CN113979781B - Temperature-resistant pearlescent mica sheet and preparation method and application thereof - Google Patents
Temperature-resistant pearlescent mica sheet and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of new materials, and discloses a temperature-resistant mica sheet and a preparation method and application thereof. The base material of the temperature-resistant mica sheet is a mica sheet, and the mica sheet is sequentially coated with a metal oxide layer and an alumina layer. According to the temperature-resistant mica sheet provided by some examples of the invention, the outermost alumina layer can play a role in improving the temperature resistance of the mica sheet and protecting the substrate and the inner metal oxide, so that the influence of high calcining temperature and glaze on the mica sheet when the ceramic glaze is calcined is avoided. The alternative multi-layer coating of the nonferrous metal oxide can also form pearlescent materials with different colors, can be applied to ceramic glaze and brings unique decorative effect.
Description
Technical Field
The invention relates to the field of new materials, in particular to a temperature-resistant mica sheet and a preparation method and application thereof.
Background
With the development of social progress, the living standard of people is increasingly improved, and the requirement on decorative appearance is also gradually improved. Because the mica sheet is a crystal, has a layered structure and is high-temperature resistant, when the mica sheet is applied to the glazed surface of a ceramic tile, the decoration effect of the ceramic tile is different by utilizing the reflection and refraction of light, various changes are generated, and the requirements of people on different decorations are met.
The former mica is usually crushed into mica powder to prepare the pearlescent pigment, and the processing technology is complex, and the mica is inflammable and explosive and is easy to oxidize and lose color in the application process. Mica is widely used in the industries of paint, plastics, automobile and cosmetics, but has little use as a crystal glittering material in the ceramic industry.
The mica sheet starts to dehydrate after being heated to about 700-800 ℃, and the mechanical and electrical properties are changed, so that the elasticity is lost and the mica sheet becomes brittle; at 1050 ℃, the structure broke down.
The existing mica sheets still cannot resist the calcining temperature of the ceramic tiles and can be corroded by some glaze materials. Therefore, the mica sheet is directly introduced into the glaze of the ceramic tile, and the refraction effect is poor, so that the application of the mica sheet is limited.
A novel mica sheet is developed, a large mica sheet is coated with one or more layers of different metal oxides, and the large mica sheet is calcined to generate different photochromic effects, so that the temperature resistance of the mica sheet is improved, the application range of the mica sheet in the ceramic industry can be certainly expanded, and the requirement of people on the decorative effect is met.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a temperature-resistant mica sheet and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
a base material of the temperature-resistant mica sheet is a mica sheet, and the mica sheet sequentially wraps a metal oxide layer and an aluminum oxide layer outside aluminum oxide from inside to outside.
In some examples, the mica platelets have a particle size of 45 μm to 850 μm.
In some examples, the metal oxide layer has a thickness of 1.4 to 2.1 μm.
In some examples, the aluminum oxide layer has a thickness of 1.05 to 1.32 μm.
In some examples, the metal element in the metal oxide layer is selected from at least one of zirconium, titanium, chromium, iron, copper, zinc, magnesium.
In a second aspect of the present invention, there is provided:
a preparation method of a temperature-resistant mica sheet comprises the following operations:
s1) dispersing mica sheets in a saturated sodium silicate solution to enable a layer of sodium silicate to be attached to the surfaces of the mica sheets, so as to obtain the mica sheets attached with the sodium silicate;
s2) dispersing the mica sheets attached with the sodium silicate into a soluble metal salt solution for forming a metal oxide layer, fully adsorbing, performing solid-liquid separation, drying, and calcining to obtain the mica sheets coated with the metal oxide layer, wherein the metal oxide layer is not aluminum oxide;
s3) dispersing the mica sheets coated with the metal oxide layer in a saturated sodium silicate solution to enable a layer of sodium silicate to be attached to the surfaces of the mica sheets to obtain the pearlescent mica sheets attached with the sodium silicate;
and S4) dispersing the pearlescent mica sheet attached with the sodium silicate into an aluminum salt solution, fully adsorbing, carrying out solid-liquid separation, drying, and calcining to form an aluminum oxide layer to obtain the temperature-resistant mica sheet.
In some examples, the metal in the metal oxide layer is selected from at least one of zirconium, titanium, chromium, iron, copper, zinc, magnesium.
In some examples, the soluble metal salt solution has a metal salt concentration of 0.35 to 0.6mol/L, based on the metal.
In some examples, the soluble metal salt is selected from zirconium oxychloride, titanium sulfate, chromium chloride, chromium nitrate, ferric chloride, copper sulfate, magnesium chloride; the aluminum salt is selected from aluminum chloride and aluminum sulfate.
In some examples, the aluminum salt has a concentration of 0.55 to 0.65 mol/L, based on Al.
In some examples, the temperature of calcination is from 1200 to 1210 ℃ when calcination forms the alumina layer.
In a third aspect of the present invention, there is provided:
a composition comprising the temperature-resistant mica sheet according to the first aspect of the present invention or prepared by the method according to the second aspect of the present invention.
In a fourth aspect of the present invention, there is provided:
the glaze layer of the ceramic contains the temperature-resistant mica sheet in the first aspect of the invention or the temperature-resistant mica sheet prepared by the preparation method in the second aspect of the invention.
The invention has the beneficial effects that:
according to the temperature-resistant mica sheet provided by the invention, the outermost alumina layer can play a role in improving the temperature resistance of the mica sheet and protecting the base material and the inner metal oxide, so that the influence of high calcining temperature and glaze on the mica sheet when the ceramic glaze is calcined is avoided.
The temperature-resistant mica sheets of some examples of the invention are coated with nonferrous metal oxides in an alternating and multilayer manner, can also form pearlescent materials with different colors, can be applied to ceramic glaze, and bring unique decorative effect.
According to the preparation method of some embodiments of the invention, sodium silicate has certain adhesiveness and alkalinity, soluble metal salt is promoted to be hydrolyzed to generate metal hydroxide, and the process operation is simple. The reaction condition is easy to control, the reaction temperature and pH do not need to be controlled, and the preparation cost is greatly reduced.
The preparation method of some embodiments of the invention has wide raw material sources and low cost.
The preparation method of some embodiments of the invention can well control the thickness of the metal oxide layer and the aluminum oxide layer by controlling the concentration and/or adsorption time of the metal salt, thereby meeting the requirements of different occasions.
Drawings
FIG. 1 is a brick surface effect diagram of a temperature-resistant mica sheet numbered A;
FIG. 2 is a brick surface effect diagram of a temperature-resistant mica sheet numbered B;
FIG. 3 is a brick surface effect diagram of temperature-resistant mica sheet numbered C;
FIG. 4 is a brick surface effect diagram of the temperature-resistant mica sheet numbered D;
FIG. 5 is a brick surface effect diagram of the serial number E temperature resistant mica sheet;
FIG. 6 is a brick surface effect diagram of the temperature-resistant mica sheet numbered F;
FIG. 7 is a brick surface effect diagram of the number G temperature resistant mica sheet;
FIG. 8 is a brick surface effect diagram of a serial number H temperature-resistant mica sheet;
FIG. 9 is a brick surface effect diagram of the temperature-resistant mica sheet numbered I;
FIGS. 10 to 12 are graphs illustrating the effects of the mica sheets of comparative examples 1 to 3, respectively;
FIGS. 13 to 16 are graphs showing the effects of the mica sheets of examples 2 to 5, respectively.
Detailed Description
In a first aspect of the present invention, there is provided:
a base material of the temperature-resistant mica sheet is a mica sheet, and the mica sheet sequentially wraps a metal oxide layer and an aluminum oxide layer outside aluminum oxide from inside to outside.
The temperature-resistant mica sheet can be used as a temperature-resistant pearlescent mica sheet and a ceramic pigment, and a unique decorative effect is obtained. Can also be applied to temperature-resistant insulating materials, corrosion-resistant pigments, special plastic functional fillers, functional fillers in the electronic field and the like.
The thickness of the metal oxide layer can be set according to different application occasions. In general, when used as a ceramic pigment, the thickness of the metal oxide layer is preferably 1.4 to 2.1 μm in order to secure the pearl effect and the effect of the metal oxide layer.
In some examples, the mica platelets are 45 μm to 850 μm in particle size.
The alumina layer is a main temperature-resistant layer and a protective layer, and the thickness of the alumina layer can be correspondingly set according to different application occasions. In some examples, the aluminum oxide layer has a thickness of 0.9 to 1.6 μm when used as a ceramic pearlescent pigment. The aluminum oxide with the thickness needs to well protect the inner color development layer in the firing process, and the fired aluminum oxide layer can react with the raw materials of the glaze layer and just disappear or does not influence the display of the effect of the pearlescent layer. If the glaze layer contains a material which is susceptible to reaction with the alumina layer, the alumina layer may be somewhat thicker.
In some examples, the metal element in the metal oxide layer is selected from at least one of zirconium, titanium, chromium, iron, copper, zinc, magnesium. In order to obtain a desired color, a plurality of metal elements may be used in combination.
In a second aspect of the present invention, there is provided:
a preparation method of a temperature-resistant mica sheet comprises the following operations:
s1) dispersing mica sheets in a saturated sodium silicate solution to enable a layer of sodium silicate to be attached to the surfaces of the mica sheets, so as to obtain the mica sheets attached with the sodium silicate;
s2) dispersing the mica sheets attached with the sodium silicate into a soluble metal salt solution for forming a metal oxide layer, fully adsorbing, performing solid-liquid separation, drying, and calcining to obtain mica sheets coated with the metal oxide layer, wherein the metal oxide layer is not aluminum oxide;
s3) dispersing the mica sheets coated with the metal oxide layer in a saturated sodium silicate solution to enable a layer of sodium silicate to be attached to the surfaces of the mica sheets to obtain the pearlescent mica sheets attached with the sodium silicate;
and S4) dispersing the pearlescent mica sheet attached with the sodium silicate into an aluminum salt solution, fully adsorbing, carrying out solid-liquid separation, drying, and calcining to form an aluminum oxide layer to obtain the temperature-resistant mica sheet.
The temperature for calcining to form the metal oxide layer can be adjusted according to different metal elements, so that the metal oxide layer can be formed without causing structural damage to the mica sheet.
The main function of the metal oxide layer is to introduce a new decorative layer. The kind of the metal is not particularly required as long as the metal oxide layer can be formed by calcination without destroying the structure of the mica sheet. In some examples, the metal in the metal oxide layer is selected from at least one of zirconium, titanium, chromium, iron, copper, zinc, magnesium. The inventors' research data also indicate that the metal oxide layer is also advantageous for improving the temperature resistance of the mica sheet.
During the preparation process, the thickness of the finally formed metal oxide layer can be adjusted by adjusting the concentration of the metal salt solution. The immersion time also has some effect on the formation of the metal oxide layer, but the effect is relatively small. In some examples, the soluble metal salt solution has a metal salt concentration of 0.35 to 0.6mol/L, based on the metal.
In some examples, the soluble metal salts include, but are not limited to, chloride, sulfate, nitrate, etc. salts of metals, specifically including, but not limited to, zirconium oxychloride, titanium sulfate, chromium chloride, chromium nitrate, ferric chloride, copper sulfate, magnesium chloride; the aluminum salt includes, but is not limited to, aluminum chloride, aluminum sulfate. These water-soluble salts are widely available and relatively low in cost.
During the preparation process, the thickness of the finally formed alumina layer can be adjusted by adjusting the concentration of the aluminum salt. In some examples, the aluminum salt is present at a concentration of 0.55 to 0.65 mol/L, based on Al.
In some examples, the temperature of calcination is from 1200 to 1210 ℃ when calcination forms the alumina layer.
In a third aspect of the present invention, there is provided:
a composition comprising the temperature-resistant mica sheet according to the first aspect of the present invention or prepared by the method according to the second aspect of the present invention.
In a fourth aspect of the present invention, there is provided:
the glaze layer of the ceramic contains the temperature-resistant mica sheet, and the temperature-resistant mica sheet is the temperature-resistant mica sheet in the first aspect of the invention or the temperature-resistant mica sheet prepared by the preparation method in the second aspect of the invention.
In some examples of the ceramic, the preparation method is selected from one of the following processes:
a blank process: the temperature-resistant mica sheets are mixed or digitally positioned and distributed in the whole body or the thin-layer cloth, and the mica sheets are not required to be stacked as much as possible. Pressing and molding, sintering, fully polishing, non-polishing, semi-polishing or matte polishing; the temperature-resistant mica sheet is the temperature-resistant mica sheet in the first aspect of the invention, or the temperature-resistant mica sheet prepared by the preparation method in the second aspect of the invention;
the glaze process comprises the following steps: on the blank or the overglaze, positioning by a dry method or a wet method or distributing and applying temperature-resistant mica sheets on the whole surface, sintering, fully polishing, not polishing, semi-polishing or matte polishing, wherein the temperature-resistant mica sheets are the temperature-resistant mica sheets of the first aspect of the invention or the temperature-resistant mica sheets prepared by the preparation method of the second aspect of the invention;
the full polishing process comprises the following steps: firstly, ink-jetting a design pattern on a blank overglaze, uniformly mixing temperature-resistant mica sheets or distributing digital cloth under full-polishing glaze, dry-particle polishing glaze or dry-particle polishing glaze on the blank overglaze by a dry method or a wet method, sintering and fully polishing, wherein the temperature-resistant mica sheets are the temperature-resistant mica sheets in the first aspect of the invention or the temperature-resistant mica sheets prepared by the preparation method in the second aspect of the invention;
and (3) a flower infiltrating process: and digitally distributing temperature-resistant mica sheets on the surface glaze or the blank body by adopting a wet method or a dry method, sintering, fully polishing, not polishing, semi-polishing or matte polishing, wherein the temperature-resistant mica sheets are the temperature-resistant mica sheets in the first aspect of the invention or the temperature-resistant mica sheets prepared by the preparation method in the second aspect of the invention.
The technical scheme of the invention is further explained by combining the examples.
In the following examples, the normal temperature means 20 to 35 ℃ unless otherwise specified; the solution refers to an aqueous solution unless otherwise specified.
The natural pure muscovite flakes used had a particle size of 45 to 850 μm, unless otherwise specified.
Example 1
A preparation method of a temperature-resistant mica sheet comprises the following specific steps:
(1) Mica pretreatment: weighing 2.5g of natural pure muscovite slices, dispersing into 8g of saturated sodium silicate solution, and uniformly stirring at normal temperature to wrap each mica slice with a layer of saturated sodium silicate solution;
(2) Preparation of reagents: zirconium oxychloride solutions with molar concentrations corresponding to those in table 1 were prepared, and the solution was stirred on a magnetic stirrer by adding magnetons. Preparing aluminum chloride solution with the molar concentration corresponding to that in the table 1, and adding magnetons to stir on a magnetic stirrer;
(3) Primary coating: dispersing the mica sheet treated in the step (1) into the zirconium oxychloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature, wherein a layer of crystalline coating is observed on the surface of the mica sheet. Pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained. Separating the mica sheets after complete drying, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute of 900 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature;
(4) Secondary coating: and (4) adding the zirconium oxide coated mica sheet obtained in the step (3) into a saturated sodium silicate solution for recoating. Dispersing the mica plate into the aluminum chloride solution prepared in the step (2), and magnetically stirring the mixture for 10 minutes at normal temperature, wherein a layer of crystalline coating is observed on the surface of the mica plate. Pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained. After the mica sheets are completely dried, the mica sheets are separated out and transferred into a rectangular crucible, calcined in a muffle furnace at the temperature rise rate of 20 ℃ per minute of 1200 ℃, kept for 7 minutes, cooled to the normal temperature and then taken out. Thus obtaining different zirconia-coated temperature-resistant mica sheets.
The temperature-resistant mica sheet coated by zirconia is mixed with proper glaze polishing/dry grain glaze and is evenly stirred and then sprayed on the surface of a green brick. And (5) firing in a kiln, and semi-polishing or non-polishing to obtain the brick surface with corresponding effect.
The brick surface effect of the temperature-resistant mica sheet with the number A is shown in figure 1, and the pearly luster effect of the temperature-resistant mica sheet is weaker. This is because the concentration of the aluminum chloride solution is too low, and a small amount of aluminum hydroxide is obtained by hydrolysis reaction, so that the aluminum oxide layer coated after calcination is too thin, and the inner color-developing oxide layer is exposed and corroded during calcination of the brick surface. Similarly, the concentration of the zirconium oxychloride solution is too low, and the hydrolysis reaction obtains too little zirconium hydroxide, so that the calcined zirconium oxide layer is thin, the pearl effect is weak, and the pearl effect is weakened.
The brick surface effect of the temperature-resistant mica sheet with the number B is shown in figure 2, and the pearly luster effect of the temperature-resistant mica sheet is weaker. The reason is that the concentration of the aluminum chloride solution is moderate, and a proper amount of aluminum hydroxide is obtained through hydrolysis reaction, so that the calcined coated aluminum oxide layer just disappears after reaction when the brick surface is calcined, and the inner color development oxide layer is exposed. Similarly, if the concentration of the zirconium oxychloride solution is too low, too little zirconium hydroxide is obtained by the hydrolysis reaction, so that the thin zirconium oxide layer after calcination has a poor pearlescent effect.
The brick surface effect of the temperature-resistant mica sheet with the number C is shown in figure 3, and the mica sheet has no pearl effect. The reason is that the concentration of the aluminum chloride solution is too high, a large amount of aluminum hydroxide is obtained through hydrolysis reaction, so that the aluminum oxide layer coated after calcination is too thick, the inner color development oxide layer cannot be exposed when the brick surface is calcined, and the pearl effect is avoided.
The brick surface effect of the temperature-resistant mica sheet with the number D is shown in figure 4, the pearlescent effect is weak, because the concentration of the aluminum chloride solution is too low, a small amount of aluminum hydroxide is obtained by hydrolysis reaction, the aluminum oxide layer coated after calcination is too thin, and the inner color-emitting oxide layer is exposed and corroded when the brick surface is calcined. Similarly, the concentration of the zirconium oxychloride solution is moderate, a proper amount of zirconium hydroxide is obtained through hydrolysis reaction, the thickness of a zirconium oxide layer after calcination is moderate, but the corroded pearlescent effect is weakened.
The brick surface effect of the temperature-resistant mica sheet with the number E is shown in figure 5, and the pearlescent effect is obvious, because the concentration of the aluminum chloride solution is moderate, and a proper amount of aluminum hydroxide is obtained by hydrolysis reaction, so that the calcined coated alumina layer just disappears by reaction, and the inner layer pearlescent is exposed when the brick surface is calcined. Similarly, the concentration of the zirconium oxychloride solution is moderate, a proper amount of zirconium hydroxide is obtained through hydrolysis reaction, the thickness of a calcined zirconium oxide layer is moderate, and the pearl effect is good under the protection of outer-layer alumina.
The brick surface effect of the temperature-resistant mica sheet numbered F is shown in figure 6, and the effect of pearlescence is avoided because the aluminum chloride solution has too high concentration, a large amount of aluminum hydroxide is obtained by hydrolysis reaction, the aluminum oxide layer coated after calcination is too thick, and the color-developed oxide layer of the inner layer can not be exposed when the brick surface is calcined.
The brick surface effect of the temperature resistant mica sheet with the number G is shown in figure 7, and the pearl effect is weaker than that of the number E. The reason is that the concentration of the aluminum chloride solution is too low, a small amount of aluminum hydroxide is obtained through hydrolysis reaction, so that the aluminum oxide layer coated after calcination is too thin, the inner color development oxide layer is exposed and corroded when the brick surface is calcined, meanwhile, the concentration of the zirconium oxychloride solution is too high, a large amount of zirconium hydroxide is obtained through hydrolysis reaction, so that the zirconium oxide layer after calcination is too thick, the original pearl effect of natural pure muscovite is covered, and the pearl effect is weakened.
The brick surface effect of the temperature-resistant mica sheet with the number H is shown in figure 8, and the pearl effect is weaker than that of the number E. The aluminum chloride solution has moderate concentration, the hydrolysis reaction obtains a proper amount of aluminum hydroxide, so that the calcined coated alumina layer just disappears, the inner color development oxide layer is exposed when the brick surface is calcined, meanwhile, the concentration of the zirconium oxychloride solution is too high, and the hydrolysis reaction obtains a large amount of zirconium hydroxide, so that the calcined zirconia layer is too thick, the original pearl effect of natural pure white mica is covered, and the pearl effect is weakened.
The brick surface effect of the temperature-resistant mica sheet with the number I is shown in figure 9, and the brick surface effect is free from pearl effect because the aluminum chloride solution has too high concentration, a large amount of aluminum hydroxide is obtained by hydrolysis reaction, so that the aluminum oxide layer coated after calcination is too thick, and the color-developed oxide layer of the inner layer cannot be exposed during the brick surface calcination. And because the concentration of the zirconium oxychloride solution is too high, the zirconium oxide layer after calcination is too thick due to the fact that a large amount of zirconium hydroxide is obtained through hydrolysis reaction, and the mica sheets obtained after two layers of zirconium oxide layers are coated are too thick, so that glaze spraying is not facilitated.
Comparative example 1
A preparation method of a mica sheet comprises the following specific steps:
(1) Preparing a reagent: preparing zirconium oxychloride solution with the molar concentration of 0.6mol/L, and adding magnetons to stir on a magnetic stirrer; preparing an aluminum chloride solution with the molar concentration of 0.4mol/L, and adding magnetons to stir on a magnetic stirrer;
(2) Primary soaking: dispersing mica sheets into the zirconium oxychloride solution prepared in the step (1), and magnetically stirring for 10 minutes at normal temperature; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained;
(3) Wrapping sodium silicate: weighing 2.5g of the mica sheets treated in the step (2), dispersing the mica sheets into 8g of saturated sodium silicate solution, and uniformly stirring at normal temperature to wrap one layer of saturated sodium silicate solution on each mica sheet; after the mica sheets are completely dried, separating the mica sheets, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute and the temperature of 900 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature;
(4) Secondary soaking: dispersing the mica sheets obtained in the step (3) into the aluminum chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained;
(5) Wrapping sodium silicate: then adding the mixture into saturated sodium silicate solution for secondary wrapping; drying again, separating the mica sheets after complete drying, transferring into a rectangular crucible, calcining in a muffle furnace at 1200 ℃ at a heating rate of 20 ℃ per minute, preserving heat for 7 minutes, cooling to normal temperature, and taking out; thus obtaining the mica sheet.
The mica sheet is mixed with proper glaze polishing/dry grain glaze and sprayed onto the surface of green brick. And (5) firing in a kiln.
The surface of the brick obtained by firing was free from pearl effect as shown in FIG. 10. This is because the zirconium chloride layer coated first in step (2) does not have saturated sodium silicate and its reaction coating layer too thin and uneven, and the aluminum oxide layer can be synthesized by the reaction of the saturated sodium silicate coated in step (3) and the aluminum chloride coated in step (4), and is just disappeared by the reaction. However, the inner color-developing oxide layer is not completely coated and has no pearl effect even if exposed. The order of reaction is critical to the pearlescent effect of the mica flakes.
Comparative example 2
A method for preparing mica sheets comprises the following specific steps:
(1) Mica pretreatment: weighing 2.5g of natural pure muscovite mica, dispersing into 8g of 15g/L sodium silicate solution, and uniformly stirring at normal temperature to wrap each mica sheet with a layer of sodium silicate solution;
(2) Preparation of reagents: preparing zirconium oxychloride solution with the molar concentration of 0.6mol/L, and adding magnetons to stir on a magnetic stirrer; preparing an aluminum chloride solution with the molar concentration of 0.4mol/L, and adding magnetons to stir on a magnetic stirrer;
(3) Primary coating: dispersing the mica sheets treated in the step (1) into the zirconium oxychloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; after the mica sheets are completely dried, separating the mica sheets, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute and the temperature of 900 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature;
(4) Secondary coating: adding the mica sheets obtained in the step (3) into 15g/L sodium silicate solution for recoating; dispersing into the aluminum chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; separating the mica sheets after complete drying, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute at the temperature of 1200 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature; thus obtaining the mica sheet.
The mica sheet is mixed with proper glaze polishing/dry grain glaze and stirred evenly, and then sprayed on the surface of a green brick to be sintered in a kiln.
The brick surface without pearl effect is obtained as shown in figure 11. This is because the unsaturated sodium silicate solution used in step (1) has reduced viscosity and alkalinity, and reacts weakly with zirconium oxychloride in step (3) and aluminum chloride in step (4), and the obtained zirconium oxide layer and aluminum oxide layer are both too thin or unevenly exposed on the mica substrate. No pearl effect. The inner and outer oxide layers are not coated completely or eroded too thinly, and have no pearl effect.
Comparative example 3
A preparation method of a mica sheet comprises the following specific steps:
(1) Mica pretreatment: weighing 2.5g of natural pure muscovite mica slices, dispersing into 8g of saturated sodium metasilicate solution, and uniformly stirring at normal temperature to wrap one layer of sodium metasilicate solution on each mica slice;
(2) Preparing a reagent: preparing zirconium oxychloride solution with the molar concentration of 0.6mol/L, and adding magnetons to stir on a magnetic stirrer; preparing an aluminum chloride solution with the molar concentration of 0.4mol/L, and adding magnetons to stir on a magnetic stirrer;
(3) Primary coating: dispersing the mica sheets treated in the step (1) into the zirconium oxychloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; after the mica sheets are completely dried, separating the mica sheets, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at 700 ℃ at the heating rate of 0 ℃ per minute, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature;
(4) Secondary coating: adding the mica sheets obtained in the step (3) into a saturated sodium metasilicate solution for recoating; dispersing into the aluminum chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; separating the mica sheets after complete drying, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute at the temperature of 1200 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature; thus obtaining the mica sheet.
The mica sheet is mixed with proper glaze polishing/dry grain glaze and stirred evenly, and then is sprayed on the surface of a green brick and is put into a kiln to be fired.
The brick surface without pearl effect is obtained as shown in figure 12. The reason is that the sodium metasilicate solution is used in the step (1), the partially saturated sodium silicate solution is weak in viscosity and easy to dissolve in water, a small amount of sodium metasilicate on the surface of the mica sheet is dissolved in the zirconium oxychloride solution in the step (3) and the aluminum chloride solution in the step (4), so that zirconium hydroxide and aluminum hydroxide are difficult to obtain, and finally, a zirconium oxide layer and an aluminum oxide layer are difficult to obtain. Mica cannot be protected and has no pearl effect.
Example 2
A preparation method of a temperature-resistant mica sheet comprises the following specific steps:
(1) Mica pretreatment: weighing 2.5g of natural pure muscovite slices, dispersing into 8g of saturated sodium silicate solution, and uniformly stirring at normal temperature to wrap each mica slice with a layer of saturated sodium silicate solution;
(2) Preparation of reagents: preparing ferric chloride solution with the molar concentration of 0.4mol/L, and adding magnetons to stir on a magnetic stirrer; preparing an aluminum chloride solution with the molar concentration of 0.6mol/L, and adding magnetons to stir on a magnetic stirrer;
(3) Primary coating: dispersing the mica sheets treated in the step (1) into the ferric chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature, wherein a layer of yellow crystalline coating is observed on the surfaces of the mica sheets; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; after the mica sheets are completely dried, separating the mica sheets, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 10 ℃ per minute and 300 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature;
(4) Secondary coating: adding the iron oxide coated mica sheet obtained in the step (3) into a saturated sodium silicate solution for secondary coating; dispersing the mica plate into the aluminum chloride solution prepared in the step (2), and magnetically stirring the mixture for 10 minutes at normal temperature to show that the surface of the mica plate is coated with a layer of crystalline coating; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing with deionized water for multiple times, and putting the Buchner funnel and the filter cloth into a 60 ℃ drying oven for drying after the solution is drained; separating the mica sheets after complete drying, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute at the temperature of 1200 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature; thus obtaining the iron oxide coated temperature-resistant mica sheet.
The temperature-resistant mica sheets coated with the iron oxide are mixed with proper glaze polishing/dry grain glaze, evenly stirred, sprayed on the surface of a green brick and put into a kiln to be fired.
A brick surface with golden pearly effect as in fig. 13 was obtained. This is because the coated alumina layer just reacted and disappeared, exposing the inner iron oxide pearlescence.
Example 3
A preparation method of a temperature-resistant mica sheet comprises the following specific steps:
(1) Mica pretreatment: weighing 2.5g of natural pure muscovite slices, dispersing into 8g of saturated sodium silicate solution, and uniformly stirring at normal temperature to wrap each mica slice with a layer of saturated sodium silicate solution;
(2) Preparation of reagents: preparing a chromium chloride solution with the molar concentration of 0.4mol/L, and adding magnetons to stir on a magnetic stirrer; preparing an aluminum chloride solution with the molar concentration of 0.6mol/L, and adding magnetons to stir on a magnetic stirrer;
(3) Primary coating: dispersing the mica sheets treated in the step (1) into the chromium chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature to show that a layer of green crystalline coating is coated on the surfaces of the mica sheets; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; separating the mica sheets after complete drying, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 5 ℃ per minute at the temperature of 250 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature;
(4) Secondary coating: adding the chromium oxide coated mica sheet obtained in the step (3) into a saturated sodium silicate solution for recoating; dispersing the mica plate into the aluminum chloride solution prepared in the step (2), and magnetically stirring the mixture for 10 minutes at normal temperature to show that the surface of the mica plate is coated with a layer of crystalline coating; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; after the mica sheets are completely dried, separating the mica sheets, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute at 1200 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature; thus obtaining the chromium oxide coated temperature-resistant mica sheet.
The chromium oxide coated heat-resistant mica sheets are mixed with proper glaze polishing/dry grain glaze, stirred uniformly, sprayed on the surface of a green brick and put into a kiln to be fired.
The brick surface with bright green pearly effect is obtained as shown in figure 14. This is because the coated alumina layer just reacted away, exposing the inner chromia bead.
Example 4
A preparation method of a temperature-resistant mica sheet comprises the following specific steps:
(1) Mica pretreatment: weighing 2.5g of natural pure muscovite mica, dispersing into 8g of saturated sodium silicate solution, and stirring uniformly at normal temperature to wrap a layer of saturated sodium silicate solution on each mica sheet;
(2) Preparation of reagents: preparing magnesium chloride solution with the molar concentration of 0.4mol/L, and adding magnetons to stir on a magnetic stirrer; preparing an aluminum chloride solution with the molar concentration of 0.6mol/L, and adding magnetons to stir on a magnetic stirrer;
(3) Primary coating: dispersing the mica sheets treated in the step (1) into the magnesium chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature to see that the surfaces of the mica sheets are coated with a layer of crystalline coating; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing with deionized water for multiple times, and putting the Buchner funnel and the filter cloth into a 60 ℃ drying oven for drying after the solution is drained; separating the mica sheets after complete drying, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at 490 ℃ at the heating rate of 5 ℃ per minute, preserving the heat for 7 minutes, cooling to the normal temperature, and taking out the mica sheets;
(4) Secondary coating: adding the magnesium oxide coated mica sheet obtained in the step (3) into a saturated sodium silicate solution for secondary coating; dispersing the mica plate into the aluminum chloride solution prepared in the step (2), and magnetically stirring the mixture for 10 minutes at normal temperature to show that the surface of the mica plate is coated with a layer of crystalline coating; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; after the mica sheets are completely dried, separating the mica sheets, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute at 1200 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature; thus obtaining the temperature-resistant mica sheet coated by the magnesium oxide.
The temperature-resistant mica sheet coated by the magnesium oxide is mixed with proper glaze polishing/dry grain glaze, evenly stirred, sprayed on the surface of a green brick and put into a kiln to be fired.
The brick surface with the pearl effect is obtained as shown in figure 15. This is because the coated alumina layer just reacted away, exposing the inner layer of magnesia pearlescence.
Example 5
A preparation method of a temperature-resistant mica sheet comprises the following specific steps:
(1) Mica pretreatment: weighing 2.5g of natural pure muscovite slices, dispersing into 8g of saturated sodium silicate solution, and uniformly stirring at normal temperature to wrap each mica slice with a layer of saturated sodium silicate solution;
(2) Preparation of reagents: preparing titanium chloride solution with the molar concentration of 0.4mol/L, and adding magnetons to stir on a magnetic stirrer; preparing an aluminum chloride solution with the molar concentration of 0.6mol/L, and adding magnetons to stir on a magnetic stirrer;
(3) Primary coating: dispersing the mica sheets treated in the step (1) into the titanium chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature, wherein a layer of crystalline coating is seen on the surfaces of the mica sheets; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; separating the mica sheets after complete drying, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at 650 ℃ at a heating rate of 10 ℃ per minute, preserving the heat for 7 minutes, cooling to the normal temperature, and taking out the mica sheets;
(4) Secondary coating: adding the titanium oxide coated mica sheet obtained in the step (3) into a saturated sodium silicate solution for recoating; dispersing into the aluminum chloride solution prepared in the step (2), and magnetically stirring for 10 minutes at normal temperature to show that a layer of crystalline coating is formed on the surface of the mica sheet; pouring the solution together with the mica sheets into a Buchner funnel for suction filtration, washing the solution with deionized water for multiple times, and drying the solution together with the funnel and the filter cloth in a 60 ℃ drying oven after the solution is drained; after the mica sheets are completely dried, separating the mica sheets, transferring the mica sheets into a rectangular crucible, calcining the mica sheets in a muffle furnace at the temperature rise rate of 20 ℃ per minute at 1200 ℃, preserving the heat for 7 minutes, and taking out the mica sheets after the temperature is reduced to the normal temperature; thus obtaining the temperature-resistant mica sheet coated by the titanium oxide.
The temperature-resistant mica sheet coated by titanium oxide is mixed with proper glaze polishing/dry grain glaze, evenly stirred, sprayed on the surface of a green brick and put into a kiln to be fired.
The brick surface with pearl effect is obtained as shown in figure 16. This is because the coated alumina layer just reacted and disappeared, exposing the inner titanium oxide pearlescence.
The foregoing is a more detailed description of the invention and is not to be taken in a limiting sense. It will be apparent to those skilled in the art that simple deductions or substitutions without departing from the spirit of the invention are within the scope of the invention.
Claims (9)
1. A preparation method of a temperature-resistant mica sheet comprises the following operations:
s1) dispersing mica sheets in a saturated sodium silicate solution to enable a layer of sodium silicate to be attached to the surfaces of the mica sheets, so as to obtain the mica sheets attached with the sodium silicate;
s2) dispersing the mica sheets attached with the sodium silicate into a soluble metal salt solution for forming a metal oxide layer, fully adsorbing, performing solid-liquid separation, drying, and calcining to obtain the mica sheets coated with the metal oxide layer, wherein the metal oxide layer is not aluminum oxide, and the metal salt concentration of the soluble metal salt solution is 0.35-0.6 mol/L in terms of metal;
s3) dispersing the mica sheets coated with the metal oxide layer in a saturated sodium silicate solution to enable a layer of sodium silicate to be attached to the surfaces of the mica sheets to obtain the pearlescent mica sheets attached with the sodium silicate;
and S4) dispersing the pearlescent mica sheet attached with the sodium silicate into an aluminum salt solution for full adsorption, performing solid-liquid separation, drying, and calcining to form an aluminum oxide layer to obtain the temperature-resistant mica sheet, wherein the concentration of the aluminum salt is 0.55-0.65 mol/L calculated by Al.
2. The production method according to claim 1, characterized in that: the metal in the metal oxide layer is at least one selected from zirconium, titanium, chromium, iron, copper, zinc and magnesium.
3. The production method according to claim 1 or 2, characterized in that: the particle size of the mica sheet is 45-850 mu m.
4. The production method according to claim 1 or 2, characterized in that: the soluble metal salt is selected from zirconium oxychloride, titanium sulfate, chromium chloride, chromium nitrate, ferric chloride, copper sulfate and magnesium chloride; the aluminum salt is selected from aluminum chloride and aluminum sulfate.
5. The production method according to claim 1, characterized in that: the thickness of the metal oxide layer is 1.4-2.1 μm.
6. The production method according to claim 1, characterized in that: the thickness of the aluminum oxide layer is 1.05-1.32 mu m.
7. The production method according to claim 1 or 2, characterized in that: when the aluminum oxide layer is formed by calcination, the calcination temperature is 1200-1210 ℃.
8. A composition characterized by: which contains the temperature-resistant mica sheet prepared by the preparation method of any one of claims 1 to 7.
9. A ceramic, characterized by: the glaze layer contains the temperature-resistant mica sheet prepared by the preparation method of any one of claims 1 to 7.
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