CN110342959B - Photochromic ceramic glaze, photochromic ceramic tile and preparation method thereof - Google Patents
Photochromic ceramic glaze, photochromic ceramic tile and preparation method thereof Download PDFInfo
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- CN110342959B CN110342959B CN201910735999.7A CN201910735999A CN110342959B CN 110342959 B CN110342959 B CN 110342959B CN 201910735999 A CN201910735999 A CN 201910735999A CN 110342959 B CN110342959 B CN 110342959B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
Abstract
The invention discloses an optically variable ceramic glaze, an optically variable ceramic tile and a preparation method thereof, wherein a color-changing agent AgBr and a catalyst CuO are added into the optically variable ceramic glaze, so that after the optically variable ceramic glaze and the optically variable ceramic tile are fired, under the irradiation of light rays with different intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different intensity light rays and the catalyst, and further the change of color and shade is shown in appearance.
Description
Technical Field
The invention relates to the field of architectural ceramic production, in particular to a photochromic ceramic glaze, a photochromic ceramic tile and a preparation method thereof.
Background
The ceramic glaze is a layer of glass material covered on the surface of a ceramic tile blank, mainly consists of silicate minerals, and has the functions of covering and protecting ceramic products, beautifying the ceramic products and improving the decorative capability of the ceramic products. Most of the building ceramic tiles are made of common ceramic products, and the surface of a blank needs to be glazed and then decorated with patterns. With the continuous development of architectural ceramic technology and the higher and higher requirements of consumers on ceramic tile products, the glaze used by the ceramic tiles is more and more abundant and diversified.
However, the glaze on the surface of the ceramic tile in the existing market always shows constant appearance color along with the change of the intensity of external light and the change of an observation angle; at any time and any angle, an observer can only show the original color of the ceramic tile.
Therefore, how to provide a ceramic glaze material with color changing along with light, a ceramic tile with color changing along with light and a preparation method thereof become problems to be solved briefly.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a photochromic ceramic glaze, a photochromic ceramic tile and a preparation method thereof, and aims to solve the problem that the color of the existing ceramic tile cannot change along with light after being fired.
In order to solve the technical problems, the invention provides the following technical scheme: the photochromic ceramic glaze comprises the following chemical components in percentage by mass:
SiO2 41.6～54.8％；Al2O3 15.3～19.6％；Fe2O3 0.02～0.15；CaO 5.1～9.4％；MgO 3.8～7.6％；Na2O 2.3～6.2％；K2O 0.22～2.1％；ZnO 3.2～8.4％；TiO2 0.05～0.12％；B2O3 3.2～6.5％；BaO 2.0～8.2％；CuO 0.01～0.03％；AgBr 0.03～1.2％。
further, the photochromic ceramic glaze specifically comprises the following chemical components in percentage by mass:
SiO2 43.59％；Al2O3 18.44％；Fe2O3 0.14％；CaO 6.43％；MgO 6.88％；Na2O 3.03％；K2O 0.34％；ZnO 7.42％；TiO2 0.11％；B2O3 4.6％；BaO 8.2％；CuO 0.02％；AgBr 0.8％。
further, the purity of the CuO is not less than 99%, and the fineness is 500 meshes;
the purity of the AgBr is not less than 99 percent, and the fineness is 500 meshes.
In order to solve the above technical problems, the present invention provides another technical solution as follows: a preparation method of photochromic ceramic glaze comprises the following steps:
A. adding 45-90 g of water into every 100g of optically variable ceramic glaze, mixing, ball-milling, and controlling the ball-milling fineness to be 325 meshes of sieve for full sieving;
B. adding 0.03-1.20 g of silver bromide serving as a color-changing agent into every 100g of ball-milled glaze slip, and uniformly stirring;
C. and adding 0.01-0.03 g of catalyst copper oxide into every 100g of ball-milled glaze slip, and uniformly stirring.
Further, the purity of the silver bromide in the step B is not less than 99%, and the fineness of the silver bromide is 500 meshes;
and C, the purity of the copper oxide in the step C is not less than 99%, and the fineness of the copper oxide is 500 meshes.
In order to solve the above technical problems, the present invention provides another technical solution as follows: a preparation method of a photochromic ceramic tile comprises the following steps:
a. pressing and molding the blank, and drying the blank in a roller kiln to obtain a ceramic tile blank;
b. applying photochromic ceramic glaze on the ceramic tile blank to obtain a photochromic glaze layer;
c. firing and forming in a kiln to obtain the ceramic tile with the color changed along with the light;
wherein the photochromic ceramic glaze is the photochromic ceramic glaze.
Further, the glazing amount of the photochromic glaze in the step b is 240-500 g/m in terms of dry materials2。
Further, the photochromic glaze in the step b is applied to the ceramic tile blank body by a glaze spraying or glaze pouring process, and the specific gravity of the photochromic glaze is 1.35-1.80;
or, when the photochromic glaze in the step b is applied to the ceramic tile blank by a silk screen or rubber roll printing process, the specific gravity of the photochromic glaze is 1.25-1.65;
furthermore, the firing temperature in the step c is 1150-1220 ℃, and the firing time is 45-55 min.
In order to solve the above technical problems, the present invention provides another technical solution as follows: the photochromic ceramic tile is prepared by the preparation method of the ceramic tile with the flexibly controlled glaze glossiness.
Has the advantages that: the invention provides an optically variable ceramic glaze, an optically variable ceramic tile and a preparation method thereof, wherein the optically variable ceramic glaze comprises the following chemical components in percentage by mass: SiO 22 41.6～54.8％；Al2O315.3～19.6％；Fe2O3 0.02～0.15；CaO 5.1～9.4％；MgO 3.8～7.6％；Na2O 2.3～6.2％；K2O 0.22～2.1％；ZnO 3.2～8.4％；TiO2 0.05～0.12％；B2O33.2-6.5%; 2.0-8.2% of BaO; 0.01-0.03% of CuO; 0.03-1.2% of AgBr. The sum of the components of the photochromic ceramic glaze is 100 percent; by adding a color-changing agent AgBr and a catalyst CuO into the photochromic ceramic glaze, the color-changing agent in the glaze can generate decomposition and reduction reactions under the irradiation of light rays with different degrees of strength and under the action of the energy of the light rays with different degrees of strength and the catalyst after the photochromic ceramic glaze is fired, and further the surface of the photochromic ceramic glaze is shown in appearanceShowing the change of color and shade; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a photochromic ceramic glaze in the invention;
FIG. 2 is a schematic flow chart of a method for preparing optically variable ceramic tiles according to the present invention;
FIG. 3 is a schematic view of a three-dimensional structure of a photochromic ceramic tile according to the present invention;
description of reference numerals:
11. a ceramic tile green body; 12. a ceramic glaze layer changing color along with light.
Detailed Description
The invention provides a ceramic tile with a glaze surface gloss flexibly controlled and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the present invention provides a photochromic ceramic glaze, wherein the photochromic ceramic glaze comprises the following chemical components, by mass:
SiO2 41.6～54.8％；Al2O3 15.3～19.6％；Fe2O3 0.02～0.15；CaO 5.1～9.4％；MgO 3.8～7.6％；Na2O 2.3～6.2％；K2O 0.22～2.1％；ZnO 3.2～8.4％；TiO2 0.05～0.12％；B2O3 3.2～6.5％；BaO 2.0～8.2％；CuO 0.01～0.03％；AgBr 0.03～1.2％。
the sum of the components of the photochromic ceramic glaze is 100 percent; by adding a color-changing agent AgBr and a catalyst CuO into the photochromic ceramic glaze, the color-changing agent in the glaze can generate decomposition and reduction reactions under the irradiation of light rays with different degrees of strength and under the action of the energy of the light rays with different strengths and catalysts after the photochromic ceramic glaze is fired, and further shows the change of color and depth in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
In some embodiments, the chemical composition of the photochromic ceramic glaze specifically comprises, in mass percent:
SiO2 43.59％；Al2O3 18.44％；Fe2O3 0.14％；CaO 6.43％；MgO 6.88％；Na2O 3.03％；K2O 0.34％；ZnO 7.42％；TiO2 0.11％；B2O3 4.6％；BaO 8.2％；CuO 0.02％；AgBr 0.8％。
in some embodiments, the CuO has a purity of not less than 99% and a fineness of 500 mesh; the purity of the AgBr is not less than 99 percent, and the fineness is 500 meshes.
Referring to fig. 1, the present invention also provides a method for preparing a photochromic ceramic glaze, which comprises:
and step 13, adding 0.01-0.03 g of catalyst copper oxide into every 100g of ball-milled glaze slip, and uniformly stirring.
The photochromic ceramic glaze is the photochromic ceramic glaze of the invention; during the processing and production, every 100g of SiO2 41.6～54.8％、Al2O3 15.3～19.6％、Fe2O3 0.02～0.15、CaO 5.1～9.4％、MgO 3.8～7.6％、Na2O 2.3～6.2％、K2O 0.22～2.1％、ZnO 3.2～8.4％、TiO20.05～0.12％、B2O3Adding 45-90 g of water into a mixture of 3.2-6.5% and BaO 2.0-8.2%, mixing, and performing ball milling, wherein the ball milling fineness is controlled to be 325 meshes and the mixture is completely sieved; then, adding a silver bromide color-changing agent and a copper oxide catalyst, and further under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, so that the change of color and shade is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, the color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze can be optically reducedThe color-changing ceramic glaze material shows the change of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
In some embodiments, the silver bromide in step 12 has a purity of not less than 99% and a fineness of 500 mesh;
the purity of the copper oxide in the step 13 is not less than 99%, and the fineness is 500 meshes.
Referring to fig. 2, the present invention further provides a method for preparing optically variable ceramic tiles, which comprises:
step 21, pressing and forming the blank, and drying the blank in a roller kiln to obtain a ceramic tile blank;
step 22, applying photochromic ceramic glaze on the ceramic tile blank to obtain a photochromic glaze layer;
step 23, putting the ceramic tiles into a kiln for firing and forming to obtain the photochromic ceramic tiles;
wherein the photochromic ceramic glaze is the photochromic ceramic glaze provided by the invention.
It can be understood that the photochromic ceramic glaze is applied on the ceramic tile green body, so that the photochromic glaze layer comprises a silver bromide color-changing agent and a copper oxide catalyst; under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, and further the color and shade change is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weak, substances decomposed by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
In some embodiments, the applying amount of the photochromic glaze in the step 22 is 240-500 g/m on a dry basis2。
In some embodiments, the photochromic glaze in step 22 is applied to the ceramic tile blank by a glaze spraying or glaze pouring process, and the specific gravity of the photochromic glaze is 1.35-1.80;
or, when the photochromic glaze in the step 22 is applied to the ceramic tile blank by a silk screen or rubber roll printing process, the specific gravity of the photochromic glaze is 1.25-1.65;
in some embodiments, the firing temperature in the step 23 is 1150-1220 ℃, and the firing time is 45-55 min.
The preparation method of the photochromic ceramic tile has the advantage that the photochromic ceramic tile obtained by the preparation method of the photochromic ceramic tile has the characteristic of low water absorption rate by controlling the firing temperature.
Referring to fig. 3, the present invention further provides an optically variable color ceramic tile, wherein the optically variable color ceramic tile is prepared by the ceramic tile with the gloss of the glaze surface flexibly controlled according to the preparation method of the present invention.
Further, the optically variable ceramic tile sequentially comprises the following components from bottom to top: a ceramic tile blank body 11 and a photochromic ceramic glaze layer 12.
It can be understood that the photochromic ceramic tile comprises silver bromide color changing agent and copper oxide catalyst by applying a photochromic ceramic glaze layer on the ceramic tile green body; under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, and further the color and shade change is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
The present invention will be described in further detail with reference to specific examples.
The first embodiment is as follows:
the embodiment provides an optically variable ceramic glaze, wherein the optically variable ceramic glaze comprises the following chemical components in percentage by mass:
SiO2 41.6～54.8％；Al2O3 15.3～19.6％；Fe2O3 0.02～0.15；CaO 5.1～9.4％；MgO 3.8～7.6％；Na2O 2.3～6.2％；K2O 0.22～2.1％；ZnO 3.2～8.4％；TiO2 0.05～0.12％；B2O3 3.2～6.5％；BaO 2.0～8.2％；CuO 0.01～0.03％；AgBr 0.03～1.2％。
the purity of the CuO is not less than 99%, and the fineness is 500 meshes; the purity of the AgBr is not less than 99 percent, and the fineness is 500 meshes.
In the embodiment, the sum of the components of the photochromic ceramic glaze in the embodiment is 100%; by adding a color-changing agent AgBr and a catalyst CuO into the photochromic ceramic glaze, the color-changing agent in the glaze can generate decomposition and reduction reactions under the irradiation of light rays with different degrees of strength and under the action of the energy of the light rays with different strengths and catalysts after the photochromic ceramic glaze is fired, and further shows the change of color and depth in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
Example two:
the embodiment provides an optically variable ceramic glaze, wherein the optically variable ceramic glaze specifically comprises the following chemical components in percentage by mass:
SiO2 43.59％；Al2O3 18.44％；Fe2O3 0.14％；CaO 6.43％；MgO 6.88％；Na2O 3.03％；K2O 0.34％；ZnO 7.42％；TiO2 0.11％；B2O3 4.6％；BaO 8.2％；CuO 0.02％；AgBr 0.8％。
the purity of the CuO is not less than 99%, and the fineness is 500 meshes; the purity of the AgBr is not less than 99 percent, and the fineness is 500 meshes.
Example three:
the embodiment provides a preparation method of a photochromic ceramic glaze, which comprises the following steps:
and step 13, adding 0.01-0.03 g of catalyst copper oxide into every 100g of ball-milled glaze slip, and uniformly stirring.
The photochromic ceramic glaze is the photochromic ceramic glaze of the invention; during the processing and production, every 100g of SiO2 41.6～54.8％、Al2O3 15.3～19.6％、Fe2O3 0.02～0.15、CaO 5.1～9.4％、MgO 3.8～7.6％、Na2O 2.3～6.2％、K2O 0.22～2.1％、ZnO 3.2～8.4％、TiO20.05～0.12％、B2O3Adding 45-90 g of water into a mixture of 3.2-6.5% and BaO 2.0-8.2%, mixing, and performing ball milling, wherein the ball milling fineness is controlled to be 325 meshes and the mixture is completely sieved; then, adding a silver bromide color-changing agent and a copper oxide catalyst, and further under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, so that the change of color and shade is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the photovariable color ceramic glaze is fired, when the photovariable color ceramic glaze is irradiated by strong light, the photovariable color ceramic glazeThe color-changing agent in the glaze can be reduced, so that the ceramic glaze with light color change shows the change of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
The purity of the silver bromide in the step 12 is not less than 99%, and the fineness is 500 meshes;
the purity of the copper oxide in the step 13 is not less than 99%, and the fineness is 500 meshes.
Example four:
the embodiment provides a preparation method of a photochromic ceramic tile, which comprises the following steps:
step 21, pressing and forming the blank, and drying the blank in a roller kiln to obtain a ceramic tile blank;
step 22, applying photochromic ceramic glaze on the ceramic tile blank to obtain a photochromic glaze layer;
step 23, putting the ceramic tiles into a kiln for firing and forming to obtain the photochromic ceramic tiles;
wherein the photochromic ceramic glaze is the photochromic ceramic glaze provided by the invention.
The glazing amount of the photochromic glaze in the step 22 is 240-500 g/m in terms of dry materials2。
In the step 22, the photochromic glaze is applied to the ceramic tile blank body by a glaze spraying or glaze pouring process, and the specific gravity of the photochromic glaze is 1.35-1.80;
the sintering temperature in the step 23 is 1150-1220 ℃, and the sintering time is 45-55 min.
It can be understood that the photochromic ceramic glaze is applied on the ceramic tile green body, so that the photochromic glaze layer comprises a silver bromide color-changing agent and a copper oxide catalyst; under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, and further the color and shade change is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature. Finally, by controlling the firing temperature, the photochromic ceramic tile obtained by the preparation method of the photochromic ceramic tile has the characteristic of low water absorption.
Example five:
the embodiment provides a preparation method of a photochromic ceramic tile, which comprises the following steps:
step 21, pressing and forming the blank, and drying the blank in a roller kiln to obtain a ceramic tile blank;
step 22, applying photochromic ceramic glaze on the ceramic tile blank to obtain a photochromic glaze layer;
step 23, putting the ceramic tiles into a kiln for firing and forming to obtain the photochromic ceramic tiles;
wherein the photochromic ceramic glaze is the photochromic ceramic glaze provided by the invention.
The glazing amount of the photochromic glaze in the step 22 is 240-500 g/m in terms of dry materials2。
When the photochromic glaze in the step 22 is applied to the ceramic tile blank by a silk screen or rubber roll printing process, the specific gravity of the photochromic glaze is 1.25-1.65;
the sintering temperature in the step 23 is 1150-1220 ℃, and the sintering time is 45-55 min.
Example six:
the invention also provides an optically variable ceramic tile, wherein the optically variable ceramic tile is prepared by the ceramic tile preparation method capable of flexibly controlling the glaze glossiness.
It can be understood that the photochromic ceramic tile comprises silver bromide color changing agent and copper oxide catalyst by applying a photochromic ceramic glaze layer on the ceramic tile green body; under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, and further the color and shade change is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
Example seven:
the invention also provides a photochromic ceramic tile, which sequentially comprises the following components from top to bottom: ceramic tile green body and photochromic ceramic glaze layer.
In summary, the photochromic ceramic glaze, the photochromic ceramic tile and the preparation method thereof provided by the invention comprise the following chemical components in percentage by mass: SiO 22 41.6～54.8％；Al2O315.3～19.6％；Fe2O3 0.02～0.15；CaO 5.1～9.4％；MgO 3.8～7.6％；Na2O 2.3～6.2％；K2O 0.22～2.1％；ZnO 3.2～8.4％；TiO2 0.05～0.12％；B2O33.2-6.5%; 2.0-8.2% of BaO; 0.01-0.03% of CuO; 0.03-1.2% of AgBr; the sum of the components of the photochromic ceramic glaze is 100%. By adding a color-changing agent AgBr and a catalyst CuO into the photochromic ceramic glaze, the color-changing agent in the glaze can generate decomposition and reduction reactions under the irradiation of light rays with different degrees of strength and under the action of the energy of the light rays with different strengths and catalysts after the photochromic ceramic glaze is fired, and further shows the change of color and depth in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, adding trace copper oxide serving as a catalyst, reacting the photochromic material with other components of the photochromic ceramic glaze at a high temperature,together forming a glass melt having two different absorption coefficients in the visible region, which can be transformed from one structure to another by the action of light, resulting in a reversible change in color.
Further, the preparation method of the photochromic ceramic glaze comprises the following steps: A. adding 45-90 g of water into every 100g of optically variable ceramic glaze, mixing, ball-milling, and controlling the ball-milling fineness to be 325 meshes of sieve for full sieving; B. adding 0.03-1.20 g of silver bromide serving as a color-changing agent into every 100g of ball-milled glaze slip, and uniformly stirring; C. and adding 0.01-0.03 g of catalyst copper oxide into every 100g of ball-milled glaze slip, and uniformly stirring. The photochromic ceramic glaze is the photochromic ceramic glaze of the invention; during the processing and production, every 100g of SiO2 41.6～54.8％、Al2O315.3～19.6％、Fe2O3 0.02～0.15、CaO 5.1～9.4％、MgO 3.8～7.6％、Na2O 2.3～6.2％、K2O 0.22～2.1％、ZnO 3.2～8.4％、TiO2 0.05～0.12％、B2O3Adding 45-90 g of water into a mixture of 3.2-6.5% and BaO 2.0-8.2%, mixing, and performing ball milling, wherein the ball milling fineness is controlled to be 325 meshes and the mixture is completely sieved; then, adding a silver bromide color-changing agent and a copper oxide catalyst, and further under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, so that the change of color and shade is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into photochromic ceramic glaze, and the photochromic material has two different typesIn the molecular or electronic structure state, micro copper oxide is added as catalyst, and forms glass melt together with other components of photochromic ceramic glaze at high temperature, and the glass has two different absorption coefficients in visible light area and can be converted from one structure to another structure under the action of light to result in reversible change of color.
Further, the preparation method of the photochromic ceramic tile comprises the following steps: a. pressing and molding the blank, and drying the blank in a roller kiln to obtain a ceramic tile blank; b. applying photochromic ceramic glaze on the ceramic tile blank to obtain a photochromic glaze layer; c. firing and forming in a kiln to obtain the ceramic tile with the color changed along with the light; wherein the photochromic ceramic glaze is the photochromic ceramic glaze provided by the invention. It can be understood that the photochromic ceramic glaze is applied on the ceramic tile green body, so that the photochromic glaze layer comprises a silver bromide color-changing agent and a copper oxide catalyst; under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, and further the color and shade change is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
Furthermore, the invention also provides an optically variable ceramic tile, wherein the optically variable ceramic tile is prepared by the ceramic tile preparation method capable of flexibly controlling the glaze glossiness.
It can be understood that the photochromic ceramic tile comprises silver bromide color changing agent and copper oxide catalyst by applying a photochromic ceramic glaze layer on the ceramic tile green body; under the irradiation of light rays with different degrees of intensity, the color-changing agent in the glaze can generate decomposition and reduction reactions under the action of energy of different light rays with different intensities and catalysts, and further the color and shade change is shown in appearance; moreover, the color change of the photochromic ceramic glaze material has reversibility; specifically, after the optically variable ceramic glaze is fired, when the optically variable ceramic glaze is irradiated by strong light, a color-changing agent in the optically variable ceramic glaze can be reduced, so that the optically variable ceramic glaze presents changes of color and depth; when light becomes dark and weakens, substances reduced by the color-changing agent in the glaze regenerate the original substance state under the catalytic action of a catalyst in the glaze, so that the color and the depth of the glaze are restored to the original state; furthermore, the photochromic ceramic glaze is prepared by adding a photochromic material into a photochromic ceramic glaze, wherein the photochromic material has two different molecular or electronic structure states, and then adding trace copper oxide serving as a catalyst to form a glass melt together with other components of the photochromic ceramic glaze at high temperature.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. The photochromic ceramic glaze is characterized by comprising the following chemical components in percentage by mass:
SiO2 41.6~54.8%；Al2O3 15.3~19.6%；Fe2O3 0.02~0.15；CaO 5.1~9.4%；MgO 3.8~7.6%；Na2O 2.3~6.2%；K2O 0.22~2.1%；ZnO 3.2~8.4%；TiO2 0.05~0.12%；B2O3 3.2~6.5%；BaO 2.0~8.2%；CuO 0.01~0.03%；AgBr 0.03~1.2%；
the sum of the components of the photochromic ceramic glaze is 100 percent;
the purity of the CuO is not less than 99%, and the fineness is 500 meshes;
the purity of the AgBr is not less than 99 percent, and the fineness is 500 meshes.
2. The photochromic ceramic glaze of claim 1, wherein the photochromic ceramic glaze comprises the following chemical components in percentage by mass:
SiO2 43.59%；Al2O3 18.44%；Fe2O3 0.14%；CaO 6.43%；MgO 6.88%；Na2O 3.03%；K2O 0.34%；ZnO 7.42%；TiO2 0.11%；B2O3 4.6%；BaO 8.2%；CuO 0.02%；AgBr 0.8%。
3. a method for preparing an optically variable ceramic glaze according to claim 1, comprising:
A. adding 45-90 g of water into every 100g of optically variable ceramic glaze, mixing and then carrying out ball milling, wherein the ball milling fineness is controlled to be 325 meshes and then passing through the sieve;
B. adding 0.03-1.20 g of silver bromide serving as a color-changing agent into every 100g of ball-milled glaze slip, and uniformly stirring;
C. and adding 0.01-0.03 g of catalyst copper oxide into every 100g of ball-milled glaze slip, and uniformly stirring.
4. The method for preparing optically variable ceramic glaze according to claim 3,
the purity of the silver bromide in the step B is not less than 99%, and the fineness of the silver bromide is 500 meshes;
and C, the purity of the copper oxide in the step C is not less than 99%, and the fineness of the copper oxide is 500 meshes.
5. The preparation method of the ceramic tile capable of changing color along with light is characterized by comprising the following steps:
a. pressing and molding the blank, and drying the blank in a roller kiln to obtain a ceramic tile blank;
b. applying photochromic ceramic glaze on the ceramic tile blank to obtain a photochromic glaze layer;
c. firing and forming in a kiln to obtain the ceramic tile with the color changed along with the light;
wherein the photochromic ceramic glaze is the photochromic ceramic glaze of any one of claims 1-2.
6. The method for preparing optically variable color ceramic tile according to claim 5,
the glazing amount of the photochromic glaze in the step b is 240-500 g/m in terms of dry materials2。
7. The method for preparing optically variable color ceramic tile according to claim 5,
in the step b, the photochromic glaze is applied to the ceramic tile blank body by a glaze spraying or glaze pouring process, and the specific gravity of the photochromic glaze is 1.35-1.80;
or, when the photochromic glaze in the step b is applied to the ceramic tile blank by a silk screen or rubber roll printing process, the specific gravity of the photochromic glaze is 1.25-1.65.
8. The method for preparing optically variable color ceramic tile according to claim 5,
and c, firing temperature in the step c is 1150-1220 ℃, and firing time is 45-55 min.
9. A ceramic tile capable of changing color along with light, which is characterized in that,
the photochromic ceramic tile is prepared by the preparation method of the photochromic ceramic tile as claimed in any one of the claims 5 to 8.
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| CN202055473U (en) * | 2011-05-06 | 2011-11-30 | 浙江世康木业有限公司 | Color-changing wood floor |
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