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WO1999054259A1 - Procedes de fabrication de verres en silice-anhydride titanique a expansion ultra faible - Google Patents

Procedes de fabrication de verres en silice-anhydride titanique a expansion ultra faible Download PDF

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Publication number
WO1999054259A1
WO1999054259A1 PCT/US1999/008777 US9908777W WO9954259A1 WO 1999054259 A1 WO1999054259 A1 WO 1999054259A1 US 9908777 W US9908777 W US 9908777W WO 9954259 A1 WO9954259 A1 WO 9954259A1
Authority
WO
WIPO (PCT)
Prior art keywords
omcts
halide
free
ipox
water
Prior art date
Application number
PCT/US1999/008777
Other languages
English (en)
Inventor
John E. Maxon
Robert Stephen Pavlik, Jr.
Original Assignee
Corning Incorporated
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to EP99919954A priority Critical patent/EP1094990A1/fr
Priority to JP2000544606A priority patent/JP2002512169A/ja
Publication of WO1999054259A1 publication Critical patent/WO1999054259A1/fr

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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • 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
    • C03B2201/02—Pure silica glass, e.g. pure fused quartz
    • 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
    • C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
    • C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium
    • 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
    • C03B2207/30—For glass precursor of non-standard type, e.g. solid SiH3F
    • C03B2207/34—Liquid, e.g. mist or aerosol
    • 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
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/40—Doped silica-based glasses containing metals containing transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
    • C03C2201/42—Doped silica-based glasses containing metals containing transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn containing titanium
    • 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
    • C03C2203/00—Production processes
    • C03C2203/40—Gas-phase processes

Definitions

  • This invention relates to ultra-low expansion glasses composed of Si0 2 and Ti ⁇ 2. More particularly, the invention relates to environmentally friendly methods for making such glasses. BACKGROUND OF THE INVENTION Historically, ultra-low expansion glasses composed of Si ⁇ 2 and TiO 2 have been made by flame hydrolysis (flame deposition) of SiCLj and TiCL.
  • the deposition process is carried out in a furnace composed of a refractory crown, which carries a series of soot producing burners, and a refractory cup, which collects the soot produced by the burners to form a glass "boule.”
  • the Ti ⁇ 2 concentration in the finished glass is typically in the 5-11% by weight range (e.g., approximately 7% by weight) and the glass has an expansion coefficient of less than 5xlO- 7 /°C. See U.S. Patent No. 2,326,059.
  • SiCl and TiCLj are clearly chlorine-containing compounds.
  • these raw materials result in the production of various chlorine -containing by-products, e.g., CI2 and HC1, which can cause environmental damage.
  • these by-products can be collected by scrubbing the emission gases which exit the glass making furnace, such scrubbing is expensive and complicates the glass making process.
  • halide- free polymethylsiloxanes have been used in the production of silica- containing glasses.
  • Ti-Ipox is exceedingly sensitive to even the smallest amounts of water and/or hydroxyl groups in OMCTS; and (2) OMCTS as commercially supplied contains amounts of dissolved water and silanols (SiOH) well above the levels to which Ti-Ipox is sensitive, even though OMCTS is considered in the art to be a hydrophobic material, e.g., commercially available OMCTS typically has a water content of around 10 ppm but can have water levels as high as 200 ppm or even higher.
  • FIG. 1 shows storage tanks 10 and 12 for OMCTS and Ti-Ipox, respectively, each storage tank being equipped with appropriate heating equipment (not shown) for converting its contents into vapor form.
  • gas e.g., nitrogen
  • tanks 10 and 12 are supplied to tanks 10 and 12 through feed lines 14 and 16, respectively, and serves to carry vaporized OMCTS and vaporized Ti-Ipox to static mixer 18 by means of conduits 20 and 22.
  • static mixer 18 the mixed vapors pass through conduit 24 to distribution manifold 26 and from there to burners 28 by means of conduits 30.
  • the OMCTS and Ti-Ipox vapors are only in contact between joint 13 and burners 28. This corresponds to a contact time of only a few seconds.
  • the water/hydroxyl groups in OMCTS were found to hydrolyze the Ti-Ipox resulting in the formation of a white precipitate at all points downstream of joint 13. This precipitate, which is believed to be Ti ⁇ 2, accumulates on, among other things, burners 28 resulting in pressure increases in distribution manifold 26 and deviations in the composition of the boule.
  • the invention in accordance with certain of its aspects provides a method for producing a silica-titania glass which comprises the steps of:
  • soot particles from the third gas stream using at least one burner, e.g., forming soot particles from the gas stream in conduit 24 by means of distribution manifold 26, conduits 30, and burners 28; and (e) producing the desired silica-titania glass from the soot particles, e.g., by collecting the soot particles produced by burners 28 to form a boule, with the boule being consolidated as the soot particles are collected or alternatively, but less preferred, after the particles are collected; wherein the concentration of water and/or hydroxyl groups in the first gas stream is sufficiently low so that mixing of the first and second gas streams does not result in the formation of a substantial amount of a precipitate as a result of hydrolysis of Ti-Ipox.
  • a "substantial amount" of precipitate is an amount which necessitates premature shut down of the glass making process for precipitate removal before a desired quantity of glass has been produced.
  • the concentration of water in the OMCTS prior to its incorporation in the first gas stream is less than 2 ppm and, most preferably, less than 1 ppm.
  • a low concentration of water is preferably achieved by pre-drying the OMCTS before it is introduced into tank 10.
  • the inert gas provided to tank 10 by conduit 14 must also be dry so that water is not reintroduced into the OMCTS.
  • the inert gas provided to tank 12 by conduit 16 must also be dry.
  • OMCTS and Ti-Ipox are the preferred starting materials for producing silica-titania glasses, other halide-free compounds can be -5-
  • Figure 1 is a schematic diagram of apparatus which can be used in the practice of the invention to produce silica-titania glasses.
  • Figure 2 is a schematic diagram of apparatus which can be used to produce "dry" OMCTS.
  • FIG. 2 shows suitable equipment for producing an OMCTS feedstock having a low water content.
  • OMCTS which is to be dried (the "wet" OMCTS) is introduced into tank 32 through conduit 34 which is equipped with shut off valve 36.
  • the wet OMCTS is heated to a temperature of, for example, 140°F, after which dry nitrogen is pumped into the tank through conduit 38.
  • Conduit 38 can be equipped with a sparger so as to produce numerous small bubbles which flow upward -6-
  • a nitrogen flow rate of 12.5 scfm has been found suitable to dry approximately 300 gallons of OMCTS in about 3.5 hours.
  • the heating of the OMCTS is preferably performed by hot oil tracing of tank 32. Although electric heating can be used, hot oil heating is preferred since it reduces the chances of hot spots along the surface of the tank which can result in undesirable polymerization of the OMCTS. Even with hot oil heating, the temperatures of the OMCTS and of the hot oil need to be monitored to avoid excessive heating and thus polymerization of the OMCTS. Because the vapor pressure of water is substantially greater than that of OMCTS, the temperature of the wet OMCTS does not have to be raised above 212°F to achieve effective water removal but only to a temperature of around 140°F.
  • Moisture sensor 44 can, for example, be a PANAMETRICS brand sensor manufactured by Panametrics Incorporated, Waltham, MA. Although this sensor gives somewhat qualitative results, it has been found to work successfully in practice.
  • the flow of nitrogen is shut off and the dried OMCTS is transferred to storage tank 50 using pump 48.
  • conduit 52 By means of conduit 52, a blanket of dry nitrogen is maintained over the "dry" OMCTS as it is being pumped into tank 50, as well as during storage in that tank.
  • the dry OMCTS is transferred to tank 10 of Figure 1 using outlet conduit 54 of tank 50 and an appropriate inlet conduit (not shown) to tank 10. -7-
  • the apparatus of Figures 1 and 2 is preferably made of stainless steel, e.g., 304L SS, except for conduits 30 in Figure 1 which are preferably PFA TEFLON.
  • Tanks 10 and 12 in Figure 1, as well as the conduits shown in that figure, are preferably hot oil traced.
  • tank 32 in Figure 2 is also hot oil traced, as are the various conduits associated with that tank which carry OMCTS.
  • the invention has been described in terms of producing glass boules of ultra-low expansion silica-titania glasses, it can also be used in the production of other silica glasses which contain titanium.
  • the invention can be used in the preparation of titanium-doped preforms from which optical waveguide fibers can be drawn.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)
  • Glass Melting And Manufacturing (AREA)

Abstract

L'invention concerne la production de verres en silice-anhydride titanique à expansion ultra faible par dépôt à la flamme d'un mélange d'octaméthylcyclotétrasiloxane (OMCTS) vaporisé et d'isopropoxyde de titane (Ti-Ipox) vaporisé. On vaporise Ti-Ipox avec de l'azote passant en bulles d'un conduit (16) dans un réservoir (12) et on vaporise OMCTS avec de l'azote passant en bulles d'un conduit (14) dans un réservoir (10). Avant son mélange avec le Ti-Ipox, l'OMCTS est séché de sorte que sa teneur en eau soit inférieure à 2 ppm et de préférence à 1 ppm. De cette manière, on évite la formation d'un précipité sur le matériel de fabrication de verre (par exemple, brûleurs (28), robinet de distribution (26), mélangeur statique (18), joint (13) et conduits (20, 22, 24 et 30)). Si on laisse se former ce précipité, il provoque un arrêt prématuré du procédé de fabrication de verre et peut entraîner des variations non voulues de la composition du verre en silice-anhydride titanique produit.
PCT/US1999/008777 1998-04-22 1999-04-21 Procedes de fabrication de verres en silice-anhydride titanique a expansion ultra faible WO1999054259A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99919954A EP1094990A1 (fr) 1998-04-22 1999-04-21 Procedes de fabrication de verres en silice-anhydride titanique a expansion ultra faible
JP2000544606A JP2002512169A (ja) 1998-04-22 1999-04-21 超低膨張シリカチタニアガラスの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8271098P 1998-04-22 1998-04-22
US60/082,710 1998-04-22

Publications (1)

Publication Number Publication Date
WO1999054259A1 true WO1999054259A1 (fr) 1999-10-28

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EP (1) EP1094990A1 (fr)
JP (1) JP2002512169A (fr)
WO (1) WO1999054259A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092172A1 (fr) * 2000-05-25 2001-12-06 Corning Incorporated Procede de fabrication d'une preforme en verre de silice dopee au dioxyde de titane
EP1390309A4 (fr) * 2001-04-27 2004-12-08 Corning Inc Procede de production de substrats de verre a base de dioxyde de titane et de silice fondue destines a la lithographie par ultraviolets extremes
EP2559669A3 (fr) * 2011-08-18 2014-01-08 Shin-Etsu Chemical Co., Ltd. Verre de silice dopé au titane et procédé de fabrication
WO2014124877A1 (fr) * 2013-02-12 2014-08-21 Heraeus Quarzglas Gmbh & Co. Kg Procédé de fabrication de verre de quartz synthétique dopé au titane
EP3002262A1 (fr) 2014-10-01 2016-04-06 Heraeus Quarzglas GmbH & Co. KG Procédé de fabrication de verre de quartz synthétique au moyen d'un polyalkylsiloxane polymérisable
EP3034476A1 (fr) 2014-12-16 2016-06-22 Heraeus Quarzglas GmbH & Co. KG Procédé de fabrication de verre de quartz synthétique à l'aide d'un dispositif de purification
EP3059212A1 (fr) 2015-02-18 2016-08-24 Heraeus Quarzglas GmbH & Co. KG Procédé et dispositif de fabrication de verre de silice à partir de polyalkaylsiloxane polymérisable avec un filtre membrane comme dispositif de purification
US11667557B2 (en) * 2020-12-14 2023-06-06 Shin-Etsu Chemical Co., Ltd. Apparatus and method for producing porous glass preform

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043002A (en) * 1990-08-16 1991-08-27 Corning Incorporated Method of making fused silica by decomposing siloxanes
JPH0474728A (ja) * 1990-07-12 1992-03-10 Sumitomo Electric Ind Ltd 石英系光導波路の製造方法および装置
US5152819A (en) * 1990-08-16 1992-10-06 Corning Incorporated Method of making fused silica
US5154744A (en) * 1991-08-26 1992-10-13 Corning Incorporated Method of making titania-doped fused silica
JPH06160657A (ja) * 1992-11-24 1994-06-07 Mitsubishi Electric Corp 光導波路の製造方法
US5451390A (en) * 1992-10-24 1995-09-19 Degussa Aktiengesellschaft Flame-hydrolytically produced titanium dioxide mixed oxide, method of its production and its use
WO1998027018A1 (fr) * 1996-12-16 1998-06-25 Corning Incorporated Composes organometalliques pour des applications de circuits optiques a onde lumineuse

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0474728A (ja) * 1990-07-12 1992-03-10 Sumitomo Electric Ind Ltd 石英系光導波路の製造方法および装置
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
US5154744A (en) * 1991-08-26 1992-10-13 Corning Incorporated Method of making titania-doped fused silica
US5451390A (en) * 1992-10-24 1995-09-19 Degussa Aktiengesellschaft Flame-hydrolytically produced titanium dioxide mixed oxide, method of its production and its use
JPH06160657A (ja) * 1992-11-24 1994-06-07 Mitsubishi Electric Corp 光導波路の製造方法
WO1998027018A1 (fr) * 1996-12-16 1998-06-25 Corning Incorporated Composes organometalliques pour des applications de circuits optiques a onde lumineuse

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092172A1 (fr) * 2000-05-25 2001-12-06 Corning Incorporated Procede de fabrication d'une preforme en verre de silice dopee au dioxyde de titane
EP1390309A4 (fr) * 2001-04-27 2004-12-08 Corning Inc Procede de production de substrats de verre a base de dioxyde de titane et de silice fondue destines a la lithographie par ultraviolets extremes
US8047023B2 (en) 2001-04-27 2011-11-01 Corning Incorporated Method for producing titania-doped fused silica glass
US9612525B2 (en) 2011-08-18 2017-04-04 Shin-Etsu Chemical Co., Ltd. Titania-doped quartz glass and making method
EP2559669A3 (fr) * 2011-08-18 2014-01-08 Shin-Etsu Chemical Co., Ltd. Verre de silice dopé au titane et procédé de fabrication
US9346700B2 (en) 2011-08-18 2016-05-24 Shin-Etsu Chemical Co., Ltd. Titania-doped quartz glass and making method
WO2014124877A1 (fr) * 2013-02-12 2014-08-21 Heraeus Quarzglas Gmbh & Co. Kg Procédé de fabrication de verre de quartz synthétique dopé au titane
US9796617B2 (en) 2013-02-12 2017-10-24 Heraeus Quarzglas Gmbh & Co. Kg Method for producing titanium-doped synthetic quartz glass
US9790120B2 (en) 2014-10-01 2017-10-17 Heraeus Quarzglas Gmbh & Co. Kg Method for the manufacture of synthetic quartz glass
EP3002262A1 (fr) 2014-10-01 2016-04-06 Heraeus Quarzglas GmbH & Co. KG Procédé de fabrication de verre de quartz synthétique au moyen d'un polyalkylsiloxane polymérisable
WO2016096811A1 (fr) 2014-12-16 2016-06-23 Heraeus Quarzglas Gmbh & Co. Kg Procédé de production de verre quartzeux de synthèse au moyen d'un dispositif de purification
EP3034476A1 (fr) 2014-12-16 2016-06-22 Heraeus Quarzglas GmbH & Co. KG Procédé de fabrication de verre de quartz synthétique à l'aide d'un dispositif de purification
US11267745B2 (en) 2014-12-16 2022-03-08 Heraeus Quarzglas Gmbh & Co. Kg Process for producing synthetic quartz glass using a cleaning device
EP3059212A1 (fr) 2015-02-18 2016-08-24 Heraeus Quarzglas GmbH & Co. KG Procédé et dispositif de fabrication de verre de silice à partir de polyalkaylsiloxane polymérisable avec un filtre membrane comme dispositif de purification
WO2016131849A1 (fr) 2015-02-18 2016-08-25 Heraeus Quarzglas Gmbh & Co. Kg Procédé et dispositif de fabrication de verre de quartz à partir d'un composé polyalkyle siloxane polymérisable au moyen d'un filtre à membrane en tant que dispositif d'épuration
US11667557B2 (en) * 2020-12-14 2023-06-06 Shin-Etsu Chemical Co., Ltd. Apparatus and method for producing porous glass preform

Also Published As

Publication number Publication date
EP1094990A1 (fr) 2001-05-02
JP2002512169A (ja) 2002-04-23

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