JPS6227352A - Production of porous glass film - Google Patents
Production of porous glass filmInfo
- Publication number
- JPS6227352A JPS6227352A JP16302685A JP16302685A JPS6227352A JP S6227352 A JPS6227352 A JP S6227352A JP 16302685 A JP16302685 A JP 16302685A JP 16302685 A JP16302685 A JP 16302685A JP S6227352 A JPS6227352 A JP S6227352A
- Authority
- JP
- Japan
- Prior art keywords
- porous glass
- silica
- phase
- rich phase
- glass film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、細孔内にゲル状シリカを含まない多孔質ガラ
ス膜の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a porous glass membrane that does not contain gel-like silica in its pores.
（従来の技術）
従来、多孔質ガラス膜は硼珪酸塩ガラスを細管に成形後
、硼酸ナトリウムに富んだ相とシリカに富んだ相に分相
させ、硼酸ナトリウムに富んだ相を酸で溶出される方法
によって製造されていた。(Prior art) Conventionally, porous glass membranes are produced by forming borosilicate glass into a thin tube, separating the phases into a sodium borate-rich phase and a silica-rich phase, and eluting the sodium borate-rich phase with acid. It was manufactured using a method that
しかしながら、この製造方法では、分相によって生じた
硼酸すｌ−ＩＪウム相に含有されたシリカ成分が、酸処
理工程でゲル状シリカとなって多孔質ガラス膜の細孔内
に堆積する。このゲル状シリカは分相構造に由来する多
孔質構造を乱すため、多孔質ガラス膜の細孔特性を精密
に制御する必要がある場合に大きな障害となった。However, in this manufacturing method, the silica component contained in the sulfur borate phase produced by phase separation becomes gel-like silica in the acid treatment step and is deposited in the pores of the porous glass membrane. Since this gel-like silica disturbs the porous structure derived from the phase separation structure, it has become a major obstacle when it is necessary to precisely control the pore characteristics of a porous glass membrane.
係漬欠点を回避するため、特公昭５３−４４５８０では
、酸処理後の多孔質ガラス細管（膜厚５〜３０μｍ）に
対し、水酸化ナトリウム溶液をガラスを処理した場合、
アルカリ溶液処理工程後の多孔質ガラス膜表面に微細な
割れを発生することが多（、多孔質ガラス膜の製造にお
いて大きな障害となった。In order to avoid the mooring defect, in Japanese Patent Publication No. 53-44580, when a sodium hydroxide solution is applied to a porous glass tube (film thickness 5 to 30 μm) after acid treatment,
Microscopic cracks often occur on the surface of the porous glass membrane after the alkaline solution treatment process (this has become a major hindrance in the production of porous glass membranes).
（発明が解決しようとする問題点）
衣発ＢＪ’ｌは、ゲル状シリカを含まない多孔質ガラス
膜の製造方法における従来の欠点即ち、アルカリ溶）夜
処理工程後の多孔質ガラス膜の表面に微細な割れが発生
するという欠点を解消せんとするものである。(Problems to be Solved by the Invention) Koroba BJ'l is aware of the drawbacks of the conventional method for producing porous glass membranes that do not contain gelled silica, namely, the surface of the porous glass membrane after the alkaline solution treatment process. The aim is to eliminate the drawback that microscopic cracks occur in the steel.
（問題点を解決するための手段）
そこで、本発明者等はｔｉ７Ｊ記従来の欠点を解決すべ
く鋭意検討の結果、多孔質ガラス膜の表面に微細なｉ’
ＰＪれを発生させずに細孔内に堆積したゲル状シリカを
除去する方法を発明した。即ち、本発明は、硼珪酸”Ａ
Ｘガラスを原料ガラスとする多孔質ガラス膜の製造方法
において、硼酸ナトリウムに富んだ相と７リカに富んだ
相に分相させ、酸で硼酸ナトリウムに富んだ相を溶出さ
せた多孔質ガラス膜を７００°Ｃ〜８００°Ｃで熱処理
した後、アルカリ溶液で処理して細孔内に堆積したゲル
状シリカと一部のンリカ骨洛を溶出させることを特徴と
する多孔質ガラス膜の製造方法である。(Means for Solving the Problems) Therefore, as a result of intensive studies in order to solve the conventional drawbacks described in ti7J, the present inventors found that fine i'
We have invented a method for removing gel-like silica deposited in pores without causing PJ erosion. That is, the present invention provides borosilicate "A"
In a method for producing a porous glass membrane using X glass as a raw material glass, the porous glass membrane is separated into a sodium borate-rich phase and a 7-liquid-rich phase, and the sodium borate-rich phase is eluted with acid. A method for producing a porous glass membrane, which comprises heat-treating at 700°C to 800°C, and then treating with an alkaline solution to elute gel-like silica deposited in the pores and some of the silica skeleton. It is.
本発明の方法において、原料ガラスとして例えば米国特
許２２８６２７５ 号に記載されているようラムに富
んだ相とシリカに富んだ相に分相させ、−硼一酸ナトリ
ウムに富んだ相を酸で溶出させて多孔−処理して焼結さ
せるが、本発明によれば、熱処理温度は７００°Ｃ〜８
００°Ｃが好ましい。熱処理温が７００ ’Ｃより低い
場合アルカリ溶液処理工程後の多孔質ガラス膜表面での
割れ発生を抑制する幼果が小さく、熱処理温度が８００
°Ｃより高い場合アルカリ溶液処理を施した後の多孔質
ガラス膜の気体（例えば水素ガス、−酸ｒヒ炭素ガス等
）の透過性が低下するので好ましくない。In the method of the present invention, the raw glass is separated into a rum-rich phase and a silica-rich phase as described in US Pat. No. 2,286,275, and the sodium boronate-rich phase is eluted with an acid. According to the present invention, the heat treatment temperature is 700°C to 8°C.
00°C is preferred. When the heat treatment temperature is lower than 700'C, the young fruit is small and the heat treatment temperature is lower than 800'C.
If the temperature is higher than .degree. C., the gas permeability of the porous glass membrane (for example, hydrogen gas, -acid, arsenic, carbon gas, etc.) decreases after the alkaline solution treatment, which is not preferable.
前１犯熱処理を行った多孔質ガラス膜をアルカリ溶液で
処理して細孔内に堆積したゲル状シリカと一部のソリカ
骨格を溶出させることにより多孔質ガラス膜を得る。A porous glass membrane is obtained by treating the porous glass membrane that has been subjected to the first heat treatment with an alkaline solution to elute gel-like silica and part of the solica skeleton deposited in the pores.
本発明によれば、アルカリ溶液処理工程で使用するアル
カリ溶液は強アルカリ溶液（例えば水酸化ナトリウム溶
液、水酸（ヒカリウム溶液等）が好ましい。又、ゲル状
シリカの堆積量は窒素吸着法−り求めた累積細孔容積曲
線の変化より判断する。According to the present invention, the alkaline solution used in the alkaline solution treatment step is preferably a strong alkaline solution (e.g., sodium hydroxide solution, hydroxide (hypotassium solution, etc.) Judgment is made based on the change in the calculated cumulative pore volume curve.
なお、多孔質ガラス膜の熱安定性を向上させる（ト′！
ｒカある場合 又は多孔質カフス膜の県域的−度を増大
させる必要がある場合には、アルカリＪ、溶液処理王程
後の多孔質ガラス膜を酸で洗浄した後に焼成することが
好ましい。酸としては硫酸、塩酸、硝酸等が用いられる
。In addition, the thermal stability of the porous glass membrane is improved (T'!
If there is a need to increase the strength of the porous cuff membrane, it is preferable to wash the porous glass membrane after alkali and solution treatment with an acid and then sinter it. As the acid, sulfuric acid, hydrochloric acid, nitric acid, etc. are used.
（実施例） 以下、本発明を実施例にもとづき詳細に説明する。(Example) Hereinafter, the present invention will be explained in detail based on examples.
実施例１
３４０２６２．５ 重量係、ｎ２ ｏ３２７．３重は
チ、ＮＪＯ７，２重融係、ｈｉＤ３．０重４７）％より
成る原料ガラスを外径２ ｍｍ 、内’ＩＩ（Ｅ １
ｍ７７１の細管に成形し、５８０°Ｃで５時間熱処理し
て分相させ°た後、１規定硫酸をガラス１００ｇに対し
１を使用し９５°Ｃで２４時間処理して多孔質ガラス膜
を得た。この多孔質ガラス膜を空気中７２５・°Ｃで４
時間処理し、０、５規定水酸化ナトｌ）ラム溶液をガラ
ス１０９に対し１を使用し１°Ｃで２０時間処理した後
、２０°Ｃのイオン交換水で５時間洗浄して多孔質ガラ
ス膜を得た。窒素吸着法で測定した多孔質ガラス膜の細
孔特性及び細孔径分布を試￥）Ｊｉｌとして表１及び第
１図に示す。表１中の平均細孔径りは細孔容積ｖ（ｉ／
ｉ＋）と細孔比表面積Ｓ（ｄ／ａ）を用いてＤ＝４ｖ
によって計算した値である。Example 1 Raw material glass consisting of 340262.5% by weight, n2 o327.3% by weight, NJO7, double melting coefficient, hiD3.0% by weight, with an outer diameter of 2 mm and an inner diameter of 2 mm (E 1
It was formed into a thin tube of m771, heat-treated at 580°C for 5 hours to cause phase separation, and then treated with 1N sulfuric acid at 95°C for 24 hours using 1 part per 100g of glass to obtain a porous glass membrane. Ta. This porous glass membrane was heated to 725°C in air for 4 hours.
After treatment for 20 hours at 1°C using 0.5N sodium hydroxide solution (1) to 109 parts of glass, the porous glass was washed with ion-exchanged water at 20°C for 5 hours. A membrane was obtained. The pore characteristics and pore size distribution of the porous glass membrane measured by the nitrogen adsorption method are shown in Table 1 and FIG. The average pore diameter in Table 1 is the pore volume v(i/
D=4v using i+) and pore specific surface area S(d/a)
This is the value calculated by
なお、本発明の範囲外であるが、細孔内のゲル状シリカ
の堆積量を比較するため、アルカリ溶液処理工程前の多
孔質ガラス膜の細孔特性及び細″′７０蚤分布を試料煮
３として表１及び第１図に示す。Although it is outside the scope of the present invention, in order to compare the amount of gelatinous silica deposited within the pores, the pore characteristics and fine 70 fleas distribution of the porous glass membrane before the alkaline solution treatment step were measured by boiling samples. 3 in Table 1 and FIG.
′ （
又、□酸処理後の多孔質ガラス膜に対して上記の子処理
を行った場合、ゲル状シリカに由来した微細礼領域で累
積細孔容積曲線が増加せず、代って分相構造に由来した
細孔径領域で累積細孔容積曲線が増加することにより、
細孔内にゲル状シリカを含まないことが理解できる。′ (Also, when the above secondary treatment is performed on the porous glass membrane after acid treatment, the cumulative pore volume curve does not increase in the microscopic region derived from gel-like silica, but instead phase separation occurs. By increasing the cumulative pore volume curve in the pore size region derived from the structure,
It can be seen that no gelled silica is contained within the pores.
実施例２
実施例１に記載した鉱酸処理工程後の多孔質ガラス膜を
７５００Ｃで４時間処理し、０．５規定水酸化すｌ−Ｉ
Ｊウム溶液をガラス１．６ｇに対し１ｉ使用し１°Ｃで
２４時間処理した後、２０°Ｃのイオン交換水で５時間
洗浄して多孔質ガラス膜を得た。窒素吸着法で測定した
多孔質ガラス膜の細孔特性及び細孔径分布を試料跪２と
して表１及び第１図に示す。第１図から試料煮１と同様
に、試料、糸２もゲル状シリカを含まないことが理解で
きる。Example 2 The porous glass membrane after the mineral acid treatment step described in Example 1 was treated at 7500C for 4 hours and treated with 0.5N hydroxide l-I.
A porous glass membrane was obtained by using 1 i of Jium solution per 1.6 g of glass and treating it at 1°C for 24 hours, followed by washing with ion-exchanged water at 20°C for 5 hours. The pore characteristics and pore size distribution of the porous glass membrane measured by the nitrogen adsorption method are shown in Table 1 and FIG. 1 as sample Knee 2. From FIG. 1, it can be seen that, like sample boiled 1, sample thread 2 also does not contain gel-like silica.
（発明の効果）
本発明によれば、次のような格別優れた効果が得られる
。(Effects of the Invention) According to the present invention, the following exceptional effects can be obtained.
（１） ゲル状シリカを含まない多孔質ガラス膜を製
造できる。(1) Porous glass membranes that do not contain gelled silica can be manufactured.
（２） アルカリ処理工程後の多孔質力゛ラス膜の表
面に微細な割れが発生しない。(2) Fine cracks do not occur on the surface of the porous glass membrane after the alkali treatment process.
第１図は本発明方法により得られる多孔質ガラス膜の細
孔径分布を示すグラフである。FIG. 1 is a graph showing the pore size distribution of a porous glass membrane obtained by the method of the present invention.
Claims (1)
の製造方法において、硼酸ナトリウムに富んだ相とシリ
カに富んだ相に分相させ、酸で硼酸ナトリウムに富んだ
相を溶出させた多孔質ガラス膜を熱処理した後、アルカ
リ溶液で処理して細孔内に堆積したゲル状シリカと一部
のシリカ骨格を溶出させることを特徴とする多孔質ガラ
ス膜の製造方法。 ２、熱処理温が、７００℃〜８００℃である特許請求の
範囲第１項記載の製造方法。[Claims] 1. In a method for producing a porous glass membrane using borosilicate glass as a raw material glass, the phase is separated into a sodium borate-rich phase and a silica-rich phase, and the sodium borate-rich phase is separated with an acid. A method for producing a porous glass membrane, which comprises heat-treating the porous glass membrane from which the phase has been eluted, and then treating it with an alkaline solution to elute gel-like silica and part of the silica skeleton deposited in the pores. . 2. The manufacturing method according to claim 1, wherein the heat treatment temperature is 700°C to 800°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16302685A JPS6227352A (en) | 1985-07-25 | 1985-07-25 | Production of porous glass film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16302685A JPS6227352A (en) | 1985-07-25 | 1985-07-25 | Production of porous glass film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6227352A true JPS6227352A (en) | 1987-02-05 |
| JPH0425226B2 JPH0425226B2 (en) | 1992-04-30 |
Family
ID=15765774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16302685A Granted JPS6227352A (en) | 1985-07-25 | 1985-07-25 | Production of porous glass film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6227352A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8157857B2 (en) | 2003-04-24 | 2012-04-17 | Cook Medical Technologies Llc | Intralumenally-implantable frames |
| US9580353B2 (en) | 2012-10-12 | 2017-02-28 | Asahi Glass Company, Limited | Manufacturing method for phase-separated glass, and phase-separated glass |
| US10940167B2 (en) | 2012-02-10 | 2021-03-09 | Cvdevices, Llc | Methods and uses of biological tissues for various stent and other medical applications |
-
1985
- 1985-07-25 JP JP16302685A patent/JPS6227352A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8157857B2 (en) | 2003-04-24 | 2012-04-17 | Cook Medical Technologies Llc | Intralumenally-implantable frames |
| US8470020B2 (en) | 2003-04-24 | 2013-06-25 | Cook Medical Technologies Llc | Intralumenally-implantable frames |
| US8771338B2 (en) | 2003-04-24 | 2014-07-08 | Cook Medical Technologies Llc | Intralumenally-implantable frames |
| US10940167B2 (en) | 2012-02-10 | 2021-03-09 | Cvdevices, Llc | Methods and uses of biological tissues for various stent and other medical applications |
| US9580353B2 (en) | 2012-10-12 | 2017-02-28 | Asahi Glass Company, Limited | Manufacturing method for phase-separated glass, and phase-separated glass |
| US9902647B2 (en) | 2012-10-12 | 2018-02-27 | Asahi Glass Company, Limited | Manufacturing method for phase-separated glass, and phase-separated glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0425226B2 (en) | 1992-04-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |