JPH02243533A - Production of raw material of fluoride optical fiber and production unit therefor - Google Patents
Production of raw material of fluoride optical fiber and production unit thereforInfo
- Publication number
- JPH02243533A JPH02243533A JP6396989A JP6396989A JPH02243533A JP H02243533 A JPH02243533 A JP H02243533A JP 6396989 A JP6396989 A JP 6396989A JP 6396989 A JP6396989 A JP 6396989A JP H02243533 A JPH02243533 A JP H02243533A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- fluoride
- gas
- optical fiber
- glass
- 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
Links
- 239000002994 raw material Substances 0.000 title claims abstract description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000013307 optical fiber Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 abstract description 9
- 239000005383 fluoride glass Substances 0.000 abstract description 7
- 150000004679 hydroxides Chemical class 0.000 abstract description 4
- 229910001632 barium fluoride Inorganic materials 0.000 abstract description 3
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 30
- 229940091249 fluoride supplement Drugs 0.000 description 19
- 238000001228 spectrum Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000004433 infrared transmission spectrum Methods 0.000 description 4
- 229910002319 LaF3 Inorganic materials 0.000 description 3
- 229910007998 ZrF4 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 3
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000003786 synthesis reaction 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
- C03C1/02—Pretreated ingredients
- C03C1/022—Purification of silica sand or other minerals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
零発朋は外的散乱損失のない低損失なフッ化物光ファイ
バ用原料の製造方法およびその製造装置に関するもので
ある。詳しくは水酸基または酸化物を含まないフッ化物
光ファイバ用原料を製造する方法およびその製造装置に
関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) Zero Hatsuho relates to a method for producing a low-loss raw material for fluoride optical fiber without external scattering loss, and an apparatus for producing the same. More specifically, the present invention relates to a method for producing a raw material for a fluoride optical fiber that does not contain hydroxyl groups or oxides, and an apparatus for producing the same.
（従来の技術）
フッ化物ガラスを素材とする光ファイバは、石英系光フ
ァイバを凌ぐ１０−” ｄＢ／ｋｍ 以下の伝送損失
をもつことが期待されており、特にフッ化物ガラスのう
ちで、ＺｒＦａを主成分とするフッ化物ガラスは、光フ
ァイバ素材として最も有望視されている。(Prior art) Optical fibers made of fluoride glass are expected to have a transmission loss of 10-" dB/km or less, which exceeds that of silica-based optical fibers. Fluoride glass, whose main component is fluoride, is considered the most promising material for optical fibers.
ＺｒＦ４系フッ化物ガラスは、通常、白金製または金製
のるつぼを用いて原料バッチを溶融した後、急冷する、
いわゆる溶融法によって合成されている。原料バッチに
用いられるＢａＦ２． ＬａＦ＋＋等の金属フッ化物
は、一般に硝酸塩等をフッ化水素溶液中でフッ素化した
後、加熱脱水して得られている。このときの反応式は、
Ｌａ（ＮＯｚ）ｚ＋ ３ＨＦ −＋ ＬａＦ３＋ ３
１１ＮＯｚ （１）で示される。ZrF4-based fluoride glass is usually produced by melting a raw material batch using a platinum or gold crucible and then rapidly cooling it.
It is synthesized by the so-called melting method. BaF2. used in the raw material batch. Metal fluorides such as LaF++ are generally obtained by fluorinating nitrates and the like in a hydrogen fluoride solution, followed by heating and dehydration. The reaction formula at this time is: La(NOz)z+ 3HF −+ LaF3+ 3
11NOz (1).
しかし、湿式反応を利用する限り、生成物のＬａＦｚ
中には必ず水酸化物が残留し、ガラス溶融過程でガラ
スの主成分であるＺＦ、と下記の（２）式、（３）式で
示すように直接反応したり、または酸化物となった後に
反応して、Ｚｒ０ｚを生成し、外的散乱損失を増大させ
る（例えば、Ｆｕｊ １ｕｒａｅｔａｌ ”Ｆｏｒｎ＋
ａｔｉｏｎ Ｒｅａｃｔｉｏｎ ｏｆ ＺｒＯ２５ｃａ
ｔｔｅｒｅｒｓｉｎ ＺｒＦｉ −Ｂａｓｅｄ Ｆｌｕ
ｏｒｉｄｅ Ｆｉｂｅｒｓ ” Ｊ、 Ａｍｅｒ。However, as long as wet reaction is used, the product LaFz
Hydroxide always remains in the glass, and during the glass melting process, it directly reacts with ZF, the main component of glass, as shown in equations (2) and (3) below, or becomes an oxide. later reacts to produce Zr0z and increase external scattering losses (e.g., Fuji 1uraetal “Forn+
ation Reaction of ZrO25ca
tterersin ZrFi -Based Flu
oride Fibers” J, Amer.
Ｃｅｒａ、 Ｓｏｃ、 Ｖｏｌ、７１． ｐｐ、４６０
〜４６４ ）。Cera, Soc, Vol, 71. pp, 460
~464).
３ＺｒＰａ ＋ ２Ｌａ（ＯＨ）＋ −３ＺｒＯｚ＋
２ＬａＦ、＋６ＨＦ３ＺｒＦ４＋ ２Ｌａｚ０３
−’ｐ ３ＺｒＯ，＋ ４ＬａＦ。3ZrPa + 2La(OH)+ -3ZrOz+
2LaF, +6HF3ZrF4+ 2Laz03
-'p3ZrO, +4LaF.
このためガラス溶融に際しては、原料中の水酸化物を除
くため、従来より原料バッチにＮ）Ｉ４Ｆ −ＨＦをフ
ッ素化剤として添加し、フッ素化処理をした後、アルゴ
ンや窒素などの不活性ガス中で溶融されてきた。For this reason, when melting glass, in order to remove hydroxides from the raw materials, N)I4F-HF is traditionally added to the raw material batch as a fluorinating agent, and after fluorination treatment, inert gas such as argon or nitrogen is added to the raw material batch. It has been melted inside.
しかしＮＨ４・）ＩＦを用いた場合、ＮＨ４”イオンの
還元効果により、ガラスの主成分ＺｒＦａの還元が起こ
ってガラスが着色し、ファイバの吸収損失を増大させる
。これを除くために溶融雰囲気に酸素ガスを導入し、還
元Ｚｒを酸化して除去し、吸収損失の低減を図っている
。しかし、この方法では酸化物が生成されてしまうので
、外的散乱損失が増大してしまうという欠点がある。However, when using NH4. Gas is introduced to oxidize and remove the reduced Zr in an attempt to reduce absorption loss.However, this method produces oxides, which has the disadvantage of increasing external scattering loss. .
したがってＮｌ（、Ｆ −）ＩＰ処理は、低損失のフッ
化物光ファイバの作製には不適当であり、他のフッ素化
処理法が望まれている。その一つとして、フッ化物ガラ
スの溶融雰囲気に、ＣＣｌ４ 、 ＣＦ４等の活性ガス
を供給してガラス溶液と反応させ、水酸基や酸素イオン
を除くことをねらったＲｅａｃｔｉｖｅＡｔｍｏｓｐｈ
ｅｒｅ Ｐｒｏｃｅｓｓｉｎｇ （Ｍａｔ、 Ｒｅｓ
、 Ｂｕｌｌ、 ｖｏｌ。Therefore, the Nl(,F-) IP process is inappropriate for fabricating low-loss fluoride optical fibers, and other fluorination processing methods are desired. One of these is Reactive Atmosph, which aims to remove hydroxyl groups and oxygen ions by supplying active gases such as CCl4 and CF4 to the melting atmosphere of fluoride glass and reacting with the glass solution.
are Processing (Mat, Res
, Bull, vol.
１５、ρｐ、７３５．１９８０）が提案されているが、
この手法も、カーボン等の反応または分解生成物のガラ
ス中への混入が起こり、低損失のフッ化物光ファイバ用
ガラス作製法として適しているとは言えない。15, ρp, 735.1980) has been proposed;
This method also causes reaction or decomposition products such as carbon to be mixed into the glass, and cannot be said to be suitable as a method for producing glass for a low-loss fluoride optical fiber.
（発明が解決しようとする課題）
本発明は、水酸化物または酸化物に起因した酸化物散乱
体による外的散乱損失を低減したフッ化物光ファイバを
製造するために必要な高純度フッ化物ガラス原料を製造
する方法およびその製造装置を提供することにある。(Problems to be Solved by the Invention) The present invention provides high-purity fluoride glass necessary for manufacturing a fluoride optical fiber that reduces external scattering loss due to oxide scatterers caused by hydroxides or oxides. An object of the present invention is to provide a method for producing raw materials and an apparatus for producing the same.
（課題を解決するための手段）
本発明は、フッ化物光ファイバ用原料の製造方法におい
て、湿式法により合成されたフッ化物原料粉末を、フッ
素ガスを含有するガスで室温ないし６００℃の温度にお
いて処理する。その製造装置はアルミニウム製の処理容
器からなり、該処理容器は、内部にガスを供給するため
のノズルおよび内部の雰囲気ガスを外部に排気するため
のノズルを有する容器、および該容器内でフッ化物原料
中にフッ素ガスを含有するガスを分散させるための分散
板とにより構成する。(Means for Solving the Problems) The present invention provides a method for producing a raw material for a fluoride optical fiber, in which a fluoride raw material powder synthesized by a wet method is heated at a temperature of room temperature to 600°C with a gas containing fluorine gas. Process. The manufacturing equipment consists of a processing container made of aluminum. It consists of a dispersion plate for dispersing gas containing fluorine gas in the raw material.
従来は、湿式法で得られたフッ化物は、加熱して真空乾
燥するなどして、フッ化物中に含まれた水分を除去して
いたが、本発明では原料中に含まれ、水酸基が生成され
る原因となる水分の除去を単に物理的に行うのではなく
、Ｆ２ガスと水分との反応により取り除く。Conventionally, fluoride obtained by a wet method was heated and vacuum-dried to remove the moisture contained in the fluoride, but in the present invention, the moisture contained in the fluoride is removed by removing the moisture contained in the raw material and generating hydroxyl groups. Rather than simply removing the moisture that causes the moisture, it is removed by a reaction between F2 gas and moisture.
（実施例）
以下、本発明の実施例について図面を参照して説明する
。(Example) Hereinafter, an example of the present invention will be described with reference to the drawings.
実施班上
第１図は、フッ化物原料をＦ２ガスで処理するための処
理容器の構成図であって、硝酸バリウム水溶液にフッ化
水素酸を加えて、得られたＢａＦｚ粉末にＦｔガスを供
給しているところを示している。Figure 1 of the implementation team is a block diagram of a processing container for treating fluoride raw materials with F2 gas, in which hydrofluoric acid is added to a barium nitrate aqueous solution and Ft gas is supplied to the BaFz powder obtained. It shows what is being done.
すなわち靜ガスで１０％に希釈したＦ２ガスを、ガス供
給ノズル１から処理容器本体２の中に供給し、分散板（
メザラ）３の上部に置かれたフッ化物原料粉末（ＢａＦ
ｚ） ４の中に拡散させた。また、処理容器内の雰囲気
ガスは、排気ノズル６から外部に排気した。このときの
処理容器内の温度は２０″Ｃであったｅ Ｆ２ガスを
２時間流した後、Ｆ２ガスの供給を止め、乾燥性ガスを
処理容器内に供給し、処理容器の内部が２５０″Ｃにな
るように、処理容器を電気炉により、２時間加熱した後
、室温まで徐冷した。That is, F2 gas diluted to 10% with quiet gas is supplied from the gas supply nozzle 1 into the processing container body 2, and the dispersion plate (
Fluoride raw material powder (BaF) placed on top of Mezzala) 3
z) Diffused into 4. Further, the atmospheric gas inside the processing container was exhausted to the outside from the exhaust nozzle 6. The temperature inside the processing container at this time was 20"C. After flowing F2 gas for 2 hours, the supply of F2 gas was stopped and drying gas was supplied into the processing container, so that the inside of the processing container reached 25"C. The processing container was heated in an electric furnace for 2 hours so that the temperature became C, and then slowly cooled to room temperature.
第２図には、上記プロセスにより得られたＢａＦ。FIG. 2 shows BaF obtained by the above process.
原料のＫＢｒ法によって測定した赤外透過スペクトル（
ａ）と、Ｆ２処理をせずに計容囲気中で加熱焼成したＢ
ａＦ、の赤外透過スペクトル（ｂ）とを示す。Infrared transmission spectrum measured by the KBr method of the raw material (
a) and B, which was heated and fired in the air without F2 treatment.
The infrared transmission spectrum (b) of aF is shown.
スペクトル（ｂ）では２５ａｍ〜３０ｕｍの波長で透過
率が低下していることがわかる。これは、ＢａＦ、中に
酸素不純物が残存したために生ずるＢａ−〇結合の振動
吸収によるものである。In the spectrum (b), it can be seen that the transmittance decreases at wavelengths of 25 am to 30 um. This is due to vibrational absorption of the Ba-- bond caused by residual oxygen impurities in BaF.
一方、スペクトル（ａ）ではＢａ −０の振動吸収によ
る透過率の低減は見られず、酸素不純物が除かれている
ことがわかる。On the other hand, in spectrum (a), no reduction in transmittance due to vibrational absorption of Ba-0 is observed, indicating that oxygen impurities are removed.
このようにＦ２ガス処理を施した原料で酸素不純物が除
去されているのは、下記の（４） 、 （５）弐に示す
ように、フッ化水素酸との反応で生成されたＢａＦ２粉
末中に含まれる水分や水酸基がＦ２ガスと反応して効率
良く除かれることにより、ＢａＦｚが加水分解されるこ
とを妨げ、また水酸化物から酸化物が生成されることを
妨げるためである。Oxygen impurities are removed from the raw material treated with F2 gas in this way, as shown in (4) and (5) 2 below, in the BaF2 powder produced by the reaction with hydrofluoric acid. This is because moisture and hydroxyl groups contained in the F2 gas are efficiently removed by reacting with the F2 gas, thereby preventing BaFz from being hydrolyzed and preventing oxides from being generated from hydroxides.
ＨｌＯ＋ Ｆ２ → ２ＨＦ ＋ （ｈ（４）
、 （５）式の反応は室温でも十分に進行するが、加熱
することにより反応の進行を促進させることができる。HlO+ F2 → 2HF + (h(4)
Although the reaction of formula (5) proceeds satisfactorily even at room temperature, the progress of the reaction can be accelerated by heating.
しかし、Ｆ２ガスを用いた場合に温度を上げ過ぎると、
処理容器がＦ２ガスと反応し始めてしまうので、処理温
度には上限がある。アルミニウム製の処理容器を用いた
場合、６００℃程度の加熱処理に耐えられる。したがっ
て処理温度としては、室温から６００’Ｃ程度まで採用
することができる。However, if the temperature is raised too much when F2 gas is used,
There is an upper limit to the processing temperature since the processing container will begin to react with the F2 gas. When a processing container made of aluminum is used, it can withstand heat treatment at about 600°C. Therefore, the processing temperature can range from room temperature to about 600'C.
叉旌班Ｉ
硝酸ランタン水溶液にフッ化水素酸を加えて得られたＬ
ａＦｚについても、実施例１と同様にＦ２ガス処理を施
した。叉挌柜I L obtained by adding hydrofluoric acid to a lanthanum nitrate aqueous solution
AFz was also subjected to F2 gas treatment in the same manner as in Example 1.
第３図には、Ｆ２ガス処理を施したＬａ５ｔと未処理の
ＬａＦ、とを、それぞれＡｒ雰囲気中で加熱焼成した後
の赤外透過スペクトルを示す。スペクトル（ｃ）はＦ２
ガス処理を施したもの、スペクトル（ｄ）は未処理のも
ののスペクトルである。FIG. 3 shows the infrared transmission spectra of La5t treated with F2 gas and untreated LaF after being fired in an Ar atmosphere. Spectrum (c) is F2
Spectrum (d) is the spectrum of the gas-treated sample and the untreated sample.
スペクトル（ｄ）では、２０μｍから２８μｍにかけて
透過特性がスペクトル（ｃ）に比べて著しく低下してい
ることがわかる。このスペクトル（ｄ）の透過特性の劣
化は、ＬａＦ３中に酸素不純物が残存しているために生
ずるり、−０結合の振動吸収によるものである。It can be seen that in the spectrum (d), the transmission characteristics are significantly decreased from 20 μm to 28 μm compared to the spectrum (c). This deterioration in the transmission characteristics in spectrum (d) is caused by the presence of oxygen impurities remaining in LaF3, and is due to vibrational absorption of the -0 bond.
一方、スペクトル（ｃ）では、Ｌ、−０の振動吸収によ
る透過率の低下は見られず、酸素不純物が除かれている
ことがわかる。On the other hand, in spectrum (c), no decrease in transmittance due to vibration absorption of L and -0 is observed, indicating that oxygen impurities are removed.
これは、Ｆ２ガス処理を施すことにより、ＬａＦ３の合
成過程で、下記の（６）式に示すように、ＬａＦ ｊ中
に残存した水酸基がＦ２ガスと反応して除かれるためで
ある。This is because, by performing the F2 gas treatment, the hydroxyl groups remaining in LaF j are removed by reacting with the F2 gas during the synthesis process of LaF3, as shown in equation (6) below.
Ｌａ（ＯｆＯｚ ＋ ３Ｆｚ →ＬａＦｚ ＋
３ＨＦ ＋ −Ｏｚ （６）実五〇生よ
昇華精製したＺｒＦ４＋ Ａ Ｅ Ｆ３ についても
Ｆ２ガス処理を施した後、実施例１、実施例２で得られ
たＢａＦ ２１ ＬａＰ ３ とともに原料として
、各原料を乾燥不活性ガス雰囲気中で所定の組成となる
ように秤量混合し、乾燥不活性ガス雰囲気中で８５０℃
で２時間溶融した後、金属モールドにキャスティングし
て母材を得た。この母材から線引きして得られた光ファ
イバにＨ，−Ｎ、レーザ光を入射したところ、ファイバ
中に散乱中心はほとんど観測されなかった。La(OfOz + 3Fz →LaFz +
3HF + -Oz (6) ZrF4+ A E F3 purified by sublimation was also subjected to F2 gas treatment. were weighed and mixed in a dry inert gas atmosphere to give a predetermined composition, and heated at 850°C in a dry inert gas atmosphere.
After melting for 2 hours, it was cast into a metal mold to obtain a base material. When H, -N, and laser beams were incident on an optical fiber obtained by drawing from this base material, almost no scattering centers were observed in the fiber.
また散乱損失とその波長依存性を測定したところ、散乱
損失α（ｄＢ／ｋｍ）と波長λ（μｍ）とは、α＝１．
１ ／λ’ ＋０．０３ （ｄＢ／ｋｍ） （７
）の関係があった。これは上式の右辺第１項および第２
項の定数が、従来の作製法で得た原料を用いると、それ
ぞれ５〜１５および０．１〜２０であったことと比較す
ると、著しく小さくなっている。Furthermore, when scattering loss and its wavelength dependence were measured, it was found that the scattering loss α (dB/km) and the wavelength λ (μm) were α=1.
1 /λ' +0.03 (dB/km) (7
). This is the first and second term on the right side of the above equation.
The constants of the term are significantly smaller than those of 5 to 15 and 0.1 to 20, respectively, when raw materials obtained by conventional production methods are used.
これは、例えばＢａＦ、中に水酸化物が残留していると
、下記の（８）式に示すように、水酸化物が、ガラスの
主成分であるＺｒＦ４と反応し、ＺｒＯ２が生成され、
ガラス融液中に酸化物散乱体として残るが、Ｆ２ガス処
理を施して原料中に残留した水酸基を除いておけば、酸
化物散乱体が残らないためである。This is because, for example, if hydroxide remains in BaF, the hydroxide reacts with ZrF4, which is the main component of glass, as shown in equation (8) below, and ZrO2 is generated.
This is because the oxide scatterers remain in the glass melt, but if the hydroxyl groups remaining in the raw materials are removed by F2 gas treatment, no oxide scatterers remain.
Ｂａ（叶）ｚ ＋ ＺｒＦａ → ＢａＦｚ ＋
Ｚｒ０ｚ ＋ ２ＨＦ （８）（発明
の効果）
以上説明したように、本発明のフッ化物光ファイバ用原
料の製造方法によれば、酸素不純物を含まないフッ化物
光ファイバ用原料を製造できるので、ひいては外的散乱
体のない低損失なフッ化物光ファイバを製造することに
寄与する利点がある。Ba(leaf)z + ZrFa → BaFz +
Zr0z + 2HF (8) (Effects of the Invention) As explained above, according to the method for producing a raw material for a fluoride optical fiber of the present invention, a raw material for a fluoride optical fiber that does not contain oxygen impurities can be produced. This has the advantage of contributing to the production of low-loss fluoride optical fibers without external scatterers.
第１図は本発明の一実施例に用いたフッ化物原料をＦ２
ガスで処理するための処理容器の構成図、第２図および
第３図は本発明の製造方法で得られたＢａＦｚ、 Ｌ
ａＦ＝の赤外透過スペクトルを示す図である。
１・・・ガス供給ノズル
２・・・処理容器本体
３・・・分散板（メザラ）
４・・・フッ化物原料粉末
５・・・フランジ
６・・・排気ノズル
７・・・ボルト
８・・・ナツトFigure 1 shows the fluoride raw material used in one example of the present invention.
The block diagram of a processing container for processing with gas, FIGS. 2 and 3 show BaFz, L obtained by the manufacturing method of the present invention.
It is a figure which shows the infrared transmission spectrum of aF=. 1... Gas supply nozzle 2... Processing container body 3... Dispersion plate (mezara) 4... Fluoride raw material powder 5... Flange 6... Exhaust nozzle 7... Bolt 8...・Natsuto
Claims (1)
式法により合成されたフッ化物原料粉末を、フッ素ガス
を含有するガスで室温ないし６００℃の温度において処
理することを特徴とする高純度フッ化物原料の製造方法
。 ２、アルミニウム製の処理容器からなり、該処理容器は
、内部にガスを供給するためのノズルおよび内部の雰囲
気ガスを外部に排気するためのノズルを有する容器と、
該容器内でフッ化物原料中にフッ素ガスを含有するガス
を分散させるための分散板とから構成されていることを
特徴とするフッ化物光ファイバ用原料の製造装置。[Claims] 1. A method for producing a fluoride optical fiber raw material, characterized in that a fluoride raw material powder synthesized by a wet method is treated with a gas containing fluorine gas at a temperature of room temperature to 600°C. A method for producing a high-purity fluoride raw material. 2. A processing container made of aluminum, the processing container having a nozzle for supplying gas to the inside and a nozzle for exhausting the internal atmospheric gas to the outside;
1. An apparatus for manufacturing a fluoride optical fiber raw material, comprising a dispersion plate for dispersing a gas containing fluorine gas in the fluoride raw material in the container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1063969A JP2670136B2 (en) | 1989-03-17 | 1989-03-17 | Fluoride optical fiber raw material manufacturing method and manufacturing apparatus therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1063969A JP2670136B2 (en) | 1989-03-17 | 1989-03-17 | Fluoride optical fiber raw material manufacturing method and manufacturing apparatus therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02243533A true JPH02243533A (en) | 1990-09-27 |
| JP2670136B2 JP2670136B2 (en) | 1997-10-29 |
Family
ID=13244631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1063969A Expired - Lifetime JP2670136B2 (en) | 1989-03-17 | 1989-03-17 | Fluoride optical fiber raw material manufacturing method and manufacturing apparatus therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2670136B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS593039A (en) * | 1982-06-25 | 1984-01-09 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of fluoride glass for optical fiber |
| JPS6163538A (en) * | 1984-09-04 | 1986-04-01 | Kokusai Denshin Denwa Co Ltd <Kdd> | Purification of fluoride glass |
| JPS6469538A (en) * | 1987-09-09 | 1989-03-15 | Sumitomo Electric Industries | Mixer for powdery raw material of fluoride glass |
-
1989
- 1989-03-17 JP JP1063969A patent/JP2670136B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS593039A (en) * | 1982-06-25 | 1984-01-09 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of fluoride glass for optical fiber |
| JPS6163538A (en) * | 1984-09-04 | 1986-04-01 | Kokusai Denshin Denwa Co Ltd <Kdd> | Purification of fluoride glass |
| JPS6469538A (en) * | 1987-09-09 | 1989-03-15 | Sumitomo Electric Industries | Mixer for powdery raw material of fluoride glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2670136B2 (en) | 1997-10-29 |
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