JP5162755B2 - Crystallized glass and photocatalytic member using the same - Google Patents
Crystallized glass and photocatalytic member using the same Download PDFInfo
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- JP5162755B2 JP5162755B2 JP2007227847A JP2007227847A JP5162755B2 JP 5162755 B2 JP5162755 B2 JP 5162755B2 JP 2007227847 A JP2007227847 A JP 2007227847A JP 2007227847 A JP2007227847 A JP 2007227847A JP 5162755 B2 JP5162755 B2 JP 5162755B2
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- 239000011521 glass Substances 0.000 title claims description 84
- 230000001699 photocatalysis Effects 0.000 title description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 97
- 239000013078 crystal Substances 0.000 claims description 57
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004031 devitrification Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004093 laser heating Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 B 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Description
本発明は、結晶化ガラス及びそれを用いた光触媒部材に関するものである。 The present invention relates to crystallized glass and a photocatalytic member using the same.
ガラス材料は、ファイバへの線引きや薄膜化など、その形態が簡便・容易かつ安価に制御できる特性を持つが、基本的に光を伝達・透過する機能のみであり、光に対して能動的に機能を発現する光機能材料としては用いられない。結晶化ガラスは、析出結晶を選択することにより、高い透明性や広い透過波長域、さらには成型加工の容易性等のガラスの特徴に、結晶材料に固有の特性を賦与したものであり、非線形光学特性（例えば、特許文献１参照。）やイオン伝導性（例えば、特許文献２参照。）を有した全く新しい機能性材料として期待されている。 Glass materials have the characteristics that the form can be controlled easily, easily and inexpensively, such as drawing into a fiber or thinning the fiber, but basically only the function to transmit and transmit light, and actively to light. It is not used as an optical functional material that exhibits its function. Crystallized glass is a non-linear material in which characteristics specific to the crystal material are given to the characteristics of the glass, such as high transparency, wide transmission wavelength range, and ease of molding, by selecting precipitated crystals. It is expected as a completely new functional material having optical properties (for example, see Patent Document 1) and ion conductivity (for example, see Patent Document 2).
一方 酸化チタン（チタニア）は、化学的安定性に優れる、高い屈折率を有するなどといった優れた特徴を有し、近年は、電子材料、触媒材料、光触媒等に使用されている結晶材料である。特に光触媒機能は、強い酸化作用と超親水作用を利用して、工業的に様々な分野で応用されている（例えば、特許文献３、特許文献４参照。）。 On the other hand, titanium oxide (titania) has excellent characteristics such as excellent chemical stability and a high refractive index, and has recently been a crystal material used for electronic materials, catalytic materials, photocatalysts and the like. In particular, the photocatalytic function is applied in various industrial fields by utilizing a strong oxidizing action and a superhydrophilic action (see, for example, Patent Document 3 and Patent Document 4).
前述の酸化チタンは、出発原料として用いる場合（例えば、特許文献５参照。）と、材料表面に酸化チタン膜を形成させて用いる場合（例えば、特許文献６、７参照。）あるいは微粒子を膜中に分散させる場合（例えば、特許文献８、９参照。）がほとんどであり、種々の作製法において、光触媒機能が材料に賦与されているという報告がある。概して、光触媒機能を有効に利用するためには、結晶あるいは微粒子として材料中に存在する方が高効率であり、そのため、酸化チタン膜を材料に塗布することにより光触媒能を利用する手法が主流となっている。 The above-described titanium oxide is used as a starting material (see, for example, Patent Document 5), a titanium oxide film is formed on the material surface (see, for example, Patent Documents 6 and 7), or fine particles are used in the film. There are reports that the photocatalytic function is imparted to the material in various production methods. In general, in order to effectively use the photocatalytic function, it is more efficient to exist in the material as crystals or fine particles. For this reason, the mainstream method is to use the photocatalytic ability by applying a titanium oxide film to the material. It has become.
前述の酸化チタン膜の作製法としては、蒸着膜、あるいはスパッタ薄膜中に析出させる手法、あるいは酸化チタン含有ゾルを用いて作製した膜を熱処理することにより結晶化させる手法などがある。特に、大面積のガラスに対しては、酸化チタンをコーティング液中に分散させ、これを材料に塗布して酸化チタンの膜を形成させて光触媒能を利用している。しかし、この手法では経時変化に伴うコーティング膜の剥離により、その触媒機能が低下する。また、定期的にコーティングする必要があり、コストやメンテナンスの問題がある。つまり、経時変化という観点では、酸化チタン膜の塗布の手法では限界がある。 As a method for producing the above-described titanium oxide film, there are a technique of depositing in a vapor deposition film or a sputtered thin film, or a technique of crystallizing a film produced using a titanium oxide-containing sol by heat treatment. In particular, for large-area glass, titanium oxide is dispersed in a coating solution, which is applied to the material to form a titanium oxide film, thereby utilizing the photocatalytic ability. However, in this method, the catalytic function is lowered due to the peeling of the coating film with time. Moreover, it is necessary to coat regularly, and there are problems of cost and maintenance. That is, from the viewpoint of change with time, there is a limit to the method of applying the titanium oxide film.
これに対して、ガラス全体に結晶化させた微粒子を分散させる手法では、経時変化による材料表面への変化がほとんどなく、半永久的に結晶化粒子の特徴を有することができる。しかし、一般にガラス中から選択的に酸化チタンを結晶化させることは困難とされている。なぜなら、酸化チタンはアルミナ、シリカなどといったガラス形成酸化物と、酸化チタン以外の結晶を形成するため、あるいは、酸化チタン以外の結晶がより低温で析出するためである。そのため、チタニアを析出させた結晶化ガラスの報告はほとんどない。 On the other hand, in the method of dispersing fine particles crystallized over the entire glass, there is almost no change to the material surface due to aging, and the characteristics of crystallized particles can be obtained semipermanently. However, it is generally difficult to selectively crystallize titanium oxide from glass. This is because titanium oxide forms glass-forming oxides such as alumina and silica and crystals other than titanium oxide, or crystals other than titanium oxide precipitate at a lower temperature. Therefore, there are few reports of crystallized glass on which titania is precipitated.
これまでに、ガラス中にチタニアを含む結晶化ガラスについては、１９７６年にコーニング社のグループがルチル型チタニアを含む結晶化ガラスについて報告している（特許文献１０参照。）しかしながら、この結晶化ガラスにおいては、針状のチタニア結晶を強度の向上のために析出させており、それ自身の光触媒機能などを利用する目的ではない。また、ガラス表面に微結晶形態として析出するわけではないので、チタニア結晶の析出よる比表面積の増大は期待できない。さらに、結晶化ガラスからは、ルチル型チタニアと同時にＡｌ４Ｂ２Ｏ９が析出するという問題がある。加えて、構成成分として環境負荷の大きい酸化鉛を含む実施例もある。 So far, as for the crystallized glass containing titania in the glass, a group of Corning Corporation reported on the crystallized glass containing rutile type titania in 1976 (see Patent Document 10). In the method, needle-like titania crystals are precipitated for the purpose of improving the strength, and the purpose is not to use their own photocatalytic function. Moreover, since it does not precipitate as a microcrystalline form on the glass surface, an increase in specific surface area due to precipitation of titania crystals cannot be expected. Furthermore, from crystallized glass, there is a problem that Al 4 B 2 O 9 precipitates simultaneously with rutile-type titania. In addition, there is an embodiment including lead oxide having a large environmental load as a constituent component.
一方、２００７年、東北大学のグループが酸化カルシウム・酸化ビスマス・酸化ホウ素・酸化アルミニウム・酸化チタンからなるガラスを基にした、チタニア結晶だけを析出させた結晶化ガラスについて報告を行なっている。酸化ホウ素を主成分とするガラスを熱処理することにより、ルチル型あるいはアナターゼ型のチタニア結晶の析出が確認されている（例えば、非特許文献１参照。）。このガラスは、新規光触媒材料としての応用が検討されている。
しかしながら、非特許文献１に記載の結晶化ガラスは、可視域における吸収が大きく、実用化を満足する透明性には満たない。結晶化ガラスの透明度を向上させることは、透明光触媒材料への応用展開に必要である。 However, the crystallized glass described in Non-Patent Document 1 has a large absorption in the visible region, and does not satisfy the transparency satisfying practical use. Improving the transparency of crystallized glass is necessary for developing applications for transparent photocatalytic materials.
本発明は、光触媒機能を保持しつつ、可視光領域の吸収を大幅に改善した結晶化ガラス及びそれを用いた光触媒部材を提供することを目的とする。 An object of the present invention is to provide a crystallized glass and a photocatalyst member using the crystallized glass that have significantly improved absorption in the visible light region while maintaining a photocatalytic function.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、ＴｉＯ２−Ｂｉ２Ｏ３−Ｂ２Ｏ３−Ａｌ２Ｏ３−ＲＯ系結晶化ガラスに、適量のＳｎＯを含有させることによって、Ａｌ４Ｂ２Ｏ９の結晶の析出を十分に防止しながらチタニア結晶だけを析出させ、しかも十分な可視光透過性を有する結晶化ガラスが得られることを見出し、本発明を提案するに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention include an appropriate amount of SnO in a TiO 2 —Bi 2 O 3 —B 2 O 3 —Al 2 O 3 —RO-based crystallized glass. Thus, it is found that a crystallized glass can be obtained in which only titania crystals are precipitated while sufficiently preventing the precipitation of Al 4 B 2 O 9 crystals, and which has sufficient visible light transmittance. It came to.
すなわち本発明の結晶化ガラスは、ＴｉＯ２ ５〜２５モル％、Ｂｉ２Ｏ３ ３〜１５モル％、Ｂ２Ｏ３ ４５〜７５モル％、Ａｌ２Ｏ３ ５〜２０モル％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ ２〜１５モル％、ＳｎＯ ０．３〜１．８モル％を含有し、且つチタニア結晶が析出したことを特徴とする。 That is, the crystallized glass of the present invention contains TiO 2 5 to 25 mol%, Bi 2 O 3 3 to 15 mol%, B 2 O 3 45 to 75 mol%, Al 2 O 3 5 to 20 mol%, MgO + CaO + SrO + BaO 2 It contains 15 mol%, SnO 0.3-1.8 mol%, and titania crystals are precipitated.
また、本発明の光触媒部材は、ＴｉＯ２ ５〜２５モル％、Ｂｉ２Ｏ３ ３〜１５モル％、Ｂ２Ｏ３ ４５〜７５モル％、Ａｌ２Ｏ３ ５〜２０モル％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ ２〜１５モル％、ＳｎＯ ０．３〜１．８モル％を含有し、且つチタニア結晶が析出した結晶化ガラスを用いてなることを特徴とする。 Moreover, the photocatalyst member of the present invention comprises TiO 2 5 to 25 mol%, Bi 2 O 3 3 to 15 mol%, B 2 O 3 45 to 75 mol%, Al 2 O 3 5 to 20 mol%, MgO + CaO + SrO + BaO 2 It is characterized by using a crystallized glass containing 15 mol%, SnO 0.3 to 1.8 mol%, and having titania crystals precipitated.
また、本発明の製造方法は、ＴｉＯ２−Ｂｉ２Ｏ３−Ｂ２Ｏ３−Ａｌ２Ｏ３−ＲＯ系結晶化ガラス（Ｒは、Ｍｇ、Ｃａ、Ｓｒ及びＢａの群から選択された１種または２種以上を示す。）を製造する方法であって、原料組成中にＳｎＯ ０．３〜１．８モル％を含有させることを特徴とする。 The manufacturing method of the present invention, TiO 2 -Bi 2 O 3 -B 2 O 3 -Al 2 O 3 -RO based glass-ceramics (R were selected from Mg, Ca, the group of Sr and Ba 1 Seeds or two or more species), wherein SnO is contained in an amount of 0.3 to 1.8 mol% in the raw material composition.
本発明の結晶化ガラスは、チタニア（酸化チタン）結晶がガラス全体に析出しているため、触媒（特に好ましくは光触媒）の材料として好適に用いることができ、触媒として利用した場合に、優れた活性及び耐久性を発揮できる。結晶化ガラスの可視域の吸収は主にビスマス酸化物、あるいは、ビスマス金属由来のものと考えられるが、本発明においては、ＳｎＯを添加することにより、ビスマス元素の価数および配位状態を変化させ、それにより吸収の低減を達成することができる。 The crystallized glass of the present invention can be suitably used as a material for a catalyst (particularly preferably a photocatalyst) because titania (titanium oxide) crystals are precipitated throughout the glass, and is excellent when used as a catalyst. It can exhibit activity and durability. Absorption in the visible region of crystallized glass is thought to be mainly derived from bismuth oxide or bismuth metal, but in the present invention, the addition of SnO changes the valence and coordination state of the bismuth element. Thereby reducing absorption.
その結果、本発明の結晶化ガラスは、可視域における透明性を従来の報告に比べて向上させることができる。 As a result, the crystallized glass of the present invention can improve the transparency in the visible range as compared with the conventional reports.
また、ＳｎＯの添加に関わらず、チタニア結晶の析出が確認できることから、ＳｎＯの添加は主にビスマスによる可視光の吸収を低減するように作用しており、以前のチタニア結晶のみが析出した結晶化ガラスの特性を保持し、透明性の点からはその特性をさらに向上させるものである。 In addition, since the precipitation of titania crystals can be confirmed regardless of the addition of SnO, the addition of SnO mainly acts to reduce the absorption of visible light by bismuth, so that only the previous titania crystals are precipitated. It retains the properties of glass and further improves the properties from the viewpoint of transparency.
また、この結晶化ガラスを用いた光触媒部材は、自動車・鉄道・船などの輸送重機、あるいは、ビルの窓への応用が可能であり、半永久的にガラスに光触媒能を賦与することができる。 In addition, the photocatalytic member using the crystallized glass can be applied to heavy transportation equipment such as automobiles, railroads, and ships, or a building window, and can impart photocatalytic activity to glass semipermanently.
本発明において、上述したように結晶化ガラスの含有成分を限定した理由を以下に述べる。 In the present invention, the reason why the components contained in the crystallized glass are limited as described above will be described below.
ＴｉＯ２の含有割合は、５〜２５モル％である。ＴｉＯ２の含有割合としては、１０〜２５モル％であることが好ましく、１４〜２３モル％であることがより好ましい。ＴｉＯ２の含有割合が５モル％未満では、得られるガラスを加熱してチタニアの結晶を析出させる際に光触媒等に使用するために十分な量の結晶が析出しなくなる。また、ＴｉＯ２の含有割合が２５モル％を超えると、白色のチタニアの粗大な結晶がガラス中に析出して透明なガラスが得られなくなる。 Content of TiO 2 is 25 mol%. The content of TiO 2, preferably 10 to 25 mol%, more preferably 14 to 23 mol%. When the content ratio of TiO 2 is less than 5 mol%, a sufficient amount of crystals to be used for a photocatalyst or the like does not precipitate when the obtained glass is heated to precipitate titania crystals. On the other hand, when the content ratio of TiO 2 exceeds 25 mol%, coarse crystals of white titania are precipitated in the glass and a transparent glass cannot be obtained.
Ｂｉ２Ｏ３の含有割合は、３〜１５モル％である。Ｂｉ２Ｏ３の含有割合としては、５〜１２モル％であることが好ましく、７〜１１モル％であることがより好ましい。Ｂｉ２Ｏ３の含有割合が３モル％未満では、結晶性ガラスを成形する際に、失透して（具体的には、粗大なチタニアの結晶の析出による失透がおこるため透明な結晶性ガラスが得られなくなり）、また、得られた結晶性ガラスを加熱してチタニアの結晶を析出させた場合、所望の形状の微小結晶が得られず、透明な結晶化ガラスが得られなくなる。また、Ｂｉ２Ｏ３の含有割合が１５モル％を超えると、酸化ビスマスを含む他の結晶が析出して、チタニア結晶による光触媒能を阻害する。 The content of Bi 2 O 3 is 3 to 15 mol%. The content of Bi 2 O 3, preferably from 5 to 12 mol%, more preferably 7-11 mol%. When the content ratio of Bi 2 O 3 is less than 3 mol%, the glass is devitrified when the crystalline glass is formed (specifically, transparent crystallinity occurs because devitrification occurs due to precipitation of coarse titania crystals). When the obtained crystalline glass is heated to precipitate titania crystals, microcrystals having a desired shape cannot be obtained, and transparent crystallized glass cannot be obtained. On the other hand, when the content ratio of Bi 2 O 3 exceeds 15 mol%, other crystals containing bismuth oxide are precipitated, thereby inhibiting the photocatalytic ability of the titania crystals.
Ｂ２Ｏ３の含有割合は、４５〜７５モル％である。Ｂ２Ｏ３の含有割合としては、５０〜７０モル％であることが好ましく、５０〜６６モル％であることがより好ましい。Ｂ２Ｏ３の含有割合が４５モル％未満では、結晶性ガラスを成形する際に、失透して（具体的には、粗大なチタニアの結晶の析出による失透がおこるため透明な結晶性ガラスが得られなくなり）、また、７５モル％を超えると、Ｂ２Ｏ３の含有割合が高くなりすぎて、ＴｉＯ２の含有量が減少することから、結晶化ガラス中に十分な量のチタニア結晶を析出させることができず、結晶化ガラスの機能性が低下する。 The content of B 2 O 3 is 45 to 75 mol%. The content of B 2 O 3, preferably 50 to 70 mol%, more preferably 50-66 mol%. When the content ratio of B 2 O 3 is less than 45 mol%, the glass is devitrified when the crystalline glass is formed (specifically, transparent crystallinity occurs because devitrification occurs due to precipitation of coarse titania crystals). When the amount exceeds 75 mol%, the content ratio of B 2 O 3 becomes too high and the content of TiO 2 decreases, so that a sufficient amount of titania is contained in the crystallized glass. Crystals cannot be precipitated, and the functionality of the crystallized glass decreases.
Ａｌ２Ｏ３の含有割合は、５〜２０モル％である。Ａｌ２Ｏ３の含有割合としては、６〜１５モル％であることが好ましく、７〜１０モル％であることがより好ましい。Ａｌ２Ｏ３の含有割合が５モル％未満では、結晶性ガラスを成形する際に、失透し（具体的には、粗大なチタニアの結晶の析出による失透がおこるため透明な結晶性ガラスが得られなくなり）、その失透したガラスを熱処理しても粗大結晶が析出する。Ａｌ２Ｏ３の含有割合が２０モル％を超えると、Ａｌ４Ｂ２Ｏ９の結晶の析出を十分に防止することができなくなる。 The content of Al 2 O 3 is 5 to 20 mol%. The content of al 2 O 3, preferably from 6 to 15 mol%, more preferably 7-10 mol%. When the content ratio of Al 2 O 3 is less than 5 mol%, the glass is devitrified when the crystalline glass is formed (specifically, a transparent crystalline glass because devitrification occurs due to precipitation of coarse titania crystals). However, even if the devitrified glass is heat-treated, coarse crystals are precipitated. When the content ratio of Al 2 O 3 exceeds 20 mol%, precipitation of Al 4 B 2 O 9 crystals cannot be sufficiently prevented.
また、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有割合は、２〜１５モル％である。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有割合としては、３〜１０モル％であることが好ましく、３〜９モル％であることがより好ましい。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有割合が２モル％未満では、結晶性ガラスを成形する際に、失透して（具体的には、粗大なチタニアの結晶の析出による失透がおこるため透明な結晶性ガラスが得られなくなり）、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有割合が１５モル％を超えると、結晶化ガラス中にチタニア結晶以外の他の結晶が析出し、チタニア結晶の光触媒能が阻害されることとなる。特にＣａＯは、クラーク数が大きく、最も入手しやすい成分であり、安価なため好ましい。 Moreover, the content rate of MgO + CaO + SrO + BaO is 2-15 mol%. As a content rate of MgO + CaO + SrO + BaO, it is preferable that it is 3-10 mol%, and it is more preferable that it is 3-9 mol%. When the content ratio of MgO + CaO + SrO + BaO is less than 2 mol%, devitrification occurs when the crystalline glass is molded (specifically, devitrification due to precipitation of coarse titania crystals occurs, so that transparent crystalline glass is obtained. When the content ratio of MgO + CaO + SrO + BaO exceeds 15 mol%, crystals other than titania crystals are precipitated in the crystallized glass, and the photocatalytic ability of the titania crystals is hindered. In particular, CaO is preferable because it has a large Clarke number, is the most readily available component, and is inexpensive.
また、ＳｎＯの含有割合は、０．３〜１．８モル％である。ＳｎＯの含有割合としては、０．４〜１．５モル％であることが好ましく、０．５〜１モル％であることがより好ましい。ＳｎＯの含有割合が０．３モル％未満では、結晶化ガラスの可視光の光透過性が低く、ＳｎＯの含有割合が１．８モル％を超えると、分相して結晶化ガラスの可視光の透過率が低下する。 Moreover, the content rate of SnO is 0.3-1.8 mol%. As a content rate of SnO, it is preferable that it is 0.4-1.5 mol%, and it is more preferable that it is 0.5-1 mol%. If the SnO content is less than 0.3 mol%, the visible light transmittance of the crystallized glass is low, and if the SnO content exceeds 1.8 mol%, phase separation occurs and the crystallized glass is visible. The transmittance of is reduced.
また、上述のように、本発明の結晶化ガラスは、ＴｉＯ２、Ｂｉ２Ｏ３、Ｂ２Ｏ３、Ａｌ２Ｏ３、ＲＯ（ＲはＭｇ、Ｃａ、Ｓｒ及びＢａの群から選択された１種又は２種以上）、及びＳｎＯを必須成分として含有するものであるが、前記必須成分以外に他の成分を含有させてもよい。このような他の成分としては特に制限されず、ガラスを製造する際に用いられる公知の成分を適宜含有させることができる。また、このような他の成分としては、希土類金属の酸化物や遷移金属の酸化物等が挙げられる。 Further, as described above, the crystallized glass of the present invention was selected from the group consisting of TiO 2 , Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , RO (R is Mg, Ca, Sr and Ba). 1 type or 2 types or more) and SnO as an essential component, but other components may be contained in addition to the essential component. Such other components are not particularly limited, and known components used when producing glass can be appropriately contained. Examples of such other components include rare earth metal oxides and transition metal oxides.
本発明の結晶化ガラスにおいて、チタニア結晶は、平均粒径の上限値が１０００ｎｍであることが好ましく、６００ｎｍであることがより好ましく、３０ｎｍであることが特に好ましい。また、前記平均粒径の下限値が、３ｎｍであることが好ましく、５ｎｍであることがより好ましい。 In the crystallized glass of the present invention, the upper limit of the average particle diameter of the titania crystal is preferably 1000 nm, more preferably 600 nm, and particularly preferably 30 nm. Further, the lower limit of the average particle diameter is preferably 3 nm, more preferably 5 nm.
チタニア結晶の平均粒径が１０００ｎｍを超えると、チタニア結晶の表面積が小さくなって、光触媒機能等を十分に発揮させることができなくなる傾向にある。一方、チタニア結晶の平均粒径は、小さければ小さいほど可視光の透過率が高くなって好ましいが、上述した本発明の組成範囲において、チタニア結晶の平均粒径を３ｎｍよりも小さくすることは製造上困難である。 When the average particle diameter of the titania crystal exceeds 1000 nm, the surface area of the titania crystal becomes small, and the photocatalytic function or the like tends not to be sufficiently exhibited. On the other hand, the smaller the average particle size of the titania crystal, the higher the visible light transmittance, which is preferable. However, in the composition range of the present invention described above, it is possible to reduce the average particle size of the titania crystal to less than 3 nm. It is difficult.
また、本発明の結晶化ガラスは、表面に３〜１０００ｎｍの平均粒径を有するチタニアの微結晶が析出したことが好ましい。このような結晶化ガラスは、比表面積が増大し、光触媒として用いた場合に、より高い性能を発揮できる傾向にある。なお、上記平均粒径は、粉末Ｘ線回折測定結果からシェラーの式を用いて求めた結晶子サイズを指し、またここでいう「微結晶」とは、ナノサイズの微小な単結晶からなるものをいう。 In the crystallized glass of the present invention, titania microcrystals having an average particle diameter of 3 to 1000 nm are preferably deposited on the surface. Such crystallized glass has an increased specific surface area and tends to exhibit higher performance when used as a photocatalyst. The above average particle diameter refers to the crystallite size obtained using the Scherrer equation from the powder X-ray diffraction measurement results, and the term “microcrystal” as used herein is composed of nano-sized fine single crystals. Say.
本発明の結晶化ガラスは、チタニア結晶がアナターゼ型結晶及び／又はルチル型結晶であることが好ましい。このようにすれば、光触媒機能が発現するからである。 In the crystallized glass of the present invention, the titania crystal is preferably an anatase type crystal and / or a rutile type crystal. This is because the photocatalytic function is manifested in this way.
また本発明の結晶化ガラスは、チタニア結晶だけが析出し、それ以外の結晶（異種結晶）が析出しないことが好ましい、このようにすれば、結晶化ガラスの光触媒機能の低下を抑制することができる。 In the crystallized glass of the present invention, it is preferable that only titania crystals are precipitated, and other crystals (heterogeneous crystals) are not precipitated. In this way, the deterioration of the photocatalytic function of the crystallized glass can be suppressed. it can.
結晶化ガラスにおいて、結晶を析出させる方法は、典型的には熱処理であるが、レーザ照射等の方法であってもよく、特に限定されない。熱処理の方法としては、材料に対して、熱処理する所定の温度範囲において、温度制御でき、材料を化学的に安定に保てるのであればよく、特に限定されない。熱処理については、たとえば、電気炉、ホットプレート、白熱灯などの熱源を用いることができる。レーザ加熱に関しても、ガラスが照射領域において均一に加熱され、温度制御可能であればレーザの種類は問わない。全体を均一に、大面積材料を容易にしかも効率的に加熱する通常の熱処理法に対して、レーザ光を用いて照射領域が限定される加熱方法は、光導波路など結晶化による光波制御の機能性がある特定の位置に限定される場合には、特に効率的な加熱法となる。 In the crystallized glass, the method for precipitating crystals is typically heat treatment, but may be a method such as laser irradiation, and is not particularly limited. The heat treatment method is not particularly limited as long as the temperature can be controlled in a predetermined temperature range for heat treatment of the material and the material can be kept chemically stable. For heat treatment, for example, a heat source such as an electric furnace, a hot plate, or an incandescent lamp can be used. Regarding the laser heating, the type of laser is not limited as long as the glass is uniformly heated in the irradiation region and the temperature can be controlled. Compared with the usual heat treatment method that heats large area materials easily and efficiently uniformly, the heating method in which the irradiation area is limited using laser light is a function of light wave control by crystallization such as an optical waveguide. When the property is limited to a specific position, the heating method is particularly efficient.
レーザ加熱については、たとえば、紫外レーザやＹＡＧレーザ、炭酸ガスレーザなど加工用のレーザを用いることができる。結晶性ガラスを結晶化させる工程（結晶化処理）において、熱処理条件は、所望の結晶相が得られる条件であれば、特に限定されない。結晶相の存在及び結晶化の程度は、Ｘ線回折により確認できる。結晶化の程度は、用途などに応じて、任意に選択することができる。ガラスの溶融ルツボはアルミナルツボであっても、白金ルツボであっても問題はない。アルミナルツボの場合においては、出発原料にアルミナを加えずに作製することができる。これは、ルツボからアルミナが溶出してくるためである。 For laser heating, for example, a processing laser such as an ultraviolet laser, a YAG laser, or a carbon dioxide laser can be used. In the step of crystallizing crystalline glass (crystallization treatment), the heat treatment conditions are not particularly limited as long as the desired crystal phase can be obtained. The presence of the crystal phase and the degree of crystallization can be confirmed by X-ray diffraction. The degree of crystallization can be arbitrarily selected according to the application. There is no problem whether the glass melting crucible is an alumina crucible or a platinum crucible. In the case of an alumina crucible, it can be produced without adding alumina to the starting material. This is because alumina is eluted from the crucible.
本発明の結晶化ガラスについて、実験例を用いて詳細に説明する。 The crystallized glass of the present invention will be described in detail using experimental examples.
表１は本発明の実験例における原料のバッチ組成を示し、表２は、本発明の実験例で得られた結晶化ガラスの組成及びその評価結果を示す。 Table 1 shows the batch composition of the raw materials in the experimental example of the present invention, and Table 2 shows the composition of the crystallized glass obtained in the experimental example of the present invention and the evaluation results thereof.
本発明の実験例は、表１のバッチ組成となるように原料を調合し、純度９９．９％のアルミナ坩堝を用いて１３００℃の電気炉中で４０分間溶融し、１６０℃の金属板上に流し出し、急冷却した後、３０分間アニールして結晶性ガラスを得た。次いで、この結晶性ガラスを、６３０℃で３時間熱処理することによって、結晶化ガラスを作製した。 In the experimental example of the present invention, the raw materials were prepared so as to have the batch composition shown in Table 1, and melted in an electric furnace at 1300 ° C. for 40 minutes using an alumina crucible with a purity of 99.9%. Then, after cooling rapidly, annealing was performed for 30 minutes to obtain a crystalline glass. Subsequently, this crystalline glass was heat-treated at 630 ° C. for 3 hours to produce crystallized glass.
結晶化ガラスの化学組成は、Ｂ２Ｏ３及びＢｉ２Ｏ３については、湿式分析法を用い、その他の成分については蛍光Ｘ線分析法を用いて求めた。結晶化ガラス中のＡｌ２Ｏ３はアルミナ坩堝からの混入によるものである。 The chemical composition of the crystallized glass was determined using a wet analysis method for B 2 O 3 and Bi 2 O 3 and using a fluorescent X-ray analysis method for the other components. Al 2 O 3 in the crystallized glass is due to contamination from the alumina crucible.
結晶化ガラスの可視域（４８８ｎｍ）での光透過率（Ｔ％）は、分光光度計（島津製ＵＶ−３１５０）を用いて測定した。尚、光透過率の測定では、結晶化ガラスの厚みを１ｍｍにし、両面を光学研磨した試料を用いた。また、析出結晶の同定は粉末Ｘ線回折装置を用いて行った。また析出結晶の平均粒径は、粉末Ｘ線回折測定結果からシェラーの式を用いて求めた。 The light transmittance (T%) in the visible region (488 nm) of the crystallized glass was measured using a spectrophotometer (Shimadzu UV-3150). In the measurement of light transmittance, a sample in which the thickness of the crystallized glass was 1 mm and both surfaces were optically polished was used. Moreover, the identification of the precipitated crystal was performed using a powder X-ray diffractometer. The average particle size of the precipitated crystals was determined from the powder X-ray diffraction measurement result using Scherrer's equation.
触媒能は、アルミナ乳鉢を用いて粉砕した０．０７ｇの結晶化ガラスの粉末試料を、１０μＭのメチレンブルー水溶液２０ｇ中に分散させ、暗所で１８時間静置した後、吸光度（Ａ０）を測定し、更に波長３６５ｎｍのブラックライトを２０時間（ｔ）照射した後も同様に吸光度（Ａ）を測定し、以下の式に従って求めたメチレンブルーの単位表面積当たりの分解速度定数で評価した。尚、触媒能は、単位表面積当たりの分解速度定数ｋが大きい程優れていることを示す。また、試料の表面積（Ｓ）は、ＢＥＴ法によって求めた１ｇ当たりの表面積と粉末試料重量とから算出した。 Catalytic activity was determined by measuring 0.07 g of crystallized glass powder sample pulverized using an alumina mortar in 20 g of 10 μM methylene blue aqueous solution and allowing it to stand for 18 hours in the dark, and then measuring the absorbance (A 0 ). In addition, the absorbance (A) was measured in the same manner after irradiating black light with a wavelength of 365 nm for 20 hours (t), and evaluated by the decomposition rate constant per unit surface area of methylene blue determined according to the following formula. In addition, it shows that the catalyst ability is so excellent that the decomposition rate constant k per unit surface area is large. The surface area (S) of the sample was calculated from the surface area per gram determined by the BET method and the weight of the powder sample.
単位表面積当たりの分解速度定数 ｋ＝ｌｎ（Ａ０／Ａ）／ｔ／Ｓ
表２からわかるように、本発明に従う実験例Ｎｏ．４、Ｎｏ．５の結晶化ガラスは、ＳｎＯを含有しない従来例（Ｎｏ．１）と比べ、可視光の光透過率が高く、Ｎｏ．１、Ｎｏ．４及びＮｏ．５の触媒能は、メチレンブルーの分解速度定数で略０．０５ｈ−１ｍ−２であり、略同等であった。
Decomposition rate constant per unit surface area k = ln (A 0 / A) / t / S
As can be seen from Table 2, Experimental Example Nos. 4, no. The crystallized glass of No. 5 has higher visible light transmittance than the conventional example (No. 1) that does not contain SnO. 1, no. 4 and no. The catalytic ability of No. 5 was about 0.05 h −1 m −2 in terms of the decomposition rate constant of methylene blue, which was substantially equivalent.
一方、実験例Ｎｏ．１〜３は、ＳｎＯの含有割合が低いため、可視光の透過率が低く、Ｎｏ．６は、ＳｎＯの含有割合が高すぎるため、結晶化ガラス中に分相が発生し、透過率が低かった。 On the other hand, Experimental Example No. Nos. 1 to 3 have a low visible light transmittance because the SnO content is low. In No. 6, since the content ratio of SnO was too high, phase separation occurred in the crystallized glass, and the transmittance was low.
尚、実験例１〜６は、平均結晶粒径が何れも５ｎｍであった。 In Examples 1 to 6, the average crystal grain size was 5 nm.
以上説明したように、チタニア結晶を含有した透明ナノ結晶化ガラスは、可視光の透明性が高く、しかも触媒能（特に光触媒能）を有するため、自動車・鉄道・船などの輸送重機、あるいは、ビルの窓にも応用が可能であり、半永久的にガラスに光触媒能を賦与することができる。従来のコーティングによる光触媒機能の賦与という作製法を、大きく変えうるため、本発明による産業界への波及効果は非常に大きいと予想される。 As described above, the transparent nanocrystallized glass containing titania crystals has high visible light transparency and also has catalytic ability (particularly photocatalytic ability), so that transportation heavy equipment such as automobiles, railways and ships, or It can also be applied to building windows and can semipermanently impart photocatalytic activity to glass. Since the production method of imparting a photocatalytic function by a conventional coating can be greatly changed, the ripple effect on the industry by the present invention is expected to be very large.
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| WO2011108472A1 (en) * | 2010-03-01 | 2011-09-09 | 株式会社 オハラ | Glass for glaze, glaze, and photocatalyst member |
| WO2011111800A1 (en) | 2010-03-12 | 2011-09-15 | 株式会社オハラ | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
| CN107555800A (en) * | 2017-08-18 | 2018-01-09 | 中国科学院理化技术研究所 | A kind of transparent Sr3Al2O6‑SrAl2O4Glass ceramics and preparation method thereof |
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| JP5039969B2 (en) * | 2006-11-15 | 2012-10-03 | 国立大学法人東北大学 | Glass, crystallized glass, crystallized glass manufacturing method and photocatalytic member |
| JP2008266091A (en) * | 2007-04-24 | 2008-11-06 | Ohara Inc | Photocatalytic glass member using ultraviolet region luminescent material |
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