AU743831B2 - Germanium chloride and siloxane feedstock for forming silica glass and method - Google Patents
Germanium chloride and siloxane feedstock for forming silica glass and method Download PDFInfo
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- AU743831B2 AU743831B2 AU84730/98A AU8473098A AU743831B2 AU 743831 B2 AU743831 B2 AU 743831B2 AU 84730/98 A AU84730/98 A AU 84730/98A AU 8473098 A AU8473098 A AU 8473098A AU 743831 B2 AU743831 B2 AU 743831B2
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- Prior art keywords
- fluid
- feedstock
- germanium
- silica
- siloxane
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 139
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 title claims description 76
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims description 63
- 238000000034 method Methods 0.000 title claims description 30
- 239000012530 fluid Substances 0.000 claims description 101
- 239000004071 soot Substances 0.000 claims description 72
- 239000000377 silicon dioxide Substances 0.000 claims description 65
- 230000003287 optical effect Effects 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 47
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 42
- 229910052732 germanium Inorganic materials 0.000 claims description 29
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 29
- 238000000151 deposition Methods 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005253 cladding Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- -1 Organometallic siloxane compounds Chemical class 0.000 description 6
- 239000003517 fume Substances 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- 239000006200 vaporizer Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 2
- 230000006838 adverse reaction Effects 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 125000000082 organogermanium group Chemical group 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- FEFXFMQVSDTSPA-UHFFFAOYSA-N trichloro(methyl)germane Chemical compound C[Ge](Cl)(Cl)Cl FEFXFMQVSDTSPA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZZBNZZCHSNOXOH-UHFFFAOYSA-N chloro(trimethyl)germane Chemical compound C[Ge](C)(C)Cl ZZBNZZCHSNOXOH-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YQECBLVSMFAWIZ-UHFFFAOYSA-N dichloro(dimethyl)germane Chemical compound C[Ge](C)(Cl)Cl YQECBLVSMFAWIZ-UHFFFAOYSA-N 0.000 description 1
- DEXWIABLZCHDAN-UHFFFAOYSA-N dichlorogermanium;2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound Cl[Ge]Cl.C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 DEXWIABLZCHDAN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical class Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CIWQSBMDFPABPQ-UHFFFAOYSA-N trichloro(phenyl)germane Chemical compound Cl[Ge](Cl)(Cl)C1=CC=CC=C1 CIWQSBMDFPABPQ-UHFFFAOYSA-N 0.000 description 1
- BOXHBPXVFJOVLX-UHFFFAOYSA-N trichloro(prop-2-enyl)germane Chemical compound Cl[Ge](Cl)(Cl)CC=C BOXHBPXVFJOVLX-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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]
- C03B37/01413—Reactant delivery systems
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1415—Reactant delivery systems
-
- 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
- C03B2201/31—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with germanium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/30—For glass precursor of non-standard type, e.g. solid SiH3F
- C03B2207/32—Non-halide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Melting And Manufacturing (AREA)
Description
WO 99/02459 PCT/US98/13401 GERMANIUM CHLORIDE AND SILOXANE FEEDSTOCK FOR FORMING SILICA GLASS AND METHOD FIELD OF THE INVENTION The present invention relates to silica feedstock compositions. More particularly, the present invention relates to silica forming feedstocks, and the methods of manufacturing optical waveguide preforms.
BACKGROUND OF THE INVENTION Various processes are known that involve the production of metal oxides from a variety of feedstocks.
Such processes require a feedstock and a means of catalyzing oxidation and combustion of the feedstock to convert the feedstock into finely divided aggregates called soot. This soot'can be heat treated to form a high purity glass article. This process is usually carried out using specialized conversion site equipment including flame generating burners.
Historically, silicon tetrachloride has been used as the main silicon containing feedstock that is converted to silica. This use of silicon tetrachloride as the silica- in forming feedstock provides a high purity silica glass and WO 99/02459 PCT/US98/13401 2 has been the commercially preferred method of manufacturing silica glass for use in optical waveguide products and particularly the manufacturing of optical waveguide fibers and their preforms.
Organometallic siloxane compounds such as octamethylcyclotetrasiloxane have been used in the manufacture of silica glass to avoid the byproduction of HC1. U.S. Patent No. 5,296,012 by Antos et al. teaches that organometallic siloxane compounds such as octamethylcyclotetrasiloxane and chlorides such as GeCl, are chemically incompatible with each other in the vapor phase and can form particulates in the vapor transport system if mixed together before oxidation and that it is desirable to keep the vapor streams separated.
U.S.
Patent No. 5,296,012 discloses a complicated multiple burner method of making GeO: doped silica glass with separate feedstock vapor streams wherein octamethylcyclotetrasiloxane vapor is delivered to a first burner and GeCl 4 vapor is delivered to a separate second burner. Another prior art method kept the organometallic compound vapors separated from the dopant halide compound in separate and different delivery conduits, such as a tube with a tube, until they exited the face.of a combustion burner having multiple concentric fume tubes.
Such a method produced a gas stream containing the organometallic compound vapor and the dopant halide compound vapor after delivery to the conversion site combustion burner, with the compounds mixing together after exiting the conversion site combustion burner face, and just prior to entering the flame of the burner. Such prior art methods are complicated and pose production problems.
In light of this, there is a need for a germanium doped silica feedstock and a method of forming optical waveguide preforms and optical waveguide products such as 3 an optical fiber which avoids the problems and complications of the prior art.
SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a silica forming feedstock and method of forming optical waveguides and optical waveguide preforms that overcomes, or at least alleviates one or more of the problems due to limitations and disadvantages of the related art.
According to the present invention, there is provided a method of making an optical waveguide preform including the steps of: a mixing a high purity siloxane with a high purity germanium chloride in a ratio ranging from 1-10 parts by weight of said siloxane to 1 part by weight of said germanium chloride to provide a fluid feedstock; delivery said fluid feedstock through a heated supply conduit having a temperature ranging from approximately 1750C to 2000C to a conversion site; converting said delivered fluid feedstock into a germanium doped silica; depositing a germanium doped silica on a deposition surface; and forming said deposited germanium doped silica into an optical waveguide preform.
The present invention also provides a method of making an optical uide fiber including the steps of: waveg providing a first fluid feedstock comprised of octamethylcyclotetrasiloxane and germanium tetrachloride; delivering said first fluid feedstock through a heated supply conduit having a temperature ranging from approximately 1750C to 200 0
C
to a conversion site; converting said delivered first fluid feedstock into GeO 2 doped Sio 2 soot; depositing said GeO 2 doped SiO 2 soot on a deposition surface; W XSHARONOTHERWMMH6W3O3amen.doc 4 providing a second fluid feedstock comprised of octamethylcyclotetrasiloxane; delivering said second fluid feedstock through a heated supply conduit having a temperature ranging from approximately 1750C to 2000C to a conversion site; converting said delivered second fluid feedstock into SiO 2 soot; depositing said SiO 2 soot over said deposited GeO 2 doped SiO 2 shoot; forming said deposited SiO 2 soot and said deposited GeO 2 soot 10 into an optical waveguide preform; and drawing said optical waveguide preform into a fiber.
The present invention further provides a silica forming feedstock fluid comprised of a high purity siloxane fluid and a high purity germanium chloride S: fluid, said siloxane fluid comprised of at least 95% by weight of octamethylcyclotetrasiloxane.
The present invention further provides a silica forming feedstock fluid consisting essentially of a siloxane and germanium chloride.
The present invention further provides an optical waveguide silica feedstock fluid consisting of octamethylcyclotetrasiloxane and germanium 20 chloride.
The principal advantage of the present invention is to provide a silica forming feedstock fluid which produces a germanium doped silica glass which allows for convenient manufacturing of optical waveguides and preforms thereof without the production of large amounts of hazardous HCI while providing the benefits of using chloride dopant precursors.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or my may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the methods and compositions of the invention particularly pointed out in the written description and claims hereof as well as the appended drawings.
Accordingly, there is provided a silica forming feedstock fluid including a RA high purity siloxane fluid and a high purity germanium chloride fluid, with the siloxane fluid preferably comprised of at least 95% by weight of W.NSHA\RONOTHERUMH600303amend.doC octamethylcyclotetrasiloxane; preferably said germanium tetrachloride.
Preferably the silica forming feedstock fluid is a vapor mixture maintained at a temperature ranging from approximately 1750C to 200 0
C.
Also disclosed herein is a method of using the inventive feedstock fluid in the formation of optical waveguide preforms and optical waveguides; preferably the method includes the steps of mixing a high purity siloxane with a high purity germanium chloride in a ratio ranging from 1-10 parts by weight of said siloxane to 1 part by weight of said germanium chloride to provide a fluid feedstock, delivering said fluid feedstock through a heated supply conduit having a 10 temperature ranging from approximately 1750C to 2000C to a conversion site, converting said delivered fluid feedstock into germanium doped silica soot, depositing said germanium doped silica soot on a deposition surface, and forming said deposited germanium doped silica soot into an optical waveguide preform. Preferably the siloxane is comprised of at least 95% by weight of octamethylcyclotetrasiloxane. Preferably the germanium chloride is comprised of at least 99% by weight of germanium tetrachloride. Preferably the method includes the step of expelling said delivered fluid feedstock through the center 0:00 tube of a conversion site burner, said center tube surrounded by an inner shield of N 2 an outer shield of 02, and an outer ring of 02 and fuel. Preferably the method includes the step of maintaining said fluid feedstock at a temperature ranging from approximately 1900C to 2000C prior to converting said feedstock into germanium doped silica soot.
Also disclosed herein is a method of making of optical waveguide preforms, which are predecessors and physical embodiments of an optical waveguide product prior to the final forming of the preform into the optical waveguide product, such as by drawing a preform into an optical waveguide fiber.
Further disclosed herein is the forming of optical waveguide preforms by such processes as depositing, cladding, drying, consolidating, stretching, caning, over cladding, and reconsolidating.
Further disclosed herein is a method of making optical fiber by converting a siloxane and germanium chloride feedstock fluid into a GeO 2 doped silica SRA glass. The method of making an optical waveguide fiber comprises the steps of: providing a first fluid feedstock comprised of octamethylcyclotetrasiloxane W:\SHARON\OTHER\MMH600303amend.doc and germanium tetrachloride, delivering said first fluid feedstock through a heated supply conduit having a temperature ranging from approximately 1750C to 2000C to a conversion site, converting said delivered first fluid feedstock into GeO 2 doped SiO 2 soot, depositing said GeO 2 doped SiO 2 soot on a deposition surface, providing a second fluid feedstock comprised of octamethylcyclotetrasiloxane, delivering said second fluid feedstock through a heated supply conduit having a temperature ranging from approximately 1750C to 200 0 C to a conversion site, converting said delivered second fluid feedstock into SiO 2 soot, depositing said SiO 2 soot over said deposited GeO 2 doped SiO 2 soot, forming said deposited SiO 2 soot and said deposited GeO 2 doped SiO 2 soot into an optical waveguide preform, and drawing said optical waveguide preform into a fiber.
Also disclosed herein is an optical waveguide preform manufacturing apparatus comprised of: a conversion site wherein a fluid feedstock delivered 15 to said conversion site is converted into germanium doped silica; a means for providing a fluid feedstock comprised of a siloxane and a germanium chloride; a Smeans for delivering said provided fluid feedstock to said conversion site; wherein said means for providing said *ooo W:\SHARON\OTHER\MMH600303amend.doc WO 99/02459 PCT/US98/13401 6 fluid feedstock includes a means for mixing said germanium chloride with said siloxane prior to delivering to said conversion site and said means for delivering said provided fluid feedstock includes a means for heating said fluid feedstock, preferably wherein said means for hearing said fluid feedstock comprises a heated delivery conduit.
It is to be understood that both the foregoing description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments and aspects of the invention and together with the description serve to explain the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 comprises a schematic representation of the method and apparatus set up of the invention.
FIG. 2 is a conversion site burner embodiment used in practicing the invention.
DETAILED DESCRIPTION OF THE INV\NTION Reference will now be made in detail to the oresent preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings.
The silica forming feedstock fluid of the inventio includes a high purity siloxane and a high purity germanium chloride. Preferably, the siloxane component Of the feedstock fluid is a polyalkysiloxane, more preferably WO 99/02459 PCT/US98/13401 7 a cyclic polyalkysiloxane, and most preferably octamethylcyclotetrasiloxane [SiO(CH 3 2 4 Preferably, the high purity siloxane is at least 95% by weight octamethylcyclotetrasiloxane, and more preferably at least 98% by weight octamethylcyclotetrasiloxane, and most preferably at least 991 by weight octamethylcyclotetrasiloxane. Preferably, the high purity germanium chloride is germanium tetrachloride (GeCl 4 Other germanium chlorides, such as R 4 -nGeCl, (where organo germanium chlorides (organochlorogermanes), and chlorinated germanium compounds may be used as alternatives to the preferred GeCl 4 Trimethylgermanium chloride (CH) ClGe] and Methyltrichlorogermane (CHClGe) are examples of such chlorinated germanium compounds. Methyltrichlorogermane (CH3Cl3Ge) Dimethyldichlorogermane
((CH
3 :r 2 Ge), Allyltrichlorogermane
(C
3 HsCl 3 Ge), Phenyltrichlorogermane (C7H9Cl3Ge) are examples of such organo germanium chlorides with the general form of RnGeCl 4 -n (where n=l to 3 and R= alkyl, aryl, or alkenyl group or any combination of these groups).
Preferably, the high purity germanium chloride is at least 99% by weight germanium tetrachloride, and more preferably contains less than 10 ppb (parts per billion) each of Al, Co, Cr, Cu, Fe, Mn, Mo, Ni, Ti, V and a combined maximum total of these less than 25 ppb, and less than 5 ppm (parts per million) OH, less than 1 ppm CH, and less than 1 ppm HC1.
The preferred silica forming feedstock fluid of the invention is a vapor mixture of octamethyc.yclotetrasiloxane and germanium chloride, with a further preferred vapor mixture including oxygen to improve the conversion of the feedstock into GeO, doped SiO 2 soot at the conversion site burner flame. The silica forming feedstock fluid vapor mixture of octamethylcyclotetra- WO 99/02459 PCTIUS98/13401 8 siloxane and germanium chloride should be maintained at a temperature of at least 175°C, preferably at least 185°C, and more preferably at least 190 0 C. Preferably this vapor mixture should be maintained at a temperature no greater than approximately 200°C. These elevated temperatures provide for the silica forming feedstock fluid vapor mixture to remain in the vapor state for efficient delivery to the conversion site burner without complications. It is preferred that the temperature not be too high in order to avoid any adverse reactions prior to reaching the conversion site flame.
To produce a silica soot and silica glass doped only with GeO, the silica forming feedstock fluid consists essentially of a siloxane and germanium chloride, preferably with octamethylcyclotetrasiloxane as the siloxane and germanium tetrachloride as the germanium chloride. To produce an optical waveguide silica glass consisting of only SiO: and GeO 2 the optical waveguide silica feedstock fluid consists of octamet-ylcylotetrasiloxane and germanium chloride.
An exemplary schematic representation of the method of making an optical waveguide preform utilizing the inventive fluid feedstock is shown in FIG. 1.
The inventive method of making an optical waveguide preform includes the steps of providing a fluid, preferably vapor, feedstock comprised of a high purity siloxane and a high purity germanium chloride and delivering the fluid feedstock through a heated supply conduit having a temperature ranging from about 175°C to 250 0 C, to maintain the feedstock temperature in this range, to a conversion site. As shown in FIG. 1, a siloxane liquid which comprises the siloxane component of the feedstock is contained in siloxane liquid container Controllable pump 22 delivers siloxane liquid through WO 99/02459 PCT/US98/13401 9 conduits and valve 24 to siloxane vaporizer 26. Means 28 for supplying a controllable flow of NZ (nitrogen) carrier gas provides nitrogen carrier gas which aids in the vaporization of the siloxane liquid and delivery of the siloxane vapor to conversion site 30, which preferably is comprised of a burner and a conversion flame. Siloxane vapors are delivered through heated siloxane vapor conduit 32, which is preferably stainless steel tubing heated and maintained at 190°C. Prior to conversion site 30, oxygen is added to the siloxane vapor to assist the conversion of the fluid feedstock. Preferably oxygen supply means 34, supplies a controllable amount cf oxygen vapors which are heated to an elevated temperature, preferably about 200°C.
Heated oxygen from conduit 36 is added to the siloxane vapor flowing to conversion site 30 at oxygen addition junction 38.
Germanium chloride vapors from germanium chloride vapor conduit 40 are mixed with the siloxane vapors at germanium chloride addition junction 42. The mixing of germanium chloride vapors with siloxane vapors provides the homogeneous fluid feedstock comprised of siloxane and germanium chloride. Germanium chloride vapors are provided through conduit 40 by a means for controllably supplying germanium chloride such as germanium chloride vaporizer 44 which comprises a heated container of liquid germanium chloride 48 and an oxygen supply 46 wherein oxygen is bubbled through the liquid germanium chloride to assist in the formation of germanium chloride vapors.
Valves 24 provide a means for controlling the amount of germanium chloride delivered through conduit 40 and mixed with siloxane vapors at junction 42. Preferably the liquid germanium chloride in container 48 is heated to 0 C and germanium chloride vapor conduit 40 is maintained at 190'C. The mixture of siloxane vapor and germanium chloride vapor fluid feedstock is provided and delivered WO 99/02459 PCT/US98/13401 through heated burner supply conduit 50, which is heated to 190 0 C, to the single fume tube of burner 52, along with the oxygen and nitrogen gases.
Burner face 51 of burner 52 is shown in FIG. 2.
Conversion site 30 includes conversion site flame 68 produced by conversion site burner 52.
The fluid vapor feedstock of siloxane and germanium chloride vapors delivered to conversion site 30 is converted by conversion site flame 68 into germanium (GeO-) doped silica (SiO:) soot. The germanium doped silica soot is then deposited on deposition surface 70. The deposited germanium doped silica soot is collected on deposition surface 70 which may comprise a rotating bait rod. The deposited doped soot forms the core of an optical waveguide preform. Forming the deposited germanium doped silica soot includes the steps of overcladding the germanium doped silica soot core preform with silica soot, removing the bait rod, and consolidating the porous soot preform into a nonporous soot preform.
The step of providing a fluid feedsto:k comprised of a high purity siloxane and a high purity germanium chloride preferably comprises the step of providing a fluid feedstock of octamethylcyclotetrasiloxane and germanium tetrachloride, and more preferably comprises the step of mixing vapors of octamethylcyclotetrasiloxane and germanium chloride prior to being delivered to conversion site 30 and burner 52. Preferably oxygen is mixed with the vapors of octamethylcyclotetrasiloxane and germanium chloride. The steps of providing and delivering a fluid feedstock of siloxane and germanium chloride preferably include the step of maintaining the fluid feedstock at a temperature range of about 175 0 C to 200 3 C, more preferably 190 0 C to 200 0 C, preferably by heating the feedstock delivery supply conduits.
WO 99/02459 PCT/US98/13401 11 The step of forming the deposited germanium doped silica soot into an optical waveguide preform includes the step of cladding the germanium doped silica soot with silica (SiO) soot. Preferably the step of cladding with silica soot includes the steps of providing a fluid feedstock of siloxane, delivering the fluid siloxane feedstock to conversion site 30 through heated supply conduits, converting the delivered fluid siloxane feedstock into silica soot, and depositing the silica soot on top of the germanium doped silica soot.
The invention includes the method of making an optical waveguide fiber which includes the steps of providing a fluid feedstock comprised of siloxane and germanium chloride, delivering the fluid feedstock to a conversion site, converting the delivered fluid feedstock into germanium (GeO 2 doped silica (SiO 2 o-.oot, depositing the GeO- doped SiO2 soot on a deposition surface, forming the deposited GeO 2 doped SiOr soot into an optical waveguide preform, and drawing the optical waveguide preform into a fiber.
The fluid feedstock of siloxane and germanium chloride, which may further include oxygen and the nitrogen (N2) carrier gas, is delivered through heated delivery conduit 50 to the center fume tube 60 of burner 52. As shown in FIG. 2, the fluid feedstock of siloxane and germanium chloride is delivered through center fume tube 60 to conversion site flame 68. Conversion site flame 68 and the conversion of the fluid feedstock into GeO: doped SiO: soot is maintained by delivering nitrogen gas to inner shield 62, oxygen (02) gas to outer shield 64, and a premixture of 02 and fuel, preferably CH 4 to fuel-oxygen outer ring 66. Inner shield N, supply 58 provides N_ gas, preferably heated and maintained at about 200°C, to nitrogen inner shield 62. Outer shield 0: supply 54 provides O0 gas to oxygen outer shield 64. Premix fuel- WO 99/02459 PCT/US98/13401 12 oxygen supply 56 provides a mixture of oxygen and fuel, preferably CH 4 to fuel-oxygen outer ring 66. This provides for a beneficial conversion of the siloxane and germanium feedstock into GeO 2 doped SiO, soot.
The method of the invention includes the step of depositing the GeO 2 doped SiO 2 soot on a deposition surface. The GeO, doped SiO soot is deposited and collected on deposition surface 70 of bait rod 72 to form the preform of an optical waveguide core. When a sufficient amount of GeO 2 doped Sio 2 soot is deposited on the deposition surface to form an optical waveguide core, the delivery of the germanium chloride and siloxane fluid feedstock mixture to burner 52 is halted.
The method of the invention further includes the step of forming the deposited GeO2 doped SiO 2 soot into an optical waveguide preform. Siloxane fluid 20 can be delivered to burner 52 in place of the feedstock mixture of siloxane and germanium chloride in order to form a cladding over the deposited GeO2 doped SiO. soot. Siloxane delivery can operate in the same manner as the germanium chloride and siloxane vapor feedstock mixture delivery system but only deliver siloxane, preferably octamethylcyclotetrasiloxane, 02, and N 2 to burner 52 which is converted at conversion site 30 by flame 68 into undoped SiO: soot. This undoped SiO 2 soot is deposited over the GeO; doped SiO 2 soot to form the preform of the optical waveguide cladding.
After a sufficient amount of undoped SiOz soot is deposited over the GeO doped SiO, soot, the deposition of soot is halted. The porous soot optical waveguide preform which has formed around the bait rod is removed from the bait rod. The porous soot preform is dried in a helium and chlorine atmosphere and sintered into a clear, fully dense consolidated glass cylindrical optical waveguide preform that is comprised of a GeO: doped silica WO 99/02459 PCT/US98/13401 13 waveguiding core structure surrounded by a silica cladding structure. This consolidated preform is stretched into an optical waveguide cane preform. This preform is overcladded with additional undoped silica soot such as produced during the formation of the cladding soot.
The overcladded preform is reconsolidated and may be drawn into an optical waveguide fiber.
Example The system and apparatus of FIG. 1 and 2 were used to produce GeO2 doped SiO 2 soot in accordance with the following table. High purity liquid octamethylcyclotetrasiloxane, which was comprised of aleast 95% by weight of octamethylcyclotetrasiloxane was pumped from container 20 to inclined plane flash vaporizer 26 which was heated above the boiling point of octamethylcyclotetrasiloxane. The octamethylcyclotetrasiloxane vapors were delivered towards conversion site 30 by the nitrogen carrier gas from N_ supply 28. Delivery supply conduits 32, 50, and 40, and delivery conduit junctions 38 and 42 comprised stainless steel tubing that was heated to 1900C. F1.ue 02 which was heated to about 200°C was supplied at junction 38 by 0: source 34 and heated conduit 36. High purity GeC14 vapor was mixed with the octamethylcyclotetrasiloxane vapor at delivery junction 42. GeCl 4 vapors were supplied by GeCl 4 vaporizer 44. GeC14 vaporizer 44 comprised a GeCl, bubbler. High purity liquid GeCl 4 comprised of at leas: 99% by weight of GeCl 4 contained in container 48 was heated to 45°C and 0 from 0: source 46 was bubbled thrsugh the heated liquid GeC14. The amount of GeC1l vapor produced could be controlled by changing the flow rate of 0O through the bubbler. This fluid feedstock vapcr mixture was delivered to conversion site flame 68 through center WO 99/02459 PCT/US98/13401 14 fume tube 60 of burner 52. This delivered fluid feedstock was converted into GeO doped SiOz soot by conversion site flame 68 and deposited on deposition surface 70. GeO.
doped SiO; soot was produced using the following conditions table: WO 99/02459 PCT/US98/13401 TABLE FOR MAKING GeOz DOPED SiO: SOOT Example 1 2 3 4 Octamethylcyclotetrasiloxane 6 6 6 8 [22] liquid delivery rate (grams/min.) Carrier N 2 rate 1.25 1.25 1.25 1.25 1.25 (liters/min.) [28] Fume 0, rate 1.8 1.8 1.8 2.5 (liters/min.)[34] Bubbler 0: rate 0.3 0.6 1.0 0.6 (liters/min.) for GeCl 4 vaporizer [44] Inner Shield N 2 rate 3 3 3 3 3 (liters/min.)[58] Outer Shield 02 6.8 6.8 6.8 8 8 (liters/min.)[54]
CH
4 rate (liters/min.) for 1.1 1.1 1.1 1.1 1.1 premix fuel-oxygen [56] O rate (liters/min.) for 0.9 0.9 0.9 0.9 0.9 premix fuel-oxygen [56] Wt.% of GeO. in the SiO, soot 14.2% 23.0% 35.3% 7.1% 9.9% WO 99/02459 PCT/US98/13401 16 It was surprising and unexpected that this method and use of the germanium chloride octamethylcyclotetrasiloxane fluid silica forming feedstock performed so well in the manufacturing of silica soot without evidence of adverse reaction between the octamethylcyclotetrasiloxane and germanium tetrachloride in delivery conduit 50, junction 42, or burner 52. No build up of unwanted soot or other troublesome byproducts were formed in burner 52 or on burner face 51 during the making of GeO 2 doped SiO- soot.
After more than 16 hours of operation no build-up, corrosion, gels or other troublesome deposits were found in junction 42, conduit 50, or burner 52. This method was able to produce germanium doped silica soot doped with about 7% to 36% GeO, by weight. The preferred weight ratio of octamethylcyclotetrasiloxane to germanium tetrachloride of the feedstock is in the range of 1.5-7.5 parts of octamethylcyclotetrasiloxane to 1 part germanium tetrachloride, and more preferred 1.9-3.6 parts of octamethylcyclotetrasiloxane to 1 part germanium tetrachloride. The preferred delivery rates to provide the fluid feedstock is about 6-10 grams/min.
octamethylcyclotetrasiloxane and 0.8-4.2 grams/min. GeCl,.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
Claims (17)
1. A method of making an optical waveguide preform including the steps of: mixing a high purity siloxane with a high purity germanium chloride in a ratio ranging from 1-10 parts by weight of said siloxane to 1 part by weight of said germanium chloride to provide a fluid feedstock; delivery said fluid feedstock through a heated supply conduit having a temperature ranging from approximately 1750C to 2000C to a conversion site; converting said delivered fluid feedstock into a germanium doped silica; depositing a germanium doped silica on a deposition surface; and forming said deposited germanium doped silica into an optical 20 waveguide preform.
2. A method as claimed in claim 1, wherein said siloxane is comprised of at least 95% by weight of octamethylcyclotetrasiloxane.
3. A method as claimed in claim 1 or 2, wherein said germanium chloride is comprised of at least 99% by weight of germanium tetrachloride.
4. A method as claimed in any preceding claim further including the step of expelling said delivered fluid feedstock through a center tube of a conversion site burner, said center tube surrounded by an inner shield of N 2 an outer shield of 02, and an outer ring of 02 and fuel. S 5. A method as claimed in claim 2, wherein the step of mixing octamethylcyclotetrasiloxane and germanium chloride further includes the step W:\SHARONOTHERMMH600303amecd.doc 18 of mixing vapors of octamethylcyclotetrasiloxane and germanium chloride prior to delivering said fluid feedstock to said conversion site.
6. A method as claimed in claim 5, wherein the step of mixing vapors of octamethylcyclotetrasiloxane and germanium chloride further includes the step of mixing vapors of octamethylcyclotetrasiloxane, germanium chloride, nitrogen and oxygen.
7. A method as claimed in any preceding claim, further including the steps of maintaining said fluid feedstock at a temperature ranging from approximately 190 0 C to 200 0 C prior to converting said feedstock onto germanium doped silica. S" 8. A method as claimed in any preceding claim, wherein the step of forming said deposited germanium doped silica into an optical waveguide preform a o 15 further includes the step of cladding said germanium doped silica with silica.
9. A method as claimed in claim 8, wherein the step of cladding said germanium doped silica with silica further includes the steps of providing a fluid feedstock comprised of a siloxane, delivering said fluid siloxane feedstock to a 20 conversion site, and converting said delivered fluid siloxane feedstock into SiO 2 A method of making an optical waveguide fiber including the steps of: providing a first fluid feedstock comprised of octamethylcyclotetrasiloxane and germanium tetrachloride; delivering said first fluid feedstock through a heated supply conduit having a temperature ranging from approximately 1750C to 2000C to a conversion site; converting said delivered first fluid feedstock into GeO 2 doped SiO 2 soot; depositing said GeO 2 doped Si0 2 soot on a deposition surface; 19 providing a second fluid feedstock comprised of octamethylcyclotetrasiloxane; delivering said second fluid feedstock through a heated supply conduit having a temperature ranging from approximately 175 0 C to 200 0 C to a conversion site; converting said delivered second fluid feedstock into SiO 2 soot; depositing said SiO 2 soot over said deposited GeO 2 doped SiO 2 soot; forming said deposited SiO 2 soot and said deposited GeO 2 doped Si0 2 soot into an optical waveguide preform; and drawing said optical waveguide preform into a fiber. 0
11. A silica forming feedstock fluid comprised of a high purity siloxane fluid 20 and a high purity germanium chloride fluid, said siloxane fluid comprised of at least 95% by weight of octamethylcyclotetrasiloxane.
12. A silica forming feedstock fluid as claimed in claim 11 wherein said germanium chloride fluid is comprised of at least 99% by weight of germanium tetrachloride.
13. A silica forming feedstock fluid as claimed in claim 11 or 12 comprised of a vapor mixture of octamethylcyclotetrasiloxane and germanium chloride maintained at a temperature ranging from approximately 1750C to 2000C.
14. A silica forming feedstock fluid consisting essentially of a siloxane and germanium chloride. A silica forming feedstock fluid as claimed in claim 14 consisting essentially of octamethylcyclotetrasiloxane and germanium chloride.
16. An optical waveguide silica feedstock fluid consisting of octamethylcyclotetrasiloxane and germanium chloride.
17. A method of making an optical waveguide perform substantially as herein described with reference to the accompanying drawings. 10 18. A method of making an optical waveguide preform substantially as herein S V described with reference to the example.
19. A method of making an optical waveguide fiber substantially as herein described with reference to the accompanying drawings.
20. A method of making an optical waveguide fiber substantially as herein described with reference to the example.
21. A silica forming feedstock fluid according to claim 14 substantially as herein described with reference to the accompanying drawings.
22. A silica forming feedstock fluid according to claim 14 substantially as herein described with reference to the example. W.ASHARON\OTHERWMH60303amend.doc
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5273797P | 1997-07-08 | 1997-07-08 | |
| US60/052737 | 1997-07-08 | ||
| PCT/US1998/013401 WO1999002459A1 (en) | 1997-07-08 | 1998-06-24 | Germanium chloride and siloxane feedstock for forming silica glass and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU8473098A AU8473098A (en) | 1999-02-08 |
| AU743831B2 true AU743831B2 (en) | 2002-02-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU84730/98A Ceased AU743831B2 (en) | 1997-07-08 | 1998-06-24 | Germanium chloride and siloxane feedstock for forming silica glass and method |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0996597A1 (en) |
| JP (1) | JP2001509469A (en) |
| KR (1) | KR20010021592A (en) |
| CN (1) | CN1259109A (en) |
| AU (1) | AU743831B2 (en) |
| BR (1) | BR9810379A (en) |
| CA (1) | CA2288769A1 (en) |
| ID (1) | ID24873A (en) |
| TW (1) | TW460424B (en) |
| WO (1) | WO1999002459A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6732551B2 (en) | 2001-05-04 | 2004-05-11 | Corning Incorporated | Method and feedstock for making silica |
| US9630872B2 (en) | 2011-09-29 | 2017-04-25 | Sumitomo Electric Industries, Ltd. | Method for manufacturing glass-fine-particle-deposited body and method for manufacturing glass base material |
| DE102011119374A1 (en) * | 2011-11-25 | 2013-05-29 | Heraeus Quarzglas Gmbh & Co. Kg | Process for the production of synthetic quartz glass |
| JP6236866B2 (en) | 2013-05-15 | 2017-11-29 | 住友電気工業株式会社 | Method for producing glass fine particle deposit and burner for producing glass fine particle deposit |
| EP3390303B1 (en) | 2015-12-18 | 2024-02-07 | Heraeus Quarzglas GmbH & Co. KG | Production of quartz glass bodies with dewpoint control in a melting furnace |
| JP6940235B2 (en) | 2015-12-18 | 2021-09-22 | ヘレウス クワルツグラス ゲーエムベーハー ウント コンパニー カーゲー | Preparation of quartz glass in a melting crucible of refractory metal |
| CN108698880B (en) | 2015-12-18 | 2023-05-02 | 贺利氏石英玻璃有限两合公司 | Preparation of opaque quartz glass bodies |
| CN109153593A (en) | 2015-12-18 | 2019-01-04 | 贺利氏石英玻璃有限两合公司 | Preparation of Synthetic Quartz Glass Particles |
| KR20180095618A (en) | 2015-12-18 | 2018-08-27 | 헤래우스 크바르츠글라스 게엠베하 ＆ 컴파니 케이지 | Preparation of silica glass bodies in multi-chamber furnaces |
| JP6981710B2 (en) | 2015-12-18 | 2021-12-17 | ヘレウス クワルツグラス ゲーエムベーハー ウント コンパニー カーゲー | Preparation of Fused Quartz from Silicon Dioxide Granules |
| EP3390304B1 (en) | 2015-12-18 | 2023-09-13 | Heraeus Quarzglas GmbH & Co. KG | Spray granulation of silicon dioxide in the production of quartz glass |
| TWI840318B (en) | 2015-12-18 | 2024-05-01 | 德商何瑞斯廓格拉斯公司 | Quartz glass body, light guide, illuminant, formed body, and process for preparing the same, and use of silicon component |
| US11339076B2 (en) | 2015-12-18 | 2022-05-24 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of carbon-doped silicon dioxide granulate as an intermediate in the preparation of quartz glass |
| WO2017103153A1 (en) | 2015-12-18 | 2017-06-22 | Heraeus Quarzglas Gmbh & Co. Kg | Glass fibers and preforms made of quartz glass having low oh, cl, and al content |
| JP6746528B2 (en) * | 2017-03-30 | 2020-08-26 | 古河電気工業株式会社 | Optical fiber porous base material manufacturing equipment |
| CN107857470B (en) * | 2017-12-07 | 2020-01-14 | 长飞光纤光缆股份有限公司 | Blowtorch for preparing large-core-diameter optical fiber base material by VAD |
| JP6793676B2 (en) * | 2018-04-02 | 2020-12-02 | 信越化学工業株式会社 | Manufacturing equipment and manufacturing method for porous glass base material for optical fibers |
| KR102388684B1 (en) * | 2021-11-25 | 2022-04-20 | 비씨엔씨 주식회사 | Synthetic quartz glass manufacturing method through OVD process with improved deposition efficincy |
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| US4604118A (en) * | 1985-08-13 | 1986-08-05 | Corning Glass Works | Method for synthesizing MgO--Al2 O3 --SiO2 glasses and ceramics |
| US5141549A (en) * | 1991-05-17 | 1992-08-25 | The Charles Stark Draper Laboratories | Method of fabricating rare earth doped planar optical waveguide for integrated optical circuit |
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| EP0146659B1 (en) * | 1983-12-22 | 1988-03-30 | Shin-Etsu Chemical Co., Ltd. | A method for the preparation of synthetic quartz glass suitable as a material of optical fibers |
| GB8905966D0 (en) * | 1989-03-15 | 1989-04-26 | Tsl Group Plc | Improved vitreous silica products |
| US5043002A (en) * | 1990-08-16 | 1991-08-27 | Corning Incorporated | Method of making fused silica by decomposing siloxanes |
| US5152819A (en) * | 1990-08-16 | 1992-10-06 | Corning Incorporated | Method of making fused silica |
| JPH04349147A (en) * | 1991-05-22 | 1992-12-03 | Fujikura Ltd | Radiation-resistant optical fiber and its production |
| US5296012A (en) * | 1992-12-28 | 1994-03-22 | Corning Incorporated | Method of making optical waveguide preforms |
| KR100473827B1 (en) * | 1995-12-19 | 2005-07-18 | 코닝 인코포레이티드 | Method and apparatus for forming fused silica by combustion of liquid reactants |
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1998
- 1998-06-24 ID IDW20000242A patent/ID24873A/en unknown
- 1998-06-24 CA CA002288769A patent/CA2288769A1/en not_active Abandoned
- 1998-06-24 JP JP2000501993A patent/JP2001509469A/en not_active Withdrawn
- 1998-06-24 CN CN98805831A patent/CN1259109A/en active Pending
- 1998-06-24 BR BR9810379-2A patent/BR9810379A/en not_active IP Right Cessation
- 1998-06-24 WO PCT/US1998/013401 patent/WO1999002459A1/en not_active Ceased
- 1998-06-24 EP EP98935493A patent/EP0996597A1/en not_active Withdrawn
- 1998-06-24 KR KR1020007000150A patent/KR20010021592A/en not_active Withdrawn
- 1998-06-24 AU AU84730/98A patent/AU743831B2/en not_active Ceased
- 1998-07-07 TW TW087111179A patent/TW460424B/en not_active IP Right Cessation
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|---|---|---|---|---|
| US4604118A (en) * | 1985-08-13 | 1986-08-05 | Corning Glass Works | Method for synthesizing MgO--Al2 O3 --SiO2 glasses and ceramics |
| US5141549A (en) * | 1991-05-17 | 1992-08-25 | The Charles Stark Draper Laboratories | Method of fabricating rare earth doped planar optical waveguide for integrated optical circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999002459A1 (en) | 1999-01-21 |
| AU8473098A (en) | 1999-02-08 |
| CA2288769A1 (en) | 1999-01-21 |
| JP2001509469A (en) | 2001-07-24 |
| BR9810379A (en) | 2000-09-05 |
| EP0996597A1 (en) | 2000-05-03 |
| KR20010021592A (en) | 2001-03-15 |
| CN1259109A (en) | 2000-07-05 |
| ID24873A (en) | 2000-08-31 |
| TW460424B (en) | 2001-10-21 |
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