JP3168302B2 - Manufacturing method of black glass - Google Patents
Manufacturing method of black glassInfo
- Publication number
- JP3168302B2 JP3168302B2 JP35686991A JP35686991A JP3168302B2 JP 3168302 B2 JP3168302 B2 JP 3168302B2 JP 35686991 A JP35686991 A JP 35686991A JP 35686991 A JP35686991 A JP 35686991A JP 3168302 B2 JP3168302 B2 JP 3168302B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- metal component
- solution
- deposit
- fine powder
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
- C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光学分析機器で用いら
れる試料セルなどに利用できる黒色ガラスの製造方法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing black glass which can be used for a sample cell used in an optical analyzer.
【０００２】[0002]
【従来の技術】光学分析機器では、試料セルの材料とし
て光吸収の少ないシリカガラスが用いられているが、そ
の試料セル内の迷光，光散乱等を防止するために黒色ガ
ラスが採用されている。現在の黒色ガラスは、シリカガ
ラスにバナジウム，モリブデンなどの金属酸化物を多孔
質ガラスに添加して製造している。この黒色ガラスはセ
ルの使用時の耐蝕性やセルの作製時に必要なシリカガラ
スとの溶着性に優れており、光学セル用の黒色ガラスに
用いられている。しかし、現在の製造方法では色むらが
出やすく、使用に耐え得る黒色ガラスを得るためには歩
留まりが悪く、コスト高になるという問題点があった。2. Description of the Related Art In an optical analyzer, silica glass having low light absorption is used as a material of a sample cell, but black glass is employed to prevent stray light, light scattering and the like in the sample cell. . At present, black glass is produced by adding a metal oxide such as vanadium or molybdenum to porous glass to silica glass. This black glass is excellent in corrosion resistance during use of the cell and adhesion to silica glass required at the time of manufacturing the cell, and is used for black glass for optical cells. However, in the current manufacturing method, there is a problem that color unevenness is likely to occur and a yield is low and a cost is high in order to obtain a black glass which can be used.
【０００３】このため、色むらがなく、耐蝕性，シリカ
ガラスとの溶着性が優れている黒色ガラスが望まれてい
る。For this reason, a black glass having no color unevenness, excellent corrosion resistance and excellent adhesion to silica glass has been desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、色むらがな
く、耐蝕性，シリカガラスとの溶着性に優れている黒色
ガラスを製造する方法を提供することを目的とするもの
である。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing black glass having no color unevenness, excellent corrosion resistance, and excellent adhesion to silica glass.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するために鋭意検討を行った結果、本発明を完
成するに至ったものである。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.
【０００６】すなわち本発明は、火炎加水分解法により
得られたシリカ微粉末堆積体を焼結し、ガラスとする方
法において、シリカ微粉末堆積体をＴｉ，Ｚｒ，Ｖ，Ｎ
ｂ，Ｃｒ，Ｍｏ及びＭｎの中から選ばれた少なくとも１
種類以上の金属成分を含む溶液中に浸漬し、乾燥後、Ｈ
２を含む還元性雰囲気中で焼結しガラス化することを特
徴とする、黒色ガラスの製造方法である。以下、本発明
を更に詳細に説明する。That is, according to the present invention, there is provided a method of sintering a silica fine powder deposit obtained by a flame hydrolysis method to obtain a glass.
at least one selected from b, Cr, Mo and Mn
Immersed in a solution containing more than one type of metal component, dried,
2. A method for producing black glass, characterized by sintering and vitrifying in a reducing atmosphere containing 2 . Hereinafter, the present invention will be described in more detail.
【０００７】本発明の黒色ガラスは、火炎加水分解法に
より得られたシリカ微粉末堆積体を主要な原料として用
いるので、黒色ガラスの耐蝕性やシリカガラスとの溶着
性はシリカガラスと同等であり、光学セルとしての使用
にはまったく問題がない。The black glass of the present invention uses a silica fine powder deposit obtained by a flame hydrolysis method as a main raw material, so that the black glass has the same corrosion resistance and adhesion to silica glass as silica glass. There is no problem in use as an optical cell.
【０００８】このシリカ微粉末堆積体を前記金属成分含
有溶液中に浸漬させる。この金属成分含有溶液は、前記
金属の塩化物、フッ化物又はアルコキシド化合物を非水
溶媒に溶解させたものが好ましい。非水溶媒としては、
例えばエタノ−ル、ベンゼン、ヘキサン等があげられ
る。[0008] The silica fine powder deposit is immersed in the metal component-containing solution. The metal component-containing solution is preferably a solution in which a chloride, fluoride or alkoxide compound of the metal is dissolved in a non-aqueous solvent. As a non-aqueous solvent,
For example, ethanol, benzene, hexane and the like can be mentioned.
【０００９】浸漬時間は、サンプルの大きさにもよる
が、減圧下でおよそ数時間、大気圧下ではおよそ一晩が
好ましい。いずれにしてもサンプル内に溶液がいきわた
るのに十分な時間浸漬させる。The immersion time depends on the size of the sample, but is preferably about several hours under reduced pressure and about overnight under atmospheric pressure. In any case, soak the solution in the sample for a sufficient time.
【００１０】シリカ微粉末堆積体は、非常に均一な孔を
持つ多孔質体であるので、金属元素含有溶液が均一にシ
リカ微粉末堆積体中に浸入することができる。そのた
め、焼結体であるガラス中に金属成分が均一に含有され
る。したがって、色むらのない黒色石英系ガラスを得る
ことができる。[0010] Since the silica fine powder deposit is a porous body having very uniform pores, the metal element-containing solution can uniformly penetrate into the silica fine powder deposit. Therefore, the metal component is uniformly contained in the sintered glass. Therefore, it is possible to obtain black quartz glass having no color unevenness.
【００１１】石英ガラス中に含有される金属成分の濃度
は、好ましくは０．０５−１０モル％であり、さらに好
ましくは０．５−３モル％である。濃度が低すぎると石
英ガラスが十分黒色に着色しない恐れがあり、高すぎる
と石英ガラスとしての性質を失う恐れがあるからであ
る。上記濃度になるよう金属成分を含有させるには、堆
積体内の全空孔体積を求め、その中に入った溶液中の金
属成分がすべて加水分解すると仮定して、溶液のおおよ
その濃度を算出し、その中に堆積体を浸漬すればよい。[0011] The concentration of the metal component contained in the quartz glass is preferably 0.05-10 mol%, more preferably 0.5-3 mol%. If the concentration is too low, the quartz glass may not be colored sufficiently black, and if the concentration is too high, the properties of the quartz glass may be lost. In order to contain the metal component at the above concentration, the total volume of the pores in the deposit is determined, and the approximate concentration of the solution is calculated assuming that all the metal components in the solution contained therein are hydrolyzed. Then, the deposit may be immersed therein.
【００１２】次いで、金属元素含有溶液中に浸漬させた
シリカ微粉末堆積体内の溶液を加水分解させ、堆積体内
に金属酸化物を含有させる。これは堆積体を放置してお
けば大気中の水によって徐々に加水分解が進行するが、
好ましくはシリカ微粉末堆積体が存在する金属成分含有
溶液中に水を添加するか、又は堆積体を水分を添加した
雰囲気下で静置させるとよい。これもサンプル内部まで
加水分解が進行するよう、十分な時間をかけるとよい。Next, the solution in the silica fine powder deposit immersed in the metal element-containing solution is hydrolyzed to contain a metal oxide in the deposit. This is because if the sediment is left untreated, the water in the atmosphere will gradually promote hydrolysis,
Preferably, water is added to the metal component-containing solution in which the silica fine powder deposit exists, or the deposit is allowed to stand in an atmosphere to which moisture is added. Again, it is advisable to take sufficient time for the hydrolysis to proceed inside the sample.
【００１３】金属成分を加水分解させたシリカ微粉末堆
積体は、溶媒除去のために乾燥させる。そのときの条件
は特に限定されないが、乾燥温度は８０−２００℃、大
気中で行うのが好ましい。The silica fine powder deposit obtained by hydrolyzing the metal component is dried to remove the solvent. The conditions at that time are not particularly limited, but the drying temperature is preferably from 80 to 200 ° C and the drying is preferably performed in the air.
【００１４】この乾燥堆積体中の残留溶媒を完全に除去
するために予備焼結として、３００−８００℃で酸素雰
囲気中で焼結するのが好ましい。酸素雰囲気で予備焼結
することにより、金属成分が完全に酸化物になるという
効果もある。[0014] In order to completely remove the residual solvent from the dried deposit, sintering at 300 to 800 ° C in an oxygen atmosphere is preferable as pre-sintering. Preliminary sintering in an oxygen atmosphere also has the effect of completely converting the metal component to an oxide.
【００１５】この予備焼結体をＨ２を含む還元性雰囲気
中で焼結することにより、黒色を呈する石英ガラスを得
ることができる。焼結温度は１４００−１６００℃、Ｈ
２の濃度は２０体積％以上が好ましい。By sintering the pre-sintered body in a reducing atmosphere containing H 2 , black quartz glass can be obtained. Sintering temperature is 1400-1600 ° C, H
The concentration of 2 is preferably 20% by volume or more.
【００１６】[0016]
【実施例】本発明を更に詳細に説明するため以下に実施
例を挙げるが、本発明はこれら実施例に限定されるもの
ではない。The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００１７】実施例１ 火炎加水分解法により得られたシリカ微粉末堆積体２０
ｇを、ベンゼン１６０ｇにＮｂ（ＯＣ４Ｈ９）５１５ｇ
を溶かした溶液に投入し、１２時間後に堆積体を取りだ
し、８０℃、大気中で乾燥させた。この乾燥堆積体を５
００℃、１時間酸素雰囲気中で予備焼結させた。次にこ
の予備焼結体を１４５０℃、Ｈ２を５０体積％含むヘリ
ウム中で焼結することにより黒色ガラスを得た。Example 1 A fine silica powder deposit 20 obtained by a flame hydrolysis method
g to 160 g of benzene and 15 g of Nb (OC 4 H 9 ) 5
Was poured into the solution in which was dissolved, and after 12 hours, the deposit was taken out and dried at 80 ° C. in the air. This dried sediment is
Pre-sintering was performed in an oxygen atmosphere at 00 ° C. for 1 hour. Next, this pre-sintered body was sintered at 1450 ° C. in helium containing 50% by volume of H 2 to obtain a black glass.
【００１８】この黒色ガラス中に含まれるＮｂの量は、
化学分析により０．７モル％であった。この黒色ガラス
を３ｍｍの厚みに切断し、２００ｎｍから２５０００ｎ
ｍの波長域で光透過度を測定したが、光透過は観察され
なかった。The amount of Nb contained in the black glass is
It was 0.7 mol% by chemical analysis. This black glass is cut into a thickness of 3 mm, and 200 nm to 25000 n.
The light transmittance was measured in the wavelength range of m, but no light transmission was observed.
【００１９】実施例２ 火炎加水分解法により得られたシリカ微粉末堆積体２０
ｇを、エタノ−ル２００ｇにＮｂＣｌ５５ｇを溶かした
溶液に投入し、２０時間後に水７ｇを添加し、２０時間
後に堆積体を取りだし、８０℃、大気中で乾燥させた。
この乾燥堆積体を５００℃、１時間酸素雰囲気中で予備
焼結させた。次にこの予備焼結体を、１４５０℃、Ｈ２
を５０体積％含むヘリウム中で焼結することにより、黒
色ガラスを得た。Example 2 Silica fine powder deposit 20 obtained by flame hydrolysis method
The g, ethanol - were charged into Le 200g to a solution of NbCl 5 5 g, water was added 7g after 20 hours, taken out stack after 20 hours, 80 ° C., dried in air.
This dried deposit was pre-sintered at 500 ° C. for one hour in an oxygen atmosphere. Next, the pre-sintered body was heated at 1450 ° C. and H 2
Was sintered in helium containing 50% by volume to obtain black glass.
【００２０】この黒色ガラス中に含まれるＮｂの量は、
化学分析により０．４モル％であった。この黒色ガラス
を３ｍｍの厚みに切断し、２００ｎｍから２５０００ｎ
ｍの波長域で光透過度を測定したが、光透過は観察され
なかった。The amount of Nb contained in the black glass is
It was 0.4 mol% by chemical analysis. This black glass is cut into a thickness of 3 mm, and 200 nm to 25000 n.
The light transmittance was measured in the wavelength range of m, but no light transmission was observed.
【００２１】[0021]
【発明の効果】以上のように、色むらがなく、２００ｎ
ｍから２５０００ｎｍの波長域で光透過のない黒色ガラ
スを、歩留まりよく作製することができる。As described above, there is no color unevenness and 200 n
A black glass having no light transmission in a wavelength range from m to 25000 nm can be manufactured with high yield.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C03B 8/04 C03B 20/00 C03C 1/10 C03C 3/06 C03C 4/02 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C03B 8/04 C03B 20/00 C03C 1/10 C03C 3/06 C03C 4/02
Claims (4)
末堆積体を焼結し、ガラスとする方法において、シリカ
微粉末堆積体をＴｉ，Ｚｒ，Ｖ，Ｎｂ，Ｃｒ，Ｍｏ及び
Ｍｎの中から選ばれた少なくとも１種類以上の金属成分
を含む溶液中に浸漬し、乾燥後、Ｈ２を含む還元性雰囲
気中で焼結しガラス化することを特徴とする、黒色ガラ
スの製造方法。1. A method of sintering a silica fine powder deposit obtained by a flame hydrolysis method to obtain a glass, wherein the silica fine powder deposit is made of Ti, Zr, V, Nb, Cr, Mo and Mn. A method for producing black glass, comprising: immersing in a solution containing at least one or more metal components selected from the group consisting of: drying, sintering and vitrification in a reducing atmosphere containing H 2 .
含有溶液が、金属の塩化物、フッ化物又はアルコキシド
化合物を非水溶媒に溶解させたものであることを特徴と
する方法。2. The method according to claim 1, wherein the metal component-containing solution is obtained by dissolving a metal chloride, fluoride or alkoxide compound in a non-aqueous solvent.
リカ微粉末堆積体を金属成分含有溶液に浸漬後、溶液中
に水を添加するか又は堆積体を水分を含む雰囲気下に静
置し、堆積体内の金属成分を加水分解させることを特徴
とする方法。3. The method according to claim 1, wherein the silica fine powder deposit is immersed in a metal component-containing solution, and then water is added to the solution or the deposit is allowed to stand in an atmosphere containing moisture. And hydrolyzing a metal component in the sediment.
おいて、ガラス中に０．０５−１０モル％の金属成分を
含有させることを特徴とする方法。4. The method according to claim 1, wherein 0.05 to 10 mol% of a metal component is contained in the glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35686991A JP3168302B2 (en) | 1991-12-26 | 1991-12-26 | Manufacturing method of black glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35686991A JP3168302B2 (en) | 1991-12-26 | 1991-12-26 | Manufacturing method of black glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05178624A JPH05178624A (en) | 1993-07-20 |
| JP3168302B2 true JP3168302B2 (en) | 2001-05-21 |
Family
ID=18451172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35686991A Expired - Fee Related JP3168302B2 (en) | 1991-12-26 | 1991-12-26 | Manufacturing method of black glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3168302B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4492123B2 (en) * | 2004-01-05 | 2010-06-30 | 旭硝子株式会社 | Silica glass |
| JP5214138B2 (en) * | 2006-06-20 | 2013-06-19 | モーメンティブ・パフォーマンス・マテリアルズ・インク | Glass product and its manufacturing method |
-
1991
- 1991-12-26 JP JP35686991A patent/JP3168302B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05178624A (en) | 1993-07-20 |
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