1. The alluvial gold glaze ceramic tile is characterized by sequentially comprising a blank layer, a ground glaze layer, an ink-jet pattern layer, a process effect layer and a protective glaze layer from bottom to top; the preparation raw materials of the process effect layer comprise placer gold crystals and placer gold glaze;

the preparation raw materials of the alluvial gold crystal comprise, by weight: 2-5 parts of albite, 1-3 parts of kaolin, 0.1-0.5 part of strontium carbonate, 85-90 parts of ferric oxide, 0.5-1 part of titanium oxide, 0.5-1 part of barium carbonate, 0.5-1 part of manganese dioxide and 1-2 parts of calcined talc;

the preparation method of the alluvial gold glaze comprises the following steps of: 40-48 parts of albite, 5-6 parts of kaolin, 3-6 parts of potassium feldspar, 3-6 parts of fluorite, 18-25 parts of ferric oxide, 2-5 parts of quartz, 6-8 parts of calcite, 2-6 parts of wollastonite and 1-2 parts of calcined talc.

2. The shajin glaze ceramic tile of claim 1, wherein the raw materials for preparing the craft effect layer further comprise colored dry granules, wherein the colored dry granules comprise black dry granules and dark green dry granules;

the preparation chemical components of the black dry granules comprise the following components in parts by weight: 39-47 parts of silicon dioxide, 12-17 parts of aluminum oxide, 0.5-2.0 parts of potassium oxide, 0.5-2.0 parts of sodium oxide, 12-16 parts of calcium oxide, 4-8 parts of magnesium oxide, 4-8 parts of barium oxide, 3-6.5 parts of diboron trioxide, 1-3 parts of fluorine, 1.5-3.0 parts of cobalt oxide and 0.5-1.5 parts of ferric oxide;

the preparation chemical components of the dark green dry granules comprise the following components in parts by weight: 39-47 parts of silicon dioxide, 7-12 parts of aluminum oxide, 0.5-2.0 parts of potassium oxide, 0.5-2.0 parts of sodium oxide, 12-16 parts of calcium oxide, 4-8 parts of magnesium oxide, 4-8 parts of barium oxide, 3-6.5 parts of diboron trioxide, 1-3 parts of fluorine, 1.5-3.0 parts of chromium oxide and 1-2 parts of cobalt oxide.

3. A method for preparing a placer gold glaze ceramic tile, which is the placer gold glaze ceramic tile as claimed in any one of claims 1 or 2, and comprises the following steps:

(1) preparing a green body layer, a ground glaze layer and an ink-jet pattern layer of the alluvial gold glaze ceramic tile from bottom to top in sequence to obtain a green body a;

(2) preparing a placer gold crystal and a placer gold glaze according to a formula, uniformly mixing the placer gold crystal and the placer gold glaze, adding a printing paste to obtain a mixed glaze x, and positioning and applying the mixed glaze x on the surface of the green body a in the step (1) to obtain a green body b;

or preparing a placer gold crystal, a placer gold glaze and colored dry particles according to a formula, then uniformly mixing the placer gold crystal, the placer gold glaze and the colored dry particles, adding printing paste to obtain a mixed glaze y, and then positioning and applying the mixed glaze y on the surface of the green body a in the step (1) to obtain a green body c;

(3) and (3) spraying a layer of protective glaze on the surface of the green body b or the green body c in the step (2), and then putting the green body b or the green body c into a roller kiln for sintering to obtain the gulch-gold glaze ceramic tile.

4. The preparation method according to claim 3, wherein in the step (2), the specific preparation method of the alluvial gold crystal comprises the following steps: weighing the preparation raw materials according to the formula, uniformly mixing, placing into a kiln, raising the temperature in the kiln from room temperature to 250-350 ℃, raising the temperature for 50min, and preserving the heat for 5 min; then the temperature is increased to 900 ℃ and 950 ℃, the temperature rise time is 80min, and the heat preservation time is 5 min; then heating to 1300 ℃ and 1400 ℃, heating for 50min, and keeping the temperature for 10 min; then cooling to 1000-1080 ℃, cooling for 10min, and preserving heat for 1-1.5 hours; then waiting for the temperature in the kiln to be naturally cooled to be below 100 ℃ to obtain a placer gold crystal; and crushing the obtained placer gold crystals, and sieving the crushed placer gold crystals with a 40-80-mesh sieve to obtain the placer gold crystals.

5. The preparation method according to claim 3, wherein in the step (2), the specific preparation method of the placer gold glaze comprises the following steps: weighing the preparation raw materials according to the formula, adding sodium tripolyphosphate and sodium methyl cellulose, and performing ball milling to obtain the alluvial gold glaze.

6. The preparation method according to claim 5, wherein in the step (2), the addition amount of the sodium tripolyphosphate is 0.15% of the weight of the alluvial gold glaze raw material, the addition amount of the sodium methylcellulose is 0.15% of the weight of the alluvial gold glaze raw material, and the fineness of the alluvial gold glaze after ball milling is 0.6-0.8% of the residue on a screen with 325 meshes.

7. The method according to claim 3, wherein in the step (2): in the mixed glaze material x, the weight ratio of the placer gold crystals to the placer gold glaze is 2-3: 7-8; in the mixed glaze material y, the weight ratio of the placer gold crystals, the placer gold glaze and the colored dry particles is 1-2: 6-8: 1-2.

8. The method according to claim 3, wherein in the step (2): the adding amount of the printing paste is 70-90% of the total weight of the mixture of the alluvial gold crystal and the alluvial gold glaze, or 70-90% of the total weight of the mixture of the alluvial gold crystal, the alluvial gold glaze and the colored dry particles; the printing paste is prepared by mixing sodium methylcellulose and water in a ratio of 1: 10 weight ratio of the mixed paste.

9. The preparation method according to claim 3, wherein in the step (2), the mixed glaze x and the mixed glaze y are both in a roller glazing manner, and the thickness of the mixed glaze x and the mixed glaze y in the positioning glazing manner is 1.5-2 mm.

10. The method for preparing ceramic tiles according to claim 3, further comprising the step of polishing the ceramic tiles subjected to step (3) to obtain the placer gold glaze ceramic tiles.

Background

Along with the iterative upgrade of the technology, the rapid development of the building ceramic tiles is realized, products with various colors and technologies overlapped from antique bricks with small specifications to large-specification rock boards in the modern fashion whole industry are obtained, a great selection space is provided for consumers, and the home environment is greatly improved. Due to the improvement of the product requirements of consumers, the public not only focuses more and more on the texture of the surface of the ceramic tile, but also pursues more and more on the aspects of art and culture. At present, pattern design materials of architectural ceramics are mostly from marble, jade, sandstone and cement, and are rarely from Chinese traditional porcelain, and the alluvial gold glaze is mainly presented in Chinese traditional artistic ceramic products, but is not presented on the architectural ceramic products at present.

The alluvial gold glaze belongs to one of crystal glazes, is a black glaze from the Han Dynasty, and the main color of the black glaze is that the alluvial gold crystal is suspended in a glaze layer after being sintered because the black glaze contains a large amount of ferric oxide and the glaze layer is thick. The crystal in the alluvial gold glaze artistic ceramic is usually ferric oxide crystallization, generally considered as a golden red and flashing crystal formed by firstly dissolving ferric oxide in glaze at high temperature and forming supersaturated solution of iron, then precipitating ferric oxide crystal, and slowly burning, insulating, slowly cooling and crystallizing glaze, wherein the sintering mode of the alluvial gold glaze is completely different from the traditional fast sintering of building ceramic tiles, if a crystallization effect is required to be generated, slow sintering and slow cooling are required, the period reaches more than 12 hours, perfect crystallization glaze can be sintered, the sintering of the building ceramic tiles is generally within 1 hour, and the crystallization of the alluvial gold glaze is difficult to realize under the existing conditions for producing the building ceramic tiles.

The invention provides a alluvial gold glaze ceramic tile and a preparation method thereof, aiming at solving the problem of how to prepare an alluvial gold glaze ceramic tile product with alluvial gold crystals on the glaze surface under the condition of quick firing.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a alluvial gold glaze ceramic tile with alluvial gold crystals on the glaze surface.

In order to achieve the purpose, the invention adopts the technical scheme that: a alluvial gold glaze ceramic tile comprises a blank layer, a ground glaze layer, an ink-jet pattern layer, a process effect layer and a protective glaze layer from bottom to top in sequence; the preparation raw materials of the process effect layer comprise placer gold crystals and placer gold glaze; the preparation raw materials of the alluvial gold crystal comprise, by weight: 2-5 parts of albite, 1-3 parts of kaolin, 0.1-0.5 part of strontium carbonate, 85-90 parts of ferric oxide, 0.5-1 part of titanium oxide, 0.5-1 part of barium carbonate, 0.5-1 part of manganese dioxide and 1-2 parts of calcined talc; the preparation method of the alluvial gold glaze comprises the following steps of: 40-48 parts of albite, 5-6 parts of kaolin, 3-6 parts of potassium feldspar, 3-6 parts of fluorite, 18-25 parts of ferric oxide, 2-5 parts of quartz, 6-8 parts of calcite, 2-6 parts of wollastonite and 1-2 parts of calcined talc.

The technological effect is applied to the ceramic tiles in the field of construction, and the main difficulty is that the iron sesquioxide is difficult to crystallize in the glaze and form placer gold crystals under the condition of quick firing of the conventional ceramic tiles. In order to solve the technical problem, the invention provides the alluvial gold glaze ceramic tile, which is prepared by preparing alluvial gold crystals and alluvial gold glaze firstly and mixing the alluvial gold crystals and the alluvial gold glaze to prepare the technological effect layer of the alluvial gold glaze ceramic tile, so that the alluvial gold glaze ceramic tile can be prepared under the conditions of the existing production of building ceramic tiles. In addition, in order to ensure that the placer gold crystals are complete and are not melted in the glaze when the placer gold crystals are added into the glaze for glaze firing, a special placer gold glaze is needed to keep the shape, size and color of the placer gold crystals stable; the special alluvial gold glaze is different from other glazes in formula, contains a large amount of ferric oxide, forms a common phase with alluvial gold crystals during firing, and ensures that the alluvial gold crystals are not dissolved in the glazes, thereby maintaining the integrity of the shape and size of the alluvial gold crystals.

In a word, the alluvial gold glaze ceramic tile provided by the invention realizes the preparation of the alluvial gold glaze ceramic tile with alluvial gold crystals on the glaze surface under the existing rapid firing process condition within 1 hour of the building ceramic tile through formulation screening of alluvial gold crystals and alluvial gold glaze and the steps of preparing the alluvial gold crystals and then mixing the two, and realizes the crystallization effect of the alluvial gold glaze.

The preparation raw materials of the alluvial gold crystal comprise, by weight: 2-5 parts of albite, 1-3 parts of kaolin, 0.5-0.1 part of strontium carbonate, 85-90 parts of ferric oxide, 0.5-1 part of titanium oxide, 0.5-1 part of barium carbonate, 0.5-1 part of manganese dioxide and 1-2 parts of calcined talc. The albite in the formula plays a role in fluxing, the range of the weight parts is most excellent from 2 to 5 parts, experiments show that the albite is preferably 3 parts, the fluxing function is not obvious enough when the albite is less, and the temperature of the formula is integrally lower when the albite is more; strontium carbonate, titanium oxide, barium carbonate and manganese dioxide are comprehensive crystallization promoters, play a role in promoting ferric oxide crystallization in the formula, the weight parts of the strontium carbonate, the titanium oxide, the barium carbonate and the manganese dioxide need to be controlled within the range, and the color of the final placer gold crystal can be changed when the strontium carbonate, the titanium oxide, the barium carbonate and the manganese dioxide are more than the total weight parts. The burning talc provides magnesium oxide, is a high-temperature flux and plays a role in reducing the temperature of the formula; ferric oxide is the primary source of the formulation that ultimately forms placer gold crystals.

The preparation raw materials of the placer gold glaze comprise the following components in parts by weight: 40-48 parts of albite, 5-6 parts of kaolin, 3-6 parts of potassium feldspar, 3-6 parts of fluorite, 18-25 parts of ferric oxide, 2-5 parts of quartz, 6-8 parts of calcite, 2-6 parts of wollastonite and 1-2 parts of calcined talc. In the formula, albite and potassium feldspar are used as main fusing agents of the glaze, so that the melting of the glaze is accelerated, and the maturing temperature of the glaze is reduced; the kaolin and the quartz are main frameworks of the glaze, and the fluorite, the calcite and the wollastonite provide calcium oxide components, so that the melting maturation of the glaze is accelerated, the high-temperature viscosity of the glaze is reduced, and the glaze is helpful for glazeFlatness of the material on the green body. The burned talc provides a magnesium oxide component, which is a high temperature flux that promotes melting of the glaze at high temperatures. Adding ferric oxide to make Fe in glaze₂O₃The content is saturated and is offset by Fe₂O₃The reverse reaction of the main alluvial gold crystal particles in the glaze is beneficial to keeping the shape of alluvial gold crystals without being melted by the glaze.

As a preferred embodiment of the sand-gold glaze ceramic tile, the raw materials for preparing the process effect layer also comprise colored dry particles; more preferably, the colored dry particles include black dry particles and dark green dry particles. The process effect layer is prepared from the raw materials of colored dry particles, and aims to decorate the colorful effect of the glaze, the colored dry particles and the alluvial gold crystals are suspended in the alluvial gold special glaze layer, different crystal surfaces reflect different light rays, and the luster effect is greatly enriched.

As a preferred embodiment of the sand-gold glaze ceramic tile, the preparation chemical components of the black dry granules comprise the following components in parts by weight: 39-47 parts of silicon dioxide, 12-17 parts of aluminum oxide, 0.5-2.0 parts of potassium oxide, 0.5-2.0 parts of sodium oxide, 12-16 parts of calcium oxide, 4-8 parts of magnesium oxide, 4-8 parts of barium oxide, 3-6.5 parts of diboron trioxide, 1-3 parts of fluorine, 1.5-3.0 parts of cobalt oxide and 0.5-1.5 parts of ferric oxide.

As a preferred embodiment of the sand-gold glaze ceramic tile, the preparation chemical components of the dark green dry granules comprise the following components in parts by weight: 39-47 parts of silicon dioxide, 7-12 parts of aluminum oxide, 0.5-2.0 parts of potassium oxide, 0.5-2.0 parts of sodium oxide, 12-16 parts of calcium oxide, 4-8 parts of magnesium oxide, 4-8 parts of barium oxide, 3-6.5 parts of diboron trioxide, 1-3 parts of fluorine, 1.5-3.0 parts of chromium oxide and 1-2 parts of cobalt oxide.

In addition, the invention also aims to provide a preparation method of the alluvial gold glaze ceramic tile, which comprises the following steps:

(1) preparing a green body layer, a ground glaze layer and an ink-jet pattern layer of the alluvial gold glaze ceramic tile from bottom to top in sequence to obtain a green body a;

(2) preparing a placer gold crystal and a placer gold glaze according to a formula, uniformly mixing the placer gold crystal and the placer gold glaze, adding a printing paste to obtain a mixed glaze x, and positioning and applying the mixed glaze x on the surface of the green body a in the step (1) to obtain a green body b;

or preparing a placer gold crystal, a placer gold glaze and colored dry particles according to a formula, then uniformly mixing the placer gold crystal, the placer gold glaze and the colored dry particles, adding printing paste to obtain a mixed glaze y, and then positioning and applying the mixed glaze y on the surface of the green body a in the step (1) to obtain a green body c;

(3) and (3) spraying a layer of protective glaze on the surface of the green body b or the green body c in the step (2), and then putting the green body b or the green body c into a roller kiln for sintering to obtain the gulch-gold glaze ceramic tile.

As a preferable embodiment of the preparation method, the preparation method further comprises the step of polishing the ceramic tile subjected to the step (3) to obtain the Sanjin glaze ceramic tile.

2-5 parts of albite, 1-3 parts of kaolin, 0.5-0.1 part of strontium carbonate, 85-90 parts of ferric oxide, 0.5-1 part of titanium oxide, 0.5-1 part of barium carbonate, 0.5-1 part of manganese dioxide and 1-2 parts of calcined talc

As a preferred embodiment of the preparation method of the present invention, in the step (2), the specific preparation method of the alluvial gold crystal comprises the following steps: weighing the preparation raw materials according to the formula, uniformly mixing, placing into a kiln, raising the temperature in the kiln from room temperature to 250-350 ℃, raising the temperature for 50min, and preserving the heat for 5 min; then the temperature is increased to 900 ℃ and 950 ℃, the temperature rise time is 80min, and the heat preservation time is 5 min; then heating to 1300 ℃ and 1400 ℃, heating for 50min, and keeping the temperature for 10 min; then cooling to 1000-1080 ℃, cooling for 10min, and preserving heat for 1-1.5 hours; then waiting for the temperature in the kiln to be naturally cooled to be below 100 ℃ to obtain a placer gold crystal; and crushing the obtained placer gold crystals, and sieving the crushed placer gold crystals with a 40-80-mesh sieve to obtain the placer gold crystals.

The water and the structural water contained in the raw materials are gradually discharged at the temperature of 250 ℃ to 350 ℃, and the intermolecular combination of the materials is more compact. Decomposing barium carbonate and strontium carbonate to discharge CO in the temperature range of 900-950 DEG C₂Leaving the fluxing materials BaO and SrO. The fluxing substances and ferric oxide react together to form a eutectic body in the temperature range of 1300 ℃ and 1400 ℃, and the eutectic bodyThe optimal temperature range of the melting reaction of each material is that the ferric oxide is not fully melted when the temperature is lower than 1300 ℃, more time and energy are needed when the temperature is higher than 1400 ℃, and the production efficiency is delayed; in the temperature reduction range of 1000-1080 ℃, the alluvial gold crystal with the main component of Fe2O3 is gradually crystallized and formed, and the sufficient temperature reduction and heat preservation time ensures the yield of the alluvial gold crystal. Under the arrangement of the temperature curve, ferric oxide in the formula of the alluvial gold crystal is firstly dissolved in glaze at high temperature to form supersaturated solution of iron, and BaO and TiO₂、Fe₂O_3、Al₂O₃And SiO₂Metastable boundary phase of system composition, Fe₂O₃Oversaturation to precipitate gold red alpha-Fe₂O₃Gradually forming crystal nucleus which grows up gradually in heat preservation. With Fe₂O₃The crystal is a gold sand glaze crystal grain with the finest yellow light and the coarsest red light, and the gold sand glaze crystal is obtained after processing, crushing and granulation. And further, crushing the alluvial gold crystal by using double-roller crushing equipment, screening the crushed powder by using a 40-80-mesh screen to obtain qualified alluvial gold crystal particles for later use, and performing reworking crushing on the powder with the particle size of more than 40 meshes by using return equipment until the particle size is controlled within the range of 40-80 meshes, wherein the powder with the particle size of less than 80 meshes can be recycled.

As a preferred embodiment of the preparation method of the present invention, in the step (2), the specific preparation method of the placer gold glaze comprises the following steps: weighing the preparation raw materials according to the formula, adding sodium tripolyphosphate and sodium methyl cellulose, and performing ball milling to obtain the alluvial gold glaze.

As a preferable embodiment of the preparation method of the present invention, in the step (2), the addition amount of the sodium tripolyphosphate is 0.15% of the alluvial gold glaze raw material, the addition amount of the sodium methylcellulose is 0.15% of the alluvial gold glaze raw material, and the fineness of the alluvial gold glaze after ball milling is 0.6-0.8% of the residue on sieve with 325 meshes. The fineness of the alluvial gold glaze after ball milling is beneficial to melting of glaze and the stability of alluvial gold crystals in the glaze.

As a preferred embodiment of the production method of the present invention, in step (2): in the mixed glaze material x, the weight ratio of the placer gold crystals to the placer gold glaze is 2-3: 7-8; in the mixed glaze material y, the weight ratio of the placer gold crystals, the placer gold glaze and the colored dry particles is 1-2: 6-8: 1-2.

As a preferred embodiment of the preparation method, the addition amount of the printing paste is 70-90% of the total weight of the mixture of the alluvial gold crystals and the alluvial gold glaze, or 70-90% of the total weight of the mixture of the alluvial gold crystals, the alluvial gold glaze and the colored dry particles; the printing paste is prepared by mixing sodium methylcellulose and water in a ratio of 1: 10 weight ratio of the mixed paste. The printing paste can prevent the placer gold crystals and the colored dry particles from precipitating or agglomerating and layering, and can keep the placer gold crystals and the colored dry particles uniformly distributed in the placer gold glaze for a long time.

As a preferable embodiment of the preparation method of the present invention, in the step (2), both the positioning glazing manner of the mixed glaze x and the positioning glazing manner of the mixed glaze y are a roller glazing manner, and the positioning glazing thickness of the mixed glaze x and the mixed glaze y is 1.5-2 mm. And (4) adopting a roller glazing mode, and rolling and printing a mixture of the sand-gold crystals, the colored dry particles and the sand-gold special glaze according to the pattern. And carrying out accurate alignment on the design and the pattern after ink jet, and printing a mixture of the placer gold crystal and the placer gold glaze according to the designed part position. The thickness of the applied and printed glaze mixture is required to be 1.5-2mm, and under the condition that the thickness is too thin, the alluvial gold crystal can not be suspended in the glaze, so that the glittering effect of the alluvial gold crystal at different angles can not be produced. The thickness is too thick, which easily causes the deformation of the green brick after firing, so the thickness of the printed glaze is preferably controlled to be 1.5-2 mm.

Further, in the preparation method of the alluvial gold glaze ceramic tile, the step (2) is a preparation step of a process effect layer of the alluvial gold glaze ceramic tile; and (3) spraying a layer of protective glaze on the surface of the green body b or the green body c to obtain the preparation step of the protective glaze layer of the gulch-gold glaze ceramic tile.

Preferably, the protective glaze is a transparent glaze.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the invention, through formulation screening of the alluvial gold crystal and the alluvial gold glaze and the steps of preparing the alluvial gold crystal and the alluvial gold glaze independently and mixing the alluvial gold crystal and the alluvial gold glaze, the alluvial gold glaze ceramic tile with the alluvial gold crystal on the glaze surface is prepared under the existing rapid firing process condition within 1 hour of the architectural ceramic tile, and the crystallization effect of the alluvial gold glaze is realized;

(2) according to the invention, the glaze effect of the alluvial gold glaze in the ancient art ceramic is applied to the building ceramic product, so that the artistic value of the building ceramic tile is greatly improved, the level of home decoration is further improved, and the alluvial gold glaze ceramic tile has a wide market prospect;

(3) the alluvial gold glaze ceramic tile provided by the invention has high wear resistance and antifouling performance;

(4) the preparation method of the alluvial gold glazed ceramic tile provided by the invention can realize quick firing in a roller kiln and can form the glazed ceramic tile with alluvial gold effect, and the kiln firing parameters for producing the ordinary ceramic tile do not need to be changed when the alluvial gold glazed ceramic tile is produced by the method.

Drawings

FIG. 1 crystal sparkle effect of placer gold crystals prepared in example 1 of the invention after application to ceramic tiles;

FIG. 2 is an SEM micrograph of a sandgold glazed ceramic tile glaze layer prepared in example 1 of the present invention;

FIG. 3 is an XRD phase analysis of the placer gold crystals prepared in example 1 of the invention;

FIG. 4 is an SEM micrograph of alluvial gold crystals prepared in example 1 of the present invention;

fig. 5 is an SEM micrograph of the layer of sandgold glazed ceramic tile glaze prepared in comparative example 1.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following detailed drawings and examples.

Example 1

The embodiment of the invention relates to a alluvial gold glaze ceramic tile, which sequentially comprises a blank layer, a ground glaze layer, an ink-jet pattern layer, a process effect layer and a protective glaze layer from bottom to top; the preparation raw materials of the process effect layer comprise placer gold crystals, placer gold glaze and colored dry particles; wherein, the preparation raw materials of the placer gold crystal, the placer gold glaze and the colored dry particles are respectively as follows:

the preparation raw materials of the alluvial gold crystal comprise, by weight: 3 parts of albite, 3 parts of kaolin, 0.1 part of strontium carbonate, 88 parts of ferric oxide, 1 part of titanium oxide, 1 part of barium carbonate, 1 part of manganese dioxide and 2 parts of calcined talc;

the preparation raw materials of the alluvial gold glaze comprise, by weight: 46 parts of albite, 6 parts of kaolin, 5 parts of potassium feldspar, 5 parts of fluorite, 20 parts of ferric oxide, 4 parts of quartz, 8 parts of calcite, 4 parts of wollastonite and 2 parts of calcined talc;

the color dry particles comprise black dry particles and dark green dry particles, and the preparation chemical components of the black dry particles comprise the following components in parts by weight: 39 parts of silicon dioxide, 12 parts of aluminum oxide, 0.5 part of potassium oxide, 0.5 part of sodium oxide, 12 parts of calcium oxide, 4 parts of magnesium oxide, 4 parts of barium oxide, 3 parts of diboron trioxide, 1 part of fluorine, 1.5 parts of cobalt oxide and 0.5 part of ferric oxide;

the preparation chemical components of the dark green dry granules comprise the following components in parts by weight: 39 parts of silicon dioxide, 12 parts of aluminum oxide, 0.5 part of potassium oxide, 0.5 part of sodium oxide, 12 parts of calcium oxide, 4 parts of magnesium oxide, 4 parts of barium oxide, 3 parts of diboron trioxide, 1 part of fluorine, 1.5 parts of chromium oxide and 1 part of cobalt oxide.

The preparation method of the alluvial gold glaze ceramic tile comprises the following steps:

(1) preparing a green body layer, a ground glaze layer and an ink-jet pattern layer of the alluvial gold glaze ceramic tile from bottom to top in sequence to obtain a green body a;

(2) preparing a placer gold crystal, a placer gold glaze and colored dry particles according to a formula, and then mixing the placer gold crystal, the placer gold glaze and the colored dry particles according to a weight ratio of 1: 6: 1, uniformly mixing, adding printing paste (the adding amount of the printing paste is 70 percent of the total weight of the mixture of the alluvial gold crystal, the alluvial gold glaze and the colored dry particles), stirring and mixing the printing paste with sodium methylcellulose and water in a weight ratio of 1: 10 to obtain mixed glaze y, and positioning and applying the mixed glaze y on the surface of the green body a in the step (1) in a roller glazing manner, wherein the glazing thickness is 1.5mm to obtain a green body c;

the specific preparation method of the alluvial gold crystal comprises the following steps: weighing the preparation raw materials according to the formula, uniformly mixing, placing into a shuttle kiln, raising the temperature in the kiln from room temperature to 300 ℃, raising the temperature for 50min, and keeping the temperature for 5 min; then the temperature in the kiln is increased from 300 ℃ to 900 ℃, the temperature rising time is 80min, and the heat preservation time is 5 min; then heating the temperature in the kiln from 900 ℃ to 1300 ℃, wherein the heating time is 50min, and the temperature is kept for 10 min; then cooling to 1080 ℃, cooling for 10min, and preserving heat for 1 hour; then waiting for the temperature in the kiln to be naturally cooled to be below 100 ℃ to obtain a placer gold crystal; crushing the obtained placer gold crystals, and screening the obtained placer gold crystals by a 40-mesh screen to obtain the placer gold crystals;

the preparation method of the alluvial gold glaze comprises the following steps: weighing the preparation raw materials according to the formula, adding sodium tripolyphosphate and sodium methyl cellulose, and performing ball milling to obtain the alluvial gold glaze; the adding amount of the sodium tripolyphosphate is 0.15 percent of the alluvial gold glaze raw material, the adding amount of the sodium methylcellulose is 0.15 percent of the alluvial gold glaze raw material, and the fineness of the alluvial gold glaze after ball milling is 0.6 percent of the rest of 325-mesh sieve;

(3) spraying a layer of protective glaze on the surface of the green body c in the step (2), and then putting the green body c into a roller kiln for sintering;

(4) and (4) polishing the ceramic tile subjected to the step (3) to obtain the gold glazed ceramic tile.

Example 2

The embodiment of the invention relates to a alluvial gold glaze ceramic tile, which sequentially comprises a blank layer, a ground glaze layer, an ink-jet pattern layer, a process effect layer and a protective glaze layer from bottom to top; the preparation raw materials of the process effect layer comprise placer gold crystals, placer gold glaze and colored dry particles; wherein, the preparation raw materials of the placer gold crystal, the placer gold glaze and the colored dry particles are respectively as follows:

the preparation raw materials of the alluvial gold crystal comprise, by weight: 2 parts of albite, 1 part of kaolin, 0.5 part of strontium carbonate, 85 parts of ferric oxide, 0.5 part of titanium oxide, 0.5 part of barium carbonate, 0.5 part of manganese dioxide and 1 part of calcined talc;

the preparation raw materials of the alluvial gold glaze comprise, by weight: 40 parts of albite, 5 parts of kaolin, 3 parts of potassium feldspar, 3 parts of fluorite, 18 parts of ferric oxide, 2 parts of quartz, 6 parts of calcite, 2 parts of wollastonite and 1 part of calcined talc;

the color dry particles comprise black dry particles and dark green dry particles, and the preparation chemical components of the black dry particles comprise the following components in parts by weight: 47 parts of silicon dioxide, 17 parts of aluminum oxide, 2.0 parts of potassium oxide, 2.0 parts of sodium oxide, 16 parts of calcium oxide, 8 parts of magnesium oxide, 8 parts of barium oxide, 6.5 parts of boron trioxide, 3 parts of fluorine, 3.0 parts of cobalt oxide and 1.5 parts of iron oxide;

the preparation chemical components of the dark green dry granules comprise the following components in parts by weight: 47 parts of silicon dioxide, 7 parts of aluminum oxide, 2.0 parts of potassium oxide, 2.0 parts of sodium oxide, 16 parts of calcium oxide, 8 parts of magnesium oxide, 8 parts of barium oxide, 6.5 parts of diboron trioxide, 3 parts of fluorine, 3.0 parts of chromium oxide and 2 parts of cobalt oxide.

The preparation method of the alluvial gold glaze ceramic tile comprises the following steps:

(1) preparing a green body layer, a ground glaze layer and an ink-jet pattern layer of the alluvial gold glaze ceramic tile from bottom to top in sequence to obtain a green body a;

(2) preparing a placer gold crystal, a placer gold glaze and colored dry particles according to a formula, and then mixing the placer gold crystal, the placer gold glaze and the colored dry particles according to a weight ratio of 2: 8: 2, uniformly mixing, adding printing paste (the adding amount of the printing paste is 90% of the total weight of the mixture of the alluvial gold crystal, the alluvial gold glaze and the colored dry particles), stirring and mixing the printing paste with sodium methylcellulose and water in a weight ratio of 1: 10 to obtain mixed glaze y, and positioning and applying the mixed glaze y on the surface of the green body a in the step (1) in a roller glazing manner, wherein the glazing thickness is 2mm to obtain a green body c;

the specific preparation method of the alluvial gold crystal comprises the following steps: weighing the preparation raw materials according to the formula, uniformly mixing, placing into a shuttle kiln, raising the temperature in the kiln from room temperature to 300 ℃, raising the temperature for 50min, and keeping the temperature for 5 min; then the temperature in the kiln is increased from 300 ℃ to 900 ℃, the temperature rising time is 80min, and the heat preservation time is 5 min; then heating the temperature in the kiln from 900 ℃ to 1300 ℃, wherein the heating time is 50min, and the temperature is kept for 10 min; then cooling to 1080 ℃, cooling for 10min, and preserving heat for 1 hour; then waiting for the temperature in the kiln to be naturally cooled to be below 100 ℃ to obtain a placer gold crystal; crushing the obtained placer gold crystals, and screening the obtained placer gold crystals by a 80-mesh screen to obtain the placer gold crystals;

the preparation method of the alluvial gold glaze comprises the following steps: weighing the preparation raw materials according to the formula, adding sodium tripolyphosphate and sodium methyl cellulose, and performing ball milling to obtain the alluvial gold glaze; the adding amount of the sodium tripolyphosphate is 0.15 percent of the alluvial gold glaze raw material, the adding amount of the sodium methylcellulose is 0.15 percent of the alluvial gold glaze raw material, and the fineness of the alluvial gold glaze after ball milling is 0.8 percent of the rest of 325-mesh sieve;

(3) spraying a layer of protective glaze on the surface of the green body c in the step (2), and then putting the green body c into a roller kiln for sintering;

(4) and (4) polishing the ceramic tile subjected to the step (3) to obtain the gold glazed ceramic tile.

Example 3

The embodiment of the invention relates to a alluvial gold glaze ceramic tile, which sequentially comprises a blank layer, a ground glaze layer, an ink-jet pattern layer, a process effect layer and a protective glaze layer from bottom to top; the preparation raw materials of the process effect layer comprise placer gold crystals, placer gold glaze and colored dry particles; wherein, the preparation raw materials of the placer gold crystal, the placer gold glaze and the colored dry particles are respectively as follows:

the preparation raw materials of the alluvial gold crystal comprise, by weight, 5 parts of albite, 3 parts of kaolin, 0.1 part of strontium carbonate, 90 parts of ferric oxide, 1 part of titanium oxide, 1 part of barium carbonate, 1 part of manganese dioxide and 2 parts of calcined talc;

the preparation raw materials of the alluvial gold glaze comprise, by weight, 48 parts of albite, 6 parts of kaolin, 6 parts of potash feldspar, 6 parts of fluorite, 25 parts of ferric oxide, 2 parts of quartz, 8 parts of calcite, 6 parts of wollastonite and 2 parts of calcined talc

The color dry particles comprise black dry particles and dark green dry particles, and the preparation chemical components of the black dry particles comprise the following components in parts by weight: 40 parts of silicon dioxide, 15 parts of aluminum oxide, 1 part of potassium oxide, 1 part of sodium oxide, 13 parts of calcium oxide, 5 parts of magnesium oxide, 6 parts of barium oxide, 4 parts of boron trioxide, 2 parts of fluorine, 2 parts of cobalt oxide and 1 part of ferric oxide;

the preparation chemical components of the dark green dry granules comprise the following components in parts by weight: 45 parts of silicon dioxide, 10 parts of aluminum oxide, 1 part of potassium oxide, 1 part of sodium oxide, 14 parts of calcium oxide, 5 parts of magnesium oxide, 5 parts of barium oxide, 4 parts of diboron trioxide, 2 parts of fluorine, 2 parts of chromium oxide and 1.5 parts of cobalt oxide.

The preparation method of the alluvial gold glaze ceramic tile comprises the following steps:

(1) preparing a green body layer, a ground glaze layer and an ink-jet pattern layer of the alluvial gold glaze ceramic tile from bottom to top in sequence to obtain a green body a;

(2) preparing a placer gold crystal, a placer gold glaze and colored dry particles according to a formula, and then mixing the placer gold crystal, the placer gold glaze and the colored dry particles according to a weight ratio of 1.5: 7: 1.5, uniformly mixing, adding a printing paste (the adding amount of the printing paste is 80% of the total weight of the mixture of the alluvial gold crystal, the alluvial gold glaze and the colored dry particles), stirring and mixing the printing paste with water according to the weight ratio of 1: 10 to obtain a mixed glaze material y, and then positioning and applying the mixed glaze material y on the surface of the green body a in the step (1) in a roller glazing manner, wherein the glazing thickness is 1.8mm to obtain a green body c;

the specific preparation method of the alluvial gold crystal comprises the following steps: weighing the preparation raw materials according to the formula, uniformly mixing, placing into a shuttle kiln, raising the temperature in the kiln from room temperature to 300 ℃, raising the temperature for 50min, and keeping the temperature for 5 min; then the temperature in the kiln is increased from 300 ℃ to 900 ℃, the temperature rising time is 80min, and the heat preservation time is 5 min; then heating the temperature in the kiln from 900 ℃ to 1300 ℃, wherein the heating time is 50min, and the temperature is kept for 10 min; then cooling to 1080 ℃, cooling for 10min, and preserving heat for 1 hour; then waiting for the temperature in the kiln to be naturally cooled to be below 100 ℃ to obtain a placer gold crystal; crushing the obtained placer gold crystals, and screening the obtained placer gold crystals by a 60-mesh screen to obtain the placer gold crystals;

the preparation method of the alluvial gold glaze comprises the following steps: weighing the preparation raw materials according to the formula, adding sodium tripolyphosphate and sodium methyl cellulose, and performing ball milling to obtain the alluvial gold glaze; the adding amount of the sodium tripolyphosphate is 0.15 percent of the alluvial gold glaze raw material, the adding amount of the sodium methylcellulose is 0.15 percent of the alluvial gold glaze raw material, and the fineness of the alluvial gold glaze after ball milling is 0.7 percent of the rest of 325-mesh sieve;

(3) spraying a layer of protective glaze on the surface of the green body c in the step (2), and then putting the green body c into a roller kiln for sintering;

(4) and (4) polishing the ceramic tile subjected to the step (3) to obtain the gold glazed ceramic tile.

Example 4

The embodiment of the invention relates to a alluvial gold glaze ceramic tile, which sequentially comprises a blank layer, a ground glaze layer, an ink-jet pattern layer, a process effect layer and a protective glaze layer from bottom to top; the preparation raw materials of the process effect layer comprise placer gold crystals and placer gold glaze; wherein, the preparation raw materials of the placer gold crystal and the placer gold glaze are respectively as follows:

the preparation raw materials of the alluvial gold crystal comprise, by weight: 5 parts of albite, 3 parts of kaolin, 0.5 part of strontium carbonate, 85 parts of ferric oxide, 1 part of titanium oxide, 1 part of barium carbonate, 1 part of manganese dioxide and 2 parts of calcined talc;

the preparation raw materials of the alluvial gold glaze comprise, by weight: 40 parts of albite, 5 parts of kaolin, 3 parts of potassium feldspar, 3 parts of fluorite, 18 parts of ferric oxide, 2 parts of quartz, 6 parts of calcite, 2 parts of wollastonite and 1 part of calcined talc.

The preparation method of the alluvial gold glaze ceramic tile comprises the following steps:

(1) preparing a green body layer, a ground glaze layer and an ink-jet pattern layer of the alluvial gold glaze ceramic tile from bottom to top in sequence to obtain a green body a;

(2) preparing a placer gold crystal and a placer gold glaze according to a formula, uniformly mixing the placer gold crystal and the placer gold glaze according to a weight ratio of 2:8, adding a printing paste (the adding amount of the printing paste is 75% of the total weight of the mixture of the placer gold crystal and the placer gold glaze, and the printing paste is a paste obtained by stirring and mixing sodium methylcellulose and water according to a weight ratio of 1: 10) to obtain a mixed glaze x, and positioning and applying the mixed glaze x on the surface of the green body a in the step (1) in a roller glazing manner, wherein the glazing thickness is 2mm to obtain a green body b;

the specific preparation method of the alluvial gold crystal comprises the following steps: weighing the preparation raw materials according to the formula, uniformly mixing, placing into a shuttle kiln, raising the temperature in the kiln from room temperature to 300 ℃, raising the temperature for 50min, and keeping the temperature for 5 min; then the temperature in the kiln is increased from 300 ℃ to 900 ℃, the temperature rising time is 80min, and the heat preservation time is 5 min; then heating the temperature in the kiln from 900 ℃ to 1300 ℃, wherein the heating time is 50min, and the temperature is kept for 10 min; then cooling to 1080 ℃, cooling for 10min, and preserving heat for 1 hour; then waiting for the temperature in the kiln to be naturally cooled to be below 100 ℃ to obtain a placer gold crystal; crushing the obtained placer gold crystals, and then sieving the obtained placer gold crystals with a 50-mesh sieve to obtain the placer gold crystals;

the preparation method of the alluvial gold glaze comprises the following steps: weighing the preparation raw materials according to the formula, adding sodium tripolyphosphate and sodium methyl cellulose, and performing ball milling to obtain the alluvial gold glaze; the adding amount of the sodium tripolyphosphate is 0.15 percent of the alluvial gold glaze raw material, the adding amount of the sodium methylcellulose is 0.15 percent of the alluvial gold glaze raw material, and the fineness of the alluvial gold glaze after ball milling is 0.8 percent of the rest of 325-mesh sieve;

(3) and (3) spraying a layer of protective glaze on the surface of the green body b in the step (2), and then putting the green body b into a roller kiln to be fired to obtain the gulch-gold glaze ceramic tile.

Comparative example 1

The contrast is a ceramic tile which sequentially comprises a body layer, a ground glaze layer, an ink-jet pattern layer, a process effect layer and a protective glaze layer from bottom to top; the preparation raw materials of the process effect layer comprise placer gold crystals, placer gold glaze and colored dry particles; wherein, the preparation raw materials of the color dry granules of the alluvial gold crystal are respectively the same as that of the example 1

The alluvial gold glaze is a conventional alluvial gold glaze in the industry, and the preparation raw materials of the alluvial gold glaze comprise, by weight: 10 parts of kaolin, 26 parts of albite, 18 parts of potassium feldspar, 7 parts of ferric oxide, 12 parts of quartz, 15 parts of calcite, 8 parts of calcined talc and 4 parts of zinc oxide.

The preparation of the ceramic tiles described above is the same as in example 1.

Experimental example 1

In this experimental example, the placer gold glaze ceramic tile of example 1 of the present invention was subjected to microstructure morphology observation (SEM) and placer gold crystal flash effect observation, and the placer gold crystal in the placer gold glaze ceramic tile of example 1 was subjected to phase analysis and microstructure morphology observation (SEM); this example also performed microstructural topography observations (SEM) of the ceramic tiles described in comparative example 1.

The experimental method comprises the following steps: observing the glistening effect of the alluvial gold crystal in the alluvial gold glaze ceramic tile by using an optical microscope, and observing the microscopic structures of the alluvial gold glaze ceramic tile in the embodiment 1, the ceramic tile in the comparative example 1 and the alluvial gold crystal by using a Helios NanoLab 600i field emission environment scanning electron microscope which is produced by the American FEI company; the placer gold crystals were subjected to phase analysis using an X-ray diffractometer (XRD) model Dmax2500VB, and the results are shown in FIGS. 1 to 5.

The experimental results are as follows: fig. 1 is a diagram of the glittering effect of the placer crystals in the placer glaze ceramic tile according to example 1 of the present invention, and the glittering effect of the placer crystals in the placer glaze ceramic tile can be clearly observed from fig. 1;

microscopic structure morphology observation (SEM) is carried out on the alluvial gold glazed ceramic tile in the embodiment 1 of the invention and the ceramic tile in the comparative example 1, electronic scanning photographs are respectively shown in figures 2 and 5, and the results in figure 2 show that alluvial gold crystals in the alluvial gold glazed ceramic tile in the embodiment 1 of the invention are still completely remained in the glaze after being fired, while the alluvial gold crystals are not observed to be remained in the glaze in figure 5; therefore, the alluvial gold glaze component can play an effective protection role on alluvial gold crystals, and the prepared alluvial gold glaze ceramic tile can show the alluvial gold crystal flashing effect.

The analysis of the alluvial gold crystal phase in the alluvial gold glazed ceramic tile in example 1 of the invention is shown in fig. 3, and the results in fig. 3 prove that the alluvial gold crystal prepared mainly consists of alpha-Fe₂O₃Crystal composition; an electron scanning micrograph of the alluvial gold crystals in the alluvial gold glazed ceramic tile according to example 1 of the present invention is shown in fig. 4, and the results of fig. 4 show that the alluvial gold crystalsMost of the glaze is flaky, and the structure can better show a glittering effect in the glaze.

Experimental example 2

In this experimental example, the general physical properties of the placer gold glaze ceramic tile described in example 1 were measured, and the measurement method and measurement results are shown in table 1.

TABLE 1 detection of various conventional physical properties of the Sandy gold glazed ceramic tiles

The properties of the alluvial gold glazed ceramic tile in the aspects of wear resistance, stain resistance, chemical corrosion resistance, low-concentration acid and alkali resistance and high-concentration acid and alkali resistance are mainly detected, and the detection data in table 1 show that the alluvial gold glazed ceramic tile in the aspects of wear resistance, stain resistance, chemical corrosion resistance, low-concentration acid and alkali resistance and high-concentration acid and alkali resistance all meet the requirements of national detection standards, except that the abrasion resistance is 3 grades and 1500 turns as common glazed tiles, the properties of other alluvial gold glazed ceramic tiles in the aspects of stain resistance, chemical corrosion resistance, low-concentration acid and alkali resistance and high-concentration acid and alkali resistance are all superior to those of common glazed tiles; therefore, the alluvial gold glaze ceramic tile has beautiful pattern effect, has the advantages of stain resistance, chemical corrosion resistance, low-concentration acid and alkali resistance and high-concentration acid and alkali resistance, and can be used as a floor tile for paving a floor tile, a wall tile for pasting a wall, and can be processed into a cabinet table top and a dining table.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.