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
  • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with 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
  • 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
  • C03C17/245—Oxides by deposition from the vapour phase
  • C03C17/2453—Coating containing SnO2
• • 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
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
  • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/23—Mixtures
• • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/152—Deposition methods from the vapour phase by cvd

Definitions

• Phosphostannate or borostannate pyrolytic layer, and glazing comprising this layer
• the invention relates to layers deposited on transparent substrates, in particular glass, and which are part of an interference set of thin layers.
• the invention relates to layers, and sets of layers, in which the former are integrated because of their characteristics, in particular of index, but also of transparency, of resistance, etc., in order to improve their characteristics.
• sublayers of such assemblies sublayers which have the function in particular of modifying the color in reflection, induced on the glazing by the presence of these assemblies.
• These are, in particular, sets of thin layers which give transparent substrates low-emissivity, sun protection or anti-reflection properties. It is indeed about these properties that these sublayers have been most studied and developed. This is not exclusive of other uses.
• Pyrolysis is the preferred mode. It has the advantage of quickly leading to thick layers suitable, which moreover offer good homogeneity and good resistance, in particular mechanical, but also chemical.
• gas phase pyrolysis, or CVD is often the one that is most suitable when it can be practiced directly on the production line of a glass ribbon.
• an underlay depends first of all on its performance. For this it is known that the sub-layer must have an index located between that of the glass substrate and that of the low-emissive, anti-sun or anti-reflective layer. As an indication, in the case of a glass sheet of the most usual soda-lime type, and of a low-emissive functional layer of tin oxide, the under-layer must have an index situated between approximately 1 , 5 and 1.9.
• the solution most frequently proposed in the literature consists in forming a mixed layer of silicon oxide, Si0 2 , and tin oxide, Sn0 2 . It has been proposed in particular to form layers of index varying gradually from that of glass to that of the low-emissivity or sunscreen layer. In the example of a layer of tin oxide, considered as a reference, this leads for example to deposit practically pure silica in contact with the glass, and to increase the content of tin oxide until there is tin oxide alone in contact with the upper layer.
• the above shows a certain difficulty in controlling the production of this type of layer under industrial conditions of implementation.
• the invention proposes to provide a layer and the means for obtaining it, which guarantee satisfactory results, under easily achievable and well reproducible conditions.
• the inventors have shown that a layer meeting these objectives can be obtained without having to use a mixed silica oxide, in other words, without forming a layer which by its composition constitutes a transition between the glass and the functional layer which is superposed on it. .
• the layer consists of a phosphate or a tin borate.
• composition of the sublayers according to the invention is remarkable in particular, by the fact that it does not contain silica. Glazing with a layer containing phosphorus can be found in the literature. This element is then used as a "dopant" for the basic constituent oxides of these layers. Compared to these doped layers, regardless of the difference in function, the layers according to the invention are distinguished by their phosphorus content. For doped layers, phosphorus is in very small proportion compared to the other constituents. In practice, this element only enters the layer for a content which does not exceed 4 atomic%, and most often is of the order of 1 to 1.5%.
• phosphorus or boron are constitutive elements of the structure of the layer, and, consequently, they are present in substantially greater proportions.
• the atomic phosphorus or boron content is not less than 6%, and most often is more than 10%.
• the layers according to the invention have an essentially amorphous structure.
• the inventors have shown that it is possible to modulate the refractive index of the layers formed by varying their phosphorus or boron content.
• the index is a function of the ratio
• the Sn / P (or Sn / B) is advantageously between 1 and 4, and preferably between 1.5 and 2.5.
• the index is around 1.9, particularly useful index values are around 1.7, in a range for example from 1.65 to 1.75, the Sn / P (or Sn / B) ratio is then advantageously from 1.85 to 2.25.
• the layers according to the invention advantageously have a refractive index of between 1.6 and 1.9.
• the layers according to the invention are of the Sn x P y O z Na w and S ⁇ B y C ⁇ Na ⁇ type.
• x, y and z represent the proportions respective atomic constituents.
• the constituent elements are in the following proportions:
• the layers according to the invention advantageously have a thickness of between 50 and 110 nanometers, and preferably between 60 and 100 nanometers.
• Preferred precursors are triethylphosphite (TEP) and triethylborate (TEB), respectively.
• the tin precursor is advantageously used monobutyltrichloretain (MBTC), tetramethyltin (TME), tin tetrachloride, tin ethylhexanoate.
• MBTC is preferred because it reacts properly at temperatures useful for pyrolysis, in particular in CVD on a production line for "float" glass. The reaction is neither too slow, which would lead to deposits that are difficult to produce, nor too rapid, which would have the counterpart of seeing it develop before contact with the glass, resulting in fouling of the apparatus and contamination of the layer by dust.
• Water can be replaced by compounds containing hydroxyl groups, or which are capable of leading to such groups under the conditions of pyrolysis.
• the low molecular weight organic alcohols and acids such as acetic acid, ethanol, or the corresponding esters such as ethyl acetate can be used.
• water concentration affects the reaction rate. This content is deliberately limited to avoid reactions which could develop in the gas phase to the detriment of the formation. of the pyrolytic layer.
• the water in the gaseous form, based on the tin precursor used, the water does not constitute more than 10% by volume.
• the water content is 3 to 7% by volume, based on the volume of the tin precursor.
• the reaction can be carried out in the complete absence of air, as indicated in the examples. This way of proceeding can be chosen in the case where the formation of the layer must imperatively take place in a non-oxidizing environment. If this condition is not required, it is advantageous to have a certain amount of air with the precursors to improve the reactivity.
• the pyrolysis temperature is advantageously chosen so that the reaction is carried out directly on a production line for flat glass.
• the preferred temperatures are between 550 and 670 ° C.
• the invention is described in detail in the following examples carried out on an industrial production line.
• the deposition of sublayers is carried out by gas phase pyrolysis on the glass ribbon leaving the "float" tank, between the latter and the drying rack.
• the glass here has a temperature of 610 ° C.
• the layer is formed from monobutyltin trichloride (MBTC) as a tin precursor, and triethylphosphite (TEP).
• MBTC monobutyltin trichloride
• TEP triethylphosphite
• the precursors are carried by nitrogen as a carrier gas. With MBTC a small amount of water vapor is introduced (3% by volume of the amount of MBTC).
• the contact time of the glass with the precursors is 5 seconds for all the tests.
• Examples 1 to 4 for which the only parameter which is modified is the air content, show that the deposition rate increases with this content, but that this does not seem to have a significant influence on the value of the index of refraction. After a certain threshold, the increase in air flow no longer has any influence on the deposition rate.
• the deposition rate also seems sensitive to the concentration of precursors (examples 1 to 4 compared to examples 5 to 8). For this reason, in a second series of tests on an industrial installation, the nitrogen flow is reduced. The conditions and results of these tests are given in the following table. As before, the processing time is 5 seconds.
• the deposition rate is significantly increased due to the reduction in the carrier gas flow rate.
• the results of these tests are shown in the following table.
• the nitrogen flow is constant at 15 liters per minute.
• the flow rates of MBTC and TEP are in milliliters per minute, that of O z , which replaces air, is in liters per minute.
• the deposit time is in seconds.
• the water content is expressed in volume% relative to the MBTC.
• Test 18 thus simultaneously shows a particularly high deposit rate, and an index which is in the most useful range. It should be noted, however, that the increase in the deposition rate obtained in this example is not proportional to that of the quantities of precursors used. In all cases, it is therefore necessary to determine the best compromise between reactivity and efficiency of the operation.
• the influence of the water concentration can be seen from Examples 17, 21 and 24.
• the deposition rate is apparently the element most sensitive to variations in the water content introduced with the precursors.
• the increase in the water content results in a higher reactivity.
• the formation of the layer is systematically accompanied by the incorporation of sodium in a significant proportion.
• the origin is necessarily a diffusion from the surface of the glass.
• the presence of sodium does not seem to generate a particular brittleness of these layers when they are covered by the low-emissivity or anti-reflective layer.
• the layers according to the invention are advantageously used as a sublayer in glazing whose low-emissivity or sunscreen layer is an oxide layer of the tin oxide, indium oxide etc. type. These oxides, according to practice in this field, are also advantageously doped. Tin oxide can thus be doped with fluorine and indium oxide can be doped with tin. It may also be a layer of tin containing antimony according to the teaching of publications BE-A 1 010 321 and 1 010 322.
• Tests for the production of assemblies have been undertaken in which a sublayer of tin phosphostannate is covered with a layer of tin oxide containing antimony.
• the sublayer and the layer are deposited by gas pyrolysis.
• the layer of tin oxide containing antimony contains 10% antimony and has a thickness of 320 nanometers.
• the sublayers are established for a series of thicknesses and for two types of composition corresponding respectively to the refractive indices 1.7 and 1.67.
• the atomic proportions of phosphorus in these sublayers are respectively 11.2 and 12.1%.
• the measurement of the indices a_and b is made for different incidences compared to the normal to the surface of the glass sheet. It is in fact the variations in coloring depending on the incidence which are at the origin of the undesirable iridescence.
• Test 30 corresponds to the reference sample.
• This sample consists of a sheet of clear soda-lime glass on which the layer of tin oxide containing the antimony is deposited without an undercoat. Observation from all angles shows a relatively high index value ç. Under 40 and 50 °, the index is even higher than the limit value of 12.
• the reference sample even according to the least severe criteria, is not neutral in reflection.
• the other tests are all carried out by superimposing a sublayer according to the invention and the layer serving as a reference, on the same clear soda-lime glass.
• the sublayers were chosen to present indices halfway between the index of the glass sheet and that of the tin oxide layer containing the antimony.
• Test 34 shows the importance of the thickness of the undercoat for obtaining the color attenuation.
• the thickness of 110 nanometers corresponds to the preferred upper value indicated for correcting undesirable reflection colorations for the typical structure chosen.
• the highest values of ç (9.18 for 0 ° and 7.60 for 10 °) are reached, under observation at an incidence close to normal to the surface.
• the test 35 carried out in contrast to the previous one with a relatively small thickness also shows values of qui which are appreciably greater than those of the examples whose thicknesses are best suited. For the assemblies considered, these values are between 75 and 85 nanometers. The corresponding samples have a value of ç much lower than the limits indicated above as being those beyond which the attenuation is no longer adequately ensured.
• the sub-layers according to the invention meet the objective pursued. Furthermore, the assemblies comprising sublayer and layer are stable in the mechanical, chemical and thermal resistance tests, and do not exhibit any optical defects. In particular, the layers are very transparent.

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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)
• Surface Treatment Of Glass (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Citations (8)

• 1999
  • 1999-09-01 LU LU90432A patent/LU90432B1/fr active
• 2000
  • 2000-08-31 EP EP00974374A patent/EP1218305A1/fr not_active Withdrawn
  • 2000-08-31 JP JP2001519614A patent/JP2003508326A/ja not_active Withdrawn
  • 2000-08-31 CZ CZ2002781A patent/CZ2002781A3/cs unknown
  • 2000-08-31 AU AU12708/01A patent/AU1270801A/en not_active Abandoned
  • 2000-08-31 PL PL00354407A patent/PL354407A1/xx unknown
  • 2000-08-31 WO PCT/EP2000/008844 patent/WO2001016043A1/fr not_active Application Discontinuation

Patent Citations (10)

Non-Patent Citations (5)

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