EP0223853A1 - Procede d'introduction de dopants dans des ebauches de fibres optiques - Google Patents
Procede d'introduction de dopants dans des ebauches de fibres optiquesInfo
- Publication number
- EP0223853A1 EP0223853A1 EP86904479A EP86904479A EP0223853A1 EP 0223853 A1 EP0223853 A1 EP 0223853A1 EP 86904479 A EP86904479 A EP 86904479A EP 86904479 A EP86904479 A EP 86904479A EP 0223853 A1 EP0223853 A1 EP 0223853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- tube
- core
- chelate
- optical fiber
- 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.)
- Withdrawn
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
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/045—Silica-containing oxide glass compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
- C03B37/01807—Reactant delivery systems, e.g. reactant deposition burners
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/34—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with rare earth metals, i.e. with Sc, Y or lanthanides, e.g. for laser-amplifiers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/80—Feeding the burner or the burner-heated deposition site
- C03B2207/81—Constructional details of the feed line, e.g. heating, insulation, material, manifolds, filters
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/80—Feeding the burner or the burner-heated deposition site
- C03B2207/85—Feeding the burner or the burner-heated deposition site with vapour generated from liquid glass precursors, e.g. directly by heating the liquid
- C03B2207/87—Controlling the temperature
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/80—Feeding the burner or the burner-heated deposition site
- C03B2207/90—Feeding the burner or the burner-heated deposition site with vapour generated from solid glass precursors, i.e. by sublimation
Definitions
- This invention relates to an optical fiber preform and a method for producing the same, and more particularly to a method of incorporating dopants in the silica core of the preform.
- Optical communications systems that is systems operating in the visible or near visible spectra, utilize clad glass fibers as the transmission medium. These clad fibers or optical fibers are produced by preparing a preform and then heating and drawing the preform into the fiber.
- the optical fibers are composed of silica and have an overall cross-sectional diameter of about 125 ym and are generally constructed of two sections, a transparent glass core and a transparent glass cladding, the cladding surrounding the core having a lower refractive index relative to the core, with a typical variation in refractive index from core to cladding being in the range of about 1.01 to 0.05.
- the core generally has a diameter of 50 ym.
- a method widely used for fabricating an optical fiber is to first prepare a preform, from which the fiber is drawn, using a chemical vapor deposition (CVD) method.
- the CVD method comprises the steps of depositing a thin layer of silica doped with various metals on the inner surface of a fused silica tube, the doped silica layer having a higher index of refraction than that of the outer surface of the tube or cladding, and then collapsing the resulting tube by heating to form a solid preform free from any interior space, with the thin doped layer then becoming the core.
- layers of fused doped silica are built up on the inside of a long silica glass tube by the oxidation of vaporized core precursor compounds dispersed in an oxygen carrier resulting in the formation of metal oxide particles which deposit and are fused on the inner wall of the tube to form the doped core of the preform.
- the deposited fused metal oxide layer becomes the fiber core and the silica glass tube the cladding.
- the source of the vapor deposited core is generally a chloride of silica as well as desired dopants tailoring the index of refraction between the core and the cladding.
- the most widely used dopant materials include chloride compounds of, for example, germanium, titanium, aluminum and phosphorus which increase the index of refraction of the deposited silica core.
- the metal chloride dopant compounds are normally liquids which are vaporizable at relatively low temperatures, e.g. 100° to 250°C and the vapors of such materials such as GeCl4, S1CI4, POCI3 or the like are entrained in a carrier gas such as oxygen and flowed as a vapor stream, at a temperature of about 100°C, into the interior of a glass cladding tube which is rotated while a torch which heats the tube to about 1000° to 1600°C repeatedly traverses its length. As the vapor stream passes through the tube and encounters a heat zone adjacent the torch, it reacts, pyrolyzing the metal compounds and forming oxides which deposit and fuse on the interior surface of the tube.
- a carrier gas such as oxygen
- the tube After numerous traversals of the torch along the length of the tube to deposit the oxide core layer, the tube is heated to even higher temperatures (e.g., 1900° to 2000°C) by the torch in several traversals to shrink the tube and in a final traversal, the tube is collapsed, resulting in a solid rod-shaped preform. Thereafter, the solid collapsed preform is drawn into an elongated filament which comprises the optical fiber.
- certain metals e.g., cerium, arsenic, europium and samarium, when used to dope optical fiber preforms, aid in. reducing radiation damage due to ionizing radiation.
- Metal species such as Ce3+, Ce ⁇ + , Sm3+ and Eu ⁇ + , when incorporated in the core glass, act as ⁇ electron sinks, and/or "hole" sinks which act to reduce the generation of optical absorption sites in a preferred spectral use region so tha't the optical transmission properties of the fiber drawn from the preform are maintained at an optimized level.
- the metals immediately enumerated above exhibit beneficial doping activity in optical fiber cores, these metals normally form compounds that have very low vapor pressures at temperatures of 100° to 250°C and it is, therefore, difficult, if not impossible, to vaporize these compounds to the level necessary for their entrainment in the gaseous metal chloride/02 streams normally used to prepare doped core layers for optical fiber preforms.
- alco ' holates of these desirable doping metals can be vaporized at relatively low temperatures, e.g., 100° to 300°C, the oxidation of the alcoholates produces an undesirable water vapor by-product.
- a method for incorporating a metal dopant in the silica core of an optical fiber preform the dopant precursor compound being a metal chelate having a sufficiently high vapor pressure whereby the chelate can be volatilized at relatively low temperatures (e.g., about 100° to 250°C) and thereby readily incorporated i- n the gaseous core precursor compound streams normally used for deposition of the doped core layer in 'the preform, the metal chelate being derived from a fluori ⁇ nated betadiketone ligand having the following general structures:
- R, R ⁇ and R2 are either fluorine or perfluorinated alkyl.
- the negative ion formed by the removal of the proton from the above keto-enol structures serves as a coordinating ligand to almost any positive ion of a metal element and forms with such ion what is known as a complex.
- the organo-metallic compounds thus derived from the coordination of the ligand ions and metal ions are known as metal ⁇ -diketonates or metal ⁇ -ketoenolates; for the purpose of this application, these compounds are referred to as metal ⁇ -diketonates.
- the metal ⁇ -diketonates have relatively high vapor pressures at temperatures of 100° to 250°C and as such may be readily vaporized in a helium stream for intro ⁇ duction into the gaseous 02/SiCl4 streams used to prepare the core layers of optical fiber preforms.
- the metal ⁇ -diketonates used in the practice of the present invention contain limited hydrogen substituency and preferably do not contain hydrogen atoms, the opportunity for the creation and incorporation of water vapor derived impurities into the core layer of the preform is minimized or eliminated.
- metal ⁇ -diketonates can be sublimed or otherwise puri'fied before introduction into the gaseous core precursor streams, the presence of tramp contaminants in the metal chelates used in the practice of the present invention is also eliminated and therefore high purity dopant metal oxides are produced by the oxidative decomposition reaction used in the formation of the core layer.
- FIG. 1 is a perspective view of an optical fiber preform prepared in accordance with the method of the present invention
- FIG. 2 illustrates in " schematic form, an apparatus suitable for carrying out the process of the present invention
- FIG. 3 illustrates in schematic form, an apparatus suitable for vaporizing a metal ⁇ -diketonate
- FIG. 4 is a cross-sectional view of the apparatus of FIG. 3 illustrating electrical leads for a heat source
- FIG. 5 is a second cross-sectional view of the apparatus of FIG. 3 illustrating the relationship between a heat source and a dopant source.
- the metal ⁇ -diketonates used in the practice of the present invention are prepared by reacting a fluorinated ⁇ -diketone ligand having the formula:
- R, Rx, and R2 are fluorine or perfluorinated alkyl or aryl, or combinations thereof, with a metal salt of the formula:
- M is a metal cation
- X is halogen, nitrate, sulfate or acetate
- n is an integer which corresponds to the electroequivalence of M.
- metals include copper, zinc, mercury, indium, lanthanum, cerium, praseodymium, neodymium, samarium, zirconium, chromium, uranium, manganese, iron, 'cobalt, nickel, platinum, palladium, cadmium, scandium, thorium, vanadium, gallium, thallium, yttrium, europium, gado ⁇ linium, hafnium, lead and plutonium, while the halogen ion, of course can be chlorine, bromine, iodine and the like.
- Illustrative examples of the fluorinated ⁇ -diketone ligand used to prepare the metal ⁇ -diketones include 1,1,1,3,5,5,5-heptafluoro-2,4-pentanadione; 3-trifluoro- methyl 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; and
- R]_, R2 and R3 must be perfluorinated alkyls or perfluorinated aryls.
- R and 2 may range from 1 to 5 carbon atoms.
- the ⁇ -diketonate ligand is completely devoid of hydrogen substituency to prevent the incorporation of hydrogen as OH" impurity in the doped core layer of the preform.
- the reaction to prepare the metal ⁇ -diket'onate from e.g., a metal chloride and fluorinated ⁇ -diketone is preferably conducted in the presence of an inert organic polar solvent such as CCI4 at a temperature of about 25° to 50°C.
- the fluorinated metal ⁇ -diketonates used in the practice of the present invention are typically solid compounds having a relatively high vapor pressure, e.g., about 10 to 50 mm Hg. at temperatures in the range of 200° to 250°C. As such, they can be readily vaporized and introduced into the gas.eous core precursor streams used to prepare optical fiber preforms.
- Dopant forming compounds normally used to prepare the doped core layer may also be used in the practice of the present invention and include, for example, metal chloride compounds which can be volatilized at relatively low temperatures, e.g., about 50° to 100°C, and function to increase the refractive index of the deposited silica layer.
- metal chloride compounds include GeCl4, TiCl4, AICI3, POCI3 which oxidize to form the dopants Ge ⁇ 2, Ti ⁇ 2, I2O3 P2O5, respectively.
- the metal ⁇ -diketonates and the metal chloride core precursor compounds (which are generally liquids at room temper- ature) are individually heated to above their vaporization temperature and carried along by a carrier gas such as He or O2, and the individual metal ⁇ -diketonate and metal chloride vapors are then mixed with oxygen gas which acts as a carrier for the vaporized mixture of metal ⁇ -diketone and metal chlorides whereby the vaporized mixture is entrained in the gaseous oxygen carrier.
- the gaseous mixture flowed into the tube from which the preform is fabricated is comprised of about 90 to 94 volume percent oxygen, about 2 to 4 volume percent SiCl4, about 0.1 to about 0.4 volume percent of the metal ⁇ -diketonate, and about 2 to about 3 volume percent of the various other dopant metal chloride compounds.
- the metal ⁇ -diketonate and metal chlorides are decomposed and oxidized to their respective oxides and uniformly deposited onto the interior surface walls of the tube by thermophoresis whereby the surface layer of the tube is modified with a doped silica layer of a higher refractive index than the tube walls.
- the time required for the deposition of the doped core layer depends upon the ' flow rate of the gaseous mixtures and the concentration of the various core forming compounds, with the tendency that the greater flow rate (within the limits of achieving deposition of the decomposition products) and the higher the concen- trations of the various core forming compounds, the shorter the processing time to deposit the doped core layer.
- a core layer of 250 ⁇ m thickness can be deposited in about 2 to 3 hours in combination with a traveling heat source, the heat source being repeatedly or recipro ⁇ cally moved a required number of times, e.g., 50 at a speed of 10 cm/min to maintain the walls, on which the core layer is deposited, at a temperature of about 1000°C to 1900°C.
- the -gaseous metal ⁇ -dike ' tonate and core precursor compounds are flowed through the tube at a pressure of about ambient.
- the gaseous mixture of metal ⁇ -diketonate and core precursor compounds is used at a total pressure of about 750 to 760 mm Hg. and a flow rate of about 1000 to 3000 cc/min.
- FIG. 1 depicts a portion of an optical fiber preform 10 constructed of a glass core 12 formed from a plurality of doped silica layers and an outer wall or cladding 11.
- FIG. 2 is a schematic drawing of a glass working lathe 20 which can be used to fabricate optical preform 10.
- Glass lathe 20 comprises apparatus known in the art and includes rotary chucks 22 and 22' which grasp tube 14 and provide rotary motion as required.
- the starting glass tube 14 which will form outer wall 11, is mounted between synchronous rotatable chucks 22-22" .
- a gas hydrogen/oxygen burner 26 which repeatedly traverses its length slowly from left to right and makes a fast return to the left after each traversal.
- Gaseous materials such as SiCl4, metal -diketonates and other gaseous dopants such as, but not limited to GeCl4 and POCI3 are introduced into tube 14 during heating through a manifold 24.
- Manifold 24 receives the input gases through a tube or tubes which are in turn connected to source material reservoirs, not shown, which are normally flasks or other containers containing liquid chloride compounds heated to the vaporization temperature of the individual compounds.
- Manifold 30 is a gas tight chamber providing a substantially sealed transfer volume between the source materials and tube 14. It is necessary that manifold 24 provides a substantially gas tight rotary seal 25 where it contacts tube 14. For this reason the preferred embodiment of manifold 24 is a chamber constructed from polytetrafluoroethylene material which provides a gas tight seal while permitting unrestrained rotary motion.
- the material properties of metal -diketonate sources generally prevent their introduction into manifold 24 in the same manner as other gaseous materials. Instead, a special heat probe 30 is employed which vaporizes the -diketonate material within the interior of tube 14. Heat probe 30 is shown in position in FIG. 2 inserted into manifold 24 through a gas tight seal 27 and into the interior of tube 14. Seal 27 is such that probe 30 can be moved axially within the interior of tube 14 in order to provide optimum positioning of the ⁇ -diketonate source. Heat probe 30 is canitilevered into tube 14 and manifold 24 by use of the walls of the probe and seal 27.. However, it will be apparent to those skilled in the art that additional clamping means or guiding and support structure, not shown, can be employed in order to position probe 30 within tube 14 and maintain a gas tight seal for manifold 24.
- FIG. 3 shows the interior details for vaporizing the ⁇ -diketonate material.
- the main structure of heat probe 30 comprises a fused silica tube 34. Within heating probe 30, there is placed a fused silica boat 40 which contains pressed pellets 42 or loose powder of the metal ⁇ -diketone to be vaporized. The heating probe is provided with a fused silica porous filter plug 38, through which the vaporized metal ⁇ -diketonate is exhausted and passed to the inner surface 16 of silica tube 14.
- Heating probe 30 is further provided with heating elements 50 which comprise resistive chromium/nickel wire connected by copper electrical leads 52 to an electrical control device, not shown for clarity, whereby heating elements 50 are activated, by applying a controlled voltage thereto, to raise the temperature of the elements to a predetermined elevated temperature at which pellets 40 are vaporized.
- Heating elements 50 are enclosed in a fused silica liner 54 to prevent any contact between the metal leads 52 and the gas stream.
- Leads 52 are enclosed in fused silica tubing 56 which is joined to the liner 54 on one end and exits through the walls 34 of probe 30 at the other end. This is illustrated in FIG. 3 and FIG. 4. The radial position of lead ' s 52 is illustrated in FIG. 4.
- FIG. 4 The radial position of lead ' s 52 is illustrated in FIG. 4.
- FIG. 5 further illustrates the radial disposition of elements 50 about the circumference of probe 30.
- High purity helium is ' introduced into heating probe 30 from a source (not shown) through a valve 32 at a flow rate of 1200 to 1500 cc/min.
- the helium gas is passed through probe 30 and over the heated metal ⁇ -diketonate pellets 40 whereby the vaporized metal ⁇ -diketonate is entrained in the flowing helium gas and the gaseous mixture is immediately exhausted from the tube via outlet 38 and into tube 14 of the preform fabricating apparatus 20.
- the heated section is inside tube 14, about 15 to 20 cm away from the maximum return position of the flame. In this way, the dopant is introduced very close to the heated zone.
- the gaseous metal ⁇ -diketonate/He mixture passed into tube 14 is comprised of about 0.1 to 2 volume percent metal ⁇ -diketone and about 98 to about 99.9 volume percent helium.
- the metal ⁇ -diketonate/He gaseous mixture flowed into tube 14 is caused to be admixed with the other core forming gaseous materials introduced through manifold 24 and this mixture of gaseous materials is passed into interior of tube 14.
- the gaseous compounds are decomposed and reacted with oxygen to produce deposits which are generally oxides of the gaseous metal compounds which serve as core precursor materials.
- the oxidized gaseous metal ⁇ -diketonates and metal chlorides are decomposed and converted to oxides, they are deposited by thermophoresis and fuse on the interior surface of tube 14, as a core layer, and unconsolidated so ⁇ t and extra carrier gases pass out of tube 14 via exhaust line 28.
- a plurality of traversals of burner 26 (e.g., about 50) are accomplished until a predetermined thickness of core layer 12 is attained.
- tube 14 is heated to a higher temperature, e.g. , 1900° to 2300°C, to cause the tube to soften, shrink and finally collapse to form the solid optical fiber preform 10 shown in FIG. 1.
- a higher temperature e.g. , 1900° to 2300°C
- This is accomplished by elevating the temperature of burner 26 to provide a localized heat zone which is slowly traversed (e.g. , about 0.5 to 0.2 mm/sec) along the tube 14 to effect localized softening of the tube wall.
- a number of traversals e.g.
- EXAMPLE A typical metal chelate (cerium diketonate) was formed as follows: 18.25 g (25 mol) Ce(S04)2 were dissolved in 200 ml water and neutralized with NH4OH to pH of about 10. To this solution was added 31.6 gm (.14 mol) 1,1 ,1 ,5,5,5-hexafluoro-2,4-pentanedione dissolved in 200 ml benzene. The aqueous phase was maintained alkaline with periodic additions of NH4OH. The mixture was allowed to react for 1 1/2 hrs at 70°C under reflux. The mixture was cooled and the immiscible layers separated in a separatory funnel. The aqueous phase was discarded.
- the crystalline solid was pressed into 2 mm diameter pellets and 1.5 to 2 grams of these pellets were charged to a fused silica boat which was placed in the heater section 23 of probe 30 shown in FIG. 3.
- a flow of dry helium gas was initiated through the probe and the heater elements were activated to raise the temperature of the boat contents to 200° to 250°C to effect the vaporization of the metal ⁇ -diketonate.
- a tube 14 of high purity fused silica of 50 cm length x 18 mm ID x 24 mm OD sealed to larger "handles" of commercial silica on each end was first cleaned by immersion in hydrofluoric acid solution for 3 minutes and was rinsed with deionized water, followed by methanol and dried by passage of 2 for several hours.
- the tube was mounted in an apparatus of the type shown in FIG. 2. Core precursor compounds were deposited on the interior wall surfaces as the tube was rotated at 100 rpm. Before the core precursor compounds were introduced into the interior of the tube, the tube was flushed with a continuous stream of- oxygen flowed into the tube at a flow rate of about 1500 to 2000 cc/min while traversing with the burner 26 a sufficient number of times to bring the wall temperature of the tube to 1900°C in order to volatilize any impurities present on the interior wall surface.
- a mixture of gaseous SiCl4, GeCl4 and POCI3 was introduced into the interior of the tube entrained on an oxygen carrier, the flow rate being 58 cc/min, SiCl4, 49 cc/min, GeCl4, 0.24 cc/min, POCI3 and 1500 cc/m'in O2.
- the gaseous mixture being comprised of approximately 3.5 percent SiCl4, 2.9 percent GeCl4 and 90 percent O2.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Peptides Or Proteins (AREA)
Abstract
Procédé permettant d'incorporer un dopant métallique dans le noyau de silice dopé d'une ébauche de fibres optiques, le composé précurseur du dopant étant un chélate métallique possédant une pression de vapeur suffisamment élevée, ce chélate pouvant être volatilisé à des températures relativement faibles (par exemple, entre 100o et 250oC), et pouvant être aisément incorporé dans les courants gazeux du composé précurseur de noyau utilisé normalement pour le dépôt du noyau dopé, ce chélate métallique étant dérivé d'un ligant de beta-dicetone fluoré de formule le générale (I), où R, R1 et R2 sont des groupes alkyle perfluorés composés de 1 à 7 atomes de carbone ou des groupes aryle perfluorés.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74068085A | 1985-06-03 | 1985-06-03 | |
US740680 | 1985-06-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0223853A1 true EP0223853A1 (fr) | 1987-06-03 |
Family
ID=24977581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86904479A Withdrawn EP0223853A1 (fr) | 1985-06-03 | 1986-04-23 | Procede d'introduction de dopants dans des ebauches de fibres optiques |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0223853A1 (fr) |
JP (1) | JPS62502748A (fr) |
MY (1) | MY102901A (fr) |
WO (1) | WO1986007348A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6132770A (en) * | 1996-01-08 | 2000-10-17 | Astrazeneca Ab | Multiple unit effervescent dosage forms comprising proton pump inhibitor |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645524A (en) * | 1985-04-22 | 1987-02-24 | Corning Glass Works | Method for making sodium-containing glass |
US4936650A (en) * | 1986-04-24 | 1990-06-26 | British Telecommunications Public Limited Company | Optical wave guides |
GB8713698D0 (en) * | 1987-06-11 | 1987-07-15 | British Telecomm | Glass compositions |
CA1294802C (fr) * | 1986-06-04 | 1992-01-28 | Benjamin J. Ainslie | Guides de lumiere et fabrication de ces guides |
US4826288A (en) * | 1987-04-09 | 1989-05-02 | Polaroid Corporation, Patent Department | Method for fabricating optical fibers having cores with high rare earth content |
GB8724736D0 (en) * | 1987-10-22 | 1987-11-25 | British Telecomm | Optical fibre |
US5145508A (en) * | 1988-03-04 | 1992-09-08 | Nippon Telegraph And Telephone Corporation | Method of making fluoride glass using barium β-diketones |
US5071460A (en) * | 1988-03-04 | 1991-12-10 | Nippon Telegraph And Telephone Corporation | Process for the preparation of fluoride glass and process for the preparation of optical fiber preform using the fluoride glass |
US5236481A (en) * | 1992-02-21 | 1993-08-17 | Corning Incorporated | Method of doping porous glass preforms |
KR100342189B1 (ko) * | 1995-07-12 | 2002-11-30 | 삼성전자 주식회사 | 휘발성복합체를사용한희토류원소첨가광섬유제조방법 |
US6192713B1 (en) | 1998-06-30 | 2001-02-27 | Sdl, Inc. | Apparatus for the manufacture of glass preforms |
EP1098857A1 (fr) * | 1998-06-30 | 2001-05-16 | SDL, Inc. | Procede et dispositif de production d'une preforme de fibre optique dopee avec une terre rare |
FI116469B (fi) * | 1998-10-05 | 2005-11-30 | Liekki Oy | Liekkiruiskutusmenetelmä ja -laitteisto monikomponenttilasin valmistamiseksi |
EP3950611A1 (fr) * | 2020-08-06 | 2022-02-09 | Heraeus Quarzglas GmbH & Co. KG | Agent de fluoration alternatif destiné à la fabrication de verre à quartz fluoré |
EP3950610A1 (fr) * | 2020-08-06 | 2022-02-09 | Heraeus Quarzglas GmbH & Co. KG | Agent de fluoration alternatif ii : fluosil et formation de suie |
CN115933081B (zh) * | 2022-11-18 | 2023-07-25 | 宏安集团有限公司 | 一种半干式光纤带光缆 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4501602A (en) * | 1982-09-15 | 1985-02-26 | Corning Glass Works | Process for making sintered glasses and ceramics |
-
1986
- 1986-04-23 JP JP61503874A patent/JPS62502748A/ja active Pending
- 1986-04-23 EP EP86904479A patent/EP0223853A1/fr not_active Withdrawn
- 1986-04-23 WO PCT/US1986/000865 patent/WO1986007348A1/fr not_active Application Discontinuation
-
1987
- 1987-09-22 MY MYPI87001857A patent/MY102901A/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO8607348A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6132770A (en) * | 1996-01-08 | 2000-10-17 | Astrazeneca Ab | Multiple unit effervescent dosage forms comprising proton pump inhibitor |
Also Published As
Publication number | Publication date |
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WO1986007348A1 (fr) | 1986-12-18 |
MY102901A (en) | 1993-03-31 |
JPS62502748A (ja) | 1987-10-22 |
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