JP2010111536A - Metal oxide dispersion and manufacturing method - Google Patents
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本発明は、金属酸化物分散液およびその製造方法に関し、特に、金属酸化物のナノ粒子が良分散した塩基性金属酸化物分散透明ゾル水溶液とその有利な製造方法に関する。本発明において、良分散とは、動的光散乱法により測定した水溶液中における金属酸化物粒子の平均分散粒子径が５０ｎｍ以下であるであることを意味する。 The present invention relates to a metal oxide dispersion and a method for producing the same, and more particularly to a basic metal oxide-dispersed transparent sol aqueous solution in which metal oxide nanoparticles are well dispersed and an advantageous method for producing the same. In the present invention, good dispersion means that the average dispersed particle diameter of metal oxide particles in an aqueous solution measured by a dynamic light scattering method is 50 nm or less.
金属酸化物はその組成により、優れた機械的、電気的、磁気的および光学的な物性を発現することから、幅広い分野で利用されている。例えば、ジルコニア（ＺｒＯ２）は高温で固体電解質となることから燃料電池や酸素センサの材料として用いられる一方、高硬度と高靭性を両立することから、ナイフや鋏の材料としても利用されている。また、チタニア（ＴｉＯ２）は強い光触媒活性を有することから、環境浄化用触媒として利用され、水の分解による一段階での水素合成、あるいは色素増感型太陽電池等への応用も期待されている。 Metal oxides are used in a wide range of fields because they exhibit excellent mechanical, electrical, magnetic and optical properties depending on their compositions. For example, zirconia (ZrO 2 ) is used as a material for fuel cells and oxygen sensors because it becomes a solid electrolyte at high temperatures, while it is also used as a material for knives and scissors because it has both high hardness and high toughness. . In addition, titania (TiO 2 ) has a strong photocatalytic activity, so it is used as a catalyst for environmental purification, and is expected to be applied to hydrogen synthesis in one step by water decomposition or dye-sensitized solar cells. Yes.
近年、ナノサイズ化による材料物性の制御が注目され、上記金属酸化物に関してもナノ粒子を製造する方法が各方面で盛んに研究開発されている（例えば、特許文献１）。また、金属酸化物ナノ粒子を効率的に利用するためには、金属酸化物ナノ粒子を溶媒に分散する手法の確立が重要である。特に、金属酸化物ナノ粒子を均一分散させた複合材料を得る場合や金属酸化物ナノ粒子を原料にした金属酸化物バルク体の製造に関しては、金属酸化物分散ゾル水溶液を製造する簡便な技術の確立が求められている。 In recent years, control of material properties by nano-sizing has attracted attention, and methods for producing nanoparticles with respect to the above metal oxide have been actively researched and developed in various fields (for example, Patent Document 1). In addition, in order to efficiently use the metal oxide nanoparticles, it is important to establish a method for dispersing the metal oxide nanoparticles in a solvent. In particular, in the case of obtaining a composite material in which metal oxide nanoparticles are uniformly dispersed or in the production of a metal oxide bulk material using metal oxide nanoparticles as a raw material, a simple technique for producing a metal oxide dispersed sol aqueous solution is used. Establishment is required.
金属酸化物粒子を分散させた水溶液を得る方法としては、チタン酸ゲルを製造した後、該チタン酸ゲルを水に溶解し、水酸化四級アンモニウムを添加して水熱処理を行う方法が提案されている（特許文献２）。しかしながら、特許文献２で開示されているのはチタニア粒子を分散させた水溶液に関してのみであり、他の金属酸化物粒子に適用可能か否かは明らかではない。また、特許文献２に開示されている製造方法でチタニア粒子分散水溶液を得るためには、原料としてチタン酸ゲルを製造する必要があり、工程が煩雑になるという問題点が存在する。 As a method for obtaining an aqueous solution in which metal oxide particles are dispersed, a method of producing a titanic acid gel, dissolving the titanic acid gel in water, adding quaternary ammonium hydroxide, and performing a hydrothermal treatment is proposed. (Patent Document 2). However, Patent Document 2 discloses only an aqueous solution in which titania particles are dispersed, and it is not clear whether it can be applied to other metal oxide particles. Moreover, in order to obtain a titania particle-dispersed aqueous solution by the production method disclosed in Patent Document 2, it is necessary to produce a titanic acid gel as a raw material, and there is a problem that the process becomes complicated.
金属酸化物ナノ粒子を効果的に利用するためには、金属酸化物ナノ粒子が溶媒中に良分散した金属酸化物分散透明ゾル水溶液を簡便に得る方法を確立する必要がある。また、種々の金属酸化物に適用可能な、汎用性のある製造方法であることが求められる。 In order to effectively use metal oxide nanoparticles, it is necessary to establish a method for easily obtaining a metal oxide-dispersed transparent sol aqueous solution in which metal oxide nanoparticles are well dispersed in a solvent. Moreover, it is calculated | required that it is a versatile manufacturing method applicable to various metal oxides.
本発明は上記課題に鑑みなされたものであり、金属酸化物分散透明ゾル水溶液およびその製造方法に関し、特に、金属酸化物のナノ粒子が良分散した塩基性透明水溶液とその有利な製造方法に関する。 The present invention has been made in view of the above problems, and relates to a metal oxide-dispersed transparent sol aqueous solution and a method for producing the same, and more particularly, to a basic transparent aqueous solution in which metal oxide nanoparticles are well dispersed and an advantageous method for producing the same.
本発明の塩基性金属酸化物分散透明ゾル水溶液の製造方法は、金属塩と第四級アンモニウム塩との中和反応を用いてアニオン性塩基性無機金属錯体を含む水溶液を製造する第１工程と、該第１工程で製造した水溶液を８０〜１５０℃の水熱条件で水熱処理する第２工程と、を有している。 The method for producing a basic metal oxide-dispersed transparent sol aqueous solution of the present invention includes a first step of producing an aqueous solution containing an anionic basic inorganic metal complex using a neutralization reaction between a metal salt and a quaternary ammonium salt. And a second step of hydrothermally treating the aqueous solution produced in the first step under a hydrothermal condition of 80 to 150 ° C.
第１工程においては、金属酸化物分散ゾル水溶液に分散している金属酸化物の等電位点以上の塩基性領域でアニオン性塩基性無機錯体を製造することが好ましく、第２工程においては、ｐＨ８以上の塩基性領域で水熱処理することが好ましい。 In the first step, it is preferable to produce an anionic basic inorganic complex in a basic region above the equipotential point of the metal oxide dispersed in the metal oxide-dispersed sol aqueous solution, and in the second step, pH 8 Hydrothermal treatment is preferably performed in the above basic region.
第１工程で製造される水溶液に含まれるアニオン性塩基性無機錯体は、金属イオンと第四級アンモニウム塩の陰イオンとが結合したアニオン性塩基性無機金属錯体であることが好ましく、該第四級アンモニウム塩は水酸化テトラメチルアンモニウム、炭酸テトラメチルアンモニウムおよび重炭酸テトラメチルアンモニウムの少なくとも１つであることが好ましい。 The anionic basic inorganic complex contained in the aqueous solution produced in the first step is preferably an anionic basic inorganic metal complex in which a metal ion and an anion of a quaternary ammonium salt are bonded. The quaternary ammonium salt is preferably at least one of tetramethylammonium hydroxide, tetramethylammonium carbonate and tetramethylammonium bicarbonate.
本発明の塩基性金属酸化物分散透明ゾル水溶液は、結晶子径が１ｎｍ以上かつ２０ｎｍ以下の金属酸化物粒子と水とから構成される塩基性金属酸化物分散透明ゾル水溶液であって、動的光散乱法により測定した水溶液中における金属酸化物粒子の平均分散粒子径が１ｎｍ以上かつ５０ｎｍ以下である塩基性金属酸化物分散透明ゾル水溶液である。ここで、結晶子径とは、金属酸化物の結晶１つの大きさを意味する。また、分散粒子径とは、水溶液中における金属酸化物の大きさを表し、金属酸化物の結晶が凝集した凝集体の大きさを含む。 The basic metal oxide-dispersed transparent sol aqueous solution of the present invention is a basic metal oxide-dispersed transparent sol aqueous solution composed of metal oxide particles having a crystallite diameter of 1 nm or more and 20 nm or less and water, A basic metal oxide-dispersed transparent sol aqueous solution having an average dispersed particle size of metal oxide particles in an aqueous solution measured by a light scattering method of 1 nm or more and 50 nm or less. Here, the crystallite size means the size of one metal oxide crystal. The dispersed particle size represents the size of the metal oxide in the aqueous solution, and includes the size of the aggregate in which the metal oxide crystals are aggregated.
塩基性金属酸化物分散透明ゾル水溶液の金属酸化物粒子の含有率は０．１体積％以上かつ６０体積％以下であることが好ましい。 The content of the metal oxide particles in the basic metal oxide-dispersed transparent sol aqueous solution is preferably 0.1% by volume or more and 60% by volume or less.
本発明の塩基性金属酸化物分散透明ゾル水溶液の製造方法によれば、種々の金属酸化物に関し、塩基性金属酸化物分散透明ゾル水溶液を簡便に製造することができる。 According to the method for producing a basic metal oxide-dispersed transparent sol aqueous solution of the present invention, a basic metal oxide-dispersed transparent sol aqueous solution can be easily produced with respect to various metal oxides.
本発明の塩基性金属酸化物分散透明ゾル水溶液は、金属酸化物ナノ粒子が水中に良分散しているため、金属酸化物ナノ粒子を均一分散させた複合材料を得る場合の原料として用いることができる。また、金属酸化物バルク体を製造する際の原料としても用いることができる。 The basic metal oxide-dispersed transparent sol aqueous solution of the present invention can be used as a raw material for obtaining a composite material in which metal oxide nanoparticles are uniformly dispersed because the metal oxide nanoparticles are well dispersed in water. it can. It can also be used as a raw material when producing a metal oxide bulk body.
本発明の塩基性金属酸化物分散ゾル水溶液の製造方法は、金属塩と第四級アンモニウム塩との中和反応を用いてアニオン性塩基性無機金属錯体を含む水溶液を製造する第１工程と、該第１工程で製造した水溶液を８０〜１５０℃の水熱条件で水熱処理する第２工程と、を有している。 The method for producing a basic metal oxide-dispersed sol aqueous solution of the present invention includes a first step of producing an aqueous solution containing an anionic basic inorganic metal complex using a neutralization reaction between a metal salt and a quaternary ammonium salt; And a second step of hydrothermally treating the aqueous solution produced in the first step under a hydrothermal condition of 80 to 150 ° C.
第１工程で用いる金属塩は特に限定されないが、例えば、ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、錫（Ｓｎ）、亜鉛（Ｚｎ）等の塩化物や、該塩化物の水和物等を用いることができる。また、第四級アンモニウム塩としては、水酸化テトラメチルアンモニウム、炭酸テトラメチルアンモニウム、重炭酸テトラメチルアンモニウム、コリン、炭酸コリン、および重炭酸コリン等を例示することができる。 The metal salt used in the first step is not particularly limited. For example, a chloride such as zirconium (Zr), titanium (Ti), tin (Sn), or zinc (Zn), or a hydrate of the chloride is used. be able to. Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, tetramethylammonium carbonate, tetramethylammonium bicarbonate, choline, choline carbonate, and choline bicarbonate.
中和方法は特に限定されないが、例えば、金属塩を水に加えて水溶液とし、該水溶液に第四級アンモニウム塩を添加することで達成される。該中和反応により、第１工程の目的であるアニオン性塩基性無機金属錯体を含む水溶液を得ることができる。アニオン性塩基性無機金属錯体としては、Ｚｒ（ＣＯ３）Ｘ（ＯＨ）４−Ｘ Ｘ−、Ｔｉ（ＯＨ）４＋Ｘ Ｘ−、およびＳｎ（ＯＨ）４＋Ｘ Ｘ−等を例示することができる。 The neutralization method is not particularly limited, and can be achieved, for example, by adding a metal salt to water to form an aqueous solution, and adding a quaternary ammonium salt to the aqueous solution. By the neutralization reaction, an aqueous solution containing the anionic basic inorganic metal complex that is the object of the first step can be obtained. Examples of the anionic basic inorganic metal complex include Zr (CO 3 ) X (OH) 4 -X X− , Ti (OH) 4 + X X− , and Sn (OH) 4 + X X− .
第１工程においては、本発明の塩基性金属酸化物分散透明ゾル水溶液の製造方法で製造される、塩基性金属酸化物分散透明ゾル水溶液に分散する金属酸化物の等電位点以上の塩基性領域でアニオン性塩基性無機金属錯体を製造することが好ましい。 In the first step, the basic region at or above the equipotential point of the metal oxide dispersed in the basic metal oxide-dispersed transparent sol aqueous solution is produced by the method for producing a basic metal oxide-dispersed transparent sol aqueous solution of the present invention. It is preferable to produce an anionic basic inorganic metal complex.
等電位点とは、金属酸化物表面の電位が見かけ上零になる溶媒のｐＨを意味する。金属酸化物の表面は、水と接すると水和を起こしてＯＨ基を持つことが知られている。このような表面では、水のｐＨ値によって該表面の電位が変化する。低いｐＨではプロトンの付加によって正の電位を帯び、ｐＨが高くなるとＯＨ基からのプロトンの引き抜きで負に帯電する。なお、等電位点の値は金属酸化物の酸性度によって異なり、同じ金属酸化物でも、該金属酸化物の生成時の条件や履歴によってＯＨ基の付き方が変わると等電位点の値も変化する場合がある。 The equipotential point means the pH of the solvent at which the potential of the metal oxide surface appears to be zero. It is known that the surface of the metal oxide hydrates when it comes into contact with water and has OH groups. On such a surface, the electric potential of the surface changes depending on the pH value of water. At a low pH, a positive potential is obtained by the addition of protons, and when the pH is increased, the protons are negatively charged by extracting the protons from the OH group. Note that the value of the equipotential point varies depending on the acidity of the metal oxide. Even if the same metal oxide is used, the value of the equipotential point changes when the OH group attachment method changes depending on the conditions and history when the metal oxide is produced. There is a case.
本発明の塩基性金属酸化物分散ゾル水溶液の製造方法の第２工程は、第１工程で製造した水溶液を８０〜１５０℃の水熱条件で水熱処理するものである。水熱処理の方法は特に限定されず、例えば、第１工程で製造された水溶液をオートクレーブ（耐熱耐圧の密閉容器）中で８０〜１５０℃に加熱し、所定の時間保持することで達成される。オートクレーブを用いた水熱処理装置としては、バッチ式処理装置と連続式（流通式）処理装置が存在するが、どちらの装置を使用してもよい。また、水熱処理はｐＨ８以上の塩基性領域で行うことが好ましい。 The 2nd process of the manufacturing method of the basic metal oxide dispersion | distribution sol aqueous solution of this invention hydrothermally processes the aqueous solution manufactured at the 1st process on 80-150 degreeC hydrothermal conditions. The method of the hydrothermal treatment is not particularly limited, and for example, it is achieved by heating the aqueous solution produced in the first step to 80 to 150 ° C. in an autoclave (heat-resistant and pressure-resistant sealed container) and holding it for a predetermined time. As a hydrothermal treatment apparatus using an autoclave, there are a batch type treatment apparatus and a continuous type (circulation type) treatment apparatus, either of which may be used. The hydrothermal treatment is preferably performed in a basic region having a pH of 8 or higher.
第１工程において製造される水溶液に含まれるアニオン性塩基性無機金属錯体は、金属イオンと第四級アンモニウム塩の陰イオンとが結合したアニオン性塩基性無機金属錯体であることが好ましい。第四級アンモニウム塩としては、水酸化テトラメチルアンモニウム、炭酸テトラメチルアンモニウム、重炭酸テトラメチルアンモニウム、コリン、炭酸コリン、および重炭酸コリン等を例示でき、これらの陰イオンと、金属塩を水に添加することで生成した金属イオンと、が結合することで、アニオン性塩基性無機金属錯体が形成される。 The anionic basic inorganic metal complex contained in the aqueous solution produced in the first step is preferably an anionic basic inorganic metal complex in which a metal ion and an anion of a quaternary ammonium salt are bonded. Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetramethylammonium carbonate, tetramethylammonium bicarbonate, choline, choline carbonate, and choline bicarbonate. These anions and metal salts can be used in water. An anionic basic inorganic metal complex is formed by combining with the metal ion generated by the addition.
本発明の塩基性金属酸化物分散ゾル水溶液の製造方法によれば、塩基性金属酸化物分散ゾル水溶液を製造するために、金属酸化物を含むゲルを製造する必要がなく、アニオン性塩基性無機金属錯体を含む水溶液を８０〜１５０℃の水熱条件で水熱処理するだけで塩基性金属酸化物分散ゾル水溶液を製造することができる。 According to the method for producing a basic metal oxide-dispersed sol aqueous solution of the present invention, it is not necessary to produce a gel containing a metal oxide in order to produce a basic metal oxide-dispersed sol aqueous solution, and an anionic basic inorganic A basic metal oxide-dispersed sol aqueous solution can be produced simply by hydrothermally treating an aqueous solution containing a metal complex under hydrothermal conditions of 80 to 150 ° C.
本発明の塩基性金属酸化物分散透明ゾル水溶液は、結晶子径が１ｎｍ以上かつ２０ｎｍ以下の金属酸化物粒子と水とから構成される塩基性金属酸化物分散透明ゾル水溶液であって、動的光散乱法により測定した水溶液中における金属酸化物粒子の平均分散粒子径が１ｎｍ以上かつ５０ｎｍ以下である塩基性金属酸化物分散透明ゾル水溶液である。ここで、結晶子径とは、金属酸化物の結晶１つの大きさを意味する。また、分散粒子径とは、水溶液中における金属酸化物の大きさを表し、金属酸化物の結晶が凝集した凝集体の大きさを含む。 The basic metal oxide-dispersed transparent sol aqueous solution of the present invention is a basic metal oxide-dispersed transparent sol aqueous solution composed of metal oxide particles having a crystallite diameter of 1 nm or more and 20 nm or less and water, A basic metal oxide-dispersed transparent sol aqueous solution having an average dispersed particle size of metal oxide particles in an aqueous solution measured by a light scattering method of 1 nm or more and 50 nm or less. Here, the crystallite size means the size of one metal oxide crystal. The dispersed particle size represents the size of the metal oxide in the aqueous solution, and includes the size of the aggregate in which the metal oxide crystals are aggregated.
動的光散乱法とは、水溶液中の粒子のブラウン運動を検出することで、該粒子の粒子径や粒度分布を測定する方法である。水溶液中に分散した粒子のブラウン運動は、大きな粒子では遅く、小さな粒子になるほど早くなる。ブラウン運動の様子は散乱光の揺らぎとして観測されるため、ブラウン運動をしている粒子にレーザー光を照射し、該粒子からの散乱光を観測および解析することで、水溶液中の粒子の粒子径や粒度分布を測定することができる。 The dynamic light scattering method is a method of measuring the particle diameter and particle size distribution of the particles by detecting the Brownian motion of the particles in the aqueous solution. The Brownian motion of particles dispersed in an aqueous solution is slower for larger particles and faster for smaller particles. Since the state of Brownian motion is observed as fluctuations in scattered light, the particle size of particles in an aqueous solution can be obtained by irradiating laser light to particles that are in Brownian motion and observing and analyzing the scattered light from the particles. And particle size distribution can be measured.
本発明の塩基性金属酸化物分散透明ゾル水溶液は、塩基性金属酸化物分散透明ゾル水溶液の金属酸化物粒子の含有率が０．１体積％以上かつ６０体積％以下であることが好ましい。通常、水溶液中の金属酸化物粒子の含有率が高くなると、該金属酸化物粒子同士が凝集するため、金属酸化物粒子が良分散した透明なゾル水溶液を得ることは非常に困難である。これに対し、本発明の塩基性金属酸化物分散透明ゾル水溶液は、塩基性金属酸化物分散透明ゾル水溶液の金属酸化物粒子の含有率が０．１体積％以上かつ６０体積％以下の範囲で該金属酸化物粒子が良分散し、水溶液は透明な状態を維持する。 In the basic metal oxide-dispersed transparent sol aqueous solution of the present invention, the content of metal oxide particles in the basic metal oxide-dispersed transparent sol aqueous solution is preferably 0.1% by volume or more and 60% by volume or less. Usually, when the content of the metal oxide particles in the aqueous solution is increased, the metal oxide particles are aggregated, and it is very difficult to obtain a transparent sol aqueous solution in which the metal oxide particles are well dispersed. On the other hand, the basic metal oxide-dispersed transparent sol aqueous solution of the present invention has a metal oxide particle content of the basic metal oxide-dispersed transparent sol aqueous solution in the range of 0.1% by volume to 60% by volume. The metal oxide particles are well dispersed, and the aqueous solution remains transparent.
本発明の塩基性金属酸化物分散透明ゾル水溶液は、上述の塩基性金属酸化物分散透明ゾル水溶液の製造方法によって、容易に製造することができる。 The basic metal oxide-dispersed transparent sol aqueous solution of the present invention can be easily produced by the above-described method for producing a basic metal oxide-dispersed transparent sol aqueous solution.
以下に本発明の実施例及び比較例を図面を参照して説明するが、本発明はこれらの実施例に限定されるものではない。
実施例１ 「塩基性ＺｒＯ２分散透明ゾル水溶液およびその製造方法」
３．２２ｇのＺｒＯＣｌ２・８Ｈ２Ｏを２０ｍｌの蒸留水に溶解し、ここに２５ｍａｓｓ％の水酸化テトラメチルアンモニウム１５ｍｌと６５ｍａｓｓ％の重炭酸テトラメチルアンモニウム１５ｍｌとの混合溶液を添加し、アニオン性塩基性Ｚｒ(IV)炭酸塩錯体水溶液を得た。次に、該アニオン性塩基性Ｚｒ(IV)炭酸塩錯体水溶液を１５０℃で１ｈ水熱処理することにより、固体含有率約０．４体積％の塩基性ＺｒＯ２分散透明ゾル水溶液を得た。
EXAMPLES Examples and comparative examples of the present invention will be described below with reference to the drawings, but the present invention is not limited to these examples.
Example 1 “Basic ZrO 2 Dispersed Transparent Sol Solution and Method for Producing the Same”
The ZrOCl 2 · 8H 2 O in 3.22g were dissolved in distilled water 20 ml, here was added a mixed solution of 25 mass% of tetramethylammonium hydroxide 15ml and 65Mass% bicarbonate tetramethylammonium 15ml, anionic A basic Zr (IV) carbonate complex aqueous solution was obtained. Next, the anionic basic Zr (IV) carbonate complex aqueous solution was hydrothermally treated at 150 ° C. for 1 h to obtain a basic ZrO 2 dispersed transparent sol aqueous solution having a solid content of about 0.4% by volume.
得られた透明ゾル水溶液を乾燥させ、残った粉末を回収した。該粉末の粉末Ｘ線回折結果を図１に示す。粉末Ｘ線回折パターンから、粉末は主に単斜晶型の結晶構造を有するＺｒＯ２であることが確認された。また、該粉末Ｘ線回折パターンからシェラー式を用いて見積もった結晶子径は約３ｎｍであった。 The obtained transparent sol aqueous solution was dried, and the remaining powder was recovered. The powder X-ray diffraction result of the powder is shown in FIG. From the powder X-ray diffraction pattern, it was confirmed that the powder was mainly ZrO 2 having a monoclinic crystal structure. The crystallite diameter estimated from the powder X-ray diffraction pattern using the Scherrer equation was about 3 nm.
得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径を動的光散乱法（使用装置：日機装株式会社製、Ｎａｎｏｔｒａｃ ＵＰＡ−ＵＴ１５１）で測定した結果を図２に示す。図２より、得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径は約１３ｎｍであることが確認された。また、得られた透明ゾル水溶液のｐＨは１０．７７であった。 FIG. 2 shows the result of measuring the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution by a dynamic light scattering method (use apparatus: manufactured by Nikkiso Co., Ltd., Nanotrac UPA-UT151). From FIG. 2, it was confirmed that the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution was about 13 nm. Moreover, pH of the obtained transparent sol aqueous solution was 10.77.
実施例２ 「塩基性ＳｎＯ２分散透明ゾル水溶液およびその製造方法」
３．５１ｇのＳｎＣｌ４・５Ｈ２Ｏを２０ｍｌの蒸留水に溶解し、ここに２５ｍａｓｓ％の水酸化テトラメチルアンモニウムを３０ｍｌ添加し、アニオン性塩基性Ｓｎ（IV）水酸化錯体水溶液を得た。次に、該アニオン性塩基性Ｓｎ(IV)水酸化錯体水溶液を１２５℃で１ｈ水熱処理することにより、固体含有率約０．４体積％の塩基性ＳｎＯ２分散透明ゾル水溶液を得た。
Example 2 "basic SnO 2 dispersed transparent sol solution and a manufacturing method thereof"
3.51 g of SnCl 4 .5H 2 O was dissolved in 20 ml of distilled water, and 30 ml of 25 mass% tetramethylammonium hydroxide was added thereto to obtain an anionic basic Sn (IV) hydroxide complex aqueous solution. Next, the anionic basic Sn (IV) hydroxide complex aqueous solution was hydrothermally treated at 125 ° C. for 1 h to obtain a basic SnO 2 dispersed transparent sol aqueous solution having a solid content of about 0.4% by volume.
得られた透明ゾル水溶液を乾燥させ、残った粉末を回収した。該粉末の粉末Ｘ線回折結果を図３に示す。粉末Ｘ線回折パターンから、粉末はルチル型の結晶構造を有するＳｎＯ２であることが確認された。また、該粉末Ｘ線回折パターンからシェラー式を用いて見積もった結晶子径は約3ｎｍであった。 The obtained transparent sol aqueous solution was dried, and the remaining powder was recovered. The powder X-ray diffraction result of the powder is shown in FIG. From the powder X-ray diffraction pattern, it was confirmed that the powder was SnO 2 having a rutile-type crystal structure. The crystallite diameter estimated from the powder X-ray diffraction pattern using the Scherrer equation was about 3 nm.
回収した粉末の透過電子顕微鏡写真を図４に示す。回収した粉末は、形状および粒径のそろったキューブ状のＳｎＯ２ナノ粒子であることが分かる。また、透過電子顕微鏡写真から判断できるＳｎＯ２ナノ粒子の粒径は約3ｎｍであり、粉末Ｘ線回折パターンからシェラー式を用いて見積もった結晶子径と一致する。 A transmission electron micrograph of the collected powder is shown in FIG. It can be seen that the recovered powder is cube-shaped SnO 2 nanoparticles having a uniform shape and particle size. Moreover, the particle diameter of SnO 2 nanoparticles which can be judged from a transmission electron micrograph is about 3 nm, which matches the crystallite diameter estimated from the powder X-ray diffraction pattern using the Scherrer equation.
得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径を動的光散乱法（使用装置：日機装株式会社製、Ｎａｎｏｔｒａｃ ＵＰＡ−ＵＴ１５１）で測定した結果を図５に示す。図５より、得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径は約５ｎｍであることが確認された。また、得られた透明ゾル水溶液のｐＨは１３．２７であった。 FIG. 5 shows the results obtained by measuring the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution by a dynamic light scattering method (use apparatus: Nanotrac UPA-UT151, manufactured by Nikkiso Co., Ltd.). From FIG. 5, it was confirmed that the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution was about 5 nm. Moreover, pH of the obtained transparent sol aqueous solution was 13.27.
実施例３ 「塩基性ＴｉＯ２分散透明ゾル水溶液およびその製造方法」
１．８９ｇのＴｉＣｌ４を２０ｍｌの蒸留水に添加し、続いて、２５ｍａｓｓ％の水酸化テトラメチルアンモニウムを３０ｍｌ添加して酸化チタン水和物分散水溶液を得た。酸化チタン水和物分散水溶液は水熱処理の昇温過程でアニオン性塩基性Ｔｉ(IV)水和錯体水溶液へと転化し、該水溶液を１２５℃で１ｈ水熱処理することにより、固体含有率約０．４体積％の塩基性ＴｉＯ２分散透明ゾル水溶液を得た。
Example 3 “Basic TiO 2 Dispersed Transparent Sol Solution and Method for Producing the Same”
1.89 g of TiCl 4 was added to 20 ml of distilled water, and then 30 ml of 25 mass% tetramethylammonium hydroxide was added to obtain a titanium oxide hydrate-dispersed aqueous solution. The aqueous solution of titanium oxide hydrate is converted into an anionic basic Ti (IV) hydrate complex aqueous solution in the temperature rising process of hydrothermal treatment, and the aqueous solution is hydrothermally treated at 125 ° C. for 1 h, so that the solid content is about 0. A 4% by volume basic TiO 2 -dispersed transparent sol aqueous solution was obtained.
得られた透明ゾル水溶液を乾燥させ、残った粉末を回収した。該粉末の粉末Ｘ線回折結果を図６に示す。粉末Ｘ線回折パターンから、粉末はアナターゼ型の結晶構造を有するＴｉＯ２であることが確認された。また、該粉末Ｘ線回折パターンからシェラー式を用いて見積もった結晶子径は約3ｎｍであった。 The obtained transparent sol aqueous solution was dried, and the remaining powder was recovered. The powder X-ray diffraction result of the powder is shown in FIG. From the powder X-ray diffraction pattern, it was confirmed that the powder was TiO 2 having an anatase type crystal structure. The crystallite diameter estimated from the powder X-ray diffraction pattern using the Scherrer equation was about 3 nm.
回収した粉末の透過電子顕微鏡写真を図７に示す。回収した粉末は、形状および粒径のそろったＴｉＯ２ナノ粒子であることが分かる。また、透過電子顕微鏡写真から判断できるＴｉＯ２ナノ粒子の粒径は約3ｎｍであり、粉末Ｘ線回折パターンからシェラー式を用いて見積もった結晶子径と一致する。 A transmission electron micrograph of the collected powder is shown in FIG. It can be seen that the recovered powder is TiO 2 nanoparticles of uniform shape and particle size. Further, the particle diameter of the TiO 2 nanoparticles that can be judged from the transmission electron micrograph is about 3 nm, which coincides with the crystallite diameter estimated from the powder X-ray diffraction pattern using the Scherrer equation.
得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径を動的光散乱法（使用装置：日機装株式会社製、Ｎａｎｏｔｒａｃ ＵＰＡ−ＵＴ１５１）で測定した結果を図８に示す。図８より、得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径は約１０ｎｍであることが確認された。また、得られた透明ゾル水溶液のｐＨは１３．８０であった。 FIG. 8 shows the result of measuring the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution by a dynamic light scattering method (use apparatus: manufactured by Nikkiso Co., Ltd., Nanotrac UPA-UT151). From FIG. 8, it was confirmed that the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution was about 10 nm. Moreover, pH of the obtained transparent sol aqueous solution was 13.80.
実施例４ 「水熱処理条件による金属酸化物の分散粒子径制御」
１．８９ｇのＴｉＣｌ４を２０ｍｌの蒸留水に添加し、続いて、２５ｍａｓｓ％の水酸化テトラメチルアンモニウムを３０ｍｌ添加して酸化チタン水和物分散水溶液を得た。続いて、２５ｍａｓｓ％の水酸化テトラメチルアンモニウムを３０ｍｌ添加して酸化チタン水和物分散水溶液を得た。酸化チタン水和物分散水溶液は水熱処理の昇温過程でアニオン性塩基性Ｔｉ(IV)水和錯体水溶液へと転化し、該アニオン性塩基性Ｔｉ(IV)水和錯体水溶液を１００、 １２５ および１５０℃で１ｈ水熱処理することにより、固体含有率約０．４体積％の塩基性ＴｉＯ２分散透明ゾル水溶液を３種類得た。
Example 4 “Dispersion Particle Size Control of Metal Oxide by Hydrothermal Treatment Conditions”
1.89 g of TiCl 4 was added to 20 ml of distilled water, and then 30 ml of 25 mass% tetramethylammonium hydroxide was added to obtain a titanium oxide hydrate-dispersed aqueous solution. Subsequently, 30 ml of 25 mass% tetramethylammonium hydroxide was added to obtain a titanium oxide hydrate-dispersed aqueous solution. The aqueous solution of titanium oxide hydrate is converted into an aqueous anionic basic Ti (IV) hydrate complex aqueous solution in the temperature rising process of hydrothermal treatment, and the aqueous anionic basic Ti (IV) hydrate complex is converted into 100, 125 and Three types of basic TiO 2 -dispersed transparent sol aqueous solutions having a solid content of about 0.4% by volume were obtained by hydrothermal treatment at 150 ° C. for 1 h.
得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径を動的光散乱法（使用装置：日機装株式会社製、Ｎａｎｏｔｒａｃ ＵＰＡ−ＵＴ１５１）で測定した結果を図９に示す。図９より、得られた透明ゾル水溶液中に分散している粒子の平均分散粒子径は水熱処理の温度によって変化し、水熱処理の温度が１００、１２５および１５０℃の場合、平均分散粒子径はそれぞれ約８ｎｍ、約１０ｎｍおよび約１２ｎｍであることが確認された。 FIG. 9 shows the results obtained by measuring the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution by a dynamic light scattering method (use apparatus: manufactured by Nikkiso Co., Ltd., Nanotrac UPA-UT151). From FIG. 9, the average dispersed particle size of the particles dispersed in the obtained transparent sol aqueous solution varies depending on the hydrothermal treatment temperature. When the hydrothermal treatment temperature is 100, 125 and 150 ° C., the average dispersed particle size is It was confirmed to be about 8 nm, about 10 nm, and about 12 nm, respectively.
得られた３種類の塩基性ＴｉＯ２分散透明ゾル水溶液の写真を図１０に示す。全ての塩基性ＴｉＯ２分散透明ゾル水溶液について、これらの水溶液を入れた透明容器の後方に配置されたパネルの文字が明確に確認される。該結果より、実施例４で製造された全ての塩基性ＴｉＯ２分散透明ゾル水溶液が高い透明性を有していることが分かる。 A photograph of the obtained three types of basic TiO 2 dispersed transparent sol aqueous solutions is shown in FIG. For all the basic TiO 2 -dispersed transparent sol aqueous solutions, the letters on the panels arranged behind the transparent containers containing these aqueous solutions are clearly confirmed. From the results, it can be seen that all the basic TiO 2 -dispersed transparent sol aqueous solutions produced in Example 4 have high transparency.
Claims (6)
前記水溶液を８０〜１５０℃の水熱条件で水熱処理する第２工程と、
を有する塩基性金属酸化物分散透明ゾル水溶液の製造方法。 A first step of producing an aqueous solution containing an anionic basic inorganic metal complex using a neutralization reaction between a metal salt and a quaternary ammonium salt;
A second step of hydrothermally treating the aqueous solution under hydrothermal conditions of 80 to 150 ° C .;
The manufacturing method of the basic metal oxide dispersion | distribution transparent sol aqueous solution which has this.
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