JP2016088827A - Method for producing vanadium dioxide - Google Patents
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- JP2016088827A JP2016088827A JP2014229055A JP2014229055A JP2016088827A JP 2016088827 A JP2016088827 A JP 2016088827A JP 2014229055 A JP2014229055 A JP 2014229055A JP 2014229055 A JP2014229055 A JP 2014229055A JP 2016088827 A JP2016088827 A JP 2016088827A
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 95
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims description 51
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 92
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
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- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 7
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Abstract
Description
本発明は、産業上有用な二酸化バナジウムを、簡便かつ安価に製造する方法に関する。 The present invention relates to a method for producing industrially useful vanadium dioxide in a simple and inexpensive manner.
二酸化バナジウムは、比較的室温に近い７０℃前後で金属−半導体転位を起こし、電気伝導性が可逆的に大きく変わることが報告されている（非特許文献１）。この金属−半導体転位は、低温側の単斜晶構造と高温側の正方晶構造が相互に構造変化することに伴うものだと言われている。この金属−半導体転位では、透過率や反射率等の光学的特性が変化するサーモクロミック現象も起こす。このサーモクロミック現象では、可視光域の変化は小さいが、特に高温側での赤外線透過率が大きく減少する。このため、近年の省エネルギーの気運から、いわゆるスマートガラスや自動調光ガラスと呼ばれるものへの応用研究が盛んに行われている。また、二酸化バナジウムは、転位に伴い体積が変わることを利用したマイクロアクチュエーターや抵抗変化メモリー素子などへの応用も研究されている。 It has been reported that vanadium dioxide causes a metal-semiconductor dislocation at around 70 ° C., which is relatively close to room temperature, and the electrical conductivity reversibly changes significantly (Non-Patent Document 1). This metal-semiconductor dislocation is said to be accompanied by a structural change between the monoclinic structure on the low temperature side and the tetragonal structure on the high temperature side. This metal-semiconductor dislocation also causes a thermochromic phenomenon in which optical characteristics such as transmittance and reflectance change. In this thermochromic phenomenon, the change in the visible light region is small, but the infrared transmittance particularly on the high temperature side is greatly reduced. For this reason, application research to what is called smart glass and automatic light control glass has been actively conducted in recent years due to energy saving. The application of vanadium dioxide to microactuators and resistance-change memory devices using the change in volume accompanying dislocation has also been studied.
スマートガラスへの応用として、スパッタ法で二酸化バナジウムを透明基板に成膜する方法が特許文献１に開示されている。しかし、スパッタ法によるスマートガラスの製造は、大きな電力を使用する上、スマートガラスを既存の建物に採用する場合にガラスの交換が必要となる問題があった。二酸化バナジウムを粉体として得ることができれば、塗料化して、二酸化バナジウムをガラスへ塗布、または二酸化バナジウムを塗布したフィルムをガラスに貼合することで、スマートガラスに変えることができる。 As an application to smart glass, Patent Document 1 discloses a method of forming a film of vanadium dioxide on a transparent substrate by a sputtering method. However, the production of smart glass by the sputtering method has a problem that, when using a large amount of electric power, the glass needs to be replaced when the smart glass is adopted in an existing building. If vanadium dioxide can be obtained as a powder, it can be converted into a smart glass by coating it and applying vanadium dioxide to glass, or bonding a film coated with vanadium dioxide to glass.
特許文献２には、二酸化バナジウム粉体を製造する方法が開示されている。これは、メタバナジン酸アンモニウム（ＮＨ4ＶＯ3）の温度と圧力を制御することで、二酸化バナジウムを製造する方法だが、反応の副産物として有毒なアンモニアガスが発生する上、加熱しながら圧力を制御するという複雑な操作が必要であり、簡便な方法とは言えない。特許文献３には、不活性ガス雰囲気下で、バナジウムを含む溶液にレーザーを照射して二酸化バナジウムを製造する方法が開示されている。しかし、これもまたレーザーという大きな電力を使用するという問題があった。 Patent Document 2 discloses a method for producing vanadium dioxide powder. This is a method for producing vanadium dioxide by controlling the temperature and pressure of ammonium metavanadate (NH 4 VO 3 ). Toxic ammonia gas is generated as a byproduct of the reaction, and the pressure is controlled while heating. Therefore, it is not a simple method. Patent Document 3 discloses a method for producing vanadium dioxide by irradiating a solution containing vanadium with a laser in an inert gas atmosphere. However, this also has a problem of using a large electric power of a laser.
特許文献４には、バナジウムアルコキシドを含む溶液と塩基性水溶液を反応させて前駆体を作成し、この前駆体を水素雰囲気で還元焼成することによって二酸化バナジウムを製造する方法が開示されている。この方法ではバナジウムアルコキシドという高価な薬剤を使用する上、水素中で還元するため、爆発の危険性があるという問題があった。また、二酸化バナジウムは、五酸化バナジウムを水素などの還元ガス内で加熱することで工業的に製造されるが、特許文献４記載の方法と同様に水素中で還元するため爆発の危険性がある。また、五酸化バナジウムの融点が６９０℃と比較的低いことから、高温で還元を行うと五酸化バナジウムが溶融するため、粉砕および分級工程が必要となる、逆に、低温で還元を行うと還元時間が長くなり、エネルギーおよび還元ガスの消費が大きくなるという問題があった。 Patent Document 4 discloses a method for producing vanadium dioxide by reacting a solution containing vanadium alkoxide with a basic aqueous solution to prepare a precursor, and reducing and firing the precursor in a hydrogen atmosphere. In this method, there is a problem that there is a risk of explosion because an expensive chemical called vanadium alkoxide is used and reduction is performed in hydrogen. In addition, vanadium dioxide is industrially produced by heating vanadium pentoxide in a reducing gas such as hydrogen. However, vanadium dioxide is reduced in hydrogen as in the method described in Patent Document 4, and thus there is a risk of explosion. . In addition, since vanadium pentoxide has a relatively low melting point of 690 ° C., reduction at a high temperature causes melting of vanadium pentoxide, so a pulverization and classification process is required. There was a problem that time was increased and consumption of energy and reducing gas was increased.
本発明は、このような事情に鑑みてなされたものであり、産業上有用な二酸化バナジウムを簡便かつ安価に製造することを目的とする。また、異種金属を添加した二酸化バナジウムを簡便かつ安価に製造することを目的とする。さらに、これらの方法によって製造された二酸化バナジウムを用いたサーモクロミック基板などの製品を提供することを目的とする。 This invention is made | formed in view of such a situation, and it aims at manufacturing industrially useful vanadium dioxide simply and cheaply. Another object of the present invention is to easily and inexpensively produce vanadium dioxide to which a different metal is added. Furthermore, it aims at providing products, such as a thermochromic board | substrate using the vanadium dioxide manufactured by these methods.
本発明者は鋭意検討を重ねた結果、五酸化バナジウム粉と炭素粉の混合物を不活性ガス雰囲気下で焼成することで五酸化バナジウムを還元し、所望の二酸化バナジウム粉が得られることを見出し、本発明の完成に至った。 As a result of intensive studies, the present inventors have found that vanadium pentoxide is reduced by firing a mixture of vanadium pentoxide powder and carbon powder in an inert gas atmosphere, and a desired vanadium dioxide powder can be obtained. The present invention has been completed.
本発明の二酸化バナジウムの製造方法は、バナジウムを含む酸化物と炭素源とを含有する混合物を焼成する。本発明の二酸化バナジウムの製造方法において、バナジウムを含む酸化物が五酸化バナジウムであることが好ましい。本発明の二酸化バナジウムの製造方法において、五酸化バナジウムに対する炭素源中の炭素の化学量論比が０.４７５〜１であることが好ましく、０.４７５〜０.５５であることがより好ましい。本発明の二酸化バナジウムの製造方法において、炭素源が炭素または炭素化合物であることが好ましい。 In the method for producing vanadium dioxide of the present invention, a mixture containing an oxide containing vanadium and a carbon source is fired. In the method for producing vanadium dioxide of the present invention, the oxide containing vanadium is preferably vanadium pentoxide. In the method for producing vanadium dioxide of the present invention, the stoichiometric ratio of carbon in the carbon source to vanadium pentoxide is preferably 0.475 to 1, and more preferably 0.475 to 0.55. In the method for producing vanadium dioxide of the present invention, the carbon source is preferably carbon or a carbon compound.
本発明の二酸化バナジウムの製造方法において、ヘリウム、ネオン、アルゴン、および窒素から選択される１以上のガス雰囲気下で混合物を焼成することが好ましく、窒素ガス雰囲気下で混合物を焼成することがより好ましい。本発明の二酸化バナジウムの製造方法において、５００〜１０００℃の温度で混合物を焼成することが好ましく、６００〜８００℃の温度で混合物を焼成することがより好ましい。 In the method for producing vanadium dioxide of the present invention, the mixture is preferably fired in one or more gas atmospheres selected from helium, neon, argon, and nitrogen, and more preferably fired in the nitrogen gas atmosphere. . In the manufacturing method of vanadium dioxide of this invention, it is preferable to bake a mixture at the temperature of 500-1000 degreeC, and it is more preferable to bake the mixture at the temperature of 600-800 degreeC.
本発明の異種金属添加二酸化バナジウムの製造方法は、バナジウムを含む酸化物と、炭素源と、バナジウム以外の金属の化合物とを含有する混合物を焼成する。本発明の他の態様の異種金属添加二酸化バナジウムの製造方法は、バナジウムを含む酸化物と、炭素源と、バナジウム以外の金属の酸化物またはこの金属のイオン溶液とを含有する混合物を焼成する。 In the method for producing a dissimilar metal-added vanadium dioxide of the present invention, a mixture containing an oxide containing vanadium, a carbon source, and a compound of a metal other than vanadium is fired. In another aspect of the present invention, a method for producing a dissimilar metal-added vanadium dioxide includes firing an oxide containing vanadium, a carbon source, an oxide of a metal other than vanadium, or an ion solution of the metal.
本発明のサーモクロミック製品は、本発明の製造方法で製造された二酸化バナジウムまたは異種金属添加二酸化バナジウムを有する。 The thermochromic product of this invention has vanadium dioxide manufactured by the manufacturing method of this invention, or a different metal addition vanadium dioxide.
本発明によれば、二酸化バナジウムが簡便かつ安価に得られる。また、本発明の他の態様によれば、異種金属を添加した二酸化バナジウムが簡便かつ安価に得られる。さらに、これらの二酸化バナジウムおよび異種金属添加二酸化バナジウムを原料として、サーモクロミック基板など、二酸化バナジウムの金属−半導体転位による光学的、物理的、磁気的特性を利用した製品を安価に製造することが可能になる。 According to the present invention, vanadium dioxide can be obtained simply and inexpensively. Moreover, according to the other aspect of this invention, the vanadium dioxide which added the different metal can be obtained simply and cheaply. Furthermore, using these vanadium dioxide and dissimilar metal-added vanadium dioxide as raw materials, it is possible to inexpensively manufacture products that use optical, physical, and magnetic properties due to metal-semiconductor dislocations of vanadium dioxide, such as thermochromic substrates. become.
以下、本発明の製造方法ついて、図面を参照しながら実施形態と実施例に基づいて詳細に説明する。なお、重複説明は適宜省略する。また、２つの数値の間に「〜」を記載して数値範囲を表す場合には、この２つの数値も数値範囲に含まれるものとする。 Hereinafter, the manufacturing method of the present invention will be described in detail based on embodiments and examples with reference to the drawings. Note that repeated explanation is omitted as appropriate. In addition, when “˜” is described between two numerical values to represent a numerical range, the two numerical values are also included in the numerical range.
本発明の二酸化バナジウムの製造方法は、バナジウムを含む酸化物と炭素源とを含有する混合物を焼成する。具体例として、バナジウムを含む酸化物の粉体と、炭素源の粉体とを混ぜ合わせて成形し、炉内で焼成する方法が挙げられる。バナジウムを含む酸化物は五酸化バナジウム（Ｖ2Ｏ5）であることが好ましい。五酸化バナジウムは、一般にウランを製造する際の副産物として、または石油を燃料とする工場の煙塵などから得られるが、特にその製法を限定するものではない。炭素源は、炭素そのものまたは炭素化合物であることが好ましい。 In the method for producing vanadium dioxide of the present invention, a mixture containing an oxide containing vanadium and a carbon source is fired. As a specific example, there is a method in which an oxide powder containing vanadium and a carbon source powder are mixed and molded and fired in a furnace. The oxide containing vanadium is preferably vanadium pentoxide (V 2 O 5 ). Vanadium pentoxide is generally obtained as a by-product in the production of uranium or from the dust of factories that use petroleum as fuel, but the production method is not particularly limited. The carbon source is preferably carbon itself or a carbon compound.
カーボンブラック、アセチレンブラック、ファーネスブラック、グラファイトなどの炭素そのものを炭素源として用いるのが簡明だが、五酸化バナジウムとともに加熱すると揮発する前に分解して炭化する化合物や焼成温度で炭素以外の不純物を残さない有機化合物を炭素源として用いることも可能である。このような化合物として、パラフィン、エチレン酢酸ビニル、セルロース、ポリエチレンオキサイド、ステアリン酸などが挙げられる。 It is easy to use carbon itself such as carbon black, acetylene black, furnace black, graphite, etc. as a carbon source. However, when heated with vanadium pentoxide, it decomposes and carbonizes before it volatilizes, and impurities other than carbon remain at the firing temperature. It is also possible to use non-organic compounds as carbon sources. Examples of such compounds include paraffin, ethylene vinyl acetate, cellulose, polyethylene oxide, and stearic acid.
これらの化合物が還元雰囲気で炭化する際は、炭化水素やフランなどの低分子量の多種多様な成分となって揮発することが知られている。このため、五酸化バナジウムと混合するこれらの化合物の量を、反応条件などに合わせる必要がある。したがって、炭素源として炭素自体を使用することが簡便である。焼成は大気中でも可能だが、二酸化バナジウムの再酸化を防ぐために、ヘリウム、ネオン、アルゴンなどの希ガス、および窒素から選択される１以上のガス雰囲気下で焼成することが好ましい。これらの中で最も安価なことから、窒素ガス雰囲気下で焼成することがより好ましい。 It is known that when these compounds are carbonized in a reducing atmosphere, they volatilize as a wide variety of low molecular weight components such as hydrocarbons and furans. For this reason, it is necessary to match the amount of these compounds mixed with vanadium pentoxide to the reaction conditions. Therefore, it is convenient to use carbon itself as a carbon source. Baking is possible in the air, but in order to prevent reoxidation of vanadium dioxide, it is preferable to bake in one or more gas atmospheres selected from rare gases such as helium, neon, and argon, and nitrogen. Since these are the cheapest of these, firing in a nitrogen gas atmosphere is more preferable.
不活性ガスは、混合物の周囲に存在する酸素による炭素源の酸化を防止する。このため、焼成時の雰囲気ガスとして、ヘリウム、ネオン、アルゴンなどの希ガスを使うことも可能だが、コスト面から窒素を使うことが適当である。また、本発明の二酸化バナジウムの製造方法では、副生成物が二酸化炭素だけなので、特別な回収・処理設備を必要としない。このため、本発明の二酸化バナジウムの製造方法は、産業的規模で実施可能である。 The inert gas prevents oxidation of the carbon source by oxygen present around the mixture. For this reason, it is possible to use a rare gas such as helium, neon, or argon as the atmospheric gas during firing, but it is appropriate to use nitrogen from the viewpoint of cost. Further, in the method for producing vanadium dioxide of the present invention, since the by-product is only carbon dioxide, no special recovery / treatment facility is required. For this reason, the manufacturing method of vanadium dioxide of this invention can be implemented on an industrial scale.
五酸化バナジウムと炭素源から二酸化バナジウムを製造するときの化学反応を式で表すと、２Ｖ2Ｏ5＋Ｃ→４ＶＯ2＋ＣＯ2となり非常にシンプルである。この化学反応を進めるためには加熱が必要である。五酸化バナジウムと炭素源とを含有する混合物を焼成するときの温度は、５００〜１０００℃が好ましく、６００〜８００℃がより好ましい。焼成温度が低過ぎると、得られる二酸化バナジウムの結晶性が低かったり、反応に時間がかかったりする問題ある。焼成温度が高過ぎると、加熱のためのエネルギー消費の増大、バナジウムの昇華によるロス、二酸化バナジウム以外の酸化バナジウムの生成などが起こりうる。 When the chemical reaction when producing vanadium dioxide from vanadium pentoxide and a carbon source is expressed by a formula, it is very simple as 2V 2 O 5 + C → 4VO 2 + CO 2 . Heating is necessary to advance this chemical reaction. 500-1000 degreeC is preferable and, as for the temperature when baking the mixture containing vanadium pentoxide and a carbon source, 600-800 degreeC is more preferable. When the calcination temperature is too low, there is a problem that the crystallinity of the obtained vanadium dioxide is low or the reaction takes time. If the firing temperature is too high, an increase in energy consumption for heating, loss due to sublimation of vanadium, production of vanadium oxide other than vanadium dioxide, and the like may occur.
本発明のように、焼成による無機合成で副産物が生じない場合は、一般的に焼成時間とともに結晶が成長するものの、その成長は飽和する傾向にある。このため、短時間焼成では結晶成長が十分に行われず、長時間焼成ではエネルギー消費が増大することが知られている。したがって、本発明の製造方法では、結晶成長が十分に行われる時間だけ焼成すればよい。 As in the present invention, when no by-product is produced by inorganic synthesis by firing, crystals generally grow with firing time, but the growth tends to be saturated. For this reason, it is known that crystal growth does not occur sufficiently in short-time firing, and energy consumption increases in long-time firing. Therefore, in the manufacturing method of the present invention, the firing may be performed only for a time during which crystal growth is sufficiently performed.
混合物中の五酸化バナジウムと炭素源中の炭素の化学量論比は、化学反応式上２：１が理想だが、不活性ガス雰囲気下での加熱焼成が少なからず還元傾向にあることから、炭素が化学量論比より少ない場合でも、五酸化バナジウムが二酸化バナジウムに還元される。また、混合物中の炭素が化学量論比より多過ぎる場合には、二酸化バナジウム以外の酸化バナジウムの生成が起こったり、生成後の二酸化バナジウムに炭素が残留したりする。このため、五酸化バナジウムと炭素源中の炭素の化学量論比、すなわち物質量比（いわゆるモル比）は、五酸化バナジウム：炭素が２：０.９５〜２：２であることが好ましく、２：０.９５〜２：１．１であることがより好ましい。換言すると、五酸化バナジウムに対する炭素源中の炭素の化学量論比が０.４７５〜１であることが好ましく、０.４７５〜０.５５であることがより好ましい。 The stoichiometric ratio of vanadium pentoxide in the mixture to carbon in the carbon source is ideally 2: 1 in terms of the chemical reaction formula, but since there is a considerable tendency to reduce heat and calcination in an inert gas atmosphere, carbon Is less than the stoichiometric ratio, vanadium pentoxide is reduced to vanadium dioxide. Moreover, when there is too much carbon in a mixture than a stoichiometric ratio, the production | generation of vanadium oxides other than vanadium dioxide will occur, or carbon will remain in the vanadium dioxide after production | generation. Therefore, the stoichiometric ratio of vanadium pentoxide to carbon in the carbon source, that is, the substance amount ratio (so-called molar ratio) is preferably vanadium pentoxide: carbon of 2: 0.95 to 2: 2. It is more preferable that it is 2: 0.95-2: 1.1. In other words, the stoichiometric ratio of carbon in the carbon source to vanadium pentoxide is preferably 0.475 to 1, and more preferably 0.475 to 0.55.
例えばスマートガラスの被覆層は、二酸化バナジウム自体の転位温度約７０℃より室温に近い転位温度を有する物質から構成されることが望まれる。バナジウムの安定酸化状態である二酸化バナジウム中のバナジウムの価数４価よりも、安定酸化状態での価数が高いニオビウムやタングステンなどが二酸化バナジウムの結晶格子内に存在すると、すなわち二酸化バナジウムにドープされていると、転移温度が７０℃より下がることが知られている。 For example, the coating layer of smart glass is desirably made of a material having a transition temperature closer to room temperature than the transition temperature of about 70 ° C. of vanadium dioxide itself. Niobium or tungsten having a higher valence in the stable oxidation state than vanadium in the vanadium dioxide, which is the stable oxidation state of vanadium, is present in the crystal lattice of vanadium dioxide, that is, vanadium dioxide is doped. The transition temperature is known to fall below 70 ° C.
本発明の異種金属添加二酸化バナジウムの製造方法は、バナジウムを含む酸化物と、炭素源と、バナジウム以外の金属の化合物を含有する混合物を焼成する方法である。また、本発明の他の異種金属添加二酸化バナジウムの製造方法は、バナジウムを含む酸化物と、炭素源と、バナジウム以外の金属の酸化物またはこの金属のイオンを含有する混合物を焼成する方法である。具体例として、バナジウムを含む酸化物の粉体と、炭素源の粉体と、安定酸化状態での価数が４価より高い金属の酸化物、この金属の塩、またはこの金属のイオン溶液とを混ぜ合わせた後に成形し、炉内で焼成する方法が挙げられる。これらの方法によって、転移温度が７０℃より低い異種金属添加二酸化バナジウムが得られる。 The manufacturing method of the dissimilar metal addition vanadium dioxide of this invention is a method of baking the mixture containing the oxide of vanadium, the carbon source, and the compound of metals other than vanadium. In addition, another method for producing a different kind of metal-added vanadium dioxide of the present invention is a method of firing a mixture containing an oxide containing vanadium, a carbon source, an oxide of a metal other than vanadium, or an ion of this metal. . As specific examples, an oxide powder containing vanadium, a carbon source powder, a metal oxide having a valence higher than tetravalent in a stable oxidation state, a salt of the metal, or an ion solution of the metal And a method of forming and baking in an oven. By these methods, dissimilar metal-added vanadium dioxide having a transition temperature lower than 70 ° C. is obtained.
なお、安定酸化状態での価数が４価より高い金属に代えて、安定酸化状態での価数が４価以下の金属、例えば安定酸化状態での価数が３価のガリウムを用いて、これらの異種金属添加二酸化バナジウムの製造方法を行ってもよい。安定酸化状態での価数が３価の金属を添加すると、転移温度が高くなる場合が多いが、転移温度が低くなる場合もあるからである。また、転移温度が高い異種金属添加二酸化バナジウムは、例えばガスセンサに使用できる。 In place of a metal having a valence in the stable oxidation state higher than tetravalent, a metal having a valence in the stable oxidation state of 4 or less, for example, gallium having a valence in the stable oxidation state of trivalent, You may perform the manufacturing method of these different metal addition vanadium dioxide. This is because when a metal having a valence of 3 in a stable oxidation state is added, the transition temperature is often increased, but the transition temperature may be lowered. Moreover, the dissimilar metal addition vanadium dioxide with a high transition temperature can be used for a gas sensor, for example.
本発明の製造方法で得られる二酸化バナジウムまたは異種金属添加二酸化バナジウムの懸濁液を透明基板に塗布・乾燥することで、サーモクロミック性に優れた基板を作製することが可能であり、この簡便かつ安価な製造方法によって更なる用途拡大の可能性が高くなる。自動調光ガラスを代表とする本発明のサーモクロミック製品は、本発明の製造方法で得られる二酸化バナジウムまたは異種金属添加二酸化バナジウムを有している。具体的には、この二酸化バナジウムまたは異種金属添加二酸化バナジウムが、ガラスの表面に被覆されている。 By applying and drying a suspension of vanadium dioxide or a dissimilar metal-added vanadium dioxide obtained by the production method of the present invention on a transparent substrate, it is possible to produce a substrate having excellent thermochromic properties. The possibility of further application expansion is increased by an inexpensive manufacturing method. The thermochromic product of the present invention typified by an automatic light control glass has vanadium dioxide or a dissimilar metal-added vanadium dioxide obtained by the production method of the present invention. Specifically, the vanadium dioxide or the dissimilar metal added vanadium dioxide is coated on the surface of the glass.
以下に実施例を掲げて本発明の態様をさらに詳しく説明するが、本発明はこれらの実施例によって何ら限定されるものではない。図１は、本発明の製造方法の焼成に用いる炉を模式的に示している。なお、図面上の炉の寸法および寸法比は、実物の寸法および寸法比と必ずしも一致していない。 Examples of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. FIG. 1 schematically shows a furnace used for firing in the production method of the present invention. In addition, the dimension and dimension ratio of the furnace on drawing do not necessarily correspond with the dimension and dimension ratio of a real thing.
１．二酸化バナジウムおよび異種金属添加二酸化バナジウムの製造
（実施例１〜１６）
まず、表１に示す化学量論比で、五酸化バナジウム（和光純薬工業社製）と、炭素源として炭素であるＣａｒｂｏｎ Ｂｌａｃｋ（Ａｌｆａ Ａｅｓａｒ社製）とを乳鉢で混合して混合物である混合粉を調製した。つぎに、この混合粉を錠剤成形機に入れて加圧成形し、ペレットを得た。そして、図１に示す管状の炉内にサンプルであるこのペレットを入れ、窒素をフローしながら毎時５００℃の昇温速度で表１に示す焼成温度まで上昇させ、この焼成温度で表１に示す焼成時間だけ保持した後、自然放冷にて室温まで下げて焼成ペレットを得た。つぎに、この焼成ペレットを乳鉢で粉砕して焼成粉を得た。
1. Production of vanadium dioxide and dissimilar metal-added vanadium dioxide (Examples 1 to 16)
First, vanadium pentoxide (manufactured by Wako Pure Chemical Industries, Ltd.) and Carbon Black (manufactured by Alfa Aesar) as a carbon source are mixed in a mortar at a stoichiometric ratio shown in Table 1, and the mixture is a mixture Powder was prepared. Next, this mixed powder was put into a tablet molding machine and subjected to pressure molding to obtain pellets. And this pellet which is a sample is put in the tubular furnace shown in FIG. 1, and it raises to the calcination temperature shown in Table 1 with the temperature increase rate of 500 degreeC / hour, flowing nitrogen, and shows in Table 1 with this calcination temperature. After holding only the firing time, it was cooled to room temperature by natural cooling to obtain fired pellets. Next, the fired pellets were pulverized in a mortar to obtain fired powder.
（実施例１７）
まず、炭素源であるパラフィン（和光純薬製）０.２ｇをトルエン２ｍＬに溶解してパラフィン溶液を作製した。つぎに、五酸化バナジウム（和光純薬工業社製）０.５０ｇにこのパラフィン溶液０.４０ｍＬを加えた後、溶剤臭がなくなるまで加温しながら乳鉢で混合して、混合物である混合粉を調製した。そして、この混合粉を実施例１と同様にして成型、焼成、粉砕し、パラフィン系焼成粉を得た。
なお、パラフィンの化学式をＣnＨ2n+2として化学量論比Ｖ2Ｏ5：Ｃを算出した。
(Example 17)
First, 0.2 g of paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) as a carbon source was dissolved in 2 mL of toluene to prepare a paraffin solution. Next, after adding 0.40 mL of this paraffin solution to 0.50 g of vanadium pentoxide (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture is mixed in a mortar while heating until the solvent odor disappears. Prepared. The mixed powder was molded, fired and pulverized in the same manner as in Example 1 to obtain a paraffin-based fired powder.
The stoichiometric ratio V 2 O 5 : C was calculated with the chemical formula of paraffin as C n H 2n + 2 .
（実施例１８）
まず、炭素源であるポリエチレングリコール（関東化学製 重合度６,０００）０.０６６ｇを五酸化バナジウム（和光純薬工業社製）０.５０ｇに加えて、乳鉢で混合して混合物である混合粉を調製した。つぎに、この混合粉を実施例１と同様にして成型、焼成、粉砕し、ＰＥＧ系焼成粉を得た。なお、ＰＥＧの化学式をＣ2nＨ4n+2Ｏnとして化学量論比Ｖ2Ｏ5：Ｃを算出した。
(Example 18)
First, 0.066 g of polyethylene glycol as a carbon source (polymerization degree 6,000, manufactured by Kanto Chemical Co., Ltd.) is added to 0.50 g of vanadium pentoxide (manufactured by Wako Pure Chemical Industries, Ltd.) and mixed in a mortar to form a mixed powder. Was prepared. Next, this mixed powder was molded, fired, and pulverized in the same manner as in Example 1 to obtain a PEG-based fired powder. Incidentally, the stoichiometric ratio of PEG formula as C 2n H 4n + 2 O n V 2 O 5: was calculated C.
（実施例１９、２０）
まず、実施例１で調製した混合粉２.０６６ｇに、Ｎｂ源であるＮｂ系ディップコート液（高純度化学研究所社製、ＳＹＭ−ＮＢ０５）を０.４４４ｍＬ（実施例１９）または１.３６ｍＬ（実施例２０）を加えた後、溶剤臭がなくなるまで加温しながら乳鉢で混合して、混合物である混合粉を調製した。つぎに、この混合粉を実施例１と同様にして成型、焼成、粉砕し、Ｎｂ１％添加焼成粉（実施例１９）またはＮｂ３％添加焼成粉（実施例２０）を得た。
(Examples 19 and 20)
First, 0.444 mL (Example 19) or 1.36 mL of Nb-based dip coat solution (manufactured by Kojundo Chemical Laboratory Co., Ltd., SYM-NB05) as an Nb source was added to 2.066 g of the mixed powder prepared in Example 1. (Example 20) was added, and then mixed in a mortar while heating until the solvent odor disappeared to prepare a mixed powder as a mixture. Next, this mixed powder was molded, fired, and pulverized in the same manner as in Example 1 to obtain Nb 1% added fired powder (Example 19) or Nb 3% added fired powder (Example 20).
（実施例２１）
まず、実施例１で調製した混合粉１.０３３ｇに、Ｇａ源であるガリウムアセチルアセトナート（Ａｌｆｅｒ Ａｅｓａｒ社製、Ｇａ(ａｃａｃ)3）を０.０８２４ｇ加えた後、乳鉢で混合して、混合物である混合粉を調製した。つぎに、この混合粉を実施例１と同様にして成型、焼成（７００℃で５時間）、粉砕し、Ｇａ２％添加焼成粉を得た。
(Example 21)
First, 0.0824 g of gallium acetylacetonate (Alfer Aesar, Ga (acac) 3 ) as a Ga source was added to 1.033 g of the mixed powder prepared in Example 1, and then mixed in a mortar. A mixed powder was prepared. Next, the mixed powder was molded, fired (at 700 ° C. for 5 hours) and pulverized in the same manner as in Example 1 to obtain a Ga 2% -added fired powder.
（比較例）
五酸化バナジウム（和光純薬工業社製）０.５ｇを、実施例１と同様にして成型、焼成、粉砕し、五酸化バナジウム焼成粉を得た。
(Comparative example)
In the same manner as in Example 1, 0.5 g of vanadium pentoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was molded, fired, and pulverized to obtain a burned vanadium pentoxide powder.
２．評価と検討
（評価−１：結晶性）
ＸＲＤ（Ｒｉｇａｋｕ社製、Ｓｍａｒｔ Ｌａｂ）を用いたＸ線回折法で、実施例および比較例で得られた二酸化バナジウムおよび異種金属添加二酸化バナジウムの焼成粉の結晶構造を特定した。なお、測定条件は、電圧４０ｋＶ、電流３０ｍＡ、スキャン速度２°／ｍｉｎ、回折角２θ＝１０〜７０°とした。綺麗なＶＯ2のピーク（（０１１）面、２θ＝２７.８°など）のみが確認された場合を「○」、ＶＯ2のピークに加えてＶ2Ｏ5など他の酸化物のピークが確認された場合、またはＶＯ2の結晶性が明らかに悪い場合を「△」、ＶＯ2のピークが確認されない場合、または試料が回収できなかった場合を「×」とした。その結果を表１に示す。
2. Evaluation and examination (Evaluation-1: Crystallinity)
The crystal structure of the burned powders of vanadium dioxide and dissimilar metal-added vanadium dioxide obtained in Examples and Comparative Examples was identified by X-ray diffraction using XRD (manufactured by Rigaku, Smart Lab). The measurement conditions were as follows:
（評価−２：金属−半導体転位温度）
実施例および比較例で得られた二酸化バナジウムおよび異種金属添加二酸化バナジウムの焼成粉を加圧成形後、ペルチェヒーター（アンペール社製、ＵＴＣ−１００）とデジタルソースメーター（Ｋｅｉｔｈｌｅｙ社製、２４００型汎用ソースメータ）を用いて、温度−抵抗特性を測定した。なお、測定条件は、温度範囲を−１０℃から１１４℃、温度ステップを４℃、測定電流を１ｍＡとした。実施例１で得られた二酸化バナジウムおよび実施例１９で得られた異種金属添加二酸化バナジウムの温度−抵抗特性を図２に示す。また、温度−抵抗特性で、昇温時の抵抗の変曲点を金属−半導体転位温度とした。その結果も表１に示す。
(Evaluation-2: Metal-semiconductor dislocation temperature)
After pressure-molding the burned powder of vanadium dioxide and dissimilar metal-added vanadium dioxide obtained in Examples and Comparative Examples, Peltier heater (Amper, UTC-100) and digital source meter (Keithley, 2400 type general-purpose source) The temperature-resistance characteristics were measured using a meter. The measurement conditions were a temperature range of −10 ° C. to 114 ° C., a temperature step of 4 ° C., and a measurement current of 1 mA. The temperature-resistance characteristics of the vanadium dioxide obtained in Example 1 and the dissimilar metal-added vanadium dioxide obtained in Example 19 are shown in FIG. In addition, in the temperature-resistance characteristics, the inflection point of the resistance at the time of temperature rise was defined as the metal-semiconductor transition temperature. The results are also shown in Table 1.
（混合粉中の五酸化バナジウムと炭素の化学量論比の検討）
表１に示すように、五酸化バナジウムと炭素源を不活性ガス雰囲気下で焼成することにより、二酸化バナジウムが生成することがわかった。実施例１および実施例３〜５より、焼成温度７００℃の場合、五酸化バナジウムと炭素源中の炭素の化学量論比は、五酸化バナジウム：炭素＝２：０.９５〜２：２のときに、Ｘ線回折で綺麗なＶＯ2のピークのみが検出された。五酸化バナジウム：炭素＝２：３である実施例６では、生成したＶＯ2の結晶性が良くなかった。五酸化バナジウム：炭素＝２：０.９である実施例２では、Ｘ線回折で原料のＶ2Ｏ5のピークが認められた。したがって、好ましい五酸化バナジウムと炭素源中の炭素の化学量論比の範囲は、五酸化バナジウム：炭素＝２：０.９５〜２：２である。
(Study of stoichiometric ratio of vanadium pentoxide and carbon in mixed powder)
As shown in Table 1, it was found that vanadium dioxide was produced by firing vanadium pentoxide and a carbon source in an inert gas atmosphere. From Example 1 and Examples 3-5, when the calcination temperature is 700 ° C., the stoichiometric ratio of vanadium pentoxide to carbon in the carbon source is vanadium pentoxide: carbon = 2: 0.95 to 2: 2. Occasionally only a clean VO 2 peak was detected by X-ray diffraction. In Example 6 where vanadium pentoxide: carbon = 2: 3, the crystallinity of the produced VO 2 was not good. In Example 2 where vanadium pentoxide: carbon = 2: 0.9, the peak of the raw material V 2 O 5 was observed by X-ray diffraction. Therefore, the preferred stoichiometric ratio of vanadium pentoxide to carbon in the carbon source is vanadium pentoxide: carbon = 2: 0.95 to 2: 2.
なお、焼成温度が７００℃のときにはＶＯ2のみが生成される五酸化バナジウム：炭素＝２：１.２５の化学量論比の混合粉を９００℃で焼成した実施例１６では、Ｘ線回折において、ＶＯ2よりもバナジウムが還元されているバナジウム酸化物と思われるピークが出現した。炭素源の量が多く、反応温度が高くなって還元力も高まった結果と考えられる。一方、五酸化バナジウム：炭素＝２：１.１の混合粉を９００℃で焼成した実施例１５では、ＶＯ2のみが生成された。したがって、より好ましい五酸化バナジウムと炭素源中の炭素の化学量論比の範囲は、五酸化バナジウム：炭素＝２：０.９５〜２：１.１である。五酸化バナジウムと炭素源中の炭素の最も好ましい化学量論比は、五酸化バナジウム：炭素がほぼ２：１のときであると言える。 In Example 16 in which a mixed powder having a stoichiometric ratio of vanadium pentoxide: carbon = 2: 1.25 in which only VO 2 is generated when the firing temperature is 700 ° C. is fired at 900 ° C. A peak that appears to be vanadium oxide in which vanadium is reduced rather than VO 2 appeared. This is probably because the amount of carbon source was large, the reaction temperature was high, and the reducing power was increased. On the other hand, in Example 15 where the mixed powder of vanadium pentoxide: carbon = 2: 1.1 was fired at 900 ° C., only VO 2 was produced. Therefore, a more preferable range of the stoichiometric ratio of vanadium pentoxide to carbon in the carbon source is vanadium pentoxide: carbon = 2: 0.95 to 2: 1.1. The most preferred stoichiometric ratio of vanadium pentoxide to carbon in the carbon source can be said to be when vanadium pentoxide: carbon is approximately 2: 1.
（焼成温度の検討）
実施例８〜１３からわかるように、五酸化バナジウム：炭素＝２：１の化学量論比の混合粉を６００〜１０００℃で焼成すれば、ＶＯ2のみが生成した。実施例７の焼成温度５５０℃でもＶＯ2が生成したが、結晶性は良くなかった。焼成温度５５０℃で焼成時間を延長すれば結晶性が良くなる可能性はあるものの、簡便かつ安価にＶＯ2を製造するためには、焼成温度は６００℃以上が好ましい。また、この混合粉を１０００℃より高温で焼成してもＶＯ2のみが生成すると思われるが、エネルギー消費抑制のため焼成温度は１０００℃以下が好ましく、８００℃以下がより好ましい。
(Examination of firing temperature)
As can be seen from Examples 8 to 13, when a mixed powder having a stoichiometric ratio of vanadium pentoxide: carbon = 2: 1 was fired at 600 to 1000 ° C., only VO 2 was produced. Although VO 2 was produced even at the firing temperature of Example 7 at 550 ° C., the crystallinity was not good. Although the crystallinity may be improved if the baking time is extended at a baking temperature of 550 ° C., the baking temperature is preferably 600 ° C. or higher in order to produce VO 2 easily and inexpensively. Moreover, even if this mixed powder is fired at a temperature higher than 1000 ° C., only VO 2 appears to be produced, but the firing temperature is preferably 1000 ° C. or lower, and more preferably 800 ° C. or lower for suppressing energy consumption.
（焼成時間の検討）
五酸化バナジウム：炭素＝２：１の化学量論比の混合粉を７００℃で焼成した実施例１、実施例１２、および実施例１３から、焼成時間の好ましい範囲を検討した。実用的と思われる焼成時間１０分〜１０時間で結晶性の違いが多少見られたものの、いずれもＶＯ2のみが生成したことから、焼成時間の範囲は特に限定されるものではなかった。
(Examination of firing time)
From Example 1, Example 12, and Example 13 in which a mixed powder having a stoichiometric ratio of vanadium pentoxide: carbon = 2: 1 was calcined at 700 ° C., a preferable range of calcining time was examined. Although some difference in crystallinity was observed at a firing time of 10 minutes to 10 hours that seemed to be practical, since only VO 2 was produced in each case, the range of the firing time was not particularly limited.
（炭素源の種類の検討）
実施例１７および実施例１８では、炭素源をパラフィンおよびポリエチレングリコールに変更してもＶＯ2が生成するか調べた。いずれの炭素源でもＶＯ2が生成した。したがって、炭素源は炭素に限定されず、混合粉の焼成温度で炭化して炭素源として残存する物質、すなわち高温の還元雰囲気で炭素が残る物質であればよいと考えられる。
(Examination of types of carbon sources)
In Example 17 and Example 18, it was examined whether VO 2 was generated even when the carbon source was changed to paraffin and polyethylene glycol. VO 2 was produced with any carbon source. Therefore, it is considered that the carbon source is not limited to carbon, and may be any substance that carbonizes at the firing temperature of the mixed powder and remains as a carbon source, that is, a substance in which carbon remains in a high-temperature reducing atmosphere.
（異種金属の添加の検討）
実施例１９および実施例２０では、焼成粉中のバナジウムと異種金属のモル比が９９：１および９７：３となるようにニオビウムをドープして異種金属添加二酸化バナジウムを得た。表１に示すように、実施例１の二酸化バナジウムの転移温度は、ほぼ文献通りの７２℃であったのに対し、実施例１９の異種金属添加二酸化バナジウムの転移温度は５６℃に、実施例２０の異種金属添加二酸化バナジウムの転移温度は４０℃にそれぞれ下がっている。これはＶＯ2の格子内にニオビウムがドープされたことを示している。したがって、本発明の二酸化バナジウムの製造方法において、焼成前の混合粉に異種金属の溶液等を混ぜることで、簡単に異種金属をドープした二酸化バナジウム、すなわち異種金属添加二酸化バナジウムが生成できることがわかった。
(Examination of addition of different metals)
In Example 19 and Example 20, niobium was doped so that the molar ratio of vanadium to the different metal in the fired powder was 99: 1 and 97: 3 to obtain a different metal-added vanadium dioxide. As shown in Table 1, the transition temperature of vanadium dioxide of Example 1 was 72 ° C., almost as described in the literature, whereas the transition temperature of dissimilar metal-added vanadium dioxide of Example 19 was 56 ° C. The transition temperature of 20 different metal added vanadium dioxides is lowered to 40 ° C., respectively. This indicates that niobium is doped in the VO 2 lattice. Therefore, in the method for producing vanadium dioxide of the present invention, it was found that vanadium dioxide doped with a different metal, that is, vanadium dioxide added with a different metal, can be easily generated by mixing a mixed metal solution or the like into the mixed powder before firing. .
（総括）
以上、実施形態および実施例に基づいて本発明を説明したが、ここに示した物質、組成、構成、および使用方法などは本発明を限定するものではなく、２Ｖ2Ｏ5＋Ｃ→４ＶＯ2＋ＣＯ2の化学反応を起こさせる原材料、炉などの設備、および環境などがあればよい。
(Summary)
The present invention has been described based on the embodiments and examples. However, the materials, compositions, configurations, usage methods, and the like shown here do not limit the present invention, and 2V 2 O 5 + C → 4VO 2 + CO It only needs to have raw materials, furnaces, and environments that can cause chemical reactions.
本発明によれば、安価な原材料を元に、特殊な装置や特殊なガスなどを使わずに、簡便かつ安価に二酸化バナジウムおよび異種金属添加二酸化バナジウムを提供することができる。二酸化バナジウムの金属−絶縁体転位による特性の変化を利用したアプリケーションには、例えばサーモクロミック特性を利用した自動調光ガラスなどがある。本発明の製造方法で製造された二酸化バナジウムおよび異種金属添加二酸化バナジウムは、転移温度での物理特性の変化を利用した自動調光ガラスを代表とするサーモクロミック製品などに利用可能である。しかし、アプリケーションや使用条件によって求められる転移温度が変わることは想像に難くない。本発明では、異種金属のドープも可能、すなわち、転位点の変更も可能である。したがって、自動調光ガラスへの応用を念頭に置いてきたが、簡便なプロセスであることから新規分野への展開の可能性が広がる。 ADVANTAGE OF THE INVENTION According to this invention, vanadium dioxide and a dissimilar-metal addition vanadium dioxide can be provided simply and cheaply without using a special apparatus, special gas, etc. based on an inexpensive raw material. Examples of applications using the change in characteristics of vanadium dioxide due to metal-insulator dislocation include automatic light control glass using thermochromic characteristics. The vanadium dioxide and the dissimilar metal-added vanadium dioxide produced by the production method of the present invention can be used for thermochromic products typified by automatic light control glass utilizing the change in physical properties at the transition temperature. However, it is not difficult to imagine that the required transition temperature varies depending on the application and use conditions. In the present invention, it is possible to dope different metals, that is, change the dislocation point. Therefore, the application to automatic light control glass has been kept in mind, but since it is a simple process, the possibility of expanding into new fields is expanded.
Claims (12)
前記バナジウムを含む酸化物が五酸化バナジウムである二酸化バナジウムの製造方法。 In claim 1,
A method for producing vanadium dioxide, wherein the oxide containing vanadium is vanadium pentoxide.
前記五酸化バナジウムに対する前記炭素源中の炭素の化学量論比が０.４７５〜１である二酸化バナジウムの製造方法。 In claim 2,
The manufacturing method of vanadium dioxide whose stoichiometric ratio of the carbon in the said carbon source with respect to the said vanadium pentoxide is 0.475-1.
前記五酸化バナジウムに対する前記炭素源中の炭素の化学量論比が０.４７５〜０.５５である二酸化バナジウムの製造方法。 In claim 2,
A method for producing vanadium dioxide, wherein the stoichiometric ratio of carbon in the carbon source to vanadium pentoxide is 0.475 to 0.55.
前記炭素源が炭素または炭素化合物である二酸化バナジウムの製造方法。 In any one of Claim 1-4,
A method for producing vanadium dioxide, wherein the carbon source is carbon or a carbon compound.
ヘリウム、ネオン、アルゴン、および窒素から選択される１以上のガス雰囲気下で前記混合物を焼成する二酸化バナジウムの製造方法。 In any one of Claim 1 to 5,
A method for producing vanadium dioxide, comprising firing the mixture under one or more gas atmospheres selected from helium, neon, argon, and nitrogen.
窒素ガス雰囲気下で前記混合物を焼成する二酸化バナジウムの製造方法。 In any one of Claim 1 to 5,
A method for producing vanadium dioxide, wherein the mixture is fired in a nitrogen gas atmosphere.
６００〜１０００℃の温度で前記混合物を焼成する二酸化バナジウムの製造方法。 In claim 6 or 7,
A method for producing vanadium dioxide, comprising firing the mixture at a temperature of 600 to 1000 ° C.
６００〜８００℃の温度で前記混合物を焼成する二酸化バナジウムの製造方法。 In claim 6 or 7,
A method for producing vanadium dioxide, comprising firing the mixture at a temperature of 600 to 800 ° C.
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