JP3203694B2 - Method for producing a quartz glass - Google Patents

Method for producing a quartz glass

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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
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suspension
quartz glass
powder
molded body
silica
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JPH0524853A (en
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修輔 山田
孝次 津久間
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東ソー株式会社
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【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【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。 The present invention relates to an method for manufacturing a silica glass, a method for producing a quartz glass in particular no optical inhomogeneities 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. BACKGROUND OF THE INVENTION mask substrate, a quartz glass sheet to be used for display or the like is conventionally Lee. 溶融及び合成石英ガラスインゴットより切り出し・ Cut than the melting and synthetic quartz glass ingot,
研削・研磨を行い石英ガラス薄板とする方法 ロ. How to the quartz glass thin perform grinding and polishing Russia. 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。 Silicon alkoxides, fine silica powder, or mixtures thereof as a starting material, is prepared by a method such methods of gel drying and sintering to quartz glass sheet obtained thereby cause the hydrolysis and dehydration polymerization reaction. 現在は、イの方法が主流である。 Currently, the method of Lee 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。 [SUMMARY OF THE INVENTION However, these methods have the following problems. 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。 Generation The conventional filtration molding method of the presence warping methods bubbles B optical inhomogeneities are present yield is difficult to obtain a thin plate of large area which is bad expensive, such methods bubbles and striae Lee filtration it 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。 [0004] The present invention is to solve these problems, there is no optical inhomogeneities such as bubbles and striae, high yield warp-free quartz glass sheet, to provide a method for inexpensively manufacturing it is intended.

【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 [Summary of a result of intense research in view of the above problems, the present inventors have a silica powder as a raw material, the specific gravity of the suspension are dispersed in a dispersion medium in the powder is 2.2 g / c
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。 floated m 3 or more liquids, precipitated silica powder using a centrifugal force, is deposited to obtain a wet molded and gradually dried dried molded the wet molded body inside in a thermostat-hygrostat maintained at high humidity and the body, by sintering it, the quartz glass is optically inhomogeneities such as 30μm or more bubbles and striae absent good yield, it discovered that can be manufactured at low cost, have reached the present invention.

【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 That is, the present invention provides a silica powder in a method of obtaining by sintering by wet molding quartz glass, after the wet molding was dispersed silica powder in a dispersion medium liquid, in advance container
入れてある比重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(以下、 Put has a specific gravity of 2.2 g / cm 3 or more specific gravity are, the liquid has little together solubility and the dispersion medium (hereinafter,
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。 The liquid pouring slurry over) "heavy liquid", subjected to a centrifugal separator rotating at 1000 revolutions per minute or more whole containers, silica powder precipitated on the heavy liquid by centrifugal force, the molding is deposited a quartz glass manufacturing method comprising. 本発明を以下詳細に説明する。 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40m /g以下さらに好ましくは10〜20m [0007] Silica powder as a raw material, preferably less more preferably a specific surface area of 40m 2 / g 10~20m 2
/gの粉末を使用する。 / G to use the powder. シリカ粉末の製法には特に限定はないが、例えばSiCl 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。 Although there is no particular limitation on the production method of the silica powder, for example a SiCl 4 was flame hydrolysis, those that have been crushed was deposited porous body, or a silicon alkoxide used such as a powder obtained by hydrolysis with an alcohol be able to. 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。 This powder, preferably 30 percent by weight percentage of powder in a dispersion medium or less, more preferably to consist of 10 to 25%, the preparation of a homogeneous suspension is dispersed in a dispersion medium while irradiating ultrasonic waves I do. 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。 Time for irradiating the ultrasonic waves over 60 minutes, preferably at least 120 minutes. 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。 Incidentally, as the temperature of the suspension during ultrasonic irradiation is not increased, it is preferable to devise such cooling or flow ultrasonic propagation medium at a constant rate.

【0008】上記のように調製された均質な懸濁液を、 [0008] The homogeneous suspension prepared as described above,
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。 Pore ​​size 5~20μm filter made of sieve or Teflon nylon - such as passed through a to remove the foreign matter and large powder agglomerates and the like. 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。 The suspension thus obtained was good to further remove diameter 1μm larger secondary particles centrifuged. 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。 Ultrasonic irradiation again suspension containing only the following particle diameter 1μm 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/cm 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。 [0009] In this way the suspension density was obtained by silica powder greater than 2.2 g / cm 3 or more, it poured quietly in a container that is initially introduced to have few liquid solubility with each other. 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。 Set this vessel centrifuge, 1000 rpm or more, preferably more than 90 minutes at 2000 revolutions per minute or more, preferably rotates over 120 minutes.
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/cm 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。 After the end of the centrifugation of the solvent and silica powder, the supernatant was discarded, gently taken out powder molded body density is floating on 2.2 g / cm 3 or more on the liquid. この時成型体を変形させないことが大切である。 It is important that this time not deform the molded body. 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。 Here the molding method using the centrifugal force more than is called a centrifugal molding method. 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。 Temperature 30 to 60 ° C. The powder molded body by centrifugal molding method, transferred to a humidity 80-90% of constant temperature and humidity vessel, to evaporate the remaining dispersion medium in the powder molded body.

【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。 [0010] The resulting dried molded body which does not react with the silica when heated, for example, a fine powder of cristobalite placed in anhydrous fused silica glass plate lined, it sets the quartz glass in a tubular furnace to furnace tube performing transparent vitrification process, for example, as follows Te. 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% Heated first, at molded remaining removal of organic matter for the purpose in an oxygen atmosphere to 800 ° C. above room temperature in as then the purpose of removal of the molded body surface and internal hydroxyl groups, 10% to 800 to 1200 ° C.
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〜 After processing the samples in a helium gas atmosphere containing chlorine gas, the temperature 1600 ° C. or less, preferably 1400 to
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。 1550 ° C., in an atmosphere containing 80% or more of helium gas, performs transparency processing in the retention time of 30 minutes or more.

【0011】以上のようにして反りがなく、かつ30μ [0011] there is no warp in the manner described above, and 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。 It can be more bubbles m to obtain a silica glass that does not exist.

【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/cm 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、 In the present invention, the dispersion medium and is not particularly limited in most specific gravity 2.2 g / cm 3 or more combinations of liquid having no solubility with each other with it, for example, a hydrophilic dispersion medium and the hydrophobic liquid, a hydrophobic sexual dispersion medium and hydrophilic liquid,
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。 More specifically distilled water and iodomethane, distilled water and diiodomethane, the combination of such hydrophilic or hydrophobic solvent and mercury and the like.

【0013】 [0013]

【作用】本発明のように比表面積が好ましくは40m It is preferably a specific surface area as of the effects of the present invention 40 m 2
/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/cm 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。 / G to less silica powder as a raw material, the specific gravity of the suspension of this powder a liquid and dispersion medium 2.2 g / cm 3 or more, floated on the liquid have little solubility with each other and the dispersion medium, the centrifugal force precipitated silica powder by, in the method of obtaining a wet molded body is deposited, such as listed below on the structure of the wet molded body, a point convenient in making high-quality glass sintering method there.

【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。 [0014] The secondary particles tightly agglomerated mixed in the slurry causing bubbles, particle size will be pushed to the surface portion of the bottom in the centrifugal force larger than the other. 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。 The slurry utilized in centrifugal molding is classified in advance by centrifugation, particles larger than the diameter 1μm is removed from the slurry. 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。 And the centrifugal molding, very fine particles in the slurry so much contained in the supernatant is removed, the particles that eventually form a wet gel body becomes of uniform relatively particle size.

【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。 [0015] In terms of the strain experienced by the molded body, the wet molded article because it is made on the liquid, the molded body is almost not undergo a frictional resistance from the interface that contact, the bubbles in the wet molded in order that cause distortion does not occur to be. 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。 When taken out from the centrifuge also moisture content, water content of the front and back of the molded body are substantially equal. よって乾燥時に生じる歪も小さい。 Therefore, the distortion that occurs during drying is also 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。 The advantage mentioned above compositely act, good free glass bubbles is estimated that could 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。 The following examples of the present invention by describing in detail. 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。 However, the present invention is not limited to 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 [0018] After the flame hydrolysis at elevated temperatures in Example 1 silicon tetrachloride, by lightly grinding the surface layer of a porous material deposited, BET
比表面積が25m /g、平均粒径0.3μmのシリカ粉末を得た。 The specific surface area was obtained 25 m 2 / g, the silica powder having an average particle diameter of 0.3 [mu] m. 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。 This powder was mixed with distilled water so that the weight percentage is 17% for 2 hours and dispersed with ultrasonic irradiation 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。 [0019] multiplied by this suspension was passed through a nylon sieve having a pore size of 10 [mu] m, a centrifuge placed about 250~280ml in a cylindrical container having a diameter of 60 mm. 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。 Centrifuge was collected supernatant in the vessel was operated for 20 minutes at 2000 revolutions per minute to. 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。 The resulting the supernatant well agitation, and dispersed for 1 hour with further irradiation of 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(CH 、比重3.33g/cm 、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。 [0020] diiodomethane to the resulting suspension previously bottom (CH 2 I 2, a specific gravity of 3.33 g / cm 3, the liquid hydrophobic) but gently poured into a cylindrical vessel which had been put. それらの容器を遠心分離機にセットし毎分2000 Each set their container to the centrifuge amount 2000
回転で2時間作動させた。 It was operated rotated at 2 hours. 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。 After the end of the centrifugation, quietly removed wet molded body floating on diiodomethane the supernatant was removed. 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 removed molded interior dried gradually over four days or more placed in a temperature 30 ° C. and 90% humidity to keep the constant temperature and humidity vessel.

【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。 [0021] The dried molded body obtained diameter 51mm thickness 6 mm, placed on anhydrous molten quartz glass plate lined with fine powder of cristobalite, transparent it sets the quartz glass in a tubular furnace to furnace tube the vitrification process was carried out as follows. 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 It was heated at a rate per hour 200 ° C. in an oxygen atmosphere to 800 ° C. above room temperature, 1 to 800 to 1000 ° C.
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。 After 1 hour at heating after 1000 ° C. at a rate per hour 200 ° C. in a helium gas atmosphere containing 0% chlorine gas, heated at a rate per hour 200 ° C. in a helium gas atmosphere to 1550 ° C., 2 hours at 1550 ° C. after the holding, and cooling in the 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 [0022] After the flame hydrolysis at high temperature in Example 2 of silicon tetrachloride, by lightly grinding the surface layer of a porous material deposited, BET
比表面積が25m /g、平均粒径0.3μmのシリカ粉末を得た。 The specific surface area was obtained 25 m 2 / g, the silica powder having an average particle diameter of 0.3 [mu] m. 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。 This powder was mixed with distilled water so that the weight percentage is 17% to prepare a suspension by dispersing for 2 hours while being irradiated with ultrasonic waves.

【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。 [0023] multiplied by this suspension was passed through a nylon sieve having a pore size of 10 [mu] m, a centrifuge placed about 250~280ml in a cylindrical container having a diameter of 60 mm. 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。 Centrifuge was collected supernatant in the vessel was operated for 20 minutes at 2000 revolutions per minute to. この操作を繰り返すことにより約1500mlの上澄み液を得た。 By repeating this operation to obtain a supernatant to about 1500 ml. 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 resulting the supernatant thoroughly stirred and dispersed for 1 hour with further irradiation of 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(CH 、比重3.33g/c [0024] The resulting suspension 200 ml, to advance the bottom diiodomethane (CH 2 I 2, specific gravity 3.33 g / c
、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。 m 3, but gently poured into a cylindrical vessel which had been put liquid) hydrophobic. 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。 Their vessel was operated 2 hours at per minute 2000 revolutions set in a centrifuge. 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。 After the end of the centrifugation, the supernatant was removed, it was topped a new suspension. 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。 It was operated for 2 hours at vessel set to per minute 2000 rpm in centrifuge again. 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。 The supernatant was removed, was repeated 5 times an operation of applying a suspension centrifuged.

【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。 [0025] centrifugation moth finished another post, the supernatant liquid wo remove diiodomethane on two floating hands are wet molded body wo quiet similar to taking out the other. 取り出した成型体を内部を温度30℃湿度9 The internal was removed molded product temperature 30 ° C. Humidity 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。 Gradually put in a constant temperature and humidity chamber maintained at 0% and dried over a period of four 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。 [0026] The dried molded body obtained diameter 51mm thickness 35 mm, placed on anhydrous molten quartz glass plate lined with fine powder of cristobalite, transparent it sets the quartz glass in a tubular furnace to furnace tube the vitrification process was carried out as follows. 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。 It was heated at a rate per hour 200 ° C. in an oxygen atmosphere to 800 ° C. from room temperature to 1 hour at 1000 ° C. After heating at a rate per hour 200 ° C. in a helium gas atmosphere containing 10% chlorine gas to 800 to 1000 ° C. , and heated at a rate per hour 200 ° C. in a helium gas atmosphere to 1550 ° C., after a 2 hour hold at 1550 ° C., and then cooled in the furnace.

【0027】実施例3 エチレンシリケート(Si(C O) )1248 [0027] Example 3 Ethylene silicate (Si (C 2 H 5 O ) 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。 g and ethanol 17 l of distilled water 1656g aqueous ammonia added together (29 wt%) 1200 g, was continued against 24 hours 撹 while maintaining the temperature at 50 ° C.. 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。 Then monodisperse spherical silica particles having an average particle diameter of 0.4μm was obtained. 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。 After removing the liquid fraction using an evaporator, and 6 hours and calcined at 900 ° C. The monodisperse spherical silica particles 500g in an oxygen atmosphere placed on a quartz glass boat. 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 The resulting powder of distilled water was added, the weight ratio of the powder and distilled water is 2: 5
である懸濁液を作製した。 The suspension was produced is. 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。 It was milled for 4 hours to put the suspension into an agate ball mill. 粉砕後の懸濁液を孔径1 Pore ​​size the suspension after grinding 1
0μmのナイロン製のフルイに通した。 It was passed through a nylon sieve of 0μm. この懸濁液に蒸留水を加え、比重が1.063g/cm になるように調製した。 Distilled water was added to this suspension, specific gravity was adjusted 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(CH [0028] obtained another suspension 200ml degree wo, pre-bottom two diiodomethane (CH 2 I 、比重3.33g 2, a specific gravity of 3.33g
/cm 、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。 / Cm 3, but gently poured into a cylindrical container of diameter 55mm which had been put liquid) hydrophobic. 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。 Their container was set in a centrifuge was operated for two hours at 2000 revolutions per minute. 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。 After the end of the centrifugation, quietly removed wet molded body floating on diiodomethane the supernatant was removed. 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。 Take out the other molded body wo wo internal temperature of 30 ℃ and 90% humidity similar to keeping the other constant temperature and humidity vessel within two put gradually the 4th ERROR bettor dried other.

【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。 [0029] The dried molded body obtained diameter 51mm thickness 6 mm, placed on anhydrous molten quartz glass plate lined with fine powder of cristobalite, transparent it sets the quartz glass in a tubular furnace to furnace tube the vitrification process was carried out as follows. 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 It was heated at a rate per hour 200 ° C. in an oxygen atmosphere to 800 ° C. above room temperature, 1 to 800 to 1000 ° C.
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。 After 1 hour at heating after 1000 ° C. at a rate per hour 200 ° C. in a helium gas atmosphere containing 0% chlorine gas, heated at a rate per hour 200 ° C. in a helium gas atmosphere to 1550 ° C., 2 hours at 1550 ° C. after the holding, and cooling in the 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 surface of the quartz glass obtained in Examples 1 to 3 are smooth and was also homogeneous 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18m /g、平均粒径0.15μ [0031] After the flame hydrolysis during the high temperature Comparative Example 1 silicon tetrachloride, by the deposited was porous body for using a mortar made of quartz glass milling, the specific surface area of 18m 2 / g, average particle diameter 0 .15μ
mのシリカ粉末を得た。 To obtain a silica powder of m. 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。 The powder of distilled water and the weight ratio of distilled water: powder = 3 were mixed at 2 to prepare a suspension by dispersing 120 minutes while applying ultrasonic waves. 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 After the suspension is passed through a nylon sieve having a pore size of 10μm and Teflon filter and the inner diameter of preparative and pore size 0.2μm to suspension SiO2 amount is 200 g 1
40mmのテフロン製の型を使用し、減圧濾過を行った。 Using Teflon mold of 40 mm, it was subjected to vacuum filtration. 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。 Although suspension of silica in the course of the vacuum filtration is a liquid when sufficiently certain solvent, the solvent becomes less becomes the gelled wet gel, innumerable cracks were caused further decreases solvent. よって割れの生じた時点で実験を中止した。 Therefore, the experiment was discontinued at the time caused the cracks.

【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18m /g、平均粒径0.15μm [0032] After the flame hydrolysis at high temperature in Comparative Example 2 of silicon tetrachloride, a porous body was deposited using a mortar made of quartz glass grinding specific surface area of 18m 2 / g by the average particle diameter of 0. 15μm
のシリカ粉末を得た。 To obtain a silica powder. 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。 The powder of distilled water and the weight ratio of distilled water: powder = 3 were mixed at 2 to prepare a suspension by dispersing 120 minutes while applying ultrasonic waves. 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SiO 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。 After the suspension is passed through a nylon sieve having a pore size of 10μm, and the suspension is separated so as SiO 2 amount is 200 g, a pore size of 0.2μm Teflon filter and the inner diameter 140mm made of Teflon using the mold, it was filtered under reduced pressure. 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。 In the course of vacuum filtration, but when a suspension of silica which sufficiently has the solvent is liquid, the solvent becomes less becomes the gelled wet gel. 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。 Suspension to stop suction when the water is less and less gelation was taken out molded on the filter. 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。 As a molded body was dried for 10 days were transferred into the interior through the thermo-hygrostat kept at 60 ° C. and 90% humidity.

【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。 [0033] Place the resulting diameter 130mm thickness 4mm dry gel of the on quartz glass, quartz glass was set in a tubular furnace to the furnace core tube was subjected to vitrification treatment as follows. 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。 It was heated at a rate per hour 200 ° C. in an oxygen gas atmosphere to 800 ° C. above room temperature, the 2 hour hold at after heating 1000 ° C. at a rate per hour 200 ° C. in a helium gas atmosphere containing 10% chlorine gas to 800 to 1000 ° C. after heated at a rate per hour 100 ° C. in a helium gas atmosphere to 1550 ° C., after a 1 hour hold at 1550 ° C., and then cooled in the 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。 [0034] substantial irregularities on the surface of the resulting quartz glass was observed. 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。 Its origin is the irregularities present in the filter paper used for filtration, it is Utsushitora intact wet gel molded body is the left also on a quartz glass after sintering. 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。 In the case the thickness of the dried molded body filter is not level becomes heterogeneous, by force became also the thickness of the quartz glass Deki by sintering heterogeneous.

【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。 According to apparent the present invention from the description above, according to the present invention, the silica powder as the raw material powder can be molded efficiently by a molding method using a centrifugal force, then molded sintered by, a large quartz glass without bubbles can be easily good yield and low cost.

Claims (1)

    (57)【特許請求の範囲】 (57) [the claims]
  1. 【請求項1】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. 1. A silica powder was sintered wet molding in the method of obtaining a silica glass after the wet molding was dispersed silica powder in a dispersion medium liquid, it is placed in a previously vessel density 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の上にスラリーを流し込み、 It has a 2 g / cm 3 or more gravity, pouring the slurry onto have few liquid solubility with each other and a dispersion medium,
    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 Subjected to centrifuge rotating at 1000 revolutions per minute or more whole containers, the specific gravity of 2.2 g / cm a silica powder by a centrifugal force
    3 以上の比重を持ち、分散媒とは互いに溶解度をほとん 3 has the above specific gravity works w each other solubility and dispersion medium
    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。 Settle on liquid that throat having a quartz glass manufacturing method characterized by molding deposited.
JP20370291A 1991-07-19 1991-07-19 Method for producing a quartz glass Expired - Fee Related JP3203694B2 (en)

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