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WO1996007621A1 - Materiaux volatils de composition du verre incorpores dans des frittes - Google Patents

Materiaux volatils de composition du verre incorpores dans des frittes Download PDF

Info

Publication number
WO1996007621A1
WO1996007621A1 PCT/GB1995/001953 GB9501953W WO9607621A1 WO 1996007621 A1 WO1996007621 A1 WO 1996007621A1 GB 9501953 W GB9501953 W GB 9501953W WO 9607621 A1 WO9607621 A1 WO 9607621A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
frit
selenium
volatile
batch
Prior art date
Application number
PCT/GB1995/001953
Other languages
English (en)
Inventor
James Victor Jones
Edward Nashed Boulos
Original Assignee
Ford Motor Company
Ford Motor Company Limited
Ford Motor Company Of Canada Limited
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 Ford Motor Company, Ford Motor Company Limited, Ford Motor Company Of Canada Limited filed Critical Ford Motor Company
Publication of WO1996007621A1 publication Critical patent/WO1996007621A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/10—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce uniformly-coloured transparent products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/028—Ingredients allowing introduction of lead or other easily volatile or dusty compounds

Definitions

  • This invention relates to the use of amorphous glass frits containing an increased concentration of normally volatile glass batch material, e.g., selenium or boron oxide, as a source of the volatile material in molten glass preparation.
  • normally volatile glass batch material e.g., selenium or boron oxide
  • glass compositions for example, soda-lime-silica glass compositions
  • batch materials like sand, soda ash, limestone, dolomite and colourants, like selenium
  • soda-lime-silica glass compositions batch materials like sand, soda ash, limestone, dolomite and colourants, like selenium, are combined and subjected to extremely high temperatures to melt the materials.
  • a portion of some of the solid materials volatilise when being converted to the glassy liquid state.
  • Such volatilised materials exit out through the furnace exhaust system with other gases and hence are essentially lost from the glass melt.
  • This volatilisation and hence removal of materials which are a vital part of the final glass product requires that excess quantities of the batch material must be included in the batch to ensure that the final product has the desired amount of the material.
  • selenium One normally highly volatile component employed in some glass compositions is selenium.
  • selenium When selenium is added to the batch as elemental selenium, about 80-90% is converted to the gaseous state and hence essentially 80-90% of the added selenium is vaporised out of the batch.
  • the problem is exacerbated when the glass tank is heated by overhead gas flames which sweep across the surfa ' cir-and help to physically remove such vaporised materials whilst batch materials are being converted into the glassy state.
  • the present invention overcomes the problems discussed above by using, as the source of normally volatile glass batch material, an amorphous glass frit containing an increased concentration, i.e., a concentration above that desired in the final glass composition, of such normally volatile glass batch material.
  • this frit, containing normally volatile batch material is added to the batch during glass making, more of the normally volatile material is retained in the molten glass batch.
  • the present inventors believe that having the normally volatile batch materials in an amorphous (glassy) state makes it much more difficult for any volatile components to leave the glass batch composition during melt processing thereof.
  • Glass frits of agglomerated sintered materials have previously been used in the glass industry added to the molten glass in the forehearth, i.e., at a point in the process where the molten glass has exited the batching furnace and is being cooled.
  • Such agglomerated glass frits are in contrast to the present invention frits which are amorphous glass frits, i.e., the normally volatile species must be in the glassy state.
  • U.S. Patent 2,955,948 to Silverman describes forming an agglomerated frit consisting essentially of selenium, niter, and arsenic oxide.
  • Such frits are added to the forehearth rather than the glass batch furnace, i.e., to a molten base glass composition exiting the batching furnace. This process allows forming glass of various colours without converting the complete glass batch in the furnace to one particular colour.
  • Okamura discloses a sintered frit made by mixing pulverised glass cullet together with the additive ingredient, i. e. selenium, and sintering at 500°C to 1200°C.
  • Patent 3,628,932 to Inoue describes another method of making a sintered frit which comprises separating a portion of the raw batch, adding selenium and a source of alkali metal oxide in an increased percentage over that desired in the final molten product, and sintering at 500°C to 1000°C.
  • the sintered product containing the increased alkali metal oxide when used as the selenium source, provides doubled selenium retention when compared to using metallic selenium as the raw material source.
  • amorphous glass frits containing selenium provides selenium retention improved even over that of the Inoue invention sintered product.
  • the present invention is directed to a process which comprises adding an amorphous glass frit containing normally volatile glass batch materials into the glass forming components present in a melting furnace during molten glass formation, the normally volatile batch material being present in the amorphous glass frit in a percentage by weight at least two times as large as that desired in the final molten glass product.
  • amorphous glass frit means a frit of a base glass composition (e.g., a soda-lime- silica glass) including an increased concentration of a normally volatile glass batch material (e.g., selenium) , in amounts as defined above.
  • Still another aspect of this invention comprises the glass product melt made by incorporating the amorphous glass frit into the glass components in the melting furnace during the glass making process.
  • the present invention is directed to a process which comprises adding an amorphous glass frit containing normally volatile glass batch material into a glass melting furnace during molten-g*_ras formation as disclosed above.
  • This frit is completely amorphous (glassy) and not merely sintered into an agglomerated frit as is the case with many prior art frits.
  • the frit used in the present invention when added to the other raw batch materials (glass components) in the glass melting furnace, goes through the same melting schedule and temperature sequences as the batch components.
  • Selenium can be used as a model of the unexpected improvement shown according to the present invention. This is because in conventional batch processing selenium addition is by means of metallic selenium added into the melting furnace as a raw material and only from 10 to 20% of the selenium from the batch is retained in the final molten glass product. That means that in conventional glass processing, the batch must include 5 to 10 times the amount of raw material selenium than is necessary in the final molten glass product. The excess amount of selenium simply goes into the atmosphere and is exhausted out of the stack. Using an embodiment of the present invention, amorphous selenium frit, eliminates a large proportion of the normal selenium emissions associated with using elemental selenium.
  • Selenium is sometimes present in a compound which, when added as a batch material, also loses a large proportion of the volatile selenium in the process of becoming part of the glass composition.
  • g- ⁇ ass melts made with amorphous selenium frits according to our invention show selenium retention which is improved by a factor of 2 to 11 compared to glass melts made conventionally using only elemental selenium.
  • the present invention process uses amorphous glass frit which comprises a concentration of the normally volatile material in the amorphous state incorporated in a glass composition generally of the type of the intended glass product.
  • amorphous glass frit containing selenium was being employed in colouring a soda-lime-silica glass, the frit would generally include an increased concentration of the colourant, selenium, in a soda-lime-silica glass.
  • the normally volatile batch material is present in the amorphous glass frit in a percentage by weight at least two times as large as that desired in the final molten glass product.
  • the percentage of volatile material in the frit is at least ten times as large as that desired in the final molten melt.
  • the optimal amount of each of the materials incorporated in the amorphous glass frit is independently selected and will depend on various factors including meltability of the frit. While selenium has been used as a model of a volatile material whose incorporation into an amorphous glass frit will improve retention of that material when the frit is used to add that material to the glass batch, the volatile materials that can be used in the frit are not so limited.
  • the frit used in this invention may include, but is not limited to, materials like lead oxide, zinc oxide, boron oxide, sulphates, fluorides, chlorides, bromides, iodides, phosphates, and suitable mixtures thereof.
  • Exemplary of a particularly useful selenium embodiment of the invention frit comprises a relatively high concentration of selenium, at least about 1.0 percent by weight, based on the total weight of the amorphous glass frit.
  • Selenium is such a strong colourant that it ⁇ has been used in glass compositions at concentrations as low as 0.0002 to 0.0035 weight % to impart a strong absorption in the spectral transmission between 400 and 500 nanometres.
  • the glass compositions that include selenium as a colourant also include iron oxide as a colourant.
  • iron oxide as a colourant.
  • Some methods used to shift the iron oxide equilibrium during melting include adding to the melt an oxidiser such as sodium or potassium nitrates or to maintain oxidising conditions in the furnace firing.
  • an oxidiser such as sodium or potassium nitrates or to maintain oxidising conditions in the furnace firing.
  • the amorphous glass frit containing selenium can still be used in glass compositions not employing iron oxide as a colourant.
  • the glass batch materials including the normally volatile material is first heated and melted into an amorphous glass melt and subsequently the melt is rapidly quenched to form the frit. This cooling may be done, e.g. , by subjecting the melt to cold water.
  • the normally volatile component e.g. , selenium
  • the normally volatile component is included into the amorphous glass frit at a much higher concentration that will be found in the final product glass made with the invention frit.
  • Exemplary of one preferred method of forming the amorphous glass frit employs a cold-top melter and is described as follows: premixed glass batch components are fed on the top of a molten glass mass that is heated below the glass level via electrodes. The batch layer completely covers the molten glass providing an insulating barrier and the top of the batch is relatively cool which generates the name "cold-top melter".
  • the cold-top melter is extremely effective in retaining a volatile species in that the thick layers""of batch form a pseudo chemical retort where volatile gases vaporise near the hot glass melt surface only to condense as the vapours meander up through the insulating batch cover and condense back to the solid state.
  • the critical factor in our invention is that we have unexpectedly discovered that glasses made with a o: .ous glass frits as the source of normally volatile batcn materials retain a much greater proportion of the volatile material in the final molten glass product than when the volatile material is used as a raw batch material (i.e., not incorporated in an amorphous glass frit) .
  • the very nature of volatile components introduced into a glass product is that a portion of the volatile component is lost to the atmosphere in the process of converting batch materials via high temperature furnace to a glass product.
  • the normally volatile materials remain in the glass, there are lower emissions of the volatile materials which may eliminate the necessity to collect the emissions.
  • some volatile glass material species also chemically attack the refractory materials meant to contain them, the ability to employ lower concentrations of such volatile materials as part of the batch components will lead to an extended useful life of the furnace since the rate of corrosion will be reduced.
  • the glass ingredients including an amorphous glass frit (which is a base glass composition with selenium) are weighed (typically being 150 grams total) on a laboratory balance and mixed with in a glass jar with a laboratory shaker for 10 minutes each.
  • Each mixed batch is placed into a platinum-rhodium crucible which is about 2" tall with about a 2.5" inside diameter and 4.5 ml. of water is mechanically mixed into the raw batch.
  • the crucibles are placed into a natural gas/air furnace pre ⁇ heated to 2600°F with 3 to 5 other crucibles.
  • the furnace temperature recovers to 2600°F in about 30 minutes and the batch materials melt. After two hours of heating the melt, each crucible is removed in turn.
  • the amorphous glass containing the colourant in the crucible is fritted by quenching in cold water to improve the homogeneity of the glass, and the fragments are mixed in the crucible and all crucibles are returned to the furnace.
  • the furnace temperature is brought back to 2600°F, that operating temperature obtained (about 45 minutes) , and the melt is heated for one hour.
  • the glass is further melted for 3 hours to form glass composition samples and each sample is poured into a 2.5" inside diameter graphite mould to shape the glass samples for subsequent grinding and polishing.
  • All samples are placed into an annealing furnace, brought up to 1050°F, held for 4 hours, then allowed to slowly cool to room temperature in about 16 hours.
  • the hardened glass samples are ground and polished and spectral properties are measured on each sample; spectral properties are calibrated to a control thickness of 4 mm.
  • the samples may then be chemically analysed via X-ray fluorescence or other tests conducted as needed.
  • the above procedure for making the glass compositions of the examples can also be used, with slight modification, to make the amorphous glass frit used in making the glass. The modification would involve fritting the glass again in cold water and subsequently drying it, after the second fritting and three hours melting discussed above.
  • the amorphous glass frit need not go through an annealing process as carried out above for the glass compositions and can simply be used in a measured amount as the source of the volatile consitiuent into the glass melt.
  • the base glass is a dark grey glass which uses iron oxide as an additional colourant.
  • the batch materials for making the glass are given in the tables below in grams per 100 grams of sand, as done in Table I.
  • Example 1 glass made with selenium frit
  • Example 2 glass made with conventional metallic selenium
  • the redox ratios as defined above and the total iron oxide as Fe 2 0 3 in the final product are nearly identical in each of the comparative pairs.
  • Increasing the salt cake or carbocite lowers the selenium retention while increasing the sodium nitrate improves the selenium retention.
  • the "Ratio of Retained Se, as Frit/Metal” is obtained by dividing the % Se retained in the comparative pairs. That is, the retained ratio of 5.33 in Example 1 (a Se Frit composition according to the present invention) is obtained by dividing 32.03% by 6.01% and indicates that 5.33 times as much Se is retained in the Example 1 glass as in the comparative Example 2 glass.
  • amorphous selenium frits retain at least twice as much up to about 10.5 times the amount of selenium when compared to conventionally made melts made using elemental selenium as the source of selenium.
  • Glass melts made incorporating volatile materials other than selenium are shown in the following tables.
  • the melts in TABLE VIII below were made using embodiments of amorphous glass frits according to the present invention and can be paired for comparison with the melts of TABLE IX made conventionally without the invention frits. That is, Examples 21, 22, and 23 can be paired, respectively, with Examples 24, 25, and 26.
  • the Example 21-23 melts contain 30% frit and 70% batch material.
  • Examples 24-26 melts contain 30% cullet and 70% of batch material.
  • Examples 21 and 24 are based on the same clear boro-soda-lime-silica base glass
  • Examples 22 and 25 are based on the same clear soda-lime-silica glass
  • Examples 23 and 26 are based on the same dark grey soda-lime-silica glass.
  • Example 21 Example 22 Example 23 wt. % of 5.74% B 2 0 3 0.62% F ⁇ 1.38% P 2 0 5 Volatile Material in
  • Example 24 Example 26 wt. % of 2.69% B 2 0 3 0.20% F ⁇ 0.39% P 2 0 5 Volatile Material in Frit wt. % of 1.66% B 2 0 3 0.13% F ⁇ 0.28% P 2 0 5

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

Abstract

L'invention concerne un procédé consistant à ajouter des frittes de verre amorphe contenant une forte concentration de matériaux normalement volatils, par exemple des colorants tels que le sélénium, dans les éléments de formation du verre qui sont présents dans un four à verre pendant cette formation, inclure ces matériaux normalement volatils dans cette fritte pour abaisser de façon significative la volatilité de ces matériaux qui, autrement reviendraient normalement à l'état gazeux aux températures élevées régnant dans ce four. Des exemples de certains matériaux de composition généralement utilisés dans une fritte, qui se volatilisent normalement à partir d'une composition de verre et se prêtent donc particulièrement à une incorporation dans une fritte de verre amorphe incluent le sélénium, l'oxyde de plomb, l'oxyde de zinc, l'oxyde de bore, les sulfates, les fluorures, les chlorures, les bromures, les iodures, les phosphates et leurs mélanges.
PCT/GB1995/001953 1994-09-08 1995-08-17 Materiaux volatils de composition du verre incorpores dans des frittes WO1996007621A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30326394A 1994-09-08 1994-09-08
US303,263 1994-09-08

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Publication Number Publication Date
WO1996007621A1 true WO1996007621A1 (fr) 1996-03-14

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003024878A1 (fr) 2001-09-21 2003-03-27 Norfeed Uk Limited Additifs pour la fabrication du verre
WO2002088042A3 (fr) * 2001-04-26 2003-10-16 Guardian Industries Procede de fabrication du verre a brulage de selenium reduit
US9056332B2 (en) 2002-03-23 2015-06-16 P2I Limited Method and apparatus for the formation of hydrophobic surfaces
US9067821B2 (en) 2008-10-07 2015-06-30 Ross Technology Corporation Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
US9074778B2 (en) 2009-11-04 2015-07-07 Ssw Holding Company, Inc. Cooking appliance surfaces having spill containment pattern
US9139744B2 (en) 2011-12-15 2015-09-22 Ross Technology Corporation Composition and coating for hydrophobic performance
US9179773B2 (en) 2008-06-27 2015-11-10 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US9388325B2 (en) 2012-06-25 2016-07-12 Ross Technology Corporation Elastomeric coatings having hydrophobic and/or oleophobic properties
US9546299B2 (en) 2011-02-21 2017-01-17 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
US9914849B2 (en) 2010-03-15 2018-03-13 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
US10317129B2 (en) 2011-10-28 2019-06-11 Schott Ag Refrigerator shelf with overflow protection system including hydrophobic layer
US11786036B2 (en) 2008-06-27 2023-10-17 Ssw Advanced Technologies, Llc Spill containing refrigerator shelf assembly

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB920174A (en) * 1960-07-11 1963-03-06 United Glass Ltd Improvements in or relating to glass manufacture
US3628932A (en) * 1968-01-10 1971-12-21 Nippon Sheet Glass Co Ltd Preparation of glass containing selenium
JPS53127517A (en) * 1977-04-13 1978-11-07 Dainippon Toryo Kk Production of lead silicate frit
US4521523A (en) * 1982-10-18 1985-06-04 Owens-Corning Fiberglas Corporation Methods of introducing fluorine into glasses
EP0618177A1 (fr) * 1993-03-29 1994-10-05 Ppg Industries, Inc. Enrobage de sélénium pour la fabrication de verre coloré

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB920174A (en) * 1960-07-11 1963-03-06 United Glass Ltd Improvements in or relating to glass manufacture
US3628932A (en) * 1968-01-10 1971-12-21 Nippon Sheet Glass Co Ltd Preparation of glass containing selenium
JPS53127517A (en) * 1977-04-13 1978-11-07 Dainippon Toryo Kk Production of lead silicate frit
US4521523A (en) * 1982-10-18 1985-06-04 Owens-Corning Fiberglas Corporation Methods of introducing fluorine into glasses
EP0618177A1 (fr) * 1993-03-29 1994-10-05 Ppg Industries, Inc. Enrobage de sélénium pour la fabrication de verre coloré

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7850, Derwent World Patents Index; Class E32, AN 78-90313A *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088042A3 (fr) * 2001-04-26 2003-10-16 Guardian Industries Procede de fabrication du verre a brulage de selenium reduit
US6672108B2 (en) 2001-04-26 2004-01-06 Guardian Industries Corp. Method of making glass with reduced Se burnoff
WO2003024878A1 (fr) 2001-09-21 2003-03-27 Norfeed Uk Limited Additifs pour la fabrication du verre
US9056332B2 (en) 2002-03-23 2015-06-16 P2I Limited Method and apparatus for the formation of hydrophobic surfaces
US10029278B2 (en) 2002-03-23 2018-07-24 Surface Innovations Limited Method and apparatus for the formation of hydrophobic surfaces
US12096854B2 (en) 2008-06-27 2024-09-24 Ssw Advanced Technologies, Llc Spill containing refrigerator shelf assembly
US11786036B2 (en) 2008-06-27 2023-10-17 Ssw Advanced Technologies, Llc Spill containing refrigerator shelf assembly
US9532649B2 (en) 2008-06-27 2017-01-03 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US11191358B2 (en) 2008-06-27 2021-12-07 Ssw Advanced Technologies, Llc Spill containing refrigerator shelf assembly
US9179773B2 (en) 2008-06-27 2015-11-10 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US9207012B2 (en) 2008-06-27 2015-12-08 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US10827837B2 (en) 2008-06-27 2020-11-10 Ssw Holding Company, Llc Spill containing refrigerator shelf assembly
US10130176B2 (en) 2008-06-27 2018-11-20 Ssw Holding Company, Llc Spill containing refrigerator shelf assembly
US9096786B2 (en) 2008-10-07 2015-08-04 Ross Technology Corporation Spill resistant surfaces having hydrophobic and oleophobic borders
US9926478B2 (en) 2008-10-07 2018-03-27 Ross Technology Corporation Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
US9279073B2 (en) 2008-10-07 2016-03-08 Ross Technology Corporation Methods of making highly durable superhydrophobic, oleophobic and anti-icing coatings
US9243175B2 (en) 2008-10-07 2016-01-26 Ross Technology Corporation Spill resistant surfaces having hydrophobic and oleophobic borders
US9067821B2 (en) 2008-10-07 2015-06-30 Ross Technology Corporation Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
US9074778B2 (en) 2009-11-04 2015-07-07 Ssw Holding Company, Inc. Cooking appliance surfaces having spill containment pattern
US9914849B2 (en) 2010-03-15 2018-03-13 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
US9546299B2 (en) 2011-02-21 2017-01-17 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
US10240049B2 (en) 2011-02-21 2019-03-26 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
US10317129B2 (en) 2011-10-28 2019-06-11 Schott Ag Refrigerator shelf with overflow protection system including hydrophobic layer
US9528022B2 (en) 2011-12-15 2016-12-27 Ross Technology Corporation Composition and coating for hydrophobic performance
US9139744B2 (en) 2011-12-15 2015-09-22 Ross Technology Corporation Composition and coating for hydrophobic performance
US9388325B2 (en) 2012-06-25 2016-07-12 Ross Technology Corporation Elastomeric coatings having hydrophobic and/or oleophobic properties

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