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
  • C03C17/34—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
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
• • 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
  • C03C2218/154—Deposition methods from the vapour phase by sputtering
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate

Definitions

• the present invention relates to glazings which have a high reflection in the visible range while retaining a significant share of transmission.
• the windows in question are useful in particular to limit natural energy intake especially in buildings exposed to sunshine. Limiting energy intake saves the need for air conditioning.
• the windows in question are also characterized by their "solar factor" magnitude designating the ratio of the energy both transmitted through the glazing and re-emitted by it inwards, after absorption, to the total energy incident.
• Glazing of this type is most often made by coating the glass sheet with a layer, or a system of so-called "hard” layers. These layers are traditionally deposited by pyrolysis on the hot glass immediately after formation of the sheet. The most common is to carry out the pyrolysis "in line” that is to say on the site of production of glass. The glass ribbon formed on the "float” line is coated while it is still at high temperature.
• a recognized feature of products obtained by pyrolysis is that they are relatively hard. They resist both chemical and mechanical aggression. For this reason they are conveniently used, possibly exposing the coated face to external hazards. This feature distinguishes the layers obtained by pyrolysis from those produced by vacuum deposition techniques by sputtering, these two types of techniques constituting the two most widely used channels for the production of thin layers on a glass support.
• the layers obtained by sputtering under vacuum are called "soft". Their mechanical resistance or insufficient chemical means that these layers are mainly used in configurations where they are not exposed to these aggressions. This is the case in multiple glazing. In these windows the layers are turned towards the spaces between the sheets.
• Vacuum cathodic sputtering facilities are independent of glass fabrication.
• the coating operations by these techniques are conducted "in recovery" according to the usual terminology, in other words on glass that has been manufactured previously and that in the meantime may have been stored, transported, redécoupé etc.
• the inventors have shown that a very specific choice of the materials constituting these layers deposited by cathodic sputtering made it possible to achieve the indicated resistance requirements.
• the inventors have also shown that by appropriate choice of the layer systems, it is also possible to subject the glazing in question to vigorous subsequent heat treatments, such as bending or tempering treatments without altering the essential characteristics conferred by these layers.
• the layer systems considered according to the invention do not contain a layer of infrared reflective metal type, including silver-based layers, systems comprising these silver-based layers systematically showing a certain fragility to external aggression.
• the object of the invention is to provide glazing that meets the requirements set out above.
• the inventors have shown that this object could be achieved by glazing as defined in claim 1. It is remarkable that the layers comprising titanium oxide combined with other oxides make it possible to achieve the desired characteristics, particularly of resistance. , while titanium oxide layers alone, as previously indicated, are insufficiently resistant. Furthermore, the reflective properties specific to titanium oxide can be maintained to a large extent, by the combination of the layer having a good mechanical strength, with one or more layers with a high refractive index.
• the reasons for the quality of the titanium oxide-based layers used according to the invention are not perfectly understood. It is likely that depositing a layer composed of mixed oxide of titanium and another metal leads to a change in the structure of the layer. The formation of crystals is certainly modified. The presence of two or more components, whose crystallographic characteristics are not the same, leads to a very specific growth, probably avoiding especially the formation of more fragile structures such as columns.
• oxides are likely to be associated with titanium oxide in this layer of mixed oxides.
• oxides that may be used, mention may be made especially of the following compounds: Al, Zr, Hf, Nb, V, Ta, Mn, Fe, Co, Ni, Cu, Si
• preferred oxides are in particular those of Al, Zr, Hf, Nb, and especially Zr oxide.
• the mixed oxides used according to the invention are mixed oxides of Ti and another of the elements indicated above. However, often one or more elements in limited proportions, usually less than 8% by weight and usually less than 5%. These include dopants whose role is primarily to improve the manufacture and / or implementation of cathodes in the production of layers in vacuum deposition techniques. These elements are traditionally intended in particular to improve the conductivity of materials constituting cathodes such as: Ti, Al. It can also be compounds stabilizing certain constituents such as Ca, Mg, or elements that appear as inseparable from others during preparation. This is the case of lanthanides such as yttrium or hafnium oxide.
• the zirconium oxide included in the mixed oxide layer based on titanium oxide is present in a proportion of 25 to 60% by weight and preferably 40 to 55%.
• Zirconium oxide is particularly advantageous in the to the extent that, in addition to imparting the sought-after strength properties, its refractive index being close to that of titanium oxide, the optical properties of the coated glazings, and in particular the reflection, are also close to those which are observed with titanium oxide.
• the strength of the titanium oxide layer depends on its composition, it also depends on its thickness. If an increase in thickness is accompanied by increased resistance, beyond a certain threshold the improvement is not significant, the additional cost for a thicker deposit becomes unnecessary.
• the layer based on titanium oxide according to the invention has a thickness of between 25 and 900 °, preferably between 50 and 500 °, and advantageously between 100 and 350 °.
• the choice of the thickness of the titanium oxide-based layer also depends on the other layers with a high refractive index. These thicknesses are such that the conditions on the reflection are satisfied.
• the reflection is at least 15% when the layer system is applied to clear glass 4 mm thick. Under the same conditions, it is advantageously between 20 and 40%.
• the light transmission is preferably at least 60%.
• the light absorbed by the glazing remains relatively low. It is advantageously less than 20% and preferably less than 10%.
• the reflection in the layer systems according to the invention depends in part on the oxide-based mixed oxide layer. titanium but also from the underlying, or high index layers.
• a particularly preferred high index layer is a titanium oxide layer.
• the layers comprising, in combination, titanium zirconium oxide (50% of titanium oxide, 46% by weight of zirconium oxide, the remainder of yttrium oxide) deposited under vacuum have an index of the order of 2.35.
• the combination of a layer of TiO 2 or TXO, or a layer of titanium oxy-nitride with a low nitrogen content (atomic ratio N / O of less than 10%), with a mixed oxide layer based on Titanium oxide thus makes it possible to simultaneously benefit from a good resistance conferred by this last layer, and overall from a higher index.
• the layers with a high refractive index (greater than 2.2) and titanium oxide mixed oxide can be combined with other layers in order to improve the properties thereof or to co nf er the properties that the first ones do not present or not to a degree appropriate to the intended use.
• the implementation of the glazing according to the invention can take place without any other modification than the setting to the desired dimensions and the introduction into frames.
• the windows in question in this case are essentially planar.
• the need for dimensioning after coating, makes the glass sheets used in the composition of these glazings are not subjected to prior heat treatment.
• the thermal treatments in question by ensuring the presence of stresses, give the glazing mechanical properties ensuring both a better impact resistance and especially, in case of violent impact, cause these windows break into multiple fragments of small dimensions.
• the transformation may require maintaining these temperatures for several minutes taking into account in particular the thermal inertia of the glass.
• the holding time at these temperatures can reach 5 minutes or more depending on the techniques used and the thickness of the treated sheets.
• Heat treatment type quenching or bending are known to be likely to alter the thin layers deposited on the glass sheets. Independently of the alterations that may appear in the structure of certain layers because of the temperature, the glass substrate can also induce undesirable modifications.
• the layers considered according to the invention do not undergo a detrimental change of structure under the conditions of these heat treatments.
• the structure of the layers remains substantially unchanged.
• glass sheets of the silico-soda-lime type in other words the most usual glasses, subjected to high temperatures can lead to an alteration of the layers of which they are coated.
• the alkaline constituents of these glasses are likely to migrate and diffuse in the layers in contact with the glass.
• the diffusion of these mobile elements often leads to the appearance of a haze more or less pronounced.
• the appearance of the veil corresponds to a light diffusion mechanism due to the presence of elements foreign to the structure of the layers.
• the products used must be very transparent.
• the proportion of light scattered relative to the transmitted light should not exceed 2% and preferably not 1%. These limits may be exceeded if no precautions are taken to protect the layers used according to the invention.
• Preferred "barrier" sub-layers used to improve the protection against the diffusion of alkaline ions from the glass sheet consist for example of at least one of the silicon compounds: oxide (SiO 2 ), nitride (Si 3 N 4 ), oxy-nitride (SiON); or oxides of SnO 2 and oxides composed of tin and zinc, or TiO 2 optionally substoichiometric or optionally in the form of oxynitride containing a low nitrogen content (N / O less than 10%).
• tin oxide layer When using a tin oxide layer it comprises at least 30% and preferably at least 40% by weight of tin oxide.
• the tin oxide layer is preferably a tin and zinc mixed oxide layer. The combination of both offers the advantage, in addition to a high deposition rate by sputtering techniques, of producing layers whose structure is stable in the heat treatments considered.
• Zinc oxide alone is undesirable as a barrier layer to diffusion because of its tendency to form columnar structures, especially when its thickness exceeds about ten nanometers, structures that are not very effective against diffusion phenomena. .
• the presence of a layer impeding the diffusion of the constituents of the glass modifies the optical properties of the glazing.
• the presence of a tin oxide layer, whose refractive index is lower than that of the titanium oxide layer modifies the reflection.
• a layer based on tin oxide is used, to adapt its thickness. This is preferably less than 1.2 times the cumulative thickness of the high refractive index layer and the titanium oxide based mixed oxide layer.
• the layers or layer systems used according to the invention must still lead to glazing whose coloration induced by these layers meets the market demand. Certain colorings especially in reflection must be discarded. This is particularly the case with globally “purple" colorations. These colorations when analyzed in the CIE (International Lighting Committee) system, the parameters a * and b * advantageously satisfy the following conditions: for an illuminant D and for a solid angle of at most 10 ° a * ⁇ 0 and b * ⁇ 6. It is particularly important to have systematically a * non positive. For negative values of a * the color is either slightly blue or slightly green. These reflection colorings are acceptable even if the preference is color neutrality.
• glazings meeting these coloring requirements preferably have, before and after heat treatment, variations of a * and b * such that ⁇ * ⁇ 2 and advantageously ⁇ * ⁇ 1, with:
• the layers which determine the optical characteristics of the glazings according to the invention Apart from the layers which determine the optical characteristics of the glazings according to the invention, and in order to further protect these layers against the risk of deterioration in subsequent operations including storage and transport, it is possible and advantageous to cover these layers by a temporary coating which is removed before the installation of these windows. It is known to coat the glazings with films of various soluble waxes or polymers which can be removed by washing. These products can be used to protect the layers used according to the invention.
• the glazings according to the invention consist of glass sheets of different thicknesses. They can also consist of sheets of clear or colored glass in the mass, mainly to give them aesthetic characteristics, but also possibly to develop their opto-energetic properties.
• the dominant wavelength in reflection A m for an illuminant D65 in a solid angle of 2 °, is between 475 and 600 nm.
• FIG. 1 shows a glazing unit 1 comprising a layer system according to the invention.
• the respective thicknesses are not respected for the sake of clarity.
• Layer 2 is a layer with a high refractive index.
• Layer 3 is a mixed oxide layer based on titanium oxide.
• FIG. 2 is a glazing unit according to the invention similar to the preceding one, further comprising a layer 4 for protecting against the diffusion of constituents of the glass sheet 1.
• FIG. 3 represents a glazing unit according to the invention which, in addition to the preceding layers, comprises a protective coating 5.
• the coating in question which is applied on a temporary basis, has the essential role of preventing scratches scratches and other mechanical alterations likely 3.
• This layer in the case of glazing undergoing heat treatment behind the formation of the functional layers, is advantageously constituted by a material which is eliminated by combustion during this heat treatment.
• a carbon layer is particularly advantageous for forming this coating.
• the products according to the invention are analyzed in particular for their qualities of mechanical or chemical resistance.
• the tests to which they are subjected are the same as those used for the evaluation of similar glazings whose functional layers are produced by pyrolysis. Glazing according to the invention must achieve equivalent performance.
• the tests systematically include moisture resistance tests (21 days in a climatic chamber), chemical resistance tests (21-day neutral salt spray and exposure to SO 2 five cycles), an abrasion resistance test (AWRT for Automatic Web Rub Test) and claws (DBT for Dry Brush Test).
• the chemical resistance tests are those described in standard EN 1096-2.
• Abrasion tests are specific to diaper tests deposited by "magnetron sputtering". These two tests are significantly more "severe” than the analogous tests described in the standard indicated above. In other words, the successful abrasion tests in the examples made are necessarily satisfactory under the conditions of this standard.
• the test in a climatic chamber consists of exposing the sample in an oven maintained at 40 ⁇ 1, 5 ° C for 21 days. The test is successful when the sample remains free of stains. Aging under these conditions for each day corresponds to a one-year exposure to usual atmospheric hazards.
• the sample should not be discolored or generally withstand defects of any kind, such as peeling off the layer.
• the sample is placed in an enclosure charged with an acid atmosphere (two liters of water per 2 liters of SO 2 ) brought to 40 ° C for 8 hours. When brought back to room temperature, the sample remains in the atmosphere for 16 hours. The same cycle is repeated 4 times. The layer should not come off.
• an acid atmosphere two liters of water per 2 liters of SO 2
• the wet rub test "AWRT" (automatic wet rub test) is performed with a circular head of Teflon coated with a cotton fabric (ADSOL P / N 40700004). This is moved under load del050g on the layer. Cotton is kept moist throughout the test with demineralised water. The oscillation frequency is 60 to 90 per minute. The samples are observed to detect the alterations of the layer.
• the dry brush test (DBT) is performed on an Erichsen model 494 equipped with a standard brush (ASTM D2486). Each fiber of the brush has a diameter of 0.3mm. The fibers are grouped into a bundle of 4mm in diameter. The total weight applied by the brush and its support is 454g. The test includes 1000 cycles of back and forth.
• the samples are made on sheets of clear float glass with a thickness of 4mm. All samples are systematically analyzed before and after heat treatment at 670 ° C. for 8 minutes 30. The samples subjected to this treatment are noted (').
• the samples receive a set of layers comprising a tin oxide layer (SnO 2 ), a titanium oxide layer deposited from ceramic cathodes (TXO), and a mixed oxide layer of titanium and zirconium (TZO), consisting of a mixed oxide of 50% by weight of TiO 2 , 46% of ZrO 2 , the rest coming from elements usually accompanying zirconium, especially yttrium oxide.
• This layer is also deposited from ceramic cathodes.
• the chemical and mechanical resistance tests and the "haze" are satisfactory before and after heat treatment.
• the optical properties of the sample are in reflection (Rc) on the side of the layer (under 2 °) and for the colorimetric data (illuminant D65 under 10 °) also in reflection:
• the samples comprise a set of three layers. From the glass it is a layer of mixed oxide of titanium and zirconium (50% by weight of titanium oxide, 46% of zirconium oxide, the remainder being essentially oxide of yttrium), a titanium oxide layer deposited from a ceramic cathode (TXO) and a mixed oxide layer of titanium and zirconium (same composition as the first).
• the respective thicknesses are in A: 200, 50, 400.
• the first layer TZO is not strictly speaking a layer intended to reduce the diffusion even if it plays part of this role. It still acts as a relatively high index layer.
• the layer opposite to the diffusion is again a layer of tin.
• the layer with high index is this time composed of a mixed oxide of titanium and niobium (TNO) deposited from ceramic cathodes.
• the layer is formed at 50% by weight of each of the oxides.
• the surface layer is again a mixed oxide layer of titanium and zirconium as in the previous examples. The thicknesses of these layers are respectively in ⁇ :

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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)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Surface Treatment Of Glass (AREA)

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• 2010
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• 2011
  • 2011-03-09 WO PCT/EP2011/053520 patent/WO2011110584A1/fr active Application Filing
  • 2011-03-09 CN CN201180011366.3A patent/CN102791644B/zh not_active Expired - Fee Related
  • 2011-03-09 BR BR112012022289A patent/BR112012022289A2/pt not_active IP Right Cessation
  • 2011-03-09 EP EP11708787A patent/EP2545012A1/de not_active Withdrawn
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