JP6231326B2 - Method for producing silica solidified body and silica solidified body - Google Patents
Method for producing silica solidified body and silica solidified body Download PDFInfo
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本発明は、高温で焼成することなく、十分な強度及び透明性を有するシリカ固化体を製造する方法に関する。 The present invention relates to a method for producing a solidified silica having sufficient strength and transparency without firing at a high temperature.
シリカ固化体の製造方法としては、シリカ粉末を型に充填し圧縮成形する方法や、シリカ粉末を分散媒に分散させたスラリーとしたのち、これを型に流し込み分散媒を蒸発させる方法により固形化する方法などが知られている。しかしながら、これらの方法では高い強度の成形体を得ることは難しいという問題が有った。 The silica solidified body is solidified by a method in which silica powder is filled into a mold and compression molded, or a slurry in which silica powder is dispersed in a dispersion medium and then poured into a mold and the dispersion medium is evaporated. The method of doing is known. However, these methods have a problem that it is difficult to obtain a molded article having high strength.
特許文献１には、ｐＨを調整したシリカ分散液を鋳型の中でゲル化させた後、ハロゲン含有ガス中で焼成を行い、さらに１２００〜１８００℃の温度範囲で焼結する透明石英ガラス体の製造方法が開示されている。しかしながら、かかる方法ではハロゲン含有ガスなどの特殊な雰囲気が必要であり、さらに高温での焼成を必要とするため、エネルギー消費の観点からは好ましくないという問題があった。 Patent Document 1 discloses a transparent quartz glass body in which a silica dispersion adjusted in pH is gelled in a mold, fired in a halogen-containing gas, and further sintered in a temperature range of 1200 to 1800 ° C. A manufacturing method is disclosed. However, this method requires a special atmosphere such as a halogen-containing gas, and further requires baking at a high temperature, which is not preferable from the viewpoint of energy consumption.
また、特許文献２には、表面がケイ酸等からなるセラミックスを摩砕した後、アルカリ金属水酸化物等を含むアルカリ水溶液で処理する方法が開示されている。しかしながら、かかる方法ではシリカ固化体の強度が十分ではなく、更には不透明であるなどの問題があった。 Patent Document 2 discloses a method in which a ceramic whose surface is made of silicic acid or the like is ground and then treated with an alkaline aqueous solution containing an alkali metal hydroxide or the like. However, such a method has a problem that the strength of the silica solidified body is not sufficient and is further opaque.
本発明は、上述した問題点を解決し、高温で焼成することなく、十分な強度及び透明性を有するシリカ固化体を製造する方法を提供するものである。 The present invention solves the above-mentioned problems and provides a method for producing a solidified silica having sufficient strength and transparency without firing at a high temperature.
本発明者らは、上述した問題点を解決すべく、鋭意検討を重ねた結果、メカノケミカル的に表面が活性化されており、表面ＯＨ基の量が所定値以上であるシリカ粉末に金属水酸化物を含む塩基性溶液（以下、単に「塩基性溶液」ということがある）を混合することにより、高温で焼成することなく、十分な強度及び透明性を有するシリカ固化体を得られることに想到した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have mechanochemically activated the surface, and the surface of the surface OH group is not less than a predetermined value. By mixing a basic solution containing an oxide (hereinafter sometimes simply referred to as “basic solution”), a solidified silica having sufficient strength and transparency can be obtained without firing at a high temperature. I came up with it.
すなわち、本発明は、シリカ粉末を乾式で摩砕することによって、表面がメカノケミカル的に活性化された、拡散反射赤外吸収スペクトルにおいて、Ｓｉ−ＯＨ吸収帯とＳｉ−Ｈ吸収帯の積分強度比（ＯＨ／ＳｉＨ）が５０以上である活性化シリカ粉末とする摩砕工程と、金属水酸化物を含む塩基性溶液により該活性化シリカ粉末の表面を溶解及び再析出させてシリカ固化体を得る塩基処理工程とを含んでなることを特徴とするシリカ固化体の製造方法である。 That is, the present invention relates to the integrated intensity of the Si—OH absorption band and the Si—H absorption band in the diffuse reflection infrared absorption spectrum in which the surface is mechanochemically activated by grinding the silica powder dry. A grinding step to obtain an activated silica powder having a ratio (OH / SiH) of 50 or more, and a surface of the activated silica powder is dissolved and re-precipitated with a basic solution containing a metal hydroxide to obtain a silica solidified body. It is a manufacturing method of the silica solidified body characterized by including the base treatment process obtained.
本発明は、塩基処理工程前に活性化シリカ粉末表面の水酸基量を増やしておくことが好ましい。 In the present invention, it is preferable to increase the amount of hydroxyl groups on the activated silica powder surface before the base treatment step.
また、本発明は、原料であるシリカ粉末が非晶質シリカを主たる成分とすることが好ましい。 In the present invention, it is preferable that the silica powder as a raw material is mainly composed of amorphous silica.
上述したシリカ固化体の製造方法で得られるシリカ固化体は、試料厚み３．５ｍｍ、波長４００ｎｍ〜７８０ｎｍにおける直線透過率が、４０％以上であるため、光学部品として利用することができる。 The silica solidified body obtained by the method for producing a silica solidified body described above can be used as an optical component because the linear transmittance at a sample thickness of 3.5 mm and a wavelength of 400 nm to 780 nm is 40% or more.
本発明のシリカ固化体の製造方法は高温を必要とせず、シリカ粉末の固化に要するエネルギー消費量を抑えることができ、高温焼成や溶融ガラス化を行わないため、電気炉や溶融炉を必要とせず経済的である。また、透明性を有するシリカ固化体が得られるため、光学部品として利用することができる。さらに、任意形状の鋳型を用いることで最終製品の形状に近いシリカ固化体が得られるため、部材コストや加工コストを抑え安価にシリカ固化体を得ることができる。 The method for producing a silica solidified body of the present invention does not require high temperature, can reduce the energy consumption required for solidification of silica powder, and does not perform high-temperature firing or molten vitrification. It is economical. Moreover, since the silica solidified body which has transparency is obtained, it can utilize as an optical component. Furthermore, since a silica solidified body close to the shape of the final product can be obtained by using a mold having an arbitrary shape, the silica solidified body can be obtained at a low cost while suppressing member costs and processing costs.
＜原料粉＞
本発明の原料粉であるシリカ粉末の平均粒径は特に問わないが、摩砕工程でのシリカ粉末表面の活性化の効率の観点から、０．１〜５００μｍであることが好ましく、０．１〜２μｍの粒径のものがより好ましい。
<Raw material powder>
The average particle size of the silica powder that is the raw material powder of the present invention is not particularly limited, but is preferably 0.1 to 500 μm from the viewpoint of the activation efficiency of the silica powder surface in the grinding step. A particle diameter of ˜2 μm is more preferable.
これらの要件を満たすシリカ粉末としては、例えば、天然シリカ粉、球状シリカ粉、気相法合成球状シリカ粉、ヒュームドシリカ粉、スート堆積物の解砕粉、破砕シリカ粉、合成シリカ粉などが挙げられるが、これらに限定されるものではない。シリカ表面の水酸基量が多く、高強度の固化体が得られやすいことから、球状シリカ粉、合成シリカ粉が好ましい。 Examples of the silica powder that satisfies these requirements include natural silica powder, spherical silica powder, vapor-phase synthetic spherical silica powder, fumed silica powder, soot deposit pulverized powder, crushed silica powder, and synthetic silica powder. Although it is mentioned, it is not limited to these. Spherical silica powder and synthetic silica powder are preferred because the amount of hydroxyl groups on the silica surface is large and a high-strength solidified body is easily obtained.
なお、原料であるシリカ粉末には、結晶質および非晶質のシリカ粉末を用いることができるが、非晶質のものがより好ましい。非晶質のシリカ粉末は、一般的に結晶質のシリカ粉末に比べ水酸基の含有量が比較的多く、本発明の効果が得られやすく、シリカ表面の原子配列が乱れているため、摩砕工程での活性化が効率的に行われるためである。 In addition, although the crystalline and amorphous silica powder can be used for the silica powder which is a raw material, an amorphous thing is more preferable. Amorphous silica powder generally has a relatively high hydroxyl group content compared to crystalline silica powder, and the effects of the present invention are easily obtained, and the atomic arrangement on the surface of the silica is disturbed. This is because the activation at is performed efficiently.
＜摩砕工程＞
摩砕工程では、シリカ粉末を乾式で摩砕することによって、表面がメカノケミカル的に活性化された活性化シリカ粉末とする。活性化シリカ粉末は、拡散反射赤外吸収スペクトルにおいて、Ｓｉ−ＯＨ吸収帯とＳｉ−Ｈ吸収帯の積分強度比（ＯＨ／ＳｉＨ）が５０以上であることが必要である。シリカ粉末を摩砕する方法は特に限定しないが、衝撃、摩擦、圧縮、剪断等の各種の力を複合的に作用させることが効果的である。このような作用を行うことができる装置としては、ボールミル、振動ミル、遊星ミル、媒体撹拌型ミル等の混合装置ボール媒体ミル、ローラーミル、乳鉢、らい潰機、ジェットミル、ビーズミル、アトライター等の粉砕機などが挙げられるが、これらに限定されるものではない。上述装置の中では、強い剪断力を付与できる、遊星ミルが特に好ましい。なお、摩砕工程においては、粒度分布の経時変化がなくなるまで、摩砕することが好ましい。
<Milling process>
In the grinding step, the silica powder is dry-ground to obtain activated silica powder whose surface is mechanochemically activated. The activated silica powder is required to have an integrated intensity ratio (OH / SiH) of Si—OH absorption band and Si—H absorption band of 50 or more in the diffuse reflection infrared absorption spectrum. The method for grinding the silica powder is not particularly limited, but it is effective to apply various forces such as impact, friction, compression, and shearing in combination. Devices that can perform such actions include ball mills, vibration mills, planetary mills, medium agitation mills and other mixing devices, ball media mills, roller mills, mortars, crushers, jet mills, bead mills, attritors, etc. However, it is not limited to these. Among the above-mentioned apparatuses, a planetary mill that can apply a strong shearing force is particularly preferable. In the grinding step, it is preferable to grind until there is no change with time in the particle size distribution.
また、摩砕装置の容器や摩砕メディアの材質としては、ジルコニア、アルミナ、シリカ、ＳｉＣなどが使用できるが、摩砕効率を優先させたい場合はアルミナ製やジルコニア製の容器やメディアが利用可能である。いっぽう、ジルコニアの汚染を嫌う場合は、シリカ製やＳｉＣ製の容器やメディアなどが好適に利用できる。 In addition, zirconia, alumina, silica, SiC, etc. can be used as the material for the grinding device container and grinding media. However, if priority is given to grinding efficiency, alumina or zirconia containers or media can be used. It is. On the other hand, when the zirconia contamination is disliked, silica or SiC containers or media can be suitably used.
＜前処理工程＞
活性化シリカ粉末表面の水酸基を増加させるため、摩砕工程後に水酸基量を増加させる前処理工程を追加しても良い。前処理の方法は特に限定しないが、水熱処理、紫外線照射処理、プラズマ処理などが利用できる。水熱処理は、高圧をかけられるオートクレーブ内に水と活性化シリカ粉末を投入し、所定の温度・時間に保持することで、シリカ表面のシロキサン開裂が起こり、水酸基が導入される。水熱処理の条件は水酸基が十分導入される物であれば特に限定はされないが、一般的には１２０℃以上の温度で５時間以上、より好ましくは１３０℃以上で２４時間以上保持することが望ましい。この際、シリカ粉末の汚染を防ぐため、使用する水は蒸留水やイオン交換水などの金属不純物を含まないものが好ましい。水熱処理後のシリカ粉末は真空加熱等により、乾燥させておく。
<Pretreatment process>
In order to increase the hydroxyl groups on the activated silica powder surface, a pretreatment step for increasing the amount of hydroxyl groups after the grinding step may be added. The pretreatment method is not particularly limited, and hydrothermal treatment, ultraviolet irradiation treatment, plasma treatment, and the like can be used. In the hydrothermal treatment, water and activated silica powder are put into an autoclave to which high pressure is applied and maintained at a predetermined temperature and time, whereby siloxane cleavage occurs on the silica surface and hydroxyl groups are introduced. The conditions of the hydrothermal treatment are not particularly limited as long as the hydroxyl group is sufficiently introduced, but generally it is desirable to hold at 120 ° C. or higher for 5 hours or longer, more preferably 130 ° C. or higher for 24 hours or longer. . At this time, in order to prevent contamination of the silica powder, the water used preferably does not contain metal impurities such as distilled water and ion exchange water. The silica powder after the hydrothermal treatment is dried by vacuum heating or the like.
＜塩基処理工程＞
塩基処理工程では、活性化シリカ粉末を、金属水酸化物を含む塩基性溶液で処理することによって、該活性化シリカ粉末の表面を溶解及び再析出させてシリカ固化体を得る。塩基性溶液としては特に制限はないが、ＫＯＨ、ＮａＯＨ等の無機強塩基の水溶液が好ましい。塩基性溶液による溶解反応は塩基性溶液のｐＨが高いほど効率よく進行するため、ｐＨ＝１２以上が好ましく、１４以上であることがより好ましい。
<Base treatment process>
In the base treatment step, the activated silica powder is treated with a basic solution containing a metal hydroxide to dissolve and re-precipitate the surface of the activated silica powder to obtain a solidified silica. Although there is no restriction | limiting in particular as a basic solution, The aqueous solution of inorganic strong bases, such as KOH and NaOH, is preferable. Since the dissolution reaction with the basic solution proceeds more efficiently as the pH of the basic solution increases, the pH is preferably 12 or more, and more preferably 14 or more.
活性化シリカ粉体と塩基性溶液との混合・混練を行うための装置としては、特に限定されるものではなく、従来公知の任意の混合機、混練機が使用できる。例えば、双腕ニーダー、加圧ニーダー、アイリッヒミキサー、スーパーミキサー、プラネタリーミキサー、バンバリーミキサー、コンティニュアスミキサー、あるいは連続混練機等が挙げられる。このとき、フィラーとして、石英粉、非晶質シリカ粉、ヒュームドシリカなどを適量加えることもできる。 The apparatus for mixing and kneading the activated silica powder and the basic solution is not particularly limited, and any conventionally known mixer or kneader can be used. Examples thereof include a double-arm kneader, a pressure kneader, an Eirich mixer, a super mixer, a planetary mixer, a Banbury mixer, a continuous mixer, and a continuous kneader. At this time, an appropriate amount of quartz powder, amorphous silica powder, fumed silica, or the like can be added as a filler.
さらに、気泡を抜くために真空土練機を用いることも好ましい。この様にすることで、シリカ固化体の中に気泡が残ることを防止することができる。 Furthermore, it is also preferable to use a vacuum kneader to remove bubbles. By doing in this way, it can prevent that a bubble remains in a silica solidified body.
上述処理により活性化シリカ粉体の表面層は溶解し、さらには脱水縮合されて、析出層が生成する。上記混合物は当初はペースト状のシリカスラリーであるが、脱水縮合反応の進行に伴い、析出層が接着剤の役割を果たしてシリカ固化体が得られる。つまり、この固化反応が完了するまでの間に、上述シリカスラリーを鋳型に充填することにより、所望形状のシリカ固化体を得ることも可能である。たとえば、リング状の鋳型にスラリーを充填し固化させることで、リング形状の高純度シリカ固化体を得ることが可能である。 By the above-described treatment, the surface layer of the activated silica powder is dissolved and further dehydrated and condensed to form a deposited layer. The mixture is initially a paste-like silica slurry, but with the progress of the dehydration condensation reaction, the precipitated layer serves as an adhesive to obtain a solidified silica. That is, it is also possible to obtain a silica solidified body having a desired shape by filling the above-described silica slurry into a mold until the solidification reaction is completed. For example, a ring-shaped high-purity silica solidified body can be obtained by filling a slurry in a ring-shaped mold and solidifying the slurry.
この塩基処理工程では、表面層の溶解反応や、脱水縮合反応は室温で行っても良いし、加熱して迅速化を図ることもできる。反応温度は原料となるシリカの種類や塩基性溶液の種類や濃度によって適宜選択すればよいが、一般的には室温〜２００°Ｃが好ましく、さらに好ましくは室温〜６０°Ｃの範囲が好適である。また、乾燥割れを防ぐため、密閉状態もしくは調湿乾燥を行う、または密閉状態での固化と調湿乾燥を連続して行うこともできる。 In this base treatment step, the dissolution reaction of the surface layer and the dehydration condensation reaction may be performed at room temperature or can be accelerated by heating. The reaction temperature may be appropriately selected depending on the type of silica used as the raw material and the type and concentration of the basic solution, but generally room temperature to 200 ° C is preferable, and room temperature to 60 ° C is more preferable. is there. Further, in order to prevent dry cracking, it is possible to carry out a sealed state or humidity-controlled drying, or to perform solidification and humidity-controlled drying in a sealed state continuously.
以下、実施例により本発明を更に具体的に説明するが、本発明はここに記載の方法に限定されるものではない。なお、ＯＨ／ＳｉＨの積分強度比は、フーリエ変換型赤外分光光度計（ＦＴ／ＩＲ−６２００：日本分光製）を用いて、窒素雰囲気下で拡散反射法による測定を行った。分解能４．０ｃｍ−１、積算回数２５６回、バックグラウンド測定にはＫＢｒを用いた。得られた拡散反射スペクトルから、ＯＨ基を示す３８００−２８７５ｃｍ−１、ＳｉＨ基を示す２２９０−２１５０ｃｍ−１の間にベースラインを引き、各々積分強度を算出した。
（実施例１）
シリカ粉末として、非晶質球状シリカ（ＳＦＰ２０ＭＸ、一次粒径０．６μｍ、電気化学工業製）を用い、遊星ボールミル（同上）を用いて、２００ｒｐｍで１５分間摩砕処理を行った。この際、容量５００ｍｌの摩砕容器に対して、シリカ粉末を５０ｇ、摩砕メディアとしてφ５ｍｍのジルコニアボール２００ｇを投入した。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the methods described herein. The integrated intensity ratio of OH / SiH was measured by a diffuse reflection method in a nitrogen atmosphere using a Fourier transform infrared spectrophotometer (FT / IR-6200: manufactured by JASCO). The resolution was 4.0 cm −1 , the number of integrations was 256 times, and KBr was used for background measurement. From the resulting diffuse reflection spectrum, 3800-2875Cm -1 indicating the OH group, pull the baseline between 2290-2150Cm -1 indicating the SiH group, it was calculated each integrated intensity.
Example 1
As the silica powder, amorphous spherical silica (SFP20MX, primary particle size 0.6 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.) was used, and grinding was performed at 200 rpm for 15 minutes using a planetary ball mill (same as above). At this time, 50 g of silica powder and 200 g of zirconia balls having a diameter of 5 mm were added as grinding media to a grinding vessel having a capacity of 500 ml.
次に水熱処理として。テフロン製内筒に活性化シリカ粉末と蒸留水を１：１の重量比で投入し、ステンレス製外容器に封入し、１３０℃で５時間保持した。その後、遠心分離を用いて固液分離し、１００℃で真空乾燥させた。水熱処理後の粉末のＯＨ／ＳｉＨの積分強度比は、５１であった。 Next as hydrothermal treatment. Activated silica powder and distilled water were introduced into a Teflon inner cylinder at a weight ratio of 1: 1, sealed in a stainless steel outer container, and held at 130 ° C. for 5 hours. Then, it separated into solid and liquid using centrifugation, and was vacuum-dried at 100 degreeC. The integrated intensity ratio of OH / SiH of the powder after hydrothermal treatment was 51.
つぎに、塩基性溶液による固化処理を行った。摩砕処理後の活性化シリカ粉末５ｇに対して５Ｍ ＫＯＨ水溶液２ｇを混合し、手で予備撹拌した後、脱泡混練機（あわとり練太郎ＡＲＥ−２５０、ＴＨＩＮＫＹ製）を用いて、回転数２０００ｒｐｍで５分間撹拌を行った。その後、６０ｍｍ×１５ｍｍのテフロン製成形型に鋳込み、４０℃で２４時間密閉した状態で保持しスラリーを固化させたのち、６０℃、湿度８０％で２４時間乾燥し、厚さ約５ｍｍで透明性を有し、十分な強度を有するシリカ固化体を得た。得られたシリカ固化体について、試料厚み３．５ｍｍにおける透過率を紫外可視近赤外分光光度計（ＵＶ−３１５０、島津製作所製）により計測したところ、波長４００ｎｍ〜７８０ｎｍの可視域での透過率は４０％以上であった。透過率の測定結果を図１に示す。
Next, the solidification process by a basic solution was performed. 2 g of 5M KOH aqueous solution is mixed with 5 g of the activated silica powder after milling, pre-stirred by hand, and then rotated using a defoaming kneader (Awatori Netaro ARE-250, manufactured by THINKY). Stirring was performed at 2000 rpm for 5 minutes. Then cast into a Teflon mold of 60 mm x 15 mm, hold in a sealed state at 40 ° C for 24 hours, solidify the slurry, and then dry at 60 ° C and 80% humidity for 24 hours. Thus, a silica solidified body having sufficient strength was obtained. About the obtained silica solidified body, the transmittance at a sample thickness of 3.5 mm was measured with an ultraviolet-visible-near-infrared spectrophotometer (UV-3150, manufactured by Shimadzu Corporation), and the transmittance in the visible range of
（実施例２）
水熱処理の条件を１３０℃１５時間保持とした以外は、実施例１と同様の手順でシリカ固化体を作製したところ、厚さ約５ｍｍで透明性を有し、十分な強度を有するシリカ固化体が得られた。水熱処理後の粉末のＯＨ／ＳｉＨの積分強度比は、５２であった。
(Example 2)
Except that the conditions of hydrothermal treatment were maintained at 130 ° C. for 15 hours, a silica solidified body was produced in the same procedure as in Example 1. As a result, the silica solidified body having a thickness of about 5 mm and having sufficient strength was obtained. was gotten. The integrated intensity ratio of OH / SiH of the powder after hydrothermal treatment was 52.
得られたシリカ固化体について、試料厚み３．５ｍｍにおける透過率を実施例１と同様の手順で計測したところ、波長４００ｎｍ〜７８０ｎｍの可視域での透過率は５０％以上であった。透過率の測定結果を図１に示す。 About the obtained silica solidified body, the transmittance at a sample thickness of 3.5 mm was measured in the same procedure as in Example 1. As a result, the transmittance in the visible range of wavelengths from 400 nm to 780 nm was 50% or more. The measurement result of the transmittance is shown in FIG.
（実施例３）
水熱処理の条件を１３０℃２４時間保持とした以外は、実施例１と同様の手順でシリカ固化体を作製したところ、厚さ約５ｍｍで透明性を有し、十分な強度を有するシリカ固化体が得られた。図２にシリカ固化体の外観を示す。水熱処理後のシリカ粉末のＯＨ／ＳｉＨの積分強度比は、６５であった。
(Example 3)
Except that the hydrothermal treatment condition was maintained at 130 ° C. for 24 hours, a silica solidified body was produced in the same procedure as in Example 1. As a result, a silica solidified body having a thickness of about 5 mm and having sufficient strength was obtained. was gotten. FIG. 2 shows the appearance of the silica solidified body. The integrated intensity ratio of OH / SiH of the silica powder after hydrothermal treatment was 65.
得られたシリカ固化体について、試料厚み３．５ｍｍにおける透過率を実施例１と同様の手順で計測したところ、波長４００ｎｍ〜７８０ｎｍの可視域での透過率は６０％以上であった。透過率の測定結果を図１に示す。 About the obtained silica solidified body, the transmittance | permeability in sample thickness 3.5mm was measured in the procedure similar to Example 1, The transmittance | permeability in the visible region of wavelength 400nm -780nm was 60% or more. The measurement result of the transmittance is shown in FIG.
（実施例４）
シリカ粉末として、高純度非晶質球状シリカ（１−ＦＸ、一次粒径０．６μｍ、龍森製）を用い、遊星ボールミル（同上）を用いて２００ｒｐｍ、３０分間摩砕処理を行った。この際、容量５００ｍｌの摩砕容器に対して、シリカ粉末を５０ｇ、摩砕メディアとしてφ１０ｍｍのボール２００ｇを投入した。得られた粉末のＯＨ／ＳｉＨの積分強度比は、４００であった。
Example 4
As silica powder, high-purity amorphous spherical silica (1-FX, primary particle size 0.6 μm, manufactured by Tatsumori) was used, and a grinding treatment was performed at 200 rpm for 30 minutes using a planetary ball mill (same as above). At this time, 50 g of silica powder and 200 g of a φ10 mm ball as grinding media were charged into a grinding container having a capacity of 500 ml. The obtained powder had an integrated intensity ratio of OH / SiH of 400.
つぎに、塩基性溶液による固化処理を行った。シリカ粉末５ｇに対して５Ｍ ＫＯＨ水溶液２ｇを混合し、手で予備撹拌した後、脱泡混練機（同上）を用いて、回転数２０００ｒｐｍで５分間撹拌を行った。その後、６０ｍｍ×１５ｍｍのテフロン製成形型に鋳込み、４０℃で２４時間密閉した状態で保持しスラリーを固化させたのち、６０℃、湿度８０％で４８時間乾燥し、厚さ約５ｍｍのシリカ固化体を得た。厚さ約５ｍｍで透明性を有し、十分な強度を有するシリカ固化体が得られた。図３にシリカ固化体の外観を示す。 Next, the solidification process by a basic solution was performed. 2 g of 5M KOH aqueous solution was mixed with 5 g of silica powder, preliminarily stirred by hand, and then stirred for 5 minutes at a rotational speed of 2000 rpm using a defoaming kneader (same as above). After that, it was cast into a Teflon mold of 60 mm × 15 mm, held in a sealed state at 40 ° C. for 24 hours to solidify the slurry, dried at 60 ° C. and 80% humidity for 48 hours, and solidified to a thickness of about 5 mm. Got the body. A solidified silica having a thickness of about 5 mm and having transparency and sufficient strength was obtained. FIG. 3 shows the appearance of the silica solidified body.
（比較例１）
水熱処理を行わなかった以外は実施例１と同様の方法で同様の手順でシリカ固化体を作製した。摩砕後の粉末のＯＨ／ＳｉＨの積分強度比は、４２であった。得られたシリカ固化体は、十分な強度を有していたが、不透明であった。
(Comparative Example 1)
A silica solidified body was produced in the same manner as in Example 1 except that hydrothermal treatment was not performed. The integrated intensity ratio of OH / SiH of the powder after milling was 42. The obtained silica solidified body had sufficient strength but was opaque.
（比較例２）
摩砕処理を行わないこと以外は、比較例１と同様の手順でシリカ固化体の作製を試みたが、得られたシリカ固化体は、形状は維持するものの強度は十分でなく、不透明であった。使用したシリカ粉末のＯＨ／ＳｉＨの積分強度比は、２８であった。
(Comparative Example 2)
Except for not performing the grinding treatment, an attempt was made to produce a silica solidified body in the same procedure as in Comparative Example 1, but the obtained silica solidified body was not sufficiently strong but opaque because it maintained its shape. It was. The integrated intensity ratio of OH / SiH of the silica powder used was 28.
本発明のシリカ成形体の製造方法は、半導体製造用治具、液晶パネル製造用治具、太陽電池製造用治具、発光ダイオード製造用治具、などの各種デバイス製造用治具のほか、化学プラントの反応容器、プロジェクターやヘッドライト等に用いられるシリカ製ランプハウス、光ファイバーアンプなどの光学製品、アクセサリーや置物などの意匠製品などの製造に用いる事が出来る。 The method for producing a silica molded body of the present invention includes jigs for manufacturing various devices such as semiconductor manufacturing jigs, liquid crystal panel manufacturing jigs, solar cell manufacturing jigs, and light emitting diode manufacturing jigs. It can be used for the production of plant products such as plant reaction vessels, silica lamp houses used in projectors and headlights, optical products such as optical fiber amplifiers, and design products such as accessories and ornaments.
また、本発明のシリカ成形方法はコーティング技術としての利用も可能である。 The silica molding method of the present invention can also be used as a coating technique.
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