WO1999015468A1 - FUSED SiO2-TiO2 GLASS METHOD - Google Patents
FUSED SiO2-TiO2 GLASS METHOD Download PDFInfo
- Publication number
- WO1999015468A1 WO1999015468A1 PCT/US1998/018067 US9818067W WO9915468A1 WO 1999015468 A1 WO1999015468 A1 WO 1999015468A1 US 9818067 W US9818067 W US 9818067W WO 9915468 A1 WO9915468 A1 WO 9915468A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- accordance
- flame
- precursor
- vapor
- particles
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
-
- 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
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
-
- 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
- C03B19/1476—Means for heating during or immediately prior to deposition
-
- 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
- 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
- C03B2207/50—Multiple burner arrangements
- C03B2207/52—Linear array of like burners
Definitions
- Relatively pure metal oxides are produced by thermal decomposition of precursors and deposition of the resulting oxides
- the precursor may take the form of a vapor, or may be carried by a vapor It may be decomposed by either flame hydrolysis or pyrolysis
- chlo ⁇ de-free precursors Specifically, a siloxane, octamethylcyclotetrasiloxane (OMCTS), and a titanium alkoxide, titanium isopropoxide, T ⁇ (OPr ⁇ ) 4 , are commercially employed
- the precursors are separately converted to vapor form and carried to a mixing manifold by a carrier gas such as nitrogen
- a carrier gas such as nitrogen
- the mixture passes, via fume lines, into a flame where the precursors are converted into S ⁇ O 2 -T ⁇ O 2 particles These particles are collected in a refractory furnace where they melt to form a solid boule
- Another purpose is to minimize material build-ups that occur in the vapor delivery system during operation
- a further purpose is to improve the quality of the T ⁇ O 2 -doped fused silica produced
- a still further purpose is to lengthen the time of a production run before it is necessary to shut the operation down for cleaning purposes SUMMARY OF THE INVENTION
- the invention resides in a method of producing, by flame hydrolysis, a fused silica glass containing titania which comprises delivering a mixture of a silica precursor and a titania precursor in vapor form to a flame, passing the mixture through the flame to form SiO 2 -TiO 2 particles, and delivering an essentially pure, titanium precursor to the flame.
- FIGURE in the accompanying drawing is a schematic representation of a system for practice of the invention.
- the conventional, boule process used in making fused silica products is a continuous process.
- a carrier gas such as nitrogen
- a silica precursor such as SiCI 4 , or OMCTS.
- the carrier gas entrains the precursor in vapor form and transports it to the site of the flame hydrolysis.
- a titania precursor is introduced. Essentially, this involves duplicating the delivery system for the silica precursor to provide entrained vapors of the titania precursor. The two separate vapor trains feed into a manifold where they are mixed. The mixture is then carried through fume lines to burners where the flame hydrolysis takes place.
- the flame converts the mixture of precursors into particles of TiO 2 - doped silica, commonly referred to as "soot "
- the particles form within a refractory furnace having a member in its base known as a cup
- the particles are deposited in the cup, and melt to form a solid body referred to as a boule
- the single FIGURE in the accompanying drawing is a schematic representation of a system for use in practicing the present invention
- the system is generally designated by the numeral 10
- System 10 includes a source 12 of the silica precursor 14
- a carrier gas 16, such as nitrogen, is introduced at or near the base of source 12 A by- pass stream of carrier gas is introduced at 18 to prevent saturation of the vaporous stream
- the vaporous stream passes through a distribution system 20 to a manifold 22
- System 10 further includes a source 24 of the titania precursor 26
- Source 24 like source 12, has an inlet 28 for a carrier gas that passes through precursor material 26 and entrains vapors thereof Again, a bypass stream is introduced at 30, and the vaporous stream passes through a distribution system 32 to manifold 22
- the two vapor streams mix in manifold 22
- the mixture passes through fume lines 34 to burners 36 mounted in the upper portion 38 of furnace 40
- the mixed vapor stream is further joined with a fuel/oxygen mixture at burners
- the silica precursor, OMCTS was found to be the source of moisture Accordingly, it has been found necessary to employ "dry" OMCTS in the present process In particular, it has been necessary to maintain the water content in the OMCTS at less than 2 ppm to inhibit the white, titania build-up in the system
- fume lines 34 are preferably insulated
- the lines may be clad with a highly conductive and reflective material such as aluminum foil
- crown 46 of furnace 40 runs hottest in its central area
- a glassy condensate tends to develop in this area
- this condensate can build-up and form a stalactite-like shape
- d ⁇ ppage onto the fused silica boule from this glassy stalactite can occur This creates effects in the boule that must be removed by grinding
- the boule lay-down cycle is shortened, thus adding to the cost of the operation At least two conditions have been found to aggravate development of the glassy condensate in the center of the crown.
- impurities in the refractory brick especially alkali and alkaline earth metal impurities.
- impurities migrate from the brick, or the silica penetrates the brick a less viscous, more fluid glass develops. This in turn more readily flows and drips onto the boule.
- This contributing factor can be minimized by employing pure materials in brick preparation; also by treatment of the furnace bricks to extract impurities prior to use of the furnace.
- the other condition manifests itself within the furnace, but it is caused by conditions in the vapor delivery system.
- the condition is turbulence in the furnace due to eddy currents developed in the flame.
- a key to controlling turbulence has been found to be maintenance of smooth, vapor flow rates. This requires more than mere inlet valve regulation and temperature control of the precursor materials. It has previously been explained that moisture must be essentially excluded to avoid dissociation of titanium alkoxide, and consequent buildup on the distribution system walls. It has been found that such buildup also creates erratic flow rates. These, in turn, cause turbulence in the furnace atmosphere.
- Titanium alkoxides are water white in a pure state, but degrade readily. This condition is exhibited by a discoloration in the material that proceeds from a pale yellow through amber to dark brown. The discoloration is due to such contaminates as higher order polymers, oxidation products, and trace elements.
- the alkoxide degrades, its properties change. In particular, its vapor pressure changes. This alters the flow-rate and thereby causes turbulence as well as composition variation. The turbulence, as noted, aggravates the buildup of glass condensate in the center of the furnace crown.
- An added benefit of using a pure titanium alkoxide is that it permits using higher temperatures in the precursor materials.
- the vapor pressure of the alkoxide increases with temperature, thus requiring a lower, carrier vapor flow rate. This lower flow rate contributes to a smoother operation and less turbulence.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69841741T DE69841741D1 (en) | 1997-09-24 | 1998-08-31 | PROCESS FOR PREPARING MELTED SiO2-TiO2 GLASS |
JP2000512783A JP4108926B2 (en) | 1997-09-24 | 1998-08-31 | Method for producing molten SiO2-TiO2 glass |
EP98945813A EP1030822B1 (en) | 1997-09-24 | 1998-08-31 | FUSED SiO2-TiO2 GLASS METHOD |
KR1020007003139A KR100574123B1 (en) | 1997-09-24 | 1998-08-31 | Fused Silica-Titania glass method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5985997P | 1997-09-24 | 1997-09-24 | |
US60/059,859 | 1997-09-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999015468A1 true WO1999015468A1 (en) | 1999-04-01 |
Family
ID=22025746
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/018067 WO1999015468A1 (en) | 1997-09-24 | 1998-08-31 | FUSED SiO2-TiO2 GLASS METHOD |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1030822B1 (en) |
JP (1) | JP4108926B2 (en) |
KR (1) | KR100574123B1 (en) |
DE (1) | DE69841741D1 (en) |
WO (1) | WO1999015468A1 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001028941A1 (en) * | 1999-10-19 | 2001-04-26 | Liekki Oy | Method and apparatus for dyeing a material |
WO2001092172A1 (en) * | 2000-05-25 | 2001-12-06 | Corning Incorporated | Method of making a titania-doped fused silica preform |
US6387511B1 (en) | 2000-07-27 | 2002-05-14 | Corning Incorporated | Light weight porous structure |
EP1358132A1 (en) * | 2000-12-21 | 2003-11-05 | Corning Incorporated | Refractories for fused silica production furnaces |
JP2004511414A (en) * | 2000-10-13 | 2004-04-15 | コーニング インコーポレイテッド | Method for avoiding striae in EUV lithography mirrors |
US6988378B1 (en) | 2000-07-27 | 2006-01-24 | Corning Incorporated | Light weight porous structure |
US7410922B2 (en) * | 2003-04-03 | 2008-08-12 | Asahi Glass Company, Limited | Silica glass containing TiO2 and process for its production |
US7429546B2 (en) * | 2003-04-03 | 2008-09-30 | Asahi Glass Company, Limited | Silica glass containing TiO2 and process for its production |
US7989378B2 (en) | 2007-12-27 | 2011-08-02 | Asahi Glass Company, Limited | TiO2-containing silica glass |
US8047023B2 (en) | 2001-04-27 | 2011-11-01 | Corning Incorporated | Method for producing titania-doped fused silica glass |
WO2012105513A1 (en) | 2011-01-31 | 2012-08-09 | 旭硝子株式会社 | Method for producing silica glass body containing titania, and silica glass body containing titania |
EP3002262A1 (en) | 2014-10-01 | 2016-04-06 | Heraeus Quarzglas GmbH & Co. KG | Method for the manufacture of synthetic quartz glass with polymerizable polyalkylsiloxane |
EP3034476A1 (en) | 2014-12-16 | 2016-06-22 | Heraeus Quarzglas GmbH & Co. KG | Method for the preparation of synthetic quartz glass with the use of a cleaning device |
EP3059212A1 (en) | 2015-02-18 | 2016-08-24 | Heraeus Quarzglas GmbH & Co. KG | Method and apparatus for making silica glass from polymerisable polyalkylsiloxane with membrane filter as cleaning device |
US10604437B2 (en) | 2014-10-20 | 2020-03-31 | Navus Automation, Inc. | Fused silica furnace system and method for continuous production of fused silica |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004092082A1 (en) * | 2003-04-11 | 2004-10-28 | Nikon Corporation | METHOD FOR PRODUCING SiO2-TiO2 BASED GLASS, SiO2-TiO2 BASED GLASS AND EXPOSURE SYSTEM |
JP5992842B2 (en) * | 2013-01-24 | 2016-09-14 | 信越石英株式会社 | Method for producing silica titania glass and method for selecting silica titania glass |
Citations (4)
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 |
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 |
US5395413A (en) * | 1993-04-16 | 1995-03-07 | Corning Incorporated | Method for producing fused silica with low sodium ion contamination level |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5632797A (en) * | 1994-12-30 | 1997-05-27 | Corning Incorporated | Method of providing vaporized halide-free, silicon-containing compounds |
US5558687A (en) * | 1994-12-30 | 1996-09-24 | Corning Incorporated | Vertical, packed-bed, film evaporator for halide-free, silicon-containing compounds |
WO1997030933A1 (en) * | 1996-02-21 | 1997-08-28 | Corning Incorporated | Pure fused silica, furnace and method |
-
1998
- 1998-08-31 KR KR1020007003139A patent/KR100574123B1/en not_active IP Right Cessation
- 1998-08-31 DE DE69841741T patent/DE69841741D1/en not_active Expired - Lifetime
- 1998-08-31 JP JP2000512783A patent/JP4108926B2/en not_active Expired - Lifetime
- 1998-08-31 EP EP98945813A patent/EP1030822B1/en not_active Expired - Lifetime
- 1998-08-31 WO PCT/US1998/018067 patent/WO1999015468A1/en active IP Right Grant
Patent Citations (4)
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 |
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 |
US5395413A (en) * | 1993-04-16 | 1995-03-07 | Corning Incorporated | Method for producing fused silica with low sodium ion contamination level |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001028941A1 (en) * | 1999-10-19 | 2001-04-26 | Liekki Oy | Method and apparatus for dyeing a material |
WO2001092172A1 (en) * | 2000-05-25 | 2001-12-06 | Corning Incorporated | Method of making a titania-doped fused silica preform |
US6387511B1 (en) | 2000-07-27 | 2002-05-14 | Corning Incorporated | Light weight porous structure |
US6988378B1 (en) | 2000-07-27 | 2006-01-24 | Corning Incorporated | Light weight porous structure |
JP2004511414A (en) * | 2000-10-13 | 2004-04-15 | コーニング インコーポレイテッド | Method for avoiding striae in EUV lithography mirrors |
EP1358132A1 (en) * | 2000-12-21 | 2003-11-05 | Corning Incorporated | Refractories for fused silica production furnaces |
EP1358132A4 (en) * | 2000-12-21 | 2004-12-29 | Corning Inc | Refractories for fused silica production furnaces |
US8047023B2 (en) | 2001-04-27 | 2011-11-01 | Corning Incorporated | Method for producing titania-doped fused silica glass |
US8329604B2 (en) | 2003-04-03 | 2012-12-11 | Asahi Glass Company, Limited | Silica glass containing TiO2 and process for its production |
US7410922B2 (en) * | 2003-04-03 | 2008-08-12 | Asahi Glass Company, Limited | Silica glass containing TiO2 and process for its production |
US7429546B2 (en) * | 2003-04-03 | 2008-09-30 | Asahi Glass Company, Limited | Silica glass containing TiO2 and process for its production |
US7538052B2 (en) | 2003-04-03 | 2009-05-26 | Asahi Glass Company, Limited | Silica glass containing TiO2 and process for its production |
US7989378B2 (en) | 2007-12-27 | 2011-08-02 | Asahi Glass Company, Limited | TiO2-containing silica glass |
WO2012105513A1 (en) | 2011-01-31 | 2012-08-09 | 旭硝子株式会社 | Method for producing silica glass body containing titania, and silica glass body containing titania |
EP3002262A1 (en) | 2014-10-01 | 2016-04-06 | Heraeus Quarzglas GmbH & Co. KG | Method for the manufacture of synthetic quartz glass with polymerizable polyalkylsiloxane |
US9790120B2 (en) | 2014-10-01 | 2017-10-17 | Heraeus Quarzglas Gmbh & Co. Kg | Method for the manufacture of synthetic quartz glass |
US10604437B2 (en) | 2014-10-20 | 2020-03-31 | Navus Automation, Inc. | Fused silica furnace system and method for continuous production of fused silica |
EP3034476A1 (en) | 2014-12-16 | 2016-06-22 | Heraeus Quarzglas GmbH & Co. KG | Method for the preparation of synthetic quartz glass with the use of a cleaning device |
WO2016096811A1 (en) | 2014-12-16 | 2016-06-23 | Heraeus Quarzglas Gmbh & Co. Kg | Method for producing synthetic quartz glass using a cleaning device |
US11267745B2 (en) | 2014-12-16 | 2022-03-08 | Heraeus Quarzglas Gmbh & Co. Kg | Process for producing synthetic quartz glass using a cleaning device |
EP3059212A1 (en) | 2015-02-18 | 2016-08-24 | Heraeus Quarzglas GmbH & Co. KG | Method and apparatus for making silica glass from polymerisable polyalkylsiloxane with membrane filter as cleaning device |
WO2016131849A1 (en) | 2015-02-18 | 2016-08-25 | Heraeus Quarzglas Gmbh & Co. Kg | Method and apparatus for producing fused quartz from a polymerizable polyalkylsiloxane compound with membrane filter as cleaning device |
Also Published As
Publication number | Publication date |
---|---|
JP4108926B2 (en) | 2008-06-25 |
DE69841741D1 (en) | 2010-08-05 |
KR20010024261A (en) | 2001-03-26 |
EP1030822A1 (en) | 2000-08-30 |
KR100574123B1 (en) | 2006-04-25 |
JP2001517597A (en) | 2001-10-09 |
EP1030822A4 (en) | 2004-12-15 |
EP1030822B1 (en) | 2010-06-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5970751A (en) | Fused SiO2 -TiO2 glass method | |
EP1030822B1 (en) | FUSED SiO2-TiO2 GLASS METHOD | |
US5152819A (en) | Method of making fused silica | |
US5043002A (en) | Method of making fused silica by decomposing siloxanes | |
KR100473827B1 (en) | Method and apparatus for forming fused silica by combustion of liquid reactants | |
US5154744A (en) | Method of making titania-doped fused silica | |
FI93822B (en) | Improved vitreous silica products | |
US5703191A (en) | Method for purifying polyalkylsiloxanes and the resulting products | |
JP2001517597A5 (en) | ||
US5879649A (en) | Method for purifying polyalkylsiloxanes and the resulting products | |
US6487879B1 (en) | Method of making titania-doped fused silica | |
EP0105325B1 (en) | Doped optical fiber | |
EP1094990A1 (en) | Methods for making ultra-low expansion silica-titania glasses | |
US4537611A (en) | Method for manufacturing glass from the gas phase | |
US6735981B2 (en) | High heat capacity burners for producing fused silica boules | |
JPS6086039A (en) | Production of fluorine-containing silica glass | |
JPH0597452A (en) | Production of synthetic silica glass member | |
US20020174684A1 (en) | Fused silica furnace and method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): JP KR US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1020007003139 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2000 512783 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1998945813 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1998945813 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020007003139 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1020007003139 Country of ref document: KR |