JPH04310541A - Production of crystallized li2o-al2o3-sio2 glass having low expansion coefficient - Google Patents
Production of crystallized li2o-al2o3-sio2 glass having low expansion coefficientInfo
- Publication number
- JPH04310541A JPH04310541A JP10045891A JP10045891A JPH04310541A JP H04310541 A JPH04310541 A JP H04310541A JP 10045891 A JP10045891 A JP 10045891A JP 10045891 A JP10045891 A JP 10045891A JP H04310541 A JPH04310541 A JP H04310541A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- li2o
- al2o3
- expansion coefficient
- crystallized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 41
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000007670 refining Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000008395 clarifying agent Substances 0.000 abstract description 2
- 239000011800 void material Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910008538 Li2O—Al2O3 Inorganic materials 0.000 description 1
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- BJTQUFONDOVFIJ-UHFFFAOYSA-N arsonooxyarsonic acid Chemical compound O[As](O)(=O)O[As](O)(O)=O BJTQUFONDOVFIJ-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、低膨張結晶化ガラスの
製造方法に関し、さらに詳細には清澄作用を促進して品
質を向上させたＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系低膨
張結晶化ガラスの製造方法に関するものである。[Industrial Application Field] The present invention relates to a method for producing low-expansion crystallized glass, and more particularly to a method for producing Li2O-Al2O3-SiO2-based low-expansion crystallized glass that improves quality by promoting fining action. It is related to.
【０００２】0002
【従来の技術】近年、熱膨張係数が極めて小さく、耐熱
性に優れた低膨張材料が多方面から求められている。こ
のような特性をほぼ満足する既存の材料として、熱膨張
係数が−５×１０−７ Ｋ−１ と非常に小さな石英ガ
ラスが知られているが、融点が高いため製造が困難であ
り、一般に高価である。また、石英ガラスと熱膨張係数
がほぼ同じか、さらに小さく耐熱性に優れた低膨張材料
として、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２ 系の結晶化
ガラスが知られている。この系の結晶化ガラスは、数多
く研究されており、その一部には商品化されているもの
もある。BACKGROUND OF THE INVENTION In recent years, there has been a demand for low-expansion materials with extremely small coefficients of thermal expansion and excellent heat resistance. As an existing material that almost satisfies these characteristics, quartz glass is known to have a very small coefficient of thermal expansion of -5 x 10-7 K-1, but its high melting point makes it difficult to manufacture and is generally not used. It's expensive. Furthermore, Li2O-Al2O3-SiO2-based crystallized glass is known as a low-expansion material that has a coefficient of thermal expansion that is approximately the same as or even smaller than that of quartz glass and has excellent heat resistance. Many studies have been conducted on this type of crystallized glass, and some of them have even been commercialized.
【０００３】0003
【発明が解決しようとする課題】しかしながら、この系
のガラスは、一般に粘性が高くガラスの清澄が困難であ
る。このため、多量のＡｓ酸化物を用いてガラスの清澄
を促進させてきた。ガラス原料に対しＡｓ酸化物の添加
量が多くなるほど清澄効果が増大するが、Ａｓ酸化物は
毒性が強く、しかも高価なため、多量に使用することは
好ましくない。また、例えば特開昭６０−２５５６３４
号公報においては、この系のガラスに対し、二酸化セリ
ウム、あるいはロウコウ化合物を清澄剤として用いてい
るが、得られた結晶化ガラスは琥珀色を呈するため好ま
しくない。However, this type of glass generally has a high viscosity and is difficult to refine. For this reason, a large amount of As oxide has been used to promote the fining of glass. The clarification effect increases as the amount of As oxide added to the glass raw material increases, but since As oxide is highly toxic and expensive, it is not preferable to use a large amount. Also, for example, JP-A-60-255634
In this publication, cerium dioxide or a wax compound is used as a refining agent for this type of glass, but this is not preferable because the obtained crystallized glass exhibits an amber color.
【０００４】本発明は、上記した従来の問題点を解決す
るためになされたもので、優れた透明性と、気泡が少な
く高品質性を有する低膨張結晶化ガラスの製造方法を提
供することを目的とする。The present invention has been made to solve the above-mentioned conventional problems, and aims to provide a method for producing low expansion crystallized glass having excellent transparency, few bubbles, and high quality. purpose.
【０００５】[0005]
【課題を解決するための手段】すなわち本発明は、ガラ
ス１００重量部に相当するガラス原料に対して、清澄剤
としてＡｓ酸化物をＡｓ２Ｏ３換算で０．２〜１．０重
量部含有させるとともに塩化物をＣｌ換算で０．０５〜
２．０重量部含有させることを特徴とするＬｉ２Ｏ−Ａ
ｌ２Ｏ３−ＳｉＯ２ 系低膨張結晶化ガラスの製造方法
である。[Means for Solving the Problems] That is, the present invention contains 0.2 to 1.0 parts by weight of As oxide as a refining agent in terms of As2O3 to a glass raw material equivalent to 100 parts by weight of glass, and 0.05~ in terms of Cl
Li2O-A characterized by containing 2.0 parts by weight
This is a method for producing l2O3-SiO2-based low expansion crystallized glass.
【０００６】ここでいうＡｓ酸化物としては、亜ヒ酸、
五酸化二砒素、ピロヒ酸などから選択することができる
。また塩化物としては、ＮａＣｌ、ＫＣｌなどから適宜
選択することができる。[0006] The As oxide mentioned here includes arsenite,
It can be selected from diarsenic pentoxide, pyroarsenic acid, etc. Further, the chloride can be appropriately selected from NaCl, KCl, etc.
【０００７】本発明者らは、Ｌｉ２Ｏ−Ａｌ２Ｏ３−Ｓ
ｉＯ２系低膨張結晶化ガラスを製造するにあたり、清澄
を促進させるために、ホウ酸系ガラスの清澄剤として従
来公知であり、安価でしかも毒性の無い塩化物について
研究を行なった。しかしながら、Ｌｉ２Ｏ−Ａｌ２Ｏ３
−ＳｉＯ２系のガラスの製造においては、塩化物を単独
で添加したのみでは十分な清澄効果は得られなかった。[0007] The present inventors have discovered that Li2O-Al2O3-S
In order to promote clarification in the production of iO2-based low-expansion crystallized glass, research was conducted on chloride, which is known as a fining agent for boric acid-based glass and is inexpensive and non-toxic. However, Li2O-Al2O3
In the production of -SiO2 glass, a sufficient clarification effect could not be obtained by adding chloride alone.
【０００８】そこでさらに研究を重ねたところ、少量の
Ａｓ酸化物と上記塩化物とをごく限られた範囲において
併用添加することにより、清澄効果が飛躍的に向上する
ことを見出した。すなわち、ガラス１００重量部に相当
するガラス原料に対し、Ａｓ酸化物をＡｓ２Ｏ３換算で
０．２〜１．０重量部含有させるとともに塩化物をＣｌ
換算で０．０５〜２．０重量部の範囲で含有させるもの
である。As a result of further research, it was discovered that the refining effect can be dramatically improved by adding a small amount of As oxide and the above-mentioned chloride in combination within a very limited range. That is, with respect to the glass raw material equivalent to 100 parts by weight of glass, 0.2 to 1.0 parts by weight of As oxide is contained in terms of As2O3, and chloride is added to Cl.
It is contained in a range of 0.05 to 2.0 parts by weight in terms of conversion.
【０００９】[0009]
【作用】このように本発明においては、清澄剤としての
Ａｓ酸化物および塩化物を併用し、しかもそれらの含有
量を最適となるように調整することで、気泡の少ないＬ
ｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２ 系低膨張結晶化ガラス
を得ることができる。[Function] In this way, in the present invention, As oxide and chloride are used together as clarifying agents, and by adjusting their contents to the optimum, L
An i2O-Al2O3-SiO2-based low expansion crystallized glass can be obtained.
【００１０】0010
【実施例】以下に、実施例および比較例を挙げて本発明
をより詳細に説明する。表１に示すようにガラス１００
重量部に相当する各ガラス原料に清澄剤としてＫＣｌお
よびＡｓ２Ｏ３を含有させて調合した。調合されたガラ
ス原料を、１日当り５０ｋｇ溶解する連続溶解窯を用い
て１５５０℃で加熱溶融し、型枠に鋳込み徐冷して試料
ガラスを得た。さらに、この試料ガラスを炉に入れて７
６０℃で１時間、８６０℃で１時間の２段階の加熱処理
をしてガラス中に微結晶を析出させて結晶化ガラスを得
た。[Examples] The present invention will be explained in more detail below with reference to Examples and Comparative Examples. Glass 100 as shown in Table 1
Each glass raw material corresponding to parts by weight was mixed with KCl and As2O3 as refining agents. The prepared glass raw material was heated and melted at 1550° C. using a continuous melting kiln capable of melting 50 kg per day, and then cast into a mold and slowly cooled to obtain a sample glass. Furthermore, this sample glass was placed in a furnace for 7
A two-step heat treatment of 1 hour at 60° C. and 1 hour at 860° C. was performed to precipitate microcrystals in the glass, thereby obtaining crystallized glass.
【００１１】比較例は、清澄剤としてのＣｌおよびＡｓ
２Ｏ３の含有割合を本発明の範囲外とした、本発明に含
まれない組成割合である。実施例と同様の方法で、ガラ
ス１００重量部に相当する各ガラス原料に清澄剤として
のＫＣｌあるいはＡｓ２Ｏ３を含有させて、または含有
させずに調合した。調合されたガラス原料を、１日当り
５０ｋｇ溶解する連続溶解窯を用いて実施例と同様の方
法で試量ガラスを作製し、さらに２段階の熱処理条件で
結晶化処理を施して結晶化ガラスを得た。[0011] A comparative example uses Cl and As as refining agents.
This is a composition ratio that is not included in the present invention, in which the content ratio of 2O3 is outside the scope of the present invention. In the same manner as in the examples, each glass raw material equivalent to 100 parts by weight of glass was prepared with or without KCl or As2O3 as a refining agent. A sample glass was prepared in the same manner as in the example using a continuous melting kiln that melts 50 kg of the prepared glass raw material per day, and a crystallized glass was obtained by further performing a crystallization treatment under two-step heat treatment conditions. Ta.
【００１２】0012
【表１】[Table 1]
【００１３】以上の結果から明らかなように、比較例の
溶融ガラスは清澄剤としてのＡｓ酸化物あるいは塩化物
をそれぞれ単独で添加したため、あるいは本発明の範囲
外の含有量で添加したため、溶融ガラス素地中に気泡が
非常に多く含まれていた。これに対して本発明では、清
澄剤としてのＡｓ酸化物および塩化物を併用して、しか
も特定の範囲内で含有させたので、溶融ガラス中に含ま
れる気泡の数が非常に減少した。As is clear from the above results, in the molten glass of the comparative example, As oxide or chloride as a refining agent was added alone or in a content outside the range of the present invention. The base material contained a large number of air bubbles. On the other hand, in the present invention, since As oxide and chloride are used together as refining agents and are contained within a specific range, the number of bubbles contained in the molten glass is greatly reduced.
【００１４】[0014]
【発明の効果】以上のように本発明によれば、清澄剤と
して用いられるＡｓ酸化物および塩化物の含有量を前記
のように非常に狭い範囲に限定したことにより、気泡が
非常に少なく、しかも高品質で透明性に優れたＬｉ２Ｏ
−Ａｌ２Ｏ３−ＳｉＯ２ 系低膨張結晶化ガラスを得る
ことが可能となるものである。As described above, according to the present invention, by limiting the content of As oxide and chloride used as the refining agent to a very narrow range as described above, there are very few bubbles. Furthermore, Li2O is of high quality and excellent transparency.
-Al2O3-SiO2-based low expansion crystallized glass can be obtained.
Claims (1)
ラス原料に対して、清澄剤としてＡｓ酸化物をＡｓ２Ｏ
３換算で０．２〜１．０重量部を含有させるとともに、
塩化物をＣｌ換算で０．０５〜２．０重量部を含有させ
ることを特徴とするＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系
低膨張結晶化ガラスの製造方法。Claim 1: As a refining agent, As2O is added to the glass raw material equivalent to 100 parts by weight of glass.
Containing 0.2 to 1.0 parts by weight in terms of 3,
A method for producing a Li2O-Al2O3-SiO2-based low-expansion crystallized glass, which comprises containing 0.05 to 2.0 parts by weight of chloride in terms of Cl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10045891A JPH04310541A (en) | 1991-04-05 | 1991-04-05 | Production of crystallized li2o-al2o3-sio2 glass having low expansion coefficient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10045891A JPH04310541A (en) | 1991-04-05 | 1991-04-05 | Production of crystallized li2o-al2o3-sio2 glass having low expansion coefficient |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04310541A true JPH04310541A (en) | 1992-11-02 |
Family
ID=14274473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10045891A Pending JPH04310541A (en) | 1991-04-05 | 1991-04-05 | Production of crystallized li2o-al2o3-sio2 glass having low expansion coefficient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04310541A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013246A1 (en) * | 1995-10-03 | 1997-04-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Optical information recording medium, method of manufacturing the medium, and target used for manufacturing the medium |
-
1991
- 1991-04-05 JP JP10045891A patent/JPH04310541A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013246A1 (en) * | 1995-10-03 | 1997-04-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Optical information recording medium, method of manufacturing the medium, and target used for manufacturing the medium |
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