JP2003048720A - Method for manufacturing colorless industrial soda-lime glass - Google Patents

Method for manufacturing colorless industrial soda-lime glass

Info

Publication number
JP2003048720A
JP2003048720A JP2001236706A JP2001236706A JP2003048720A JP 2003048720 A JP2003048720 A JP 2003048720A JP 2001236706 A JP2001236706 A JP 2001236706A JP 2001236706 A JP2001236706 A JP 2001236706A JP 2003048720 A JP2003048720 A JP 2003048720A
Authority
JP
Japan
Prior art keywords
lime glass
glass
cathode
colorless
industrial soda
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.)
Granted
Application number
JP2001236706A
Other languages
Japanese (ja)
Other versions
JP3837476B2 (en
Inventor
Tetsuji Yano
哲司 矢野
Masayuki Yamane
正之 山根
Shuichi Shibata
修一 柴田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Institute of Technology NUC
Original Assignee
Tokyo Institute of Technology NUC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokyo Institute of Technology NUC filed Critical Tokyo Institute of Technology NUC
Priority to JP2001236706A priority Critical patent/JP3837476B2/en
Publication of JP2003048720A publication Critical patent/JP2003048720A/en
Application granted granted Critical
Publication of JP3837476B2 publication Critical patent/JP3837476B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/173—Apparatus for changing the composition of the molten glass in glass furnaces, e.g. for colouring the molten glass
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Glass Compositions (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing industrial soda-lime glass which is made colorless without using a harmful selenium compound. SOLUTION: In manufacturing the colorless industrial soda-lime glass from the raw material of the industrial soda-lime glass containing iron which is the cause for coloring in a low valence state, this method is furnished with a process step of preparing a glass melt by adding tin oxide to the raw material, then melting the raw material and a process step of inserting an anode and cathode into the glass melt, impressing a DC voltage between the anode and the cathode to continuously generate oxygen air bubbles, thereby making the iron in the glass melt into the high valence.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、無色工業用ソーダ
石灰ガラスの製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing colorless industrial soda-lime glass.

【０００２】[0002]

【従来の技術】鉄を不純物として含む工業用ソーダ石灰
ガラスは、その製造過程で青色に着色される。これは、
工業用ソーダ石灰ガラスの製造時に前記鉄（Ｆｅ）が溶
融過程でイオンとなって赤色域から近赤外域に吸収を持
つＦｅ2+が生成することに起因するものである。このＦ
ｅ2+イオンは、高温での反応により生成され、一旦ガラス
融液中に生成されると、色を呈しないＦｅ3+に酸化され
ることなく製品ガラスに残存する。Industrial soda-lime glass containing iron as an impurity is colored blue during the manufacturing process. this is,
This is due to the fact that the iron (Fe) turns into ions in the melting process during the production of industrial soda-lime glass to produce Fe 2+ having absorption from the red region to the near infrared region. This F
The e 2+ ions are generated by the reaction at a high temperature, and once generated in the glass melt, they remain in the product glass without being oxidized to Fe 3+ which does not exhibit a color.

【０００３】このようなことから、従来、工業用ソーダ
石灰ガラスの着色を防止するために、赤色のセレン（Ｓ
ｅ）化合物をガラス原料に添加して青色と赤色を相殺し
て見かけ上、無色の工業用ソーダ石灰ガラスを製造する
ことが行われている。Therefore, in order to prevent coloring of industrial soda-lime glass, red selenium (S) has been conventionally used.
e) Compounds are added to glass raw materials to cancel blue and red colors to produce an apparently colorless industrial soda-lime glass.

【０００４】しかしながら、セレン化合物は有害で、ガ
ラス融液状態で蒸発しやすいために、作業環境の悪化を
招く問題があった。However, since the selenium compound is harmful and easily vaporizes in the glass melt state, there is a problem that the working environment is deteriorated.

【０００５】一方、特開平６−９２２４号公報には酸化
物溶融体中に電解により酸素（精製ガス）を発生させる
ことにより不必要なガスが高度に除去され、環境に対し
て有害な精製用化学薬品を不用にするかその使用を著し
く制限することが可能な酸化物溶融体の精製方法が開示
されている。On the other hand, in JP-A-6-9224, unnecessary gas is highly removed by generating oxygen (purified gas) in the oxide melt by electrolysis, and for purification that is harmful to the environment. Disclosed is a method of refining an oxide melt which makes it possible to dispense with chemicals or to significantly limit its use.

【０００６】[0006]

【発明が解決しようとする課題】本発明は、有害なセレ
ン化合物を用いることなく、無色化された工業用ソーダ
石灰ガラスの製造方法を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention is intended to provide a method for producing a colorless industrial soda-lime glass for industrial use without using a harmful selenium compound.

【０００７】[0007]

【課題を解決するための手段】本発明に係る無色工業用
ソーダ石灰ガラスの製造方法は、低原子価の状態で着色
の原因になる鉄を含む工業用ソーダ石灰ガラスの原料か
ら無色の工業用ソーダ石灰ガラスを製造するにあたり、
前記原料に酸化錫を加えた後、溶融してガラス融液を調
製する工程と、前記ガラス融液に陽極および陰極を挿入
し、これら陽極と陰極の間に直流電圧を印加して酸素気
泡を連続的に発生させて前記ガラス融液中の鉄を高原子
価にする工程とを具備したことを特徴とするものであ
る。The method for producing a colorless industrial soda-lime glass according to the present invention is a method for producing a colorless industrial soda-lime glass from a raw material of an industrial soda-lime glass containing iron which causes coloring in a low valence state. In producing soda lime glass,
After adding tin oxide to the raw material, a step of melting to prepare a glass melt, and inserting an anode and a cathode into the glass melt, apply a DC voltage between these anode and cathode to generate oxygen bubbles. A step of continuously generating iron in the glass melt to have a high valence.

【０００８】[0008]

【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

【０００９】（第１工程）まず、低原子価の状態で着色
の原因になる鉄を含む工業用ソーダ石灰ガラスの原料に
酸化錫（ＳｎＯ2）を加えた後、溶融してガラス融液を
調製する。(First Step) First, tin oxide (SnO 2 ) is added to a raw material of industrial soda-lime glass containing iron which causes coloring in a low valence state, and then melted to form a glass melt. Prepare.

【００１０】前記工業用ソーダ石灰ガラスは、ＳｉＯ2
６０〜７５モル％，ＣａＯ５〜１５モル％，Ｎａ2Ｏ１
０〜２０モル％，Ａｌ2Ｏ3０〜５モル％，Ｆｅ2Ｏ3０．
１モル％以下およびＭｇＯのような不可避的不純物を１
モル％以下含む組成を有する。The industrial soda-lime glass is made of SiO 2
60-75 mol%, CaO 5-15 mol%, Na 2 O 1
0-20 mol%, Al 2 O 3 0-5 mol%, Fe 2 O 3 0.
1 mol% or less and 1 unavoidable impurities such as MgO
It has a composition containing less than or equal to mol%.

【００１１】前記酸化錫は、前記原料に対して０．１〜
２モル％添加することが好ましい。この酸化錫の添加量
を０．１モル％未満にすると、工業用ソーダ石灰ガラス
を無色化する効果を十分に達成することが困難になる。
一方、前記酸化錫の添加量が２モル％を超えると工業用
ソーダ石灰ガラスの物理的性質そのものを変えてしまう
虞がある。より好ましい酸化錫の添加量は、０．１〜１
モル％である。The tin oxide is 0.1 to 0.1% based on the raw material.
It is preferable to add 2 mol%. If the amount of tin oxide added is less than 0.1 mol%, it will be difficult to sufficiently achieve the effect of making industrial soda lime glass colorless.
On the other hand, if the amount of tin oxide added exceeds 2 mol%, the physical properties themselves of industrial soda-lime glass may be changed. More preferable addition amount of tin oxide is 0.1 to 1
Mol%.

【００１２】（第２工程）次いで、前記ガラス融液に陽
極および陰極を挿入し、これら陽極と陰極の間に直流電
圧を印加して前記陽極から酸素気泡を連続的に発生させ
て前記ガラス融液中の鉄を高原子価にすることによって
無色の工業用ソーダ石灰ガラスを製造する。(Second step) Next, an anode and a cathode are inserted into the glass melt, and a DC voltage is applied between the anode and the cathode to continuously generate oxygen bubbles from the anode to melt the glass melt. A colorless industrial soda-lime glass is produced by making iron in the liquid a high valence.

【００１３】前記陰極は、前記ガラス融液の液面近傍に
挿入され、かつ前記陽極は前記陰極より下方の前記ガラ
ス融液に挿入されることが好ましい。It is preferable that the cathode is inserted in the vicinity of the liquid surface of the glass melt, and the anode is inserted in the glass melt below the cathode.

【００１４】前記陽極と陰極の間に印加する直流電圧
は、０．２Ｖ以上であることが好ましい。The DC voltage applied between the anode and the cathode is preferably 0.2 V or more.

【００１５】前記酸素気泡は、ガラス融液への対流作用
を高め、かつ通電処理後においてガラス融液からの抜け
を容易にする観点から、平均径が１ｍｍ以上であること
が好ましい。特に、前記酸素気泡は平均径が１ｍｍ以上
で、かつ最大径と最小径との差が１ｍｍ以下であること
が好ましい。The oxygen bubbles preferably have an average diameter of 1 mm or more from the viewpoint of enhancing the convection action to the glass melt and facilitating the escape from the glass melt after the energization treatment. Particularly, it is preferable that the oxygen bubbles have an average diameter of 1 mm or more and a difference between the maximum diameter and the minimum diameter of 1 mm or less.

【００１６】前述したガラス融液への直流電圧の印加
は、例えば図１に示す通電装置を用いて行うことができ
る。The application of the DC voltage to the above-mentioned glass melt can be carried out, for example, by using the energizing device shown in FIG.

【００１７】図１の支持部材１には、充填剤２が収納さ
れている。溶融るつぼ３は、その下部が前記支持部材１
内の充填剤２に埋め込まれて支持されている。なお、こ
の溶融るつぼ３の周囲には投入されたガラスを加熱溶融
してガラス融液Ｇとするためのヒータが配置されてい
る。例えば筒状の陽極４は、前記溶融るつぼ３内の底面
に配置され、リード５を通して図示しない直流電圧に接
続されている。例えば筒状の陰極６は、絶縁性支持棒７
で支持されて前記溶融るつぼ３内のガラス融液Ｇ表面近
傍に浸漬されている。前記陰極６は、前記支持棒７に倦
回されたリード８を通して図示しない直流電圧に接続さ
れている。A filler 2 is contained in the support member 1 shown in FIG. The lower portion of the melting crucible 3 is the support member 1
It is embedded in and supported by the filler 2 inside. A heater for heating and melting the charged glass into a glass melt G is arranged around the melting crucible 3. For example, a cylindrical anode 4 is arranged on the bottom surface of the melting crucible 3 and is connected to a DC voltage (not shown) through a lead 5. For example, the cylindrical cathode 6 has an insulating support rod 7
And is immersed in the vicinity of the surface of the glass melt G in the melting crucible 3. The cathode 6 is connected to a DC voltage (not shown) through a lead 8 wound around the support rod 7.

【００１８】以上説明したように本発明によれば、低原
子価の状態で着色の原因になる鉄を含む工業用ソーダ石
灰ガラスの原料に酸化錫を加えた後、溶融してガラス融
液を調製し、このガラス融液に陽極および陰極を挿入
し、これら陽極と陰極の間に直流電圧を印加して酸素気
泡を連続的に発生させて前記ガラス融液中の鉄を高原子
価にすることによって、環境に有害な金属を含まない無
色の工業用ソーダ石灰ガラスを製造することができる。As described above, according to the present invention, tin oxide is added to a raw material of industrial soda-lime glass containing iron which causes coloring in a low valence state, and then melted to form a glass melt. Prepare, insert an anode and a cathode in this glass melt, apply a DC voltage between these anode and cathode to continuously generate oxygen bubbles to make iron in the glass melt a high valence As a result, a colorless industrial soda-lime glass containing no harmful metal to the environment can be produced.

【００１９】すなわち、前記原料に添加する酸化錫は酸
化アンチモンのような酸化物に比べて毒性が極めて低
く、環境に優しい酸化物であり、かつ還元反応時に４価
の酸化物から２価の酸化物に変化し、５価の酸化物から
３価の酸化物に変化する酸化アンチモンと同等の酸素放
出量を示すという特徴を有する。That is, tin oxide added to the above-mentioned raw material is an environment-friendly oxide having extremely low toxicity as compared with an oxide such as antimony oxide, and is a tetravalent oxide to a divalent oxide during the reduction reaction. It has a characteristic that it shows the same amount of released oxygen as antimony oxide that changes into a substance and changes from a pentavalent oxide to a trivalent oxide.

【００２０】したがって、前記酸化錫が添加された工業
用ソーダ石灰ガラスを溶融してガラス融液とし、このガ
ラス融液に陽極および陰極を挿入し、これら陽極と陰極
の間に直流電圧を印加することによって、前記陽極から
前記酸化錫の還元により酸素気泡を連続的に発生させる
ことができる。このとき、前記原料の溶融過程でイオン
として生成されたＦｅ2+が発生した酸素により酸化され
て高原子価に変換される。つまり色を呈しないＦｅ3+に
変換される。その結果、有害な物質を含まず、無色の工
業用ソーダ石灰ガラスを製造することができる。Therefore, the industrial soda lime glass containing tin oxide is melted to form a glass melt, and an anode and a cathode are inserted into the glass melt, and a DC voltage is applied between the anode and the cathode. Thus, oxygen bubbles can be continuously generated by reducing the tin oxide from the anode. At this time, Fe 2+ generated as ions in the melting process of the raw material is oxidized by oxygen generated and converted into high valence. In other words, it is converted to Fe 3+ which does not exhibit color. As a result, it is possible to produce a colorless industrial soda-lime glass containing no harmful substances.

【００２１】特に、図１に示すように溶融るつぼ３内に
ガラス融液Ｇを収容し、陽極４を前記溶融るつぼ３内の
底部に配置し、陰極６をガラス融液Ｇの液面近傍に挿入
し、陽極４，陰極６間に直流電圧を印加することによっ
て、陰極６においても雰囲気中の酸素ガスを還元してイ
オンとすることができ、この酸素を前記ガラス融液Ｇに
取り込むことができるため、ガラス融液Ｇへのトータル
酸素量を増大できる。その結果、ガラス融液中のＦｅ2+
をより効果的に高原子価にして無色の工業用ソーダ石灰
ガラスを製造することができる。In particular, as shown in FIG. 1, the glass melt G is housed in the melting crucible 3, the anode 4 is arranged at the bottom of the melting crucible 3, and the cathode 6 is located near the surface of the glass melt G. By inserting and applying a DC voltage between the anode 4 and the cathode 6, the oxygen gas in the atmosphere can also be reduced to ions in the cathode 6, and this oxygen can be taken into the glass melt G. Therefore, the total amount of oxygen in the glass melt G can be increased. As a result, Fe 2+ in the glass melt
Can be made to have a higher valence more effectively to produce colorless industrial soda-lime glass.

【００２２】また、図１に示す陽極４、陰極６の配置に
おいて、陽極４と陰極６の間に印加する直流電圧を制御
して前記陽極４から平均径が１ｍｍ以上の酸素気泡を連
続的に発生させれば、前記ガラス融液Ｇに対流力および
撹拌力を付与することができるため、前記陰極６で取り
込んだ酸素を前記るつぼ３内部のガラス融液Ｇに十分供
給できる。このため、ガラス融液中のＦｅ2+をより一層
効果的に高原子価にして無色の工業用ソーダ石灰ガラス
を製造することができる。しかも、大きな酸素気泡を発
生することによって通電処理後においてガラス融液から
酸素気泡を容易に逃散させることができる。このため、
透光性の高い無色工業用ソーダ石灰ガラスを製造するこ
とができる。Further, in the arrangement of the anode 4 and the cathode 6 shown in FIG. 1, the DC voltage applied between the anode 4 and the cathode 6 is controlled to continuously generate oxygen bubbles having an average diameter of 1 mm or more from the anode 4. If generated, the convection force and the stirring force can be applied to the glass melt G, so that the oxygen taken in by the cathode 6 can be sufficiently supplied to the glass melt G inside the crucible 3. Therefore, Fe 2+ in the glass melt can be more effectively made to have a high valence, and a colorless industrial soda-lime glass can be manufactured. Moreover, by generating large oxygen bubbles, the oxygen bubbles can easily escape from the glass melt after the energization treatment. For this reason,
A highly transparent colorless industrial soda-lime glass can be produced.

【００２３】[0023]

【実施例】以下、本発明の好ましい実施例を前述した図
１を参照して説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will be described below with reference to FIG.

【００２４】（実施例１）まず、下記表１に示す酸化鉄
（Ｆ2Ｏ3）および酸化錫（ＳｎＯ2）を含む工業用ソー
ダ石灰ガラスを溶解槽にて１５００℃で２４時間溶融
し、急冷固化してガラスロッドを得た。Example 1 First, industrial soda lime glass containing iron oxide (F 2 O 3 ) and tin oxide (SnO 2 ) shown in Table 1 below was melted in a melting tank at 1500 ° C. for 24 hours, It was rapidly cooled and solidified to obtain a glass rod.

【００２５】＜工業用ソーダ石灰ガラス組成＞ ＳｉＯ2；７４．６モル％、 ＣａＯ；１２．９モル％、 Ｎａ2Ｏ；１３．３モル％、 Ｆｅ2Ｏ3；０．０２５モル％、 ＳｎＯ2；０．５モル％。<Industrial soda-lime glass composition> SiO 2 ; 74.6 mol%, CaO; 12.9 mol%, Na 2 O; 13.3 mol%, Fe 2 O 3 ; 0.025 mol%, SnO 2 ; 0.5 mol%.

【００２６】次いで、前記ガラスロッドを前述した図１
に示す筒状の白金製陽極４が底部に設置されたアルミナ
製の溶融るつぼ３内に入れ、図示しないヒータにより１
３００℃まで加熱してガラス融液Ｇとした。つづいて、
前記ガラス融液Ｇの液面に白金製陰極６を挿入し、図示
しない直流電源から１．３５Ｖの電圧を前記陽極４，陰
極６間に１時間印加した。この間、前記陽極４から平均
径約２ｍｍの酸素気泡が連続的に発生し、上部液面に達
した。ひきつづき、前記陰極６を取り去り、１０分間保
持した後、６〜７℃／分の条件で室温まで冷却した。Next, the glass rod is shown in FIG.
The cylindrical platinum anode 4 shown in Fig. 1 is placed in the alumina melting crucible 3 installed at the bottom, and the
It was heated to 300 ° C. to obtain a glass melt G. Continuing,
A platinum cathode 6 was inserted into the surface of the glass melt G, and a voltage of 1.35 V was applied between the anode 4 and the cathode 6 for 1 hour from a DC power source (not shown). During this time, oxygen bubbles having an average diameter of about 2 mm were continuously generated from the anode 4 and reached the upper liquid surface. Subsequently, the cathode 6 was removed, held for 10 minutes, and then cooled to room temperature under the condition of 6 to 7 ° C./minute.

【００２７】通電前のガラスと通電後のガラスを１ｃｍ
の厚さに切り出して２つの試料を作製し、これら試料に
光学研磨を施した後、光吸収スペクトルを測定した。そ
の結果を図２に示す。1 cm of glass before and after energization
Two samples were prepared by cutting out to a thickness of 2, and the samples were subjected to optical polishing, and then the light absorption spectrum was measured. The result is shown in FIG.

【００２８】図２から明らかなように通電後のガラス
は、１０００ｎｍ付近にピークを有する青色の着色原因
であるＦｅ2+の吸収が大きく減少し、見かけ上無色であ
ることが確認された。As is apparent from FIG. 2, it was confirmed that the glass after energization had a significantly reduced absorption of Fe 2+ , which is a cause of coloring blue having a peak near 1000 nm, and was apparently colorless.

【００２９】また、酸化錫が添加されていない以外、実
施例１と同様な工業用ソーダ石灰ガラスを実施例１と同
様な通電処理を施すことにより得られたガラス（比較例
１）と本実施例１で得られたガラスについて、通電前に
対する通電後のＦｅ2+／Ｆｅ 3+比の減少率を測定した。
その結果、比較例１のガラスはその減少率が２０％であ
ったのに対し、本実施例１のガラスはその減少率が約１
５％になり、Ｆｅ2+を効果的に減少できた。In addition, except that tin oxide was not added,
The same industrial soda lime glass as in Example 1 was used as in Example 1.
Glass obtained by applying a current-carrying treatment (comparative example
1) and the glass obtained in this Example 1, before energization
Fe after energizing2+/ Fe 3+The rate of decrease of the ratio was measured.
As a result, the reduction ratio of the glass of Comparative Example 1 was 20%.
In contrast, the reduction rate of the glass of Example 1 is about 1
5%, Fe2+Can be effectively reduced.

【００３０】[0030]

【発明の効果】以上詳述したように、本発明によれば有
害なセレン化合物を用いることなく、酸化錫の添加、ガ
ラス融液への通電処理により環境に有害な金属を含まな
い無色工業用ソーダ石灰ガラスを製造し得る方法を提供
することができる。As described in detail above, according to the present invention, it is possible to add tin oxide and to energize the glass melt without the use of harmful selenium compounds. A method capable of producing soda-lime glass can be provided.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の無色工業用ソーダ石灰ガラスを製造す
るための通電装置を示す概略図。FIG. 1 is a schematic view showing an energization device for producing a colorless industrial soda-lime glass of the present invention.

【図２】本発明の実施例１における通電前および通電後
のガラスの光吸収スペクトルを示す図。FIG. 2 is a diagram showing optical absorption spectra of glass before and after conducting electricity in Example 1 of the present invention.

【符号の説明】[Explanation of symbols]

１…支持部材、 ３…溶融るつぼ、 ４…陽極、 ６…陰極。 1 ... Support member, 3 ... melting crucible, 4 ... Anode, 6 ... Cathode.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 低原子価の状態で着色の原因になる鉄を
含む工業用ソーダ石灰ガラスの原料から無色の工業用ソ
ーダ石灰ガラスを製造するにあたり、前記原料に酸化錫
を加えた後、溶融してガラス融液を調製する工程と、 前記ガラス融液に陽極および陰極を挿入し、これら陽極
と陰極の間に直流電圧を印加して酸素気泡を連続的に発
生させて前記ガラス融液中の鉄を高原子価にする工程と
を具備したことを特徴とする無色工業用ソーダ石灰ガラ
スの製造方法。1. In producing a colorless industrial soda-lime glass from a raw material of industrial soda-lime glass containing iron that causes coloring in a low valence state, after tin oxide is added to the raw material, melting is performed. And a step of preparing a glass melt, insert an anode and a cathode in the glass melt, a direct current voltage is applied between the anode and the cathode to generate oxygen bubbles continuously, and in the glass melt And a step of making iron have a high valence. 【請求項２】 前記酸化錫は、前記原料に対して０．１
〜２モル％添加することを特徴とする請求項１記載の無
色工業用ソーダ石灰ガラスの製造方法。2. The tin oxide is 0.1 to the raw material.
The method for producing a colorless industrial soda-lime glass according to claim 1, wherein the amount is ˜2 mol%. 【請求項３】 前記陰極は、前記ガラス融液の液面近傍
に挿入され、かつ前記陽極は前記陰極より下方の前記ガ
ラス融液に挿入されることを特徴とする請求項１記載の
無色工業用ソーダ石灰ガラスの製造方法。3. The colorless industry according to claim 1, wherein the cathode is inserted near the liquid surface of the glass melt, and the anode is inserted in the glass melt below the cathode. For producing soda-lime glass for automobiles. 【請求項４】 前記陽極と陰極の間に印加する直流電圧
は、０．２Ｖ以上であることを特徴とする請求項１記載
の無色工業用ソーダ石灰ガラスの製造方法。4. The method for producing colorless industrial soda-lime glass according to claim 1, wherein the DC voltage applied between the anode and the cathode is 0.2 V or more. 【請求項５】 前記酸素気泡は、平均径が１ｍｍ以上で
あることを特徴とする請求項１記載の無色工業用ソーダ
石灰ガラスの製造方法。5. The method for producing colorless industrial soda-lime glass according to claim 1, wherein the oxygen bubbles have an average diameter of 1 mm or more. 【請求項６】 前記酸素気泡は、平均径が１ｍｍ以上
で、かつ最大径と最小径との差が１ｍｍ以下であること
を特徴とする請求項１記載の無色工業用ソーダ石灰ガラ
スの製造方法。6. The method for producing colorless industrial soda-lime glass according to claim 1, wherein the oxygen bubbles have an average diameter of 1 mm or more and a difference between a maximum diameter and a minimum diameter of 1 mm or less. .
JP2001236706A 2001-08-03 2001-08-03 Method for producing colorless industrial soda-lime glass Expired - Lifetime JP3837476B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2001236706A JP3837476B2 (en) 2001-08-03 2001-08-03 Method for producing colorless industrial soda-lime glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001236706A JP3837476B2 (en) 2001-08-03 2001-08-03 Method for producing colorless industrial soda-lime glass

Publications (2)

Publication Number Publication Date
JP2003048720A true JP2003048720A (en) 2003-02-21
JP3837476B2 JP3837476B2 (en) 2006-10-25

Family

ID=19067926

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2001236706A Expired - Lifetime JP3837476B2 (en) 2001-08-03 2001-08-03 Method for producing colorless industrial soda-lime glass

Country Status (1)

Country Link
JP (1) JP3837476B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104926086A (en) * 2015-06-29 2015-09-23 江苏华尔石英材料股份有限公司 Electrode unit for melting of large-size quartz crucibles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104926086A (en) * 2015-06-29 2015-09-23 江苏华尔石英材料股份有限公司 Electrode unit for melting of large-size quartz crucibles

Also Published As

Publication number Publication date
JP3837476B2 (en) 2006-10-25

Similar Documents

Publication Publication Date Title
JP6911085B2 (en) Highly transparent glass with high solarization resistance, their use and method of manufacturing them
JP4790783B2 (en) Manufacturing method of glass plate
JP5361157B2 (en) Glass manufacturing method and system capable of avoiding chemical reduction of glass components
CN1208273C (en) Palely colored glass having transmittance and method for producing the same
TWI303240B (en) Producing glass using outgassed frit
JP5389450B2 (en) Apparatus and method for continuous clarification of glass with high purity specifications
EP2601148B1 (en) Lithium aluminosilicate glasses; glass-ceramics of -quartz and/or -spodumene; articles in said glasses and glass-ceramics; methods for obtaining the same
JP2011513183A (en) Glass manufacturing method
JP7425128B2 (en) composite glass
JP2007126296A (en) Method and apparatus for manufacturing optical glass
KR20070040335A (en) Method for coloring surface of zirconium-based metallic glass component
JPH11217235A (en) High-temperature resistant aluminosilicate glass for lamp bulb and its use
JP4298980B2 (en) High transmission glass plate and method of manufacturing high transmission glass plate
JP2008105940A (en) Glass/frit with iron selenide complex
US3940531A (en) Stain decorated glass-ceramic article
JP2003048720A (en) Method for manufacturing colorless industrial soda-lime glass
DE2532969A1 (en) METHOD OF MANUFACTURING GLASS
JPWO2017110906A1 (en) Method for producing borosilicate glass
JPH0432018B2 (en)
US3852052A (en) Method of producing decorated glass-ceramic surfaces
JP5028679B2 (en) Lead-free crystal ice manufacturing method and decorative plate glass manufacturing method using the same
JP7094492B2 (en) Treatment method of glass for radiation detection
JP2007308348A (en) Fluorescence emitting glass and method of manufacturing the same
JP2007126297A (en) Method of and device for producing optical glass
US2408468A (en) Glass composition

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20010803

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20040227

A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A712

Effective date: 20040521

RD03 Notification of appointment of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7423

Effective date: 20040729

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20050301

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20050408

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20060425

R155 Notification before disposition of declining of application

Free format text: JAPANESE INTERMEDIATE CODE: R155

R150 Certificate of patent or registration of utility model

Ref document number: 3837476

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

EXPY Cancellation because of completion of term