Coated article comprising protective coating layers made of titanium nitride zirconium hafnium and carbon
Patent Information
- Application Number
- BR112022015397
- Authority / Receiving Office
- BR · BR
- Patent Type
- Patents
- Current Assignee / Owner
- Publication Date
- 2026-09-15
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Abstract
Description
1 / 31 Coated article comprising protective coating layers made of titanium nitride, zirconium, hafnium and... CARBON
[001] The present description refers, in general, to a coated glass article including a stack of layers that act upon solar radiation, and more specifically to a coated article provided with one or more protective coatings comprising titanium, zirconium, hafnium or their nitride with or without carbon overlaying the stack of layers that act upon solar radiation. FOUNDATION
[002] Solar control glass has a major role to play in the future of construction, as outside temperatures will continue to rise and so will expectations for comfort. Solar control coatings provided with a stack of glass / Si3N4 / NiCr / Si3N4 and glass / Si3N4 / Nb / Si3N4 layers are known in the art, wherein the metallic NiCr layer and Nb layer are the only infrared (IR) absorbing layers, respectively, in the coating stacks. These infrared (IR) absorbing layers can be nitrided. For example, see US Patent No. 5,837,108; US Publication No. 2002-0192473; US Patent No. 6,994,910 and PCT Publication No. WO2005-105687.
[003] Unfortunately, although these layered stacks provide efficient solar control, they are deficient in terms of mechanical performance, such as scratch resistance. The susceptibility to scratches is particularly problematic in environments such as construction sites, where the layered stacks are on already installed glazing inside buildings. However, they are prone to Petition 870220068937, dated 03 / 08 / 2022, page 14 / 51 2 / 31 Deposition of construction debris, often cleaned with sharp objects / harsh chemicals, makes the coated surface vulnerable to scratches. Another restriction is progressively imposed: when glazing may have to undergo one or more heat treatments, such as bending if we want to shape them (window / automotive industry application), tempering or annealing if they are to become stronger / less dangerous in case of impacts.
[004] Although the existing silicon nitride layer of such coated articles is hard, it has been found to have a tendency to scratch due to the high friction and roughness of the surface, and such scratches can open up other layer(s) to chemical attack (i.e., corrosion). Thus, it can be seen that even though silicon nitride provides good optical characteristics and is hard, it has chemical and / or mechanical durability problems.
[005] There are existing prior art documents that teach the provision of protective coating layers over a solar control coating or similar in order to increase durability. However, in some cases, these coatings may experience stress as deposited, or may experience stress when heated, during heat treatment, heat bending, thermal tempering and the like. In certain cases, the stress on these coatings may negatively affect the overall durability of the coating. Therefore, it may sometimes be desirable to provide a window unit or other glass article(s) coated with a more durable coating. Petition 870220068937, dated 03 / 08 / 2022, page 15 / 51 3 / 31
[006] Despite the presence of these protective coating layers, scratches appear very frequently in the stack. Once these scratches are created on a substrate, their visibility increases considerably when the substrate is subjected to a heat treatment of the hardening type. Susceptibility to scratches is detrimental in terms of aesthetics and production yield. This can cause an abnormally high rejection rate, especially in the case where these materials are curved / tempered windows.
[007] It is known to use coating layers comprising zirconium oxide (ZrOx), zirconium oxide and titanium (TiZrOx), titanium oxide (TiOx), or their nitrides. For example, see U.S. Publication No. 2017-355639; U.S. Patent No. 8,389,121 and U.S. Publication No. 2017-355639. In addition, protective coating layers comprising other materials are provided in U.S. Publication No. 2018-208503; U.S. Patent No. 8,043,707 and U.S. Patent No. 8,389,121. These coating layers are being used for stacks of silver-based and non-silver-based layers. However, since articles coated with stacks of silver-based layers are generally used in double-glazed configurations, the role of the coating layers in these products is limited to preventing scratches during the handling process alone.Considering that coated articles comprising stacks of non-silver layers are widely used in single-glass units and therefore require coating layers to resist scratches not only during handling but also during the life of the coated article (where they are commonly used in applications of...). Petition 870220068937, dated 03 / 08 / 2022, page 16 / 51 4 / 31 window and facade) due to their exposure to external conditions and susceptibility to more severe mechanical and chemical interaction.
[008] Furthermore, these coating layers also need to be chosen based on whether the resulting coated glass product is to be annealed or tempered. While it is true that the art describes certain coating layers for annealed products and certain others for tempered products, a protective coating that is effective on both variants of coated articles will be advantageous.
[009] In view of the above, it will be appreciated that there is a need in the art for a layer and / or coating that can be deposited on a solar control stack in order to increase the overall mechanical performance such as the scratch resistance of the coated article, but which is still capable of acceptable solar control (e.g., blocking a reasonable amount of IR and / or UV radiation) and / or heat treatment with a fairly low AE* value (reflectance and / or transmission of the glass side and coating side). It is a purpose of this description to eliminate disadvantages of the prior art discussed above and to meet the needs of ideal coating protection layers, the details of which will become apparent to the skilled technician once the following description is given.
[0010] Some exemplary embodiments of this invention relate to a coated article that is durable and has increased thermal stability and mechanical performance, while maintaining the optical characteristics of the article. Certain exemplary embodiments of this invention also relate Petition 870220068937, dated 03 / 08 / 2022, p. 17 / 51 5 / 31 with a method for manufacturing the same. The description teaches the use of protective coating layers comprising titanium zirconium hafnium or its nitride with or without carbon. The protective coating, according to certain embodiments of the present description, is a double layer 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 coating, according to some other embodiments of the present description, is a single layer comprising titanium zirconium hafnium or titanium zirconium hafnium nitride optionally doped with carbon. Summary of the Description
[0011] In one aspect of the present description, a coated article comprising a stack of layers acting on solar radiation provided on the surface of a glass substrate comprising at least one functional layer and one or more protective coating layers deposited over at least part of the functional layers is described. The functional layers are free of silver and silver-containing metal alloys and the protective coating layers are composed of TiZrHf or TiZrHfN with or without carbon. The protective coating layers contribute to the scratch resistivity of the coated article before heat treatment up to 5N in the Erichsen scratch test.
[0012] Other features and aspects of this description will become apparent from the following description and accompanying drawings. Brief Description of the Drawings Petition 870220068937, dated 03 / 08 / 2022, p. 18 / 51 6 / 31
[0013] The modalities are illustrated by way of example and are not limited to those shown in the accompanying figures.
[0014] Figure 1 illustrates an article of coated solar control glass, according to an embodiment of the present description; Figure 2 illustrates a sample of coated solar control glass article A, together with a comparative sample B, according to another embodiment of the present description; and Figure 3 illustrates a sample of coated solar control glass article C according to yet another embodiment of the present description, together with a comparative sample D.
[0015] Skilled technicians appreciate that the elements of the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of embodiments of the invention. Detailed description
[0016] Whenever possible, the same reference numbers will be used throughout the drawings to refer to the same or similar parts. The embodiments described herein relate to the coated solar control glass article comprising protective coating layers made of titanium zirconium hafnium or its nitride with or without carbon.
[0017] A 100 coated solar control glass article according to an embodiment of the present description is Petition 870220068937, dated 03 / 08 / 2022, p. 19 / 51 7 / 31 illustrated in Figure 1. In this embodiment, the coated solar control glass article 100 is provided with a layer stack 110 comprising a two-layer protective coating 120 comprising a titanium zirconium hafnium (TiZrHf) or titanium zirconium hafnium nitride (TiZrHfNx) layer coated with a layer comprising carbon. The two-layer protective coating 120 is provided over a plurality of underlying layers including a functional layer, i.e., an infrared (IR) absorption layer 112 (e.g., Nb, Ta, Zr, Ni or their alloys or nitrides or the like) sandwiched between at least one overlying layer 113 and an underlying layer 111.In the two-layer protective coating 120 of TiZrHf / TiZrHfNx and carbon, TiZrHf / TiZrHfNx provides mechanical and chemical durability (e.g., scratch resistance and corrosion resistance from alkaline and similar solutions), and the overlying carbon layer helps reduce friction before quenching and during quenching.
[0018] Thus, the carbon layer, in certain embodiments of the present description, allows the coated solar control glass article = 100 to have an AE*Rg; AE*rc and AE*t value (reflection and / or transmission of the glass side) of up to 3.5, due to heat treatment and abrasion tests of up to 2,000 cycles. Thus, surprisingly, it was found that the combination of TiZrHf / TiZrHfNx and carbon in a two-layer protective coating 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 Petition 870220068937, dated 03 / 08 / 2022, page 20 / 51 8 / 31 reflectance, to be heat treatable and / or flexible in a commercially acceptable manner, and have significantly improved mechanical and chemical resistivity. It was also surprisingly found that the combination of TiZrHf / TiZrHfNx and carbon in a two-layer protective coating significantly improves the resistance of the coated solar control glass article to damage, thus improving its shelf life.
[0019] Figure 1 illustrates a cross-sectional side view of the coated solar control glass article 100. The coated solar control glass article 100 includes a glass substrate 101 which may be clear, green, bronze, gray, blue or blue-green substrate measuring about 1.0 to 12.0 mm thick; at least one underlying layer 112 comprising silicon or aluminum nitride or oxide or oxynitride or aluminum oxynitride or a mixture of at least two of these compounds provided above the glass substrate 101; at least one functional layer, that is, IR absorption layer 112 comprising at least one metal or metal alloy or niobium, tantalum, zirconium or nickel nitride disposed above the underlying layer 111 and at least one overlying layer 113 comprising silicon or aluminum nitride or oxide or oxynitride or oxynitride or a mixture of at least two of these compounds disposed above the IR absorption layer 112.The stack of layers 110 of the coated solar control glass article 100 is overlapped and protected by the two-layer protective coating 120. In certain embodiments of the present description, the two-layer protective coating 120 comprises a layer containing TiZrHf. Petition 870220068937, dated 03 / 08 / 2022, page 21 / 51 9 / 31 or TiZrHfNx 114 is placed above the IR absorption layer 112 and another carbon layer 115 is superimposed on and in direct contact with the layer containing TiZrHf or TiZrHfx. The carbon layer 115 is the most distant and the outermost layer of the coated solar control glass article 100.
[0020] In one embodiment of the present description, the underlying layer 111 and overlying layer 113 are typically the dielectric layers of the 110-layer stack and comprise silicon nitride, silicon oxide, silicon oxynitride or aluminum oxynitride and silicon or aluminum nitride, aluminum oxide, aluminum oxynitride or aluminum-doped silicon nitride. In a preferred aspect of the present embodiment, the underlying layer 111 and the overlying layer 113 dielectric layers may essentially be composed of silicon nitride. It should be noted that the terms “oxide” and “nitride” as used herein include various stoichiometries.
[0021] Thus, the total coating of the coated solar control glass article 100 includes layers 111 to 115. Layers 111 to 115 can be deposited by magnetron sputtering or other types of sputtering or other suitable techniques. Other layers may be provided between layers illustrated in certain other embodiments of the present description. In still other embodiments of the present description, certain illustrated layers may be excluded. Thus, for example, the layer system and the layers thereof shown in Figure 1 are considered to be on the substrate 101 even when other layers (not shown) are provided between them. Furthermore, more than one IR absorption layer may Petition 870220068937, dated 03 / 08 / 2022, page 22 / 51 10 / 31 to be provided in certain modalities, for example, as described herein.
[0022] Figure 2 illustrates two samples of coated solar control glass articles for comparison purposes. Sample (A) is composed of the following stack: glass / Si3N4 / NbN / Si3N4 / TiZrHfN / C, thus including a two-layer protective coating according to the embodiment of the present description illustrated in Figure 1. For comparison sample purposes (B) is composed of the following stack: glass / Si3N4 / NbN / Si3N4, without the two-layer protective coating.
[0023] Sample (A) demonstrated a significant improvement in scratch resistance compared to sample (B). In particular, before heat treatment of samples (A) and (B), sample (A) could not be significantly scratched with an Erichsen scratch hardness tester. After heat treatment of sample (A), the sample's scratch resistance was found to be slightly worn, but the post-heat treatment resistivity of sample (A) was found to be higher than that of sample (B). Sample (B) showed some level of post-heat treatment scratches that were visible in reflection. Thus, the presence of the protective coating layers on sample (A) contributed to (i) the scratch resistivity of sample (A) before heat treatment and (ii) the higher scratch resistivity of sample (A) after heat treatment. Sample (B) was not found to be scratch resistant before or after heat treatment.Therefore, the use of the protective coating layers described herein is advantageous for products that are not heat treated. Petition 870220068937, dated 03 / 08 / 2022, page 23 / 51 11 / 31 also applies to products that undergo heat treatment.
[0024] In another embodiment of the present description, the coated solar control glass article may include a single-layer protective coating 130 comprising TiZrHf or TiZrHfN. For example, the coated solar control glass article according to this embodiment is composed of the following stack: glass / Si3N4 / NbN / Si3N4 / TiZrHfN. Similarly, a comparison of the scratch resistance of a manufactured sample of the stack: Si3N4 / NbN / Si3N4 / TiZrHfN (sample (C)) with another manufactured sample of the stack: Si3N4 / NbN / Si3N4 (Sample (D)) illustrated in Figure 3, showed that the former sample (C) exhibited greater scratch resistance when compared to sample (D) due to the presence of the single-layer protective coating composed of TiZrHfN.However, it should be noted that the scratch resistivity provided to sample C from the use of the single-layer protective coating is almost as equivalent (if not less) to the scratch resistivity provided by the use of the double-layer protective coating for sample (A).
[0025] To improve scratch resistance, conventional solutions use hard layers comprising materials with high hardness, such as titanium oxide or amorphous DLC (diamond-like carbon). The protective coating layer according to the present description is clearly distinguished from these known hard layers. The mechanism behind obtaining good scratch protection is not in the hardness of the layer, but rather in the reduction of the coefficient of friction between the Petition 870220068937, dated 03 / 08 / 2022, page 24 / 51 12 / 31 underlying layer and protective coating layers. The protective coating layer, according to the present description, performs the function of an anti-friction layer. This effect is easily observed by rubbing lightly with a cloth or paper on the surface of sample B provided with a stack of layers. In the absence of the protective coating layers according to the present description, the upper surface of the stack was penetrated. Whereas, in sample A, including the protective coating layer, the surface is smooth. The use of metal alloys together with a polymeric compound such as carbon is advantageous because it improves the friction phenomena that are crucial during the transport steps.
[0026] In fact, coated glass articles are generally transported with the aid of glass harp carts. These harp carts comprise metal strings coated with a polymeric sheath that are held against coated glass items. Contacts between these strings and the stack of layers, which may occur during the insertion of the coated glass articles and / or during their transport, represent one of the main causes of scratch generation. The tribological coefficient of friction of the metal alloy / layers of the penetrator stack is decreased when the stack includes protective coating layers according to the present description. The improvement in scratch resistance appears to be able to be connected to this reduction in the coefficient of friction.
[0027] The protective coating layer 115 is deposited by reactive sputtering of a meta comprising at least 70% to 100% carbon. The layer Petition 870220068937, dated 03 / 08 / 2022, page 25 / 51 Protective coating 114 is deposited by reactive sputtering of a meta-comprising at least 60% to 90%, and more preferably 70% to 80% Ti; at least 5% to 40%, and more preferably 10% to 30% Zr; at least 0.1% to 30%, and more preferably 0.1% to 10% Hf. In the embodiments of the present description comprising a protective coating layer 114 comprising TiZrHfN, the atomic percentage of nitrogen present in the layer varies from 0.1% to 50%.
[0028] In yet another embodiment of the present description, the coating layers may include alternating layers of TiZrHfN / Carbon. For example, in an alternative embodiment of the present description, the coating layers may include the following layers that extend away from the glass substrate: TiZrHfN / Carbon / TiZrHfN / Carbon / TiZrHfN / Carbon (where the TiZrHfN may not be nitrided to be a metallic TiZrHf layer).
[0029] While Figure 1 illustrates a coated solar control glass article according to one embodiment of this invention in monolithic form, coated articles according to other embodiments of the present description may include IG (insulating glass) window units provided as double and triple glazing units. In the IG embodiments, the coatings of Figure 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.
[0030] Various thicknesses can be used consistent with one or more of the modalities discussed. However, for example purposes only, the thicknesses in the example for Petition 870220068937, dated 03 / 08 / 2022, page 26 / 51 14 / 31 the respective layers 111 to 115 on the glass substrate 101 are given in the following table. Table 1: Thickness ranges of the 100 coated solar control glass article in Figure 1 Stack Layers Thickness (nm) Layer 111 10 to 100 Layer 112 0.5 to 40 Layer 113 10 to 100 Layer 114 0.5 to 5 Layer 115 0.1 to 5
[0031] The coating layer thicknesses also vary depending on whether they are used as a single-layer protective coating or as a double-layer protective coating. While used as a single-layer protective coating, the thickness of the TiZrHf or TiZrHfN layer varies between 0.5 and 5 nm. Similarly, the thickness of the TiZrHf or TiZrHfN layer varies between 0.5 and 5 nm and that of carbon varies between 0.1 and 5 nm while used as a double-layer protective coating. Unless otherwise indicated, the thicknesses mentioned in this description are physical thicknesses and the layers are thin films. The term thin film refers to a layer with a thickness between 0.1 nm and 100 nm.
[0032] Throughout the description, the glass substrate according to the present description is considered to be placed horizontally. The stack of thin layers is deposited above the glass substrate. The direction of the expressions “above,” “below,” and “bottom” and “top” should be considered in relation to this orientation. In the absence of specific stipulation, the expressions “above” and “below” do not necessarily mean that two layers and / or coatings are placed in contact with each other. Petition 870220068937, dated 03 / 08 / 2022, page 27 / 51 15 / 31 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.
[0033] Functional layer 112 can be a metallic or non-metallic layer completely free of silver and silver-containing metallic alloys. According to multiple embodiments of the present description, functional layer 112 is based on niobium, tantalum, zirconium, nickel. In specific embodiments, functional layer 112 can be selected from the group consisting of niobium, niobium nitride, tantalum, zirconium, zirconium nitride, or nickelchromium. The thickness of the functional layer varies between 0.5 nm and 40 nm, preferably between 1 nm and 30 nm, and more preferably between 1.5 nm and 25 nm. According to the described embodiment, functional layer 112 can comprise a single layer or more than one layer.
[0034] In all embodiments of the present description, the functional layer 112 (one or more layers) is deposited between at least one overlying layer and at least one underlying layer. The overlying and underlying layers are generally dielectric layers that 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 attack. The overlying and underlying layers 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.
[0035] The overlying layer and the underlying layer with Petition 870220068937, dated 03 / 08 / 2022, page 28 / 51 16 / 31 Based on dielectric materials, these layers are deposited by magnetically assisted sputtering. These layers act as barriers for the functional layer, protecting against the diffusion of oxygen and water at high temperatures and providing a stabilizing function. The overlying and underlying layers are based on silicon or aluminum nitride, oxide, oxynitride, or a mixture of at least two of these compounds.
[0036] The stack of layers acting on solar radiation therefore 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, such that each of the functional layers is disposed between two coatings based on dielectric materials. The dielectric layers may be located above and / or below at least one functional layer or above and / or below each of the functional layers and is directly in contact with or separated by overlying layers and additional underlying layers.
[0037] According to one embodiment, the overlying layer is below the protective coating layer, preferably in contact with the protective coating layer 114. The protective coating layer 115 is preferably the last layer in the stack, i.e., the layer furthest from the glass substrate coated with the stack of layers.
[0038] The underlying and overlying layers may comprise the same material as the layer Petition 870220068937, dated 03 / 08 / 2022, page 29 / 51 17 / 31 overlying layer 113 and underlying layer 111, as described in the previous embodiment, or may comprise materials other than layers 113 and 111. The purpose of additional underlying and overlying layers is to protect the functional layer from potential degradation associated with the deposition of a coating based on dielectric materials and degradation as a result of heat treatment. According to an optional embodiment of the present description, there may be at least one additional underlying layer located below and in contact with the functional layer and at least one additional overlying layer above and in direct contact with the functional layer. In a preferred embodiment, the additional underlying layer and the additional overlying layer may be metallic layers made of titanium.The thickness of each of the additional overlying layers and the additional underlying layers directly sandwiching the functional layer can be at least 2 nm or at least 10 nm.
[0039] Therefore, the stack of layers that act on solar radiation according to one embodiment of the present description comprises, starting from the glass substrate: - an underlying layer comprising a dielectric material - optional additional underlying layer - at least one functional layer free of silver - optional additional overlay layer - an overlying layer comprising a dielectric material - protective coating layer comprising TiZrHf or TiZrHfN Petition 870220068937, dated 03 / 08 / 2022, page 30 / 51 18 / 31 - protective coating layer comprising carbon.
[0040] According to another embodiment of the present description, the stack of layers that act on solar radiation comprises, starting from the glass substrate: - an underlying layer comprising a dielectric material - at least one functional layer free of silver - an overlying layer comprising a dielectric material - protective coating layer comprising TiZrHf or TiZrHfN - protective coating layer comprising carbon.
[0041] The coated solar control glass article according to the teachings of the present description may be annealed or may be subjected to heat treatments at temperatures exceeding 400°C, preferably more than 500°C or more preferably exceeding 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 herein, namely scratch resistance, are independent of any heat treatment. This means that the protective coating layers proposed by the present description provide scratch resistance to the coated solar control glass articles intended to be annealed, tempered, heat strengthened, reinforced, hardened and / or bent or folded or laminated. Petition 870220068937, dated 03 / 08 / 2022, page 31 / 51 19 / 31
[0042] Traditionally, the protective coating layer comprising zirconium oxide and titanium, when deposited above a layer stack comprising a silver-free functional layer or silver-containing alloys, provides scratch resistance in coated solar control glass articles if the glass articles are intended to be annealed. Whereas the zirconium oxide and titanium coating layer does not improve the scratch resistance of coated solar control glass articles intended to be heat-treated, for example, tempered. The above finding is true for the protective coating layer comprising carbon, since the carbon layer is completely oxidized and burned off during the heat treatment of the glass article.Although the protective coating layer comprising zirconium oxide and titanium and the protective coating layer comprising carbon improve the scratch resistance of annealed glass articles, they do not improve the scratch resistance of thermally treated glass articles.
[0043] On the other hand, the protective coating layers proposed in the present description improve the scratch resistance of coated solar control glass articles that are annealed or thermally treated.
[0044] The present description also relates to a method for manufacturing a solar control coated glass article provided with a stack of thin layers deposited by magnetically assisted sputtering, the method comprising the steps of: Petition 870220068937, dated 03 / 08 / 2022, page 32 / 51 20 / 31 deposit at least one underlying layer based on dielectric material on the surface of the glass substrate; deposit at least one functional layer above the underlying layer; deposit at least one overlay layer based on dielectric material above the functional layer; deposit a protective coating layer comprising TiZrHf or TiZrHfN and, optionally, depositing a protective coating layer comprising carbon above the overlay layer comprising TiZrHf or TiZrHfN. The method further includes the step of heat treating the coated solar control glass article at temperatures above 400°C, preferably above 500°C and more preferably above 600°C.
[0045] The coated solar control glass article thus obtained can be used for the manufacture of glass for applications including, but not limited to, insulated glass windows or glazing for buildings and laminated glazing for safety glass applications. In multiple embodiments, the coated solar control glass article can be tempered, annealed, enameled, laminated and / or bent. Examples Example 1
[0046] Different stacks of thin layers according to the teachings of the present description have been sputter-applied onto glass substrates of more than 4 mm manufactured by Saint-Gobain India Private Limited. The specification of the multilayer coatings is as follows. Petition 870220068937, dated 03 / 08 / 2022, page 33 / 51 21 / 31 Table 1: Layer stack for coated solar control glass articles Glass / Si3N4 [Thickness in nm] NiCr [Thickness in nm] Silver [Thickness in nm] NbN [Thickness in nm] Nb [Thickness in nm] NiCr [Thickness in nm] Si3N4 [Thickness in nm] TiZrHfN [Thickness in nm] Sample 1 37 1.6 7 - - 1.5 54 - Sample 2 37 1.6 7 - - 1.5 52 2 Sample 3 10 - - 1.5 - - 30 - Sample 4 10 - - 1.5 - - 28 2 Sample 5 10 - - - 35 28 2
[0047] Samples 2, 4, and 5 are prepared according to the teachings of the present description with a protective coating layer comprising TiZrHfN, and samples 1 and 3 are comparative samples that do not include any protective coating layer. The optical and solar control properties of the aforementioned glass samples are summarized in Table 2. Table 2: Optical and solar control properties Tl Outside Inside Emissivity Rext a*G b*G Rint a*C b*CE Sample 1 58 22.3 -1.8 -8.2 10.5 1.2 -3.2 0.13 Sample 2 58.2 22 -1.9 -7.9 10.7 1.9 -3.7 0.13 Sample 3 66.5 19 -2.2 -6.8 19 -1 -4 0.87 Sample 4 66.9 18.9 -2.1 -7.4 20 -1.2 -4.1 0.87 Sample 5 8.2 44.0 -2.3 0.4 34.9 -0.5 20.9 0.13 Rext = External reflection; a*G, b*G = values a*, b* measured on the outside, i.e., the glass side; Rint = Internal reflection; values a*C, b*C = a*, b* measured on the inside, i.e., the coating side.
[0048] The light transmission of samples 1, 2, 3, and 4 are similar and comparable. The thickness of the TiZrHfN protective coating layer in samples 2, 4, and 5 was designed in such a way that the optical properties of samples 1 and 3 remain unchanged even after inclusion. Petition 870220068937, dated 03 / 08 / 2022, page 34 / 51 22 / 31 of the TiZrHfN protective coating layer. Particularly, the optical values of samples 1 and 2 and samples 3 and 4 can be seen as similar. Test for resistance to visible scratches
[0049] Resistance to visible scratches is an important criterion for coated solar control glass articles. This resistance to visible scratches provides mechanical resistance against scratches that may appear during the cutting and edge grinding of the glass, resulting in edge chipping, and also against rough handling of the samples. All coated glass samples were observed for visible scratches under both annealing and post-thermal treatment conditions. Thus, the calculated scratch resistance of the samples is summarized in Table 3. Table 3: Scratch Resistance Sample Scratch resistant (N) Annealed Tempered Sample 1 <0.5 <0.3 Sample 2 <1.5 <0.3 Sample 3 <0.5 <0.3 Sample 4 >5 >2 Sample 5 <2 <0.5
[0050] Table 3 shows scratch strength up to scratches that are not visible. For sample 4, in annealed form, scratches are not visible up to a force of 5N. 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 coating layer when provided above a stack of layers comprising a functional layer that is silver-free (sample 4) provides much improved scratch resistance (both in Petition 870220068937, dated 03 / 08 / 2022, page 35 / 51 23 / 31 annealed sample as tempered) than when provided above a layer stack comprising a functional layer comprising silver (sample 2). Furthermore, the above results also demonstrate that providing a protective coating layer according to the teachings of the present description above a functional layer that is silver-free is not obvious from the prior art references that teach the use of the TiZrHfN protective coating layer above the layer stack comprising a silver functional layer.
[0051] This occurs because the scratch resistance shown by sample 5 is much lower than that recorded by sample 4, when both samples are provided with a silver-free functional layer. Thus, the deposition of the TiZrHfN protective coating layer does not always improve the scratch resistance of the coated solar control glass articles. Since the thickness of the TiZrHfN layer is much smaller, the stress field generated during the scratch test will penetrate through the TiZrHfN layer and reach the functional layer and possibly the glass substrate as well. Therefore, the functional layer plays a fundamental role in improving the scratch resistance of the coated glass article. This is one of the reasons why the scratch resistance of sample 4 is greater than the scratch resistance of sample 2.
[0052] To further demonstrate this effect, the stack of layers comprising a very thick functional niobium layer was deposited with a TiZrHfN coating layer (sample 5). Due to the increased thickness of the niobium layer, the load-bearing capacity of this Petition 870220068937, dated 03 / 08 / 2022, page 36 / 51 Sample 24 / 31 is better than sample 2, but still not as good as sample 4. This clearly implies that adding a protective coating alone will not necessarily improve scratch resistance as much as desired. Comparative examples Comparative Example 1
[0053] Different stacks of thin layers according to the teachings of the present description were spray-applied to glass substrates of more than 4 mm manufactured by Saint-Gobain India Private Limited. The specification of the multilayer coatings is as follows. Table 4: Stack of layers for coated solar control glass articles Glass / Si3 N4 [Thickness in nm] NbN [Thickness in nm] NiCr [Thickness in nm] Si3N4 [Thickness in nm] TiZrOx [Thickness in nm] TiZrHfN [Thickness in nm] Carbon [Thickness in nm] Sample Comp.1 11 1.5 32 - - - Sample Comp.2 11 1.5 28 4 - - Sample 6 11 1.5 30 - - 1.5 Sample 7 11 1.5 30 - 1.4 - Sample 8 12.9 1.4 25.3 - 1.7 1.5 Sample 9 40 8.2 57 1.5
[0054] Samples 6, 7, 8 and 9 are prepared according to the teachings of the present description, which comprise the various proposed protective coating layers TiZrHf, TiZrHfN and carbon. Comparative samples 1 and 2 are prepared according to the teachings of the prior art. Erichsen scratch test (EST):
[0055] The samples in Table 4 were rotated in such a way Petition 870220068937, dated 03 / 08 / 2022, page 37 / 51 25 / 31 circular in the machine against a sharp indenter with increasing load. It was observed that no scratches were seen in samples 6, 7 and 8 and comparative sample 2 up to 5N. In another variant of the test method, the sample in Table 4 was then treated at a temperature of 650°C after the Erichsen scratch test (EST TT). This step reveals the presence of small scratches that occurred during the test procedure. It was found that the scratch resistance of the samples remains unchanged. Thus, the heating process did not impact the scratch resistance of the samples.
[0056] In another experiment, the samples were first treated at a temperature of 650°C and then subjected to the Erichsen scratch test procedure (TT EST). The scratch resistance of these annealed (EST), tempered after EST (EST TT) and tempered before EST (TT EST) samples are summarized in Table 5. The values in the table represent the maximum load that was supported by the samples. Table 5: Erichsen scratch test results Annealed (EST) Tempered (EST TT) Tempered (TT EST) Comparative Sample 1 < 0.5 N < 0.5 N < 0.3 N Comparative Sample 2 >5 >5 <1 Sample 6 >5 >5 <0.3 N Sample 7 >5 >5 <2 Sample 8 >5 >5 <2 Sample 9 >5 >5 <3
[0057] Although comparative sample 2 increases the scratch resistance of annealed samples, it does not improve the scratch resistance of tempered samples. The same applies to sample 6 supplied with a layer of Petition 870220068937, dated 03 / 08 / 2022, pp. 38 / 51 26 / 31 protective coating comprising carbon. Whereas samples 7, 8 and 9 which make up the protective coating layer comprising TiZrHfN with or without carbon improve the scratch resistance of samples in the annealed state as well as in the tempered state. Color change after heat treatment:
[0058] The color change of the samples in Table 4 after heat treatment (ΔE*) was measured and is summarized in Table 6. Table 6: Color change Color change after heat treatment Sample ΔE*T δε*^ ΔE* Rg Comparative sample 1 1.7 2 2.3 Comparative sample 2 1 3 3.1 Sample 6 1.1 1.9 1.6 Sample 7 0.7 1.9 2.1 Sample 8 2.5 3.2 3.4 RC = Lateral reflection of coating; RG = Lateral reflection of glass; T = Transmission
[0059] As can be seen in the table above, ΔE* values of less than 2 can be achieved using the single-layer TiZrHfN protective coating. Whereas ΔE* values of less than 3.4 can be achieved using the two-layer protective coating comprising one layer of TiZrHfN and another layer of carbon. Example 2 Thickness vs Scratch Resistance
[0060] The scratch resistance of coated solar control glass articles also depends on the thickness of the protective coating layer used above the stack of layers. The impact of varying thicknesses of the layer of Petition 870220068937, dated 03 / 08 / 2022, pp. 39 / 51 The scratch resistance of the 27 / 31 TiZrHfN coating provided above on coated glass articles is illustrated in Table 7. The samples shown in Table 7 are all supplied with the following stack: Glass / Si3N4 / NbN / Si3N4. Scratch resistance values are presented for annealed and tempered samples. The optical characteristics of all samples were found to be similar. Table 7: Coating layer thickness vs. scratch resistance Thickness of TiZrHfNx EST TT EST 0.5 nm <3 <0.5 1 nm <4 <0.7 1.4 nm >5 <2 1.9 nm >5 < = 5 Industrial Applicability
[0061] The coated solar control glass articles described in this description find application as a glazed element in construction. In this application, the glazing can form a double or triple glazing with the coated side of the glass facing the enclosed space within the multiple glazing. The glazing can also form a laminated glazing where the stack of layers can be in contact with the thermoplastic adhesive material that connects the substrates, generally PVB. The glazing according to the invention is, however, particularly useful when the multilayer stack faces the external environment, whether it is a single pane or a laminated pane, but also optionally a multiple pane. The glazing can also be glazed.
[0062] The coated solar control glass articles of the present description may also be annealed, Petition 870220068937, dated 03 / 08 / 2022, pages 40 / 51 28 / 31 reinforced, hardened, tempered, or curved and / or bent. The extensive durability in terms of scratch resistance of the coated solar control glass article provides a prolonged product lifespan.
[0063] Tempered coated solar control glass can also be used in the construction of wall cladding panels for interior applications. In addition, tempered coated solar control glass can also be used as a side window, rear window or sunroof for an automobile or other vehicle.
[0064] Note that not all activities described above in the general description or examples are necessary, that a part of a specific activity may not be necessary, and that one or more additional activities may be performed beyond those described. Furthermore, the order in which the activities are listed is not necessarily the order in which they are performed.
[0065] Benefits, other advantages and solutions to problems have been described above with respect to specific modalities. However, benefits, advantages, solutions to problems and any feature(s) that may cause any benefit, advantage or solution to occur or become more pronounced should not be interpreted as a critical, necessary or essential characteristic of any or all of the claims.
[0066] The descriptive report and illustrations of the modalities described herein are intended to provide a general understanding of the structure of the various modalities. The descriptive report and illustrations are not intended to Petition 870220068937, dated 03 / 08 / 2022, pages 41 / 51 29 / 31 serve as an exhaustive and comprehensive description of all elements and characteristics of apparatus and systems that use the structures or methods described herein. Certain characteristics, which for clarity are described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, several characteristics which are, for brevity, described in the context of a single embodiment, may also be provided separately or in a sub-combination. Furthermore, the reference to values indicated in ranges includes each value within that range. Many other embodiments may be apparent to qualified technicians only after reading this descriptive report. Other embodiments may be used and derived from the description, such that a structural substitution, logical substitution, or other alteration may be made without departing from the scope of the description. Thus, the description should be considered illustrative and not restrictive.
[0067] The description in combination with the figures is provided to aid in understanding the teachings presented here, and should not be interpreted as a limitation on the scope or applicability of the teachings. However, other teachings may certainly be used in this application.
[0068] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “has,” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a method, article, or device that makes up a list of resources is not an exclusive inclusion. Petition 870220068937, dated 03 / 08 / 2022, pages 42 / 51 30 / 31 is necessarily limited to only these features, but may include other features not expressly listed or inherent to that method, article, or device. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or not an exclusive or. For example, a condition A or B is satisfied by any 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).
[0069] Furthermore, the use of “a” or “an” is employed to describe elements and components described herein. This is done only for convenience and to give a general sense of the scope of the invention. This description should be read to include “a” or “at least one,” and the singular also includes the plural, or vice versa, unless it is clearly intended otherwise. For example, when a single item is described herein, more than one item may be used in place of a single item. Similarly, when more than one item is described herein, a single item may be substituted for more than one item.
[0070] Unless otherwise defined, all technical and scientific terms used herein have the same meaning commonly understood by a person skilled in the art to which this invention pertains. The materials, methods, and examples are for illustrative purposes only and are not intended to be exhaustive. To the extent that certain details about specific materials and processing acts are not described, such details may include conventional approaches, which can be verified in reference books and other sources within Petition 870220068937, dated 03 / 08 / 2022, pages 43 / 51 31 / 31 of manufacturing techniques.
[0071] Although aspects of the present description have been particularly shown and described with reference to the embodiments above, it will be understood by those skilled in the art that various additional embodiments may be contemplated by modifying the disclosed machines, systems, and methods without departing from the spirit and scope of what is described. Such embodiments should be understood within the scope of the present description as determined based on the claims and any equivalents. List of Elements TITLE: COATED ARTICLE COMPRISING LAYERS OF Protective coating made of titanium nitride, zirconium, hafnium, and carbon. 100 Coated Solar Control Glass Article 101 Glass substrate 110 Layer Stack 111 Underlying layer 112 Functional Layer 113 Overlying layer 114 Layer containing TiZrHf or TiZrHfNx 115 Carbon-containing layer 120 Double-layer protective coating 130 Single-layer protective coating Petition 870220068937, dated 03 / 08 / 2022, pages 44 / 51
Claims
1 / 4 CLAIMS 1. Coated article comprising a stack of layers provided on the surface of the glass substrate, the stack of layers acting on solar radiation, characterized in that it comprises: at least one functional layer and one or more protective coating layers deposited over at least part of the functional layer, wherein the stack of layers is free of silver and silver-containing metal alloys; wherein the protective coating layers comprise TiZrHf or TiZrHfN with or without carbon and contribute to the scratch resistivity of the coated article before heat treatment up to 5N in the Erichsen Scratch Test, wherein the thickness of the protective coating layers comprising TiZrHf or TiZrHfN varies between 0.5 nm and 5 nm.
2. Coated article, according to claim 1, characterized in that the protective coating layers comprise a layer of TiZrHf or TiZrHfN provided directly under and in contact with another carbon layer.
3. Coated article, according to claim 1, characterized in that the protective coating layers comprise TiZrHf or TiZrHfN, possibly doped with carbon.
4. Coated article, according to claim 1, characterized in that the protective coating layers are deposited by reactive sputtering of a target comprising 70% to 80% Ti, 10% to 30% Zr and 0.1% to 10% Hf, in the presence of argon and nitrogen. Petition 870260001983, dated 09 / 01 / 2026, page 11 / 18 2 / 4 5. Coated article, according to claim 1, characterized in that the protective coating layers comprise nitrogen, the atomic percentage of which varies from 0.1% to 50%.
6. Coated article, according to any one of claims 1 to 5, characterized in that the coated article is tempered or annealed.
7. Coated article, according to any one of claims 1 to 6, characterized in that the coated article is tempered, enameled, laminated and / or bent.
8. Coated article, according to any one of claims 1 to 7, characterized in that at least one functional layer predominantly comprises at least one metal or metal alloy belonging to the group consisting of niobium, tantalum, zirconium, nickel.
9. Coated article, according to any one of claims 1 to 8, characterized in that at least one functional layer is the layer based on a partially or wholly nitrided metal belonging to the group consisting of niobium, tantalum, zirconium, nickel.
10. Coated article, according to any one of claims 1 to 9, characterized in that at least one functional layer is the layer that is positioned between at least one overlying layer based on silicon or aluminum nitride or oxide or oxynitride or oxynitride or a mixture of at least two of these compounds and at least one underlying layer based on silicon or aluminum nitride or oxide or oxynitride or oxynitride or a mixture of at least two of these compounds. Petition 870260001983, dated 09 / 01 / 2026, page 12 / 18 3 / 4 11. Coated article, according to any one of claims 1 to 10, characterized in that the stack of layers comprises a plurality of underlying layers between the glass substrate and the functional layer and / or a plurality of overlying layers between the functional layer and the protective coating layers.
12. Coated article, according to any one of claims 1 to 11, characterized in that the stack of layers comprises one or more functional layers made of Nb or NbN or Ta or Zr or ZrN or NiCr, an overlying layer made of silicon nitride and an underlying layer made of silicon nitride.
13. Coated article, according to any one of claims 1 to 12, characterized in that the stack of layers comprises one or more functional layers made of Nb or NbN or Ta or Zr or ZrN or NiCr, an overlying layer made of silicon nitride, an underlying layer made of silicon nitride, an additional coating layer between the functional layers and the protective coating layers, and an additional underlying layer between the glass substrate and the functional layers.
14. Coated article, according to any one of claims 1 to 13, characterized in that the thickness of the protective coating layers comprising TiZrHf or TiZrHfN varies between 0.5 nm and 5 nm and of the protective coating layers comprising carbon varies between 0.1 nm and 5 nm. Petition 870260001983, dated 09 / 01 / 2026, p. 13 / 18 4 / 4 15. Coated article, according to any one of claims 1 to 14, characterized in that the coated article has a colorimetric variation in the lateral reflection of the glass and in the lateral reflection of the coating, AE*Rg and AE*rc, of less than 3.5 when said coated article is subjected to a temperature of at least 630°C and not more than 670°C. Petition 870260001983, dated 09 / 01 / 2026, p. 14 / 18