Ceramic glaze, ceramic product and preparation method thereof

Abstract

The invention relates to a ceramic glaze, a ceramic product and a preparation method thereof. The ceramic glaze material comprises a ground glaze material and a surface glaze material, the ground glaze material comprises a first basic glaze material and a toughening material, the toughening material comprises zirconium oxide or a product obtained by modifying zirconium oxide with a silane coupling agent, and the mass ratio of the first basic glaze material to the toughening material is 100: (15-30); the surface glaze material comprises a second basic glaze material and tungsten carbide, and the mass ratio of the second basic glaze material to the tungsten carbide is 100: (10-20). According to the ceramic glaze, through the cooperation of the ground glaze and the cover glaze, the hardness and the wear resistance of the ceramic glaze are improved.

Description

Technical Field

[0001] This application relates to the field of ceramic surface decoration, and in particular to ceramic glazes, ceramic products and their preparation methods. Background Technology

[0002] Ceramic surface decorative materials, through techniques such as spraying, printing, and laser engraving, form a composite surface layer on the ceramic substrate that combines decorative and functional properties, balancing aesthetic expression and durability. However, traditional ceramic decorative materials used in ceramic products still suffer from low hardness and poor wear resistance. Summary of the Invention

[0003] Based on this, this application provides a ceramic glaze with high hardness and good wear resistance.

[0004] In addition, this application also provides a ceramic article and a method for preparing the same.

[0005] A ceramic glaze, comprising a base glaze and a top glaze;

[0006] The base glaze includes a first base glaze and a toughening material. The toughening material includes zirconium oxide or a product of zirconium oxide modified by a silane coupling agent. The mass ratio of the first base glaze to the toughening material is 100:(15~30).

[0007] The surface glaze includes a second base glaze and tungsten carbide, wherein the mass ratio of the second base glaze to the tungsten carbide is 100:(10~20).

[0008] Optionally, the toughening material comprises a product of zirconium oxide modified with a silane coupling agent.

[0009] Optionally, the preparation steps of the toughening material include: calcining zirconium oxide at 800℃~950℃ for 2h~3h, mixing the calcined powder with a silane coupling agent, and ultrasonically dispersing for 20min~40min.

[0010] Optionally, the mass of the silane coupling agent is 0.5% to 1% of the mass of the zirconium oxide.

[0011] Optionally, the zirconium oxide is a nanoscale powder.

[0012] Optionally, the tungsten carbide is ball-milled using a mixed solution of ethanol and glycerol as the medium.

[0013] Optionally, the tungsten carbide is a nano-sized powder.

[0014] Optionally, the surface glaze further includes a colorant, wherein the mass ratio of the colorant to the second base glaze is (10~20):100.

[0015] Optionally, the colorant includes rare earth pre-melted particles, which, by mass percentage, comprise 20% to 40% rare earth oxides and 60% to 80% ceramic phase.

[0016] Optionally, in the base glaze, the mass percentage of particles with a particle size of less than 10 mm is 65% to 69%.

[0017] Optionally, in the glaze, the mass percentage of particles with a particle size of 10 mm or less is 80% to 84%.

[0018] Optionally, by weight percentage, the first base glaze comprises 25%~35% quartz, 25%~35% potassium feldspar, 10%~15% calcite, 3%~5% dolomite, 2.5%~3.5% zinc oxide, 1.5%~2.5% alumina, 8%~10% zirconium silicate, 3.5%~4.5% kaolin and 3.5%~4.5% wollastonite.

[0019] Optionally, by weight percentage, the second base glaze comprises 25% to 30% quartz, 15% to 20% potassium feldspar, 10% to 15% calcite, 1% to 3% zinc oxide, 3% to 5% alumina, 3% to 5% kaolin, 8% to 10% wollastonite, 3% to 4% calcined talc, and 20% to 25% frit.

[0020] A ceramic article includes a ceramic body and a glaze layer disposed on the surface of the ceramic body, the glaze layer being made of the aforementioned ceramic glaze.

[0021] Optionally, the glaze layer includes a base glaze layer and a top glaze layer, wherein the thickness of the base glaze layer is 80μm~100μm; and / or, the thickness of the top glaze layer is 40μm~60μm.

[0022] A method for preparing a ceramic product includes the following steps:

[0023] Ceramic products are prepared by applying ceramic glaze to the surface of a ceramic body and sintering it.

[0024] The ceramic glaze is as described above.

[0025] Optionally, the sintering step includes:

[0026] The temperature is increased to 500℃~600℃ at a first heating rate of 5℃ / min~10℃ / min;

[0027] The temperature was increased to 1180℃~1230℃ at a second heating rate of 3℃ / min~5℃ / min, and held at that temperature for 1.5h~2.5h.

[0028] Cool to 500℃~600℃ at a rate of 2℃ / min~5℃ / min.

[0029] Optionally, the step of applying a ceramic glaze to the surface of the ceramic body includes:

[0030] The base glaze and the top glaze are mixed with water to form a base glaze slurry and a top glaze slurry, respectively. The base glaze slurry and the top glaze slurry are then applied sequentially to the surface of the ceramic body by spraying.

[0031] Optionally, the pressure for each spraying is 0.4 MPa to 0.6 MPa;

[0032] Optionally, after spraying, the coating should be dried at 100℃~120℃ for 30min~60min.

[0033] The ceramic glaze of this application includes a base glaze and a top glaze. The base glaze contains a certain amount of toughening material, including zirconium oxide or a product of zirconium oxide modified with a silane coupling agent. The top glaze contains a certain amount of tungsten carbide (WC). During sintering, zirconium oxide undergoes a phase transformation from tetragonal to monoclinic, accompanied by volume expansion, forming a compressive stress field within the glaze layer, inhibiting crack propagation and improving toughness. The WC added to the top glaze acts as a hard reinforcing phase, uniformly dispersed in the glass phase of the second base glaze to form a hard framework. Combined with SiO2 in the second base glaze filling the pores of the glass phase, this reduces the risk of material spalling during friction and improves wear resistance.

[0034] Therefore, the above-mentioned ceramic glaze improves the hardness and wear resistance of the ceramic glaze through the synergy of the base glaze and the top glaze. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 The image shows the fading results of the ceramic products prepared in Example 1 and Comparative Example 1 of this application after being kept at 800°C for 100 hours. Detailed Implementation

[0037] To facilitate understanding of this application, a more comprehensive description of the application will be provided below in conjunction with specific embodiments. Preferred embodiments of the application are given in the specific embodiments. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0039] Unless otherwise stated or in case of conflict, the terms or phrases used in this application shall have the following meanings:

[0040] In this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" and "second" may explicitly or implicitly include at least one of those features.

[0041] In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.

[0042] In this application, "one or more" refers to any one, two, or more of the listed items. "Multiple" refers to any two or more of the listed items.

[0043] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0044] In this application, terms such as "further," "even more," "particularly," "for example," "like," "example," and "exemplary" are used for descriptive purposes to indicate a connection in the coverage of different technical solutions presented earlier and later, but should not be construed as limiting the preceding technical solution or restricting the scope of protection herein. Unless otherwise specified herein, A (e.g., B) indicates that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0045] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it is selected from either "present" or "absent." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent. In this application, descriptions such as "optionally contains" and "optionally includes" indicate "contains or does not contain." "Optional component X" indicates whether component X exists or does not exist, or whether component X is contained or not.

[0046] When a numerical range is disclosed in this application, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed in this application should be understood to include any and all subranges to which they are included.

[0047] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0048] The terms "comprising" and "having," and any variations thereof, used in the embodiments of this application, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the steps or units listed, but may optionally include steps or units not listed, or may optionally include other steps or components inherent to such processes, methods, products, or devices.

[0049] In this application, the reference to "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this application can be combined with other embodiments.

[0050] The first aspect of this application provides a ceramic glaze, including a base glaze and a top glaze;

[0051] The base glaze includes a first base glaze and a toughening material. The toughening material includes zirconium oxide or zirconium oxide modified by a silane coupling agent. The mass ratio of the first base glaze to the toughening material is 100:(15~30).

[0052] The surface glaze includes a second base glaze and tungsten carbide, with a mass ratio of the second base glaze to tungsten carbide of 100:(10~20).

[0053] The ceramic glaze of this application includes a base glaze and a top glaze. The base glaze contains a certain amount of toughening material, including zirconium oxide or a product of zirconium oxide modified with a silane coupling agent. The top glaze contains a certain amount of tungsten carbide (WC). During sintering, zirconium oxide undergoes a phase transformation from tetragonal to monoclinic, accompanied by volume expansion, forming a compressive stress field within the glaze layer, inhibiting crack propagation and improving toughness. The WC added to the top glaze acts as a hard reinforcing phase, uniformly dispersed in the glass phase of the second base glaze to form a hard framework. Combined with SiO2 in the second base glaze filling the pores of the glass phase, this reduces the risk of material spalling during friction and improves wear resistance.

[0054] Traditional ceramic surface decoration materials result in ceramic products with low surface hardness, making them prone to scratches from prolonged friction. However, the ceramic glazes in some embodiments of this application, through the synergy of the base glaze and the top glaze, improve the wear resistance and hardness of the ceramic products.

[0055] In some embodiments, the mass ratio of the first base glaze to the toughening material is 100:(15~30). For example, the mass ratio of the first base glaze to the toughening material may be, but is not limited to, 100:15, 100:18, 100:20, 100:22, 100:24, 100:25, 100:26, 100:28, 100:30, or a range of any two of these values. It is understood that when the toughening material includes zirconium oxide, zirconium oxide refers to zirconium oxide that has not undergone any modification treatment.

[0056] In some embodiments, the toughening material comprises a product of zirconium oxide modified with a silane coupling agent. Modification with a silane coupling agent improves the compatibility of zirconium oxide with the first base glaze and the dispersibility of zirconium oxide in the first base glaze, further enhancing the wear resistance and hardness of the ceramic glaze.

[0057] Specifically, the preparation steps of the toughening material include: calcining zirconium oxide at 800℃~950℃ for 2h~3h, mixing the calcined powder with a silane coupling agent, and ultrasonically dispersing for 20min~40min.

[0058] Specifically, the mass of the silane coupling agent is 0.5% to 1% of the mass of zirconium oxide.

[0059] High-temperature calcination of zirconium oxide can increase the hydroxyl content on its surface, further enhancing the modification effect of silane coupling agents and thus improving the acid and alkali corrosion resistance of ceramic products.

[0060] In some embodiments, the silane coupling agent includes, but is not limited to, KH570.

[0061] In some embodiments, zirconium oxide is in the form of nanoscale powder. Using nanoscale zirconium oxide is beneficial for further improving the hardness and wear resistance of ceramic glazes.

[0062] In some embodiments, the mass percentage of particles with a particle size of less than 10 mm in the base glaze is 65% to 69%.

[0063] In some embodiments, the first base glaze comprises quartz, potassium feldspar, calcite, dolomite, zinc oxide, alumina, zirconium silicate, kaolin, and wollastonite. Specifically, by mass percentage, the first base glaze comprises 25%–35% quartz, 25%–35% potassium feldspar, 10%–15% calcite, 3%–5% dolomite, 2.5%–3.5% zinc oxide, 1.5%–2.5% alumina, 8%–10% zirconium silicate, 3.5%–4.5% kaolin, and 3.5%–4.5% wollastonite.

[0064] It is understood that the above only provides a relatively specific composition of the first base glaze, but it is not limited to this. Other commonly used base glazes can also be used as the first base glaze of this application.

[0065] In some embodiments, the mass ratio of the second base glaze to tungsten carbide is 100:(10~20). For example, the mass ratio of the second base glaze to tungsten carbide may be, but is not limited to, 100:10, 100:12, 100:14, 100:15, 100:16, 100:18, 100:20, or any range of two of these values.

[0066] In some embodiments, tungsten carbide is ball-milled using a mixed solution of ethanol and glycerol as the medium. This ball-milling process improves the dispersibility of tungsten carbide in the second base glaze, thereby further enhancing the wear resistance and hardness of the ceramic glaze.

[0067] Specifically, tungsten carbide is mixed with a solution of ethanol and glycerol and ball-milled for 2-3 hours. The volume ratio of ethanol to glycerol is 3:1. In one example, the ball milling speed is 200 rpm.

[0068] In some embodiments, tungsten carbide is a nano-sized powder. Using nano-sized powder is beneficial for further improving the hardness and wear resistance of ceramic glazes.

[0069] In some embodiments, the surface glaze further includes a colorant, wherein the mass ratio of the colorant to the second base glaze is (10~20):100. For example, the mass ratio of the colorant to the second base glaze may be, but is not limited to, 10:100, 12:100, 14:100, 15:100, 16:100, 18:100, 20:100, or any range of two of these values.

[0070] Specifically, the colorant includes rare earth pre-melted particles. In this application, rare earth pre-melted particles refer to particles obtained by mixing and melting rare earth oxides with ceramic phases such as silicon dioxide, so that the rare earth oxides are encapsulated inside the silicon dioxide or other materials. Specifically, suitable rare earth oxides can be selected according to different colors. For example, if the colorant is red, the rare earth oxide can be europium oxide (Eu2O3), etc.; if the colorant is yellow-green, the rare earth oxide can be praseodymium oxide (Pr2O3), cerium oxide (CeO2), etc.; if the colorant is blue-purple, the rare earth oxide can be neodymium oxide (Nd2O3), thulium oxide (Tm2O3), etc.

[0071] Specifically, the rare earth pre-melted particles comprise a shell and rare earth oxides encapsulated within the shell. The shell comprises at least silicon oxide. In the rare earth pre-melted particles, the rare earth oxides are encapsulated within the particles, allowing the rare earth elements to react with the Si in the particles during sintering. 4+ O 2- By combining these elements, a rare earth-oxygen-silicon ternary crystal is formed, exhibiting strong chemical stability and resisting fading caused by ultraviolet radiation, high temperatures, and acid / alkali corrosion, thus solving the problem of easy fading in traditional ceramic decorative materials. If rare earth oxides are directly added to the glaze, it is difficult to form a stable rare earth-oxygen-silicon ternary crystal, and fading easily occurs in high-temperature and acid / alkali environments.

[0072] In some embodiments, the rare earth pre-melted particles comprise 20% to 40% rare earth oxides and 60% to 80% ceramic phase by weight percentage.

[0073] In some embodiments, the mass percentage of particles with a diameter of 10 mm or less in the glaze is 80% to 84%. This configuration helps to further improve the density and wear resistance of the glaze layer.

[0074] In some embodiments, the second base glaze comprises quartz. Specifically, the second base glaze comprises quartz, potassium feldspar, calcite, zinc oxide, alumina, kaolin, wollastonite, calcined talc, and frit. Specifically, by mass percentage, the second base glaze comprises 25%–30% quartz, 15%–20% potassium feldspar, 10%–15% calcite, 1%–3% zinc oxide, 3%–5% alumina, 3%–5% kaolin, 8%–10% wollastonite, 3%–4% calcined talc, and 20%–25% frit.

[0075] It is understood that the above only provides a relatively specific composition of the second base glaze, but it is not limited to this. Other base glazes commonly used in the art can also be used as the second base glaze of this application.

[0076] The second aspect of this application provides a ceramic article, including a ceramic body and a glaze layer disposed on the surface of the ceramic body, the glaze layer being made of the ceramic glaze described in the first aspect.

[0077] It is understandable that in ceramic glaze, the base glaze forms the base glaze layer, and the top glaze forms the top glaze layer, with the base glaze layer placed between the ceramic body and the top glaze layer.

[0078] In some embodiments, the thickness of the base glaze layer is 80μm~100μm.

[0079] In some embodiments, the thickness of the surface glaze layer is 40 μm to 60 μm.

[0080] In some embodiments, the surface hardness of the ceramic article is ≥ Mohs 6. Further, the surface hardness of the ceramic article is ≥ Mohs 7. Even further, the surface hardness of the ceramic article is ≥ Mohs 8.

[0081] In some embodiments, the color difference change ΔE of the ceramic product before and after heat treatment at 800℃ for 100 hours is less than 1. ΔE = (ΔL) 2 +Δa 2 +Δb 2 ) 1 / 2 .

[0082] A third aspect of this application provides a method for preparing a ceramic article, comprising the following steps:

[0083] Ceramic products are prepared by applying ceramic glaze to the surface of a ceramic body and sintering it.

[0084] Among them, the ceramic glaze is the ceramic glaze mentioned in the first aspect above.

[0085] In some embodiments, the sintering step includes:

[0086] The temperature is increased to 500℃~600℃ at a first heating rate of 5℃ / min~10℃ / min;

[0087] The temperature was increased to 1180℃~1230℃ at a second heating rate of 3℃ / min~5℃ / min, and held at that temperature for 1.5h~2.5h.

[0088] Cool to 500℃~600℃ at a rate of 2℃ / min~5℃ / min.

[0089] The temperature is raised from room temperature to 500℃~600℃ to remove organic impurities. Then, the temperature is raised from 500℃~600℃ to 1180℃~1230℃, causing a phase transition in ZrO2 and the precipitation of rare earth-silicon-oxygen ternary crystals. The temperature is then lowered from 1180℃~1230℃ to 500℃~600℃ at a slow rate to prevent glaze cracking. Finally, the temperature is allowed to cool naturally below 500℃~600℃.

[0090] In some embodiments, the base glaze and the top glaze are mixed with water to prepare a base glaze slurry and a top glaze slurry, and the base glaze slurry and the top glaze slurry are applied sequentially to the surface of the ceramic body by spraying.

[0091] Specifically, the pressure for each spraying is 0.4MPa to 0.6MPa.

[0092] Specifically, after spraying, dry at 100℃~120℃ for 30min~60min.

[0093] Specifically, the base glaze is mixed with water and ball-milled until the mass percentage of particles with a particle size of less than 10 mm is 65% to 69%.

[0094] In one example, the mass ratio of water to the first base glaze in the base glaze is 50:100.

[0095] In one example, the ball-to-material ratio during the ball milling process was 3:1, and the rotation speed was 300 rpm.

[0096] After ball milling, the mixture is passed through a 200-mesh sieve to obtain the base glaze slurry.

[0097] Specifically, the surface glaze is mixed with water and ball-milled until the mass percentage of particles with a diameter of less than 10 mm is 80%~84%. The mass ratio of water to the second base glaze in the surface glaze is (50~60):100.

[0098] In one example, the mass ratio of water to the mass of the second base glaze in the top glaze is 50:100.

[0099] To make the objectives and advantages of this application clearer, the ceramic glaze, ceramic products, and their effects are further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only for explaining this application and should not be used to limit this application. Unless otherwise specified, the following embodiments do not include components other than unavoidable impurities. Unless otherwise specified, the drugs and instruments used in the embodiments are conventional choices in the art. Experimental methods in the embodiments that do not specify specific conditions are implemented according to conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0100] Example 1

[0101] This embodiment provides a ceramic glaze, including a base glaze and a top glaze. By weight, the base glaze comprises 100 parts of a first basic glaze and 20 parts of a product modified with a silane coupling agent from zirconium oxide. The first basic glaze comprises 31 parts quartz, 30 parts potassium feldspar, 13 parts calcite, 4 parts dolomite, 3 parts zinc oxide, 2 parts alumina, 9 parts zirconium silicate, 4 parts kaolin, and 4 parts wollastonite. The top glaze consists of 100 parts of a second basic glaze, 15 parts dispersed nano-WC, and 15 parts rare earth pre-melted particles. The second basic glaze comprises 29 parts quartz, 19 parts potassium feldspar, 10 parts calcite, 2 parts zinc oxide, 3.5 parts alumina, 3.5 parts kaolin for glaze, 8 parts wollastonite, 3 parts calcined talc, and 22 parts frit. The rare earth pre-melted particles were purchased from Zibo Fulu New Materials Co., Ltd.

[0102] The preparation steps for the zirconium oxide modified with a silane coupling agent are as follows: Nano-ZrO2 powder is calcined at 800℃ for 2 hours, and a silane coupling agent (KH570) accounting for 0.5% of the mass percentage of the nano-ZrO2 powder is added and ultrasonically dispersed for 30 minutes to obtain the zirconium oxide modified with a silane coupling agent. The preparation steps for the dispersed WC powder are as follows: WC powder is mixed with an ethanol-glycerol mixture (volume ratio 3:1) and ball-milled for 2 hours at a ball milling speed of 200 rpm to obtain the dispersed WC powder.

[0103] This embodiment also provides a ceramic product, the preparation method of which includes the following steps:

[0104] (1) Weigh out 30 parts quartz, 30 parts potassium feldspar, 13 parts calcite, 4 parts dolomite, 3 parts zinc oxide, 2 parts alumina, 9 parts zirconium silicate, 4 parts kaolin, and 4 parts wollastonite according to the formula as the first base glaze. Add 20 parts zirconium oxide modified with silane coupling agent and 50 parts water. Mix and ball mill until the mass percentage of particles with a particle size of less than 10 mm is 65%~69%. During the mixing and ball milling process, the ball-to-material ratio is 3:1 and the rotation speed is 300 rpm. After ball milling, pass through a 200-mesh sieve to obtain the base glaze slurry.

[0105] Weigh out 29 parts quartz, 19 parts potassium feldspar, 10 parts calcite, 2 parts zinc oxide, 3.5 parts alumina, 3.5 parts kaolin for glaze, 8 parts wollastonite, 3 parts calcined talc, and 22 parts frit as the second base glaze. Add 15 parts dispersed nano-WC, 15 parts rare earth pre-melted particles, and 50 parts water. Mix and ball-mill until the mass percentage of particles with a diameter of less than 10 mm is 80%~84%. During the ball milling process, the ball-to-material ratio is 3:1, and the rotation speed is 300 rpm. After ball milling, pass through a 200-mesh sieve to obtain the surface glaze slurry.

[0106] (2) The base glaze and top glaze were sequentially sprayed onto the surface of the ceramic body using a high-pressure spraying method, so that the thickness of the base glaze layer was 90μm and the thickness of the top glaze layer was 50μm, and the spraying pressure was 0.4MPa. After spraying, the ceramic body was dried at 120℃ for 30 minutes.

[0107] (3) The dried ceramic intermediate was sintered by heating from room temperature to 600°C at a heating rate of 5°C / min; then the temperature was increased from 600°C to 1180°C at a heating rate of 3°C / min and held for 2 hours. After the holding period, the temperature was reduced from 1180°C to 600°C at a cooling rate of 2°C / min and allowed to cool naturally below 600°C to obtain the ceramic product of this embodiment.

[0108] Example 2

[0109] This embodiment provides a ceramic glaze, including a base glaze and a top glaze. By weight, the base glaze comprises 100 parts of a first basic glaze and 15 parts of zirconium oxide modified with a silane coupling agent. The first basic glaze comprises 30 parts of quartz, 30 parts of potassium feldspar, 13 parts of calcite, 4 parts of dolomite, 3 parts of zinc oxide, 2 parts of alumina, 9 parts of zirconium silicate, 4 parts of kaolin, and 4 parts of wollastonite. The top glaze comprises 100 parts of a second basic glaze, 10 parts of dispersed nano-WC, and 10 parts of rare earth pre-melted particles. The second basic glaze consists of 29 parts of quartz, 19 parts of potassium feldspar, 10 parts of calcite, 2 parts of zinc oxide, 3.5 parts of alumina, 3.5 parts of kaolin for glaze, 8 parts of wollastonite, 3 parts of calcined talc, and 22 parts of frit.

[0110] The preparation method of the ceramic product in this embodiment is the same as that of the ceramic product in Example 1, and will not be repeated here.

[0111] Example 3

[0112] This embodiment provides a ceramic glaze, including a base glaze and a top glaze. By weight, the base glaze comprises 100 parts of a first basic glaze and 30 parts of zirconium oxide modified with a silane coupling agent. The first basic glaze comprises 30 parts of quartz, 30 parts of potassium feldspar, 13 parts of calcite, 4 parts of dolomite, 3 parts of zinc oxide, 2 parts of alumina, 9 parts of zirconium silicate, 4 parts of kaolin, and 4 parts of wollastonite. The top glaze comprises 100 parts of a second basic glaze, 15 parts of dispersed nano-WC, and 15 parts of rare earth pre-melted particles. The second basic glaze consists of 29 parts of quartz, 19 parts of potassium feldspar, 10 parts of calcite, 2 parts of zinc oxide, 3.5 parts of alumina, 3.5 parts of kaolin for glaze, 8 parts of wollastonite, 3 parts of calcined talc, and 22 parts of frit.

[0113] The preparation method of the ceramic product in this embodiment is the same as that of the ceramic product in Example 1, and will not be repeated here.

[0114] Example 4

[0115] This embodiment provides a ceramic glaze, similar to the ceramic glaze of Example 1, except that the preparation steps of the product modified by silane coupling agent in the base glaze are different. In this embodiment, the preparation steps of the product modified by silane coupling agent include: adding 0.5% by mass of silane coupling agent (KH570) to nano ZrO2 powder and ultrasonically dispersing for 30 minutes to obtain the product modified by silane coupling agent.

[0116] The preparation method of the ceramic product in this embodiment is the same as that of the ceramic product in Example 1, and will not be repeated here.

[0117] Example 5

[0118] This embodiment provides a ceramic glaze, which is similar to the ceramic glaze in Embodiment 1. The difference is that the tungsten carbide powder in the surface glaze is not dispersed in a mixed solution of ethanol and propylene glycol, but is directly mixed with the second base glaze.

[0119] The preparation method of the ceramic product in this embodiment is the same as that of the ceramic product in Example 1, and will not be repeated here.

[0120] Example 6

[0121] This embodiment provides a ceramic glaze, which is the same as the ceramic glaze in Embodiment 1.

[0122] The preparation method of the ceramic product in this embodiment is similar to that of the ceramic product in Example 1, except that the sintering process is different. The sintering steps in this embodiment include: heating from room temperature to 600°C at a heating rate of 5°C / min; then heating from 600°C to 1150°C at a heating rate of 3°C / min and holding at that temperature for 2 hours. After holding at that temperature, cooling from 1150°C to 600°C at a cooling rate of 2°C / min, and then allowing it to cool naturally below 600°C to obtain the ceramic product of this embodiment.

[0123] Comparative Example 1

[0124] Comparative Example 1 provides a ceramic glaze similar to that of Example 1, except that nano-zirconia is not added to the base glaze, tungsten carbide is not added to the top glaze, and rare earth pre-melted particles are replaced with rare earth oxides. Specifically, in the ceramic glaze of Comparative Example 1, by mass parts, the base glaze consists of 30 parts quartz, 30 parts potassium feldspar, 13 parts calcite, 4 parts dolomite, 3 parts zinc oxide, 2 parts alumina, 9 parts zirconium silicate, 4 parts kaolin, and 4 parts wollastonite. The top glaze includes 100 parts of a second base glaze and 15 parts of rare earth oxides. The second base glaze consists of 29 parts quartz, 19 parts potassium feldspar, 10 parts calcite, 2 parts zinc oxide, 3.5 parts alumina, 3.5 parts kaolin for glaze, 8 parts wollastonite, 3 parts calcined talc, and 22 parts frit.

[0125] The preparation method of the ceramic product in Comparative Example 1 is the same as that in Example 1, and will not be repeated here.

[0126] Comparative Example 2

[0127] Comparative Example 2 provides a ceramic glaze similar to that of Example 1, except that the base glaze does not contain nano-zirconia, while the nano-zirconia is incorporated into the top glaze. Specifically, in Comparative Example 2, the base glaze, by mass parts, consists of 30 parts quartz, 30 parts potassium feldspar, 13 parts calcite, 4 parts dolomite, 3 parts zinc oxide, 2 parts alumina, 9 parts zirconium silicate, 4 parts kaolin, and 4 parts wollastonite. The top glaze comprises 100 parts of a second base glaze, 20 parts of zirconium oxide modified with a silane coupling agent, 15 parts of dispersed nano-WC, and 15 parts of rare earth pre-melted particles. The second base glaze consists of 29 parts quartz, 19 parts potassium feldspar, 10 parts calcite, 2 parts zinc oxide, 3.5 parts alumina, 3.5 parts kaolin for glaze, 8 parts wollastonite, 3 parts calcined talc, and 22 parts frit.

[0128] The preparation method of the ceramic product in Comparative Example 2 is the same as that in Example 1, and will not be repeated here.

[0129] Comparative Example 3

[0130] Comparative Example 3 provides a ceramic glaze similar to that of Example 1, except that the composition of the surface glaze is different. The surface glaze consists of 100 parts of a second base glaze, 5 parts of dispersed nano-WC, and 15 parts of rare earth pre-melted particles. Everything else is the same as in Example 1 and will not be repeated here.

[0131] The preparation method of the ceramic product in Comparative Example 3 is the same as that in Example 1, and will not be repeated here.

[0132] The ceramic products prepared in each embodiment and comparative example were tested using the following methods:

[0133] (1) Surface hardness: The surface scratch hardness is determined according to the Mohs hardness scale. Select the sharp part of the sample to be tested and scratch it on the plane of a flat mineral hardness tester with known hardness. The scratch hardness test is performed sequentially from low to high. Observe whether there are facets on the plane of the hardness tester. Gently wipe the plane to prevent the powder of the sample from being left on the hardness tester and causing misjudgment. If there are scratches on the plane of the hardness tester, the sample hardness is greater than that of the hardness tester. Then test the hardness tester of the next higher level until it is between two hardness levels or equivalent to a certain hardness tester.

[0134] (2) Abrasion resistance test: Abrasion resistance test is conducted according to GB / T 18301-2012. The sample is fixed on a rotating platform and the sample surface is rubbed by two standard grinding wheels under a load of 1000g. The abrasion resistance is evaluated by measuring the mass loss before and after friction.

[0135] (3) High-temperature color change test: The high-temperature color change test of ceramics was carried out in accordance with GB / T 30757-2014. First, the initial L, a, and b values ​​of the sample were measured. Then, the sample was placed in a high-temperature chamber, and the temperature was set to 800℃ and the time to 100h. After cooling, the L, a, and b values ​​of the sample were measured again. The color difference ΔE was calculated according to the following formula: ΔE = (ΔL) / (a, b) / (a, b) 2 +Δa 2 +Δb 2 ) 1 / 2 .

[0136] (4) Acid and alkali corrosion resistance test: The acid and alkali corrosion resistance test of ceramics was carried out in accordance with JC / T 2138-2012. The ceramic samples were immersed in 10% H2SO4 solution and 10% NaOH solution at room temperature for 72 hours respectively, and the corrosion resistance was evaluated by measuring the change in surface morphology.

[0137] The test results of the ceramic products of each embodiment and comparative example are shown in Table 1 below. The high-temperature color change results of the ceramic products prepared in Example 1 and Comparative Example 1 after being kept at 800℃ for 100 hours are as follows: Figure 1 As shown. Figure 1 In the figure, the left side corresponds to the ceramic product of Example 1, and the right side corresponds to the ceramic product of Comparative Example 1. As can be seen from the figure, the ceramic product of Comparative Example 1 faded after high-temperature treatment.

[0138] Table 1 Performance data of ceramic products prepared in each embodiment and comparative example

[0139]

[0140] As can be seen from Table 1 above, the ceramic products prepared using the ceramic glaze of the present application embodiment have higher hardness, better wear resistance, and are less prone to discoloration compared to the comparative example.

[0141] The comparison between Comparative Example 1 and Example 1 shows that, compared to Example 1, Comparative Example 1, which did not contain nano-zirconia in its base glaze and tungsten carbide in its top glaze, exhibited significantly lower Mohs hardness and wear resistance. Furthermore, the top glaze of the Comparative Example, which directly contained rare earth oxides, showed noticeable color changes and fading after being kept at 800℃ for 100 hours, and also exhibited poor resistance to acid and alkali corrosion.

[0142] As can be seen from the comparison between Comparative Example 2 and Example 1, the base glaze of Comparative Example 2 did not contain nano-zirconia, but was set in the top glaze. Compared with Example 1, the Mohs hardness and wear resistance were significantly reduced, and the acid and alkali corrosion resistance was poor.

[0143] As can be seen from the comparison between Comparative Example 3 and Example 1, the tungsten carbide content in the surface glaze of Comparative Example 3 is lower, and compared with Example 1, the Mohs hardness and wear resistance are significantly reduced, and the acid and alkali corrosion resistance is poor.

[0144] Furthermore, as can be seen from the examples, calcining zirconium oxide helps to further improve the acid and alkali corrosion resistance of ceramic products. Ball milling and dispersing tungsten carbide helps to further improve the Mohs hardness and wear resistance of ceramic products. Optimizing the sintering process of ceramic products helps to further improve the Mohs hardness, wear resistance, acid and alkali corrosion resistance, and high-temperature discoloration resistance of ceramic products.

[0145] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0146] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A ceramic glaze, characterized in that, Including base glaze and top glaze; The base glaze includes a first base glaze and a toughening material. The toughening material includes zirconium oxide or a product of zirconium oxide modified by a silane coupling agent. The mass ratio of the first base glaze to the toughening material is 100:(15~30). The surface glaze includes a second base glaze and tungsten carbide, wherein the mass ratio of the second base glaze to the tungsten carbide is 100:(10~20).

2. The ceramic glaze according to claim 1, characterized in that, The toughening material includes a product of zirconium oxide modified with a silane coupling agent; Optionally, the preparation steps of the toughening material include: calcining zirconium oxide at 800℃~950℃ for 2h~3h, mixing the calcined powder with a silane coupling agent, and ultrasonically dispersing for 20min~40min; Optionally, the mass of the silane coupling agent is 0.5% to 1% of the mass of the zirconium oxide; Optionally, the zirconium oxide is a nanoscale powder.

3. The ceramic glaze according to claim 1, characterized in that, The tungsten carbide is ball-milled using a mixed solution of ethanol and glycerol as the medium; and / or, The tungsten carbide is a nano-sized powder.

4. The ceramic glaze according to claim 1, characterized in that, The surface glaze also includes a colorant, and the mass ratio of the colorant to the second base glaze is (10~20):100; Optionally, the colorant comprises rare earth pre-melted particles, which, by mass percentage, comprise 20% to 40% rare earth oxides and 60% to 80% ceramic phase.

5. The ceramic glaze according to any one of claims 1 to 4, characterized in that, In the base glaze, the mass percentage of particles with a particle size of less than 10 mm is 65% to 69%; and / or, In the glaze, the mass percentage of particles with a diameter of 10 mm or less is 80% to 84%; and / or, By weight percentage, the first base glaze comprises 25%–35% quartz, 25%–35% potassium feldspar, 10%–15% calcite, 3%–5% dolomite, 2.5%–3.5% zinc oxide, 1.5%–2.5% alumina, 8%–10% zirconium silicate, 3.5%–4.5% kaolin, and 3.5%–4.5% wollastonite; and / or, The second base glaze comprises, by weight percentage, 25% to 30% quartz, 15% to 20% potassium feldspar, 10% to 15% calcite, 1% to 3% zinc oxide, 3% to 5% alumina, 3% to 5% kaolin, 8% to 10% wollastonite, 3% to 4% calcined talc, and 20% to 25% frit.

6. A ceramic product, characterized in that, It includes a ceramic body and a glaze layer disposed on the surface of the ceramic body, the glaze layer being made of the ceramic glaze as described in any one of claims 1 to 5.

7. The ceramic product according to claim 6, characterized in that, The glaze layer includes a base glaze layer and a top glaze layer, wherein the thickness of the base glaze layer is 80μm~100μm; and / or, the thickness of the top glaze layer is 40μm~60μm.

8. A method for preparing a ceramic product, characterized in that, Includes the following steps: Ceramic products are prepared by applying ceramic glaze to the surface of a ceramic blank and sintering it. The ceramic glaze is the ceramic glaze as described in any one of claims 1 to 5.

9. The method for preparing ceramic products according to claim 8, characterized in that, The sintering process includes: The temperature is increased to 500℃~600℃ at a first heating rate of 5℃ / min~10℃ / min; The temperature is increased to 1180℃~1230℃ at a second heating rate of 3℃ / min~5℃ / min, and held at that temperature for 1.5h~2.5h. Cool to 500℃~600℃ at a rate of 2℃ / min~5℃ / min.

10. The method for preparing ceramic articles according to claim 8 or 9, characterized in that, The steps of applying ceramic glaze to the surface of a ceramic body include: The base glaze and the top glaze are mixed with water to prepare a base glaze slurry and a top glaze slurry, respectively. The base glaze slurry and the top glaze slurry are then applied sequentially to the surface of the ceramic body by spraying. Optionally, the pressure for each spraying is 0.4 MPa to 0.6 MPa; Optionally, after spraying, the coating should be dried at 100℃~120℃ for 30min~60min.

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