WO2002018286A1 - Verre resistant aux taches et produits a base de ce verre - Google Patents

Verre resistant aux taches et produits a base de ce verre Download PDF

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Publication number
WO2002018286A1
WO2002018286A1 PCT/TR2000/000049 TR0000049W WO0218286A1 WO 2002018286 A1 WO2002018286 A1 WO 2002018286A1 TR 0000049 W TR0000049 W TR 0000049W WO 0218286 A1 WO0218286 A1 WO 0218286A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
article
boron
modified
stain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/TR2000/000049
Other languages
English (en)
Inventor
Reha AKÇAKAYA
Bülent YOLDAS
Hasim Ekici
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Turkiye Sise Ve Cam Fabrikalari AS
Original Assignee
Turkiye Sise Ve Cam Fabrikalari AS
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 Turkiye Sise Ve Cam Fabrikalari AS filed Critical Turkiye Sise Ve Cam Fabrikalari AS
Priority to AU2000276988A priority Critical patent/AU2000276988A1/en
Priority to PCT/TR2000/000049 priority patent/WO2002018286A1/fr
Publication of WO2002018286A1 publication Critical patent/WO2002018286A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass

Definitions

  • This invention is related to a method of manufacturing glass surface which is modified by boron in order to prevent alkali diffusion that causes stains and corrosion.
  • This invention relates to any sodium containing glass product, such as soda-lime-silica glass, whose surface is modified by applying a thin film of boron oxide precursor and heat treating the glass surface in order to incorporate boron into the surface structure, thus to prevent the onset of chemical corrosion and resultant staining that occurs when such surfaces come in contact with a stagnant layer of condensed water during the storage, transportation and usage.
  • This invention is also related to a method of inducing such a glass surface modification either during the manufacturing of articles or after the articles manufactured.
  • Glass industry addressed this problem either by dealkalizing the glass surface by exposure to such gasses as SO 2 (US 5093196) or by placing materials in the interleaving that neutralizes the basic conditions, such as paper, or weak acidic powders including HBO 3 , B 2 O 3 , etc (US5962565).
  • WO9903791 utilizes boric acid for stain and dirt resistance.
  • said coating is not a permanent part of the modified surface as described in the present patent, but is washable from the glass surface and acts as a neutrilizing material in case of chemical contact with other materials and also acts as a lubricant for the reduction of friction in case of mechanical contact with other objects.
  • Patent WO8502395 describes a boria added glass composition for the enhancement of alkali resistance, hence not a surface modification with boria, as described in the present patent.
  • the mechanism can be interrupted by the interruption of the alkali diffusion from the glass surface. This interruption is achieved by the introduction of boron into the preformed glass surfaces.
  • Boron can be reacted with the surface of a soda-lime-silica glass at relatively moderate temperatures, e.g. 400°C - 500°C, leading to formation of a thin layer of modified surface. This occurs when the boron is maintained within a relatively shallow surface layer rather than scattered throughout the glass.
  • Particularly suitable boron precursors include: trimethylborate, B(OCH 3 ) 3 ; boric anhydride, B 2 O 3 ; boric acid, H 3 BO 3 . These compounds and all of their high temperature derivatives are water soluble presenting no problem in spray units. Adaptation of the process to the float lines also require a well engineered integration of the time-temperature conditions in the lehr as will be evident in the examples. Our tests indicate that the boron application can be performed by an on-line spray of the solution on a float glass ribbon at 500°C - 600°C on existing float lines.
  • sodium has formed compounds with boron thus the electrochemical association of Na is shifted from oxygen to boron tetrahedra with a profound effect on the mobility of sodium in the network.
  • Na + is associated with negative charge of the non-bridging oxygen in silica network it is in delocalized ⁇ bonding which allows relative mobility within the sphere of non-bridging oxygen sites, throughout the glass.
  • diffusion of boron into these sites and conversion of the non-bridging oxygen (Si-O Na + ) into bridging oxygen ( ⁇ Si-O-B ⁇ ) change boron coordination from 3 to 4 and demobilize sodium ions in the network.
  • the main parameters mat control the effectiveness of born modification are: the amount of boron oxide delivered per unit area, the uniformity of boron coverage, the temperature and time of the heat treatment.
  • These main parameters can be expressed as secondary application and manufacturing parameters which includes: Concentration and type of boron precursor in the spray solution, spray system (nozzle diameter, pressure, distance from the surface etc), speed of line, glass thickness and temperature during the spray, the rate of cooling, duration of time the temperature maintained.
  • Concentration and type of boron precursor in the spray solution spray system (nozzle diameter, pressure, distance from the surface etc), speed of line, glass thickness and temperature during the spray, the rate of cooling, duration of time the temperature maintained.
  • Periodic sampling of the water showed that there was substantial sodium leaching from the untreated glass, as much as 1 Omg, whereas the boron treated glass showed essentially no sodium leaching even after two months of testing.
  • the untreated control glass showed heavy staining after two months of testing whereas the boron treated glass showed no observable stain during the same period.
  • Example 1 Experiment described in Example 1 was conducted by performing the heat treatment at
  • Example 1 The experiment described in Example 1 was performed exactly the same, except the heat treatment time was extended to 60 minutes at 550°C.
  • the resultant sample substantially stained under the accelerated weathering test showing that heat treatment time was too long for an effective surface modification.
  • Example 1 The experiment described in Example 1 was performed exactly the same, except the heat treatment temperature was 600°C.
  • the resultant sample was stained substantially by the same weathering tests, showing that this temperature was too high for the desired effect under the same condition.
  • Examples 1 - 4 show that there is a window of heat treatment, limited by upper and lower limits in both temperature and time.
  • Example 1 The experiment described in Example 1 was performed exactly the same except the amount of boron oxide deposited on the sample was half as much, 5mg.
  • the resultant sample was heat treated similarly and subjected to the exact accelerated weathering test.
  • the sample was partly stained during these tests showing that there is a minimum requirement on boron concentration.
  • B(OH) 3 was dissolved in 1900g of water producing 5% boric acid concentration (or 2.8% wt. B 2 O 3 ). To this 0.2g FSN surfactant was added. This solution was sprayed on the glass samples similar to in Example 1 at a coverage of 17-20 mg per lOcmXlOcm samples. Example 1 through 5 were repeated. The result was similar showing that B(OH) 3 is also an excellent source of B 2 O 3 .

Landscapes

  • 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)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une surface de verre, ledit verre étant modifié avec du bore de manière à éviter la diffusion d'alcalins source de taches et de corrosion.
PCT/TR2000/000049 2000-09-01 2000-09-01 Verre resistant aux taches et produits a base de ce verre Ceased WO2002018286A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2000276988A AU2000276988A1 (en) 2000-09-01 2000-09-01 Stainresistant glass and articles made thereof
PCT/TR2000/000049 WO2002018286A1 (fr) 2000-09-01 2000-09-01 Verre resistant aux taches et produits a base de ce verre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TR2000/000049 WO2002018286A1 (fr) 2000-09-01 2000-09-01 Verre resistant aux taches et produits a base de ce verre

Publications (1)

Publication Number Publication Date
WO2002018286A1 true WO2002018286A1 (fr) 2002-03-07

Family

ID=21619306

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2000/000049 Ceased WO2002018286A1 (fr) 2000-09-01 2000-09-01 Verre resistant aux taches et produits a base de ce verre

Country Status (2)

Country Link
AU (1) AU2000276988A1 (fr)
WO (1) WO2002018286A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995260A (zh) * 2019-05-27 2020-11-27 维达力实业(深圳)有限公司 玻璃盖板及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB441603A (en) * 1934-08-23 1936-01-22 British Thomson Houston Co Ltd Improvements in and relating to alkali metal vapour electric discharge devices
DE1040198B (de) * 1957-10-11 1958-10-02 Kurz Fredrik W A Verfahren zur Erhoehung der chemischen Widerstandsfaehigkeit von Glasgegenstaenden
DD104281A5 (fr) * 1972-01-27 1974-03-05
WO1999003791A1 (fr) * 1997-07-16 1999-01-28 Nippon Electric Glass Co., Ltd. Article en verre possedant un revetement de surface a base d'acide borique et procede de fabrication de cet article
DE19840525A1 (de) * 1998-09-06 2000-03-09 Inst Neue Mat Gemein Gmbh Verfahren zur Herstellung optischer Schichten von gleichmäßiger Schichtdicke

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB441603A (en) * 1934-08-23 1936-01-22 British Thomson Houston Co Ltd Improvements in and relating to alkali metal vapour electric discharge devices
DE1040198B (de) * 1957-10-11 1958-10-02 Kurz Fredrik W A Verfahren zur Erhoehung der chemischen Widerstandsfaehigkeit von Glasgegenstaenden
DD104281A5 (fr) * 1972-01-27 1974-03-05
WO1999003791A1 (fr) * 1997-07-16 1999-01-28 Nippon Electric Glass Co., Ltd. Article en verre possedant un revetement de surface a base d'acide borique et procede de fabrication de cet article
DE19840525A1 (de) * 1998-09-06 2000-03-09 Inst Neue Mat Gemein Gmbh Verfahren zur Herstellung optischer Schichten von gleichmäßiger Schichtdicke

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995260A (zh) * 2019-05-27 2020-11-27 维达力实业(深圳)有限公司 玻璃盖板及其制备方法

Also Published As

Publication number Publication date
AU2000276988A1 (en) 2002-03-13

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