A ceramic product with metallic luster and a preparation method thereof

Abstract

The present invention discloses a ceramic product with metallic luster, which comprises a green body, an underglaze layer, a top glaze layer and a transparent glaze layer. The underglaze layer comprises: 35-45 parts of potassium feldspar, 25-30 parts of clay, 15-20 parts of white corundum, 5-8 parts of talc, 5-8 parts of bentonite, 5-8 parts of zirconium silicate, 5-7 parts of zinc oxide; The top glaze layer comprises: 30-35 parts of quartz, 20-25 parts of feldspar, 10-15 parts of talcum powder, 8-15 parts of mica, 5-10 parts of zirconium silicate, 5-8 parts of lithium porcelain stone, 1-5 parts of colorant A; The transparent glaze layer is composed of a transparent frit and colorant B. Through the component design of the underglaze, top glaze and transparent glaze, the present invention makes the difference in thermal expansion coefficients between the two glaze layers small and the shrinkage rate small; The underglaze and top glaze are first fired at a low temperature, and then the transparent glaze is applied and fired at a high temperature, which can form a stable glaze layer and produce uniform and dense microcrystalline grains with good metallic luster. Moreover, the two firings reduce the stress between the glaze layers and improve the yield rate.

Description

Technical Field

[0001] The present invention belongs to the technical field of ceramic products, and particularly relates to a ceramic product with metallic luster and a preparation method thereof. Background Art

[0002] Metallic luster glaze refers to a glaze with a certain composition that, after being processed (or fired), produces appearance properties such as hue and luster similar to those of a certain metal. Such as copper metallic luster glaze similar to copper, imitation gold luster glaze similar to gold, and silver metallic luster glaze similar to silver. Broadly speaking, metallic luster glaze is a technology for metalizing the surface of ceramic products. The research by Professor Chen Xianqiu of the Shanghai Institute of Ceramics, Chinese Academy of Sciences, in the article "Microstructural Analysis of Imitation Celadon Pottery" shows that its metallic luster comes from the reflection characteristics of cobalt ferrite spinel microcrystals in the direction parallel to the surface of the object. This is mainly due to the strict parallelism of the {1,1,1} crystal plane with a relatively large reticular density to the surface, presenting a strong reflection of light. The grain size, distribution state, and integrity of these microcrystals can all affect the metallic luster. The main principle of metallic luster glaze is to add coloring metal oxides to raw materials with a certain composition, so that crystals are precipitated due to supersaturation during firing and cooling, producing metallic lusters with various different effects.

[0003] Existing metallic luster glazes usually use lead-containing frit. Due to its good high-temperature fluidity, wide firing range, and good glaze glossiness, it has been widely used in metal ceramic products. However, lead is a heavy metal material and is listed as a toxic and harmful substance. Therefore, the development of lead-free and environmentally friendly metal glazes is a major research direction of metal glazes. In addition, as is well known in this field, due to the differences in the dispersibility and fluidity of metal oxides during the preparation process, it is relatively difficult to add metal oxides only in the surface glaze layer to achieve the effect of forming metallic luster, and the yield of the obtained ceramic products is low. Summary of the Invention

[0004] Aiming at the defects in the prior art, the purpose of the present invention is to provide a lead-free ceramic product with metallic luster, which adopts a unique ceramic glaze formula and production process to obtain a ceramic product with an imitation metal effect, having strong metallic luster, good quality stability, and high yield.

[0005] Another purpose of the present invention is to provide a preparation method of the ceramic product with metallic luster.

[0006] To achieve the above purposes, the technical solutions provided by the present invention are as follows:

[0007] A ceramic product with metallic luster, comprising a body and a bottom glaze layer, a surface glaze layer, and a transparent glaze layer provided on the body.

[0008] The underglaze layer is prepared from the following components in parts by weight: 35-45 parts of potassium feldspar, 25-30 parts of clay, 15-20 parts of white corundum, 5-8 parts of talc, 5-8 parts of bentonite, 5-8 parts of zirconium silicate, and 5-7 parts of zinc oxide;

[0009] The topcoat glaze layer is prepared from the following components in parts by weight: 30-35 parts of quartz, 20-25 parts of feldspar, 10-15 parts of talc powder, 8-15 parts of mica, 5-10 parts of zirconium silicate, 5-8 parts of spodumene, and 1-5 parts of colorant A; The colorant A includes one or more of iron oxide, copper oxide, vanadium oxide, and nickel oxide;

[0010] The transparent glaze layer is composed of a transparent frit and colorant B. The chemical composition of the transparent frit includes, by weight percentage: 48-55% of SiO2, 7-9% of Al2O3, 7-9% of MgO, 5-7% of Na2O, 3-5% of K2O, 3-5% of ZrO2, 1-2% of ZnO, 1-2% of TiO2, 1-2% of CaO, 1-2% of BaO, 0.5-1% of CeO2, and 0.5-1% of Li2O;

[0011] The preparation method of the colorant B is as follows:

[0012] S1: Ultrasonically disperse the metal oxide powder, CMC, and water, and then wet ball mill until the fineness of the slurry passes through a 300-mesh sieve;

[0013] S2: Spray dry the ground slurry to obtain uniform granular material.

[0014] In the present invention, in order to improve the presentation effect of the metallic luster of the ceramic product, first, an underglaze layer, a topcoat glaze layer, and a transparent glaze layer are provided, and the formulations of each layer are studied and optimized to make the metal oxide have good fluidity and good quality stability during firing. Secondly, in order to significantly improve the metallic texture, colorant A is added to the topcoat glaze layer and colorant B is added to the transparent glaze layer. Through the two colorants in the transparent glaze and the topcoat glaze, they complement each other, making the color more abundant and at the same time improving the gloss of the metal. Finally, the colorant B in the transparent glaze is obtained by spray drying into tiny particles, which can make the colorant mix evenly with other materials, and the tiny crystals formed during firing are evenly distributed.

[0015] In the present invention, through the component design of the topcoat glaze and the transparent glaze, the difference in the thermal expansion coefficient between the two glaze layers is small, the shrinkage rate is small, and at the same time, the topcoat glaze layer presents a rich and three-dimensional effect.

[0016] In the present invention, preferably, the bottom glaze layer is prepared from the following components by weight: 40 parts of potassium feldspar, 30 parts of clay, 16 parts of white corundum, 6 parts of talc, 7 parts of bentonite, 6 parts of zirconium silicate, and 6 parts of zinc oxide. Adding white corundum to the bottom glaze layer makes the glaze white and warm, with a dense and delicate surface, and makes the color development effect of the top glaze layer good.

[0017] In the present invention, preferably, the surface glaze layer is prepared from the following components in parts by weight: 35 parts of quartz, 23 parts of feldspar, 12 parts of talc, 10 parts of mica, 7 parts of zirconium silicate, 5 parts of lithium porcelain stone, and 2 parts of colorant A. The components and dosage of the surface glaze layer are selected based on the coloring effect of the colorant A and the components, as well as the uniform fluidity during the firing process.

[0018] In the present invention, preferably, in the transparent glaze layer, the weight ratio of the transparent frit to the colorant B is 40 to 50: 1. More preferably, the weight ratio of the transparent frit to the colorant B is 45: 1. The weight ratio of the transparent frit to the colorant B affects the dispersibility and color effect of the colorant. After many attempts, the inventors have obtained a ratio range with better effects.

[0019] In the present invention, preferably, the chemical composition of the transparent frit includes, by weight percentage: SiO2 53.2%, Al2O3 7.8%, MgO 8.6%, Na2O 6.1%, K2O 4.2%, ZrO2 4.6%, ZnO 1.7%, TiO2 1.7%, CaO 1.6%, BaO 1.5%, CeO2 0.7%, Li2O 0.6%, and the remainder is ignition loss.

[0020] In the present invention, preferably, in S1, the mass ratio of metal oxide powder, CMC and water is 40-50:1:2-10. More preferably, the mass ratio of metal oxide powder, CMC and water is 45:1:8. The metal oxide powder is spray-dried and granulated by CMC and water to improve the dispersion uniformity of the metal oxide in the transparent glaze and the high-temperature fluidity. The metal oxide in the colorant B can be selected according to needs and color effects, and the present invention is not limited to this.

[0021] The present invention also provides a method for preparing the ceramic product with metallic luster, comprising the following steps:

[0022] S1. Blank preparation;

[0023] S2. Applying the bottom glaze: Mix the raw materials for the bottom glaze layer and wet-ball grind them to a material fineness of 300-400 mesh, sieve to remove iron, add water to obtain the bottom glaze slurry, the solid content of the bottom glaze slurry is 30-40%; pour the bottom glaze slurry on the body, and then dry it for later use;

[0024] S3. Apply the surface glaze: Mix the raw materials of the surface glaze layer and then perform wet ball milling until the fineness of the material is 400 - 500 mesh. Add water to obtain the surface glaze slurry, and the solid content of the surface glaze slurry is 45 - 50%; Pour the surface glaze slurry onto the underglaze, and then dry it for standby;

[0025] S4. Low - temperature firing: Fire at 750 - 900 °C for 100 - 150 minutes;

[0026] S5. Apply the transparent glaze: Mix the transparent frit and colorant B and then perform wet ball milling until the fineness of the material is 200 - 300 mesh. Add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 45 - 50%; Pour the transparent glaze slurry onto the surface glaze layer after firing and cooling;

[0027] S6. High - temperature firing: Continue firing after the transparent glaze layer is dried. The firing temperature is 1100 - 1300 °C and the firing time is 3 - 4 hours.

[0028] The preparation method of the present invention can well control the yield rate of ceramic products through two - stage firing. The underglaze and surface glaze are first fired at a low temperature to form an enamel layer, and then after pouring the transparent glaze, it is fired at a high temperature to further form a stable enamel layer and generate uniform and dense micro - crystalline grains, with good metallic luster. Moreover, compared with single - stage firing, two - stage firing can reduce the stress between enamel layers and reduce the proportion of defective products.

[0029] In the present invention, preferably, when pouring the underglaze, the specific gravity of the glaze is 1.45 - 1.55 g / ml, and the glazing amount is 400 - 450 g / m 2 ; when pouring the surface glaze, the specific gravity of the glaze is 1.60 - 1.70 g / ml, and the glazing amount is 600 - 700 g / m 2 ; when pouring the transparent glaze, the specific gravity of the glaze is 1.70 - 1.80 g / ml, and the glazing amount is 700 - 750 g / m 2 . Further preferably, when pouring the underglaze, the specific gravity of the glaze is 1.48 g / ml, and the glazing amount is 425 g / m 2 ; when pouring the surface glaze, the specific gravity of the glaze is 1.67 g / ml, and the glazing amount is 674 g / m 2 ; when pouring the transparent glaze, the specific gravity of the glaze is 1.75 g / ml, and the glazing amount is 737 g / m 2 . By adjusting the specific gravity and glazing amount of the underglaze, surface glaze and transparent glaze, the thickness and density of the enamel layer can be controlled, thereby obtaining a better gloss effect. The ranges of the specific gravity and glazing amount of the above - mentioned enamel layers are obtained by the inventor through multiple experimental adjustments.

[0030] In the present invention, preferably, S4. Low - temperature firing: Fire at 800 °C for 120 minutes; S6. High - temperature firing: Continue firing after the transparent glaze layer is dried. The firing temperature is 1200 °C and the firing time is 3 hours.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) In order to improve the metallic luster of ceramic products, the present invention sets a base glaze layer, a surface glaze layer and a transparent glaze layer, and studies and optimizes the formula of each layer so that the metal oxide has good fluidity and good quality stability during the firing process. White corundum is added to the base glaze layer, so that the glaze is white and warm, the surface is dense and delicate, and the color development effect of the surface glaze layer is good. Through the component design of the surface glaze and the transparent glaze, the thermal expansion coefficients between the two layers of glaze are not much different, the shrinkage rate is small, and at the same time, the surface glaze layer presents a rich three-dimensional effect.

[0033] (2) In order to significantly improve the metallic texture, the present invention adds colorant A to the surface glaze layer and colorant B to the transparent glaze layer. The two colorants in the transparent glaze and the surface glaze complement each other, making the colors richer and improving the glossiness of the metal.

[0034] (3) The colorant B in the transparent glaze of the present invention is a tiny particle obtained by spray drying, which can make the colorant and other materials mixed evenly, and the tiny crystals formed by firing are evenly distributed, so that the color is uniform. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the embodiments.

[0036] The raw materials used in the following examples are all commercially available.

[0037] Embodiment 1:

[0038] The preparation of ceramic products with metallic luster comprises the following steps:

[0039] S1. Blank preparation;

[0040] S2. Applying base glaze: Mix the raw materials for the base glaze layer and wet-mill them until the material fineness is 300 mesh, sieve to remove iron, add water to obtain base glaze slurry, the solid content of the base glaze slurry is 30%; pour the base glaze slurry on the body, and then dry it for use; when pouring the base glaze, the specific gravity of the glaze is 1.45g / ml, and the glaze amount is 450g / m 2 ;

[0041] S3. Applying top glaze: Mix the raw materials for the top glaze layer and wet-mill them until the material fineness is 400 mesh, add water to obtain the top glaze slurry, the solid content of the top glaze slurry is 45%; pour the top glaze slurry on the base glaze, and then dry it for later use; when pouring the top glaze, the specific gravity of the glaze is 1.60g / ml, and the glaze amount is 700g / m 2 ;

[0042] S4. Low-temperature firing: Fire at 750 °C for 150 minutes;

[0043] S5. Apply transparent glaze: Mix the transparent frit and colorant B, then perform wet ball milling until the fineness of the material is 300 mesh, add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 50%; Pour the transparent glaze on the surface glaze layer after firing and cooling; When pouring the transparent glaze, the specific gravity of the glaze is 1.70 g / ml, and the glaze application amount is 750 g / m 2 ;

[0044] S6. High-temperature firing: Continue firing after the transparent glaze layer is dried, the firing temperature is 1100 °C, and the firing time is 4 hours.

[0045] The raw materials of the underglaze layer are as follows: 35 Kg of potassium feldspar, 25 Kg of clay, 15 Kg of white corundum, 5 Kg of talc, 5 Kg of bentonite, 5 Kg of zirconium silicate, and 5 Kg of zinc oxide.

[0046] The raw materials of the surface glaze layer are as follows: 30 Kg of quartz, 20 Kg of feldspar, 10 Kg of talc powder, 8 Kg of mica, 5 Kg of zirconium silicate, 5 Kg of lithium porcelain stone, and 1 Kg of colorant A; The colorant A is copper oxide.

[0047] The transparent glaze layer is composed of a transparent frit and colorant B, and the weight ratio of the transparent frit to colorant B is 40:1. The colorant B is iron oxide. The chemical composition of the transparent frit includes, by weight percentage: 53.5% of SiO2, 8.52% of Al2O3, 8.12% of MgO, 6.12% of Na2O, 3.58% of K2O, 4.25% of ZrO2, 1.52% of ZnO, 1.35% of TiO2, 1.53% of CaO, 1.68% of BaO, 0.68% of CeO2, 0.78% of Li2O, and the balance is loss on ignition. The preparation method of the colorant B is as follows: S1: Ultrasonically disperse iron oxide, CMC, and water, and then perform wet ball milling until the fineness of the slurry passes through a 300-mesh sieve; The mass ratio of iron oxide, CMC, and water is 40:1:2; S2: Spray-dry the milled slurry to obtain uniform granular material.

[0048] Example 2:

[0049] The preparation of a ceramic product with metallic luster includes the following steps:

[0050] S1. Prepare the green body;

[0051] S2. Apply the underglaze: Mix the raw materials of the underglaze layer, perform wet ball milling until the fineness of the material is 400 mesh, remove iron by sieving, add water to obtain the underglaze slurry, and the solid content of the underglaze slurry is 40%; Pour the underglaze slurry on the green body, and then dry for standby; When pouring the underglaze, the specific gravity of the glaze is 1.55 g / ml, and the glaze application amount is 400 g / m 2;

[0052] S3. Apply the surface glaze: Mix the raw materials of the surface glaze layer, then perform wet ball milling until the fineness of the material is 500 mesh, add water to obtain the surface glaze slurry, and the solid content of the surface glaze slurry is 50%; Pour the surface glaze slurry onto the underglaze, and then dry it for standby; When pouring the surface glaze, the specific gravity of the glaze is 1.70 g / ml, and the glazing amount is 600 g / m 2 ;

[0053] S4. Low-temperature firing: Fire at 900 °C for 100 minutes;

[0054] S5. Apply the transparent glaze: Mix the transparent frit and colorant B, then perform wet ball milling until the fineness of the material is 300 mesh, add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 50%; Pour the transparent glaze slurry onto the surface glaze layer after firing and cooling; When pouring the transparent glaze, the specific gravity of the glaze is 1.80 g / ml, and the glazing amount is 700 g / m 2 ;

[0055] S6. High-temperature firing: Continue firing after the transparent glaze layer is dried, the firing temperature is 1300 °C, and the firing time is 3 hours.

[0056] The raw materials of the underglaze layer are as follows: 45 Kg of potassium feldspar, 30 Kg of clay, 20 Kg of white corundum, 8 Kg of talc, 8 Kg of bentonite, 8 Kg of zirconium silicate, and 7 Kg of zinc oxide.

[0057] The raw materials of the surface glaze layer are as follows: 35 Kg of quartz, 25 Kg of feldspar, 15 Kg of talc powder, 15 Kg of mica, 10 Kg of zirconium silicate, 8 Kg of lithium porcelain stone, and 5 Kg of colorant A; The colorant A is iron oxide.

[0058] The transparent glaze layer is composed of a transparent frit and colorant B, and the weight ratio of the transparent frit to colorant B is 50:1. The colorant B is iron oxide. The chemical composition of the transparent frit includes, by weight percentage: 52.12% of SiO2, 8.24% of Al2O3, 8.35% of MgO, 6.21% of Na2O, 4.53% of K2O, 3.25% of ZrO2, 1.23% of ZnO, 1.56% of TiO2, 1.45% of CaO, 1.55% of BaO, 0.78% of CeO2, 0.68% of Li2O, and the balance is loss on ignition. The preparation method of the colorant B is as follows: S1: Ultrasonically disperse iron oxide, CMC, and water, and then perform wet ball milling until the fineness of the slurry passes through a 300-mesh sieve; The mass ratio of iron oxide, CMC, and water is 50:1:10; S2: Spray-dry the ground slurry to obtain uniform granular material.

[0059] Example 3:

[0060] Preparation of a ceramic product with metallic luster, including the following steps:

[0061] S1. Green body preparation;

[0062] S2. Applying the base glaze: Mix the raw materials of the base glaze layer and then perform wet ball milling until the fineness of the material is 350 mesh. Screen to remove iron, add water to obtain the base glaze slurry, and the solid content of the base glaze slurry is 35%; Pour the base glaze slurry on the green body and then dry for standby; When pouring the base glaze, the specific gravity of the glaze is 1.50 g / ml, and the glaze application amount is 420 g / m 2 ;

[0063] S3. Applying the surface glaze: Mix the raw materials of the surface glaze layer and then perform wet ball milling until the fineness of the material is 450 mesh. Add water to obtain the surface glaze slurry, and the solid content of the surface glaze slurry is 48%; Pour the surface glaze slurry on the base glaze and then dry for standby; When pouring the surface glaze, the specific gravity of the glaze is 1.67 g / ml, and the glaze application amount is 652 g / m 2 ;

[0064] S4. Low-temperature firing: Fire at 800 °C for 120 minutes;

[0065] S5. Applying the transparent glaze: Mix the transparent frit and colorant B and then perform wet ball milling until the fineness of the material is 250 mesh. Add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 48%; Pour the transparent glaze slurry on the surface glaze layer after firing and cooling; When pouring the transparent glaze, the specific gravity of the glaze is 1.75 g / ml, and the glaze application amount is 737 g / m 2 ;

[0066] S6. High-temperature firing: Continue firing after the transparent glaze layer is dried, the firing temperature is 1200 °C, and the firing time is 3.5 hours.

[0067] The raw materials of the base glaze layer are as follows: 40 Kg of potassium feldspar, 28 Kg of clay, 17 Kg of white corundum, 7 Kg of talc, 6 Kg of bentonite, 7 Kg of zirconium silicate, and 6 Kg of zinc oxide.

[0068] The raw materials of the surface glaze layer are as follows: 32 Kg of quartz, 23 Kg of feldspar, 12 Kg of talc powder, 10 Kg of mica, 7 Kg of zirconium silicate, 6 Kg of lithium porcelain stone, and 2 Kg of colorant A; The colorant A is copper oxide.

[0069] The transparent glaze layer is composed of a transparent frit and pigment B. The weight ratio of the transparent frit to pigment B is 45:1, and pigment B is copper oxide. The chemical composition of the transparent frit by weight percentage includes: SiO2 54.10%, Al2O3 7.89%, MgO 8.56%, Na2O 6.12%, K2O 4.32%, ZrO2 4.38%, ZnO 1.56%, TiO2 1.68%, CaO 1.86%, BaO 1.56%, CeO2 0.75%, Li2O 0.77%, and the balance is loss on ignition. The preparation method of pigment B is as follows: S1: Ultrasonically disperse copper oxide, CMC, and water, and then wet ball mill until the fineness of the slurry passes through a 300-mesh sieve; the mass ratio of copper oxide, CMC, and water is 45:1:8; S2: Spray dry the milled slurry to obtain uniform granular material.

[0070] Example 4:

[0071] Preparation of a ceramic product with metallic luster, including the following steps:

[0072] S1. Green body preparation;

[0073] S2. Apply the base glaze: Mix the raw materials of the base glaze layer and then wet ball mill until the fineness of the material is 300 mesh, screen to remove iron, add water to obtain the base glaze slurry, and the solid content of the base glaze slurry is 35%; Pour the base glaze slurry on the green body and then dry for standby; When applying the base glaze, the specific gravity of the glaze is 1.48 g / ml, and the glazing amount is 425 g / m 2 ;

[0074] S3. Apply the top glaze: Mix the raw materials of the top glaze layer and then wet ball mill until the fineness of the material is 400 mesh, add water to obtain the top glaze slurry, and the solid content of the top glaze slurry is 48%; Pour the top glaze slurry on the base glaze and then dry for standby; When applying the top glaze, the specific gravity of the glaze is 1.67 g / ml, and the glazing amount is 674 g / m 2 ;

[0075] S4. Low-temperature firing: Fire at 800 °C for 120 minutes;

[0076] S5. Apply the transparent glaze: Mix the transparent frit and pigment B and then wet ball mill until the fineness of the material is 300 mesh, add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 50%; Pour the transparent glaze on the top glaze layer after firing and cooling; When applying the transparent glaze, the specific gravity of the glaze is 1.75 g / ml, and the glazing amount is 737 g / m 2 ;

[0077] S6. High-temperature firing: Continue to fire after the transparent glaze layer is dry, the firing temperature is 1200 °C, and the firing time is 3 hours.

[0078] The raw materials of the bottom glaze layer are as follows: 40 Kg of potassium feldspar, 30 Kg of clay, 16 Kg of white corundum, 6 Kg of talc, 7 Kg of bentonite, 6 Kg of zirconium silicate, and 6 Kg of zinc oxide;

[0079] The raw materials of the top glaze layer are as follows: 35 Kg of quartz, 23 Kg of feldspar, 12 Kg of talc powder, 10 Kg of mica, 7 Kg of zirconium silicate, 5 Kg of lithium porcelain stone, and 2 Kg of colorant A; the colorant A is vanadium oxide.

[0080] The transparent glaze layer is composed of a transparent frit and colorant B, and the weight ratio of the transparent frit to colorant B is 45:1. The colorant B is copper oxide. The chemical composition of the transparent frit includes, by weight percentage: 52.23% of SiO2, 8.25% of Al2O3, 8.36% of MgO, 6.45% of Na2O, 4.68% of K2O, 4.23% of ZrO2, 1.47% of ZnO, 1.65% of TiO2, 1.49% of CaO, 1.85% of BaO, 0.78% of CeO2, and 0.76% of Li2O. The preparation method of the colorant B is as follows: S1: Ultrasonically disperse copper oxide, CMC, and water, and then wet ball mill until the fineness of the slurry passes through a 300-mesh sieve; the mass ratio of copper oxide, CMC, and water is 42:1:3; S2: Spray-dry the ground slurry to obtain uniform granular material.

[0081] Example 5:

[0082] The preparation of a ceramic product with metallic luster includes the following steps:

[0083] S1. Body preparation;

[0084] S2. Applying the bottom glaze: Mix the raw materials of the bottom glaze layer and then wet ball mill until the fineness of the material is 300 mesh, remove iron by sieving, add water to obtain the bottom glaze slurry, and the solid content of the bottom glaze slurry is 36%; pour the bottom glaze slurry on the body and then dry for standby; when applying the bottom glaze, the specific gravity of the glaze is 1.52 g / ml, and the glazing amount is 435 g / m 2 ;

[0085] S3. Applying the top glaze: Mix the raw materials of the top glaze layer and then wet ball mill until the fineness of the material is 400 mesh, add water to obtain the top glaze slurry, and the solid content of the top glaze slurry is 48%; pour the top glaze slurry on the bottom glaze and then dry for standby; when applying the top glaze, the specific gravity of the glaze is 1.63 g / ml, and the glazing amount is 685 g / m 2 ;

[0086] S4. Low-temperature firing: Fire at 850 °C for 120 minutes;

[0087] S5. Apply transparent glaze: Mix the transparent frit and colorant B, then perform wet ball milling until the fineness of the material reaches 300 mesh, add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 47%; Pour the transparent glaze on the surface glaze layer after firing and cooling; When pouring the transparent glaze, the specific gravity of the glaze is 1.73 g / ml, and the glazing amount is 749 g / m 2 ;

[0088] S6. High-temperature firing: After the transparent glaze layer is dried, continue firing at a firing temperature of 1250 °C for 3 hours.

[0089] The raw materials of the underglaze layer are as follows: 38 Kg of potassium feldspar, 28 Kg of clay, 17 Kg of white corundum, 6 Kg of talc, 5 Kg of bentonite, 6 Kg of zirconium silicate, and 7 Kg of zinc oxide.

[0090] The raw materials of the surface glaze layer are as follows: 33 Kg of quartz, 23 Kg of feldspar, 12 Kg of talc powder, 11 Kg of mica, 7 Kg of zirconium silicate, 7 Kg of lithium porcelain stone, and 2 Kg of colorant A; The colorant A is nickel oxide.

[0091] The transparent glaze layer is composed of a transparent frit and colorant B, and the weight ratio of the transparent frit to colorant B is 43:1. The colorant B is copper oxide. The chemical composition of the transparent frit includes, by weight percentage: 54.21% of SiO2, 8.53% of Al2O3, 8.14% of MgO, 6.42% of Na2O, 3.65% of K2O, 4.57% of ZrO2, 1.48% of ZnO, 1.36% of TiO2, 1.58% of CaO, 1.56% of BaO, 0.74% of CeO2, and 0.85% of Li2O. The preparation method of the colorant B is as follows: S1: Ultrasonically disperse copper oxide, CMC, and water, then perform wet ball milling until the fineness of the slurry passes through a 300-mesh sieve; The mass ratio of copper oxide, CMC, and water is 48:1:4; S2: Spray-dry the milled slurry to obtain uniform granular material.

[0092] Comparative Example 1:

[0093] Compared with Example 3, the formula raw materials of the ceramic product are the same, and the firing process is a single firing. The specific preparation process is as follows.

[0094] S1. Prepare the green body;

[0095] S2. Apply the underglaze: Mix the raw materials of the underglaze layer, then perform wet ball milling until the fineness of the material reaches 350 mesh, remove iron by sieving, add water to obtain the underglaze slurry, and the solid content of the underglaze slurry is 35%; Pour the underglaze slurry on the green body, then dry for standby; When pouring the underglaze, the specific gravity of the glaze is 1.50 g / ml, and the glazing amount is 420 g / m 2 ;

[0096] S3. Applying surface glaze: Mix the raw materials of the surface glaze layer and perform wet ball milling until the fineness of the material reaches 450 mesh. Add water to obtain the surface glaze slurry, and the solid content of the surface glaze slurry is 48%; Pour the surface glaze slurry on the underglaze, and then dry for standby; When pouring the surface glaze, the specific gravity of the glaze is 1.67 g / ml, and the glazing amount is 652 g / m 2 ;

[0097] S4. Applying transparent glaze: Mix the transparent frit and colorant B and perform wet ball milling until the fineness of the material reaches 250 mesh. Add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 48%; Pour the transparent glaze on the surface glaze layer, and then dry for standby; When pouring the transparent glaze, the specific gravity of the glaze is 1.75 g / ml, and the glazing amount is 737 g / m 2 ;

[0098] S5. High-temperature firing: After the transparent glaze layer is dried, continue firing. The firing temperature is 1200 °C, and the firing time is 5.5 hours.

[0099] Performance testing:

[0100] Perform the following performance tests on the finally prepared ceramic products with metallic luster in Examples 1-5 and Comparative Example 1.

[0101] 1. Glossiness test: Use an intelligent glossiness tester to test the glossiness of the glaze surface according to the test method of 45° specular glossiness of ceramic products in GB / T 3295-1996. According to the measurement results, when the glossiness is greater than 57, the glaze surface is bright; when it is between 43-48, it is matte; when it is less than 40, it is non-glossy.

[0102] The evaluation of the metallic luster effect is divided into three grades: excellent, good and general.

[0103] 2. Tests of thermal stability and coefficient of expansion

[0104] Use a ceramic thermal stability tester and a thermal dilatometer to measure according to the method for measuring the average linear thermal expansion coefficient of ceramic materials in QB / T 1321-1991. Test the thermal stability (i.e., whether there is glaze shrinkage, bubbles or cracks) of each ceramic product through an atomic force microscope (AFM).

[0105] 3. Inspection of the qualified product rate

[0106] Inspect the qualified product rate of the batch (1000 pieces) of ceramic products prepared in Examples 1-5 and Comparative Example 1. The inspection method uses the conventional method in this field.

[0107] The test results are shown in Table 1.

[0108]

[0109] As shown in Table 1, the ceramic products with metallic luster prepared by the present invention have good surface metallic luster effect, good thermal stability and high yield. Through the component design of the surface glaze and the transparent glaze, the thermal expansion coefficients between the two layers of glaze are not much different, the shrinkage rate is small, and at the same time, the surface glaze layer presents a rich three-dimensional effect. The bottom glaze and the surface glaze are first fired at a low temperature to form a glaze layer, and then the transparent glaze is sprayed and fired at a high temperature to further form a stable glaze layer and produce uniform and dense microcrystalline grains, with good metallic luster. Moreover, compared with single firing, the two-stage firing can reduce the stress between the glaze layers and reduce the proportion of defective products.

[0110] According to the disclosure and teachings of the above specification, those skilled in the art to which the present invention pertains can also make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the invention should also fall within the protection scope of the claims of the present invention. In addition, although some specific terms are used in this specification, these terms are only for convenience of description and do not constitute any limitation to the present invention.

Claims

1. A ceramic product with metallic luster, characterized in that, It includes a green body, and a bottom glaze layer, a surface glaze layer and a transparent glaze layer provided on the green body. The bottom glaze layer is prepared from the following components in parts by weight: 35-45 parts of potassium feldspar, 25-30 parts of clay, 15-20 parts of white corundum, 5-8 parts of talc, 5-8 parts of bentonite, 5-8 parts of zirconium silicate, 5-7 parts of zinc oxide. The surface glaze layer is prepared from the following components in parts by weight: 30-35 parts of quartz, 20-25 parts of feldspar, 10-15 parts of talc powder, 8-15 parts of mica, 5-10 parts of zirconium silicate, 5-8 parts of lithium porcelain stone, 1-5 parts of colorant A; The colorant A includes one or more of iron oxide, copper oxide, vanadium oxide, nickel oxide. The transparent glaze layer is composed of a transparent frit and a colorant B. The chemical composition of the transparent frit includes, by weight percentage: 48-55% of SiO2, 7-9% of Al2O3, 7-9% of MgO, 5-7% of Na2O, 3-5% of K2O, 3-5% of ZrO2, 1-2% of ZnO, 1-2% of TiO2, 1-2% of CaO, 1-2% of BaO, 0.5-1% of CeO2, 0.5-1% of Li2O. The preparation method of the colorant B is as follows: S1: Ultrasonically disperse the metal oxide powder, CMC and water, and then wet ball mill until the fineness of the slurry passes through a 300-mesh sieve. S2: Spray dry the ground slurry to obtain uniform granular material.

2. The ceramic product with metallic luster according to claim 1, characterized in that, The bottom glaze layer is prepared from the following components in parts by weight: 40 parts of potassium feldspar, 30 parts of clay, 16 parts of white corundum, 6 parts of talc, 7 parts of bentonite, 6 parts of zirconium silicate, 6 parts of zinc oxide.

3. The ceramic product with metallic luster according to claim 1, characterized in that, The surface glaze layer is prepared from the following components in parts by weight: 35 parts of quartz, 23 parts of feldspar, 12 parts of talc powder, 10 parts of mica, 7 parts of zirconium silicate, 5 parts of lithium porcelain stone, 2 parts of colorant A.

4. The ceramic product with metallic luster according to claim 1, characterized in that, In the transparent glaze layer, the weight ratio of the transparent frit to the colorant B is 40-50:

1.

5. The ceramic product with metallic luster according to claim 1, characterized in that, The chemical composition of the transparent frit includes, by weight percentage: 53.2% of SiO2, 7.8% of Al2O3, 8.6% of MgO, 6.1% of Na2O, 4.2% of K2O, 4.6% of ZrO2, 1.7% of ZnO, 1.7% of TiO2, 1.6% of CaO, 1.5% of BaO, 0.7% of CeO2, 0.6% of Li2O, and the balance is loss on ignition.

6. The ceramic product with metallic luster according to claim 1, characterized in that, In S1, the mass ratio of the metal oxide powder, CMC and water is 40-50:1:2-10.

7. A method for preparing the ceramic product with metallic luster according to any one of claims 1 - 6, characterized in that, It includes the following steps: S1. Green body preparation; S2. Applying the bottom glaze: Mix the raw materials of the bottom glaze layer and then wet ball mill until the fineness of the material is 300-400 mesh, screen to remove iron, add water to obtain the bottom glaze slurry, and the solid content of the bottom glaze slurry is 30-40%; Pour the bottom glaze slurry on the green body, and then dry for standby. S3. Applying the surface glaze: Mix the raw materials of the surface glaze layer and then wet ball mill until the fineness of the material is 400-500 mesh, add water to obtain the surface glaze slurry, and the solid content of the surface glaze slurry is 45-50%; Pour the surface glaze slurry on the bottom glaze, and then dry for standby. S4. Low-temperature firing: Fire at 750-900 °C for 100-150 minutes. S5. Apply transparent glaze: Mix the transparent frit and colorant B, then perform wet ball milling until the fineness of the material reaches 200 - 300 mesh, add water to obtain the transparent glaze slurry, and the solid content of the transparent glaze slurry is 45 - 50%; Pour the transparent glaze on the surface glaze layer after firing and cooling. S6. High - temperature firing: After the transparent glaze layer is dried, continue firing. The firing temperature is 1100 - 1300 °C, and the firing time is 3 - 4 hours.

8. The method for preparing the ceramic product with metallic luster according to claim 7, characterized in that, When applying the bottom glaze, the specific gravity of the glaze is 1.45 - 1.55 g / ml, and the glaze application amount is 400 - 450 g / m 2 ; when applying the top glaze, the specific gravity of the glaze is 1.60 - 1.70 g / ml, and the glaze application amount is 600 - 700 g / m 2 ; when applying the transparent glaze, the specific gravity of the glaze is 1.70 - 1.80 g / ml, and the glaze application amount is 700 - 750 g / m 2 .

9. The method for preparing the ceramic product with metallic luster according to claim 8, characterized in that, When applying the bottom glaze, the specific gravity of the glaze is 1.48 g / ml, and the glaze application amount is 425 g / m 2 ; when applying the top glaze, the specific gravity of the glaze is 1.67 g / ml, and the glaze application amount is 674 g / m 2 ; when applying the transparent glaze, the specific gravity of the glaze is 1.75 g / ml, and the glaze application amount is 737 g / m 2 .

10. The method for preparing the ceramic product with metallic luster according to claim 7, characterized in that, S4. Low - temperature firing: Fire at 800 °C for 120 minutes; S6. High - temperature firing: After the transparent glaze layer is dried, continue firing. The firing temperature is 1200 °C, and the firing time is 3 hours.

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