A kind of sapphire-effect dry granules, a ceramic tile with an imitation sapphire effect and a preparation method thereof

Abstract

The present invention relates to the field of architectural ceramics and discloses sapphire-effect dry particles, tiles with a simulated sapphire effect, and methods for preparing the same. The sapphire-effect dry particles include blue dry particles and transparent dry particles. The raw materials for the blue dry particles include: 1.5-3.5 parts ultrafine tin dioxide, 15-19.5 parts cobalt oxide, 4.5-7.5 parts titanium oxide, 8-14 parts zinc oxide, 32-43 parts calcined aluminum oxide, 8-13 parts quartz, 10-16 parts potassium feldspar, and 2.5-4.5 parts boric acid; the raw materials for the transparent dry particles include: 8-15 parts zinc oxide, 5-10 parts aluminum oxide, 24-28 parts quartz, 1-2.5 parts nano-silicon nitride, and 7-11 parts cryolite. By mixing the two dry particles, frit dry particles with a three-dimensional effect and an ice-cracked texture, imitating the texture of sapphire crystals, can be prepared. The sapphire-effect dry particles can be used to prepare tiles with a simulated sapphire effect.

Description

Technical Field

[0001] The invention relates to the field of building ceramics, in particular to sapphire-effect dry particles, ceramic tiles with imitation sapphire effects and a preparation method thereof. Background Art

[0002] Currently, imitation marble tiles are typically manufactured using scanned patterns of marble, often only replicating the surface texture and failing to perfectly reproduce the crystalline quality of natural stone. Precious stones like sapphire are particularly difficult to replicate in ceramic products, as they lack the ability to create the sapphire-like three-dimensional texture and ice-crack effect achieved through glaze.

[0003] However, with rising consumer demand, the diversity of imitation marble tiles is facing challenges. Currently, blue glazed tiles are typically produced by adding cobalt blue pigment or blue ink to the glaze. This only allows for color depth adjustment and surface effects, but fails to truly reproduce the deep, three-dimensional, ice-cracked texture of sapphire. Therefore, a tile process that can create a sapphire-like effect is urgently needed to address this issue. Summary of the Invention

[0004] The main purpose of the present invention is to provide a sapphire effect dry particle, which can form a bright, thick and deep imitation sapphire color effect.

[0005] To achieve the above object, the present invention provides a sapphire effect dry particle, wherein the sapphire effect dry particle comprises: 85-90% blue dry particles and 10-15% transparent dry particles, based on the total weight of the sapphire effect dry particles as 100%;

[0006] The raw materials for preparing the blue dry particles include the following components in parts by weight: 1.5-3.5 parts of ultrafine tin dioxide, 15-19.5 parts of cobalt oxide, 4.5-7.5 parts of titanium oxide, 8-14 parts of zinc oxide, 32-43 parts of calcined aluminum oxide, 8-13 parts of quartz, 10-16 parts of potassium feldspar, and 2.5-4.5 parts of boric acid;

[0007] The raw materials for preparing the transparent dry particles include the following components in parts by weight: 8-15 parts of zinc oxide, 5-10 parts of aluminum oxide, 24-28 parts of quartz, 1-2.5 parts of nano silicon nitride and 7-11 parts of cryolite.

[0008] The present invention utilizes a mixture of blue dry particles and transparent dry particles to produce fritted dry particles with a three-dimensional effect and an ice-cracked texture that mimics sapphire crystals. The blue dry particles utilize cobalt oxide and calcined alumina to form a cobalt-blue coloring system, which is enhanced by ultrafine tin dioxide, titanium oxide, and boric acid to create a sapphire crystal effect. The transparent dry particles utilize a combination of cryolite and nano-silicon nitride to promote the formation of a blue dry particle melt while providing stable support during sintering and melting, maintaining the material boundaries of the blue dry particles and enhancing the visual texture of the blue dry particles, recreating the unique texture of authentic sapphire stone.

[0009] Preferably, in percentage by mass:

[0010] The chemical composition of the blue dry particles includes: SiO2 10.3-16.2%, Al2O3 35.3-46.2%, SnO2 1.6-4.2%, K2O 1.9-3.6%, ZnO 8.6-13.7%, B2O3 1.5-2.7%, CoO 14.3-22.3%, TiO2 5.9-12.6% and LOI 2.4-5.8%;

[0011] The chemical composition of the transparent dry particles includes: SiO2 45.3-56.2%, Al2O3 8.3-16.6%, ZnO 12.6-23.7%, Si3N4 1.6-4.2%, NaF 3.6-7.7% and LOI 4.4-6.8%.

[0012] Preferably, the blue dry particles are obtained by mixing the raw materials, melting them at 1250-1350° C., and water quenching and grinding, and the particle size distribution is: 10-20 mesh accounts for 45-60%, 20-40 mesh accounts for 25-30%, and 40-80 mesh accounts for 12-30%; the transparent dry particles are obtained by mixing the raw materials, melting them at 1300-1450° C., and water quenching and grinding, and the particle size is 400-600 mesh.

[0013] In a second aspect, the present invention also provides a ceramic tile with an imitation sapphire effect, which comprises a body layer, a base glaze layer, a pattern layer, a sapphire dry particle layer and a dry particle protective glaze layer in sequence; the sapphire dry particle layer is prepared using the sapphire effect dry particles as described above.

[0014] Preferably, the dry particle protective glaze layer is prepared from a dry particle protective glaze slurry; based on the total weight of the dry particle protective glaze slurry being 100%, the dry particle protective glaze slurry comprises 50-55% of protective dry particles and 45-50% of a dry particle suspending agent;

[0015] The raw materials for preparing the protective dry particles include the following components in parts by weight: 23-27 parts of potassium feldspar, 3-5 parts of calcined alumina, 10-15 parts of kaolin, 4-8 parts of zinc oxide and 8-13 parts of quartz;

[0016] The chemical composition of the protected dry particles, calculated by mass percentage, includes: SiO2 59.6-64.3%, Al2O3 14.9-18.6%, K2O 3.5-5.9%, ZnO 6.5-11.2% and LOI 4.1-7.5%.

[0017] The protected dry particles are obtained by mixing raw materials, melting them at 1300-1450° C., and then quenching and grinding them with water.

[0018] The dry particle protective glaze slurry is prepared with protective dry particles with a high viscosity formula and covered on the surface of the sapphire effect dry particles, which can further maintain the color texture of the sapphire effect dry particles and form a deep visual effect of gem inlay.

[0019] Preferably, the raw materials for preparing the base glaze layer include the following components in parts by weight: 5-10 parts of zinc oxide, 1-3 parts of barium carbonate, 15-20 parts of potassium feldspar, 10-15 parts of sodium feldspar, 1.5-3.5 parts of calcined talc, 1-3.5 parts of calcite, 13-19 parts of quartz, 5-8 parts of dolomite, 7-11 parts of calcined kaolin, 8.5-12 parts of washed kaolin and 6-12 parts of aluminum oxide;

[0020] The chemical composition of the base glaze layer, calculated by mass percentage, includes: SiO2 48.1-56.3%, Al2O3 16.3-19.1%, ZnO 5.9-10.7%, CaO 2.3-3.9%, MgO 1.9-4.8%, K2O 3.5-4.8%, Na2O 3.3-4.7%, BaO 0.6-1.6% and LOI 2.3-5.9%.

[0021] The base glaze's formula promotes stable color development in the sapphire effect layer.

[0022] Preferably, the raw materials for preparing the green body layer include the following components in parts by weight: 9.5-11.5 parts of raw ore mud, 1.3-3.5 parts of bentonite, 6.6-9.5 parts of kaolin, 8.5-11.5 parts of washed mud, 33.5-38.3 parts of stone powder, 16.2-22.3 parts of high-aluminum potassium sand and 1-3 parts of talc;

[0023] The chemical composition of the green body layer, calculated in percentage by mass, includes: SiO2 60.3-67.3%, Al2O3 19.7-23.2%, CaO 1.1-2.5%, MgO 0.2-0.8%, K2O 2.3-4.5%, Na2O 0.6-1.3%, Fe2O3 0.2-0.6% and LOI 3.3-7.6%.

[0024] In a third aspect, the present invention further provides a method for preparing the above-mentioned ceramic tile having an imitation sapphire effect, comprising the following steps:

[0025] S1, preparing a green body and obtaining a green body layer;

[0026] S2, applying a base glaze on the surface of the green body layer to obtain a base glaze layer;

[0027] S3, inkjet printing a color pattern on the surface of the base glaze layer to obtain a pattern layer;

[0028] S4, after inkjet printing positioning glue on the surface of the pattern layer, applying sapphire effect dry particles to obtain a sapphire dry particle layer;

[0029] S5, applying dry particle protective glaze slurry on the surface of the sapphire dry particle layer to obtain a dry particle protective glaze layer;

[0030] S6, sending the ceramic tile into a kiln for firing to obtain the ceramic tile with the imitation sapphire effect.

[0031] Preferably, in step S4, the amount of the positioning glue applied is 130-200 g / m 2 The printed pattern of the positioning glue accounts for 60-90%. The amount of the sapphire effect dry particles is controlled by the amount of positioning glue applied, thereby achieving a differentiated effect of different shades of blue crystals.

[0032] Preferably, in step S4, the amount of the sapphire effect dry particles applied is 200-360 g / m 2 .

[0033] Preferably, in step S5, the amount of dry particle protective glaze slurry applied is 450-600 g / m 2 , specific gravity is 1.50~1.55 g / mL.

[0034] Preferably, in step S6, the sintering process includes:

[0035] Preheating stage: heating rate is 25~35℃ / min, temperature range is room temperature~350℃;

[0036] Oxidation decomposition stage: heating rate is 30~40℃ / min, temperature range is 350~950℃;

[0037] High temperature stage: heating rate is 20~25℃ / min, temperature range is 950℃~maximum firing temperature;

[0038] High fire insulation stage: time 2~5min;

[0039] And cooling stage: the cooling rate in the temperature range from the highest firing temperature to 600℃ is 25~35℃ / min; the cooling rate in the temperature range from 600~500℃ is 15~20℃ / min; the cooling rate in the temperature range from 500℃ to room temperature is 35~40℃ / min;

[0040] The maximum firing temperature is 1150~1210℃.

[0041] The present invention selects a fast firing process that is more suitable for sapphire effect dry particles and dry particle protective glaze layer, and adopts a shorter high-temperature insulation stage to further coordinate the firing effect of the two mixed dry particles in the sapphire effect dry particles, so as to achieve a more perfect imitation sapphire texture. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0043] Figure 1 This is a physical diagram of Example 3;

[0044] Figure 2 This is a physical diagram of Comparative Example 4;

[0045] Figure 3 This is a physical picture of Comparative Example 5.

[0046] The realization of the objectives, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0047] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. It should be noted that the embodiments in this application and the features in the embodiments can be combined with each other unless there is a conflict. At the same time, the raw materials mentioned below that are not described in detail are all commercially available products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0048] The present invention provides a sapphire effect dry particle. Based on the total weight of the sapphire effect dry particle being 100%, the sapphire effect dry particle comprises 85-90% of blue dry particles and 10-15% of transparent dry particles.

[0049] Among them, the raw materials for preparing blue dry particles include the following components in parts by weight: 1.5-3.5 parts of ultrafine tin dioxide, 15-19.5 parts of cobalt oxide, 4.5-7.5 parts of titanium oxide, 8-14 parts of zinc oxide, 32-43 parts of calcined aluminum oxide, 8-13 parts of quartz, 10-16 parts of potassium feldspar and 2.5-4.5 parts of boric acid; the raw materials for preparing transparent dry particles include the following components in parts by weight: 8-15 parts of zinc oxide, 5-10 parts of aluminum oxide, 24-28 parts of quartz, 1-2.5 parts of nano-silicon nitride and 7-11 parts of cryolite.

[0050] The blue dry particles of the present invention are mainly composed of a cobalt blue coloring system formed by cobalt oxide and calcined aluminum oxide, which promotes the formation of a dark blue color in the glaze melt as a whole, and presents a sapphire crystal effect after rapid cooling and crushing. The ultrafine tin dioxide in the formula system accounts for a relatively small proportion, and it can still retain fine grains at a high temperature of 1280°C, forming a delicate and slightly opacified effect, presenting a thick and deep visual effect of the melt. It is particularly noted that the ultrafine tin dioxide described in the present invention specifically refers to particles with a particle size of 2000~2800 mesh. The tin dioxide at this particle size has better uniformity, presents a uniform translucent blue color after firing, and has a better decorative effect. The amount of titanium oxide added is regulated so that it is transformed into rutile crystals during high-temperature firing. This crystal form has an appearance such as cold ice, columnar or needle-like, and combines with the molten liquid phase quartz body to present a dense block crystal effect. It should be noted that excessive addition of titanium oxide powder may cause the glaze to form a rutile color, which affects the cobalt blue base color. Therefore, how to use titanium oxide to present a crystalline texture without affecting the royal blue color is a major problem to be solved by the present invention. The boric acid added to the formula acts as a mineralizer to promote the crystallization effect; zinc oxide promotes color development, making the cobalt blue color more vivid. Quartz powder and potassium feldspar provide a glass phase, which maintains the visual effect of the ice-like material after the melt is rapidly cooled. The transparent dry particles adopt a zinc-aluminum-silicon structure and will not affect the color of the blue dry particles. At the same time, the cryolite in the formula forms a complex ionic structure in the molten state and can interact with alumina. The aluminum ions and fluoride ions in the cryolite structure interact with the aluminum ions and cations in alumina to form relatively stable complex ions, thereby changing the crystal structure of alumina, causing it to melt at a lower temperature, and promoting the formation of a blue dry particle melt. At the same time, the three-dimensional lattice structure of nano-silicon nitride in the formula has high thermal stability at high temperatures. The nano-scale powder forms a uniform and stable support in the blue dry particle melt, ensuring that the blue dry particles and transparent dry particles can still maintain their respective material boundaries when fired into a molten state, thereby forming a unique imitation stone texture.

[0051] Furthermore, in terms of mass percentage:

[0052] The chemical composition of the blue dry granules includes: SiO2 10.3-16.2%, Al2O3 35.3-46.2%, SnO2 1.6-4.2%, K2O 1.9-3.6%, ZnO 8.6-13.7%, B2O3 1.5-2.7%, CoO 14.3-22.3%, TiO2 5.9-12.6%, and LOI 2.4-5.8%. The chemical composition of the transparent dry granules includes: SiO2 45.3-56.2%, Al2O3 8.3-16.6%, ZnO 12.6-23.7%, Si3N4 1.6-4.2%, NaF 3.6-7.7%, and LOI 4.4-6.8%. It should be noted that both the blue and transparent dry granules are prepared using the well-known frit process. In the present invention, the preparation process of blue dry granules includes: mixing the raw materials of blue dry granules, melting them in a high-temperature furnace at 1250-1350°C, rapidly cooling the melt, crushing and grinding it, and sieving it to the required mesh size. The particle size distribution of blue dry granules is: 10-20 mesh accounts for 45-60%, 20-40 mesh accounts for 25-30%, and 40-80 mesh accounts for 12-30%. The preparation process of transparent dry granules includes: mixing the raw materials of transparent dry granules, melting them in a high-temperature furnace at 1300-1450°C, rapidly cooling the melt, crushing and grinding it, and sieving it through a standard sieve of 400-600 mesh to obtain transparent dry granules. Strictly controlling the particle size of blue dry granules and transparent dry granules helps the two frits form a clearly defined crystalline texture through the mixing effect, presenting the jade-like texture of real stone.

[0053] The present invention also provides a ceramic tile with an imitation sapphire effect, which comprises a body layer, a base glaze layer, a pattern layer, a sapphire dry particle layer and a dry particle protective glaze layer in sequence; the sapphire dry particle layer is prepared using the sapphire effect dry particles described above.

[0054] Furthermore, the dry particle protective glaze layer is prepared from a dry particle protective glaze slurry; based on the total weight of the dry particle protective glaze slurry being 100%, the dry particle protective glaze slurry comprises 50-55% of protective dry particles and 45-50% of a dry particle suspension agent;

[0055] The raw materials for preparing the protected dry particles include the following components in parts by weight: 23-27 parts of potassium feldspar, 3-5 parts of calcined alumina, 10-15 parts of kaolin, 4-8 parts of zinc oxide and 8-13 parts of quartz; the chemical composition of the protected dry particles, in mass percentage, includes: SiO2 59.6-64.3%, Al2O3 14.9-18.6%, K2O 3.5-5.9%, ZnO 6.5-11.2% and LOI 4.1-7.5%.

[0056] The dry granule protective glaze slurry used in the present invention is mainly composed of high-viscosity protective dry particles. The viscosity under high-temperature firing is 7200-8100 Pa·s. At this viscosity, the molten sapphire-effect dry particles can maintain the particle shape of sapphires, ultimately presenting a gemstone-like visual effect. In addition, the formula of the protective dry particles uses a zinc-silicon system, which does not affect the color presentation of the sapphire-effect dry particles. The protective dry particles can also be prepared using a known frit preparation process. The raw materials for the protective dry particles are mixed and melted in a high-temperature furnace at 1300-1450°C. The melt is quenched and then crushed and ground. The fineness of the protective dry particles is controlled to 0.1-0.4% on a 325-mesh sieve. The dry particle suspending agent in the dry particle protective glaze slurry is a known commercially available suspending agent, such as the 9022A dry particle suspending agent provided by Jiangxi Qiantao New Materials Co., Ltd. The dry particle protective glaze slurry is applied on the sapphire dry particle layer. On the one hand, it plays a protective role. On the other hand, the dry particle protective glaze slurry covers the surface of the sapphire effect dry particles without affecting the color effect of the sapphire effect dry particles. At the same time, after firing, it presents a wrapping feeling that simulates the visual effect of gems inlaid inside, with a transparent texture.

[0057] Furthermore, the raw materials for preparing the underglaze layer include the following components in parts by weight: 5-10 parts of zinc oxide, 1-3 parts of barium carbonate, 15-20 parts of potassium feldspar, 10-15 parts of sodium feldspar, 1.5-3.5 parts of calcined talc, 1-3.5 parts of calcite, 13-19 parts of quartz, 5-8 parts of dolomite, 7-11 parts of calcined kaolin, 8.5-12 parts of washed kaolin and 6-12 parts of aluminum oxide; the chemical composition of the underglaze layer, in mass percentage, includes: SiO2 48.1-56.3%, Al2O3 16.3-19.1%, ZnO 5.9-10.7%, CaO 2.3-3.9%, MgO 1.9-4.8%, K2O 3.5-4.8%, Na2O 3.3-4.7%, BaO 0.6-1.6% and LOI 2.3-5.9%.

[0058] On the one hand, the base glaze creates a concealing effect on the body. On the other hand, the main flux in the formula is zinc oxide, which promotes the color development of the sapphire effect dry particles, ensuring that the sapphire effect dry particles present a bright and stable royal blue color.

[0059] Furthermore, the raw materials for preparing the green body layer include the following components in parts by weight: 9.5-11.5 parts of raw ore mud, 1.3-3.5 parts of bentonite, 6.6-9.5 parts of kaolin, 8.5-11.5 parts of washed mud, 33.5-38.3 parts of stone powder, 16.2-22.3 parts of high-aluminum potassium sand and 1-3 parts of talc; the chemical composition of the green body layer, in mass percentage, includes: SiO2 60.3-67.3%, Al2O3 19.7-23.2%, CaO 1.1-2.5%, MgO 0.2-0.8%, K2O 2.3-4.5%, Na2O 0.6-1.3%, Fe2O3 0.2-0.6% and LOI 3.3-7.6%.

[0060] The present invention also provides a method for preparing the ceramic tile having the imitation sapphire effect, comprising the following steps:

[0061] S1. Prepare a green body to obtain a green body layer; the pressing thickness of the green body can be 10.5~13mm.

[0062] S2, applying a base glaze on the surface of the body layer to obtain a base glaze layer;

[0063] S3, inkjet printing a color pattern on the surface of the base glaze layer to obtain a pattern layer;

[0064] S4, after inkjet printing positioning glue on the surface of the pattern layer, applying sapphire effect dry particles to obtain a sapphire dry particle layer;

[0065] S5, applying dry particle protective glaze slurry on the surface of the sapphire dry particle layer to obtain a dry particle protective glaze layer;

[0066] S6, sending the ceramic tile into a kiln for firing to obtain the ceramic tile with imitation sapphire effect.

[0067] In step S4, positioning glue is used to attach sapphire effect dry particles. The positioning glue is purchased from Foshan Yidajia Precision Ceramics Technology Co., Ltd. and is CIK-AD1109 glue. It is sprayed on the surface of the brick after the base glaze is applied by an inkjet machine. The amount of sprayed glue is preferably 130~200 g / m 2 The optimal proportion of the printed pattern with the positioning glue is 60-90%. By adjusting the amount of positioning glue, the number of sapphire effect dry particles in different positions can be adjusted to adjust the depth of the blue crystal effect after firing.

[0068] Optimally, in step S4, the amount of sapphire effect dry particles applied is 200-360 g / m 2 In step S5, the dry granular protective glaze slurry is applied in a conventional spray cabinet. By adjusting the swing frequency of the equipment, the application amount of the dry granular protective glaze slurry is preferably 450~600 g / m 2, specific gravity is 1.50~1.55 g / mL.

[0069] Furthermore, in step S6, the firing process includes:

[0070] Preheating stage: heating rate is 25~35℃ / min, temperature range is room temperature~350℃;

[0071] Oxidation decomposition stage: heating rate is 30~40℃ / min, temperature range is 350~950℃;

[0072] High temperature stage: heating rate is 20~25℃ / min, temperature range is 950℃~maximum firing temperature;

[0073] High fire insulation stage: time 2~5min;

[0074] And cooling stage: the cooling rate in the temperature range from the highest firing temperature to 600℃ is 25~35℃ / min; the cooling rate in the temperature range from 600~500℃ is 15~20℃ / min; the cooling rate in the temperature range from 500℃ to room temperature is 35~40℃ / min;

[0075] The maximum firing temperature is 1150~1210℃.

[0076] It should be noted that the above preparation method also includes the steps of polishing, waxing and edge grinding the fired tiles.

[0077] Since the glaze of the present invention mainly adopts frit glaze with small firing loss, a special fast firing process is adopted for the glaze system of the present invention to shorten the high-temperature heat preservation time to further match the firing effect after the blue dry particles and transparent dry particles in the sapphire effect dry particles are mixed.

[0078] The following examples are further listed to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific process parameters of the following examples are also only examples within a suitable range, that is, those skilled in the art can make selections within a suitable range through the description herein, and are not intended to be limited to the specific numerical values of the examples below. For those in the examples where specific conditions are not specified, proceed according to conventional conditions or the conditions recommended by the manufacturer.

[0079] Example 1

[0080] A ceramic tile with an imitation sapphire effect, the preparation method comprising the following steps:

[0081] S1. Prepare ceramic raw materials into a green body to obtain a green body layer; wherein the raw materials for preparing the green body layer include the following components in parts by weight: 10 parts of raw ore mud, 3 parts of bentonite, 7.5 parts of kaolin, 10 parts of washed mud, 34 parts of stone powder, 18 parts of high-aluminum potassium sand, and 2 parts of talc; the chemical composition of the green body layer, in mass percentage, includes SiO2 65.3%, Al2O3 21.7%, CaO 1.4%, MgO 0.3%, K2O 3.7%, Na2O 0.9%, Fe2O3 0.4%, and LOI 6.3%.

[0082] S2. Apply a ground glaze to the surface of the green body layer to form a ground glaze layer. The ground glaze (in this example, a conventional commercially available ground glaze) comprises the following components, by weight: 55 parts albite, 5 parts quartz, 16 parts calcined kaolin, 7 parts washed kaolin, 14 parts alumina, and 10 parts zirconium silicate. The chemical composition of the ground glaze layer, by weight percentage, is 52.4% SiO2, 23.5% Al2O3, 6.4% ZrO2, 12.3% Na2O, and 5.4% LOI.

[0083] S3, inkjet printing a color pattern on the surface of the base glaze layer to obtain a pattern layer;

[0084] S4. Inkjet print positioning glue on the surface of the pattern layer. The glue amount is 160 g / m 2 , the printing pattern accounts for 75%; the sapphire effect dry particles are applied, and the application amount is 230 g / m 2 , obtaining a sapphire dry particle layer; wherein the sapphire effect dry particles include 85% blue dry particles and 15% transparent dry particles;

[0085] The blue dry granules include the following components, by weight: 1.5 parts ultrafine tin dioxide, 15 parts cobalt oxide, 5.5 parts titanium oxide, 9 parts zinc oxide, 40 parts calcined alumina, 9 parts quartz, 11 parts potassium feldspar, and 2.5 parts boric acid. The chemical composition of the blue dry granules includes: SiO2 14.3%, Al2O3 43.7%, SnO2 2.1%, K2O 2.2%, ZnO 9.2%, B2O3 2.3%, CoO 14.7%, TiO2 6.0%, and LOI 5.5.

[0086] The raw materials of the blue dry particles are mixed evenly, melted at 1300° C., and then water-quenched and ground to prepare the blue dry particles with a particle size distribution of 50% for particles above 10-20 mesh, 30% for particles above 20-40 mesh, and 20% for particles above 40-80 mesh.

[0087] The transparent dry particles include the following components in parts by weight: 8 parts of zinc oxide, 6 parts of aluminum oxide, 28 parts of quartz, 2 parts of nano silicon nitride and 7 parts of cryolite.

[0088] The transparent dry granules are prepared by uniformly mixing the raw materials, melting them at 1350°C, quenching them with water, grinding them, and then passing them through a 400-mesh sieve. The chemical composition of the transparent dry granules includes: SiO2 55.3%, Al2O3 14.2%, ZnO 15.8%, Si3N4 3.9%, NaF 6.2%, and LOI 4.6%.

[0089] S5. Apply dry particle protective glaze slurry on the surface of the sapphire dry particle layer at a rate of 460 g / m 2 , with a specific gravity of 1.50 g / mL, to obtain a dry particle protective glaze layer; wherein the dry particle protective glaze slurry comprises 50% protective dry particles and 50% 9022A dry particle suspension;

[0090] The protected dry granules comprise the following components, measured by weight: 23 parts potassium feldspar, 5 parts calcined alumina, 10 parts kaolin, 7 parts zinc oxide, and 13 parts quartz. The chemical composition of the protected dry granules, measured by mass percentage, comprises: 62.2% SiO2, 17.5% Al2O3, 3.8% K2O, 9.9% ZnO, and 6.6% LOI.

[0091] The raw materials of the protected dry granules are mixed uniformly, melted at 1300° C., quenched with water, ground, and passed through a 325-mesh sieve with a residue of 0.1-0.4% to obtain the protected dry granules.

[0092] S6. Place the ceramic tile in a kiln for firing. The firing process is as follows: heating rate from room temperature to 350°C at 30°C / min; heating rate from 350°C to 950°C at 35°C / min; heating rate from 950°C to 1200°C at 25°C / min; holding temperature for 2 minutes; cooling rate from 1200°C to 600°C at 30°C / min; cooling rate from 600°C to 500°C at 15°C / min; and cooling rate from 500°C to room temperature at 35°C / min. This produces a ceramic tile with a sapphire-like effect.

[0093] Example 2

[0094] A ceramic tile with an imitation sapphire effect, the preparation method comprising the following steps:

[0095] S1. Prepare ceramic raw materials into a green body to obtain a green body layer; wherein the raw materials for preparing the green body layer include the following components in parts by weight: 10 parts of raw ore mud, 3 parts of bentonite, 7.5 parts of kaolin, 10 parts of washed mud, 34 parts of stone powder, 18 parts of high-aluminum potassium sand, and 2 parts of talc; the chemical composition of the green body layer, in mass percentage, includes SiO2 65.3%, Al2O3 21.7%, CaO 1.4%, MgO 0.3%, K2O 3.7%, Na2O 0.9%, Fe2O3 0.4%, and LOI 6.3%.

[0096] S2. Applying a ground glaze on the surface of the green body layer to form a ground glaze layer; wherein the ground glaze comprises the following components, by weight: 9 parts zinc oxide, 3 parts barium carbonate, 19 parts potassium feldspar, 15 parts sodium feldspar, 3.5 parts calcined talc, 2 parts calcite, 13 parts quartz, 5 parts dolomite, 7 parts calcined kaolin, 8.5 parts washed kaolin, and 7 parts aluminum oxide. The chemical composition of the ground glaze layer, by mass percentage, comprises: SiO2 53.3%, Al2O3 18.2%, ZnO 9.5%, CaO 2.9%, MgO 2.1%, K2O 3.9%, Na2O 3.5%, BaO 0.9%, and LOI 5.7%.

[0097] S3, inkjet printing a color pattern on the surface of the base glaze layer to obtain a pattern layer;

[0098] S4. Inkjet print positioning glue on the surface of the pattern layer. The glue amount is 130 g / m 2 , the printing pattern accounts for 60%; the sapphire effect dry particles are applied, and the application amount is 200 g / m 2 , obtaining a sapphire dry particle layer; wherein the sapphire effect dry particles include 90% blue dry particles and 10% transparent dry particles;

[0099] The blue dry granules include the following components, by weight: 3 parts ultrafine tin dioxide, 19 parts cobalt oxide, 7.5 parts titanium oxide, 14 parts zinc oxide, 33 parts calcined alumina, 13 parts quartz, 15 parts potassium feldspar, and 4.5 parts boric acid. The chemical composition of the blue dry granules includes: SiO2 12.3%, Al2O3 38.6%, SnO2 2.7%, K2O 2.9%, ZnO 12.8%, B2O3 2.6%, CoO 17.2%, TiO2 6.3%, and LOI 4.6%.

[0100] The raw materials of the blue dry particles are uniformly mixed, melted at 1340° C., and then water-quenched and ground to prepare the blue dry particles with a particle size distribution of 10-20 mesh accounting for 60%, 20-40 mesh accounting for 25%, and 40-80 mesh accounting for 15%.

[0101] The transparent dry particles include the following components in parts by weight: 13 parts of zinc oxide, 8 parts of aluminum oxide, 26 parts of quartz, 1 part of nano silicon nitride and 9 parts of cryolite.

[0102] The transparent dry granules are prepared by uniformly mixing the raw materials, melting them at 1400°C, quenching them with water, grinding them, and then passing them through a 500-mesh sieve. The chemical composition of the transparent dry granules includes: SiO2 46.3%, Al2O3 15.1%, ZnO 22.8%, Si3N4 2.2%, NaF 6.9%, and LOI 6.7%.

[0103] S5. Apply transparent protective glaze slurry on the surface of the sapphire dry particle layer at a rate of 590 g / m 2 , with a specific gravity of 1.55 g / mL, to obtain a protective glaze layer. The transparent protective glaze (this example uses a conventional commercially available transparent protective glaze) comprises the following components, by weight: 10 parts albite, 15 parts potassium feldspar, 6 parts calcined talc, 8 parts wollastonite, 5 parts strontium carbonate, 15 parts quartz, 15 parts dolomite, 17 parts calcined kaolin, and 10 parts washed kaolin. The chemical composition of the transparent protective glaze, by mass percentage, includes: SiO₂ 57.8%, Al₂O₃ 18.9%, K₂O 3.1%, NaO 22.7%, SrO 4.6%, CaO 4.1%, MgO 3.7%, and LOI 5.1%.

[0104] S6. Place the ceramic tile in a kiln for firing. The firing process is as follows: heating rate from room temperature to 350°C at 33°C / min; heating rate from 350°C to 950°C at 38°C / min; heating rate from 950°C to 1200°C at 21°C / min; holding at this temperature for 4 minutes; cooling rate from 1200°C to 600°C at 35°C / min; cooling rate from 600°C to 500°C at 15°C / min; and cooling rate from 500°C to room temperature at 38°C / min. This results in a ceramic tile with a sapphire-like effect.

[0105] Example 3

[0106] A ceramic tile with an imitation sapphire effect, the preparation method comprising the following steps:

[0107] S1. Prepare ceramic raw materials into a green body to obtain a green body layer; wherein the raw materials for preparing the green body layer include the following components in parts by weight: 10 parts of raw ore mud, 3 parts of bentonite, 7.5 parts of kaolin, 10 parts of washed mud, 34 parts of stone powder, 18 parts of high-aluminum potassium sand, and 2 parts of talc; the chemical composition of the green body layer, in mass percentage, includes SiO2 65.3%, Al2O3 21.7%, CaO 1.4%, MgO 0.3%, K2O 3.7%, Na2O 0.9%, Fe2O3 0.4%, and LOI 6.3%.

[0108] S2. Applying a ground glaze on the surface of the green body layer to form a ground glaze layer; wherein the ground glaze comprises the following components, by weight: 7 parts zinc oxide, 2 parts barium carbonate, 17 parts potassium feldspar, 13 parts sodium feldspar, 2.5 parts calcined talc, 2.5 parts calcite, 16 parts quartz, 7 parts dolomite, 9 parts calcined kaolin, 10 parts washed kaolin, and 9 parts aluminum oxide. The chemical composition of the ground glaze layer, by mass percentage, comprises: SiO2 54.6%, Al2O3 18.1%, ZnO 8.6%, CaO 2.9%, MgO 2.3%, K2O 3.7%, Na2O 3.4%, BaO 0.9%, and LOI 5.5%.

[0109] S3, inkjet printing a color pattern on the surface of the base glaze layer to obtain a pattern layer;

[0110] S4. Inkjet print positioning glue on the surface of the pattern layer. The glue amount is 180 g / m 2 , the printing pattern accounts for 85%; the sapphire effect dry particles are applied, and the application amount is 300 g / m 2 , obtaining a sapphire dry particle layer; wherein the sapphire effect dry particles include 88% blue dry particles and 12% transparent dry particles;

[0111] The blue dry granules include the following components, by weight: 2.5 parts ultrafine tin dioxide, 18 parts cobalt oxide, 6.5 parts titanium oxide, 11 parts zinc oxide, 38 parts calcined alumina, 10 parts quartz, 13 parts potassium feldspar, and 3.5 parts boric acid. The chemical composition of the blue dry granules includes: SiO₂ 14.2%, Al₂O₃ 39.8%, SnO₂ 2.7%, K₂O 2.3%, ZnO 10.5%, B₂O₃ 1.7%, CoO 17.4%, TiO₂ 6.9%, and LOI 4.5%.

[0112] The raw materials of the blue dry particles are mixed evenly, melted at 1310° C., and then water-quenched and ground to prepare the blue dry particles with a particle size distribution of 10-20 mesh accounting for 52%, 20-40 mesh accounting for 28%, and 40-80 mesh accounting for 20%.

[0113] The transparent dry particles include the following components in parts by weight: 12 parts of zinc oxide, 7 parts of aluminum oxide, 26 parts of quartz, 1.5 parts of nano silicon nitride and 9 parts of cryolite.

[0114] The transparent dry granules are prepared by uniformly mixing the raw materials, melting them at 1380°C, quenching them with water, grinding them, and then passing them through a 600-mesh sieve. The chemical composition of the transparent dry granules includes: SiO2 51.5%, Al2O3 13.5%, ZnO 21.8%, Si3N4 2.6%, NaF 4.5%, and LOI 6.1%.

[0115] S5. Apply dry particle protective glaze slurry on the surface of the sapphire dry particle layer at a rate of 530 g / m 2 , with a specific gravity of 1.53 g / mL, to obtain a dry particle protective glaze layer; wherein the dry particle protective glaze slurry comprises 53% of protective dry particles and 47% of 9022A dry particle suspension;

[0116] The protected dry granules comprise the following components, measured by weight: 25 parts potassium feldspar, 4 parts calcined alumina, 12 parts kaolin, 6 parts zinc oxide, and 11 parts quartz. The chemical composition of the protected dry granules, measured by mass percentage, comprises: 61.3% SiO2, 16.6% Al2O3, 5.6% K2O, 10.5% ZnO, and 6.0% LOI.

[0117] The raw materials of the protected dry granules are mixed uniformly, melted at 1390° C., quenched with water, ground, and passed through a 325-mesh sieve with a residue of 0.1-0.4% to obtain the protected dry granules.

[0118] S6. Place the ceramic tile in a kiln for firing. The firing process is as follows: heating rate from room temperature to 350°C at 33°C / min; heating rate from 350°C to 950°C at 38°C / min; heating rate from 950°C to 1200°C at 23°C / min; holding at this temperature for 3 minutes; cooling rate from 1200°C to 600°C at 33°C / min; cooling rate from 600°C to 500°C at 19°C / min; and cooling rate from 500°C to room temperature at 38°C / min. This produces a ceramic tile with a sapphire-like effect.

[0119] Comparative Examples 1 to 5

[0120] The preparation methods and parameters of the tiles of Comparative Examples 1 to 5 are the same as those of Example 3, with the only difference being that the raw materials for preparing the sapphire effect dry particles are adjusted as shown in Tables 1 to 3.

[0121] Table 1 Preparation materials of blue dry granules of comparative examples 1 to 5 (parts by weight)

[0122]

[0123] Table 2 Raw materials for the preparation of transparent dry granules of Comparative Examples 1 to 5 (parts by weight)

[0124]

[0125] Table 3 Raw materials for the preparation of sapphire effect dry particles in Comparative Examples 1 to 5 (%)

[0126]

[0127] Comparative Example 6

[0128] This comparative example adopts the same preparation process and parameters as Example 3, except that the firing process is adjusted as shown in Table 4 and Table 5:

[0129] Table 4 Heating stage

[0130]

[0131] Table 5 Cooling stage

[0132]

[0133] The pattern texture clarity and glaze effect of the tiles prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were observed, and the specific test results are shown in Table 6.

[0134] Table 6

[0135]

[0136] Note: The glaze decoration effect is directly observed by the naked eye by 30 inspectors. The main purpose is to compare the similarity of color and texture between the tiles of this scheme and natural sapphire stone. If ≥ 27 people think that the surface effects of the two are similar, it is marked as excellent; if 24-26 people think that the surface effects of the two are similar, it is marked as good; if 20-23 people think that the surface effects of the two are similar, it is marked as fair; the rest are marked as poor.

[0137] As shown in Table 6, the tiles prepared by this scheme have bright colors and clear patterns and textures. Figure 1 (Example 3) shows that the similarity with sapphire stone is high. In comparative examples 1 to 4, the formula components of sapphire effect dry particles were adjusted to varying degrees, causing the compounding effect to be unbalanced, affecting the crystal texture after firing, resulting in poor pattern texture clarity, unclear boundaries, and general decorative effects. Figure 2 (Comparative Example 4) is shown. Comparative Example 5 uses only blue dry particles. After firing, the glaze surface is blue as a whole, the texture is blurred, the clarity is low, and the decorative effect is poor. Figure 3 Comparative Example 6 adjusts the firing process, the heating and cooling rates are both fast, and the holding time is too long, which is not conducive to crystal formation, resulting in unclear pattern interfaces and average decorative effects.

[0138] Example 4

[0139] The conditions in this example were the same as those in Example 1, with the only difference being that the base glaze comprised the following components: 7 parts zinc oxide, 3 parts barium carbonate, 16 parts potassium feldspar, 14 parts sodium feldspar, 3 parts calcined talc, 1.5 parts calcite, 14 parts quartz, 6 parts dolomite, 8 parts calcined kaolin, 9.5 parts washed kaolin, and 10 parts aluminum oxide. The chemical composition of the base glaze layer, by mass percentage, included: SiO₂ 54.2%, Al₂O₃ 18.9%, ZnO 7.5%, CaO 3.1%, MgO 2.5%, K₂O 3.7%, Na₂O 3.4%, BaO 1.3%, and LOI 5.4%.

[0140] Example 5

[0141] The conditions in this embodiment are the same as those in Example 2, except that a dry particle protective glaze slurry is applied to the surface of the sapphire dry particle layer, and the dry particle protective glaze slurry comprises 51% protective dry particles and 49% 9022A dry particle suspension agent;

[0142] The protected dry granules comprise the following components, measured by weight: 23 parts potassium feldspar, 5 parts calcined alumina, 11 parts kaolin, 7 parts zinc oxide, and 10 parts quartz. The chemical composition of the protected dry granules, measured by mass percentage, comprises: SiO₂ 59.9%, Al₂O₃ 17.8%, K₂O 5.2%, ZnO 10.9%, and LOI 6.2%.

[0143] The raw materials of the protected dry granules are mixed uniformly, melted at 1370° C., quenched with water, ground, and passed through a 325-mesh sieve with a residue of 0.1-0.4% to obtain the protected dry granules.

[0144] The pattern texture clarity and glaze effect of the tiles prepared in Examples 4 and 5 were observed, and the specific test results are shown in Table 7.

[0145] Table 7

[0146]

[0147] As shown in Table 7, as shown in the results of Examples 1 and 4, the base glaze provided by this solution achieves better integration between the base glaze and the sapphire-effect dry particles at the interface, promotes color development, and achieves a better sapphire-like effect. As shown in the results of Examples 2 and 5, the dry particle protective glaze provided by this solution creates a jade-like wrapping effect on the blue crystals, giving the glaze surface a visual effect similar to that of a gemstone inlay and a stronger sense of transparency.

[0148] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention specification under the inventive concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A sapphire effect dry particle, characterized in that: Based on the total weight of the sapphire effect dry particles being 100%, the sapphire effect dry particles comprise: 85-90% blue dry particles and 10-15% transparent dry particles; The raw materials for preparing the blue dry particles include the following components by weight: 1.5-3.5 parts of ultrafine tin dioxide, 15-19.5 parts of cobalt oxide, 4.5-7.5 parts of titanium oxide, 8-14 parts of zinc oxide, 32-43 parts of calcined aluminum oxide, 8-13 parts of quartz, 10-16 parts of potassium feldspar, and 2.5-4.5 parts of boric acid; wherein the particle size of the ultrafine tin dioxide is 2000-2800 mesh; The raw materials for preparing the transparent dry particles include the following components in parts by weight: 8-15 parts of zinc oxide, 5-10 parts of aluminum oxide, 24-28 parts of quartz, 1-2.5 parts of nano silicon nitride and 7-11 parts of cryolite.

2. The sapphire effect dry particles according to claim 1, characterized in that In mass percentage: The chemical composition of the blue dry particles includes: SiO2 10.3-16.2%, Al2O3 35.3-46.2%, SnO2 1.6-4.2%, K2O 1.9-3.6%, ZnO 8.6-13.7%, B2O3 1.5-2.7%, CoO 14.3-22.3%, TiO2 5.9-12.6% and LOI 2.4-5.8%; The chemical composition of the transparent dry particles includes: SiO2 45.3-56.2%, Al2O3 8.3-16.6%, ZnO 12.6-23.7%, Si3N4 1.6-4.2%, NaF 3.6-7.7% and LOI 4.4-6.8%.

3. The sapphire effect dry particles according to claim 1, characterized in that The blue dry particles are obtained by mixing the raw materials, melting them at 1250-1350° C., and water quenching and grinding. The particle size distribution is: 10-20 mesh accounts for 45-60%, 20-40 mesh accounts for 25-30%, and 40-80 mesh accounts for 12-30%. The transparent dry particles are obtained by mixing the raw materials, melting them at 1300-1450° C., and water quenching and grinding. The particle size is 400-600 mesh.

4. A ceramic tile with imitation sapphire effect, characterized in that: The invention comprises a body layer, a bottom glaze layer, a pattern layer, a sapphire dry particle layer and a dry particle protective glaze layer in sequence; the sapphire dry particle layer is prepared by using the sapphire effect dry particles according to any one of claims 1 to 3.

5. The ceramic tile with imitation sapphire effect according to claim 4, characterized in that: The dry particle protective glaze layer is prepared from a dry particle protective glaze slurry; based on the total weight of the dry particle protective glaze slurry being 100%, the dry particle protective glaze slurry comprises 50-55% of protective dry particles and 45-50% of a dry particle suspending agent; The raw materials for preparing the protective dry particles include the following components in parts by weight: 23-27 parts of potassium feldspar, 3-5 parts of calcined alumina, 10-15 parts of kaolin, 4-8 parts of zinc oxide and 8-13 parts of quartz; The chemical composition of the protected dry particles, calculated by mass percentage, includes: SiO2 59.6-64.3%, Al2O3 14.9-18.6%, K2O 3.5-5.9%, ZnO 6.5-11.2% and LOI 4.1-7.5%.

6. The ceramic tile with imitation sapphire effect according to claim 5, characterized in that: The protected dry particles are obtained by mixing raw materials, melting them at 1300-1450° C., and then quenching and grinding them with water.

7. The ceramic tile with imitation sapphire effect according to claim 4, characterized in that: The raw materials for preparing the base glaze layer include the following components in parts by weight: 5-10 parts of zinc oxide, 1-3 parts of barium carbonate, 15-20 parts of potassium feldspar, 10-15 parts of sodium feldspar, 1.5-3.5 parts of calcined talc, 1-3.5 parts of calcite, 13-19 parts of quartz, 5-8 parts of dolomite, 7-11 parts of calcined kaolin, 8.5-12 parts of washed kaolin and 6-12 parts of aluminum oxide; The chemical composition of the base glaze layer, calculated by mass percentage, includes: SiO2 48.1-56.3%, Al2O3 16.3-19.1%, ZnO 5.9-10.7%, CaO 2.3-3.9%, MgO 1.9-4.8%, K2O 3.5-4.8%, Na2O 3.3-4.7%, BaO 0.6-1.6% and LOI 2.3-5.9%.

8. The ceramic tile with imitation sapphire effect according to claim 4, characterized in that: The raw materials for preparing the green body layer include the following components by weight: 9.5-11.5 parts of raw ore mud, 1.3-3.5 parts of bentonite, 6.6-9.5 parts of kaolin, 8.5-11.5 parts of washed mud, 33.5-38.3 parts of stone powder, 16.2-22.3 parts of high-aluminum potassium sand and 1-3 parts of talc; The chemical composition of the green body layer, calculated in percentage by mass, includes: SiO2 60.3-67.3%, Al2O3 19.7-23.2%, CaO 1.1-2.5%, MgO 0.2-0.8%, K2O 2.3-4.5%, Na2O 0.6-1.3%, Fe2O3 0.2-0.6% and LOI 3.3-7.6%.

9. A method for preparing a ceramic tile having an imitation sapphire effect according to any one of claims 4 to 8, characterized in that: The steps include: S1, preparing a green body and obtaining a green body layer; S2, applying a base glaze on the surface of the green body layer to obtain a base glaze layer; S3, inkjet printing a color pattern on the surface of the base glaze layer to obtain a pattern layer; S4, after inkjet printing positioning glue on the surface of the pattern layer, applying sapphire effect dry particles to obtain a sapphire dry particle layer; S5, applying dry particle protective glaze slurry on the surface of the sapphire dry particle layer to obtain a dry particle protective glaze layer; S6, sending the ceramic tile into a kiln for firing to obtain the ceramic tile with the imitation sapphire effect; In step S6, the firing process includes: Preheating stage: heating rate is 25~35℃ / min, temperature range is room temperature~350℃; Oxidation decomposition stage: heating rate is 30~40℃ / min, temperature range is 350~950℃; High temperature stage: heating rate is 20~25℃ / min, temperature range is 950℃~maximum firing temperature; High fire insulation stage: time 2~5min; And cooling stage: the cooling rate in the temperature range from the highest firing temperature to 600℃ is 25~35℃ / min; the cooling rate in the temperature range from 600~500℃ is 15~20℃ / min; the cooling rate in the temperature range from 500℃ to room temperature is 35~40℃ / min; The maximum firing temperature is 1150~1210℃.

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