JPH06183780A - Porous glass ceramic and its production - Google Patents
Porous glass ceramic and its productionInfo
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- JPH06183780A JPH06183780A JP4058096A JP5809692A JPH06183780A JP H06183780 A JPH06183780 A JP H06183780A JP 4058096 A JP4058096 A JP 4058096A JP 5809692 A JP5809692 A JP 5809692A JP H06183780 A JPH06183780 A JP H06183780A
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- glass
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- porous glass
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は多孔質ガラスセラミック
スおよびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous glass ceramic and a method for producing the same.
【０００２】[0002]
【背景技術】多孔質セラミックスは、分離用フィルタ
ー、触媒担体、ガスセンサーなどの分野に使用されてい
る。またこれらは、バイオテクノロジーの分野において
極めて有望な材料であり、酵素固定のための担体や、液
体クロマトグラフィーでアミノ酸と蛋白質を分離するた
めの充填剤として使用されている。BACKGROUND ART Porous ceramics are used in fields such as separation filters, catalyst carriers and gas sensors. Further, these are extremely promising materials in the field of biotechnology, and are used as carriers for immobilizing enzymes and packing materials for separating amino acids and proteins by liquid chromatography.
【０００３】多孔質ガラスや多孔質セラミックスの研究
開発は、１９３４年のバイコール（Vycor R ）ガラスの
発明以来、シリケート系を主体に行なわれており、例え
ばＮａ2 Ｏ−Ｂ2 Ｏ3 −ＳｉＯ2 系多孔質ガラスを改良
するため、数多くの試みがなされてきた。[0003] Research and development of porous glass or porous ceramics, since the invention of Vycor (Vycor R) glass of 1934 has been performed silicate mainly, for example, Na 2 O-B 2 O 3 -SiO 2 Many attempts have been made to improve the porous glass.
【０００４】これに対して本発明者は、シリケート系で
なくホスフェート系の新規多孔質ガラスセラミックス
を、ＣａＯ−ＴｉＯ2 −Ｐ2 Ｏ5 系ガラスを結晶化し次
いで酸溶出処理することにより製造し、このホスフェー
ト系多孔質ガラスセラミックスをＪ．Ａｍ．Ｃｅｒａ
ｍ．Ｓｏｃ．７２（１９８９）１５８７において発表し
ている。On the other hand, the inventor of the present invention produced a novel porous glass-ceramic, not silicate-based, by crystallizing CaO-TiO 2 -P 2 O 5 -based glass and then subjecting it to acid elution treatment, This phosphate-based porous glass-ceramic was prepared according to J. Am. Cera
m. Soc. 72 (1989) 1587.
【０００５】しかし、同様にホスフェート系化合物であ
る含水素オルトリン酸チタニウムからなる多孔質ガラス
セラミックスは、この含水素オルトリン酸チタニウム自
体の合成法が古くから知られているにも拘らず、従来全
く知られていなかった。However, a porous glass-ceramic made of hydrogen-containing titanium orthophosphate, which is also a phosphate-based compound, has never been known in the past, although the method for synthesizing the hydrogen-containing titanium orthophosphate itself has long been known. It wasn't done.
【０００６】[0006]
【発明の目的】従って本発明の目的は、含水素オルトリ
ン酸チタニウムからなる新規多孔質ガラスセラミックス
およびその製造方法を提供することにある。OBJECTS OF THE INVENTION It is therefore an object of the present invention to provide a novel porous glass-ceramic comprising hydrogen-containing titanium orthophosphate and a method for producing the same.
【０００７】[0007]
【目的を達成するための手段】本発明者は、この目的を
達成するために研究を重ねた結果、Ｌｉ2 Ｏ−ＣａＯ−
ＴｉＯ2 −Ｐ2 Ｏ5 系ガラスを結晶化し、得られたガラ
スセラミックスを酸処理して可溶性成分を溶出させるこ
とにより、含水素リン酸チタニウムを骨格とする新規多
孔質ガラスセラミックスが得られることを見い出した。Means for Achieving the Purpose The present inventor has conducted research to achieve this object, and as a result, Li 2 O--CaO--
By crystallizing a TiO 2 —P 2 O 5 based glass and subjecting the obtained glass ceramics to an acid treatment to elute soluble components, a novel porous glass ceramics having titanium hydrogen phosphate as a skeleton can be obtained. I found it.
【０００８】従って本発明は、含水素オルトリン酸チタ
ニウムを骨格とすることを特徴とする多孔質ガラスセラ
ミックスを要旨とする。Therefore, the gist of the present invention is a porous glass-ceramic having a skeleton of hydrogen-containing titanium orthophosphate.
【０００９】また本発明は、Ｌｉ2 Ｏ−ＣａＯ−ＴｉＯ
2 −Ｐ2 Ｏ5 系ガラスを結晶化し、得られたガラスセラ
ミックスを酸処理して可溶性成分を溶出させることを特
徴とする前記多孔質ガラスセラミックスの製造方法を要
旨とする。The present invention also relates to Li 2 O-CaO-TiO
The 2 -P 2 O 5 based glass crystallization method of the porous glass ceramics by the acid treatment and the resulting glass-ceramic and wherein the eluting the soluble components and gist.
【００１０】以下本発明を詳説する。The present invention will be described in detail below.
【００１１】本発明の多孔質ガラスセラミックスは、含
水素オルトリン酸チタニウムを骨格とするものである。
含水素オルトリン酸チタニウムは、式Ｔｉ（ＨＰＯ4 ）
2 ・２Ｈ2 Ｏによって示される化合物である。本発明の
多孔質ガラスセラミックスにおいて、含水素オルトリン
酸チタニウム骨格は、２次元層構造を有する。The porous glass-ceramic of the present invention has hydrogen-containing titanium orthophosphate as a skeleton.
Hydrogen-containing titanium orthophosphate has the formula Ti (HPO 4 ).
Is a compound represented by the 2 · 2H 2 O. In the porous glass ceramics of the present invention, the hydrogen-containing titanium orthophosphate skeleton has a two-dimensional layer structure.
【００１２】本発明の多孔質ガラスセラミックスの平均
孔径は１０〜４０nm、表面積は５０〜１５０ｍ2 ／ｇ、
空孔率は、４０〜６０％であるのが好ましい。上記平均
孔径、表面積および空孔率を有することにより、本発明
の多孔質ガラスセラミックスは、分離用フィルター、触
媒担体、ガスセンサー、酵素固定担体、クロマトグラフ
ィー用充填剤などの用途に好ましく用いられる。The porous glass-ceramics of the present invention have an average pore diameter of 10 to 40 nm and a surface area of 50 to 150 m 2 / g.
The porosity is preferably 40 to 60%. The porous glass ceramics of the present invention having the above average pore diameter, surface area and porosity are preferably used for applications such as a separation filter, a catalyst carrier, a gas sensor, an enzyme-immobilized carrier and a packing material for chromatography.
【００１３】次に多孔質ガラスセラミックスを製造する
ための本発明の方法について述べる。Next, the method of the present invention for producing a porous glass-ceramic will be described.
【００１４】本発明の方法においては、先ずＬｉ2 Ｏ−
ＣａＯ−ＴｉＯ2 −Ｐ2 Ｏ5 系ガラスを結晶化させる。
結晶化は、一工程加熱処理によって行なっても良いが、
二工程加熱処理によって行なうのが好ましい。二工程加
熱処理においては、先ずガラスを比較的低い温度で加熱
する第１工程によって、核を生成させた後、冷却するこ
となく、比較的高い温度で加熱する第２工程によってガ
ラスを結晶化させる。前記第１工程において、加熱温度
は、ガラスのガラス転移点（Ｔg ）よりも１０〜４０℃
高い温度とするのが好ましく、ガラスは、この加熱温度
で１〜１０時間保持されることによって核を生成する。
また第２工程において、加熱温度は、Ｔg よりも８０〜
１５０℃高い温度とするのが好ましく、第１工程によっ
て核を生成したガラスは、この加熱温度で１〜１０時間
保持されることによって結晶化する。In the method of the present invention, first, Li 2 O-
Crystallize the CaO—TiO 2 —P 2 O 5 based glass.
The crystallization may be performed by a one-step heat treatment,
It is preferably carried out by a two-step heat treatment. In the two-step heat treatment, first, nucleation is performed by the first step of heating the glass at a relatively low temperature, and then the glass is crystallized by the second step of heating at a relatively high temperature without cooling. . In the first step, the heating temperature is 10 to 40 ° C. higher than the glass transition point (Tg) of the glass.
Elevated temperatures are preferred and the glass is nucleated by being held at this heating temperature for 1-10 hours.
In addition, in the second step, the heating temperature is 80 to
The temperature is preferably 150 ° C. higher, and the glass having nucleated in the first step is crystallized by being held at this heating temperature for 1 to 10 hours.
【００１５】得られたガラスセラミックスは、ＬｉＴｉ
2 （ＰＯ4 ）3 とＣａ3 （ＰＯ4 ）2 とからなり、Ｌｉ
Ｔｉ2 （ＰＯ4 ）3 とＣａ3 （ＰＯ4 ）2 との比率は、
前者が０．９〜１．１、後者が０．９〜１．３の範囲で
あるのが好ましい。The obtained glass ceramics are LiTi
2 (PO 4 ) 3 and Ca 3 (PO 4 ) 2
The ratio of Ti 2 (PO 4 ) 3 and Ca 3 (PO 4 ) 2 is
The former is preferably 0.9 to 1.1 and the latter is preferably 0.9 to 1.3.
【００１６】ガラスセラミックスにおけるＬｉＴｉ
2 （ＰＯ4 ）3 とＣａ3 （ＰＯ4 ）2 との比率を上記の
範囲とすることは、出発ガラス中の成分であるＬｉ
2 Ｏ、ＣａＯ、ＴｉＯ2 およびＰ2 Ｏ5 の割合を適宜調
整することによって可能である。LiTi in glass ceramics
Setting the ratio of 2 (PO 4 ) 3 to Ca 3 (PO 4 ) 2 within the above range means that Li which is a component in the starting glass.
It is possible by appropriately adjusting the proportions of 2 O, CaO, TiO 2 and P 2 O 5 .
【００１７】ガラスセラミックスにおけるＬｉＴｉ
2 （ＰＯ4 ）3 とＣａ3 （ＰＯ4 ）2 との比率は、前者
１．０に対して後者が１．１であるのが特に好ましく、
この場合には、６Ｌｉ2 Ｏ・３９ＣａＯ・２４ＴｉＯ2
・３１Ｐ2 Ｏ5 （モル％）のガラスが出発ガラスとして
用いられる。LiTi in glass ceramics
The ratio of 2 (PO 4 ) 3 to Ca 3 (PO 4 ) 2 is particularly preferably 1.0 for the former and 1.1 for the latter.
In this case, 6Li 2 O.39CaO.24TiO 2
Glass · 31P 2 O 5 (mol%) is used as the starting glass.
【００１８】得られたガラスセラミックスがＬｉＴｉ2
（ＰＯ4 ）3 とＣａ3 （ＰＯ4 ）2とからなることは、
粉末ＸＲＤ（Ｘ線回折）によって確認される。The glass ceramic obtained is LiTi 2
What consists of (PO 4 ) 3 and Ca 3 (PO 4 ) 2 is
Confirmed by powder XRD (X-ray diffraction).
【００１９】本発明の方法においては、上で得られたガ
ラスセラミックスを酸処理して可溶性成分を溶出させ
る。酸処理に用いる酸としては、塩酸、硝酸、硫酸など
の無機酸を用いるのが好ましい。酸処理は、ガラスセラ
ミックスを上記の酸に浸漬して通常還流下６０℃以上で
３〜２０時間行なわれる。この酸処理によってガラスセ
ラミックス中の可溶性成分（ＬｉおよびＣａ）が溶出さ
れ、２次元層状構造のＴｉ（ＨＰＯ4 ）2 ・２Ｈ2 Ｏ骨
格からなる多孔質ガラスセラミックスが得られる。可溶
性成分であるＬｉおよびＣａが除去され、Ｔｉ（ＨＰＯ
4 ）2 ・２Ｈ2 Ｏ骨格からなる多孔質ガラスセラミック
スが得られていることは、酸処理による重量減、ＩＣＰ
（高周波プラズマ分光）分析、および粉末ＸＲＤによっ
て確認される。In the method of the present invention, the glass ceramic obtained above is acid-treated to dissolve soluble components. As the acid used for the acid treatment, it is preferable to use an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid. The acid treatment is carried out by immersing the glass ceramic in the above acid and usually under reflux at 60 ° C. or higher for 3 to 20 hours. By this acid treatment, soluble components (Li and Ca) in the glass ceramics are eluted and a porous glass ceramics having a two-dimensional layered structure of Ti (HPO 4 ) 2 .2H 2 O skeleton is obtained. Soluble components Li and Ca are removed, and Ti (HPO
4) the porous glass ceramics are obtained consisting of 2 · 2H 2 O backbone, weight loss by acid treatment, ICP
Confirmed by (high frequency plasma spectroscopy) analysis and powder XRD.
【００２０】本発明の方法により得られた多孔質ガラス
セラミックスは、上述のように１０〜４０nmの平均孔
径、５０〜１５０ｍ2 ／ｇの表面積、４０〜６０％の空
孔率を有するのが好ましい。得られた多孔質ガラスセラ
ミックスは、上述のように分離用フィルター、触媒担
体、ガスセンサー、酵素固定担体、クロマトグラフィー
用充填剤などの用途に用いられる。The porous glass ceramic obtained by the method of the present invention preferably has an average pore diameter of 10 to 40 nm, a surface area of 50 to 150 m 2 / g and a porosity of 40 to 60% as described above. . The obtained porous glass-ceramics are used for applications such as a separation filter, a catalyst carrier, a gas sensor, an enzyme-immobilized carrier and a packing material for chromatography as described above.
【００２１】[0021]
【実施例】以下、実施例により本発明をさらに説明す
る。EXAMPLES The present invention will be further described below with reference to examples.
【００２２】（ｉ）ガラスの調製 ６ＬｉＯ2 ・３９ＣａＯ・２４ＴｉＯ2 ・３１Ｐ2 Ｏ5
（モル％）のガラスが得られるように、ＣａＣＯ3 、Ｌ
ｉ2 ＣＯ3 、ＴｉＯ2 （アナターゼ）およびＨ3 ＰＯ4
（８５％）を混合し、得られた混合物をＳｉＯ2 ガラス
製ボウルに入れ、水を加えた後撹拌してスラリーを得
た。このスラリーを赤外線ランプで乾燥し、乾燥物を白
金るつぼに入れて、大気中、１３５０℃で１時間溶融
し、融液を炭素製の型に注入してアニーリングした。得
られたガラスはＴｉ3+（この含量は、ＥＰＲによる測定
により総Ｔｉイオンの約０．１％であることが確認され
た）によるバイオレットカラーを呈していた。(I) Preparation of glass 6LiO 2 · 39CaO · 24TiO 2 · 31P 2 O 5
CaCO 3 , L so that (mol%) glass is obtained
i 2 CO 3 , TiO 2 (anatase) and H 3 PO 4
(85%) were mixed, the obtained mixture was put into a SiO 2 glass bowl, water was added, and the mixture was stirred to obtain a slurry. This slurry was dried with an infrared lamp, the dried product was put into a platinum crucible, and the mixture was melted in the atmosphere at 1350 ° C. for 1 hour, and the melt was poured into a carbon mold and annealed. The resulting glass exhibited a violet color due to Ti 3+ (this content was confirmed by EPR to be about 0.1% of the total Ti ions).
【００２３】（ii）ガラスの結晶化によるガラスセラミ
ックスの製造 （ｉ）で得られたガラスを２×２×０．５cmの大きさの
板状に切断し、研磨した。得られた板状ガラスを２工程
熱処理により結晶化した。すなわち、板状ガラス（Ｔg
＝６００℃）を６２０℃に加熱し、この温度を２０時間
保持して核を生成させた後、室温に冷却することなく、
７３０℃に加熱し、この温度に１２時間保持して結晶化
させてガラスセラミックスを得た。(Ii) Production of glass-ceramics by crystallizing glass The glass obtained in (i) was cut into a plate having a size of 2 × 2 × 0.5 cm and polished. The obtained plate glass was crystallized by a two-step heat treatment. That is, plate glass (Tg
= 600 ° C.) to 620 ° C., this temperature is kept for 20 hours to generate nuclei, and then, without cooling to room temperature,
It was heated to 730 ° C. and kept at this temperature for 12 hours for crystallization to obtain glass ceramics.
【００２４】得られたガラスセラミックスの粉末ＸＲＤ
パターンを図１（ａ）に示す。図１（ａ）より、このガ
ラスセラミックスは、ＬｉＴｉ2 （ＰＯ4 ）3 相とβ−
Ｃａ3 （ＰＯ4 ）2 相からなることが判明した。Obtained glass-ceramic powder XRD
The pattern is shown in FIG. From FIG. 1 (a), this glass-ceramic has LiTi 2 (PO 4 ) 3 phase and β-
It was found to consist of a Ca 3 (PO 4 ) 2 phase.
【００２５】(iii) 酸処理による多孔質ガラスセラミッ
クスの製造 得られたガラスセラミックスをナイロン製バスケットに
入れ、１Ｎ ＨＣｌ（ＨＮＯ3 、Ｈ2 ＳＯ4 を用いても
よい）中に浸漬し、還流下でその沸点付近で１２〜２４
時間加熱することにより、可溶性成分を溶出して多孔質
ガラスセラミックスを得た。(Iii) Production of Porous Glass-Ceramics by Acid Treatment The obtained glass-ceramics are placed in a nylon basket, immersed in 1N HCl (HNO 3 , H 2 SO 4 may be used), and refluxed. And around its boiling point 12-24
By heating for a period of time, the soluble component was eluted and a porous glass ceramic was obtained.
【００２６】得られた多孔質ガラスセラミックスの粉末
ＸＲＤパターンを図１（ｂ）に示す。図１（ｂ）より明
らかなように、酸処理前に認められたＬｉＴｉ2 （ＰＯ
4 ）3 相およびβ−Ｃａ3 （ＰＯ4 ）2 相に基づくピー
クが消失し、２θ＝８．７°において特徴的なピーク
が、数多くのブロードなピークとともに出現した。また
酸処理後の重量減は約５０％であったが、元の形状は保
持されていた。ＩＣＰ分析によれば、ガラスセラミック
ス中の大部分のＬｉ（９７％）およびＣａ（９８％）が
酸で溶出されていた。The powder XRD pattern of the obtained porous glass-ceramic is shown in FIG. 1 (b). As is clear from FIG. 1 (b), LiTi 2 (PO
4 ) The peaks based on the 3 phase and β-Ca 3 (PO 4 ) 2 phase disappeared, and the characteristic peak at 2θ = 8.7 ° appeared with many broad peaks. The weight loss after acid treatment was about 50%, but the original shape was retained. According to ICP analysis, most of Li (97%) and Ca (98%) in the glass ceramics were eluted with acid.
【００２７】また得られた多孔質ガラスセラミックスを
有機アミン類で処理すると、図２（ａ）に示す多孔質ガ
ラスセラミックスの粉末ＸＲＤパターン中の２θ＝８．
７°のメインピークが、同図（ｂ）に示すように２θ＝
４．２°にシフトしていることから、この多孔質ガラス
セラミックスは、有機アミン類のインターカレーション
（挿入反応）が容易に可能であることが確認された。When the obtained porous glass-ceramics were treated with organic amines, 2θ = 8.x in the powder XRD pattern of the porous glass-ceramics shown in FIG. 2 (a).
The main peak at 7 ° is 2θ =, as shown in FIG.
Since it was shifted to 4.2 °, it was confirmed that this porous glass-ceramic can easily intercalate (insertion reaction) organic amines.
【００２８】以上のことから、得られた多孔質ガラスセ
ラミックスは２次元層状構造のＴｉ（ＨＰＯ4 ）2 骨格
からなることが明らかとなった。From the above, it was clarified that the obtained porous glass-ceramic had a Ti (HPO 4 ) 2 skeleton having a two-dimensional layered structure.
【００２９】図３は、得られた多孔質ガラスセラミック
スの孔径分布を示す。多孔質ガラスセラミックスの平均
孔径および表面積は、それぞれ１５nmおよび１２０ｍ2
／ｇであり、空孔率は４３vol.％であった。FIG. 3 shows the pore size distribution of the obtained porous glass ceramics. The average pore size and surface area of the porous glass ceramics are 15 nm and 120 m 2 respectively.
/ G, and the porosity was 43 vol.%.
【００３０】[0030]
【発明の効果】本発明によれば、含水素オルトリン酸チ
タニウムを骨格とする新規多孔質ガラスセラミックスお
よびその製造方法が提供された。According to the present invention, a novel porous glass-ceramic having hydrogen-containing titanium orthophosphate as a skeleton and a method for producing the same are provided.
【図１】酸処理前のガラスセラミックスおよび酸処理後
に得られた本発明の多孔質ガラスセラミックスの粉末Ｘ
ＲＤパターン図である。FIG. 1 Powder X of a glass ceramics before acid treatment and a porous glass ceramics of the present invention obtained after acid treatment X
It is a RD pattern figure.
【図２】本発明の多孔質ガラスセラミックスのアミン処
理前と後の粉末ＸＲＤパターン図である。FIG. 2 is a powder XRD pattern diagram before and after amine treatment of the porous glass ceramics of the present invention.
【図３】本発明で得られた多孔質ガラスセラミックスの
孔径分布図である。FIG. 3 is a pore diameter distribution diagram of the porous glass ceramics obtained by the present invention.
Claims (2)
することを特徴とする多孔質ガラスセラミックス。1. A porous glass ceramic having a skeleton of hydrogen-containing titanium orthophosphate.
系ガラスを結晶化し、得られたガラスセラミックスを酸
処理して可溶性成分を溶出させることを特徴とする請求
項１に記載の多孔質ガラスセラミックスの製造方法。2. Li 2 O—CaO—TiO 2 —P 2 O 5
The method for producing a porous glass-ceramic according to claim 1, wherein the system glass is crystallized, and the obtained glass-ceramic is acid-treated to dissolve the soluble component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4058096A JPH06183780A (en) | 1992-03-16 | 1992-03-16 | Porous glass ceramic and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4058096A JPH06183780A (en) | 1992-03-16 | 1992-03-16 | Porous glass ceramic and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06183780A true JPH06183780A (en) | 1994-07-05 |
Family
ID=13074426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4058096A Withdrawn JPH06183780A (en) | 1992-03-16 | 1992-03-16 | Porous glass ceramic and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06183780A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0757024A1 (en) | 1995-07-26 | 1997-02-05 | Sumitomo Electric Industries, Ltd. | Silicon nitride porous body and method of preparing the same |
| KR100388281B1 (en) * | 2000-07-28 | 2003-06-19 | 강원호 | Preparation of a Composite for a Glass Ceramics having far-infrared Radiation and Antibacterial Properties |
| WO2010041760A1 (en) * | 2008-10-10 | 2010-04-15 | 株式会社オハラ | Glass ceramics and process for production thereof, process for producing sintered glass ceramics, process for producing complex, molded article having photocatalytic function, and hydrophilic molded article |
| JP2010111573A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2010111574A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2010111575A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2010111571A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2010275175A (en) * | 2009-04-30 | 2010-12-09 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2011235283A (en) * | 2006-05-01 | 2011-11-24 | Ibiden Co Ltd | Honeycomb structure, method for production of the honeycomb structure, honeycomb filter, and method for production of the honeycomb filter |
| EP2545992A1 (en) * | 2010-03-12 | 2013-01-16 | Ohara Inc. | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
| JP2013193895A (en) * | 2012-03-16 | 2013-09-30 | Citizen Finetech Miyota Co Ltd | Porous molding member and method of manufacturing the same |
| JP2016155707A (en) * | 2015-02-24 | 2016-09-01 | 株式会社住田光学ガラス | Method for producing ltp or latp crystal particle |
-
1992
- 1992-03-16 JP JP4058096A patent/JPH06183780A/en not_active Withdrawn
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846460A (en) * | 1995-07-26 | 1998-12-08 | Sumitomo Electric Industries, Ltd. | Method of preparing silicon nitride porous body |
| EP0757024A1 (en) | 1995-07-26 | 1997-02-05 | Sumitomo Electric Industries, Ltd. | Silicon nitride porous body and method of preparing the same |
| KR100388281B1 (en) * | 2000-07-28 | 2003-06-19 | 강원호 | Preparation of a Composite for a Glass Ceramics having far-infrared Radiation and Antibacterial Properties |
| JP2011235283A (en) * | 2006-05-01 | 2011-11-24 | Ibiden Co Ltd | Honeycomb structure, method for production of the honeycomb structure, honeycomb filter, and method for production of the honeycomb filter |
| WO2010041760A1 (en) * | 2008-10-10 | 2010-04-15 | 株式会社オハラ | Glass ceramics and process for production thereof, process for producing sintered glass ceramics, process for producing complex, molded article having photocatalytic function, and hydrophilic molded article |
| JP2010111573A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2010111574A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2010111575A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| JP2010111571A (en) * | 2008-10-10 | 2010-05-20 | Ohara Inc | Glass ceramics and method for producing the same |
| CN102177102A (en) * | 2008-10-10 | 2011-09-07 | 株式会社小原 | Glass ceramics and process for production thereof, process for producing sintered glass ceramics, process for producing complex, molded article having photocatalytic function, and hydrophilic molded article |
| JP2010275175A (en) * | 2009-04-30 | 2010-12-09 | Ohara Inc | Glass ceramics and method for producing the same |
| EP2545992A1 (en) * | 2010-03-12 | 2013-01-16 | Ohara Inc. | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
| EP2545992A4 (en) * | 2010-03-12 | 2013-09-18 | Ohara Kk | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
| TWI510292B (en) * | 2010-03-12 | 2015-12-01 | Ohara Kk | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building materials and cleaning materials |
| JP2013193895A (en) * | 2012-03-16 | 2013-09-30 | Citizen Finetech Miyota Co Ltd | Porous molding member and method of manufacturing the same |
| JP2016155707A (en) * | 2015-02-24 | 2016-09-01 | 株式会社住田光学ガラス | Method for producing ltp or latp crystal particle |
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| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990518 |