Wear-resistant glaze throwing brick with good color and strong transparency and its preparation process

Abstract

This invention belongs to the field of ceramic glazes, specifically a wear-resistant polished glazed tile with excellent color development and high translucency, and its preparation process. This invention features a unique nucleus-inducing layer that guides the crystal growth of the gradient wear-resistant glaze layer, giving the glaze layer a metal-like stress dispersion capability, fundamentally improving wear resistance. Furthermore, the gradient wear-resistant glaze layer of this invention employs a layered design of a lower high-transparency glaze and an upper nano-reinforced glaze, providing high hardness while forming a refractive index gradient interface, breaking through the light scattering bottleneck of homogeneous glaze layers. For the first time, through the synergistic structural design of the "nucleus-inducing layer + gradient wear-resistant glaze layer," a unity of wear resistance and optical performance is achieved, solving the long-standing industry problem of "high-hardness materials leading to decreased light transmittance and color distortion."

Description

Technical Field

[0001] This invention belongs to the field of ceramic glazes, specifically a wear-resistant polished glazed tile with good color development and strong transparency, and its preparation process. Background Technology

[0002] As a mainstream product in modern architectural ceramics, the core performance indicators of glazed tiles are concentrated in two dimensions: glaze decorative effect and physical durability. In terms of decorative performance, high transparency (light transmittance ≥ 85%) and vibrant color (ΔE ≤ 1.5) are key requirements for high-end products; while in terms of physical performance, Mohs hardness ≥ 5 and abrasion resistance ≥ 4 (tested according to GB / T3810.7 standard) are basic requirements to ensure service life. However, under the current technological system, these two types of performance have an inherent contradiction that is difficult to reconcile.

[0003] Firstly, the high-silica transparent glaze system with SiO2 as the main component improves light transmittance by reducing the Al2O3 content. However, the excessive proportion of the glass phase results in a glaze layer with a microhardness of only 4-5, and a maximum wear resistance of only 2100 revolutions (level 4). More seriously, the excessive glass phase is prone to generating microcracks during polishing, becoming stress concentration points.

[0004] Secondly, by increasing the Al2O3 content in the high-alumina wear-resistant glaze system, a corundum phase can be formed to improve hardness (6-7 level). However, the refractive index of Al2O3 is significantly higher than that of the glass matrix, causing light scattering and causing the transmittance to drop sharply to below 70%. At the same time, it suppresses the color development of color-emitting ions (color saturation ΔE > 2.0).

[0005] Existing technologies generally employ a three-layer structure of "base glaze + colorant layer + transparent glaze" in an attempt to reconcile the inherent contradictions, but this has also exposed new problems. Firstly, the coefficient of thermal expansion (CTE) of each layer differs by more than 15% (e.g., the base glaze layer has a CTE of 7.5 × 10⁻⁻⁻⁴). 6 / K, transparent glaze CTE 5.8×10⁻ 6 During firing and cooling, the interfacial shear stress exceeds 28 MPa, easily inducing microcracks (detection rate ≥12%). Secondly, existing technologies improve the bonding between glaze layers by adding a transition layer (such as ZrSiO4), which increases scattering and causes light transmission loss. Finally, the thickness of the wear-resistant layer is limited; when the thickness of the high-alumina wear-resistant layer is >100 μm, the light transmittance deteriorates, but when it is <50 μm, the wear resistance is less than 6000 revolutions.

[0006] Therefore, there is an urgent need to develop an innovative glaze structure and preparation process to control crystal phase growth and interface behavior at the molecular scale, fundamentally solving the contradiction between transparency and wear resistance. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a wear-resistant glazed tile with good color development and high transparency, as well as its preparation process.

[0008] A wear-resistant glazed tile with good color development and strong transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a gradient wear-resistant glaze layer.

[0009] Preferably, the body layer is a conventional ceramic body. More preferably, the whiteness of the body layer is ≥68% to ensure the pure color of the glaze and avoid the yellowing of the body interfering with the glaze color.

[0010] Preferably, the base glaze layer is a conventional monochrome glaze, which is printed by inkjet printing onto the body layer and has a thickness of 50-100 μm; more preferably, the base glaze layer is a conventional monochrome glaze with 9-11 wt% ZrO2 added, which is printed by inkjet printing onto the body layer and has a thickness of 50-80 μm.

[0011] Because the ceramic body contains impurities such as Fe2O3, some light is absorbed by the body, while some is diffusely reflected. This leads to a mismatch in refractive indices between the ceramic body and the glaze, resulting in a grayish glaze color and reduced saturation. Therefore, a base glaze layer is needed to shield the body from light. ZrO2 has a significantly higher refractive index than the glaze glass matrix, achieving efficient light shielding through Mie scattering. Compared to traditional zircon (ZrSiO4) light-shielding agents, the amount of pure ZrO2 required is greatly reduced.

[0012] Preferably, the inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, thereby enhancing the aesthetics of the tile.

[0013] Preferably, the glaze formulation of the nucleation induction layer, by mass percentage, consists of the following raw materials: 67-69wt% SiO2, 7-9wt% Al2O3, 3-5wt% ZnO, 1-3wt% barium titanate, 1-2wt% silicon carbide whiskers, 11-13wt% potassium sodium feldspar, 3-4wt% polyacrylate emulsion, and 1-2wt% sodium carboxymethyl cellulose, and the thickness of the nucleation induction layer is 70-90μm.

[0014] Preferably, the gradient wear-resistant glaze layer comprises a lower high-transparency glaze and an upper nano-reinforced glaze.

[0015] More preferably, the glaze formula of the lower high-transparency glaze, by mass percentage, consists of the following raw materials: 40-45wt% zirconium silicate, 30-35wt% quartz glass powder, 8-12wt% lithium oxide, 5-8wt% barium oxide, 1-3wt% yttrium oxide, and 2-4wt% aluminum oxide.

[0016] The glaze formula of the upper nano-reinforced glaze, by mass percentage, consists of the following raw materials: 35-40wt% yttrium-stabilized zirconium oxide, 10-15wt% silicon carbide whiskers, 5-8wt% boron nitride nanosheets, 20-40wt% zirconium silicate, 3-5wt% cerium oxide, and 1-2wt% cobalt molybdate.

[0017] To achieve high hardness, traditional wear-resistant glazes must contain a large number of hard particles (such as zirconium oxide and corundum). These particles are piled up in a disordered manner, like countless small mirrors facing different directions. When light hits them, it is reflected (scattered) everywhere, resulting in the glaze surface becoming white, hazy, and opaque (low light transmittance).

[0018] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0019] (1) A base glaze with a thickness of 50-70μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0020] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0021] (3) A 70-90μm thick crystal nucleation induction layer glaze is applied to the inkjet printing layer by inkjet printing and dried to obtain the crystal nucleation induction layer;

[0022] (4) A layer of high-transparency glaze with a thickness of 30-50 μm is first coated on the nucleus induction layer by inkjet printing. After drying, a layer of nano-reinforced glaze with a thickness of 30-50 μm is then coated on the nucleus induction layer. After drying, a gradient wear-resistant glaze layer is obtained.

[0023] (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0024] The beneficial effects of this invention are:

[0025] This invention features a unique nucleus-inducing layer that guides crystal growth in a gradient wear-resistant glaze layer, giving the glaze layer a metal-like stress-dispersing ability and fundamentally improving wear resistance. Furthermore, the gradient wear-resistant glaze layer employs a layered design with a lower high-transparency glaze and an upper nano-reinforced glaze, providing high hardness while forming a refractive index gradient interface, overcoming the light scattering bottleneck of homogeneous glaze layers. For the first time, through the synergistic structural design of the "nucleus-inducing layer + gradient wear-resistant glaze layer," a unified approach to wear resistance and optical performance is achieved, solving the long-standing industry problem of "high-hardness materials leading to decreased light transmittance and color distortion." Existing technologies, by simply increasing the glaze layer thickness or modifying a single component, cannot simultaneously optimize wear resistance and light transmittance. The synergistic structural design of the "nucleus-inducing layer + gradient wear-resistant glaze layer" far exceeds the expectations of simply adding components together. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below through embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be prepared by known methods.

[0028] Polyacrylate emulsion: Product No.: EFKA FL 3772, Shanghai Zhenlishi Network Technology Co., Ltd.

[0029] Sodium carboxymethyl cellulose: CAS: 9004-32-4.

[0030] Quartz glass powder, grade: SF96, produced by Lingshou County Shunlei Mineral Products Processing Plant.

[0031] Yttrium stabilized zirconia: Item No.: R30Y8, Hangzhou Jiupeng New Materials Co., Ltd.

[0032] Silicon carbide whiskers, brand name: DH-SIC, Dinghong (Shanghai) New Materials Technology Co., Ltd.

[0033] Boron nitride nanosheets: Product No.: XH-BN-100, Shanghai Xiaohuang Nanotechnology Co., Ltd.

[0034] Example 1

[0035] A wear-resistant glazed tile with good color development and strong transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a gradient wear-resistant glaze layer.

[0036] The green body layer is a conventional ceramic green body with a whiteness of 70%.

[0037] The base glaze layer is a conventional monochrome glaze with 10wt% ZrO2 added, and is printed on the body layer by inkjet printing, with a thickness of 60μm.

[0038] The inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, which enhances the aesthetics of the tile.

[0039] The glaze formula of the nucleation induction layer, by mass percentage, consists of the following raw materials: 68wt% SiO2, 8wt% Al2O3, 4wt% ZnO, 2wt% barium titanate, 1.5wt% silicon carbide whiskers, 12wt% potassium sodium feldspar, 3.2wt% polyacrylate emulsion, and 1.3wt% sodium carboxymethyl cellulose. The thickness of the nucleation induction layer is 80μm.

[0040] The gradient wear-resistant glaze layer comprises a lower high-transparency glaze and an upper nano-reinforced glaze.

[0041] The glaze formula of the lower high-transparency glaze, by mass percentage, consists of the following raw materials: 43wt% zirconium silicate, 34wt% quartz glass powder, 10wt% lithium oxide, 7wt% barium oxide, 3wt% yttrium oxide, and 3wt% aluminum oxide.

[0042] The glaze formula of the upper nano-reinforced glaze, by mass percentage, consists of the following raw materials: 40wt% yttrium-stabilized zirconium oxide, 13wt% silicon carbide whiskers, 6wt% boron nitride nanosheets, 35wt% zirconium silicate, 4wt% cerium oxide, and 2wt% cobalt molybdate.

[0043] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0044] (1) A base glaze with a thickness of 60μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0045] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0046] (3) A nucleation induction layer glaze with a thickness of 80μm is applied to the inkjet printing layer and dried to obtain the nucleation induction layer;

[0047] (4) A layer of high-transparency glaze with a thickness of 40 μm is first coated on the nucleus induction layer by inkjet printing. After drying, a layer of nano-reinforced glaze with a thickness of 40 μm is then coated on the top layer. After drying, a gradient wear-resistant glaze layer is obtained.

[0048] (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0049] Example 2

[0050] A wear-resistant glazed tile with good color development and strong transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, and a gradient wear-resistant glaze layer.

[0051] The green body layer is a conventional ceramic green body with a whiteness of 70%.

[0052] The base glaze layer is a conventional monochrome glaze with 10wt% ZrO2 added, and is printed on the body layer by inkjet printing, with a thickness of 60μm.

[0053] The inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, which enhances the aesthetics of the tile.

[0054] The gradient wear-resistant glaze layer comprises a lower high-transparency glaze and an upper nano-reinforced glaze.

[0055] The glaze formula of the lower high-transparency glaze, by mass percentage, consists of the following raw materials: 43wt% zirconium silicate, 34wt% quartz glass powder, 10wt% lithium oxide, 7wt% barium oxide, 3wt% yttrium oxide, and 3wt% aluminum oxide.

[0056] The glaze formula of the upper nano-reinforced glaze, by mass percentage, consists of the following raw materials: 40wt% yttrium-stabilized zirconium oxide, 13wt% silicon carbide whiskers, 6wt% boron nitride nanosheets, 35wt% zirconium silicate, 4wt% cerium oxide, and 2wt% cobalt molybdate.

[0057] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0058] (1) A base glaze with a thickness of 60μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0059] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0060] (3) Using inkjet printing, a layer of high-transparency glaze with a thickness of 40μm is first covered on the inkjet printing layer, and after drying, a layer of nano-reinforced glaze with a thickness of 40μm is then covered on the inkjet printing layer. After drying, a gradient wear-resistant glaze layer is obtained.

[0061] (4) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0062] Example 3

[0063] A wear-resistant glazed tile with good color development and strong transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a wear-resistant glaze layer.

[0064] The green body layer is a conventional ceramic green body with a whiteness of 70%.

[0065] The base glaze layer is a conventional monochrome glaze with 10wt% ZrO2 added, and is printed on the body layer by inkjet printing, with a thickness of 60μm.

[0066] The inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, which enhances the aesthetics of the tile.

[0067] The glaze formula of the nucleation induction layer, by mass percentage, consists of the following raw materials: 68wt% SiO2, 8wt% Al2O3, 4wt% ZnO, 2wt% barium titanate, 1.5wt% silicon carbide whiskers, 12wt% potassium sodium feldspar, 3.2wt% polyacrylate emulsion, and 1.3wt% sodium carboxymethyl cellulose. The thickness of the nucleation induction layer is 80μm.

[0068] The wear-resistant glaze is made by mixing the glaze of the lower high-transparency glaze and the glaze of the upper nano-reinforced glaze in a mass ratio of 1:1.

[0069] The glaze formula of the lower high-transparency glaze, by mass percentage, consists of the following raw materials: 43wt% zirconium silicate, 34wt% quartz glass powder, 10wt% lithium oxide, 7wt% barium oxide, 3wt% yttrium oxide, and 3wt% aluminum oxide.

[0070] The glaze formula of the upper nano-reinforced glaze, by mass percentage, consists of the following raw materials: 40wt% yttrium-stabilized zirconium oxide, 13wt% silicon carbide whiskers, 6wt% boron nitride nanosheets, 35wt% zirconium silicate, 4wt% cerium oxide, and 2wt% cobalt molybdate.

[0071] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0072] (1) A base glaze with a thickness of 60μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0073] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0074] (3) A nucleation induction layer glaze with a thickness of 80μm is applied to the inkjet printing layer and dried to obtain the nucleation induction layer;

[0075] (4) A wear-resistant glaze layer with a thickness of 80 μm is printed on the nucleus induction layer by inkjet printing and dried to obtain the wear-resistant glaze layer;

[0076] (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0077] Example 4

[0078] A wear-resistant glazed tile with good color development and strong transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a gradient wear-resistant glaze layer.

[0079] The green body layer is a conventional ceramic green body with a whiteness of 70%.

[0080] The base glaze layer is a conventional monochrome glaze with 10wt% ZrO2 added, and is printed on the body layer by inkjet printing, with a thickness of 60μm.

[0081] The inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, which enhances the aesthetics of the tile.

[0082] The glaze formula of the nucleation induction layer, by mass percentage, consists of the following raw materials: 68wt% SiO2, 8wt% Al2O3, 4wt% ZnO, 2wt% barium titanate, 1.5wt% silicon carbide whiskers, 12wt% potassium sodium feldspar, 3.2wt% polyacrylate emulsion, and 1.3wt% sodium carboxymethyl cellulose. The thickness of the nucleation induction layer is 40μm.

[0083] The gradient wear-resistant glaze layer comprises a lower high-transparency glaze and an upper nano-reinforced glaze.

[0084] The glaze formula of the lower high-transparency glaze, by mass percentage, consists of the following raw materials: 43wt% zirconium silicate, 34wt% quartz glass powder, 10wt% lithium oxide, 7wt% barium oxide, 3wt% yttrium oxide, and 3wt% aluminum oxide.

[0085] The glaze formula of the upper nano-reinforced glaze, by mass percentage, consists of the following raw materials: 40wt% yttrium-stabilized zirconium oxide, 13wt% silicon carbide whiskers, 6wt% boron nitride nanosheets, 35wt% zirconium silicate, 4wt% cerium oxide, and 2wt% cobalt molybdate.

[0086] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0087] (1) A base glaze with a thickness of 60μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0088] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0089] (3) A 40μm thick crystal nucleation induction layer glaze is applied to the inkjet printing layer by inkjet printing and dried to obtain the crystal nucleation induction layer;

[0090] (4) A layer of high-transparency glaze with a thickness of 40 μm is first coated on the nucleus induction layer by inkjet printing. After drying, a layer of nano-reinforced glaze with a thickness of 40 μm is then coated on the top layer. After drying, a gradient wear-resistant glaze layer is obtained.

[0091] (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0092] Example 5

[0093] A wear-resistant glazed tile with good color development and strong transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a gradient wear-resistant glaze layer.

[0094] The green body layer is a conventional ceramic green body with a whiteness of 70%.

[0095] The base glaze layer is a conventional monochrome glaze with 10wt% ZrO2 added, and is printed on the body layer by inkjet printing, with a thickness of 60μm.

[0096] The inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, which enhances the aesthetics of the tile.

[0097] The glaze formula of the nucleation induction layer, by mass percentage, consists of the following raw materials: 68wt% SiO2, 8wt% Al2O3, 4wt% ZnO, 2wt% barium titanate, 1.5wt% silicon carbide whiskers, 12wt% potassium sodium feldspar, 3.2wt% polyacrylate emulsion, and 1.3wt% sodium carboxymethyl cellulose. The thickness of the nucleation induction layer is 80μm.

[0098] The gradient wear-resistant glaze layer comprises a lower high-transparency glaze and an upper nano-reinforced glaze.

[0099] The glaze formula of the lower high-transparency glaze, by mass percentage, consists of the following raw materials: 43wt% zirconium silicate, 34wt% quartz glass powder, 10wt% lithium oxide, 7wt% barium oxide, 3wt% yttrium oxide, and 3wt% aluminum oxide.

[0100] The glaze formula of the upper nano-reinforced glaze, by mass percentage, consists of the following raw materials: 40wt% yttrium-stabilized zirconium oxide, 13wt% silicon carbide whiskers, 6wt% boron nitride nanosheets, 35wt% zirconium silicate, 4wt% cerium oxide, and 2wt% cobalt molybdate.

[0101] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0102] (1) A base glaze with a thickness of 60μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0103] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0104] (3) A nucleation induction layer glaze with a thickness of 80μm is applied to the inkjet printing layer and dried to obtain the nucleation induction layer;

[0105] (4) A layer of high-transparency glaze with a thickness of 40 μm is first coated on the nucleus induction layer by inkjet printing. After drying, a layer of nano-reinforced glaze with a thickness of 120 μm is then coated on the top layer. After drying, a gradient wear-resistant glaze layer is obtained.

[0106] (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0107] Comparative Example 1

[0108] Referring to Example 3 disclosed in CN115536272B, a preparation process for a wear-resistant glazed tile with good color development, strong transparency, and high hardness includes the following steps:

[0109] A. Prepare ceramic blanks, press them, dry them, and then spray them with water to obtain the body layer; the water spraying amount in the water spraying step is 100g / m³. 2 ;

[0110] G. Apply a base glaze to form a base glaze layer; wherein the amount of base glaze applied is 300g / m². 2 According to the mass fraction, the raw materials of the base glaze include 30 parts potassium feldspar, 10 parts sodium feldspar, 3 parts washed kaolin, 10 parts calcined kaolin, 5 parts quartz, 5 parts calcined alumina, 3 parts talc, 2 parts limestone, and 5 parts zirconium silicate.

[0111] B. Spraying a color-enhancing protective glaze, which dries to form a color-enhancing protective glaze layer; wherein, calculated by mass percentage, the chemical composition of the color-enhancing protective glaze includes SiO2 70%, Al2O3 4%, K2O 5.5%, Na2O 2.4%, CaO 9.4%, MgO 2.8% and ZnO 5.6%, with the balance being other trace oxides;

[0112] C. Print colored ink according to the preset pattern to form an inkjet printing layer;

[0113] F. Print according to the preset pattern with an inkjet volume of 50g / m³. 2 The fine engraving ink forms a fine engraving ink layer;

[0114] D. Apply a high-temperature wear-resistant transparent glaze to form a high-temperature wear-resistant transparent glaze layer; wherein, the amount of high-temperature wear-resistant transparent glaze applied is 600g / m². 2 According to mass percentage, the chemical composition of the high-temperature wear-resistant transparent glaze includes 78% SiO2, 35% Al2O3, 1.5% K2O, 0.5% Na2O, 10.5% CaO, 0.2% MgO, 1% BaO, and 3% ZnO, with the balance being other trace oxides.

[0115] E. After drying, the product is fired in a kiln and then polished to obtain the wear-resistant glazed brick with good color, strong transparency, and high hardness.

[0116] Comparative Example 2

[0117] A wear-resistant glazed tile with good color development and strong transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a nano-reinforced glaze layer.

[0118] The green body layer is a conventional ceramic green body with a whiteness of 70%.

[0119] The base glaze layer is a conventional monochrome glaze with 10wt% ZrO2 added, and is printed on the body layer by inkjet printing, with a thickness of 60μm.

[0120] The inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, which enhances the aesthetics of the tile.

[0121] The glaze formula of the nucleation induction layer, by mass percentage, consists of the following raw materials: 68wt% SiO2, 8wt% Al2O3, 4wt% ZnO, 2wt% barium titanate, 1.5wt% silicon carbide whiskers, 12wt% potassium sodium feldspar, 3.2wt% polyacrylate emulsion, and 1.3wt% sodium carboxymethyl cellulose. The thickness of the nucleation induction layer is 80μm.

[0122] The glaze formula of the nano-reinforced glaze layer, by mass percentage, consists of the following raw materials: 40wt% yttrium-stabilized zirconium oxide, 13wt% silicon carbide whiskers, 6wt% boron nitride nanosheets, 35wt% zirconium silicate, 4wt% cerium oxide, and 2wt% cobalt molybdate.

[0123] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0124] (1) A base glaze with a thickness of 60μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0125] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0126] (3) A nucleation induction layer glaze with a thickness of 80μm is applied to the inkjet printing layer and dried to obtain the nucleation induction layer;

[0127] (4) A nano-reinforced glaze with a thickness of 80 μm was printed on the nucleus induction layer by inkjet printing and dried to obtain the nano-reinforced glaze layer.

[0128] (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0129] Comparative Example 3

[0130] A wear-resistant glazed tile with good color development and high transparency includes, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a high-transparency glaze layer.

[0131] The green body layer is a conventional ceramic green body with a whiteness of 70%.

[0132] The base glaze layer is a conventional monochrome glaze with 10wt% ZrO2 added, and is printed on the body layer by inkjet printing, with a thickness of 60μm.

[0133] The inkjet printing layer is printed with colored ink according to a preset pattern to form an inkjet printing layer, which enhances the aesthetics of the tile.

[0134] The glaze formula of the nucleation induction layer, by mass percentage, consists of the following raw materials: 68wt% SiO2, 8wt% Al2O3, 4wt% ZnO, 2wt% barium titanate, 1.5wt% silicon carbide whiskers, 12wt% potassium sodium feldspar, 3.2wt% polyacrylate emulsion, and 1.3wt% sodium carboxymethyl cellulose. The thickness of the nucleation induction layer is 80μm.

[0135] The glaze formula of the high-transparency glaze layer, by mass percentage, consists of the following raw materials: 43wt% zirconium silicate, 34wt% quartz glass powder, 10wt% lithium oxide, 7wt% barium oxide, 3wt% yttrium oxide, and 3wt% aluminum oxide.

[0136] A preparation process for a wear-resistant glazed tile with good color development and strong translucency includes the following steps:

[0137] (1) A base glaze with a thickness of 60μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer;

[0138] (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying;

[0139] (3) A nucleation induction layer glaze with a thickness of 80μm is applied to the inkjet printing layer and dried to obtain the nucleation induction layer;

[0140] (4) A high-transparency glaze layer with a thickness of 80μm is printed on the nucleus induction layer by inkjet printing and dried to obtain the high-transparency glaze layer;

[0141] (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

[0142] Test Example 1

[0143] Abrasion resistance test: The abrasion resistance of the polished glaze of the example and comparative glaze was tested according to the test method in GB / T3810.7-2016 Ceramic Tile Test Methods Part 7: Determination of Abrasion Resistance of Glazed Tile Surface. 240-grit sandpaper was fixed to a 1kg counterweight and rubbed back and forth at a frequency of 50 times / minute. The number of rubbing times that resulted in the first visible scratch was recorded.

[0144] Mohs hardness: Place the sample brick stably on a hard support with the finished surface facing up. Select standard minerals with different Mohs values ​​from low to high to scratch the sample surface. Apply force evenly and vertically to scratch the sample surface with a fresh cutting edge of the mineral. The lowest hardness value that just produces a noticeable scratch is taken as the test result. The lowest value among all test values ​​of the sample is the test result.

[0145] The results of the wear resistance test are shown in Table 1;

[0146] Table 1: Test Results of Wear Resistance Performance

[0147]

[0148] Test Example 2

[0149] The color difference of the glazed tiles prepared in the examples and comparative examples was determined according to the test methods in GB / T 3810.16-2016 "Test Methods for Ceramic Tiles - Part 16: Determination of Small Color Differences";

[0150] The results of the optical performance tests are shown in Table 2.

[0151] Table 1: Optical Performance Test Results

[0152]

[0153] As can be seen from Tables 1 and 2, the glazed tile prepared in Example 1 of this invention exhibits the best wear resistance, Mohs hardness, and optical properties. This invention attributes this to the synergistic effect of the nucleation-inducing layer and the gradient wear-resistant glaze. Example 2 lacks a nucleation-inducing layer, resulting in direct contact between the inkjet layer and the wear-resistant glaze, leading to refractive index mismatch and intensified light scattering. The nucleation-inducing layer helps balance the refractive indices between the inkjet layer and the gradient wear-resistant glaze layer, thereby reducing color difference. Furthermore, the absence of a nucleation-inducing layer results in disordered crystal growth in the gradient wear-resistant glaze layer, a loose glaze structure, and a significant decrease in wear resistance.

[0154] Example 3: The glaze of the lower high-transparency glaze and the upper nano-reinforced glaze are mixed as a wear-resistant glaze layer. This disrupts the gradient design, the hard phase (such as ZrO2) is unevenly distributed, stress concentration causes microcracks, and disordered phase interfaces are easily formed, resulting in disordered optical paths and a significant increase in ΔE.

[0155] Example 4 reduced the thickness of the nucleation-inducing layer, resulting in a decrease in both wear resistance and optical properties compared to Example 1. This indicates that the thickness of the nucleation-inducing layer significantly affects the performance of the gradient wear-resistant glaze layer. During high-temperature sintering, a thinner nucleation-inducing layer is less likely to effectively influence the crystal arrangement of the gradient wear-resistant glaze layer, or its diffusion properties may be insufficient to penetrate the lower high-transparency glaze, thus affecting the upper nano-reinforced glaze. Therefore, the performance of Example 4 is reduced.

[0156] Example 5 increased the thickness of the upper nano-reinforced glaze layer, which produced the opposite result to the traditional method of increasing wear resistance by increasing the thickness of the glaze layer. Its performance also decreased compared to Example 1. The present invention believes that this is because the nucleation-inducing layer has difficulty in affecting the glaze of the excessively thick upper nano-reinforced glaze, resulting in a decrease in its wear resistance and Mohs hardness. Moreover, the thicker nano-reinforced glaze layer has a significant impact on optical properties. Therefore, the appropriate thickness of the nucleation-inducing layer and the gradient wear-resistant glaze layer have a significant impact on the balanced optical properties and wear resistance of glazed tiles.

[0157] Comparative Example 1 lacks nucleation induction and gradient design, resulting in wear resistance limited by the homogeneous glaze layer. Furthermore, the traditional structure lacks a refractive index gradient, leading to significant light loss. For instance, Example 3, using a mixed glaze, exhibits a marked decrease in optical performance compared to Example 1. The data here clearly demonstrate that the present invention utilizes the synergistic effect of a nucleation induction layer and a gradient wear-resistant glaze, overcoming the traditional ceramic contradiction of "high wear resistance requiring high-hardness materials (high refractive index)" and "high light transmittance requiring low refractive index," thus achieving a balance between wear resistance and light transmittance.

[0158] Comparative Example 2 uses a single nano-reinforced glaze layer, which improves hardness, but the refractive index does not match the inkjet layer, resulting in a deterioration of ΔE. Comparative Example 3 uses a single high-transparency glaze layer, which has a better refractive index match, but the hardness is insufficient and the wear resistance is poor, indirectly affecting the surface smoothness and increasing ΔE, making it difficult to achieve a balance between wear resistance and light transmittance.

Claims

1. A wear-resistant glazed tile with good color development and strong transparency, comprising, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a crystal nucleation induction layer, and a gradient wear-resistant glaze layer; The glaze formula of the crystal nucleus inducing layer consists of the following raw materials in percentage by mass: The composition is 67-69 wt% SiO2, 7-9 wt% Al2O3, 3-5 wt% ZnO, 1-3 wt% barium titanate, 1-2 wt% silicon carbide whiskers, 11-13 wt% potassium sodium feldspar, 3-4 wt% polyacrylate emulsion, and 1-2 wt% sodium carboxymethyl cellulose. The thickness of the nucleation-inducing layer is 70-90 μm. The gradient wear-resistant glaze layer includes a lower high-transparency glaze and an upper nano-reinforced glaze. The glaze formula of the lower high-transparency glaze, by mass percentage, consists of the following raw materials: 40-45wt% zirconium silicate, 30-35wt% quartz glass powder, 8-12wt% lithium oxide, 5-8wt% barium oxide, 1-3wt% yttrium oxide, and 2-4wt% aluminum oxide. The glaze formula of the upper nano-reinforced glaze, by mass percentage, consists of the following raw materials: 35-40wt% yttrium-stabilized zirconium oxide, 10-15wt% silicon carbide whiskers, 5-8wt% boron nitride nanosheets, 20-40wt% zirconium silicate, 3-5wt% cerium oxide, and 1-2wt% cobalt molybdate. The thickness of the base glaze layer is 50-100 μm; the thickness of the nucleation-inducing layer is 70-90 μm; the thickness of the lower high-transparency glaze is 30-50 μm; and the thickness of the upper nano-reinforced glaze is 30-50 μm.

2. The wear-resistant glazed tile with good color development and strong translucency as described in claim 1, characterized in that, The blank layer is a conventional ceramic blank.

3. The wear-resistant glazed tile with good color development and strong translucency as described in claim 1, characterized in that, The base glaze layer is a conventional monochrome glaze, which is printed by inkjet printing to cover the body layer, with a thickness of 50-100μm.

4. A preparation process for a wear-resistant glazed tile with good color development and strong translucency as described in any one of claims 1-3, characterized in that, Includes the following steps: (1) A base glaze with a thickness of 50-100μm is applied to the ceramic body by inkjet printing and dried to form a base glaze layer; (2) Print colored ink on the base glaze layer according to the preset pattern, and form an inkjet printing layer after drying; (3) A 70-90μm thick crystal nucleation induction layer glaze is applied to the inkjet printing layer by inkjet printing and dried to obtain the crystal nucleation induction layer; (4) A layer of high-transparency glaze with a thickness of 30-50 μm is first coated on the nucleus induction layer by inkjet printing. After drying, a layer of nano-reinforced glaze with a thickness of 30-50 μm is then coated on the nucleus induction layer. After drying, a gradient wear-resistant glaze layer is obtained. (5) After firing in a kiln and polishing, the wear-resistant glazed brick with good color and strong transparency is obtained.

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