JPH0444619B2 - - Google Patents
Info
- Publication number
- JPH0444619B2 JPH0444619B2 JP5013987A JP5013987A JPH0444619B2 JP H0444619 B2 JPH0444619 B2 JP H0444619B2 JP 5013987 A JP5013987 A JP 5013987A JP 5013987 A JP5013987 A JP 5013987A JP H0444619 B2 JPH0444619 B2 JP H0444619B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- chalcogenide glass
- present
- raw material
- infrared
- 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
Links
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000005387 chalcogenide glass Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 7
- -1 silicon telluride compound Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 description 15
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000003708 ampul Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
Description
［産業上の利用分野］
本発明は１〜16μm領域に赤外透過性を有する
カルコゲナイドガラス、特にSi、Teを成分とし
て含有するガラスの製造方法に関するものであ
る。
［従来の技術］
カルコゲナイドガラスに於いては、Teは安定
でしかも赤外線を良く透過するガラスが得られる
ため、溶融温度、化学的耐久性を向上させ得る点
で有利であるが、溶解が困難であるという欠点を
有している。
従来、波長１〜16μm領域の赤外透過性を有す
るカルコゲナイドガラス製造方法はガラス組成原
料に酸化物になり易い金属、例えばAl，Zr，Mg
などを100ppm以下添加し、洗浄した石英アンプ
ルに充填した後、真空封入した石英アンプルを加
熱溶融することにより得ていた。
［発明が解決しようとする問題点］
ところがSiを含むカルコゲナイドガラスを上記
の方法を用いて、溶融すると、Siがガラス中に溶
け込みにくく、最後まで粒子として残留し、これ
が散乱の原因となり、赤外、特に2μm以上の波長
域の透過損失を著しく増大せしめていた。
さらにSi原料は、表面が酸化されやすく、この
酸素がカルコゲナイドガラス中に溶解し、透過損
失と原因となつていた。又Teは酸素を含有しや
すく、これも透過損失の原因となつていた。
従つて、本発明の目的は第１にSi、Teを含む
カルコゲナイドガラスに於いて、ガラスを安定に
し、溶融温度、化学的耐久性を向上させ得るSiを
ガラス中に粒子として残留させることなく、溶解
せしめる方法を提供することにあり、第２には、
酸素の含有率が極めて少ないSi、Teを含むカル
コゲナイドガラスの製造方法を提供することにあ
る。
［問題点を解決するための手段］
本発明はこれらの問題点は下記の手段を採用す
ることにより解決し得ることを見出してなつても
のである。すなわち、本発明はSi、Teを含有す
るカルコゲナイドガラスの製造方法に於いて、原
料としてテルル化珪素化合物を使用することから
なるもので、このような手段により、容易にSiを
ガラス中に溶解せしめることが可能となる。
また表面が酸化されたSi原料はフツ酸水溶液で
処理することにより、表面の酸化された部分を除
去することが可能であり、Te中の酸素は酸化物
になり易い金属、例えばAl、Mg、Zrを微量添加
して蒸留精製することにより除去することができ
る。
テルル化珪素化合物は上記の方法によつて得ら
れたSi、Geを非酸化性の雰囲気中で所定の割合
秤量、混合し、洗浄、空焼きした石英アンプル中
に充填後、真空封入し、かつ溶融することにより
得られる。
［作用］
上記のように本発明の方法によれば、Siの原料
をSiとTeの化合物の形で使用するため、Siにこ
の化合物は、単味の融点よりも著しく低くなり、
Siは完全にガラス中に溶解し得る。Si原料の酸化
された表面はフツ酸水溶液で処理することにより
溶解、除去されるため、酸素はガラス中に混入す
ることはない。又Te原料中の酸素は、微量の酸
化物になり易い金属結合し、蒸留により除去され
る。
［実施例］
10％のフツ酸水溶液で１時間処理した純度
99.9999％のSiは加熱処理を行う。純度99.9999％
のTeは酸化物になり易い金属Mgを100ppm加え、
蒸留精製を行う。
各々処理を行つたSiとTeをアルゴン雰囲気中
で１：５の割合で秤量し、洗浄、空焼きした石英
アンプルに充填した後、真空封入した。電気炉に
アンプルを入れ攪拌しながら、550℃で２時間余
熱した後、1000℃に加熱し、50時間保持した。次
に電気炉の電源を切り、ただちに石英アンプルを
取り出し、空気中で冷却した。このように作製し
たテルル化珪素化合物50％、Ge10％、As40％、
を再度アルゴンガス雰囲気中で秤量し、洗浄、空
焼きした石英アンプルに充填した後、真空封入し
た。次にテルル化シリコン化合物を得た方法を用
い、加熱溶融及び冷却を行い、ガラスロツドを得
た。
下表に本発明を実施して作製したSi20Te80の
DSC（示差走査熱量計）の測定結果及びSiの融点
（参考文献：岩波理化学辞典）を比較したものを
示す。
[Industrial Application Field] The present invention relates to a method for producing chalcogenide glass having infrared transparency in the 1-16 μm region, particularly glass containing Si and Te as components. [Prior art] In chalcogenide glass, Te is stable and can transmit infrared rays well, so it is advantageous in that it can improve the melting temperature and chemical durability, but it is difficult to melt. It has some drawbacks. Conventionally, chalcogenide glass manufacturing methods that have infrared transmittance in the wavelength range of 1 to 16 μm use metals that easily become oxides, such as Al, Zr, and Mg, as raw materials for glass composition.
It was obtained by adding 100 ppm or less of such substances, filling them into a cleaned quartz ampoule, and then heating and melting the vacuum-sealed quartz ampoule. [Problems to be solved by the invention] However, when chalcogenide glass containing Si is melted using the above method, Si is difficult to dissolve in the glass and remains as particles until the end, which causes scattering and infrared radiation. In particular, the transmission loss in the wavelength range of 2 μm or more was significantly increased. Furthermore, the surface of the Si raw material is easily oxidized, and this oxygen dissolves into the chalcogenide glass, causing transmission loss. Furthermore, Te tends to contain oxygen, which also causes transmission loss. Therefore, the first object of the present invention is to stabilize a chalcogenide glass containing Si and Te without leaving Si as particles in the glass, which can improve the melting temperature and chemical durability of the glass. The second purpose is to provide a method for dissolving
The object of the present invention is to provide a method for producing chalcogenide glass containing Si and Te with extremely low oxygen content. [Means for Solving the Problems] The present invention has found that these problems can be solved by adopting the following means. That is, the present invention is a method for producing chalcogenide glass containing Si and Te, which consists of using a silicon telluride compound as a raw material, and by such means, Si can be easily dissolved into the glass. becomes possible. In addition, by treating Si raw materials with oxidized surfaces with a hydrofluoric acid aqueous solution, it is possible to remove the oxidized parts of the surface, and the oxygen in Te can be used to remove metals that easily become oxides, such as Al, Mg, etc. It can be removed by adding a small amount of Zr and purifying it by distillation. A silicon telluride compound is prepared by weighing and mixing Si and Ge obtained by the above method in a predetermined proportion in a non-oxidizing atmosphere, filling it into a cleaned and air-baked quartz ampoule, and then vacuum-sealing it. Obtained by melting. [Function] As described above, according to the method of the present invention, since the Si raw material is used in the form of a compound of Si and Te, the melting point of this compound in Si is significantly lower than that of the simple substance.
Si can be completely dissolved in glass. Since the oxidized surface of the Si raw material is dissolved and removed by treatment with a hydrofluoric acid aqueous solution, oxygen does not mix into the glass. Furthermore, the oxygen in the Te raw material is likely to form a trace amount of metal bonding to form an oxide, which is removed by distillation. [Example] Purity treated with 10% hydrofluoric acid aqueous solution for 1 hour
99.9999% Si is heat treated. Purity 99.9999%
For Te, add 100ppm of Mg, a metal that easily becomes an oxide.
Perform distillation purification. The treated Si and Te were weighed at a ratio of 1:5 in an argon atmosphere, filled into a cleaned and fired quartz ampoule, and then vacuum sealed. The ampoule was placed in an electric furnace and preheated at 550°C for 2 hours while stirring, then heated to 1000°C and held for 50 hours. The electric furnace was then turned off, and the quartz ampoules were immediately removed and cooled in air. The silicon telluride compound prepared in this way was 50%, Ge10%, As40%,
The sample was weighed again in an argon gas atmosphere, filled into a cleaned and air-baked quartz ampoule, and then vacuum sealed. Next, using the method used to obtain the silicon telluride compound, heating and melting and cooling were performed to obtain a glass rod. The table below shows the Si 20 Te 80 produced by implementing the present invention.
A comparison of the measurement results of DSC (differential scanning calorimeter) and the melting point of Si (reference: Iwanami Dictionary of Physical and Chemical Sciences) is shown.
【表】
明らかにSiと比較するとSi20Te80は融点が低
い。図に本発明を実施して作製したSi10ョe10As40
Te40の赤外透過性を本発明を実施しないガラス
サンプルと比較して示した。図から明らかな通
り、本発明を実施したガラスの赤外透過性Ａは本
発明を実施しないガラスサンプルの赤外透過性Ｂ
と比較して短波長側の落ちこみは非常に少ない。
故に同一条件で製造したガラスでも本発明を実施
たガラスは均一化に大きな効果を有し、１〜
16μmの赤外波長域の光学特性の改善に役立つこ
とがわかる。
［発明の効果］
実施例で示したように本発明によれば、カルコ
ゲナイドガラスの原料の調合に際し、溶解しなく
いSi原料をより融点の低いテルル化珪素化合物の
形で使用するため、Siはガラス中で粒子として残
留することがないため、散乱によつて生ずる透過
損失の少ない安定で、融点、化学的耐久性の高い
カルコゲナイドガラスを得ることができる。又テ
ルル化珪素化合物を得るに際し、Si原料はその表
面をフツ酸水溶液で処理することにより、表面の
酸化物を除去し、Te原料中の微量の酸化物にな
い注水金属を加え、蒸留により除去するため、酸
素の吸収の少ないカルコゲナイドガラスが得られ
る。[Table] Obviously, compared to Si, Si 20 Te 80 has a lower melting point. The figure shows Si 10 10 As 40 produced by implementing the present invention.
The infrared transmission of Te 40 is shown in comparison to a glass sample not implementing the invention. As is clear from the figure, the infrared transmittance A of the glass that implemented the present invention is the infrared transmittance B of the glass sample that did not implement the present invention.
Compared to , the drop on the short wavelength side is very small.
Therefore, even if the glass is manufactured under the same conditions, the glass according to the present invention has a great effect on uniformity, and
It can be seen that this is useful for improving optical properties in the infrared wavelength region of 16 μm. [Effects of the Invention] As shown in the examples, according to the present invention, when preparing the raw material for chalcogenide glass, an undissolved Si raw material is used in the form of a silicon telluride compound with a lower melting point. Since it does not remain as particles in the glass, it is possible to obtain a stable chalcogenide glass with little transmission loss caused by scattering, a high melting point, and high chemical durability. In addition, when obtaining a silicon telluride compound, the surface of the Si raw material is treated with an aqueous solution of hydrofluoric acid to remove the oxides on the surface, a water injection metal that is not present in trace amounts of oxides in the Te raw material is added, and then removed by distillation. Therefore, a chalcogenide glass with low oxygen absorption can be obtained.
図は本発明の製造方法によつて得られたカルコ
ゲナイドガラスSi10Ge10As40Te40の分光透過率Ａ
と従来の製造方法によつて得られたカルコゲナイ
ドガラスSi10Ge10As40Te40の分光透過率Ｂを比較
して示したものである。
The figure shows the spectral transmittance A of chalcogenide glass Si 10 Ge 10 As 40 Te 40 obtained by the manufacturing method of the present invention.
The figure shows a comparison of the spectral transmittance B of chalcogenide glass Si 10 Ge 10 As 40 Te 40 obtained by a conventional manufacturing method.
Claims (1)
製造方法に於いて、原料としてテルル化珪素化合
物を使用することを特徴とするカルコゲナイドガ
ラスの製造方法。 ２ Siはフツ酸水溶液により、Teは酸化物にな
り易い金属を加え蒸留することにより精製するこ
とを特徴とする特許請求の範囲第１項記載のカル
コゲナイドガラスの製造方法。[Claims] 1. A method for producing chalcogenide glass containing Si and Te, characterized in that a silicon telluride compound is used as a raw material. 2. The method for producing chalcogenide glass according to claim 1, wherein Si is purified by an aqueous hydrofluoric acid solution, and Te is purified by adding a metal that easily becomes an oxide and distilling the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5013987A JPS63218521A (en) | 1987-03-06 | 1987-03-06 | Production of chalcogenide glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5013987A JPS63218521A (en) | 1987-03-06 | 1987-03-06 | Production of chalcogenide glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63218521A JPS63218521A (en) | 1988-09-12 |
| JPH0444619B2 true JPH0444619B2 (en) | 1992-07-22 |
Family
ID=12850814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5013987A Granted JPS63218521A (en) | 1987-03-06 | 1987-03-06 | Production of chalcogenide glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63218521A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034494C (en) * | 1992-07-11 | 1997-04-09 | 武汉工业大学 | Glass composition containing sulfure halide |
| CN1278927A (en) * | 1997-11-04 | 2001-01-03 | 康宁股份有限公司 | Stable cladding glasses for sulphide fibres |
-
1987
- 1987-03-06 JP JP5013987A patent/JPS63218521A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63218521A (en) | 1988-09-12 |
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