JPH0825749B2 - Method for producing high fluorine content glass - Google Patents
Method for producing high fluorine content glassInfo
- Publication number
- JPH0825749B2 JPH0825749B2 JP5112287A JP5112287A JPH0825749B2 JP H0825749 B2 JPH0825749 B2 JP H0825749B2 JP 5112287 A JP5112287 A JP 5112287A JP 5112287 A JP5112287 A JP 5112287A JP H0825749 B2 JPH0825749 B2 JP H0825749B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- fluorine content
- high fluorine
- present
- melting
- 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 - Lifetime
Links
- 239000011521 glass Substances 0.000 title claims description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052731 fluorine Inorganic materials 0.000 title claims description 13
- 239000011737 fluorine Substances 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 239000005383 fluoride glass Substances 0.000 description 2
- 239000005303 fluorophosphate glass Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】 ［産業上の技術分野］ 本発明は、白金等の貴金属製のガラス溶融容器の劣化
損傷を防止しつつ、実質的に泡や容器溶出物のない高品
質の弗燐酸塩ガラスや弗化物ガラス等の弗素高含有ガラ
スを製造する方法に関する。Description: TECHNICAL FIELD The present invention relates to a high-quality fluorophosphoric acid substantially free from bubbles and container elution while preventing deterioration and damage of a glass melting container made of a precious metal such as platinum. The present invention relates to a method for producing a high fluorine content glass such as salt glass or fluoride glass.
［従来の技術］ 従来、上記の弗素高含有ガラスの用途として、光学用
ガラス、フィルターガラスおよびレーザー用ガラス等が
知られている。しかし、これらのガラスは、溶融中に微
小泡が多数発生し、これが消失し難いため、製品中に残
留して品質を著しく低下させる欠点がある。[Prior Art] Optical glass, filter glass, laser glass, and the like have been conventionally known as applications of the above-mentioned fluorine-rich glass. However, these glasses have a drawback that a large number of micro bubbles are generated during melting and are hard to disappear, so that they remain in the product and significantly deteriorate the quality.
一般に、ガラスの脱泡方法としては、As2O3やSb2O3等
の清澄剤を添加した粉末バッチ原料を溶融する方法が知
られているが、弗素高含有ガラスの場合は、溶融温度が
低いため、この方法を用いても殆ど効果がない。上記問
題の解決を試みたガラスとして、たとえば特開昭55−10
9242号公報には、沃素および／または臭素を0.1アニオ
ニック％以上添加してなる弗燐酸塩ガラスが開示されて
いる。この公報には、上記成分の具体的添加方法につい
て、何ら開示されていないが、添加量が多いため、ガラ
ス溶融の際、これらの成分が白金等の容器を侵して次第
に脆化させ、また容器にクラック等の損傷を招きやすい
欠点がある。また、上記容器の脆化損傷は、ガラスの汚
染原因となり、その品質を劣化させやすい。Generally, as a method for defoaming glass, a method of melting a powder batch raw material to which a fining agent such as As 2 O 3 or Sb 2 O 3 is added is known, but in the case of a glass having a high fluorine content, a melting temperature is high. Is low, this method has almost no effect. As a glass attempting to solve the above problems, for example, JP-A-55-10
Japanese Patent Publication No. 9242 discloses a fluorophosphate glass obtained by adding iodine and / or bromine in an amount of 0.1 anionic% or more. This publication does not disclose any specific addition method of the above components, but since the addition amount is large, when glass is melted, these components attack a container such as platinum and gradually embrittle, and Has a drawback that it is apt to cause damage such as cracks. In addition, the embrittlement damage of the container is a cause of glass contamination, and the quality thereof is likely to deteriorate.
［発明が解決しようとする問題点］ 本発明は、上記の状況にかんがみてなされたもので、
その目的とするところは、溶融容器の脆化損傷を防止し
つつ、脱泡均質化を行い、実質的に微小泡や容器からの
溶出物のない高品質の弗素高含有ガラスを製造する新規
な方法を提供することにある。[Problems to be Solved by the Invention] The present invention has been made in consideration of the above situation,
The purpose is to carry out defoaming homogenization while preventing brittle damage to the melting vessel, and to produce a high-quality fluorine-rich glass that is substantially free of fine bubbles and elution from the vessel. To provide a method.
［問題点を解決するための手段］ 本発明者は、上記目的を達成するため鋭意試験研究を
重ねた結果、弗素高含有ガラスの製造に当たり、清澄剤
の添加を通常行なわれる多成分調合粉末原料（バッチ原
料）中に添加するのではなく、バッチ原料溶融後生成す
るガラス体の存在下において塩素および／または沃素お
よび／または臭素を添加する場合は、意外にも、これら
の成分の添加量は、極めて少量で所期の効果が得られる
ことをみいだし、本発明をなすに至った。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, in the production of a fluorine-rich glass, a fining agent is usually added to prepare a multi-component blended powder raw material. Surprisingly, when chlorine and / or iodine and / or bromine are added in the presence of the glass body produced after melting the batch raw material, instead of adding it into the (batch raw material), the addition amount of these components is It was found that the desired effect can be obtained with an extremely small amount, and the present invention has been completed.
本発明にかかる弗素高含有ガラスの製造方法は、特許
請求の範囲に記載のとおり、弗素高含有ガラスを製造す
るに当り、バッチ原料溶融後生成されたガラス体の存在
下において、アニオニック％で0.0001〜0.1％未満の塩
素、沃素および臭素の１種以上の成分を添加した後、脱
泡均質化することを特徴とする。As described in the scope of the claims, the method for producing a glass having a high fluorine content according to the present invention, when producing a glass having a high fluorine content, in the presence of a glass body produced after melting a batch raw material, 0.0001 as an anion% Characteristically, defoaming is homogenized after adding at least one component of chlorine, iodine and bromine of less than 0.1%.
上記添加剤のガラス中の含有量の総量は、上記溶融容
器の浸食脆化を防止し、かつ、所望の清澄均質化効果を
得るため、アニオニック％で、0.0001〜0.1％未満、好
ましくは0.001〜0.1％未満であることが必要である。な
お、本発明の方法において、ガラスの溶融雰囲気は、必
要に応じ、中性または酸化性等の雰囲気を適宜選び得
る。また、上記添加剤は、固状ないし液状の状態下にあ
る上記ガラス体に適宜添加し得る。The total content of the additives in the glass, to prevent erosion embrittlement of the melting vessel, and to obtain the desired fining homogenization effect, in anionic%, 0.0001 ~ less than 0.1%, preferably 0.001 ~. It must be less than 0.1%. In addition, in the method of the present invention, the melting atmosphere of the glass may be appropriately selected from a neutral atmosphere, an oxidizing atmosphere, or the like, if necessary. Further, the above-mentioned additives can be appropriately added to the above-mentioned glass body in a solid or liquid state.
［実施例］ つぎに、本発明の方法を実施例にもとづき説明する。EXAMPLES Next, the method of the present invention will be described based on examples.
本発明の方法の実施に当っては、実質的に、カチオニ
ック％で、1/2P2O50〜60％、PF50〜20％、RIF（LiF＋Na
F＋KF等）０〜40％、RIIF（MgF2＋CaF2＋SrF2＋BaF2＋Z
nF2＋PbF2等）10〜70％、RIIIF（AlF3＋YF3＋LaF3等）
５〜45％、RIVF（ZrF4＋HfF4等）０〜30％、1/2B2O30〜
30％、1/2Nd2O30〜５％の組成を有する弗素高含有ガラ
スを基礎として使用することが好ましい。表−１は、そ
の好適な基礎ガラス組成（比較例）と本発明の方法によ
り、この基礎ガラスに塩素（Cl）、沃素（Ｉ）および臭
素（Br）を外割添加して得られるガラス組成例とについ
て、脱泡状況比較試験結果とともに示したものである。Is the practice of the method of the present invention, essentially, by cationic%, 1 / 2P 2 O 5 0~60%, PF 5 0~20%, R I F (LiF + Na
0 to 40%, R II F (MgF 2 + CaF 2 + SrF 2 + BaF 2 + Z)
nF 2 + PbF 2 etc.) 10 to 70%, R III F (AlF 3 + YF 3 + LaF 3 etc.)
5 to 45%, R IV F (ZrF 4 + HfF 4, etc.) 0 to 30%, 1 / 2B 2 O 3 0 to
Preference is given to using a high fluorine content glass with a composition of 30%, 1/2 Nd 2 O 3 0-5%. Table 1 shows a glass composition obtained by adding externally added chlorine (Cl), iodine (I) and bromine (Br) to this basic glass by the preferred basic glass composition (comparative example) and the method of the present invention. It is shown together with the results of the defoaming situation comparison test for the examples.
表記のガラスが得られるように調合したバッチ原料を
炉内白金るつぼ中に投入し、組成による溶融の難易度に
応じて900〜1150℃でバッチがかなり残存するもガラス
化してガラス体が存在する状態に粗溶融した後、炉温を
約550〜700℃に低下し、溶融ガラス中にCl、ＩおよびBr
を表記のアニオニック％量で外割添加して撹拌混合す
る。ついで、再度炉温を900〜1150℃に上げ脱泡均質化
処理を行なった後、再び炉温を500〜700℃に下げガラス
を鋳型に鋳込みブロックを得る。Put the batch raw material prepared so as to obtain the indicated glass into the platinum crucible in the furnace, and depending on the degree of difficulty of melting due to the composition, even if the batch remains considerably at 900 to 1150 ° C, there is vitrified glass body After roughly melting into a state, the furnace temperature was lowered to about 550-700 ° C, and Cl, I and Br were added to the molten glass.
Is added in an aliquot% of the indicated anionic amount and mixed with stirring. Then, the furnace temperature is raised again to 900 to 1150 ° C. to carry out defoaming homogenization treatment, and then the furnace temperature is lowered again to 500 to 700 ° C. and glass is cast into a mold to obtain a block.
これらの実施例および比較例により得られたブロック
を研磨し、ガラス100ml中の泡の断面積を測定し、その
総和Ａ（mm2）を求めたところ、表記の結果を得た。The blocks obtained in these Examples and Comparative Examples were polished, the cross-sectional area of bubbles in 100 ml of glass was measured, and the total A (mm 2 ) thereof was determined. The results shown were obtained.
表にみられるとおり、本発明の方法により得られるガ
ラスのＡ値は、0.08以下であるのに対し、比較例の各ガ
ラスのＡ値は、いずれも1.3以上であり、両各例の差は
顕著であると認められる。 As can be seen from the table, the A value of the glass obtained by the method of the present invention is 0.08 or less, whereas the A value of each glass of the comparative example is 1.3 or more, and the difference between both examples is Remarkable.
以上、本発明の実施例につき説明したが、本発明は、
上記実施例の方法に限定されるものではなく、たとえ
ば、添加剤の添加に際しては、バッチ原料を完全にガラ
ス化させた後の溶融ガラス体に添加してもよく、あるい
は、ガラスカレットを必要に応じバッチ原料とともに再
生利用する過程で添加してもよく、本発明の技術思想を
逸脱しない範囲で適宜改変しうる。The embodiments of the present invention have been described above.
The method is not limited to the method of the above-mentioned example, and for example, in the case of adding an additive, it may be added to the molten glass body after the batch raw material is completely vitrified, or a glass cullet is required. Accordingly, it may be added together with the batch raw material in the process of recycling, and may be appropriately modified without departing from the technical idea of the present invention.
なお、本発明の方法により得られる弗素高含有ガラス
中に含まれる上記添加剤の量は、比較的微量であるが、
高精度で検出測定可能であるので、最適添加含有量を工
程管理することが可能である。The amount of the above additive contained in the fluorine-rich glass obtained by the method of the present invention is relatively small,
Since it is possible to detect and measure with high accuracy, it is possible to control the optimum addition content in the process.
［発明の効果］ 上述のとおり、本発明にかかる弗素高含有ガラスの製
造方法は、ガラス化状態のガラス体の存在化において、
アニオニック％で0.0001〜0.1％未満の微量の塩素、沃
素および臭素の１種以上の成分を添加した後、脱泡均質
化する構成であるから、泡と貴金属溶出粒子が実質的に
ない光学用、フィルター用およびレーザー用等の弗燐酸
塩ガラスや弗化物ガラスを安定して取得し得る。[Effects of the Invention] As described above, the method for producing a glass having a high fluorine content according to the present invention, in the presence of a glass body in a vitrified state,
After adding a trace amount of one or more components of chlorine, iodine, and bromine in anionic% of 0.0001 to less than 0.1%, defoaming is homogenized, so that bubbles and noble metal elution particles are substantially absent for optics. It is possible to stably obtain fluorophosphate glass and fluoride glass for filters and lasers.
Claims (1)
ッチ原料溶融後生成されたガラス体の存在下において、
アニオニック％で0.0001〜0.1％未満の塩素、沃素およ
び臭素の１種以上の成分を添加した後、脱泡均質化する
ことを特徴とする弗素高含有ガラスの製造方法。1. When producing a glass having a high fluorine content, in the presence of a glass body produced after melting a batch raw material,
A method for producing a glass having a high fluorine content, which comprises adding 0.001 to less than 0.1% by weight of anion of one or more components of chlorine, iodine and bromine, and homogenizing the defoaming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5112287A JPH0825749B2 (en) | 1987-03-04 | 1987-03-04 | Method for producing high fluorine content glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5112287A JPH0825749B2 (en) | 1987-03-04 | 1987-03-04 | Method for producing high fluorine content glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63215524A JPS63215524A (en) | 1988-09-08 |
| JPH0825749B2 true JPH0825749B2 (en) | 1996-03-13 |
Family
ID=12877999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5112287A Expired - Lifetime JPH0825749B2 (en) | 1987-03-04 | 1987-03-04 | Method for producing high fluorine content glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0825749B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358817C (en) * | 2000-08-17 | 2008-01-02 | Hoya株式会社 | Method for producing glass and apparatus for melting glass |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01224231A (en) * | 1988-03-01 | 1989-09-07 | Nippon Sheet Glass Co Ltd | Production of glass |
| JPH06340445A (en) * | 1993-05-28 | 1994-12-13 | Kirin Brewery Co Ltd | Yellow colored glass |
-
1987
- 1987-03-04 JP JP5112287A patent/JPH0825749B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358817C (en) * | 2000-08-17 | 2008-01-02 | Hoya株式会社 | Method for producing glass and apparatus for melting glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63215524A (en) | 1988-09-08 |
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