JP7410249B2 - Negative thermal expansion material, its manufacturing method and composite material - Google Patents
Negative thermal expansion material, its manufacturing method and composite material Download PDFInfo
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- JP7410249B2 JP7410249B2 JP2022161761A JP2022161761A JP7410249B2 JP 7410249 B2 JP7410249 B2 JP 7410249B2 JP 2022161761 A JP2022161761 A JP 2022161761A JP 2022161761 A JP2022161761 A JP 2022161761A JP 7410249 B2 JP7410249 B2 JP 7410249B2
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- thermal expansion
- negative thermal
- expansion material
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- 239000011135 tin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Description
本発明は、温度上昇に対して収縮する負熱膨張材、その製造方法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, a method for producing the same, 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"), which conversely decrease in volume 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).
また、下記特許文献６には、一般式：Ｃｕ２―ｘＲｘＶ２―ｙＭｙＯ７（ＲはＺｎ、Ｇａ、Ｆｅ、Ｓｎ、Ｍｎから選ばれる少なくとも１種の元素、ＭはＭｇ、Ｓｉ、Ａｌ、Ｔｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｓｎから選ばれる少なくとも１種の元素、０≦ｘ＜２、０＜ｙ＜２）で表される負熱膨張材が開示されている。 Furthermore, Patent Document 6 below describes the general formula: Cu 2-x R x V 2-y M y O 7 (R is at least one element selected from Zn, Ga, Fe, Sn, Mn, M is Mg Disclosed is a negative thermal expansion material represented by at least one element selected from , Si, Al, Ti, Cr, Mn, Fe, Co, Ni, and Sn, 0≦x<2, 0<y<2). ing.
しかしながら、特許文献６でＭ元素を含む負熱膨張材として実際に実施しているものは、Ｍ元素がＳｉとＭｎのみであり、よって、特許文献６において、Ｍ元素としてＡｌの例示は何ら技術的な根拠がないものである。 However, in Patent Document 6, the negative thermal expansion material containing the M element is actually implemented only with Si and Mn. There is no basis for this.
非特許文献１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可能性があり、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ていることから、更に、負熱膨張特性を向上させることも要求されている。 The copper vanadium composite oxide of Non-Patent Document 1 may have a smaller coefficient of linear expansion than zirconium tungstate phosphate, can be manufactured using cheaper raw materials, and can be manufactured industrially advantageously. Since it has excellent water resistance, it is also required to improve negative thermal expansion characteristics.
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。また、本発明は、工業的に有利な方法で該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. Another object of the present invention is to provide the negative thermal expansion material using an industrially advantageous method.
上記課題は、以下の本発明によって解決される。
すなわち、本発明（１）は、Ａｌ原子が固溶している下記一般式（１）：
ＣｕｘＭｙＶｚＯｔ （１）
（式中、ＭはＣｕ、Ｖ及びＡｌ以外の原子番号１１以上の金属元素を示す。ｘは１．６０≦ｘ≦２．４０、ｙは０．００≦ｙ≦０．４０、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。また、Ｍ元素を含有するときは、Ａｌ原子の原子換算のモル数＞Ｍ原子の原子換算のモル数である。）
で表される銅バナジウム複合酸化物粉体からなることを特徴とする負熱膨張材を提供するものである。
The above problems are solved by the following invention.
That is, the present invention (1) has the following general formula (1) in which an Al atom is solidly dissolved:
Cu x M y V z O t (1)
(In the formula, M represents a metal element with an atomic number of 11 or more other than Cu, V and Al. x is 1.60≦x≦2.40, y is 0.00≦y≦0.40, z is 1 .70≦z≦2.30, t indicates 6.00≦t≦9.00.However, 1.00≦x+y≦3.00.Also, when containing M element, the Al atom Number of moles in terms of atoms>Number of moles in terms of atoms of M atoms.)
The present invention provides a negative thermal expansion material comprising a copper-vanadium composite oxide powder represented by:
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、Ａｌ原子が固溶している下記一般式（１）：
ＣｕｘＭｙＶｚＯｔ （１）
（式中、ＭはＣｕ、Ｖ及びＡｌ以外の原子番号１１以上の金属元素を示す。ｘは１．６０≦ｘ≦２．４０、ｙは０．００≦ｙ≦０．４０、ｚは１．７０≦ｚ≦２．３０、ｔは６．００≦ｔ≦９．００を示す。但し、１．６０≦ｘ＋ｙ≦２．８０である。また、Ｍ元素を含有するときは、Ａｌ原子の原子換算のモル数＞Ｍ原子の原子換算のモル数である。）で表される銅バナジウム複合酸化物粉体からなり、前記バナジウム複合酸化物粉体は、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し、Ａｌ原子の含有量が、１０００～２６０００質量ｐｐｍであ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) in which Al atoms are dissolved in solid solution:
Cu x M y V z O t (1)
(In the formula, M represents a metal element with an atomic number of 11 or more other than Cu, V and Al. x is 1.60≦x≦2.40, y is 0.00≦y≦0.40, z is 1 .70≦z≦2.30, t indicates 6.00≦t≦9.00.However, 1.60 ≦x+y≦ 2.80.Also , when containing M element, the Al atom The vanadium composite oxide powder is composed of a copper vanadium composite oxide powder represented by the following formula: number of moles in terms of atoms> number of moles in terms of atoms of M atoms, and the vanadium composite oxide powder has a single phase of Ziesite phase (β phase). Alternatively, it is characterized by having a mixed phase crystal structure of Ziesite phase (β phase) and Blossite phase (α phase), and having an Al atom content of 1000 to 26000 ppm by mass .
Ａｌ原子を固溶させて含有させる銅バナジウム複合酸化物は、下記一般式（１）：
ＣｕｘＭｙＶｚＯｔ （１）
で表される銅バナジウム複合酸化物である。
The copper vanadium composite oxide containing Al atoms as a solid solution has the following general formula (1):
Cu x M y V z O t (1)
It is a copper vanadium composite oxide represented by
一般式（１）中、Ｍは負熱膨張性の向上、負熱特性の調整、樹脂分散性の改良等を目的として必要により含有させる金属元素である。ＭはＣｕ、Ｖ及びＡｌ以外の原子番号１１以上の金属元素を示し、Ｚｎ、Ｇａ、Ｆｅ、Ｍｇ、Ｃｏ、Ｍｎ、Ｂａ及びＣａから選ばれる１種又は２種以上であることが好ましく、特にＣａが優れた負熱膨張特性を有したものになる観点から好ましい。 In the general formula (1), M is a metal element that is included as necessary for the purpose of improving negative thermal expansion, adjusting negative thermal properties, improving resin dispersibility, etc. M represents a metal element with an atomic number of 11 or more other than Cu, V and Al, and is preferably one or more selected from Zn, Ga, Fe, Mg, Co, Mn, Ba and Ca, particularly Ca is preferable from the viewpoint of having excellent negative thermal expansion characteristics.
一般式（１）中、ｘは１．６０≦ｘ≦２．４０、好ましくは１．７０≦ｘ≦２．３０である。ｘが上記範囲にあることにより、負熱膨張特性がより高くなる。 In general formula (1), x is 1.60≦x≦2.40, preferably 1.70≦x≦2.30. When x is within the above range, the negative thermal expansion property becomes higher.
一般式（１）中、ｙは０．００≦ｙ≦０．４０、好ましくは０．００≦ｙ≦０．３５である。ｙが上記範囲にあることにより、負熱膨張特性がより高くなる。 In general formula (1), y is 0.00≦y≦0.40, preferably 0.00≦y≦0.35. When y is within the above range, the negative thermal expansion characteristics become higher.
一般式（１）中、ｚは１．７０≦ｚ≦２．３０、好ましくは１．８０≦ｚ≦２．２０である。ｚが上記範囲にあることにより、負熱膨張特性がより高くなる。 In general formula (1), z is 1.70≦z≦2.30, preferably 1.80≦z≦2.20. When z is within the above range, the negative thermal expansion property becomes higher.
一般式（１）中、ｔは６．００≦ｔ≦９．００、好ましくは６．００≦ｔ≦８．００である。ｔが上記範囲にあることにより、負熱膨張特性がより高くなる。 In general formula (1), t is 6.00≦t≦9.00, preferably 6.00≦t≦8.00. When t is within the above range, the negative thermal expansion property becomes higher.
一般式（１）中、ｘ＋ｙは１．００≦ｘ＋ｙ≦３．００、好ましくは１．５０≦ｘ＋ｙ≦２．５０である。ｘ＋ｙが上記範囲にあることにより、負熱膨張特性がより高くなる。 In general formula (1), x+y is 1.00≦x+y≦3.00, preferably 1.50≦x+y≦2.50. When x+y is within the above range, the negative thermal expansion property becomes higher.
また、一般式（１）において、Ｍ元素を含有するときは、Ａｌ原子の原子換算のモル数＞Ｍ原子の原子換算のモル数である。 Further, in the general formula (1), when the M element is contained, the number of moles of Al atoms in terms of atoms>the number of moles of M atoms in terms of atoms.
本発明の負熱膨張材では、一般式（１）で表される銅バナジウム複合酸化物に、Ａｌ原子が固溶している。つまり、本発明の負熱膨張材は、一般式（１）で表される銅バナジウム複合酸化物からなり、且つ、該銅バナジウム複合酸化物にはＡｌ原子が粒子内部に固溶して含有されている。通常の負熱膨張材とＡｌ金属との複合体は、負熱膨張材粒子にＡｌ金属が単に強固に付着して存在するものであり、本発明のように負熱膨張材粒子の粒子内部までＡｌ原子が固溶して存在させるものではない。
本発明の負熱膨張材が、Ａｌ原子が固溶している一般式（１）で表される銅バナジウム複合酸化物粉体であることにより、Ａｌ原子が固溶して含有されていない一般式（１）と同様の組成を有する銅バナジウム複合酸化物粉体に比べて、負熱膨張特性が向上する。すなわち、本発明の負熱膨張材が、Ａｌ原子が固溶している一般式（１）で表される銅バナジウム複合酸化物粉体であることにより、Ａｌ原子が固溶して含有されていない一般式（１）と同様の組成を有する銅バナジウム複合酸化物粉体に比べて、熱膨張係数が小さくなる。
In the negative thermal expansion material of the present invention, Al atoms are dissolved in the copper vanadium composite oxide represented by the general formula (1). That is, the negative thermal expansion material of the present invention is made of a copper-vanadium composite oxide represented by the general formula (1), and the copper-vanadium composite oxide contains Al atoms in solid solution inside the particles. ing. In a normal composite of a negative thermal expansion material and an Al metal, the Al metal simply adheres firmly to the negative thermal expansion material particles, and as in the present invention, the Al metal is simply firmly attached to the negative thermal expansion material particles. Al atoms are not present as a solid solution.
Since the negative thermal expansion material of the present invention is a copper-vanadium composite oxide powder represented by the general formula (1) in which Al atoms are dissolved in solid solution, the material does not contain Al atoms in solid solution. The negative thermal expansion property is improved compared to a copper vanadium composite oxide powder having a composition similar to that of formula (1). That is, since the negative thermal expansion material of the present invention is a copper vanadium composite oxide powder represented by the general formula (1) in which Al atoms are dissolved in solid solution, Al atoms are not contained in solid solution. The coefficient of thermal expansion is smaller than that of a copper-vanadium composite oxide powder having a composition similar to that of general formula (1).
本発明の負熱膨張材中、Ａｌ原子の含有量は、好ましくは１００～３００００質量ｐｐｍ、より好ましくは５００～２８０００質量ｐｐｍ、特に好ましくは１０００～２６０００質量ｐｐｍである。負熱膨張材中のＡｌ原子の含有量が上記範囲にあることにより、Ｘ線回折的に単相で負熱膨張特性が優れる点で好ましい。なお、本発明において、負熱膨張材中のＡｌ原子の含有量は、負熱膨張材を酸分解した溶液をＩＣＰ発光法で分析することにより求められる。 In the negative thermal expansion material of the present invention, the content of Al atoms is preferably 100 to 30,000 mass ppm, more preferably 500 to 28,000 mass ppm, particularly preferably 1,000 to 26,000 mass ppm. It is preferable that the content of Al atoms in the negative thermal expansion material is within the above range, since it is a single phase in terms of X-ray diffraction and has excellent negative thermal expansion characteristics. In the present invention, the content of Al atoms in the negative thermal expansion material is determined by analyzing a solution obtained by acid decomposing the negative thermal expansion material using an ICP emission method.
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０．１～１０ｍ２／ｇ、一層好ましくは０．１～５ｍ２／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。 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 0.1 to 10 m 2 /g, and even more preferably 0.1 to 5 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.
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０．３～８０μｍ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５０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 0.3 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, regarding the average particle diameter of the negative thermal expansion material, the arithmetic mean value of the particle diameters of 50 particles arbitrarily extracted at a magnification of 1000 times was determined as the average particle diameter 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の熱膨張係数は、Ａｌ原子が固溶して含有されていない一般式（１）と同様の組成を有する銅バナジウム複合酸化物粉体に比べて、熱膨張係数が低くなる限りは、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、好ましくは－１０×１０－６／Ｋ以下、より好ましくは－１２×１０－６／Ｋ以下、いっそう好ましくは－１５×１０－６／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－４０×１０－６／Ｋ以上、好ましくは－３７×１０－６／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、本発明の負熱膨張材の熱膨張係数は、特に好ましくは－３５×１０－６～－１３×１０－６／Ｋである。 The thermal expansion coefficient of the negative thermal expansion material of the present invention is higher than that of a copper vanadium composite oxide powder having a composition similar to general formula (1), which does not contain Al atoms in solid solution. Although not limited as long as it is low, the thermal expansion coefficient of the negative thermal expansion material of the present invention is preferably −10×10 −6 /K or less, more preferably −12×10 −6 /K or less. , more preferably -15 x 10 -6 /K or less, and the lower limit is not particularly limited, but is approximately -40 x 10 -6 /K or more, preferably -37 x 10 -6 /K That's all. In the negative thermal expansion material of the present invention, the coefficient of thermal expansion of the negative thermal expansion material of the present invention is particularly preferably -35×10 −6 to −13×10 −6 /K.
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、負熱膨張材試料１．０ｇとバインダー樹脂０．０５ｇとを混合し、φ６ｍｍの金型に全量充填し、次いで、バンドプレスを用いて０．５ｔの圧力で成形して 成形体を作成する。この成形体を電気炉中７００℃で４時間大気雰囲気で焼成して、セラミック成形体を得る。得られるセラミック成形体を、熱機械測定装置を用いて、窒素雰囲気で、荷重１０ｇ、温度５０～４２５℃にて繰り返し２回測定し、繰り返し２回目の５０～４００℃間の測定値を熱膨張係数とする。熱機械測定装置としては、例えば、ＮＥＴＺＳＣＨ ＪＡＰＡＮ製 ＴＭＡ４００ＳＥを用いることができる。 In addition, in this invention, a thermal expansion coefficient is calculated|required by the following procedure. First, 1.0 g of a negative thermal expansion material sample and 0.05 g of binder resin were mixed, and the entire amount was filled into a φ6 mm mold, and then molded using a band press at a pressure of 0.5 t to create a molded body. do. This molded body is fired in an electric furnace at 700° C. for 4 hours in the air to obtain a ceramic molded body. The obtained ceramic molded body was repeatedly measured twice in a nitrogen atmosphere at a load of 10 g and a temperature of 50 to 425°C using a thermomechanical measuring device, and the measured value between 50 and 400°C for the second repeated measurement was calculated as thermal expansion. Let it be a coefficient. As the thermomechanical measuring device, for example, TMA400SE manufactured by NETZSCH JAPAN can be used.
本発明の負熱膨張材において、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。
なお、本発明において一般式（１）で表される銅バナジウム複合酸化物が単相であるとは、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。
In the negative thermal expansion material of the present invention, the copper-vanadium composite oxide represented by the general formula (1) basically has a Ziesite phase (β phase) and a Blossite phase (α phase). There are also mixed phases. 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.
In addition, in the present invention, the copper-vanadium composite oxide represented by the general formula (1) is a single phase, which means that the Ziesite phase (β phase) of the copper-vanadium composite oxide represented by the general formula (1) is alone. It refers to the existence of a single Blossite phase (α phase), or the existence of a mixed phase of Ziesite phase (β phase) and Blossite phase (α phase). , means that no diffraction peaks other than those of the copper vanadium composite oxide represented by general formula (1) are detected.
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).
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、Ａｌ源と、Ｃｕ源と、Ｖ源と、必要により添加されるＭ源と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 preparing a raw material mixture by mixing an Al source, a Cu source, a V source, and an M source added as necessary;
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、Ａｌ源と、Ｃｕ源と、Ｖ源と、必要により添加されるＭ源と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 preparing a raw material mixture by mixing an Al source, a Cu source, a V source, and an optionally added M source.
第１工程に係るＡｌ源としては、例えば、アルミニウムの酸化物、水酸化物、硝酸アルミニウム、硫酸アルミニウム、重リン酸アルミニウム、塩化アルミニウム、乳酸アルミニウム等が挙げられる。 Examples of the Al source for the first step include aluminum oxides, hydroxides, aluminum nitrate, aluminum sulfate, aluminum biphosphate, aluminum chloride, aluminum lactate, and the like.
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工程に係る必要により混合されるＭ源としては、例えば、Ｍ源のカルボン酸塩、ハロゲン化物、酸化物、水酸化物等が挙げられ、Ｍ源のカルボン酸塩としては、例えば、グルコン酸塩、クエン酸塩、乳酸塩等が挙げられる。 Examples of the M source to be mixed as necessary in the first step include carboxylates, halides, oxides, hydroxides, etc. of the M source, and examples of the carboxylate of the M source include gluconate, etc. Examples include acid salts, citrates, lactates, and the like.
第１工程に係る原料混合物の調製において、Ｃｕ源、Ｖ源及び必要により添加されるＭ源の混合量は、原料混合物中のＣｕ、Ｖ及びＭ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、適宜調節されることが好ましい。また、第１工程に係る原料混合物の調製において、Ａｌ源の混合量は、得られる負熱膨張材に対して、好ましくは１００～３００００質量ｐｐｍ、より好ましくは５００～２８０００質量ｐｐｍ、特に好ましくは１０００～２６０００質量ｐｐｍとなるように、適宜調節されることが好ましい。 In the preparation of the raw material mixture according to the first step, the amounts of the Cu source, V source, and optionally added M source are such that the atomic molar ratio of Cu, V, and M in the raw material mixture is determined by the general formula (1 ) It is preferable to adjust the composition as appropriate so that the composition of the copper vanadium composite oxide is expressed as follows. In the preparation of the raw material mixture in the first step, the amount of the Al source mixed is preferably 100 to 30,000 mass ppm, more preferably 500 to 28,000 mass ppm, particularly preferably It is preferable to adjust it appropriately so that it is 1,000 to 26,000 ppm by mass.
第１工程では、Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加されるＭ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。 In the first step, the mixing process of the Al source, Cu source, V source, and optionally added M source can be carried out in a wet or dry process, but this process is advantageous in that a uniform raw material mixture can be easily obtained. It is preferable to carry out the mixing treatment in a wet manner.
湿式混合処理に用いられる溶媒としては、Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加されるＭ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。 Examples of the solvent used in the wet mixing process include water, methanol, ethanol, etc., although they vary depending on the type of Al source, Cu source, V source, and optionally added M source.
Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加されるＭ源が不溶性又は難溶性のものを用いる場合は、Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加されるＭ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。 When the Al source, Cu source, V source, and optionally added M source are insoluble or poorly soluble, the average particle diameter of the Al source, Cu source, V source, and optionally added M source is: In terms of high reactivity, the average particle diameter (D50) determined by laser diffraction is preferably 50 μm or less, particularly preferably 0.1 to 40 μm.
Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加されるＭ源が不溶性又は難溶性のものを用いる場合の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。 When using insoluble or poorly soluble Al sources, Cu sources, V sources, and optionally added M sources, the apparatus for performing wet mixing processing is especially suitable if a slurry in which each raw material is uniformly dispersed is obtained. There are no restrictions. 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.
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, 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、Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加されるＭ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、Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加されるＭ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Ａｌ源としては、例えば、硝酸アルミニウム、硫酸アルミニウム、重リン酸アルミニウム、塩化アルミニウム、乳酸アルミニウム等が挙げられる。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 Al source, Cu source, V source, and optionally added M source in a water solvent, and then removing the water solvent. In this case, the Al source, Cu source, V source, and optionally added M source may be those that are soluble in the water solvent. Examples of the Al source that dissolves in the water solvent include aluminum nitrate, aluminum sulfate, aluminum biphosphate, aluminum chloride, and aluminum lactate. Examples of the Cu source include copper salts of organic carboxylic acids, copper salts of mineral acids, and the like. Further, examples of the V source soluble in the water solvent include vanadate and its sodium salt, potassium salt, ammonium salt, carboxylic acid 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、Ａｌ源及び必要により添加するＭ源を混合して、Ｃｕ源、Ａｌ源、Ｖ源及び必要により添加するＭ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, an Al source, and an optionally added M source to obtain a raw material mixture containing a Cu source, an Al source, a V source, and an optionally added M source, Next, the water solvent may be removed from the raw material mixture to prepare a raw material mixture.
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Ａｌ源、Ｃｕ源、Ｖ源及び必要により添加するＭ源中のＡｌ、Ｃｕ、Ｖ及びＭ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 Al source, Cu, The atomic molar ratio of Al, Cu, V, and M in the source, V source, and optionally added M source almost matches.
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.
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反応を行う。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。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、原料混合物中の原料のほぼ全てが、Ａｌ原子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負熱膨張材となる。なお、本発明において一般式（１）で表される銅バナジウム複合酸化物が単相であるとは、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。 The firing time in the second step is not particularly limited, and the reaction is carried out for a sufficient time until the negative thermal expansion material of the present invention is produced. 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 the second step, the firing time is often 1 hour or more, preferably 2 to 20 hours, and almost all of the raw materials in the raw material mixture are expressed by the general formula (1) in which Al atoms are solidly dissolved. It becomes a negative thermal expansion material made of copper vanadium composite oxide. In addition, in the present invention, the copper-vanadium composite oxide represented by the general formula (1) is a single phase, which means that the Ziesite phase (β phase) of the copper-vanadium composite oxide represented by the general formula (1) is alone. It refers to the existence of a single Blossite phase (α phase), or the existence of a mixed phase of Ziesite phase (β phase) and Blossite phase (α phase). , means that no diffraction peaks other than those of the copper vanadium composite oxide represented by general formula (1) are detected.
また、第２工程において、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。 Moreover, in the second step, the firing atmosphere 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、本発明の負熱膨張材を得る。 After firing, the material is appropriately cooled and, if necessary, pulverized, crushed, classified, etc., to obtain the negative thermal expansion material of the present invention.
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。 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 thermally expandable materials.
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。
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負熱膨張材の走査型電子顕微鏡観察法により求められる平均粒子径は、好ましくは０．１～１００μｍ、特に好ましくは０．３～８０μｍであり、また、ＢＥＴ比表面積は、０．０５～５０ｍ２／ｇ、特に好ましくは０．１～１０ｍ２／ｇである。負熱膨張材の平均粒子径、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 obtained by the method for producing a negative thermal expansion material of the present invention, as determined by scanning electron microscopy, is preferably 0.1 to 100 μm, particularly preferably 0.3 to 80 μm. , and the BET specific surface area is 0.05 to 50 m 2 /g, particularly preferably 0.1 to 10 m 2 /g. It is preferable that the average particle diameter and BET specific surface area of the negative thermal expansion material are within the above ranges, since the negative thermal expansion material can be easily handled when 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、本発明の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、焼成を行い得られた負熱膨張材に対し、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 of the present invention, for the purpose of improving resin dispersibility and moisture resistance of the negative thermal expansion material, if necessary, the negative thermal expansion material obtained by baking is applied to the surface of the negative thermal expansion material. Processing 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、－１０×１０－６／Ｋ以下、好ましくは－１２×１０－６／Ｋ以下、いっそう好ましくは－１５×１０－６／Ｋ以下であり、下限値については概ね－４０×１０－６／Ｋ以上、好ましくは－３７×１０－６／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は、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－３５×１０－６～－１３×１０－６／Ｋである。 The coefficient of thermal expansion of the negative thermal expansion material obtained by carrying out the method for producing a negative thermal expansion material of the present invention is -10×10 -6 /K or less, preferably -12×10 -6 /K or less, more preferably - 15×10 −6 /K or less, and the lower limit is approximately −40×10 −6 /K or more, preferably −37×10 −6 /K or more. The coefficient of thermal expansion of the negative thermal expansion material obtained by the method for producing a negative thermal expansion material of the present invention is particularly important in that the coefficient of thermal expansion easily offsets the positive expansion when combined with a positive thermal expansion material. Preferably it is -35×10 −6 to −13×10 −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.
（Ｘ線回折装置）
実施例ではＸ線回折装置（リガク社製 ＵｌｔｉｍａＩＶ）を用いて、下記の測定条件で測定を行った。
線源：Ｃｕ－Ｋα
管電圧：４０ｋＶ
管電流：４０ｍＡ
走査速度：４°／ｓｅｃ
(X-ray diffraction device)
In the examples, measurements were performed using an X-ray diffraction device (Rigaku Corporation Ultima IV) under the following measurement conditions.
Radiation source: Cu-Kα
Tube voltage: 40kV
Tube current: 40mA
Scanning speed: 4°/sec
（実施例１）
（第１工程）
バナジン酸アンモニウム（ＮＨ４ＶＯ３）３．００ｇ、アンモニア水６ｍｌ、純水８０ｍｌをビーカーに入れ、攪拌しながら６０℃に加熱してＡ液を得た。次にグルコン酸銅（扶桑化学工業製）１１．３５ｇを純水５０ｍｌに加えて攪拌し、Ｂ液を得た。次に硝酸アルミニウム９水和物０．２４ｇを純水１０ｍｌに加えて攪拌し、Ｃ液を得た。次にＡ液に対してＢ液、Ｃ液の順に加えて各原料が溶解した溶液である原料混合液を得た。
得られた原料混合液を攪拌しながら沸騰状態を維持する温度に加熱して水を除去し、ペースト状の原料混合物を得た。
（第２工程）
得られたペースト状の原料混合物を坩堝中、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°付近にメインの回析ピークを持つＺｉｅｓｉｔｅ相の単相のＣｕ２．００Ｖ２．００Ｏ７．００が検出された。焼成品のＸ線回折図を図１に示す。また、得られた焼成品を酸分解した溶液をＩＣＰ発光分析し、焼成品中のＡｌ原子の含有量を求めたところ、Ａｌ原子の含有量は３９８０質量ｐｐｍであった。これらの結果、焼成品は、Ａｌ原子が３９８０質量ｐｐｍ固溶しているＺｉｅｓｉｔｅ相の単相の銅バナジウム複合酸化物であることがわかった。
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 1)
(1st step)
3.00 g of ammonium vanadate (NH 4 VO 3 ), 6 ml of aqueous ammonia, and 80 ml of pure water were placed in a beaker and heated to 60° C. while stirring to obtain a solution A. Next, 11.35 g of copper gluconate (manufactured by Fuso Chemical Industries) was added to 50 ml of pure water and stirred to obtain Solution B. Next, 0.24 g of aluminum nitrate nonahydrate was added to 10 ml of pure water and stirred to obtain Solution C. Next, liquid B and liquid C were sequentially added to liquid A to obtain a raw material mixture solution in which each raw material was dissolved.
The obtained raw material mixture was stirred and heated to a temperature that maintained a boiling state to remove water, thereby obtaining a paste-like raw material mixture.
(Second process)
The obtained paste-like raw material mixture was fired in a crucible in the atmosphere at 700°C for 4 hours to obtain a fired product.
When the obtained fired product was subjected to X-ray diffraction analysis, single-phase Cu 2.00 V 2.00 O 7.00 of Ziesite phase with a main diffraction peak near 2θ=25° was detected. The X-ray diffraction diagram of the fired product is shown in Figure 1. Further, the solution obtained by acid decomposition of the obtained fired product was subjected to ICP emission analysis to determine the content of Al atoms in the fired product, and the content of Al atoms was 3980 ppm by mass. As a result, it was found that the fired product was a single-phase copper-vanadium composite oxide having a Ziesite phase in which 3980 mass ppm of Al atoms were solidly dissolved.
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）
（第１工程）
バナジン酸アンモニウム（ＮＨ４ＶＯ３）３．００ｇ、アンモニア水６ｍｌ、純水８０ｍｌをビーカーに入れ、攪拌しながら６０℃に加熱してＡ液を得た。次にグルコン酸銅（扶桑化学工業製）１１．０６ｇを純水５０ｍｌに加えて攪拌し、Ｂ液を得た。次に硝酸アルミニウム９水和物０．４８ｇを純水１０ｍｌに加えて攪拌し、Ｃ液を得た。次にＡ液に対してＢ液、Ｃ液の順に加えて各原料が溶解した溶液である原料混合液を得た。
前記原料混合液を攪拌しながら沸騰状態を維持する温度に加熱して水を除去し、ペースト状の反応混合物を得た。
（第２工程）
前記ペースト状の反応混合物を坩堝中、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°付近にメインの回析ピークを持つＺｉｅｓｉｔｅ相の単相のＣｕ２．００Ｖ２．００Ｏ７．００が検出された。焼成品のＸ線回折図を図２に示す。また、得られた焼成品を酸分解した溶液をＩＣＰ発光分析し、焼成品中のＡｌ原子の含有量を求めたところ、Ａｌ原子の含有量は８０００質量ｐｐｍであった。これらの結果、焼成品は、Ａｌ原子が８０００質量ｐｐｍ固溶しているＺｉｅｓｉｔｅ相の単相の銅バナジウム複合酸化物であることがわかった。
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 2)
(1st step)
3.00 g of ammonium vanadate (NH 4 VO 3 ), 6 ml of aqueous ammonia, and 80 ml of pure water were placed in a beaker and heated to 60° C. while stirring to obtain a solution A. Next, 11.06 g of copper gluconate (manufactured by Fuso Chemical Industries) was added to 50 ml of pure water and stirred to obtain Solution B. Next, 0.48 g of aluminum nitrate nonahydrate was added to 10 ml of pure water and stirred to obtain Solution C. Next, liquid B and liquid C were sequentially added to liquid A to obtain a raw material mixture solution in which each raw material was dissolved.
The raw material mixture was stirred and heated to a temperature that maintained a boiling state to remove water, thereby obtaining a paste-like reaction mixture.
(Second process)
The paste-like reaction mixture was fired at 700° C. for 4 hours in the atmosphere in a crucible to obtain a fired product.
When the obtained fired product was subjected to X-ray diffraction analysis, single-phase Cu 2.00 V 2.00 O 7.00 of Ziesite phase with a main diffraction peak near 2θ=25° was detected. The X-ray diffraction diagram of the fired product is shown in FIG. Further, the solution obtained by acid decomposition of the obtained fired product was subjected to ICP emission analysis to determine the content of Al atoms in the fired product, and the content of Al atoms was 8000 ppm by mass. As a result, it was found that the fired product was a single-phase copper-vanadium composite oxide having a Ziesite phase in which 8000 mass ppm of Al atoms were solidly dissolved.
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）
（第１工程）
バナジン酸アンモニウム（ＮＨ４ＶＯ３）３．００ｇ、アンモニア水６ｍｌ、純水８０ｍｌをビーカーに入れ、攪拌しながら６０℃に加熱してＡ液を得た。次にグルコン酸銅（扶桑化学工業製）１０．１９ｇを純水５０ｍｌに加えて攪拌し、Ｂ液を得た。次に硝酸アルミニウム９水和物１．２０ｇを純水２０ｍｌに加えて攪拌し、Ｃ液を得た。次にＡ液に対してＢ液、Ｃ液の順に加えて各原料が溶解した溶液である原料混合液を得た。
前記原料混合液を攪拌しながら沸騰状態を維持する温度に加熱して水を除去し、ペースト状の原料混合物を得た。
（第２工程）
前記ペースト状の原料混合物を坩堝中、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°付近にメインの回析ピークを持つＺｉｅｓｉｔｅ相の単相のＣｕ２．００Ｖ２．００Ｏ７．００が検出された。焼成品のＸ線回折図を図３に示す。また、得られた焼成品を酸分解した溶液をＩＣＰ発光分析し、焼成品中のＡｌ原子の含有量を求めたところ、Ａｌ原子の含有量は２０３３０質量ｐｐｍであった。これらの結果、焼成品は、Ａｌ原子が２０３３０質量ｐｐｍ固溶しているＺｉｅｓｉｔｅ相の単相の銅バナジウム複合酸化物であることがわかった。
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 3)
(1st step)
3.00 g of ammonium vanadate (NH 4 VO 3 ), 6 ml of aqueous ammonia, and 80 ml of pure water were placed in a beaker and heated to 60° C. while stirring to obtain a solution A. Next, 10.19 g of copper gluconate (manufactured by Fuso Chemical Industries) was added to 50 ml of pure water and stirred to obtain Solution B. Next, 1.20 g of aluminum nitrate nonahydrate was added to 20 ml of pure water and stirred to obtain Solution C. Next, liquid B and liquid C were sequentially added to liquid A to obtain a raw material mixture solution in which each raw material was dissolved.
The raw material mixture was stirred and heated to a temperature that maintained a boiling state to remove water, thereby obtaining a paste-like raw material mixture.
(Second process)
The paste-like raw material mixture was fired at 700° C. for 4 hours in the atmosphere in a crucible to obtain a fired product.
When the obtained fired product was subjected to X-ray diffraction analysis, single-phase Cu 2.00 V 2.00 O 7.00 of Ziesite phase with a main diffraction peak near 2θ=25° was detected. The X-ray diffraction diagram of the fired product is shown in FIG. Further, the solution obtained by acid decomposition of the obtained fired product was subjected to ICP emission analysis to determine the content of Al atoms in the fired product, and the content of Al atoms was 20,330 ppm by mass. As a result, it was found that the fired product was a single-phase copper-vanadium composite oxide having a Ziesite phase in which 20,330 mass ppm of Al atoms were solidly dissolved.
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に乾燥して原料混合物を得た。この粉末を大気下で、６５０℃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Ｂｌｏｓｓｉｔｅ相の単相のＣｕ２．００Ｖ２．００Ｏ７．００が検出された。焼成品のＸ線回折図を図４に示す。
つまり、比較例１では、Ａ１源を用いておらず、得られるＣｕ２Ｖ２Ｏ７の銅バナジウム複合酸化物は、Ａｌ原子が固溶したものではない。
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。
(Comparative example 1)
After pulverizing and mixing 1.71 g of vanadium pentoxide (V 2 O 5 : average particle size 1.0 μm), 1.50 g of copper oxide (CuO: average particle size 1.5 μm), and 30 ml of ethanol as a dispersion medium in a mortar for 20 minutes. A raw material mixture was obtained by drying. This powder was fired at 650° 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 Cu 2.00 V 2.00 O 7.00 of a Blossite phase with a main diffraction peak near 2θ=27° was detected. The X-ray diffraction diagram of the fired product is shown in FIG.
That is, in Comparative Example 1, the A1 source was not used, and the resulting copper vanadium composite oxide of Cu 2 V 2 O 7 did not contain Al atoms in solid solution.
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.
（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５０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 50 arbitrarily extracted particles from the observation field, and calculate the arithmetic mean value of the arithmetic mean value of the negative thermal expansion material sample. 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℃間での熱膨張係数は－４．４×１０―６／Ｋであった。 Note that the thermal 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４）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１６．２質量部、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１３．５質量部、水酸化アルミニウム（Ａｌ（ＯＨ）３：平均粒子径（１．２）μｍ）０．５質量部を計量し、純水６９．７質量部を分散媒として３０分間攪拌して３０．２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、０．５４μｍ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。得られた焼成品をＸ線回折分析したところ、２θ＝２５°付近にメインの回析ピークを持つＺｉｅｓｉｔｅ相の単相のＣｕ２．００Ｖ２．００Ｏ７．００が検出された。また、得られた焼成品を酸分解した溶液をＩＣＰ発光分析し、焼成品中のＡｌ原子の含有量を求めたところ、Ａｌ原子の含有量は５６００質量ｐｐｍであった。これらの結果、焼成品は、Ａｌ原子が５６００質量ｐｐｍ固溶しているＺｉｅｓｉｔｅ相の単相の銅バナジウム複合酸化物であることがわかった。
次いで、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。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。
(Example 4)
16.2 parts by mass of vanadium pentoxide (V 2 O 5 : average particle diameter 1.0 μm), 13.5 parts by mass of copper oxide (CuO: average particle diameter 1.5 μm), aluminum hydroxide (Al(OH) 3 : A 30.2% by mass slurry was prepared by weighing 0.5 parts by mass (average particle diameter (1.2) μm) and stirring for 30 minutes using 69.7 parts by mass of pure water as a dispersion medium.
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 0.54 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. When the obtained fired product was subjected to X-ray diffraction analysis, single-phase Cu 2.00 V 2.00 O 7.00 of Ziesite phase with a main diffraction peak near 2θ=25° was detected. Further, the solution obtained by acid decomposition of the obtained fired product was subjected to ICP emission analysis to determine the content of Al atoms in the fired product, and the content of Al atoms was 5600 ppm by mass. These results revealed that the fired product was a single-phase copper-vanadium composite oxide of Ziesite phase in which 5600 mass ppm of Al atoms were solidly dissolved.
Next, the fired product was pulverized in a mortar and then pulverized in a jet mill to obtain a pulverized product. 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.
（実施例５）
原料混合物の焼成温度を６５０℃とした以外は実施例４と同様にして粉砕物を得た。
得られた粉砕物をＸ線回折分析したところ、銅バナジウム複合酸化物（Ｃｕ２．００Ｖ２．００Ｏ７．００）の単相であり、２θ＝２５°付近にＺｉｅｓｉｔｅ相に起因したメインの回折ピークを持ち、また２θ＝２７°付近にＢｌｏｓｓｉｔｅ相の回析ピークも観察された。これをＡｌ原子が５６００質量ｐｐｍ固溶している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。
(Example 5)
A pulverized product was obtained in the same manner as in Example 4 except that the firing temperature of the raw material mixture was 650°C.
X-ray diffraction analysis of the obtained pulverized material revealed that it was a single phase of copper vanadium composite oxide (Cu 2.00 V 2.00 O 7.00 ), with a main phase originating from the Ziesite phase near 2θ=25°. The diffraction peak of the Blossite phase was also observed near 2θ=27°. This was used as a negative thermal expansion material sample in which 5600 mass ppm of Al atoms were dissolved in solid solution.
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.
（実施例６）
五酸化バナジウム（Ｖ２Ｏ５：平均粒子径１．０μｍ）１６．２質量部、酸化銅（ＣｕＯ：平均粒子径１．５μｍ）１３．４質量部、水酸化アルミニウム（Ａｌ（ＯＨ）３：平均粒子径１．２μｍ）０．５質量部、炭酸カルシウム(ＣａＣＯ３：平均粒子径２．４μｍ)０．２質量部を計量し、純水６９．７質量部を分散媒として３０分間攪拌して３０．３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、０．５２μｍ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。得られた焼成品をＸ線回折分析したところ、２θ＝２５°付近にメインの回析ピークを持つＺｉｅｓｉｔｅ相の単相のＣｕ２．００Ｖ２．００Ｏ７．００が検出された。また、得られた焼成品を酸分解した溶液をＩＣＰ発光分析し、焼成品中のＡｌ原子の含有量を求めたところ、Ａｌ原子の含有量は５６００質量ｐｐｍであった。これらの結果、焼成品は、Ａｌ原子が５６００質量ｐｐｍ固溶しているＺｉｅｓｉｔｅ相の単相の銅バナジウム複合酸化物（Ｃｕ１．９８Ｃａ０．０２Ｖ２．００Ｏ７．００）であることがわかった。
次いで、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。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。
(Example 6)
16.2 parts by mass of vanadium pentoxide (V 2 O 5 : average particle diameter 1.0 μm), 13.4 parts by mass of copper oxide (CuO: average particle diameter 1.5 μm), aluminum hydroxide (Al(OH) 3 : Weighed 0.5 parts by mass of calcium carbonate (CaCO 3 :average particle diameter 2.4 μm) and 0.2 parts by mass of calcium carbonate (CaCO 3 :average particle diameter 2.4 μm), and stirred for 30 minutes using 69.7 parts by mass of pure water as a dispersion medium. A 30.3% by mass slurry was prepared.
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 0.52 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. When the obtained fired product was subjected to X-ray diffraction analysis, single-phase Cu 2.00 V 2.00 O 7.00 of Ziesite phase with a main diffraction peak near 2θ=25° was detected. Further, the solution obtained by acid decomposition of the obtained fired product was subjected to ICP emission analysis to determine the content of Al atoms in the fired product, and the content of Al atoms was 5600 ppm by mass. As a result, the fired product is a Ziesite phase single-phase copper vanadium composite oxide (Cu 1.98 Ca 0.02 V 2.00 O 7.00 ) in which 5600 mass ppm of Al atoms are solidly dissolved. I understand.
Next, the fired product was pulverized in a mortar and then pulverized in a jet mill to obtain a pulverized product. 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.
（物性評価）
実施例４、実施例５及び実施例６で得られた負熱膨張材試料について、実施例１～３と同様にして平均粒子径、ＢＥＴ比表面積及び熱膨張係数を測定した。また、下記の方法で球状粒子の含有率を求めた。また、実施例４で得られた負熱膨張材試料のＳＥＭ写真を図５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
(Evaluation of the physical properties)
For the negative thermal expansion material samples obtained in Examples 4, 5, and 6, the average particle diameter, BET specific surface area, and coefficient of thermal expansion were measured in the same manner as in Examples 1 to 3. In addition, the content of spherical particles was determined by the following method. Further, a SEM photograph of the negative thermal expansion material sample obtained in Example 4 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
なお、実施例５の負熱膨張材試料と実施例４の負熱膨張材はＡｌ原子の含有量が同じであるのに関わらず実施例５の焼成温度を６５０℃としたものの方が実施例４の焼成温度を７００℃とした負熱膨張材試料に比べて、負熱膨張性が優れたものになった。これは、熱膨張係数の測定用のセラミック成形体の調製の７００℃での焼成の際に、実施例５の負熱膨張材試料では銅バナジウム複合酸化物中のＢｌｏｓｓｉｔｅ相のＺｉｅｓｉｔｅ相への転換が促進され、更に７００℃での焼成の際に個々の粒子が更に粒成長することによりセラミック成形体自体で粒子間の間隙もより一層少なくなるため、実施例４の負熱膨張材を用いて調製したセラミック成形体に比べて、実施例５の負熱膨張材を用いて調製したセラミック成形体は、より緻密なものが得られるためと考えられる。 Although the negative thermal expansion material sample of Example 5 and the negative thermal expansion material of Example 4 have the same Al atom content, the one in which the firing temperature of Example 5 was set to 650°C is better than that of Example 5. Compared to the negative thermal expansion material sample No. 4 in which the firing temperature was 700° C., the negative thermal expansion property was excellent. This is due to the conversion of the Blossite phase in the copper vanadium composite oxide to the Ziesite phase in the negative thermal expansion material sample of Example 5 during firing at 700°C to prepare a ceramic molded body for measuring the coefficient of thermal expansion. is promoted, and the individual particles further grow during firing at 700°C, which further reduces the gaps between particles in the ceramic molded body itself. Therefore, using the negative thermal expansion material of Example 4, This is thought to be because the ceramic molded body prepared using the negative thermal expansion material of Example 5 is more dense than the prepared ceramic molded body.
Claims (12)
ＣｕｘＭｙＶｚＯｔ （１）
（式中、ＭはＣｕ、Ｖ及びＡｌ以外の原子番号１１以上の金属元素を示す。ｘは１．６０≦ｘ≦２．４０、ｙは０．００≦ｙ≦０．４０、ｚは１．７０≦ｚ≦２．３０、ｔは６．００≦ｔ≦９．００を示す。但し、１．６０≦ｘ＋ｙ≦２．８０である。また、Ｍ元素を含有するときは、Ａｌ原子の原子換算のモル数＞Ｍ原子の原子換算のモル数である。）で表される銅バナジウム複合酸化物粉体からなり、前記バナジウム複合酸化物粉体は、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し、Ａｌ原子の含有量が、１０００～２６０００質量ｐｐｍであることを特徴とする負熱膨張材。 The following general formula (1) in which an Al atom is solidly dissolved:
Cu x M y V z O t (1)
(In the formula, M represents a metal element with an atomic number of 11 or more other than Cu, V and Al. x is 1.60≦x≦2.40, y is 0.00≦y≦0.40, z is 1 .70≦z≦2.30, t indicates 6.00≦t≦9.00.However, 1.60 ≦x+y≦ 2.80.Also , when containing M element, the Al atom The vanadium composite oxide powder is composed of a copper vanadium composite oxide powder represented by the following formula: number of moles in terms of atoms> number of moles in terms of atoms of M atoms, and the vanadium composite oxide powder has a single phase of Ziesite phase (β phase). Or a negative thermal expansion material having a mixed phase crystal structure of Ziesite phase (β phase) and Blossite phase (α phase) and having an Al atom content of 1000 to 26000 ppm by mass.
Ａｌ源と、Ｃｕ源と、Ｖ源と、必要により添加されるＭ源とを混合し、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負熱膨張材の製造方法。 A method for producing a negative thermal expansion material comprising the copper vanadium composite oxide powder according to claim 1,
A first step of preparing a raw material mixture by mixing an Al source, a Cu source, a V source, and an optionally added M source;
a second step of firing the raw material mixture to obtain a negative thermal expansion material;
A method for producing a negative thermal expansion material, comprising:
の製造方法。 9. The first step includes a step of preparing a raw material mixture solution in which an Al source, a Cu source, a V source, and an M source added as necessary are dissolved in a water solvent. A method for producing the negative thermal expansion material described above.
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| CN105648248A (en) | 2016-01-06 | 2016-06-08 | 郑州大学 | Controllable thermal expansion composite conductive ceramic material alpha-Cu2V2O7-Al |
| WO2020095518A1 (en) | 2018-11-09 | 2020-05-14 | 国立大学法人名古屋大学 | Method for producing negative thermal expansion material |
| WO2020148886A1 (en) | 2019-01-18 | 2020-07-23 | 株式会社ケミカルゲー ト | Microparticles of negative thermal expansion material, composite material and method for manufacturing same |
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| CN105648248A (en) | 2016-01-06 | 2016-06-08 | 郑州大学 | Controllable thermal expansion composite conductive ceramic material alpha-Cu2V2O7-Al |
| WO2020095518A1 (en) | 2018-11-09 | 2020-05-14 | 国立大学法人名古屋大学 | Method for producing negative thermal expansion material |
| WO2020148886A1 (en) | 2019-01-18 | 2020-07-23 | 株式会社ケミカルゲー ト | Microparticles of negative thermal expansion material, composite material and method for manufacturing same |
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