JPS62223030A - Production of glass - Google Patents
Production of glassInfo
- Publication number
- JPS62223030A JPS62223030A JP6666586A JP6666586A JPS62223030A JP S62223030 A JPS62223030 A JP S62223030A JP 6666586 A JP6666586 A JP 6666586A JP 6666586 A JP6666586 A JP 6666586A JP S62223030 A JPS62223030 A JP S62223030A
- Authority
- JP
- Japan
- Prior art keywords
- wet gel
- glass
- temperature
- liquid
- article
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011240 wet gel Substances 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims abstract description 5
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 229920002545 silicone oil Polymers 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 150000004703 alkoxides Chemical class 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- -1 alkoxy metals Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
- Silicon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
ビ）産業上の利用分野
この発明は、アルコキシ金属を加水分解することからな
るいわゆるゾル−ゲル法によるガラスの製造法の改良に
関する。DETAILED DESCRIPTION OF THE INVENTION B) Industrial Application Field This invention relates to an improvement in the method for producing glass by the so-called sol-gel method, which consists of hydrolyzing alkoxy metals.
（ロ）従来の技術
前記ゾル−ゲル法書ζよって得られるガラスは、分離膜
、分析機器や自動車排ガス処理用の燃焼怠媒の担体、固
定化酵累用担体、分析用セル、半専体製造用のマスクな
ど広く工業界で利用されている。(b) Prior art The glass obtained by the above-mentioned sol-gel method ζ can be used for separation membranes, analytical instruments, carriers for combustion retardant for automobile exhaust gas treatment, carriers for immobilized fermentation, analytical cells, semi-dedicated It is widely used in industry, such as in manufacturing masks.
従来＋ｊｉｌ記ゾルーゲル法では、アルコキシ金属の水
性溶媒溶液（ζ加水分解触媒を添加してアルコキシ金属
を加水分解してゾルとしこれを成形型に入れて所定温度
で放置しく例えば約４０゛Ｃで約２４ｈｒ）ウェットゲ
ル成形体とし、これを脱水してドライゲルの成形体のガ
ラスを成形しているが、最後の脱水方法としては次のよ
うな方法が行われている。Conventionally, in the sol-gel method, an aqueous solvent solution of an alkoxy metal (ζ hydrolysis catalyst is added to hydrolyze the alkoxy metal to form a sol, which is put into a mold and left at a predetermined temperature, for example, at about 40°C). 24 hr) A wet gel molded body is formed, and this is dehydrated to form a glass of a dry gel molded body, and the final dehydration method is as follows.
すなわち、前記ウェットゲルを複数個の小さな通孔（例
えば直径１〜２ａｓ）を有する成形型にいれ、乾燥器内
にて比較的低温で（例えば約ＴＯ’Ｃ）低い乾燥速度で
乾燥脱水するのが一般的である。That is, the wet gel is put into a mold having a plurality of small holes (for example, diameter 1 to 2 as), and dried and dehydrated in a dryer at a relatively low temperature (for example, about TO'C) and a low drying rate. is common.
この場合乾燥温度を高くしたり容器をオーブンにしたり
して乾燥速度を上げれば乾燥時間が短かくなるという利
点があるが、生成したガラスにひびや肌れが生じたり変
形したりするので、成形型もオーブンにせず小通孔をあ
ける程度にしてしかも乾燥温度は８０℃程度までしか上
げずに７〜２０日もの長期間をかけて極めてゆっくりと
乾燥しなければならない。しかもこのような乾燥を行っ
ても厚みが薄い（例えば１罵程度）板状の場合はそって
しまうことが多かった。In this case, increasing the drying speed by increasing the drying temperature or using the container in an oven has the advantage of shortening the drying time, but this may cause cracks, peeling, or deformation in the resulting glass. The mold must be dried extremely slowly over a long period of 7 to 20 days, with only small holes made and the drying temperature only raised to about 80°C, without using an oven. Moreover, even if such drying is performed, in the case of a plate having a thin thickness (for example, about 1 mm thick), it often warps.
ン惇 発明がＮＴｈしようとする問題点この発明は、上
記のごとき従来技術の問題点を改善するためになされた
もので、製品のガラスが割れたり変形することなしにし
かも短時間で脱水する方法からなるガラスの製造法を目
的とするものである。NTh Problems that the Invention Attempts to Solve This invention was made in order to improve the problems of the prior art as described above. The purpose of this invention is to provide a method for producing glass consisting of.
に） 問題点を解決するための手段と作用この発明は、
アルコキシ金属含有の水もしくは水性溶媒に加水分解触
媒を添加して金属アルコシドを加水分解してゾルとし、
これを成形型に入れて所定温度で放置しウェットゲル成
形体とし、さらに脱水してドライゲルの成形体のガラス
を製造する方法において。) Means and operation for solving the problems This invention has the following features:
A hydrolysis catalyst is added to alkoxy metal-containing water or an aqueous solvent to hydrolyze the metal alkoxide to form a sol,
In a method of producing glass of a dry gel molded body by putting this into a mold and leaving it at a predetermined temperature to form a wet gel molded body, and then dehydrating it.
前記ウェットゲルの成形体を、実質的に水と混和せず沸
点が約２００℃を超え少なくとも約２００℃までの温度
では安定でかつ前記ウェットゲルに対して不活性な液体
中に浸漬し、約２００ ’Ｃまでの温度に加熱して脱水
することを特徴とするガラスの製造法を提供するもので
ある。The wet gel molded body is immersed in a liquid that is substantially immiscible with water, has a boiling point of more than about 200°C, is stable at temperatures up to at least about 200°C, and is inert to the wet gel, and The present invention provides a method for producing glass characterized by dehydration by heating to a temperature of up to 200'C.
この発明に用いられるアルコキシ金属としては、Ｓｉ（
ＯＣ２Ｈ５）４、Ａ６（０−１ｃａＨｙ）ａ、Ｂ（ＯＣ
２Ｈ５）３、Ｔｉ （０−ＩＣ８）１７）４、Ｎａα■
８、Ｃ１１（ＯＣ２Ｈ６）２などが挙げられる。The alkoxy metal used in this invention is Si(
OC2H5)4, A6(0-1caHy)a, B(OC
2H5)3, Ti (0-IC8)17)4, Naα■
8, C11(OC2H6)2, and the like.
前記の水性溶媒としては従来法と同様に、水とメタノー
ル、エタノール、プロパツールなどの低級アルコールと
の混合物が用いられる。加水分解触媒は従来法と同様に
塩酸、硝酸、アンモニア水溶液などが用いられる。As the aqueous solvent, a mixture of water and a lower alcohol such as methanol, ethanol, propatool, etc. is used, as in the conventional method. Hydrochloric acid, nitric acid, ammonia aqueous solution, etc. are used as the hydrolysis catalyst as in the conventional method.
アルコキシ金ｊ４を加水分解してゾルとする場合、アル
コキシ金属含有の水もしくは水性溶媒に前記加水分解触
媒を添加して常温で撹拌して行うことができるが、若干
昇温しで加水分解反応を速めてもよい。また上記加水分
解反応は、アルコキシ金属、水もしくは水性溶媒、およ
び加水分解触媒を同時に混合して行ってもよい。When alkoxy gold j4 is hydrolyzed to form a sol, the hydrolysis catalyst can be added to alkoxy metal-containing water or an aqueous solvent and stirred at room temperature. You can speed it up. Further, the above hydrolysis reaction may be carried out by simultaneously mixing the alkoxy metal, water or an aqueous solvent, and a hydrolysis catalyst.
このようにして得られたゾルは従来法と同様に成形型に
入れて所定温度で放置しく例えば４０℃で２４ ｈｒ
）ウェットゲル成形体とされる。The sol thus obtained is placed in a mold as in the conventional method and left at a predetermined temperature, for example at 40°C for 24 hours.
) It is considered as a wet gel molded body.
前記ウェットゲルの成形体を浸漬して脱水するのに用い
る液体としては、実質的に水と混和せず沸点が約２００
℃を超え、少なくとも約２００’０までの温度では安定
でかつ該ウェットゲルに対して不活性な液体であればよ
いが流動パラフィン、シリコンオイル、なたね油などが
挙げられる。The liquid used to immerse and dehydrate the wet gel molded body is a liquid that is substantially immiscible with water and has a boiling point of about 200 ml.
Any liquid that is stable at temperatures above 200'C and at least about 200'C and inert to the wet gel may be used, and examples thereof include liquid paraffin, silicone oil, rapeseed oil, and the like.
なお前記アルコキシ金属と、アルコキシ金属の少なくと
も一つのアルコキシ基が脂肪族もしくは芳香族の炭化水
素基、アミノ基またはアルキルアミノ基で置換された置
換アルコキシ金属とを用いてもよい。Note that the above alkoxy metal and a substituted alkoxy metal in which at least one alkoxy group of the alkoxy metal is substituted with an aliphatic or aromatic hydrocarbon group, an amino group, or an alkylamino group may be used.
水と混和しうる液体とか、脱水する場合の温度で沸騰し
たり不安定な化合物は前記ウェットゲルの脱水が成形体
全体から均一に行われない傾向が認められひびわれが発
生しやすいため好ましくない。また脱水の温度は約２０
０℃を超えると製品が変形したりわれが生じ始めるので
脱水は約２００℃までで行われ、特に１００〜２００℃
で行うのが脱水時間が短かくなり好ましい。Liquids that are miscible with water, or compounds that boil at the dehydration temperature or are unstable are undesirable because the wet gel tends not to be dehydrated uniformly throughout the molded product and cracks are likely to occur. Also, the dehydration temperature is approximately 20
If the temperature exceeds 0°C, the product will deform or cracks will begin to form, so dehydration should be carried out at temperatures up to about 200°C, especially between 100 and 200°C.
It is preferable to do this because the dehydration time will be shorter.
（ホ）実施例
この発明を実施例によって説明するがこの発明を限定す
るものではない。(e) Examples This invention will be explained by examples, but this invention is not limited to the following.
実施例１
て撹拌してシリカゾルを得た。このゾル約８０ｘｔを０
９０Ｂ内径で深さ１５鵡のポリスチロール製型容器に入
れ、４０℃で２４ｈｒＤｆｆｌしウェットシリカゲルを
得た。２００ｍ１Ｊｌ内径深さ８０１１ｍのガラス容器
に流動パラフィン（５００ｓｇｔ）ｅ入れておいてその
中に、前記ウェットシリカゲルを全体が流動パラフィン
内に入るように浸漬する。次いでこのガラス容器にふた
をして１２０℃の恒温槽内に静置して脱水した。４８ｈ
ｒ後に前記ゲルは約８５朋径で厚みが約１，５關の円板
状の多孔質のガラスが得られた。これをとりだして放置
してもひびができたり割れもせず円板状のガラスが従来
法よりも著しく短詩ｆｆ４１で得られた。Example 1 A silica sol was obtained by stirring. This sol is about 80xt
The mixture was placed in a polystyrene molded container with an inner diameter of 90B and a depth of 15 mm, and heated at 40° C. for 24 hours to obtain a wet silica gel. Liquid paraffin (500 sgt) is placed in a glass container with an inner diameter of 200 ml and a depth of 8011 m, and the wet silica gel is immersed therein so that the entire liquid paraffin is contained therein. Next, this glass container was covered with a lid and left to stand in a constant temperature bath at 120° C. for dehydration. 48h
After the gel was heated, a disc-shaped porous glass with a diameter of about 85 mm and a thickness of about 1.5 mm was obtained. Even when this glass was taken out and allowed to stand, it did not crack or break, and disk-shaped glass was obtained with a significantly shorter length than the conventional method.
なお得られた円板状ガラスを常法により、例えば約５０
℃／ｈｒの昇温連間で１０００℃まで昇湿しさらに約１
０ｈｒ １０００℃で保持することにより多孔質ではな
くて透明なガラスが得られた。Note that the obtained disk-shaped glass is heated by a conventional method, for example, about 50
The humidity is increased to 1000℃ with continuous temperature increase of ℃/hr, and the temperature is further increased by about 1
By holding at 1000° C. for 0 hr, a non-porous and transparent glass was obtained.
実施例２
ウェットシリカゲルを脱水するのに用いる流動パラフィ
ンの代りにシリコンオイルを用いること以外実施例１と
同様に行ったが実施例１と同様の結果が得られた。Example 2 The same procedure as in Example 1 was carried out except that silicone oil was used instead of the liquid paraffin used to dehydrate wet silica gel, and the same results as in Example 1 were obtained.
上記の実施例によれば、極めて短時間にウェットゲルの
脱水ができてしかも得られたガラスかわれたりひびが生
じず、変形せず所望の形態のものが得られる。According to the above embodiments, the wet gel can be dehydrated in an extremely short period of time, and the resulting glass does not crack or crack, and the desired shape can be obtained without deformation.
（へ）発明の交果
この発明によれば、アルコキシ金ｈｉＥを原料としてゾ
ル−ゲル法でガラスを２Ｌ造する場合に、ウェットゲル
の脱水を極めて短時間に行うことができ、しかも１与ら
れたガラスかわれたりひびが生じることなく、変形せず
所望の形態のものが得られる。(F) Achievements of the invention According to this invention, when producing 2L of glass by the sol-gel method using alkoxy gold hiE as a raw material, the wet gel can be dehydrated in an extremely short time, and moreover, it is possible to dehydrate the wet gel in a very short time. The desired shape can be obtained without deformation, without cracking or cracking.
Claims (1)
解触媒を添加して金属アルコシドを加水分解してゾルと
し、これを成形型に入れて所定温度で放置しウェットゲ
ル成形体とし、さらに脱水してドライゲルの成形体のガ
ラスを製造する方法において、 前記ウェットゲルの成形体を、実質的に水と混和せず沸
点が約２００℃を超え少なくとも約２００℃までの温度
では安定でかつ前記ウェットゲルに対して不活性な液体
中に浸漬し、約２００℃までの温度に加熱して脱水する
ことを特徴とするガラスの製造法。 ２、前記ウェットゲルを浸漬する液体がシリコンオイル
もしくは流動パラフィンである特許請求の範囲第１項記
載の製造法。[Claims] 1. A hydrolysis catalyst is added to alkoxy metal-containing water or an aqueous solvent to hydrolyze the metal alkoside to form a sol, which is placed in a mold and left at a predetermined temperature to produce a wet gel molded body. and further dehydrated to produce glass of a dry gel molded body, the wet gel molded body being substantially immiscible with water and having a boiling point exceeding about 200°C and being stable at temperatures up to at least about 200°C. A method for producing glass, characterized in that the glass is immersed in a liquid that is inert to the wet gel and heated to a temperature of up to about 200° C. to dehydrate it. 2. The manufacturing method according to claim 1, wherein the liquid in which the wet gel is immersed is silicone oil or liquid paraffin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6666586A JPS62223030A (en) | 1986-03-25 | 1986-03-25 | Production of glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6666586A JPS62223030A (en) | 1986-03-25 | 1986-03-25 | Production of glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62223030A true JPS62223030A (en) | 1987-10-01 |
Family
ID=13322423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6666586A Pending JPS62223030A (en) | 1986-03-25 | 1986-03-25 | Production of glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62223030A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0506843A1 (en) * | 1989-12-19 | 1992-10-07 | Orion Lab Inc | Sol-gel process for glass and ceramic articles. |
| US6132649A (en) * | 1999-01-29 | 2000-10-17 | Lucent Technologies Inc. | Fabrication including sol-gel processing |
-
1986
- 1986-03-25 JP JP6666586A patent/JPS62223030A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0506843A1 (en) * | 1989-12-19 | 1992-10-07 | Orion Lab Inc | Sol-gel process for glass and ceramic articles. |
| US6132649A (en) * | 1999-01-29 | 2000-10-17 | Lucent Technologies Inc. | Fabrication including sol-gel processing |
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