may be used in the form of a paste by dispersing it in a solvent and/or a liquid resin with low viscosity, and further containing a binder, a flux material, a dispersant, etc., if necessary.
本発明の負熱膨張材は、正熱膨張材として、各種有機化合物又は無機化合物と併用され、複合材料として用いられる。本発明の複合材料は、本発明の負熱膨張材と、正熱膨張材と、を含む。 The negative thermal expansion material of the present invention is used as a positive thermal expansion material in combination with various organic compounds or inorganic compounds to form a composite material. The composite material of the present invention includes the negative thermal expansion material of the present invention and the positive thermal expansion material.
正熱膨張材として用いられる有機化合物としては、特に限定されないが、ゴム、ポリオレフィン、ポリシクロオレフィン、ポリスチレン、ＡＢＳ、ポリアクリレート、ポリフェニレンスルファイド、フェノール樹脂、ポリアミド樹脂、ポリイミド樹脂、エポキシ樹脂、シリコーン樹脂、ポリカーボネート樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリエチレンテレフタラート樹脂（ＰＥＴ樹脂）及びポリ塩化ビニル樹脂などを挙げられる。また、正熱膨張材として用いられる無機化合物としては、二酸化ケイ素、珪酸塩、グラファイト、サファイア、各種のガラス材料、コンクリート材料、各種のセラミック材料などが挙げられる。 Organic compounds used as positive thermal expansion materials include, but are not limited to, rubber, polyolefin, polycycloolefin, polystyrene, ABS, polyacrylate, polyphenylene sulfide, phenol resin, polyamide resin, polyimide resin, epoxy resin, and silicone resin. , polycarbonate resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin (PET resin), and polyvinyl chloride resin. Examples of inorganic compounds used as positive thermal expansion materials include silicon dioxide, silicates, graphite, sapphire, various glass materials, concrete materials, and various ceramic materials.
本発明の複合材料は、負熱膨張特性に優れる本発明の負熱膨張材を含んでいるため、他の化合物との配合比率によって、負熱膨張率、零熱膨張率又は低熱膨張率を実現することが可能である。 Since the composite material of the present invention contains the negative thermal expansion material of the present invention that has excellent negative thermal expansion characteristics, it can achieve a negative thermal expansion coefficient, zero thermal expansion coefficient, or low thermal expansion coefficient depending on the blending ratio with other compounds. It is possible to do so.
以下、本発明を実施例により説明するが、本発明はこれらに限定されるわけではない。 EXAMPLES Hereinafter, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.
（実施例１）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１．７３ｇ、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１．５１ｇ、炭酸カルシウム（ＣａＣＯ３：平均粒子径２．４μｍ）０．０３ｇを計量し、エタノール３０ｍｌを分散媒として乳鉢で２０分間粉砕混合した後、全量乾燥して原料混合物を得た。この原料混合物を大気下で、７００℃で４時間焼成して焼成品を得た。得られた焼成品をＸ線回折分析したところ、２θ＝２５°付近にメインの回折ピークを持つＺｉｅｓｉｔｅ相の単相の銅バナジウム複合酸化物（Ｃｕ２．００Ｃａ０．０３）Ｖ２．００Ｏ７．００を得た。焼成品のＸ線回折図を図１に示す。
次いで、焼成品を乳鉢で粉砕処理し、これを負熱膨張材試料とした。
なお、この負熱膨張材試料を電子顕微鏡観察（倍率４００）で任意に抽出した粒子５０個について観察した結果、粒子形状は破砕状であった。
(Example 1)
Vanadium pentoxide (V 2 O 5 : average particle size 1.0 μm) 1.73 g, copper oxide (CuO: average particle size 1.5 μm) 1.51 g, calcium carbonate (CaCO 3 : average particle size 2.4 μm) 0 After weighing 0.03 g and pulverizing and mixing in a mortar for 20 minutes using 30 ml of ethanol as a dispersion medium, the entire amount was dried to obtain a raw material mixture. This raw material mixture was baked at 700° C. for 4 hours in the atmosphere to obtain a baked product. X-ray diffraction analysis of the obtained fired product revealed that it was a single-phase copper-vanadium composite oxide (Cu 2.00 Ca 0.03 ) V 2.00 with a main diffraction peak near 2θ=25°. O 7.00 was obtained. The X-ray diffraction diagram of the fired product is shown in FIG.
Next, the fired product was pulverized in a mortar and used as a negative thermal expansion material sample.
In addition, as a result of observing 50 randomly extracted particles of this negative thermal expansion material sample using an electron microscope (magnification: 400), the particle shape was found to be crushed.
（実施例２）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１．７３ｇ、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１．５１ｇ、炭酸カルシウム（ＣａＣＯ３：平均粒子径２．４μｍ）０．１９０ｇを計量し、エタノール３０ｍｌを分散媒として乳鉢で２０分間粉砕混合した後、全量乾燥して原料混合物を得た。この原料混合物を大気下で、７００℃で４時間焼成して焼成品を得た。得られた焼成品をＸ線回折分析したところ、２θ＝２５°付近にメインの回折ピークを持つＣｕ２Ｖ２Ｏ７のＺｉｅｓｉｔｅ相及び２θ＝２７°付近にメインの回析ピークを持つＢｌｏｓｓｉｔｅ相が検出される銅バナジウム複合酸化物（Ｃｕ２．００Ｃａ０．２０）Ｖ２．００Ｏ７．００を得た。焼成品のＸ線回折図を図２に示す。
次いで、焼成品を乳鉢で粉砕処理し、これを負熱膨張材試料とした。
なお、この負熱膨張材試料を電子顕微鏡観察（倍率４００）で任意に抽出した粒子５０個について観察した結果、粒子形状は破砕状であった。
(Example 2)
Vanadium pentoxide (V 2 O 5 : average particle size 1.0 μm) 1.73 g, copper oxide (CuO: average particle size 1.5 μm) 1.51 g, calcium carbonate (CaCO 3 : average particle size 2.4 μm) 0 .190 g was weighed out, pulverized and mixed in a mortar for 20 minutes using 30 ml of ethanol as a dispersion medium, and then the entire amount was dried to obtain a raw material mixture. This raw material mixture was baked at 700° C. for 4 hours in the atmosphere to obtain a baked product. X-ray diffraction analysis of the obtained fired product revealed a Ziesite phase of Cu 2 V 2 O 7 with a main diffraction peak around 2θ = 25° and a Blossite phase with a main diffraction peak around 2θ = 27°. A copper vanadium composite oxide (Cu 2.00 Ca 0.20 ) V 2.00 O 7.00 in which is detected was obtained. The X-ray diffraction diagram of the fired product is shown in FIG.
Next, the fired product was pulverized in a mortar and used as a negative thermal expansion material sample.
In addition, as a result of observing 50 randomly extracted particles of this negative thermal expansion material sample using an electron microscope (magnification: 400), the particle shape was found to be crushed.
（実施例３）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１．７６ｇ、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１．５１ｇ、炭酸カルシウム（ＣａＣＯ３：平均粒子径２．４μｍ）０．０３ｇを計量し、エタノール３０ｍｌを分散媒として乳鉢で２０分間粉砕混合した後、全量乾燥して原料混合物を得た。この原料混合物を大気下で、７００℃で４時間焼成して焼成品を得た。得られた焼成品をＸ線回折分析したところ、２θ＝２５°付近にメインの回折ピークを持つＣｕ２Ｖ２Ｏ７のＺｉｅｓｉｔｅ相及び２θ＝２７°付近にメインの回析ピークを持つＢｌｏｓｓｉｔｅ相が検出される銅バナジウム複合酸化物（Ｃｕ１．９７Ｃａ０．０３）Ｖ２．００Ｏ７．００を得た。焼成品のＸ線回折図を図３に示す。
次いで、焼成品を乳鉢で粉砕処理し、これを負熱膨張材試料とした。
なお、この負熱膨張材試料を電子顕微鏡観察（倍率４００）で任意に抽出した粒子５０個について観察した結果、粒子形状は破砕状であった。
(Example 3)
Vanadium pentoxide (V 2 O 5 : average particle size 1.0 μm) 1.76 g, copper oxide (CuO: average particle size 1.5 μm) 1.51 g, calcium carbonate (CaCO 3 : average particle size 2.4 μm) 0 After weighing 0.03 g and pulverizing and mixing in a mortar for 20 minutes using 30 ml of ethanol as a dispersion medium, the entire amount was dried to obtain a raw material mixture. This raw material mixture was baked at 700° C. for 4 hours in the atmosphere to obtain a baked product. X-ray diffraction analysis of the obtained fired product revealed a Ziesite phase of Cu 2 V 2 O 7 with a main diffraction peak around 2θ = 25° and a Blossite phase with a main diffraction peak around 2θ = 27°. A copper vanadium composite oxide (Cu 1.97 Ca 0.03 ) V 2.00 O 7.00 in which is detected was obtained. The X-ray diffraction diagram of the fired product is shown in FIG.
Next, the fired product was pulverized in a mortar and used as a negative thermal expansion material sample.
In addition, as a result of observing 50 randomly extracted particles of this negative thermal expansion material sample using an electron microscope (magnification: 400), the particle shape was found to be crushed.
（実施例４）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）２．０４ｇ、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１．５１ｇ、炭酸カルシウム（ＣａＣＯ３：平均粒子径２．４μｍ）０．３４ｇを計量し、エタノール３０ｍｌを分散媒として乳鉢で２０分間粉砕混合した後、全量乾燥して原料混合物を得た。この原料混合物を大気下で、７００℃で４時間焼成して焼成品を得た。得られた焼成品をＸ線回折分析したところ、２θ＝２５°付近にメインの回折ピークを持つＣｕ２Ｖ２Ｏ７のＺｉｅｓｉｔｅ相及び２θ＝２７°付近にメインの回析ピークを持つＢｌｏｓｓｉｔｅ相が検出される銅バナジウム複合酸化物（Ｃｕ１．７０Ｃａ０．３０）Ｖ２．００Ｏ７．００を得た。焼成品のＸ線回折図を図４に示す。
次いで、焼成品を乳鉢で粉砕処理し、これを負熱膨張材試料とした。
なお、この負熱膨張材試料を電子顕微鏡観察（倍率４００）で任意に抽出した粒子５０個について観察した結果、粒子形状は破砕状であった。
(Example 4)
Vanadium pentoxide (V 2 O 5 : average particle size 1.0 μm) 2.04 g, copper oxide (CuO: average particle size 1.5 μm) 1.51 g, calcium carbonate (CaCO 3 : average particle size 2.4 μm) 0 .34 g was weighed, pulverized and mixed in a mortar for 20 minutes using 30 ml of ethanol as a dispersion medium, and then the entire amount was dried to obtain a raw material mixture. This raw material mixture was baked at 700° C. for 4 hours in the atmosphere to obtain a baked product. X-ray diffraction analysis of the obtained fired product revealed a Ziesite phase of Cu 2 V 2 O 7 with a main diffraction peak around 2θ = 25° and a Blossite phase with a main diffraction peak around 2θ = 27°. A copper vanadium composite oxide (Cu 1.70 Ca 0.30 ) V 2.00 O 7.00 in which is detected was obtained. The X-ray diffraction diagram of the fired product is shown in FIG.
Next, the fired product was pulverized in a mortar and used as a negative thermal expansion material sample.
In addition, as a result of observing 50 randomly extracted particles of this negative thermal expansion material sample using an electron microscope (magnification: 400), the particle shape was found to be crushed.
（比較例１）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１．７１ｇ、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１．５０ｇ、エタノール３０ｍｌを分散媒として乳鉢で２０分間粉砕混合した後、乾燥して原料混合物を得た。この粉末を大気下で、７００℃で４時間焼成して焼成品を得た。得られた焼成品をＸ線回折分析したところ、２θ＝２７°付近にメインの回析ピークを持つＣｕ２Ｖ２Ｏ７のＢｌｏｓｓｉｔｅ相の単相が検出された。焼成品のＸ線回折図を図５に示す。
次いで、焼成品を乳鉢で粉砕処理し、これを負熱膨張材試料とした。
なお、この負熱膨張材試料を電子顕微鏡観察（倍率４００）任意に抽出した粒子５０個について観察した結果、粒子形状は破砕状であった。
(Comparative example 1)
After pulverizing and mixing in a mortar for 20 minutes using 1.71 g of vanadium pentoxide (V 2 O 5 : average particle size 1.0 μm), 1.50 g copper oxide (CuO: average particle size 1.5 μm), and 30 ml of ethanol as a dispersion medium, , and dried to obtain a raw material mixture. This powder was fired at 700° C. for 4 hours in the atmosphere to obtain a fired product. When the obtained fired product was subjected to X-ray diffraction analysis, a single phase of the Blossite phase of Cu 2 V 2 O 7 having a main diffraction peak near 2θ=27° was detected. The X-ray diffraction diagram of the fired product is shown in FIG.
Next, the fired product was pulverized in a mortar and used as a negative thermal expansion material sample.
In addition, as a result of observing 50 arbitrarily extracted particles of this negative thermal expansion material sample using an electron microscope (magnification: 400), the particle shape was found to be crushed.
（物性評価）
実施例及び比較例で得られた負熱膨張材試料について、平均粒子径、ＢＥＴ比表面積及び熱膨張係数を測定した。なお、平均粒子径及び熱膨張係数は下記のようにして測定した。その結果を表１に示す。
(Evaluation of the physical properties)
The average particle diameter, BET specific surface area, and thermal expansion coefficient of the negative thermal expansion material samples obtained in Examples and Comparative Examples were measured. In addition, the average particle diameter and thermal expansion coefficient were measured as follows. The results are shown in Table 1.
（平均粒子径）
負熱膨張材試料を、走査型電子顕微鏡で倍率１０００倍で観察し、観察視野から、任意に抽出した粒子２０個の最長径を測定し、それらの算術平均値を、負熱膨張材試料の平均粒子径として求めた。
(Average particle size)
Observe the negative thermal expansion material sample with a scanning electron microscope at a magnification of 1000 times, measure the longest diameter of 20 arbitrarily extracted particles from the observation field, and calculate the arithmetic mean value of them. It was determined as an average particle diameter.
（熱膨張係数の測定）
＜成型体の作製＞
試料１．００ｇにプロピレンカーボネート０．０５ｇを加えて乳鉢で３分間粉砕混合した後、０．１５ｇを計量し、φ６ｍｍの金型に全量充填した。次いで、ハンドプレスを用いて、０．５ｔの圧力で成型して粉末成型体を作製した。得られた粉末成型体を電気炉にて７００℃まで３時間で昇温し４時間保持してセラミック成型体を作製した。
＜熱膨張係数の測定＞
作製したセラミック成形体について、熱機械測定装置（ＮＥＴＺＳＣＨ ＪＡＰＡＮ製 ＴＭＡ４０００ＳＥ）を用いて熱膨張係数を測定した。測定条件を、窒素雰囲気、荷重１０ｇ、温度範囲５０℃～４２５℃と、繰り返し２回測定した。繰り返し２回目の測定の５０～４００℃間での熱膨張係数を、負熱膨張材試料の熱膨張係数とした。
(Measurement of thermal expansion coefficient)
<Preparation of molded body>
After adding 0.05 g of propylene carbonate to 1.00 g of the sample and pulverizing and mixing in a mortar for 3 minutes, 0.15 g was weighed and the entire amount was filled into a φ6 mm mold. Next, a powder molded body was produced by molding using a hand press at a pressure of 0.5 t. The temperature of the obtained powder molded body was raised to 700° C. over 3 hours in an electric furnace and held for 4 hours to produce a ceramic molded body.
<Measurement of thermal expansion coefficient>
The thermal expansion coefficient of the produced ceramic molded body was measured using a thermomechanical measuring device (TMA4000SE manufactured by NETZSCH JAPAN). The measurement conditions were a nitrogen atmosphere, a load of 10 g, and a temperature range of 50°C to 425°C, and the measurements were repeated twice. The thermal expansion coefficient between 50 and 400°C measured in the second repeated measurement was taken as the thermal expansion coefficient of the negative thermal expansion material sample.
なお、比較例１の負熱膨張材試料の５０～３００℃間での線膨張係数は－４．４×１０―６／Ｋであった。 Note that the linear expansion coefficient of the negative thermal expansion material sample of Comparative Example 1 between 50 and 300° C. was −4.4×10 −6 /K.
（実施例５）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１．７３ｇ、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１．５１ｇ、炭酸カルシウム（ＣａＣＯ３：平均粒子径２．４μｍ）０．０２９ｇ、８５質量％リン酸（Ｈ３ＰＯ４）０．０３３ｇを計量し、エタノール３０ｍｌを分散媒として乳鉢で２０分間粉砕混合した後、全量乾燥して原料混合物を得た。この原料混合物を大気下で、７００℃で４時間焼成して焼成品を得た。
得られた焼成品をＸ線回折分析したところ、２θ＝２７°付近にメインの回析ピークを持つＣｕ２Ｖ２Ｏ７のＢｌｏｓｓｉｔｅ相の単相が検出される銅バナジウム複合酸化物（Ｃｕ２．００Ｃａ０．０６）（Ｖ２．００Ｐ０．０６）Ｏ７．００を得た。
次いで、焼成品を乳鉢で粉砕処理し、これを負熱膨張材試料とした。
なお、この負熱膨張材試料を電子顕微鏡観察（倍率４００）で任意に抽出した粒子５０個について観察した結果、粒子形状は破砕状であった。
(Example 5)
Vanadium pentoxide (V 2 O 5 : average particle size 1.0 μm) 1.73 g, copper oxide (CuO: average particle size 1.5 μm) 1.51 g, calcium carbonate (CaCO 3 : average particle size 2.4 μm) 0 After weighing 0.033 g of 85% by mass phosphoric acid (H 3 PO 4 ) and pulverizing and mixing in a mortar for 20 minutes using 30 ml of ethanol as a dispersion medium, the entire amount was dried to obtain a raw material mixture. This raw material mixture was baked at 700° C. for 4 hours in the atmosphere to obtain a baked product.
When the obtained fired product was analyzed by X-ray diffraction, a single phase of the Blossite phase of Cu 2 V 2 O 7 with the main diffraction peak near 2θ = 27° was detected . .00 Ca 0.06 ) (V 2.00 P 0.06 )O 7.00 was obtained.
Next, the fired product was pulverized in a mortar and used as a negative thermal expansion material sample.
In addition, as a result of observing 50 randomly extracted particles of this negative thermal expansion material sample using an electron microscope (magnification: 400), the particle shape was found to be crushed.
（実施例６）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１６．６質量部、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１４．１質量部、炭酸カルシウム（ＣａＣＯ３：平均粒子径２．４μｍ）０．５質量部を計量し、純水６８．５質量部を分散媒として３０分間攪拌して３１．３質量％スラリーを調製した。
次いで、前記スラリーに分散剤としてポリカルボン酸アンモニウム塩を０．１質量部仕込み、スラリーを攪拌しながら、直径０．５ｍｍのジルコニアビーズを仕込んだ。次いで、前記スラリーをメディア攪拌型ビーズミルへ供給し、湿式粉砕を行った。湿式粉砕後の固形分の平均粒子径をレーザー回折・散乱法により求めたところ、０．５９μｍであった。
次いで、湿式粉砕処理後のスラリーを２２０℃に設定したスプレードライヤーに、３．３Ｌ／ｈの供給速度で供給して、噴霧乾燥を行い、原料混合物を得た。
次いで、原料混合物を７００℃で４時間大気中で焼成して焼成品を得た。焼成品を乳鉢で粉砕処理し、次いでジェットミルで粉砕を行い、粉砕物を得た。得られた粉砕物をＸ線回折分析したところ、粉砕物は２θ＝２５°付近にメインの回折ピークを持つＺｉｅｓｉｔｅ相の銅バナジウム複合酸化物（Ｃｕ１．９４Ｃａ０．０６）Ｖ２．００Ｏ７．００が確認された。これを負熱膨張材試料とした。
なお、この負熱膨張材試料を電子顕微鏡観察（倍率４００）で任意に抽出した粒子５０個について観察した結果、粒子形状は球状であった。
（物性評価）
実施例５～６で得られた負熱膨張材試料について、平均粒子径、ＢＥＴ比表面積及び熱膨張係数を測定した。なお、平均粒子径及び熱膨張係数を実施例１～４と同様に測定した。また、実施例６の負熱膨張材試料の負熱膨張材試料については、下記の方法で球形度を求めた。また、実施例６で得られた負熱膨張材試料のＳＥＭ写真を図６に示す。
（球形粒子の含有率の測定）
画像解析装置ルーゼックス（ニレコ社製）を用いて、倍率４００倍で任意に抽出した５０個の粒子について、以下の計算式により球形度を求め、個数基準で球形度が０．７０以上１．００以下である球形粒子の含有率を評価した。
球形度＝等面積円相当径／外接円径
等面積円相当径：粒子の周長に円周が相当する円の直径
外接円径：粒子の最長径
(Example 6)
Vanadium pentoxide ( V2O5 : average particle size 1.0 μm) 16.6 parts by mass, copper oxide (CuO: average particle size 1.5 μm) 14.1 parts by mass, calcium carbonate ( CaCO3 : average particle size 2) .4 μm) was weighed out and stirred for 30 minutes using 68.5 parts by mass of pure water as a dispersion medium to prepare a 31.3% by mass slurry.
Next, 0.1 part by mass of polycarboxylic acid ammonium salt as a dispersant was added to the slurry, and while stirring the slurry, zirconia beads having a diameter of 0.5 mm were added. Next, the slurry was supplied to a media stirring type bead mill and subjected to wet pulverization. The average particle diameter of the solid content after wet pulverization was determined by laser diffraction/scattering method, and was found to be 0.59 μm.
Next, the slurry after the wet pulverization treatment was supplied to a spray dryer set at 220° C. at a supply rate of 3.3 L/h to perform spray drying to obtain a raw material mixture.
Next, the raw material mixture was fired in the air at 700°C for 4 hours to obtain a fired product. The baked product was pulverized in a mortar and then pulverized in a jet mill to obtain a pulverized product. X-ray diffraction analysis of the obtained pulverized material revealed that the pulverized material was a Ziesite phase copper vanadium composite oxide (Cu 1.94 Ca 0.06 ) V 2.00 with a main diffraction peak near 2θ=25°. O 7.00 was confirmed. This was used as a negative thermal expansion material sample.
In addition, as a result of observing 50 randomly extracted particles of this negative thermal expansion material sample using an electron microscope (magnification: 400), the particle shape was spherical.
(Evaluation of the physical properties)
For the negative thermal expansion material samples obtained in Examples 5 and 6, the average particle diameter, BET specific surface area, and thermal expansion coefficient were measured. Note that the average particle diameter and thermal expansion coefficient were measured in the same manner as in Examples 1 to 4. Further, the sphericity of the negative thermal expansion material sample of Example 6 was determined by the following method. Further, a SEM photograph of the negative thermal expansion material sample obtained in Example 6 is shown in FIG.
(Measurement of content of spherical particles)
Using the image analysis device Luzex (manufactured by Nireco), the sphericity of 50 particles arbitrarily extracted at a magnification of 400 times is calculated using the following calculation formula, and the sphericity is 0.70 or more and 1.00 based on the number of particles. The following content of spherical particles was evaluated.
Sphericity = Equal area circle equivalent diameter / Circumscribed circle diameter Equal area circle equivalent diameter: Diameter of a circle whose circumference corresponds to the circumference of the particle Circumscribed circle diameter: The longest diameter of the particle
Claims (8)
ＣｕｘＣａｙＶｚＯｔ （１）
（式中、ｘは１．５０≦ｘ≦２．２０、ｙは０＜ｙ≦０．４０、ｚは１．７０≦ｚ≦２．３０、ｔは６．００≦ｔ≦９．００を示す。但し、１．５０＜ｘ＋ｙ≦２．６０である。）
で表される銅バナジウム複合酸化物からなり、該銅バナジウム複合酸化物はＣｕ２Ｖ２Ｏ７に起因するＺｉｅｓｉｔｅ相（β相）の単相又はＺｉｅｓｉｔｅ相（β相）とＢｌｏｓｓｉｔｅ相（α相）との混相の結晶構造を有することを特徴とする負熱膨張材。 General formula (1) below:
Cu x Ca y V z O t (1)
(In the formula, x is 1.50≦x≦2.20, y is 0<y≦0.40, z is 1.70≦z≦2.30, and t is 6.00≦t≦9.00. (However, 1.50 < x+y≦ 2.60 .)
The copper-vanadium composite oxide consists of a single Ziesite phase (β phase) or a Ziesite phase (β phase) and a Blossite phase (α phase) caused by Cu 2 V 2 O 7 . ) Negative thermal expansion material characterized by having a mixed phase crystal structure.
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