JPH0361621B2 - - Google Patents
Info
- Publication number
- JPH0361621B2 JPH0361621B2 JP58054556A JP5455683A JPH0361621B2 JP H0361621 B2 JPH0361621 B2 JP H0361621B2 JP 58054556 A JP58054556 A JP 58054556A JP 5455683 A JP5455683 A JP 5455683A JP H0361621 B2 JPH0361621 B2 JP H0361621B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- glass
- infrared
- csbr
- cucl
- 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
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 15
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 5
- 239000005283 halide glass Substances 0.000 claims description 4
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims 2
- 239000000463 material Substances 0.000 description 19
- 239000011521 glass Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000005383 fluoride glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 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
-
- 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
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/041—Non-oxide glass compositions
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)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
本発明は赤外線の伝送に有用な赤外透過用ハラ
イドガラスに関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an infrared transmitting halide glass useful for transmitting infrared rays.
従来から使用されている光伝送体は主として石
英（SiO2）を主体とした酸化物ガラスであつた。
しかし、この種のガラスはその網目を形成するSi
とＯの間の結合が強く、波長4μm以上の、赤外域
においてSi−Ｏ結合の格子振動に起因する吸収が
存在するため、赤外線伝送用には使えなかつた。
赤外領域において透明な窓を有する材料として現
在までに知られているものには、フツ化ジルコニ
ウム（ZrF4）あるいはフツ化ベリリウム（BeF2）
を主体としたフツ化物ガラス、塩化亜鉛
（ZnCl2）あるいは塩化ビスマス（BiCl3）を主体
としたハライドガラス（Ｆは含まれない）、及び
タリウム（Tll）、銀（Ag）、アルカリ（Na，Ｋ，
Cs）のハロゲン化物を主体とした多結晶体、あ
るいは単結晶体がある。しかし、フツ化物ガラス
は、酸化物ガラスと同様に4μm以上に骨格の振動
による吸収が存在するため、透過し得る波長領域
は２〜4μmと狭い。また、他のハライドガラス
は、主成分になるZnCl2，BiCl3の著しい潮解性
のために実用性に欠ける。 Conventionally used optical transmission bodies have been mainly oxide glasses mainly composed of quartz (SiO 2 ).
However, this type of glass has Si that forms its network.
Because the bond between and O is strong, and there is absorption due to lattice vibration of the Si--O bond in the infrared region with a wavelength of 4 μm or more, it could not be used for infrared transmission.
Materials currently known to have transparent windows in the infrared region include zirconium fluoride (ZrF 4 ) and beryllium fluoride (BeF 2 ).
fluoride glass mainly composed of zinc chloride (ZnCl 2 ) or bismuth chloride (BiCl 3 ) (no F included), and thallium (Tll), silver (Ag), alkali (Na, K,
There are polycrystalline and single-crystalline forms mainly composed of halides of Cs). However, like oxide glass, fluoride glass exhibits absorption due to vibration of its skeleton at 4 μm or more, so the wavelength range that can be transmitted is narrow, from 2 to 4 μm. In addition, other halide glasses lack practicality due to the significant deliquescent properties of ZnCl 2 and BiCl 3 , which are the main components.
さらに多結晶体の場合は、粒界散乱による損失
が大きいために、また単結晶体の場合は結晶成長
速度が遅いために、長尺フアイバーとしての利用
が困難である。 Furthermore, polycrystalline fibers have a large loss due to grain boundary scattering, and single crystalline fibers have a slow crystal growth rate, making it difficult to use them as long fibers.
本発明は上記の種々の欠点を除去するためにな
されたもので、赤外の幅広い波長領域において透
明な窓を有し、潮解性のない材料を、製造が容易
で、量産性に優れるガラス体で実現することを目
的としている。 The present invention was made in order to eliminate the various drawbacks mentioned above, and it is possible to create a glass body using a non-deliquescent material that has a transparent window in a wide infrared wavelength range and is easy to manufacture and has excellent mass production. The aim is to achieve this.
上記の要求を満たす本発明のガラスは、CuCl
を28〜46モル％、PbBr2を42〜62モル％、及び
CsCl，CsBr，CsIの内の少なくとも一種類を８〜
23モル％の割合で含有する。 The glass of the present invention that satisfies the above requirements is CuCl
28-46 mol% of PbBr2, 42-62 mol% of PbBr2 , and
At least one of CsCl, CsBr, CsI from 8 to
Contains at a rate of 23 mol%.
上記ガラス組成においてCuClとPbBr2はガラ
ス構成主成分として用いられ、両者共に2.5〜
25μmの赤外領域において何ら吸収をもたず、か
つ吸湿性、毒性が少ない。CuClの含有量は28〜
46モル％、好ましくは32〜42モル％であり、下限
より少ない量、あるいは上限より多い量では結晶
化速度が著しく速くなり安定なガラス体が得られ
にくい。PbBr2の含有量は42〜62モル％、好まし
くは45〜52モル％であり、下限より少ない量、あ
るいは上限より多い量では結晶化速度が著しく速
くなり、安定なガラス体が得られにくい。上記ガ
ラス組成において、第３成分として用いられる
CsCl，CsBr，Cslの内の少なくとも一種類はガラ
ス形成助剤としての働きを有し、いずれも毒性が
なく、2.5〜25μmの赤外領域には何ら吸収をもた
ない。CsCl，CsBr，Cslの内の少なくとも一種類
の含有量は８〜23モル％好ましくは13〜17モル％
であり、下限より少ない量、上限より多い量では
結晶化速度が著しく速くなり、安定なガラス体が
得られにくい。 In the above glass composition, CuCl and PbBr 2 are used as the main components of the glass, and both have a concentration of 2.5 to
It has no absorption in the infrared region of 25μm, and has low hygroscopicity and toxicity. The content of CuCl is 28 ~
The amount is 46 mol%, preferably 32 to 42 mol%, and if the amount is less than the lower limit or more than the upper limit, the crystallization rate will be extremely high, making it difficult to obtain a stable glass body. The content of PbBr2 is 42 to 62 mol%, preferably 45 to 52 mol%, and if the amount is less than the lower limit or more than the upper limit, the crystallization rate will be extremely high, making it difficult to obtain a stable glass body. Used as the third component in the above glass composition
At least one of CsCl, CsBr, and Csl functions as a glass forming aid, and all of them are nontoxic and have no absorption in the infrared region of 2.5 to 25 μm. The content of at least one of CsCl, CsBr, and Csl is 8 to 23 mol%, preferably 13 to 17 mol%
If the amount is less than the lower limit or more than the upper limit, the crystallization rate will be extremely high, making it difficult to obtain a stable glass body.
次に、本発明を実施例に基づいて説明するが、
本発明はこれによつて何ら限定されるものではな
い。 Next, the present invention will be explained based on examples.
The present invention is not limited thereby.
実施例 １
CuCl37モル％、PbBr248モル％、CsBr15モル
％の割合になるように調合したCuCl−PbBr2−
CsBr混合粉末を直径10mm長さ85mmのパイレツク
ス試験管に入れ、窒素ガスを融液中へ吹き込みな
がら450℃で１時間溶融した後、ステンレス板上
へ流し出し、他のステンレス板で上から押えて直
径50mm、厚さ0.5mmの円板形の淡黄色透光性材料
を得た。この材料は、第１図ａのＸ線回折図形に
示すように、結晶質特有の鋭いピークが観察され
ないことから、ガラス状態であることが確認され
た。またこの材料の赤外線透過特性を2.5〜25μm
の範囲で測定した結果、第２図に示したように
2.9及び6.3μの水の吸収を除けば2.5〜17μmの波長
領域において透明であつた。さらに、この材料
は、室温で大気中に７日間以上放置しておいても
潮解性を示さなかつた。Example 1 CuCl−PbBr 2 − prepared to have a ratio of 37 mol% CuCl, 48 mol% PbBr 2 , and 15 mol% CsBr
The CsBr mixed powder was placed in a Pyrex test tube with a diameter of 10 mm and a length of 85 mm, and after melting at 450°C for 1 hour while blowing nitrogen gas into the melt, it was poured onto a stainless steel plate and pressed from above with another stainless steel plate. A disc-shaped light yellow transparent material with a diameter of 50 mm and a thickness of 0.5 mm was obtained. As shown in the X-ray diffraction pattern of FIG. 1a, this material was confirmed to be in a glassy state because no sharp peaks characteristic of crystalline materials were observed. In addition, the infrared transmission property of this material is 2.5~25μm.
As shown in Figure 2, the results were measured in the range of
It was transparent in the wavelength range of 2.5 to 17 μm, except for water absorption at 2.9 and 6.3 μm. Furthermore, this material did not exhibit deliquescent properties even after being left in the air at room temperature for more than 7 days.
実施例 ２〜11
第１表に示した割合になるように調合した原料
混合粉末を実施例１と同様の方法で溶融、急冷す
ることによつて直径50mm、厚さ0.3〜0.5mmの円板
形の淡黄色透光性材料を得た。実施例２〜11の各
材料のＸ線回折図形はすべて実施例１の材料とほ
ぼ同一のハロー図形であつたことから、各材料は
ガラス状態であることが確認された。Examples 2 to 11 Discs with a diameter of 50 mm and a thickness of 0.3 to 0.5 mm were prepared by melting and rapidly cooling raw material mixed powder prepared in the proportions shown in Table 1 in the same manner as in Example 1. A pale yellow translucent material of the shape was obtained. Since the X-ray diffraction patterns of each of the materials of Examples 2 to 11 were all halo shapes that were almost the same as those of the material of Example 1, it was confirmed that each material was in a glass state.
代表例として実施例２のＸ線回折図形を第１図
ｂに示した。また実施例２〜11の各材料の赤外線
透過特性を2.5〜25μmの範囲で測定した結果を第
２図に示す。図からわかるようにずれの材料も実
施例１の材料とほぼ同様に、2.9及び6.3μｍの水
の吸収を除けば2.5〜17μmの波長領域において透
明であつた。さらに各材料は室温で大気中に７日
間以上放置しておいても潮解性を示さなかつた。 As a representative example, the X-ray diffraction pattern of Example 2 is shown in FIG. 1b. Further, the results of measuring the infrared transmission characteristics of each material of Examples 2 to 11 in the range of 2.5 to 25 μm are shown in FIG. As can be seen from the figure, almost the same as the material of Example 1, the material of the material was transparent in the wavelength range of 2.5 to 17 μm, except for absorption of water at wavelengths of 2.9 and 6.3 μm. Furthermore, each material did not exhibit deliquescent properties even when left in the air at room temperature for 7 days or more.
比較例 １，２
比較例１として、CuCl40モル％、PbBr240モ
ル％、CsBr20モル％、比較例２として、CuCl25
モル％、PbBr255モル％、CsBr20モル％の割合
になるように調合したCuCl−PbBr2−CsBrの各
混合粉末を実施例１と同様の方法で溶融、急冷す
ることによつて直径50mm、厚さ0.3mmの淡黄色円
板形材料を得た。比較例１及び２の各材料につい
てＸ線回折を調べた結果、各々第１図ｃ，ｄに示
すように、実施例１〜７の材料が示したガラス特
有のハローの他に、結晶質の場合に見られる鋭い
ピークが現われた。従つて、比較例１及び２の各
材料は部分的に結晶化していることがわかる。Comparative Examples 1, 2 As Comparative Example 1, CuCl40 mol%, PbBr2 40 mol%, CsBr20 mol%, Comparative Example 2, CuCl25
Each mixed powder of CuCl-PbBr 2 -CsBr prepared to have a ratio of 55 mol% PbBr 2 mol% and 20 mol% CsBr was melted and rapidly cooled in the same manner as in Example 1 to obtain a powder with a diameter of 50 mm. A pale yellow disk-shaped material with a thickness of 0.3 mm was obtained. As a result of examining X-ray diffraction for each material of Comparative Examples 1 and 2, as shown in Figure 1c and d, in addition to the halo peculiar to glass exhibited by the materials of Examples 1 to 7, crystalline A sharp peak appeared in the case. Therefore, it can be seen that the materials of Comparative Examples 1 and 2 are partially crystallized.
以上説明したように、本発明の赤外線透過用ハ
ライドガラスは従来のSiO2系ガラス、またはフ
ツ化物ガラスに比べてはるかに広い透明な窓を赤
外領域に有し（水の吸収を除けば2.5〜17μmの波
長領域で透明）、またZnCl2系あるいはBiCl3系ガ
ラスの様な潮解性がなく、製造が容易であること
から、赤外透過用材料として有用である。 As explained above, the halide glass for infrared transmission of the present invention has a much wider transparent window in the infrared region than conventional SiO 2 glass or fluoride glass (excluding water absorption, it has a transparent window of 2.5 It is useful as an infrared transmitting material because it is transparent in the wavelength range of ~17 μm), does not have deliquescent properties like ZnCl 2 or BiCl 3 glasses, and is easy to manufacture.
第１図は本発明のガラスおよび比較例ガラスの
Ｘ線回折図形、第２図ないし第１２図はそれぞれ
本発明の実施例１ないし実施例11のガラスの赤外
吸収特性を示すグラフである。
FIG. 1 is an X-ray diffraction pattern of the glass of the present invention and comparative glass, and FIGS. 2 to 12 are graphs showing the infrared absorption characteristics of the glasses of Examples 1 to 11 of the present invention, respectively.
Claims (1)
鉛（PbBr2）を42〜62モル％、及び塩化セシウム
（CsCl）あるいは臭化セシウム（CsBr）あるいは
ヨウ化セシウム（CsI）の内の少なくとも一種類
を８〜23モル％の割合で含有することを特徴とす
る赤外透過用ハライドガラス。1 28 to 46 mol% of cuprous chloride (CuCl), 42 to 62 mol% of lead bromide (PbBr 2 ), and cesium chloride (CsCl), cesium bromide (CsBr), or cesium iodide (CsI). An infrared transmitting halide glass characterized by containing at least one of the following in a proportion of 8 to 23 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58054556A JPS59182248A (en) | 1983-03-30 | 1983-03-30 | Halide glass for transmitting infrared rays |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58054556A JPS59182248A (en) | 1983-03-30 | 1983-03-30 | Halide glass for transmitting infrared rays |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59182248A JPS59182248A (en) | 1984-10-17 |
| JPH0361621B2 true JPH0361621B2 (en) | 1991-09-20 |
Family
ID=12973954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58054556A Granted JPS59182248A (en) | 1983-03-30 | 1983-03-30 | Halide glass for transmitting infrared rays |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59182248A (en) |
-
1983
- 1983-03-30 JP JP58054556A patent/JPS59182248A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59182248A (en) | 1984-10-17 |
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