EP2488460A2 - Procede d'obtention d'une feuille de verre comprenant de l'oxyde d'antimoine - Google Patents

Procede d'obtention d'une feuille de verre comprenant de l'oxyde d'antimoine

Info

Publication number
EP2488460A2
EP2488460A2 EP10782341A EP10782341A EP2488460A2 EP 2488460 A2 EP2488460 A2 EP 2488460A2 EP 10782341 A EP10782341 A EP 10782341A EP 10782341 A EP10782341 A EP 10782341A EP 2488460 A2 EP2488460 A2 EP 2488460A2
Authority
EP
European Patent Office
Prior art keywords
glass
glass frit
frit
glass sheet
antimony
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.)
Withdrawn
Application number
EP10782341A
Other languages
German (de)
English (en)
French (fr)
Inventor
Olivier Mario
Edouard Brunet
Octavio Cintora
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.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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 Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP2488460A2 publication Critical patent/EP2488460A2/fr
Withdrawn legal-status Critical Current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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/173—Apparatus for changing the composition of the molten glass in glass furnaces, e.g. for colouring the molten glass
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form

Definitions

  • Glass sheets are useful in many applications: glazing for the building or the automobile, energy production, especially photovoltaic systems or mirrors for the concentration of solar energy, screens of visualization ...
  • antimony oxide is incompatible with certain glass forming processes, including the float process, in which the molten glass is poured onto a liquid metal, usually tin.
  • antimony oxide by adding antimony to the glass batch is not possible in the case of a single oven connected to several forming devices, at least one of which is a device floating.
  • the storage and handling of antimony oxide must be strictly controlled in terms of the environment and industrial hygiene and safety.
  • the subject of the invention is a process for obtaining a glass sheet comprising antimony oxide, said process comprising a step of melting a vitrifiable mixture, a step of transporting the glass melted to at least one forming device, and a forming step, in which glass frit comprising a weight content of antimony oxide of between 2 and 30%, in particular between 2 and 20%, is added, cumulatively or alternatively , to said batch, during said melting step, or during said step of transporting the molten glass to at least one forming device.
  • the invention also relates to a glass frit comprising a weight content of antimony oxide of between 2 and 30%, especially between 2 and 20%.
  • the glass frit according to the invention or employed in the process according to the invention preferably has one or more of the following preferred characteristics, according to any possible combination: the weight content of antimony oxide is preferably between 8 and 15%; a content of the order of 10% makes it possible to obtain a weight content of 0.2 to 0.3% with dilution ratios perfectly achievable on an industrial scale,
  • the proportion of pentavalent antimony (Sb 5+ ) relative to the totality of antimony is preferably greater than or equal to 20%. This proportion can be determined by Môssbauer spectroscopy.
  • the high amount of pentavalent antimony makes it possible to oxidize ferrous iron more effectively when adding the frit to the molten glass.
  • An oxidized frit, close to the final oxidation state of the glass, also makes it possible to avoid the risks of reboiling linked to the presence of sulphate in the glass or due to the release of oxygen during an excessive reduction of 1 antimony,
  • the viscosity at a temperature of 1050 ° C. is between 30 and 300 poles; these last two preferred features make it possible to facilitate the melting of the frit when it is added to the molten glass, generally at a temperature of between 1000 and 1150 ° C., and to facilitate mixing between the molten frit and the molten glass,
  • the frit preferably comprises the following constituents in a content varying within the weight limits defined below:
  • the composition of the frit is advantageously free of boron, arsenic, oxides of transition elements such as CoO, CuO, Cr 2 C> 3, MnO 2 , rare earth oxides such as CeO 2 , La 2 03, Nd 2 C> 3, or else elementary coloring agents such as Se, Ag, Cu, Au,
  • the subject of the invention is also the process for obtaining the frits according to the invention.
  • the frits are preferably obtained by melting a vitrifiable powder mixture.
  • the melting may be continuous (for example in a pond furnace) or discontinuous (for example in a pot furnace).
  • the energy required to obtain the melted frit can be provided by flames (for example by means of overhead or submerged burners) or by electricity (for example by means of electrodes, in particular molybdenum electrodes, immersed in the bath of molten glass).
  • the raw materials are typically selected from silica sand, feldspar, syenite nepheline, sodium carbonate, potassium carbonate, limestone, dolomite.
  • the antimony carrier is preferably pentavalent antimony oxide (Sb 2 O 5), rather than trivalent (Sb 2 O 3) so as to obtain the richest frit possible with pentavalent antimony.
  • the melting temperature preferably does not exceed 1400 ° C., especially 1350 ° C. or 1300 ° C., since it has been observed that the lower temperatures make it possible to retain a more oxidized frit.
  • an oxidant such as sulphates or nitrates, into the vitrifiable mixture, for example sodium sulphate or nitrate.
  • the frit shaping can in particular be done by rolling and crushing and grinding to obtain flakes.
  • the forming is preferably carried out by rolling between several rollers. At least one of the rolling rolls is preferably textured so as to form reliefs on at least one side of the glass sheet. As explained in more detail in the rest of the text, some reliefs can trap light and increase the amount of energy at the photovoltaic cells.
  • Other forming processes are possible, such as, for example, the drawing method Fourcault or a down-draw process.
  • the glass sheet preferably has a composition of the silico-soda-lime type, for reasons of ease of fusion and implementation.
  • other types of glasses may be employed, in particular borosilicate, aluminosilicate or aluminoborosilicate type glasses.
  • BaO 0 - 5% preferably 0.
  • the glass sheet obtained according to the invention is preferably such that its light transmission according to ISO 9050: 2003 is greater than or equal to 90%, in particular 90.5% or even 91%, for a thickness of 3, 2 mm.
  • the glass sheet obtained according to the invention is preferably flat or curved. It is advantageously curved in a cylindro-parabolic shape when it is intended to be used for the manufacture of parabolic mirrors for the concentration of solar energy.
  • the glass sheet according to the invention can be of any size, generally between 0.5 and 6 meters. Its thickness is generally between 1 and 10 mm, especially between 2 and 6 mm.
  • the melting can be performed in continuous furnaces, heated with electrodes and / or using burners, air and / or immersed and / or arranged in the vault of the furnace so that the flame comes impact raw materials or the glass bath.
  • the raw materials are generally pulverulent and include natural materials (sand, feldspars, limestone, dolomite, nepheline syenite altogether or artificial (sodium or potassium carbonate, boric anhydride, sodium sulphate ).
  • the raw materials are charged and then undergo fusion reactions in the physical sense of the term and various chemical reactions leading to obtaining a glass bath.
  • the molten glass is then fed to a forming step during which the glass sheet will take shape.
  • the glass sheet obtained according to the invention is advantageously used in photovoltaic cells, solar cells, flat or parabolic mirrors for the concentration of solar energy, or diffusers for backlighting of LCD-type display screens (screens liquid crystal). It can still be used in flat screens or lamps based on organic light-emitting diodes.
  • the glass sheet may advantageously be coated with at least one transparent and electroconductive thin layer, for example based on Sn0 2 : F, SnO 2 : Sb, ZnO: Al, ZnO: Ga.
  • These layers may be deposited on the substrate by various deposition methods, such as chemical vapor deposition (CVD) or sputtering deposition, in particular assisted by magnetic field (magnetron process).
  • CVD chemical vapor deposition
  • sputtering deposition in particular assisted by magnetic field (magnetron process).
  • magnetic field magnetic field
  • halide or organometallic precursors are vaporized and transported by a carrier gas to the surface of the hot glass, where they decompose under the effect of heat to form the thin layer.
  • the advantage of the CVD process is that it is possible to implement it within the glass sheet forming process, especially when it is a method of floating.
  • the glass sheet coated with a transparent and electroconductive layer may in turn be coated with an amorphous or polycrystalline silicon semiconductor, with chalcopyrites (in particular of the CIS-CuInSe2 or CIGS-CuInGaSe2 type) or with CdTe for to form a photovoltaic cell. It may in particular be a second thin layer based on amorphous silicon, CIS or CdTe.
  • another advantage of the CVD process lies in obtaining a higher roughness, which generates a phenomenon of trapping of light, which increases the amount of photons absorbed by the semiconductor ⁇ .
  • the glass sheet may be coated on at least one of its faces with an antireflection coating.
  • This coating may comprise a layer (for example based on porous silica with a low refractive index) or several layers: in the latter case a stack of layers based on dielectric material alternating layers with low and high refractive indices and ending by a low refractive index layer is preferred. It may especially be a stack described in WO 01/94989 or WO 2007/077373.
  • the antireflection coating may also comprise in the last layer a self-cleaning and antisoiling layer based on photocatalytic titanium oxide, as taught in the application WO 2005/110937. We can thus to obtain a weak reflection lasting in time.
  • the antireflection coating is disposed on the outer face, that is to say the face in contact with the atmosphere, while the optional transparent electroconductive layer is disposed on the internal face, on the side semiconductor.
  • the surface of the glass sheet may be textured, for example have patterns (especially pyramid), as described in WO 03/046617, WO 2006/134300, WO 2006/134301 or WO 2007/015017. These textures are generally obtained using a glass forming by rolling.
  • Figure 1 shows the transmission optical spectra obtained for the various examples.
  • Two frits containing antimony were produced. Their composition (expressed in percentages by weight) is indicated in Table 1 below. As indicated in the table, one part of the sodium oxide (a20) is added in nitrate form, the other part in carbonate form. The two frits are obtained by melting for 2 hours at 1300 ° C. They are shaped grains of a few millimeters in diameter, by grinding. Oxides Frit A% Frit B%
  • Each of the frits is used to obtain a glass whose composition is the following (expressed in percentages by weight):
  • the frit is added either to the vitrifiable mixture (before the melting step) or after the melting step, at a temperature of 1300 ° C.
  • Table 2 summarizes the redox and energetic transmissions obtained, indicating in each case the frit used (A or B) and the mode of introduction of the frit, by addition to the batch (batch mode) or after fusion ("feeder" mode).
  • the energetic transmission denoted TE, is calculated according to the ISO 9050: 2003 standard for a glass thickness of 3.2 mm.
  • antimony oxide in the form of frit makes it possible to reduce the redox, to a degree similar to the addition of triantimony pentoxide.
  • the addition of the frit after the melting step is more efficient in terms of reduction of the redox, and allows to reach glass sheets whose light and energy transmission is much higher.
  • the oxidation effect is also visible on the optical spectra of FIG. 1, where the reduction of the absorption band due to ferrous iron (centered around 1000 nm) can be observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Photovoltaic Devices (AREA)
EP10782341A 2009-10-12 2010-10-11 Procede d'obtention d'une feuille de verre comprenant de l'oxyde d'antimoine Withdrawn EP2488460A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0957113A FR2951157A1 (fr) 2009-10-12 2009-10-12 Fritte de verre
PCT/FR2010/052145 WO2011045517A2 (fr) 2009-10-12 2010-10-11 Procede d'obtention d'une feuille de verre

Publications (1)

Publication Number Publication Date
EP2488460A2 true EP2488460A2 (fr) 2012-08-22

Family

ID=42115125

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10782341A Withdrawn EP2488460A2 (fr) 2009-10-12 2010-10-11 Procede d'obtention d'une feuille de verre comprenant de l'oxyde d'antimoine

Country Status (9)

Country Link
US (1) US20130053233A1 (es)
EP (1) EP2488460A2 (es)
JP (1) JP2013507322A (es)
KR (1) KR20120095358A (es)
CN (1) CN102712519A (es)
EA (1) EA201270541A1 (es)
FR (1) FR2951157A1 (es)
MX (1) MX2012004015A (es)
WO (1) WO2011045517A2 (es)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102288738B1 (ko) * 2012-12-21 2021-08-12 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. 고밀도 플루오로중합체 필름
CN103896494A (zh) * 2014-03-10 2014-07-02 苏州捷德瑞精密机械有限公司 一种玻璃光纤及其制备方法
CN103896553B (zh) * 2014-03-10 2015-11-25 新昌县镜岭镇凌康机械厂 一种用于手机屏幕的不易磨损材料及其制备方法
US9902644B2 (en) 2014-06-19 2018-02-27 Corning Incorporated Aluminosilicate glasses
CN106007370B (zh) * 2016-05-19 2018-09-21 台玻安徽玻璃有限公司 一种防霉浮法玻璃
CN115572048B (zh) * 2022-11-10 2023-11-17 中国洛阳浮法玻璃集团有限责任公司 一种提高超白浮法玻璃太阳光透过率的方法

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Also Published As

Publication number Publication date
WO2011045517A2 (fr) 2011-04-21
EA201270541A1 (ru) 2012-09-28
KR20120095358A (ko) 2012-08-28
JP2013507322A (ja) 2013-03-04
US20130053233A1 (en) 2013-02-28
WO2011045517A3 (fr) 2011-07-07
CN102712519A (zh) 2012-10-03
MX2012004015A (es) 2012-05-08
FR2951157A1 (fr) 2011-04-15

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