JP3203694B2 - Manufacturing method of quartz glass - Google Patents
Manufacturing method of quartz glassInfo
- Publication number
- JP3203694B2 JP3203694B2 JP20370291A JP20370291A JP3203694B2 JP 3203694 B2 JP3203694 B2 JP 3203694B2 JP 20370291 A JP20370291 A JP 20370291A JP 20370291 A JP20370291 A JP 20370291A JP 3203694 B2 JP3203694 B2 JP 3203694B2
- Authority
- JP
- Japan
- Prior art keywords
- quartz glass
- powder
- suspension
- silica
- specific gravity
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は石英ガラスの製造方法に
関し、特に気泡や脈理等の光学的不均質部分が存在しな
い石英ガラスの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing quartz glass, and more particularly to a method for producing quartz glass free from optically inhomogeneous portions such as bubbles and striae.
【０００２】[0002]
【従来の技術】マスク用基板、ディスプレイ等に使用さ
れる石英ガラス薄板は従来 イ．溶融及び合成石英ガラスインゴットより切り出し・
研削・研磨を行い石英ガラス薄板とする方法 ロ．珪素のアルコキシド、シリカ微粉末又はそれらの混
合物を出発原料とし、加水分解・脱水重合反応をおこさ
せ得られたゲルを乾燥・焼結し石英ガラス薄板とする方
法 等の方法により作製されている。現在は、イの方法が主
流である。2. Description of the Related Art Thin quartz glass plates used for mask substrates, displays and the like have been conventionally used. Cut out from fused and synthetic quartz glass ingots
Method of grinding and polishing to make a thin quartz glass plate b. It is manufactured by a method such as a method of drying and sintering a gel obtained by subjecting a alkoxide of silicon, a fine powder of silica or a mixture thereof as a starting material to a hydrolysis and dehydration polymerization reaction to obtain a thin quartz glass plate. At present, method A is the mainstream.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
の方法には以下のような問題がある。 イの方法 気泡や脈理等の光学的不均質部分が存在 歩留りが悪い 高価である 大面積の薄板を得ることが困難である ロの方法 気泡の存在 反りの発生 また従来の濾過成型法は濾過に長時間を要する場合があ
る。However, these methods have the following problems. Method (a) Optically inhomogeneous parts such as air bubbles and striae are present. Yield is poor. It is difficult to obtain a large-area thin plate. (B) Air bubbles exist. Warpage occurs. May take a long time.
【０００４】本発明はこれらの問題点を解決するため
に、気泡や脈理等の光学的不均質部分が存在せず、反り
のない石英ガラス薄板を歩留りよく、安価に製造する方
法を提供するものである。In order to solve these problems, the present invention provides a method of manufacturing a quartz glass thin plate having no optically inhomogeneous portions such as bubbles and striae and having no warp with a good yield and at a low cost. Things.
【０００５】[0005]
【課題を解決するための手段】上記問題点に鑑み鋭意研
究の結果、本発明者らはシリカ粉末を原料とし、この粉
末を分散媒中に分散させた懸濁液を比重が２．２ｇ／ｃ
ｍ３以上の液体に浮かせ、遠心力を用いてシリカ粉末を
沈降、堆積させ湿潤成型体を得、その湿潤成型体を内部
を高湿度に保った恒温恒湿器内で徐々に乾燥させ乾燥成
型体とし、それを焼結する事により、３０μｍ以上の気
泡や脈理等の光学的不均質部分が存在しない石英ガラス
を歩留まり良く、安価に製造できることを発見し、本発
明に到達した。Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that a silica powder is used as a raw material and a suspension obtained by dispersing the powder in a dispersion medium has a specific gravity of 2.2 g / g. c
m 3 or more, and the silica powder is sedimented and deposited using centrifugal force to obtain a wet molded body, and the wet molded body is gradually dried in a thermo-hygrostat in which the inside is kept at a high humidity to dry mold. The present inventors have found that a quartz glass having no optically inhomogeneous portions such as bubbles or striae having a size of 30 μm or more can be produced at a good yield and at low cost by sintering it, and the present invention has been achieved.
【０００６】すなわち本発明は、シリカ粉末を湿式成型
し焼結して石英ガラスを得る方法において、湿式成型が
シリカ粉末を液体の分散媒に分散させた後、予め容器に
入れてある比重２．２ｇ／ｃｍ3以上の比重を持ち、分
散媒とは互いに溶解度をほとんど持たない液体（以下、
この液体を「重液」という）の上にスラリーを流し込
み、容器全体を毎分１０００回転以上で回転する遠心分
離器にかけ、シリカ粉末を遠心力で重液上に沈降、堆積
させ成型することを特徴とする石英ガラス製造方法であ
る。本発明を以下詳細に説明する。That is, the present invention relates to a method for obtaining silica glass by wet molding and sintering silica powder. In the wet molding, the silica powder is dispersed in a liquid dispersion medium and then placed in a container in advance.
A liquid having a specific gravity of 2.2 g / cm 3 or more and having almost no solubility with respect to the dispersion medium (hereinafter, referred to as “ dispersion medium”) .
The slurry is poured onto this liquid ("heavy liquid") , the whole container is centrifuged at 1000 rpm or more, and the silica powder is settled and deposited on the heavy liquid by centrifugal force to form. This is a method for producing quartz glass. The present invention will be described in detail below.
【０００７】原料となるシリカ粉末は、好ましくは比表
面積４０ｍ２／ｇ以下さらに好ましくは１０〜２０ｍ２
／ｇの粉末を使用する。シリカ粉末の製法には特に限定
はないが、例えばＳｉＣｌ４を火炎加水分解し、堆積さ
せたた多孔質体を粉砕したもの、または珪素のアルコキ
シドをアルコールで加水分解して得た粉末などを用いる
ことができる。この粉末を、分散媒に対して粉末の重量
百分率で好ましくは３０パーセント以下、さらに好まし
くは１０から２５パーセントになるように、超音波を照
射しながら分散媒に分散させ均質な懸濁液の調製を行
う。超音波を照射する時間は６０分間以上、好ましくは
１２０分間以上が良い。なお超音波照射中に懸濁液の温
度が上昇しないように、超音波伝搬媒体を一定割合でフ
ローするか冷却する等の工夫をするとよい。[0007] Silica powder as a raw material, preferably less more preferably a specific surface area of 40m 2 / g 10~20m 2
/ G of powder. The method for producing the silica powder is not particularly limited. For example, a powder obtained by flame-hydrolyzing SiCl 4 and pulverizing the deposited porous material or a powder obtained by hydrolyzing silicon alkoxide with alcohol is used. be able to. This powder is dispersed in the dispersion medium while irradiating ultrasonic waves such that the weight percentage of the powder to the dispersion medium is preferably 30% or less, more preferably 10 to 25%, to prepare a homogeneous suspension. I do. The time for irradiating the ultrasonic wave is preferably 60 minutes or more, and more preferably 120 minutes or more. In order to prevent the temperature of the suspension from rising during the ultrasonic irradiation, it is advisable that the ultrasonic wave propagation medium be flowed or cooled at a constant rate.
【０００８】上記のように調製された均質な懸濁液を、
孔径５〜２０μｍのナイロン製のフルイもしくはテフロ
ン製のフィルタ−等を通過させ異物や大きな粉末凝集体
等の除去を行なう。このようにして得た懸濁液をさらに
遠心分離機にかけ直径１μｍより大きい二次粒子を取り
除くとよい。直径１μｍ以下の粒子のみを含む懸濁液に
再び超音波を照射し均質化を図る。[0008] The homogeneous suspension prepared as described above,
Foreign matter and large powder aggregates are removed by passing through a nylon filter or Teflon filter having a pore size of 5 to 20 μm. The suspension thus obtained may be further centrifuged to remove secondary particles larger than 1 μm in diameter. The suspension containing only particles having a diameter of 1 μm or less is again irradiated with ultrasonic waves to achieve homogenization.
【０００９】このようにして得た懸濁液を比重がシリカ
粉末より大きい２．２ｇ／ｃｍ３以上で、互いに溶解度
をほとんど持たない液体を予め入れてある容器の中に靜
かに流し込む。この容器を遠心分離機にセットし、毎分
１０００回転以上、好ましくは毎分２０００回転以上で
９０分間以上、好ましくは１２０分間以上回転させる。
溶媒とシリカ粉末の遠心分離が終わった後、上澄み液を
捨て、比重が２．２ｇ／ｃｍ３以上の液体上に浮いてい
る粉末成型体を静かに取り出す。この時成型体を変形さ
せないことが大切である。以上の遠心力を利用した成型
法をここでは遠心成型法と呼ぶ。遠心成型法による粉末
成型体を温度３０〜６０℃、湿度８０〜９０％の恒温恒
湿器内へ移し、粉末成型体中に残った分散媒を蒸発させ
る。The suspension thus obtained is gently poured into a container in which liquids having a specific gravity of 2.2 g / cm 3 or more larger than that of silica powder and having little solubility with respect to each other are previously placed. This container is set in a centrifuge, and rotated at 1000 rpm or more, preferably 2000 rpm or more, for 90 minutes or more, preferably 120 minutes or more.
After the solvent and the silica powder are centrifuged, the supernatant liquid is discarded, and a powder molded body floating on a liquid having a specific gravity of 2.2 g / cm 3 or more is gently taken out. At this time, it is important not to deform the molded body. The molding method utilizing the above centrifugal force is herein referred to as a centrifugal molding method. The powder compact obtained by centrifugal molding is transferred into a thermo-hygrostat at a temperature of 30 to 60 ° C. and a humidity of 80 to 90%, and the dispersion medium remaining in the powder compact is evaporated.
【００１０】得られた乾燥成型体を加熱時にシリカと反
応しない物、たとえばクリストバライトの微粉末を敷い
た無水溶融石英ガラス板上に置き、それを石英ガラスを
炉心管とする管状炉内にセットして透明ガラス化処理を
例えば以下のように行う。まず初めに成型体中に残った
有機分の除去を目的とし室温より８００℃まで酸素雰囲
気中において加熱し、次に成型体表面および内部の水酸
基の除去を目的として、８００〜１２００℃まで１０％
塩素ガスを含むヘリウムガス雰囲気中において試料を処
理した後、温度１６００℃以下、好ましくは１４００〜
１５５０℃、８０％以上のヘリウムガスを含む雰囲気中
において、保持時間３０分以上の条件において透明化処
理を行なう。The obtained dried molded article is placed on a substance which does not react with silica at the time of heating, for example, an anhydrous fused silica glass sheet on which fine powder of cristobalite is spread, and it is set in a tubular furnace using quartz glass as a furnace tube. The transparent vitrification treatment is performed, for example, as follows. First, the molded body is heated from room temperature to 800 ° C. in an oxygen atmosphere for the purpose of removing organic components remaining in the molded body, and then 10% from 800 to 1200 ° C. for the purpose of removing hydroxyl groups on the surface and inside of the molded body.
After processing the sample in a helium gas atmosphere containing chlorine gas, the temperature is 1600 ° C. or less, preferably 1400 ° C.
The clearing process is performed at 1550 ° C. in an atmosphere containing 80% or more helium gas under the condition of a holding time of 30 minutes or more.
【００１１】以上のようにして反りがなく、かつ３０μ
ｍ以上の気泡が存在しない石英ガラスを得ることができ
る。As described above, there is no warpage and 30 μm.
It is possible to obtain quartz glass having no bubbles of m or more.
【００１２】本発明では、分散媒及びそれと互いに溶解
度をほとんど持たない比重２．２ｇ／ｃｍ３以上の液体
の組み合わせには特に限定はないが、例えば親水性の分
散媒と疎水性の液体、疎水性の分散媒と親水性の液体、
さらに具体的には蒸留水とヨードメタン、蒸留水とジヨ
ードメタン、親水性または疎水性の溶媒と水銀のなどの
組み合わせがあげられる。In the present invention, there is no particular limitation on the combination of a dispersion medium and a liquid having a specific gravity of 2.2 g / cm 3 or more which has little solubility with respect to each other. Dispersion medium and hydrophilic liquid,
More specifically, a combination of distilled water and iodomethane, distilled water and diiodomethane, a hydrophilic or hydrophobic solvent and mercury, and the like can be given.
【００１３】[0013]
【作用】本発明のように比表面積が好ましくは４０ｍ２
／ｇ以下のシリカ粉末を原料とし、液体を分散媒とする
この粉末の懸濁液を比重が２．２ｇ／ｃｍ３以上の、分
散媒とは互いにほとんど溶解度を持たない液体に浮か
べ、遠心力によってシリカ粉末を沈降、堆積させ湿潤成
型体を得る方法においては、湿潤成型体の構造に次に挙
げるような、焼結法で良質なガラスを作製するのに都合
の良い点が有る。The specific surface area is preferably 40 m 2 as in the present invention.
/ G of silica powder having a specific gravity of 2.2 g / cm 3 or more and having little or no solubility with respect to the dispersion medium, and centrifugal force In this method, the silica powder is settled and deposited to obtain a wet molded product, which has advantages in producing a high quality glass by a sintering method as described below in the structure of the wet molded product.
【００１４】泡の原因となるスラリー中に混入した固く
凝集した二次粒子は、粒径が他より大きいために遠心力
で底の表面部分に押し出されてしまう。また遠心成型に
利用されるスラリーはあらかじめ遠心分離により分級さ
れており、直径１μｍより大きな粒子はスラリー中から
除かれている。かつ遠心成型では、スラリー中の非常に
細かい粒子は上澄み液中に含まれ多くが取り除かれるの
で、結局湿潤ゲル体を形成している粒子は粒径の比較的
揃ったものとなる。The hardly agglomerated secondary particles mixed in the slurry causing the bubbles are extruded to the bottom surface portion by centrifugal force due to the larger particle size. The slurry used for centrifugal molding is classified in advance by centrifugation, and particles larger than 1 μm in diameter are removed from the slurry. In addition, in the centrifugal molding, very fine particles in the slurry are contained in the supernatant liquid and removed in a large amount, so that the particles forming the wet gel body have relatively uniform particle diameters.
【００１５】成型体の受ける歪の点から見ると、湿潤成
型体は液体上で作られるため、成型体は接している界面
からの摩擦抵抗をほとんど受けず、そのため湿潤成型体
中には気泡の原因となる歪が生じない。含水率について
も遠心分離機から取り出した時には、成型体の表と裏の
含水率はほぼ等しい。よって乾燥時に生じる歪も小さ
い。[0015] From the point of view of the strain on the molded body, since the wet molded body is made of a liquid, the molded body is hardly subjected to frictional resistance from the interface with which it is in contact. No causal distortion occurs. As for the moisture content, when the molded article is taken out of the centrifuge, the moisture content of the front and back of the molded article is almost equal. Therefore, distortion generated during drying is small.
【００１６】以上に挙げた利点が複合的に作用し、泡の
ない良質なガラスが作製できたものと推定される。It is presumed that the above-mentioned advantages act in combination, and that high-quality glass without bubbles can be produced.
【００１７】[0017]
【実施例】本発明を以下の実施例により詳細に説明す
る。しかし本発明はこれら実施例のみに限定されるもの
ではない。The present invention will be described in detail with reference to the following examples. However, the present invention is not limited to only these examples.
【００１８】実施例１ 四塩化珪素を高温中において火炎加水分解後、堆積させ
た多孔質体の表面層を軽く粉砕することにより、ＢＥＴ
比表面積が２５ｍ２／ｇ、平均粒径０．３μｍのシリカ
粉末を得た。この粉末を重量百分率が１７％になるよう
に蒸留水と混合し、超音波を照射しながら２時間分散さ
せ、懸濁液を調製した。Example 1 After flame hydrolysis of silicon tetrachloride at a high temperature, the surface layer of the deposited porous material was lightly pulverized to obtain a BET.
A silica powder having a specific surface area of 25 m 2 / g and an average particle diameter of 0.3 μm was obtained. This powder was mixed with distilled water so that the weight percentage was 17%, and dispersed for 2 hours while irradiating ultrasonic waves to prepare a suspension.
【００１９】この懸濁液を孔径１０μｍのナイロン製の
フルイを通過させた後、２５０〜２８０ｍｌ程度を直径
６０ｍｍの円筒形の容器に入れ遠心分離機にかけた。遠
心分離機を毎分２０００回転で２０分間作動させ容器中
の上澄み液を採集した。得られた上澄み液を良く撹はん
した後、さらに超音波を照射しながら１時間分散した。After passing this suspension through a nylon sieve having a pore diameter of 10 μm, about 250 to 280 ml was placed in a cylindrical vessel having a diameter of 60 mm and centrifuged. The centrifuge was operated at 2000 rpm for 20 minutes, and the supernatant in the container was collected. After the obtained supernatant liquid was stirred well, it was dispersed for 1 hour while further irradiating ultrasonic waves.
【００２０】得られた懸濁液をあらかじめ底にジヨード
メタン（ＣＨ２Ｉ２、比重３．３３ｇ／ｃｍ３、疎水性
の液体）を入れておいた円筒形の容器に静かに流し込ん
だ。それらの容器を遠心分離機にセットし毎分２０００
回転で２時間作動させた。遠心分離が終わった後、上澄
み液を取り除きジヨードメタン上に浮いている湿潤成型
体を静かに取り出した。取り出した成型体を内部を温度
３０℃湿度９０％に保った恒温恒湿器内にいれ徐々に四
日以上かけて乾燥させた。The obtained suspension was gently poured into a cylindrical container in which diiodomethane (CH 2 I 2 , specific gravity 3.33 g / cm 3 , hydrophobic liquid) was previously placed at the bottom. Place the containers in a centrifuge and 2,000 per minute
Run for 2 hours with rotation. After the centrifugation, the supernatant was removed and the wet molded body floating on diiodomethane was gently removed. The removed molded product was placed in a thermo-hygrostat maintained at a temperature of 30 ° C. and a humidity of 90%, and gradually dried over four days or more.
【００２１】得られた直径５１ｍｍ厚さ６ｍｍの乾燥成
型体を、クリストバライトの微粉末を敷いた無水溶融石
英ガラス板上に置き、それを石英ガラスを炉心管とする
管状炉内にセットして透明ガラス化処理を以下のように
行った。室温より８００℃まで酸素雰囲気中において毎
時２００℃の速度で加熱し、８００〜１０００℃まで１
０％塩素ガスを含むヘリウムガス雰囲気中において毎時
２００℃の速度で加熱後１０００℃で１時間保持した
後、１５５０℃までヘリウムガス雰囲気中において毎時
２００℃の速度で加熱し、１５５０℃で２時間保持をし
た後、炉内で冷却した。The obtained dry molded body having a diameter of 51 mm and a thickness of 6 mm is placed on an anhydrous fused silica glass plate on which fine powder of cristobalite is spread, and the transparent molded body is set in a tubular furnace using quartz glass as a furnace tube. The vitrification treatment was performed as follows. Heat from room temperature to 800 ° C in an oxygen atmosphere at a rate of 200 ° C per hour, and
After heating at a rate of 200 ° C./hour in a helium gas atmosphere containing 0% chlorine gas and holding at 1000 ° C. for 1 hour, heating to 1550 ° C. in a helium gas atmosphere at a rate of 200 ° C./hour and 1550 ° C. for 2 hours After holding, it was cooled in a furnace.
【００２２】実施例２ 四塩化珪素を高温中において火炎加水分解後、堆積させ
た多孔質体の表面層を軽く粉砕することにより、ＢＥＴ
比表面積が２５ｍ２／ｇ、平均粒径０．３μｍのシリカ
粉末を得た。この粉末を重量百分率が１７％になるよう
に蒸留水と混合し、超音波を照射しながら２時間分散さ
せ懸濁液を調製した。Example 2 BET was obtained by flame hydrolysis of silicon tetrachloride at a high temperature and then lightly pulverizing the surface layer of the deposited porous material.
A silica powder having a specific surface area of 25 m 2 / g and an average particle diameter of 0.3 μm was obtained. This powder was mixed with distilled water so that the weight percentage became 17%, and dispersed for 2 hours while irradiating ultrasonic waves to prepare a suspension.
【００２３】この懸濁液を孔径１０μｍのナイロン製の
フルイを通過させた後、２５０〜２８０ｍｌ程度を直径
６０ｍｍの円筒形の容器に入れ遠心分離機にかけた。遠
心分離機を毎分２０００回転で２０分間作動させ容器中
の上澄み液を採集した。この操作を繰り返すことにより
約１５００ｍｌの上澄み液を得た。得られた上澄み液を
良く撹拌した後、さらに超音波を照射しながら１時間分
散させた。The suspension was passed through a nylon sieve having a pore diameter of 10 μm, and about 250 to 280 ml was placed in a cylindrical vessel having a diameter of 60 mm and centrifuged. The centrifuge was operated at 2000 rpm for 20 minutes, and the supernatant in the container was collected. By repeating this operation, about 1500 ml of a supernatant was obtained. After the obtained supernatant liquid was stirred well, it was dispersed for 1 hour while further irradiating ultrasonic waves.
【００２４】得られた懸濁液２００ｍｌを、あらかじめ
底にジヨードメタン（ＣＨ２Ｉ２、比重３．３３ｇ／ｃ
ｍ３、疎水性の液体）を入れておいた円筒形の容器に静
かに流し込んだ。それらの容器を遠心分離機にセットし
毎分２０００回転で２時間作動させた。遠心分離が終わ
った後、上澄み液を取り除き、新たに懸濁液を注ぎ足し
た。再び容器を遠心分離機にセットし毎分２０００回転
で２時間作動させた。上澄み液を取り除き、懸濁液を遠
心分離機にかけるという操作を５回繰り返した。200 ml of the obtained suspension was previously added to the bottom with diiodomethane (CH 2 I 2 , specific gravity 3.33 g / c).
(m 3 , hydrophobic liquid) was gently poured into a cylindrical container. The containers were set in a centrifuge and operated at 2000 revolutions per minute for 2 hours. After the centrifugation was completed, the supernatant was removed and a new suspension was added. The container was set again in the centrifuge and operated at 2,000 rpm for 2 hours. The operation of removing the supernatant and centrifuging the suspension was repeated five times.
【００２５】遠心分離が終わった後、上澄み液を取り除
きジヨードメタン上に浮いている湿潤成型体を静かに取
り出した。取り出した成型体を内部を温度３０℃湿度９
０％に保った恒温恒湿器内に入れ徐々に四日以上かけて
乾燥させた。After the centrifugation was completed, the supernatant was removed and the wet molded body floating on diiodomethane was gently taken out. The inside of the molded product is taken out at a temperature of 30 ° C and a humidity of 9
The sample was placed in a thermo-hygrostat kept at 0% and gradually dried over 4 days.
【００２６】得られた直径５１ｍｍ厚さ３５ｍｍの乾燥
成型体を、クリストバライトの微粉末を敷いた無水溶融
石英ガラス板上に置き、それを石英ガラスを炉心管とす
る管状炉内にセットして透明ガラス化処理を以下のよう
に行った。室温より８００℃まで酸素雰囲気中において
毎時２００℃の速度で加熱し、８００〜１０００℃まで
１０％塩素ガスを含むヘリウムガス雰囲気中において毎
時２００℃の速度で加熱後１０００℃で１時間保持した
後、１５５０℃までヘリウムガス雰囲気中において毎時
２００℃の速度で加熱し、１５５０℃で２時間保持をし
た後、炉内で冷却した。The obtained dry molded product having a diameter of 51 mm and a thickness of 35 mm is placed on an anhydrous fused silica glass plate on which fine powder of cristobalite is spread, and is set in a tubular furnace using quartz glass as a furnace tube, and is transparent. The vitrification treatment was performed as follows. After heating from room temperature to 800 ° C. in an oxygen atmosphere at a rate of 200 ° C./hour, from 800 to 1000 ° C. in a helium gas atmosphere containing 10% chlorine gas at a rate of 200 ° C./hour, and then holding at 1000 ° C. for 1 hour , In a helium gas atmosphere at a rate of 200 ° C./hour, kept at 1550 ° C. for 2 hours, and then cooled in a furnace.
【００２７】実施例３ エチレンシリケート（Ｓｉ（Ｃ２Ｈ５Ｏ）４）１２４８
ｇとエタノール１７リットルと蒸留水１６５６ｇとアン
モニア水（２９重量％）１２００ｇを加え合わせ、温度
を５０℃に保ちながら２４時間撹はんし続けた。すると
平均粒径０．４μｍの単分散球状シリカ粒子が得られ
た。エバポレーターを用いて液体分を取り除いた後、こ
の単分散球状シリカ粒子５００ｇを石英ガラスボートに
乗せ酸素雰囲気中で９００℃で６時間仮焼した。得られ
た粉末に蒸留水を加え、粉末と蒸留水の重量比が２：５
である懸濁液を作製した。この懸濁液をメノウ製ボール
ミルに入れて４時間粉砕した。粉砕後の懸濁液を孔径１
０μｍのナイロン製のフルイに通した。この懸濁液に蒸
留水を加え、比重が１．０６３ｇ／ｃｍ３になるように
調製した。Example 3 1248 Ethylene silicate (Si (C 2 H 5 O) 4 )
g, 17 liters of ethanol, 1656 g of distilled water and 1200 g of aqueous ammonia (29% by weight) were added, and the mixture was continuously stirred for 24 hours while maintaining the temperature at 50 ° C. As a result, monodispersed spherical silica particles having an average particle diameter of 0.4 μm were obtained. After removing the liquid using an evaporator, 500 g of the monodispersed spherical silica particles were placed on a quartz glass boat and calcined at 900 ° C. for 6 hours in an oxygen atmosphere. Distilled water was added to the obtained powder, and the weight ratio of the powder to distilled water was 2: 5.
Was prepared. This suspension was placed in an agate ball mill and ground for 4 hours. Pulverize suspension after grinding
It was passed through a nylon sieve of 0 μm. Distilled water was added to this suspension to adjust the specific gravity to 1.063 g / cm 3 .
【００２８】得られた懸濁液２００ｍｌ程度を、あらか
じめ底にジヨードメタン（ＣＨ２Ｉ ２、比重３．３３ｇ
／ｃｍ３、疎水性の液体）を入れておいた直径５５mmの
円筒形の容器に静かに流し込んだ。それらの容器を遠心
分離機にセットし、毎分２０００回転で２時間作動させ
た。遠心分離が終わった後、上澄み液を取り除きジヨー
ドメタン上に浮いている湿潤成型体を静かに取り出し
た。取り出した成型体を内部を温度３０℃湿度９０％に
保った恒温恒湿器内にいれ徐々に四日以上かけて乾燥さ
せた。About 200 ml of the obtained suspension is roughly
Diiodomethane (CH2I 2, Specific gravity 3.33g
/ Cm3, Hydrophobic liquid) containing 55mm diameter
Gently poured into a cylindrical container. Centrifuge those containers
Set it on the separator and let it run at 2000 rpm for 2 hours
Was. After centrifugation, remove the supernatant and remove
Gently remove the wet molded body floating on the methane
Was. The inside of the molded product taken out is kept at a temperature of 30 ° C and a humidity of 90%.
Place in a kept constant temperature and humidity chamber and gradually dry it for 4 days or more.
I let you.
【００２９】得られた直径５１ｍｍ厚さ６ｍｍの乾燥成
型体を、クリストバライトの微粉末を敷いた無水溶融石
英ガラス板上に置き、それを石英ガラスを炉心管とする
管状炉内にセットして透明ガラス化処理を以下のように
行った。室温より８００℃まで酸素雰囲気中において毎
時２００℃の速度で加熱し、８００〜１０００℃まで１
０％塩素ガスを含むヘリウムガス雰囲気中において毎時
２００℃の速度で加熱後１０００℃で１時間保持した
後、１５５０℃までヘリウムガス雰囲気中において毎時
２００℃の速度で加熱し、１５５０℃で２時間保持をし
た後、炉内で冷却した。The obtained dry molded body having a diameter of 51 mm and a thickness of 6 mm is placed on an anhydrous fused silica plate on which fine powder of cristobalite is laid, and the transparent molded body is set in a tubular furnace using quartz glass as a furnace tube. The vitrification treatment was performed as follows. Heat from room temperature to 800 ° C in an oxygen atmosphere at a rate of 200 ° C per hour, and
After heating at a rate of 200 ° C./hour in a helium gas atmosphere containing 0% chlorine gas and holding at 1000 ° C. for 1 hour, heating to 1550 ° C. in a helium gas atmosphere at a rate of 200 ° C./hour and 1550 ° C. for 2 hours After holding, it was cooled in a furnace.
【００３０】実施例１〜３で得られた石英ガラスの表面
は滑らかであり、かつ厚さも均質であった。The surfaces of the quartz glasses obtained in Examples 1 to 3 were smooth and uniform in thickness.
【００３１】比較例 １ 四塩化珪素を高温中において火炎加水分解後、堆積させ
た多孔質体を石英ガラス製の乳鉢を使用し粉砕すること
により、比表面積が１８ｍ２／ｇ、平均粒径０．１５μ
ｍのシリカ粉末を得た。この粉末を蒸留水と重量比が蒸
留水：粉末＝３：２になるように混合し、超音波を照射
しながら１２０分間分散させ懸濁液を調製した。この懸
濁液を孔径１０μm のナイロン製のフルイを通過させた
後、懸濁液をＳｉＯ２ 量が２００ｇになるように分取
し孔径０．２μｍのテフロン製のフィルター及び内径１
４０ｍｍのテフロン製の型を使用し、減圧濾過を行っ
た。減圧濾過の過程でシリカの懸濁液は充分に溶媒があ
る時は液状であるが、溶媒が少なくなるとゲル化し湿潤
ゲルとなり、さらに溶媒が少なくなると無数の割れが生
じた。よって割れの生じた時点で実験を中止した。Comparative Example 1 After flame hydrolysis of silicon tetrachloride in a high temperature, the deposited porous material was ground using a mortar made of quartz glass to have a specific surface area of 18 m 2 / g and an average particle size of 0. .15μ
m of silica powder was obtained. This powder was mixed with distilled water in a weight ratio of distilled water: powder = 3: 2 and dispersed for 120 minutes while irradiating ultrasonic waves to prepare a suspension. The suspension was passed through a nylon sieve having a pore size of 10 μm, and the suspension was fractionated so that the amount of SiO 2 became 200 g. A Teflon filter having a pore size of 0.2 μm and an inner diameter of 1 μm were prepared.
Vacuum filtration was performed using a 40 mm Teflon mold. In the process of filtration under reduced pressure, the silica suspension was in a liquid state when there was a sufficient amount of solvent, but when the amount of the solvent was reduced, the silica gelled and became a wet gel. Therefore, the experiment was stopped when the crack occurred.
【００３２】比較例 ２ 四塩化珪素を高温中において火炎加水分解後、堆積させ
た多孔質体を石英ガラス製の乳鉢を使用し粉砕すること
により比表面積が１８ｍ２／ｇ、平均粒径０．１５μｍ
のシリカ粉末を得た。この粉末を蒸留水と重量比が蒸留
水：粉末＝３：２になるように混合し、超音波を照射し
ながら１２０分間分散させ懸濁液を調製した。この懸濁
液を孔径１０μm のナイロン製のフルイを通過させた
後、懸濁液をＳｉＯ２量が２００ｇになるように分取
し、孔径０．２μｍのテフロン製のフィルター及び内径
１４０ｍｍのテフロン製の型を使用し、減圧濾過を行っ
た。減圧濾過の過程で、シリカの懸濁液は充分に溶媒が
ある時は液状であるが、溶媒が少なくなるとゲル化し湿
潤ゲルとなった。懸濁液に水が少なくなりゲル化した時
点で吸引を中止し、フィルター上の成型体を取り出し
た。その成型体を、内部を６０℃湿度９０％に保った恒
温恒湿器内に移し１０日間乾燥させた。COMPARATIVE EXAMPLE 2 After flame hydrolysis of silicon tetrachloride in a high temperature, the deposited porous material was pulverized using a mortar made of quartz glass to have a specific surface area of 18 m 2 / g and an average particle diameter of 0.1 m 2 / g. 15 μm
Was obtained. This powder was mixed with distilled water in a weight ratio of distilled water: powder = 3: 2 and dispersed for 120 minutes while irradiating ultrasonic waves to prepare a suspension. The suspension was passed through a nylon sieve having a pore diameter of 10 μm, and the suspension was fractionated so that the amount of SiO 2 became 200 g. , And vacuum filtration was performed. In the process of filtration under reduced pressure, the silica suspension was liquid when there was sufficient solvent, but gelled and became a wet gel when the solvent was reduced. The suction was stopped when the water content of the suspension was reduced to gel, and the molded body on the filter was taken out. The molded body was transferred into a thermo-hygrostat maintained at 60 ° C. and 90% humidity, and dried for 10 days.
【００３３】得られた直径１３０ｍｍ厚さ４ｍｍの乾燥
ゲルを石英ガラス上に置き、石英ガラスを炉芯管とする
管状炉内にセットし、透明ガラス化処理を以下のように
行った。室温より８００℃まで酸素ガス雰囲気中におい
て毎時２００℃の速度で加熱し、８００〜１０００℃ま
で１０％塩素ガスを含むヘリウムガス雰囲気中において
毎時200 ℃の速度で加熱後１０００℃で２時間保持をし
た後、１５５０℃までヘリウムガス雰囲気中において毎
時１００℃の速度で加熱し、１５５０℃で１時間保持を
した後、炉内で冷却した。The obtained dried gel having a diameter of 130 mm and a thickness of 4 mm was placed on quartz glass, set in a tubular furnace using quartz glass as a furnace tube, and subjected to a transparent vitrification treatment as follows. Heat from room temperature to 800 ° C. in an oxygen gas atmosphere at a rate of 200 ° C./hour, and from 800 to 1000 ° C. in a helium gas atmosphere containing 10% chlorine gas at a rate of 200 ° C./hour and hold at 1000 ° C. for 2 hours. After that, it was heated at a rate of 100 ° C./hour in a helium gas atmosphere to 1550 ° C., kept at 1550 ° C. for 1 hour, and then cooled in a furnace.
【００３４】得られた石英ガラスの表面にはかなりの凹
凸が見られた。その成因は濾過に使用した濾紙に存在す
る凹凸であり、それがそのまま湿潤ゲル成型体に写し取
られ、焼結後の石英ガラス上にも残ったのである。また
乾燥成型体の厚さは濾過器が水平でない場合は不均質に
なり、しいては焼結してできた石英ガラスの厚さも不均
質となった。The surface of the obtained quartz glass had considerable irregularities. The origin is the unevenness present in the filter paper used for filtration, which was directly copied to the wet gel molding and remained on the sintered quartz glass. When the filter was not horizontal, the thickness of the dried molded article was non-uniform, and the thickness of the sintered quartz glass was also non-uniform.
【００３５】[0035]
【発明の効果】以上の説明からも明らかなように本発明
によれば、シリカ粉末を原料としこの粉末を遠心力を利
用した成型法により効率良く成型することができ、その
後成型体を焼結することにより、泡のない大型の石英ガ
ラスを容易に歩留り良くかつ安価に製造できる。As is apparent from the above description, according to the present invention, silica powder can be used as a raw material and this powder can be efficiently molded by a molding method utilizing centrifugal force. By doing so, large quartz glass without bubbles can be easily produced with good yield and at low cost.
Claims (1)
スを得る方法において、湿式成型がシリカ粉末を液体の
分散媒に分散させた後、予め容器に入れてある比重２．
２ｇ／ｃｍ3以上の比重を持ち、分散媒とは互いに溶解
度をほとんど持たない液体の上にスラリーを流し込み、
容器全体を毎分１０００回転以上で回転する遠心分離器
にかけ、シリカ粉末を遠心力で前記比重２．２ｇ／ｃｍ
3 以上の比重を持ち、分散媒とは互いに溶解度をほとん
ど持たない液体上に沈降、堆積させ成型することを特徴
とする石英ガラス製造方法。In a method for obtaining silica glass by wet molding and sintering silica powder, the specific gravity of silica powder dispersed in a liquid dispersion medium and placed in a container beforehand is obtained by wet molding.
A slurry having a specific gravity of 2 g / cm 3 or more and a dispersion medium and a slurry having little solubility with respect to each other,
The whole container is centrifuged at 1000 rpm or more, and the silica powder is centrifuged at a specific gravity of 2.2 g / cm.
It has a specific gravity of 3 or more and has almost the same solubility with the dispersion medium.
A method for producing quartz glass, which comprises setting, depositing, and forming on a liquid that does not have it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20370291A JP3203694B2 (en) | 1991-07-19 | 1991-07-19 | Manufacturing method of quartz glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20370291A JP3203694B2 (en) | 1991-07-19 | 1991-07-19 | Manufacturing method of quartz glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0524853A JPH0524853A (en) | 1993-02-02 |
| JP3203694B2 true JP3203694B2 (en) | 2001-08-27 |
Family
ID=16478438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20370291A Expired - Fee Related JP3203694B2 (en) | 1991-07-19 | 1991-07-19 | Manufacturing method of quartz glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3203694B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
| US6331056B1 (en) | 1999-02-25 | 2001-12-18 | Kimberly-Clark Worldwide, Inc. | Printing apparatus and applications therefor |
| US6342305B1 (en) | 1993-09-10 | 2002-01-29 | Kimberly-Clark Corporation | Colorants and colorant modifiers |
| US6368396B1 (en) | 1999-01-19 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| US6368395B1 (en) | 1999-05-24 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Subphthalocyanine colorants, ink compositions, and method of making the same |
| US6503559B1 (en) | 1998-06-03 | 2003-01-07 | Kimberly-Clark Worldwide, Inc. | Neonanoplasts and microemulsion technology for inks and ink jet printing |
| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| US10220602B2 (en) | 2011-03-29 | 2019-03-05 | Apple Inc. | Marking of fabric carrying case for a portable electronic device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4504036B2 (en) * | 2004-01-30 | 2010-07-14 | 東ソー株式会社 | Amorphous silica molded body and method for producing the same |
| DE102006014689A1 (en) | 2006-03-28 | 2007-10-11 | Heraeus Noblelight Gmbh | Infrared radiation unit |
-
1991
- 1991-07-19 JP JP20370291A patent/JP3203694B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6342305B1 (en) | 1993-09-10 | 2002-01-29 | Kimberly-Clark Corporation | Colorants and colorant modifiers |
| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| US6503559B1 (en) | 1998-06-03 | 2003-01-07 | Kimberly-Clark Worldwide, Inc. | Neonanoplasts and microemulsion technology for inks and ink jet printing |
| US6368396B1 (en) | 1999-01-19 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| US6331056B1 (en) | 1999-02-25 | 2001-12-18 | Kimberly-Clark Worldwide, Inc. | Printing apparatus and applications therefor |
| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
| US6368395B1 (en) | 1999-05-24 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Subphthalocyanine colorants, ink compositions, and method of making the same |
| US10220602B2 (en) | 2011-03-29 | 2019-03-05 | Apple Inc. | Marking of fabric carrying case for a portable electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0524853A (en) | 1993-02-02 |
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| LAPS | Cancellation because of no payment of annual fees |