Coated Substrate

Abstract

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Certain coated substrates and manufacturing methods for producing the coated substrates are disclosed herein.

Description

[Background technology]

[0001] A substrate, such as a glass or glass ceramic plate, is usually used to cover the hob. The upper surface of the glass plate can be covered with one or more coatings. For example, the glass plate can have a scratch-resistant coating to reduce scratches on the surface of the glass plate, and additionally a decoration to indicate a cooking zone between the scratch-resistant coating and the substrate. Some scratch-resistant coatings are already known, for example from WO 2014 / 135490 A1 and WO 2012 / 013302 A1. [Prior art documents] [Patent documents]

[0002] [Patent Document 1] International Publication No. 2014 / 135490 [Patent Document 2] International Publication No. 2012 / 013302 Summary of the Invention [Problem to be solved by the invention]

[0003] However, since the requirements regarding the quality of scratch-resistant coatings are constantly increasing, the present application aims to provide a coated substrate having improved quality, as well as a method for producing said coated substrate. In particular, the present invention aims to provide a method for producing a coated substrate having improved quality, as well as a method for producing said coated substrate. Improved scratch resistance, Improved heat resistance, Improved resistance to alkaline solutions, Improved resistance to acidic solutions, Improved slip characteristics, Improve adhesion of coatings, or coatings and decorations; Reduced delamination, and / or Improved protection of substrates and / or decorations The object of the present invention is to provide a coated substrate which exhibits the following properties:

[0004] Furthermore, it is an object of the present invention to provide an improved method for producing a coated substrate. In particular, it is an object of the present invention to provide a method for producing a coated substrate, preferably a coated substrate according to any of the embodiments described herein, comprising one or more of the following: Reliable production of the coated substrates described herein; Increased speed of application, Reduced costs; Increased manufacturing reliability, and / or Reduced manufacturing fluctuations The object of the present invention is to provide a method as described above, which shows that [Means for solving the problem]

[0005] These problems are solved by a coated substrate for a hob, said substrate comprising a coating comprising a layer, said layer consisting of a composition A comprising yttrium and zirconium, wherein the zirconium content in composition A is equal to or less than 75% by weight, preferably equal to or less than 65% by weight, more preferably equal to or less than 55% by weight, said coating having a Martens hardness equal to or greater than 4.5 GPa and, after heat treatment, a color difference ΔE equal to or less than 4.0.

[0006] The Martens hardness of the coating can also be 5.0 GPa or more. Preferably, the Martens hardness of the coating is 5.5 GPa or more, more preferably 6.0 GPa or more, more preferably 6.5 GPa or more, more preferably 7.0 GPa or more, more preferably 7.5 GPa or more, more preferably 8.0 GPa or more, more preferably 8.5 GPa or more, more preferably 9.0 GPa or more, and / or preferably and the Martens hardness of the coating is 20.0 GPa or less, preferably 18.0 GPa or less, more preferably 16.0 or less, more preferably 14.0 or less, more preferably 12.0 or less, more preferably 11.0 or less, more preferably 10.0 or less. In this way, the scratch resistance can be further improved. In particular, when the Martens hardness of the coating is 6.0 GPa or more, more preferably 6.5 GPa or more, more preferably 7.0 GPa or more, more preferably 7.5 GPa or more, more preferably 8.0 GPa or more, more preferably 8.5 GPa or more, more preferably 9.0 GPa or more, the scratch resistance is significantly improved.

[0007] After heat treatment, the color difference ΔE can also be 3.5 or less. Preferably, after heat treatment, the color difference ΔE is 3.0 or less, more preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less, more preferably 1.0 or less, more preferably 0.5 or less. If the coated substrate meets this parameter, the heat resistance is further improved. In particular, if after heat treatment, the color difference ΔE is 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less, more preferably 1.0 or less, more preferably 0.5 or less, the heat resistance is significantly improved.

[0008] Preferably, the heat treatment consists in heating the coated substrate at a temperature T1 for a time t1, wherein the temperature T1 is 300° C., preferably 400° C., more preferably 490° C., more preferably 580° C., more preferably 670° C., more preferably 760° C., more preferably 850° C., more preferably 940° C., and / or preferably and the time t1 is 15 h, preferably 30 h, more preferably 45 h, more preferably 60 h, more preferably 75 h, more preferably 90 h, more preferably 105 h, more preferably 120 h, more preferably 135 h, more preferably 150 h. The inventors have surprisingly realised that the coated substrate is particularly suitable for gas hobbing when the temperature T1 is 300° C., preferably 400° C., more preferably 490° C., and the time t1 is 75 h, preferably 90 h, more preferably 120 h, more preferably 150 h, and the colour difference ΔE is within the above range. Furthermore, the inventors have surprisingly realized that the coated substrate is even more particularly suitable for induction hobbing if the temperature T1 is 580°C, preferably 670°C, and the time t1 is 75 hours, preferably 90 hours, more preferably 120 hours, more preferably 150 hours, and the color difference ΔE is within the above range. Furthermore, the inventors have surprisingly realized that the coated substrate is even more particularly suitable for radiant hobbing if the temperature T1 is 670°C, preferably 760°C, and the time t1 is 75 hours, preferably 90 hours, more preferably 120 hours, more preferably 150 hours, and the color difference ΔE is within the above range. Furthermore, the inventors have surprisingly realized that the coated substrate is even more particularly suitable for particularly advanced applications if the temperature T1 is 850°C, preferably 940°C, and the time t1 is 105 hours, preferably 120 hours, more preferably 135 hours, more preferably 150 hours, and the color difference ΔE is within the above range.

[0009] The crystallinity of the coating is not particularly limited. Preferably, the coating is at least partially crystalline, more preferably at least partially hexagonal, rhombohedral, and / or cubic, more preferably at least partially cubic. The inventors have unexpectedly realized that the resistance of the coating is improved and the peeling is reduced when the coating is at least partially crystalline, preferably at least partially hexagonal, rhombohedral, and / or cubic, more preferably at least partially cubic. In particular, the coating is at least partially crystalline, preferably at least partially hexagonal, rhombohedral, and / or cubic, more preferably at least partially cubic. III (Z2 IV O7), the resistance of the coating is further improved and the delamination is further reduced.

[0010] According to a preferred embodiment, the coating exhibits a peak between 33° and 36° on the 2θ scale in the XRD analysis, and / or the coating exhibits a peak between 28° and 30° on the 2θ scale. In this way, the resistance of the coating is improved and the peeling is reduced. In particular, when the coating exhibits a peak between 33° and 36° and a peak between 28° and 30° on the 2θ scale, the resistance of the coating is significantly improved and the peeling is significantly reduced.

[0011] The crystallite size and March-Dollase coefficient of the coating are not particularly limited. Preferably, the crystallite size of the coating is 1 nm to 30 nm or less, preferably 5 nm to 20 nm, more preferably 10 nm to 15 nm, and / or the March-Dollase coefficient of the coating is 0.2 or more, preferably 0.3 or more, more preferably 0.4 or more, more preferably 0.5 or more, and / or preferably and 1.0 or less. In this way, the scratch resistance and sliding properties are further improved and the peeling is further reduced.

[0012] The friction and roughness of the coating are not particularly limited. Preferably, the friction of the coating is less than 0.3, preferably less than 0.20, more preferably less than 0.18. If this parameter is met, the slip properties of the coating are further improved, and therefore the sensitivity of the coating to scratches is further reduced.

[0013] In a preferred embodiment, the coating comprises regions with a roughness Sq on an area of ​​300x300 μm, preferably measured by interferometry at a magnification of 50x, of 10 nm to 500 nm, preferably 15 nm to 250 nm, more preferably 20 nm to 200 nm, and / or the coating comprises regions with an arithmetic mean roughness Ra of 10 nm to 90 nm, preferably 20 nm to 80 nm, more preferably 30 nm to 70 nm. More preferably, the entire coating exhibits the above mentioned roughness. If this / these parameters are met, the sliding properties of the coating are further improved and therefore the susceptibility of the coating to scratches is further reduced.

[0014] The thickness of the coating is not particularly limited. Preferably, the thickness of the coating is 300 nm or more, preferably 400 nm or more, more preferably 500 nm or more, more preferably 600 nm or more, more preferably 700 nm or more, more preferably 800 nm or more, more preferably 900 nm or more, more preferably 1000 nm or more, more preferably 1100 nm or more, more preferably 1200 nm or more, more preferably 1300 nm or more, more preferably 1400 nm or more, and / or preferably, the thickness of the coating is 5000 nm or less, preferably 4500 nm or less, more preferably 4000 nm or less, more preferably 3500 nm or less, more preferably 3000 nm or less, more preferably 2500 nm or less, more preferably 2000 nm or less, more preferably 1900 nm or less, more preferably 1800 nm or less, more preferably 1700 nm or less, more preferably 1600 nm or less, more preferably 1500 nm or less. The thicker the coating, the better the protection of the substrate was observed. The thinner the coating, the less peeling was observed. In this way, protection is significantly improved and peeling is significantly reduced when the coating thickness is 300 nm or more, preferably 800 nm or more, more preferably 1000 nm or more, and / or preferably and up to 3000 nm, preferably 2000 nm or less, more preferably 1800 nm or less.

[0015] In a preferred embodiment, after the acid treatment, the color difference ΔE is 3 or less, more preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less, more preferably 1.0 or less, more preferably 0.5 or less. More preferably, the acid treatment is to contact the coating of the coated substrate with an aqueous solution having a pH value P2 and a temperature T2, preferably CH3COOH.aq or HCl.aq or H3PO4.aq or C6H8O7.aq (citric acid), more preferably H3PO4.aq, for a time t2, where the pH value P2 is 6, preferably 5, more preferably 4, more preferably 3, more preferably 2, more preferably 1, more preferably 0, the temperature T2 is 20°C, preferably 30°C, more preferably 50°C, more preferably 80°C, more preferably 90°C, more preferably 100°C, more preferably set at the boiling point of the aqueous solution, and the time t2 is 1 hour, preferably 6 hours, more preferably 12 hours, more preferably 24 hours, more preferably 48 hours, more preferably 72 hours. If the coated substrate meets this parameter, the resistance to acidic solutions is further improved. In particular, the resistance to acidic solutions is significantly improved if, after acid treatment, the color difference ΔE is ≦1.5, preferably ≦1.0, more preferably ≦0.5. The inventors have surprisingly realized that the coated substrate is particularly suitable for hobs in normal use if the pH value P2 is 3, preferably 2 (H3PO4.aq or C6H8O7.aq, preferably H3PO4.aq), the temperature T2 is 20° C., preferably 30° C., the time t2 is 24 h, preferably 48 h, more preferably 72 h, and the color difference ΔE is ≦1.5, preferably ≦1.0, more preferably ≦0.5. Furthermore, the inventors have surprisingly realised that the coated substrate is further particularly suitable for extensive applications such as professional hobs if the pH value P2 is 3, preferably 2 (H3PO4.aq or C6H8O7.aq, preferably H3PO4.aq), the temperature T2 is set to the boiling point of the aqueous solution, the time t2 is 1 h, preferably 6 h, more preferably 24 h, and the colour difference ΔE is less than or equal to 1.5, preferably less than or equal to 1.0, more preferably less than or equal to 0.5.

[0016] In a preferred embodiment, after the alkaline treatment, the color difference ΔE is 3 or less, more preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less, more preferably 1.0 or less, more preferably 0.5 or less. More preferably, the alkaline treatment is to contact the coating of the coated substrate with an aqueous solution having a pH value P3 and a temperature T3, preferably NaOH.aq or KOH.aq or Na2CO3.aq, more preferably Na2CO3.aq, for a time t3, where the pH value P3 is 8, preferably 9, more preferably 10, more preferably 11, more preferably 12, more preferably 13, more preferably 14, the temperature T3 is 20°C, preferably 30°C, more preferably 50°C, more preferably 80°C, more preferably 90°C, more preferably 100°C, more preferably set at the boiling point of the aqueous solution, and the time t3 is 1 hour, preferably 6 hours, more preferably 12 hours, more preferably 24 hours, more preferably 48 hours, more preferably 72 hours. If the coated substrate meets this parameter, the resistance to alkaline solutions is further improved. In particular, the resistance to alkaline solutions is significantly improved if, after the alkaline treatment, the color difference ΔE is 1.5 or less, preferably 1.0 or less, more preferably 0.5 or less. The inventors have unexpectedly realized that the coated substrate is particularly suitable for hobbing in normal use if the pH value P3 is 12, preferably 13, the temperature T3 is 20° C., preferably 30° C., the time t3 is 24 hours, preferably 48 hours, more preferably 72 hours, and the color difference ΔE is 1.5 or less, preferably 1.0 or less, more preferably 0.5 or less. Furthermore, the inventors have unexpectedly realized that the coated substrate is even more particularly suitable for large-scale applications such as professional hobbing if the pH value P3 is 12, preferably 13, the temperature T3 is set to the boiling point of the aqueous solution, the time t3 is 1 hour, preferably 6 hours, more preferably 24 hours, and the color difference ΔE is 1.5 or less, preferably 1.0 or less, more preferably 0.5 or less.

[0017] The compressive stress of the coating is not particularly limited. In a preferred embodiment, the coating exhibits a compressive stress of 100 to 3000 MPa, preferably 100 to 2000 MPa, more preferably 100 to 1200 MPa, more preferably 200 to 1000 MPa. In this way, the resistance, especially the scratch resistance, is improved.

[0018] The color value and opacity in transmission of the coating are not particularly limited. In a preferred embodiment, the coating has a color value in transmission C * 20 or less, preferably 15 or less, more preferably 10 or less, more preferably 8 or less, more preferably 7 or less, more preferably 6 or less, more preferably 5 or less, and / or the coating exhibits an opacity of 0.0-0.3, more preferably 0.01-0.25, preferably 0.05-0.15. In this way, when the substrate is used in a hob, the color change of the display under the coated substrate in the hob can be reduced and the sharpness of the display can be increased. As a result, the application area of ​​the coated substrate is increased.

[0019] The coating can include one or more coating layers, and the total number is not particularly limited.Preferably, the coating includes one or more layers, preferably 2, 3, 4, 5, 6, 7, 8, 9 or 10 layers, and preferably all layers are the same.When the coating includes two or more identical layers, the coating can be produced faster.The inventors have realized that the properties are not significantly different between one thick layer and a coating that has the same layer thickness and includes several thin layers.

[0020] In a preferred embodiment, the coating consists of said layers and / or the coating is a single layer. In this way, the homogeneity of the coating can be further improved and the coating can be applied in one step.

[0021] The position of the layer described in this application within the coating is not particularly limited. Preferably, said layer is the outermost layer of the coating. In this way, said layer protects all the layers and the substrate underneath, which results in a further improvement in resistance, especially scratch resistance.

[0022] The coating described in this application can be in direct contact with the substrate or the coated substrate comprises a decoration, preferably a color decoration, more preferably the decoration is between the coating and the substrate. Preferably the coating is at least partially in direct contact with the substrate. The decoration can be applied by inkjet printer methods or by screen printing methods, for example as described in EP1743003 A1, WO2016 / 008848 A1, EP3067334 A1 and EP0978493 A1, which are incorporated herein by reference. The inventors have unexpectedly realized that if the decoration is between the coating and the substrate, the adhesion of the decoration is further improved, so that the peeling in the area where the decoration is present is also reduced, thus improving the adhesion.

[0023] Another aspect of the present invention is the use of the coated substrates described within this application in hobs, ovens, tables, shower walls, radiators, cars, consumer electronics, mobile phones, tablets, watches, smart watches, optical filters, interference filters, anti-reflective filters, mirrors, more preferably in induction hobs, radiant hobs or gas hobs.

[0024] Further aspects of the present invention are hobs, ovens, tables, shower walls, radiators, cars, consumer electronics, mobile phones, tablets, watches, smart watches, optical filters, interference filters, anti-reflective filters, mirrors, more preferably induction hobs, radiant hobs, or gas hobs, comprising the coated substrates described within this application.

[0025] Another aspect of the present invention is a method for producing a coated substrate, preferably a coated substrate as described herein, comprising the steps of: providing a substrate; applying a layer of composition A comprising yttrium and zirconium by physical vapor deposition onto the substrate to obtain a coated substrate as described herein, wherein the zirconium content in composition A is equal to or less than 75% by weight, preferably equal to or less than 65% by weight, more preferably equal to or less than 55% by weight; When the method described within this application is used, the above mentioned coating can be obtained.

[0026] In a preferred embodiment, the physical vapor deposition method is a sputter deposition or evaporation method, preferably a sputter deposition method, more preferably a magnetron sputtering method, more preferably an in-line magnetron sputtering method, more preferably a high target utilization sputtering (HiTUS) method, or a high power impulse magnetron sputtering (HiPIMS) method. In particular, when a magnetron sputtering method is used to produce the coated substrates described in this application, the coating can be applied reliably.

[0027] The method of applying the coating is not particularly limited. Preferably, applying a layer of composition A containing yttrium and zirconium, in which the zirconium content in composition A is 75% by mass or less, preferably 65% ​​by mass or less, more preferably 55% by mass or less, on a substrate by physical vapor deposition is Deposition onto a substrate by sputtering a target, preferably in the presence of a process gas. In this way the coating can be applied reliably.

[0028] In this application, "depositing a target onto a substrate" refers to the transfer of target material from the target onto the surface of a substrate during a sputtering process.

[0029] In a preferred embodiment, the target comprises, preferably consists of, composition B, which contains yttrium, zirconium and unavoidable impurities, and the zirconium content in composition B is 75% by weight or less, preferably 65% ​​by weight or less, more preferably 55% by weight or less. Composition B of the target and composition A of the coating can be the same or different. Preferably, they are different, for example the oxygen content (in weight %) in the coating can be higher than the oxygen content (in weight %) in the target. Preferably, the ratio of elements contained in the target and in the coating is similar, i.e. within ±10%, preferably ±5%, more preferably the same. In this way, the coating can be produced reliably.

[0030] In a preferred embodiment, the target is a planar target or a rotating target, preferably a rotating target, in this way coatings can be produced reliably.

[0031] The magnetic flux density used in the magnetron sputtering method is not particularly limited. In a preferred embodiment, the magnetic flux density is preferably set to 5mT-200mT, preferably 10mT-150mT, more preferably 15mT-100mT, and most preferably 20mT-80mT on at least a portion of the surface of the target. When the magnetic flux density is within this range, the uniformity of the coating can be improved, the control of the thickness of the coating can be improved, and the thermal variation of the substrate can be reduced, which leads to improved resistance of the coating and reduced peeling.

[0032] The applied current in the magnetron sputtering method is not particularly limited. In a preferred embodiment, the applied current in the physical vapor deposition method is set to 1 A to 1000 A, preferably 20 A to 500 A, more preferably 100 A to 200 A. In this way, the sputtering rate can be further improved, and the chemical, mechanical and thermal properties can be improved. As a result, the resistance of the coating and the adhesion of the coating can be improved.

[0033] The voltage applied in the magnetron sputtering method is not particularly limited. In a preferred embodiment, the voltage applied in the physical vapor deposition method is set to 50V to 2000V, preferably 100V to 1000V, more preferably 200V to 700V. In this way, the sputtering rate can be further improved, and the optical properties, chemical properties, mechanical properties, and thermal properties can be improved. As a result, the resistance of the coating and the adhesion of the coating can be improved.

[0034] The pressure during the physical vapor deposition is not particularly limited. In a preferred embodiment, the pressure during the physical vapor deposition is 0.5×10 -3 bar~1×10 -2 bar, preferably 1×10 -3 bar~1×10 -2 bar, most preferably 2×10 -3 bar~8×10 -3 The pressure during physical vapor deposition is set at 2×10 -3 bar, 3×10 -3 bar, 4×10 -3 bar, 5×10 -3 bar, 6×10 -3 bar, 7×10 -3 bars, or 8 x 10 -3 bar. In this way the optical, chemical, mechanical and thermal properties can be improved and the stability of the plasma can be improved, which in turn improves the durability of the coating.

[0035] The distance between the target and the substrate during the physical vapor deposition and the position where the process gas is supplied are not particularly limited. In a preferred embodiment, the distance between the target and the substrate during the physical vapor deposition is 2-40 cm, preferably 4-40, more preferably 5-20 cm, most preferably 10-15 cm, and / or the process gas / said process gas is supplied between the target and the substrate during the physical vapor deposition. In this way, the stability of the plasma and the control of the uniformity of the thickness of the coating can be improved, which improves the durability of the coating.

[0036] The oxygen gas flow rate is not particularly limited. Preferably, the process gas contains oxygen, and the oxygen gas flow rate is preferably set to 1 sccm to 10,000 sccm, preferably 100 sccm to 5,000 sccm, more preferably 300 sccm to 3,000 sccm. When the gas flow rate is 1 sccm or more, preferably 100 sccm or more, more preferably 300 sccm or more, the opacity of the coating can be reduced. When the oxygen gas flow rate is set to 10,000 sccm or less, preferably 5,000 sccm or less, more preferably 3,000 sccm or less, the stability of the coating method can be improved and the sputtering rate can be increased.

[0037] The gas flow rate of argon is not particularly limited. Preferably, the process gas contains argon, and the gas flow rate of argon is preferably set to 1 sccm to 10,000 sccm, preferably 100 sccm to 5,000 sccm, more preferably 300 sccm to 4,000 sccm. When the gas flow rate of argon is set to 1 sccm or more, preferably 100 sccm or more, more preferably 300 sccm or more, the stability of plasma can be improved. When the gas flow rate of argon is set to 10,000 sccm or less, preferably 5,000 sccm or less, more preferably 4,000 sccm or less, plasma polymerization can be avoided, and optical properties, chemical properties, mechanical properties, and thermal properties can be improved.

[0038] In a preferred embodiment, the method further comprises a step of annealing the substrate, preferably before and / or during the magnetron sputtering process, at 100° C. to 500° C., preferably at 200° C. to 400° C. In this way, the adhesion of the coating on the substrate can be improved and the wear of the coating can be reduced. Unless otherwise stated, the temperature of the substrate is measured on the substrate surface.

[0039] The deposition rate of the layer is not particularly limited. Preferably, the layer is applied at a deposition rate of 10 nm·m / min to 1000 nm·m / min, preferably 30 nm·m / min to 500 nm·m / min, more preferably 40 nm·m / min to 100 nm·m / min, more preferably 45 nm·m / min to 80 nm·m / min, more preferably 50 nm·m / min to 75 nm·m / min. In this way, the resistance of the coating can be improved.

[0040] In a preferred embodiment, the application step is preferably repeated 2 times, preferably 3 times, more preferably 4 times, more preferably 5 times, more preferably 6 times, more preferably 7 times, more preferably 8 times, more preferably 9 times, more preferably 10 times to obtain a coated substrate, the coating comprising one or more, preferably 2, 3, 4, 5, 6, 7, 8, 9 or 10 layers, preferably all layers being the same. In this way, a coating with improved quality and reduced number of cycles is obtained.

[0041] As mentioned above, composition A and / or B comprises yttrium and zirconium. According to a further embodiment, composition A and / or B further comprises one or more of silicon, aluminum, titanium and / or hafnium. Composition A and / or B may further comprise unavoidable impurities. Preferably, the inevitable impurities are selected from Fe, Ti, Zn, Cu, Mn, Co, Ca, Nb, Gd, Eu, Er, Mo, La, Lu, Mg, Pr, Sm, W, Ni, Yb, Nd, O, N and / or the inevitable impurities have a content of less than 5% by weight, preferably less than 4% by weight, more preferably less than 3% by weight, more preferably less than 2% by weight, more preferably less than 1% by weight, more preferably less than 0.8% by weight, more preferably less than 0.6% by weight, more preferably less than 0.4% by weight, more preferably less than 0.2% by weight, more preferably less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.01% by weight, more preferably less than 0.005% by weight, more preferably less than 0.001% by weight. In this way, the resistance of the coating can be further improved.

[0042] In a preferred embodiment, the yttrium content in compositions A and / or B is 25% by weight or more. It has been found that corresponding coatings containing 25% by weight or more of yttrium and 75% by weight or less of zirconium can exhibit particularly high Martens hardnesses of 6 GPa or more.

[0043] In a preferred embodiment, compositions A and / or B contain yttrium and zirconium and have the following formula: ((Zr / (Zr+Y))×100≧40, preferably ((Zr / (Zr+Y))×100≧45, and ((Y / (Zr+Y))×100≧40, preferably ((Y / (Zr+Y))×100≧45 is satisfied, where Zr is the zirconium content (% by weight) in composition A and / or B; Y is the yttrium content (% by mass) in composition A and / or B; The Martens hardness of the coating is 6 GPa or more, preferably 7 GPa or more, and after heat treatment, the color difference ΔE is ≦4, preferably ΔE is ≦3, most preferably ΔE is ≦2. Corresponding coatings can be obtained, for example, by reactive magnetron sputtering, often in an oxygen and argon-containing atmosphere, or from ceramic targets, often in an argon-containing atmosphere, the pressure of the sputtering process being, for example, 1-8×10 -3 It can be set to mbar.

[0044] In the above embodiment, more preferably, compositions A and / or B further comprise silicon and have the following formula: ((Zr / (Zr+Y+Si))×100≧40, preferably ((Zr / (Zr+Y+Si))×100≧45, more preferably ((Zr / (Zr+Y+Si))×100≧50, ((Y / (Zr+Y+Si))×100≧40, preferably ((Y / (Zr+Y+Si))×100≧45, and 0.1≦((Si / (Zr+Y+Si))×100≦4, preferably 0.1≦((Si / (Zr+Y+Si))×100≦2 is satisfied, where Zr is the zirconium content (% by weight) in composition A and / or B; Y is the yttrium content (% by mass) in composition A and / or B; Si is the silicon content (mass%) in composition A and / or B; The coating has a Martens hardness of 6 GPa, preferably 7 GPa or more, and after heat treatment, the color difference ΔE is less than 4, preferably ΔE is less than 3, most preferably ΔE is less than 2. For example, corresponding coatings can be obtained by reactive magnetron sputtering, often in an oxygen and argon-containing atmosphere, or from ceramic targets, often in an argon-containing atmosphere, the pressure of the sputtering process being, for example, 1-8×10 -3 It can be set to mbar.

[0045] In the above embodiment, more preferably, compositions A and / or B further comprise aluminum and have the following formula: 0.5≦((Al / (Zr+Y+Si+Al))×1000≦50, preferably 1≦((Al / (Zr+Y+Si+Al))×1000≦10 is satisfied, where Al is the aluminum content (% by mass) in composition A and / or B.

[0046] In the above embodiment, more preferably, compositions A and / or B further comprise hafnium and have the following formula: 0.1≦((Hf / (Zr+Y+Si+Al+Hf))×100≦5, preferably 1≦((Hf / (Zr+Y+Si+Al+Hf))×100≦2 is satisfied, where Hf is the hafnium content (mass %) in composition A and / or B.

[0047] In the above embodiment, more preferably, compositions A and / or B further comprise hafnium and have the following formula: ((Zr / (Zr+Y+Si+Hf))×100≧50, ((Y / (Zr+Y+Si+Hf))×100≧45, 1≦((Si / (Zr+Y+Si+Hf))×100≦2, 0.5≦((Al / (Zr+Y+Si+Al+Hf))×1000≦10, and 0.1≦((Hf / (Zr+Y+Si+Al+Hf))×100≦5 is satisfied, where Zr is the zirconium content (% by weight) in composition A and / or B; Y is the yttrium content (% by mass) in composition A and / or B; Si is the silicon content (mass%) in composition A and / or B; Al is the aluminum content (wt%) in composition A and / or B, and Hf is the hafnium content (mass %) in composition A and / or B.

[0048] In a further preferred embodiment, compositions A and / or B comprise zirconium, yttrium and silicon and have the following formula: ((Zr / (Zr+Y+Si))×100≧30, and ((Y / (Zr+Y+Si))×100≦10 is satisfied, where Zr is the zirconium content (% by weight) in composition A and / or B; Y is the yttrium content (% by mass) in composition A and / or B; Si is the silicon content (mass%) in composition A and / or B; The Martens hardness of the coating is greater than or equal to 4.5 GPa and, after heat treatment, the color difference ΔE is less than or equal to 4, preferably less than or equal to 3, preferably less than or equal to 2, preferably less than or equal to 1. For example, corresponding coatings can be obtained by reactive magnetron sputtering, often in an oxygen- and argon-containing atmosphere, or from ceramic targets, often in an argon-containing atmosphere, the pressure of the sputtering process being, for example, 1-8×10 -3 It can be set to mbar.

[0049] In the above embodiment, more preferably, the compound has the formula: 30≦((Si / (Zr+Y+Si))×100≦60 is satisfied, and after heat treatment, the color difference ΔE is 2 or less, preferably 1 or less, and most preferably 0.5 or less.

[0050] In a further preferred embodiment, compositions A and / or B further comprise carbon.

[0051] In the above embodiment, more preferably, compositions A and / or B comprise yttrium, zirconium, aluminum, silicon, hafnium and carbon and have the following formula: ((Zr / (Zr+Y+Si+Hf+C))×100≧50, ((Y / (Zr+Y+Si+Hf+C))×100≧45, 1≦((Si / (Zr+Y+Si+Hf+C))×100≦2, 0.5≦((Al / (Zr+Y+Si+Al+Hf+C))×1000≦10, 1≦((Hf / (Zr+Y+Si+Hf+C))×100≦2, and 0.5≦((C / (Zr+Y+Si+Al+Hf+C))×1000≦10 is satisfied, where Zr is the zirconium content (% by weight) in composition A and / or B; Y is the yttrium content (% by mass) in composition A and / or B; Si is the silicon content (mass%) in composition A and / or B; Al is the aluminum content (% by mass) in composition A and / or B; Hf is the hafnium content (wt%) in composition A and / or B, and C is the carbon content (% by mass) in composition A and / or B.

[0052] The size and shape of the substrate are not particularly limited. It may be flat or curved or have a complex shape. Preferably, the substrate is a plate, preferably having a length of 10 cm to 700 cm, preferably 20 cm to 200 cm, more preferably 50 cm to 150 cm, and / or preferably and a width of 10 cm to 400 cm, preferably 20 cm to 200 cm, more preferably 50 cm to 150 cm, and / or preferably and a height of 0.1 mm to 5 cm, preferably 1 mm to 10 mm, more preferably 2 to 6 mm. In particular, when the substrate is a plate, the sliding properties and adhesion of the coating are improved. When the plate has a length and width of 20 cm to 200 cm, preferably 50 cm to 150 cm, and a height of 1 mm to 10 mm, preferably 2 to 6 mm, the layer can be applied homogeneously and reliably, so that production fluctuations are reduced.

[0053] The area of ​​the coating is not particularly limited. If the substrate is a plate, the coating can be applied on one side of the plate or on both sides of the plate. Preferably, the substrate has a surface area of ​​at least 50% [cm 2 / cm 2 ], preferably at least 75% [cm 2 / cm 2 ], more preferably at least 80% [cm 2 / cm 2 ], more preferably at least 90% [cm 2 / cm 2 ], more preferably at least 95% [cm 2 / cm 2 ] is coated, more preferably the plate comprises a surface where the entire surface, i.e. one side of the substrate is coated. In this way, the protection of the substrate and / or the decoration is improved. In a further preferred embodiment, the plate is coated only on one side, and this side is the side that faces up when the hob is installed.

[0054] The material of the substrate is not particularly limited. Preferably, the substrate is a glass ceramic or glass, and preferably has the following composition in mass %: SiO2 60-90%, preferably 76%-90%, B2O30-20%, Al2O30-20%, Li2O 0~10%, Na2O 0-10%, K2O 0~10%, MgO 0-10%, CaO 0-10%, SrO 0-10%, and BaO 0-10%, Preferred and unavoidable impurities The glass ceramic or glass comprises or consists of:

[0055] In this way, adhesion of the coating, or coating and decoration, is improved, peeling is reduced and protection of the substrate and / or decoration is improved.

[0056] Preferably, the substrate is a glass or glass ceramic. More preferably, the substrate is a borosilicate glass, an aluminosilicate glass, a lithium aluminosilicate glass, a soda-lime glass, a sapphire glass, and / or a glass ceramic, preferably a lithium aluminosilicate glass ceramic, more preferably the substrate is chemically and / or thermally strengthened or not strengthened, more preferably a not strengthened glass ceramic, more preferably a not strengthened lithium aluminosilicate glass ceramic. In this way, the adhesion of the coating, or the coating and the decoration, is improved, spalling is reduced, and the protection of the substrate and / or the decoration is improved.

[0057] In a preferred embodiment, the coated substrate is producible, and preferably is producible, by the methods described herein, such that the coated substrate can be reliably provided and the improvements described herein can be reliably achieved.

[0058] definition Preferably, unless otherwise stated, the parameters described within this application are specified according to the following: Color difference: Color difference can be measured using a portable spherical spectrophotometer with vertical configuration, e.g. Konica Minolta CM-700d or CM-600d, measuring range 400-700nm, illumination CIE-D65, gloss 8°, calibrated against a black surface. Color difference is the change in Lab value measured before and after each treatment, where untreated and treated coated substrates are each placed on the same black surface while measuring the Lab value.

[0059] Martens Hardness: Martens hardness can be measured by a nanoindenter device equipped with a Berkovich indenter, for example a nanoindenter CSM NHT, with a load of 5 mN.

[0060] Contents: The content of elements in the coating, such as yttrium, zirconium, silicon, aluminium, oxygen and nitrogen, may be measured using EDX spectroscopy, for example using an EDX spectrometer, model Inca x-act, manufactured by Oxford instruments.

[0061] Crystalline system and peaks on the 2θ scale: The crystalline system and / or peaks on the 2θ scale of a layer or coating can be measured by XRD, for example a thin film XRD from Philips, model X'pert pro.

[0062] Crystallite size and March-Dollase coefficient: The crystallite size (KGR) and the relative phase fraction (wt%) were determined using Rietveld refinement. The relative phase fraction indicates the proportion of crystals in the layer compared to the substrate (HQMK). This means that the thicker and / or more crystalline the layer, the lower the measured proportion of substrate (HQMK). The crystalline phases of the layer showed a strong preferred orientation. The preferred orientation was corrected using the so-called March-Dollase coefficient (MD coefficient). The lower the coefficient, the more favorable the Zr3Y4O 12 In the (122) direction of the phase, and in the Y 0.12 Zr 0.85 O 1.93 The phase has strong texture in the (010) and (011) directions, respectively (MD=1.0 is no preferred direction).

[0063] Friction: Friction can be measured by a CSM Micro Combitester (CSM).

[0064] Roughness: The roughness Rq and the arithmetic mean roughness Ra can be measured using a white light interferometry system, for example a Keyence model VK.

[0065] Coating thickness: The thickness is measured by a spectrometer of the company NXT, model TCM, using a reflectance measurement system. Preferably, the coating thickness is measured in a position where the coating is in direct contact with the substrate, with no decoration between the coating and the substrate.

[0066] Compressive stress: Compressive stress is measured by measuring the warpage of an uncoated substrate, coating it, and measuring the warpage again after coating to obtain the difference in warpage caused by the coating. The calculation of the stress is performed by Stoney's formula. For the measurements a Cyberscan CT 300 can be used.

[0067] Color values: Color values ​​in transmission are measured by Lambda 950 at 2° with D65, C * The value can be calculated.

[0068] Opacity: The opacity of a coating can be measured on a transparent substrate, for example Borofloat 33, by means of a densitometer, for example a densitometer X-rite 361T.

[0069] Magnetic Flux Density: The magnetic flux density can be determined by a magnetometer, e.g. PCE-MFM 3000.

[0070] Coating application method: The coating is preferably applied by physical vapor deposition, preferably by magnetron sputtering, in an in-line machine, e.g. Leybold ZV 1200.

[0071] There are several ways how to advantageously design and further develop the teaching of the present invention. For this purpose, reference is made to the patent claims that depend on the independent patent claims, the above description of preferred embodiments, the examples of the present invention, and the following examples of embodiments illustrated by the drawings. In this application, all preferred embodiments of the coated substrate also apply to the methods and uses described in this application, and vice versa. More preferred are combinations of two or more preferred embodiments, for example 2, 3, 4 or 5. [Brief description of the drawings]

[0072] [Figure 1] FIG. 1 is a schematic side view of a coated substrate according to one embodiment. [Diagram 2]X-ray diffraction spectrum of the coating. EXAMPLES

[0073] With regard to the above-mentioned preferred embodiments and items, generally preferred embodiments and further developments of the teachings are explained with the aid of figures and examples.

[0074] Example 1 (reference example) A glass ceramic substrate (SCHOTT CERAN®) with a size of 50 cm × 50 cm × 4 mm was cleaned in an ultrasonic bath. The cleaned substrate was then inserted into the chamber of a magnetron sputtering system ZV1200 (Leybold). The chamber was heated to a final pressure of 5 × 10 -5 The vacuum was then drawn down to 5×10 mbar and the pressure was then reduced to 5×10 mbar with argon. -3 The pressure was then set at 100 psi (mbar). The coating was then applied using the following settings: Target: Planar target, Zr:Y=92:8, purity 99.9 (3N), Magnetic flux: 50mT, Current: 20A, Voltage: 300V, Pressure: 5×10 -3 bar, Distance between target and substrate: 15cm; Oxygen gas flow rate: 55sccm, Argon gas flow rate: 170sccm, Base material temperature: 250℃, Deposition rate: 29.7nm m / min, Number of layers: 8.

[0075] In this way, a coating was obtained that was at least partially cubic and had a thickness of 1500 nm, and which further exhibited scratch resistance (Martens hardness was 8 GPa and compressive stress=1000 MPa), heat resistance (580° C. and 75 h→ΔE=3.5), resistance to alkaline solutions (Na2CO3.aq, pH=10, T=20° C., t 12 h→ΔE=0.7) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH=3, T=20° C., t 12 h→ΔE=1.2).

[0076] Example 2 (reference example) Example 2 was produced in the same manner as Example 1, but with a planar target of Mg:Al=30:70. The coating shows a ΔE of 9.1 (75 hours and 580° C.).

[0077] Example 3 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y=50:50 mass%, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0078] The coating exhibits good scratch resistance due to a hardness of at least 7 GPa, good heat resistance with ΔE=2 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH=10, T=20 °C, t 12 h → ΔE=1) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH=3, T=20 °C, t 12 h → ΔE=1.5).

[0079] Example 4 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y:Si=51:47:2 mass%, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0080] The coating exhibits good scratch resistance due to a hardness of at least 7 GPa, good heat resistance with ΔE=1.5 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH=10, T=20 °C, t 12 h → ΔE=1.1) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH=3, T=20 °C, t 12 h → ΔE=1).

[0081] Example 5 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y:Si:Al=51:47:1.5:0.5% by mass, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0082] The coating exhibits good scratch resistance due to a hardness of at least 6 GPa, good heat resistance with ΔE=2 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH=10, T=20 °C, t 12 h → ΔE=0.8) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH=3, T=20 °C, t 12 h → ΔE=1.1).

[0083] Example 6 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y:Si:Al:Hf=50.6:46.6:1.4:0.1:1.2 mass%, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0084] The coating exhibits good scratch resistance due to a hardness of at least 7 GPa, good heat resistance with ΔE = 0.32 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH = 10, T = 20 °C, t 12 h → ΔE = 1) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH = 3, T = 20 °C, t 12 h → ΔE = 1.5).

[0085] Example 7 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y:Si=61.3:5.3:33.3 mass%, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0086] The coating exhibits good scratch resistance due to a hardness of at least 4.5 GPa, good heat resistance with ΔE = 0.34 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH = 10, T = 20 °C, t 12 h → ΔE = 0.43) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH = 3, T = 20 °C, t 12 h → ΔE = 0.42).

[0087] Example 8 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y:Si=46:4:50 mass%, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0088] The coating exhibits good scratch resistance due to a hardness of at least 4.5 GPa, good heat resistance with ΔE = 0.46 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH = 10, T = 20 °C, t 12 h → ΔE = 0.29) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH = 3, T = 20 °C, t 12 h → ΔE = 0.2).

[0089] Example 9 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y:Si=30.6:2.6:66.6 mass%, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0090] The coating exhibits good scratch resistance due to a hardness of at least 4.5 GPa, good heat resistance with ΔE=0.5 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH=10, T=20 °C, t 12 h → ΔE=0.34) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH=3, T=20 °C, t 12 h → ΔE=0.9).

[0091] Example 10 (Example of the present invention) Glass-ceramic substrates (SCHOTT CERAN®) with a size of 50 cm x 50 cm x 4 mm were cleaned, for example by ultrasonic cleaning, by brush cleaning, by flame pretreatment, by temperature loading or equivalent known cleaning options. The sputtering process was carried out in a conventional magnetron sputtering system. The coatings were applied using the following settings: Target composition: Zr:Y:Si:Al:Hf:C=50.6:46.6:1.4:0.1:1.1:0.2 mass%, Reactive sputtering in an atmosphere containing primarily oxygen and argon, or from a ceramic target in an atmosphere containing primarily argon, Pressure: 1~8×10 -3 mbar, Coating thickness: 1000~1800nm.

[0092] The coating exhibits good scratch resistance due to a hardness of at least 5 GPa, good heat resistance with ΔE=0.7 at 580 °C, resistance to alkaline solutions (Na2CO3.aq, pH=10, T=20 °C, t 12 h → ΔE=0.5) and resistance to acidic solutions (C6H8O7.aq (citric acid), pH=3, T=20 °C, t 12 h → ΔE=1.0).

[0093] In the following description of embodiments, the same reference numbers refer to similar elements.

[0094] 1 shows a schematic side view of a coated substrate 1 according to one embodiment. The substrate 1 is coated with a coating 3 having a thickness 5. Between the coating 3 and the substrate 2, or underneath the substrate 2, there may be a decoration 4. The decoration 4 may be deposited on top of the coating 3.

[0095] Figure 2 shows the X-ray diffraction spectrum of Example 1. As can be seen, there is a peak between 33° and 36°, and an additional peak between 28° and 30° on the 2θ scale. [Explanation of symbols]

[0096] 1. Coated substrate 2 Base material 3. Coating 4. Decoration 5 Coating thickness

Claims

1. A coated substrate for a hob, comprising: the substrate comprises a coating comprising a layer; the layer is made of composition A containing yttrium and zirconium; The zirconium content in composition A is 75% by mass or less, The Martens hardness of the coating is 4.5 GPa or more, The coated substrate, wherein after heat treatment, the color difference ΔE is 4.0 or less.

2. 2. The coated substrate of claim 1, wherein the coating exhibits a peak between 33° and 36° and / or the coating exhibits a peak between 28° and 30° on the 2θ scale in XRD analysis.

3. A method for producing a coated substrate, preferably a coated substrate according to claim 1, comprising the following steps: - providing a substrate; applying a layer of composition A comprising yttrium and zirconium onto a substrate by physical vapor deposition to obtain a coated substrate according to claim 1, wherein the zirconium content in composition A is not more than 75% by weight. Preferably in this order.

4. said applying a layer onto a substrate by physical vapor deposition comprises sputtering and depositing a target onto the substrate; The target comprises a composition B containing yttrium, zirconium, and unavoidable impurities, wherein the zirconium content in composition B is 75 mass% or less. The method of claim 3.

5. the target is a planar target or a rotating target; and / or a magnetic flux density is preferably set over at least a portion of the surface of the target to between 5 mT and 200 mT, preferably between 20 mT and 80 mT; and / or The applied current in the physical vapor deposition method is set to 1 A to 1000 A, and / or The applied voltage in the physical vapor deposition method is set to 50 V to 2000 V, preferably 200 V to 700 V; and / or The pressure during the physical vapor deposition is 0.5×10 -3 bar ~ 1 x 10 -2 bar, preferably 2 x 10 -3 bar ~ 8 x 10 -3 bar, and / or the distance between the target and the substrate during the physical vapor deposition is 2 to 40 cm, more preferably 10 to 15 cm; The method of claim 4.

6. 3. The coated substrate of claim 1 or 2 and / or the method of claim 3, wherein composition A and / or B further comprises one or more of silicon, aluminum, titanium and / or hafnium.

7. 4. The coated substrate according to claim 1 or 2 and / or the method according to claim 3, wherein the yttrium content in composition A and / or B is 25% by weight or more.

8. The compositions A and / or B contain yttrium and zirconium and have the following formula: ((Zr / (Zr+Y))×100≧40, and ((Y / (Zr+Y))×100≧40, is satisfied, where Zr is the zirconium content (% by mass) in composition A and / or B; Y is the yttrium content (wt%) in composition A and / or B; The Martens hardness of the coating is 6 GPa or more, and after heat treatment, the color difference ΔE is 4 or less.

4. A coated substrate according to claim 1 or 2 and / or a method according to claim 3.

9. The compositions A and / or B further comprise silicon and have the following formula: ((Zr / (Zr+Y+Si))×100≧40, ((Y / (Zr+Y+Si))×100≧40, and 0.1≦((Si / (Zr+Y+Si))×100≦4 is satisfied, where Zr is the zirconium content (% by mass) in composition A and / or B; Y is the yttrium content (wt%) in composition A and / or B; Si is the silicon content (mass%) in composition A and / or B; The Martens hardness of the coating is 6 GPa or more, and after heat treatment, the color difference ΔE is 4 or less.

9. The coated substrate and / or method of claim 8.

10. The compositions A and / or B further comprise aluminum and have the following formula: 0.5≦((Al / (Zr+Y+Si+Al))×1000≦50 is satisfied, where 10. The coated substrate and / or method of claim 9, wherein Al is the aluminum content (wt%) in composition A and / or B.

11. The compositions A and / or B further comprise hafnium and have the following formula: 0.1≦((Hf / (Zr+Y+Si+Al+Hf))×100≦5 is satisfied, where 11. The coated substrate and / or method of claim 10, wherein Hf is the hafnium content (wt%) in composition A and / or B.

12. The composition A and / or B comprises zirconium, yttrium and silicon and has the following formula: ((Zr / (Zr+Y+Si))×100≧30, and ((Y / (Zr+Y+Si))×100≦10 is satisfied, where Zr is the zirconium content (% by mass) in composition A and / or B; Y is the yttrium content (wt%) in composition A and / or B; Si is the silicon content (mass%) in composition A and / or B; The coating has a Martens hardness of 4.5 GPa or more, and after heat treatment, the color difference ΔE is 4 or less.

4. A coated substrate according to claim 1 or 2 and / or a method according to claim 3.

13. The following formula: 30≦((Si / (Zr+Y+Si))×100≦60 is satisfied, and after heat treatment, the color difference ΔE is 2 or less. The coated substrate and / or method of claim 12.

14. 3. The coated substrate of claim 1 or 2 and / or the method of claim 3, wherein composition A and / or B further comprises carbon.

15. 3. The coated substrate according to claim 1 or 2 and / or the method according to claim 3, wherein the substrate is a borosilicate glass, an aluminosilicate glass, a lithium aluminosilicate glass, a soda-lime glass, a sapphire glass, and / or a glass ceramic, preferably a lithium aluminosilicate glass ceramic, more preferably the substrate is chemically and / or thermally strengthened or not strengthened, more preferably an not strengthened glass ceramic, more preferably an not strengthened lithium aluminosilicate glass ceramic.

16. 3. A hob, oven, table, shower wall, radiator, car, consumer electronics, mobile phone, tablet, watch, smartwatch, optical filter, interference filter, anti-reflection filter, mirror, more preferably an induction hob, radiant hob or gas hob, comprising the coated substrate of claim 1 or 2.

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