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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
• • 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
  • C03C17/3429—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 at least one of the coatings being a non-oxide coating
  • C03C17/3435—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 at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3634—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing carbon, a carbide or oxycarbide
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3639—Multilayers containing at least two functional metal layers
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
• • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
  • C03C17/366—Low-emissivity or solar control 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
  • 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
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3681—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
• • 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
  • C03C2217/70—Properties of coatings
  • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant

Definitions

• the present disclosure relates, in general to a coated glass article including a stack of layers acting on solar radiation, and more specifically to a coated article provided with one or more protective overcoats comprising titanium zirconium hafnium or its nitride with or without carbon overlying the stack of layers acting on solar radiation.
• Solar control glass has a large part to play in the future of construction, as external temperatures will continue to rise and so will the expectations of comfort.
• Solar control coatings provided with a layer stack of glass/ SEN ⁇ /NiCr/SENi and glass/SislNU/Nb/SislN are known in the art, where the metallic NiCr layer and Nb layer are the sole infrared (IR) absorbing layers, respectively in the coating stacks.
• IR infrared
• silicon nitride layer of such coated articles is hard, it has been found to have a tendency to scratch due to high surface friction and roughness, and such scratches can open other layer(s) to chemical attacks (i.e., corrosion). Thus, it can be seen that even though silicon nitride provides for good optical characteristics and is hard, it has chemical and/or mechanical durability issues.
• overcoat layers comprising zirconium oxide (ZrOx), titanium zirconium oxide (TiZrOx), titanium oxide (TiOx) or their nitrides.
• ZrOx zirconium oxide
• TiZrOx titanium zirconium oxide
• TiOx titanium oxide
• overcoat layers comprising other materials are provided in U.S. Publication No. US2018-208503; U.S. Patent No. 8,043,707 and U.S. Patent No. 8,389,121.
• Such overcoat layers are being used for both silver-based and non- silver-based layer stacks.
• coated articles with silver-based layer stacks are generally used in double glazing configurations, the role of overcoat layers in these products are limited to preventing scratches during the handling process alone.
• coated articles comprising non- silver-based layer stacks are widely used in single glazed units and hence necessitate overcoat layers to resist scratches not only during handling but also during the life of the coated article (where they are generally used in window & facade applications) due to their exposure to external conditions and susceptibility to harsher mechanical and chemical interaction.
• overcoat layers need to be chosen also based on whether the resultant coated glass product is to be annealed or tempered. While it is true that the art describes certain overcoat layers for annealed and certain others for tempered products, a protective overcoat that is effective across both the variants of coated articles will be advantageous.
• Certain example embodiments of this invention relate to a coated article that is durable and has an increased thermal stability and mechanical performance while retaining the optical characteristics of the article. Certain example embodiments of this invention also relate to a method of making the same.
• the disclosure teaches the use of protective overcoat layers comprising titanium zirconium hafnium or its nitride with or without carbon.
• the protective overcoat according to certain embodiments of the present disclosure is double-layered comprising a layer of titanium zirconium hafnium or titanium zirconium hafnium nitride provided directly under and in contact with another layer of carbon.
• the protective overcoat according to certain other embodiments of the present disclosure is a single layer comprising titanium zirconium hafnium or titanium zirconium hafnium nitride optionally doped with carbon.
• a coated article including a stack of layers acting on solar radiation provided on the surface of the glass substrate comprising at least one functional layer and one or more protective overcoat layers deposited over at least a part of the functional layers.
• the functional layers are free of silver and silver containing metal alloys and the protective overcoat layers comprise of TiZrHf or TiZrHfN with or without carbon.
• the protective overcoat layers contribute to scratch resistivity of the coated article before heat treatment for up to 5N in Erichsen scratch testing.
• FIG. 1 illustrates a coated solar control glass article, according to one embodiment of the present disclosure
• FIG. 2 illustrates a coated solar control glass article sample A along with a comparative sample B, according to another embodiment of the present disclosure.
• FIG. 3 illustrates a coated solar control glass article sample C according to yet another embodiment of the present disclosure along with a comparative sample D.
• Embodiments disclosed herein are related to coated solar control glass article comprising protective overcoat layers made from titanium zirconium hafnium or its nitride with or without carbon.
• a coated solar control glass article 100 according to one embodiment of the present disclosure is illustrated in FIG. 1.
• the coated solar control glass article 100 is provided with a layer stack 110 which includes a double-layered protective overcoat 120 comprising a layer of titanium zirconium hafnium (TiZrHf) or titanium zirconium hafnium nitride (TiZrHfN x ) overlaid with a layer comprising carbon.
• TiZrHf titanium zirconium hafnium
• TiZrHfN x titanium zirconium hafnium nitride
• the double-layered protective overcoat 120 is provided over a plurality of underlying layers which include a functional layer i.e., an infrared (IR) absorbing layer 112 (e.g., Nb, Ta, Zr, Ni or their alloys or nitrides or the like) sandwiched between at least one overlayer 113 and one underlayer 111.
• a functional layer i.e., an infrared (IR) absorbing layer 112 (e.g., Nb, Ta, Zr, Ni or their alloys or nitrides or the like) sandwiched between at least one overlayer 113 and one underlayer 111.
• IR infrared
• the TiZrHf/ TiZrHfN x provides mechanical and chemical durability (e.g., scratch resistance and resistance to corrosion from alkaline solutions and the like) and the overlying carbon layer helps in reducing the friction before tempering and burns off while tempering.
• the carbon layer in certain embodiments of the present disclosure enables the coated solar control glass article 100 to have a AE* Rg ; AE* RC & DE*t value (glass side reflective and/or transmission) of no greater than 3.5, due to heat treatment and abrasion tests up to 2000 cycles.
• AE* Rg AE* RC & DE*t value
• the combination of TiZrHf/ TiZrHfN x & carbon in a double-layered protective overcoat allows the coated solar control glass article 100 which is otherwise mechanically and chemically susceptible, to have desired optical characteristics such as transmission and/or reflectance, to be heat treatable and/or bendable in a commercially acceptable manner and have significantly improved mechanical and chemical resistivity.
• FIG. 1 illustrates a side cross-sectional view of the coated solar control glass article 100.
• the coated solar control glass article 100 includes a glass substrate 101 which can be clear, green, bronze, grey, blue or blue-green substrate measuring about 1.0 to 12.0 mm thick; at least one underlayer 112 comprising nitride or oxide or oxynitride or aluminum oxynitirde of silicon or aluminum or a mixture of at least two of these compounds provided above the glass substrate 101; at least one functional layer i.e., IR absorbing layer 112 comprising at least one metal or metal alloy or nitride of niobium, tantalum, zirconium or nickel arranged above the underlayer 111 and at least one over layer 113 comprising nitride or oxide or oxynitride or aluminum oxynitirde of silicon or aluminum or a mixture of at least two of these compounds arranged above the IR absorbing layer 112.
• IR absorbing layer 112 comprising at least one metal or metal alloy or nitride of niobium, tantalum, zirconium or nickel
• the layer stack 110 of the coated solar control glass article 100 is overlaid and protected by the double-layered protective overcoat 120.
• the double-layered protective overcoat 120 comprises of a layer containing TiZrHf or TiZrHfN x 114 arranged above the IR absorbing layer 112 and another layer of carbon 115 overlaid and in direct contact with the layer containing TiZrHf or TiZrHfN x.
• the carbon layer 115 is farthest and the outermost layer of the coated solar control glass article 100.
• the underlayer 111 and over layer 113 are typically the dielectric layers of the layer stack 110 and comprise of either silicon nitride, silicon oxide, silicon oxynitride or silicon aluminum oxynitride or aluminum nitride, aluminum oxide, aluminum oxynitride or aluminum doped silicon nitride.
• the underlayer 111 and overlayer 113 dielectrics may essentially comprise of silicon nitride. It should be noted that the terms “oxide” and “nitirde” as used herein includes various stoichiometries.
• the overall coating of the coated solar control glass article 100 includes layers 111 - 115.
• Layers 111 - 115 may be deposited through magnetron sputtering or other types of sputtering or other suitable techniques.
• Other layers may be provided between illustrated layers in certain other embodiments of the present disclosure.
• certain illustrated layers may be deleted.
• the layer system and layers thereof shown in FIG. 1 are considered "on" the substrate 101 even when other layer(s) (not shown) are provided therebetween.
• more than one IR absorbing layer may be provided in certain example embodiments of the present disclosure.
• FIG. 2 illustrates two samples of coated solar control glass articles for the purpose of comparison.
• the sample (A) is made up of the following stack: glass/ Si 3 N 4 /NbN/Si 3 N 4 /TiZrHfN/C thereby including a double-layered protective overcoat according to the embodiment of the present disclosure illustrated in FIG. 1.
• sample (B) is made up of the following stack: glass/ Si 3 N 4 /NbN/Si 3 N 4 , without the double-layered protective overcoat.
• Sample (A) demonstrated a significant improvement in scratch resistance compared to the sample (B). Particularly, before the heat treatment of samples (A) and (B), sample (A) could not be significantly scratched with a Erichsen Scratch hardness tester. Post the heat treatment of sample (A), the sample’s resistance to scratchability was found to be slightly depleted, yet the scratch resistivity of sample (A) post heat treatment was found to be greater than that of sample (B). Sample (B) showed some level of scratches post heat treatment which were visible in reflection. Thus the presence of the protective overcoat layers in sample (A) has contributed to (i) the scratch resistivity of the sample (A) before heat treatment and (ii) enhanced scratch resistivity of the sample (A) post heat treatment. Sample (B) was not found to be resistant to scratches before or after the heat treatment. Therefore, the use of the protective overcoat layers of the present disclosure is advantageous for products which are not heat treated and also to products which undergo heat treatment.
• the coated solar control glass article may comprise a single-layered protective overcoat 130 comprising TiZrHf or TiZrHfN.
• the coated solar control glass article according to this embodiment is made up of the following stack: glass/ Si 3 N 4 /NbN/Si 3 N 4 /TiZrF[fN.
• the conventional solutions use "hard” layers that comprise of materials having a high hardness such as titanium oxide or the DLC (Diamond-like carbon) type amorphous carbon.
• the protective overcoat layer according to the present disclosure is clearly distinguished from these layers known as "hard”.
• the mechanism behind obtaining a good protection to scratch lies not on the hardness of the layer but rather on lowering the coefficient of friction between the underlying layer and the protective overcoat layers.
• the protective overcoat layers, according to the present disclosure perform the function of antifriction layer. This effect is easily observed by rubbing with a cloth or paper slightly on the surface of the sample B provided with a stack of layers. In the absence of the protective overcoat layers according to the present disclosure, the upper surface of the stack was penetrated. Whereas, in sample A including the protective overcoat layers, the surface is "smooth".
• the use of metallic alloys along with a polymeric compound such as carbon is advantageous because this improves the friction phenomena that is crucial during the steps of transportation.
• the coated glass articles are in general, transported with the aid of glass harp carts.
• These harp carts comprise metallic strings coated with a polymeric sheath which are held against the coated glass articles.
• the contacts between these strings and the stack of layers which may occur during insertion of the coated glass articles and/or during their transport, represent one of the principal causes of the generation of scratches.
• the tribological friction coefficient of the indenter metallic alloy/ layers of the stack is lowered when the stack includes protective overcoat layers according to the present disclosure.
• the improvement of the scratch resistance appears to be able to be connected to this reduction in the coefficient of friction.
• the protective overcoat layer 115 is deposited by reactive sputtering from a target comprising at least 70% to 100% carbon.
• the protective overcoat layer 114 is deposited by reactive sputtering from a target comprising at least 60% to 90%, and more preferably 70% to 80% of Ti; at least 5% to 40% and more preferably 10% to 30% of Zr; at least 0.1% to 30% and more preferably 0.1% to 10% of Hf.
• the atomic percentage of nitrogen present in the layer varies from 0.1 % to 50% .
• the overcoat layers may comprise alternating layers of TiZrHfN/Carbon.
• the overcoat layers may comprise the following layers going away from the glass substrate: T iZrHfN/Carbon/ T iZrHfN/Carbon/ T iZrHfN/Carbon (where the T iZrHfN may be non-nitrided to be a metallic layer of TiZrHf).
• coated articles according to other embodiments of the present disclosure may comprise IG (insulating glass) window units provided as double and triple glazed units.
• IG embodiments coatings from FIG. 1 may be provided on the inner wall of the outer substrate of the IG unit, and/or on the inner wall of the inner substrate, or in any other suitable location.
• Table 1 Thickness Ranges of Coated Solar Control Glass Article 100 in FIG. 1
• the thicknesses of the overcoat layers also vary depending on whether they as used as a single-layered protective overcoat or as double-layered protective overcoat. While being used as a single-layered protective overcoat, the thickness of the TiZrHf or TiZrHfN layer ranges between 0.5 to 5 nm. Likewise, the thickness of the TiZrHf or TiZrHfN layer ranges between 0.5 to 5 nm and that of carbon ranges between 0.1 to 5 nm while being used as a double-layered protective overcoat. Unless otherwise indicated, the thicknesses mentioned in the present disclosure are physical thicknesses and the layers are thin films. The term thin layer, a layer having a thickness of between 0.1 nm and 100 nm.
• the glass substrate according to the present disclosure is considered to be placed horizontally.
• the stack of thin layers is deposited above the glass substrate.
• the expressions “above” and “below” does not necessarily mean that two layers and/or coatings are placed in contact with one another. When it is specified that a layer is deposited in "contact with” another layer or coating, this means that there cannot be one or more layers interposed between these two layers.
• the functional layer 112 can be a metallic or a non-metallic layer completely free of silver and silver containing metal alloys. According to multiple embodiments of the present disclosure, the functional layer 112 is based on niobium, tantalum, zirconium, nickel. In specific embodiments, the functional layer 112 may be selected from the group consisting of niobium, niobium nitride, tantalum, zirconium, zirconium nitride or nickel chromium. The thickness of the functional layer ranges between 0.5 nm and 40 nm, preferably between lnm and 30 nm and more preferably between 1.5 nm and 25 nm. According to the embodiment described in, the functional layer 112 may comprise a single layer or more than one layer.
• the functional layer 112 (one layer or more than one layer) are deposited between at least one overlayer and at least one underlayer.
• the overlayer and underlayer are generally the dielectric layers which make it possible to adjust the optical properties of the coated solar control glass article. These dielectric layers also make it possible to protect the functional layer from chemical and mechanical attacks.
• the overlayer and underlayer based on dielectric materials have a thickness greater than 10 nm, preferably between 10 and 80 nm and more preferably between 10 and 50 nm.
• the overlayer and underlayer based on dielectric materials are deposited by sputtering assisted by a magnetic field. These layers’ act as barriers for the functional layer, protecting against the diffusion of oxygen and water at high temperatures and do a stabilizing function.
• the overlayer and underlayer are based on nitride or oxide or oxynitride or aluminum oxynitirde of silicon or aluminum or a mixture of at least two of these compounds.
• the stack of layers acting on solar radiation therefore advantageously comprises at least one functional layer preferably free of silver, at least two coatings based on dielectric materials, each coating including at least one dielectric layer, so that each of the functional layer is disposed between two coatings based on dielectric materials.
• the dielectric layers may be located above and/or below of at least one functional layer or above and/or below of each of the functional layers and is either directly in contact with or is separated by additional underlayers and over layers.
• the overlayer is below the protective overcoat layers, preferably, in contact with the protective overcoat layer 114.
• the protective overcoat layer 115 is preferably the last layer of the stack, i.e. the layer furthest away from the glass substrate coated with the stack of layers.
• the additional underlayers and overlayers can comprise of the same material as that of the over layer 113 and underlayer 111 as described in the previous embodiment or can comprise of materials different from the layers 113 and 111.
• the purpose of additional underlayers and over layers is to protect the functional layer from possible degradation linked to the deposition of a coating based on dielectric materials and degradation as a result of heat treatment.
• the additional underlayer and additional overlayer can be metallic layers made of titanium.
• the thickness of each of the additional overlayer and additional underlayer directly sandwiching the functional layer can be at least 2 nm or at least 10 nm.
• the stack of layers acting on solar radiation comprises starting away from the glass substrate: a underlayer comprising a dielectric material optional additional underlayer at least one functional layer free of silver optional additional overlayer an overlayer comprising a dielectric material protective overcoat layer comprising TiZrHf or TiZrHfN protective overcoat layer comprising carbon
• the stack of layers acting on solar radiation comprises starting away from the glass substrate: a underlayer comprising a dielectric material at least one functional layer free of silver an overlayer comprising a dielectric material protective overcoat layer comprising TiZrHf or TiZrHfN protective overcoat layer comprising carbon
• the coated solar control glass article according to the teachings of the present disclosure can be annealed or can be intended to undergo thermal treatments at temperatures greater than 400 °C, preferably more than 500 °C or more preferably greater than 600 °C.
• the inclusion of a heat treatment or not depends entirely on the intended use of the coated solar control glass article.
• the properties of the coated solar control glass article demonstrated here, namely the scratch resistance, are independent of any thermal treatment.
• the protective overcoat layers proposed by the present disclosure provide scratch resistance to coated solar control glass articles which are intended to be annealed, tempered, heat strengthened, toughened, hardened and / or curved or bent or laminated.
• protective overcoat layer comprising titanium zirconium oxide when deposited above a layer stack comprising a functional layer free of silver or silver containing alloys provide scratch resistance to coated solar control glass articles if the glass articles are intended to be annealed. Whereas titanium zirconium oxide overcoat layer does not improve the scratch resistance of coated solar control glass articles which are intended to be thermally treated, for example, tempered.
• protective overcoat layer comprising carbon as the carbon layer is completely oxidized and burnt off during the thermal treatment of the glass article.
• the protective overcoat layer comprising titanium zirconium oxide and protective overcoat layer comprising carbon improve the scratch resistance of annealed glass articles, they do not improve the scratch resistance of thermally treated glass articles.
• the protective overcoat layers proposed in the present disclosure improve the scratch resistance of coated solar control glass articles that are annealed or thermally treated.
• the present disclosure also relates to a method of manufacturing a solar control coated glass articles provided with a stack of thin layers deposited by sputtering assisted by a magnetic field, the method comprising the steps of: depositing at least one underlayer based on dielectric material over the surface of the glass substrate; depositing at least one functional layer above the underlayer; depositing at least one overlayer based on dielectric material above the functional layer; depositing a protective overcoat layer comprising TiZrHf or TiZrHfN and optionally depositing a protective overcoat layer comprising carbon above the overlayer comprising TiZrHf or TiZrHfN.
• the method further includes the step of thermal treatment of the coated solar control glass article at temperatures greater than 400 °C, preferably greater than 500 °C and more preferably greater than 600 °C.
• the coated solar control coated glass article thus obtained can be used for the manufacture of a glazing for applications including but not limited to glass window or insulated glazing’s for buildings and laminated glazing for glass safety applications.
• the coated solar control coated glass article can be tempered, annealed, enameled, laminated and/or bent. Examples Example 1
• Table 1 Stack of Layers for Coated Solar Control Glass Articles Samples 2, 4 & 5 are prepared according to the teachings of the present disclosure with protective overcoat layer comprising TiZrHfN and samples 1 & 3 are comparative samples that do not include any protective overcoat layer. Optical and solar control properties of the above mentioned glass samples are summarized in Table 2.
• R ext External reflection
• a*G, b*G a*, b* values measured on the external side, i.e., the glass side
• Ri nt Internal reflection
• a*C, b*C a*, b* values measured on the internal side, i.e., the coating side
• samples 1, 2, 3 & 4 are similar and comparable.
• the thickness of the protective overcoat layer TiZrHfN in samples 2, 4 & 5 have been engineered such that the optical properties of the samples 1 & 3 remain unchanged even after the inclusion of the protective overcoat layer TiZrHfN.
• Particularly the optical values of samples 1 & 2 and samples 3 & 4 can be seen to be similar.
• the visible scratch resistance is an important criterion for coated solar control glass articles. This visible scratch resistance provides mechanical resistance against scratches that can appear during cutting and edge grinding of glass that result in chipping off of edges and also against rough handling of samples. All the coated glass samples were observed for visible scratch in both annealed condition and post thermal treatment of the samples. Thus calculated scratch resistance of the samples are summarized in Table 3. Table 3: Scratch Resistance
• Table 3 shows scratch force up to which scratches are not visible. For sample 4, in annealed form scratches are not visible till 5N force. Therefore, its scratch resistance is greater than 5N. In tempered form, scratches are visible after 2N, so its scratch resistance is less than 2N. Table 3 demonstrates that the protective overcoat layer when provided above a stack of layers comprising a functional layer that is free of silver (sample 4) provides much enhanced scratch resistance (both in annealed and tempered sample) than when provided above a stack of layers comprising a functional layer that comprises silver (sample 2).
• Sample 6, 7, 8 & 9 are prepared according to the teaching of the present disclosure comprising the various proposed protective overcoat layers 15 TiZrHf, TiZrHfN and carbon. Comparative samples 1 & 2 are prepared as per teachings of the prior art.
• the samples in table 4 were rotated in a circular manner on the machine against a sharp indenter with increasing load. It was observed that no 20 scratch could be seen on the samples 6, 7 & 8 and comparative sample 2 up to 5N.
• the sample in table 4 were then heat treated at a temperature of 650 °C after the Erichsen scratch test (EST TT). This step reveals the presence of any minor scratches that occurred during the test procedure. It was found that the scratch resistance of the samples remains unchanged. Thus the heating process has not impacted the scratch resistance of the samples.
• comparative sample 2 increases the scratch resistance of annealed samples, it does not improve the scratch resistance of tempered samples.
• sample 6 provided with a carbon comprising protective overcoat layer.
• samples 7, 8 & 9 that comprise of protective overcoat layer comprising TiZrHfN with or without carbon improve the scratch resistance of samples in the annealed state as well as in the tempered state.
• DE* of less than up to 2 can be achieved using the single-layered protective overcoat layer TiZrHfN.
• DE* of less than up to 3.4 can be achieved using the double-layered protective overcoat layer comprising one layer of TiZrHfN and another layer of carbon.
• the scratch resistance of coated solar control glass articles also depends on the thickness of the protective overcoat layer used above the stack of layers.
• the impact of varying thicknesses of TiZrHfN overcoat layer provided above coated glass articles on their scratch resistance is illustrated in Table 7.
• Samples shown in Table 7 are all provided with the following stack: Glass/ Si3N4/NbN/Si3N4. Scratch resistance values for annealed samples and tempered samples are presented. The optical characteristics of all samples were seen to be similar.
• the coated solar control glass articles described in the present disclosure finds application as a glazed element in building.
• the glazing may form a double or triple glazing with the coating side of the glass arranged facing the closed space inside the multiple glazing.
• the glazing may also form a laminated glazing whose stack of layers may be in contact with the thermoplastic adhesive material connecting the substrates, in general PVB.
• the glazing according to the invention is, however, particularly useful when the multilayer stack is facing the outer environment, whether it is a single glazing or a laminated glazing, but also optionally a multiple glazing.
• the glazing may also be enameled.
• coated solar control glass articles of the present disclosure can also be annealed, strengthened, toughened, tempered or curved and/or bent.
• the extensive durability in terms of scratch resistivity of the coated solar control glass article provides for an extended life of the product.
• the tempered coated solar control glass article can also be used in building wall cladding panel of curtain walling for interior applications. Further the tempered coated solar control glass article can also be used as a side window, rear window or sunroof for an automobile or other vehicle.
• the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• a method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such method, article, or apparatus.
• “or” refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
• TITLE COATED ARTICLE COMPRISING PROTECTIVE OVERCOAT LAYERS MADE FROM TITANIUM ZIRCONIUM HAFNIUM NITRIDE AND CARBON

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• 2021
  • 2021-02-03 EP EP21751338.1A patent/EP4100191A4/de active Pending
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