CN114014697A - Metal decorative glaze marble ceramic tile and preparation method thereof - Google Patents
Metal decorative glaze marble ceramic tile and preparation method thereof Download PDFInfo
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- CN114014697A CN114014697A CN202111243001.5A CN202111243001A CN114014697A CN 114014697 A CN114014697 A CN 114014697A CN 202111243001 A CN202111243001 A CN 202111243001A CN 114014697 A CN114014697 A CN 114014697A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces
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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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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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
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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Abstract
The invention discloses a metal decorative glaze surface marble ceramic tile and a preparation method thereof. The preparation method comprises the following steps: selecting a marble tile with a concave surface; spraying the pearlescent mica slurry on the surface of the marble ceramic tile; the pearlescent mica slurry comprises: by mass percentage, 6-15% of pearlescent mica pigment, 6-10% of low-temperature glass flux powder and 75-88% of sodium carboxymethylcellulose aqueous solution; and extruding the surface of the marble ceramic tile sprayed with the pearlescent mica slurry by using a flat rubber sheet to extrude at least part of the pearlescent mica slurry into the depressions of the marble ceramic tile, and then sintering at a low temperature and polishing to obtain the metal decorative glaze marble ceramic tile.
Description
Technical Field
The invention relates to the field of architectural ceramics, in particular to a metal decorative glaze surface marble ceramic tile and a preparation method thereof.
Background
The metallic texture of the tile surface gives a feeling of luxury and luxury, and thus a hot tide for manufacturing metallic-texture tiles has recently been popular. At present, the metal texture marble ceramic tile is mainly prepared by a vacuum coating method and an electroplating method. The vacuum coating gold-polished brick is characterized in that a brick blank is hung in a vacuum electric furnace, metals such as copper, aluminum, titanium and the like are sputtered on the surface of the ceramic brick through high-pressure ionization to form a metal film, the brick blank is taken out from the furnace after cooling, and then polishing treatment is carried out. The electroplating method is to form the color effects of gold, silver and the like on the ceramic tile through an electroplating process, thereby realizing the magnificent decorative effect. For example, chinese patent CN112374920 discloses a method for preparing an over-glaze three-dimensional gold-plated composite glazed tile, which comprises covering a layer of isolation layer on the surface of a tile, placing the tile in an electroplating bath to electroplate titanium metal, and removing the isolation layer by low-temperature firing to retain the titanium metal film in the pattern-allowed region. The method has the defects that the metal film of copper, tin and titanium has poor acid-base resistance under natural conditions, and the metal decoration effect has short stabilization time under the normal temperature environment. In addition, the vacuum coating method and the electroplating method both belong to intermittent production, the labor intensity of workers is high, the production cost is high, and the production process is easy to pollute the environment.
The pearlescent mica pigment is prepared by coating a layer of nano oxide on the surface of mica particles, and the pigment presents special metal effect by utilizing the composite effect of the reflection of layered mica particles to light and the refraction of nano oxide to light. The pearlescent mica pigment has stable chemical property, strong interference and strong metal texture in normal temperature environment, and has rich colors of gold, silver, copper red, magical color and the like. At present, the pearl mica pigment is widely applied to the industries of paint and cosmetics. However, the special structure and composition of the pearlescent mica pigment enable the metal effect to be rapidly faded when the pearlescent mica pigment is exposed to high temperature (870 ℃ C.), which limits the decorative application of the pearlescent mica pigment on ceramic tiles. In addition, the pearlescent mica pigment has poor wear resistance, and the pearlescent mica pigment on the surface of the ceramic tile is easy to lose the metal decoration effect due to severe friction in the using process. In view of this, the pearl mica pigment is currently used for decorating ceramic tiles.
Disclosure of Invention
Aiming at the problems, the invention designs the metal decorative glaze surface marble ceramic tile and the preparation method thereof, the method uses the pearlescent mica pigment on the surface of the ceramic tile, not only keeps the metal decorative effect, but also overcomes the defect that the pearlescent mica pigment is not wear-resistant, and fundamentally overcomes the limitation of the pearlescent mica pigment on the aspect of ceramic tile decoration. The method realizes the automatic production of the metal decorative glaze marble ceramic tile on a production line, and has low production cost and environmental protection.
In a first aspect, the invention provides a preparation method of a metal decorative glazed marble ceramic tile. The preparation method comprises the following steps: selecting a marble tile with a concave surface; spraying the pearlescent mica slurry on the surface of the marble ceramic tile; the pearlescent mica slurry comprises: by mass percentage, 6-15% of pearlescent mica pigment, 6-10% of low-temperature glass flux powder and 75-88% of sodium carboxymethylcellulose aqueous solution; and extruding the surface of the marble ceramic tile sprayed with the pearlescent mica slurry by using a flat rubber sheet to extrude at least part of the pearlescent mica slurry into the depressions of the marble ceramic tile, and then sintering at a low temperature and polishing to obtain the metal decorative glaze marble ceramic tile.
Preferably, the initial melting temperature of the low-temperature glass flux powder is 500-700 ℃, preferably 580-650 ℃.
Preferably, the chemical composition of the low-temperature glass flux powder comprises: by mass percent, SiO2 35-45％，Al2O3 2-8％，B2O3 20-35％，ZnO 6-9％，Na2O 10-20％，P2O5 1-4％，Li2O 3-7％。
Preferably, the particle size of the pearlescent mica pigment is 400-800 meshes.
Preferably, the maximum firing temperature of the low-temperature firing is 500-700 ℃, preferably 580-650 ℃; the heat preservation time at the highest sintering temperature is 5-8 minutes.
Preferably, the specific gravity of the pearlescent mica slurry is 1.1-1.3g/cm3The glazing amount is 180-2。
Preferably, the mass percentage of the sodium carboxymethyl cellulose aqueous solution is 0.8-2.5%.
Preferably, the marble tile with the surface having the depressions is a marble tile with the depressions formed by at least one of green brick with grooves, finishing carving ink decoration and sinking glaze decoration.
Preferably, the specification of the marble tile is that when the length is 600-; the specification of the marble tile is 1200mm in length, 1200mm in width, 800 mm, 1200mm in thickness and 3-10mm in thickness, and the firing time is 75-105 minutes.
In a second aspect, the invention provides a preparation method of a metal decorative glaze marble ceramic tile. The preparation method comprises the following steps: selecting a marble ceramic tile with a smooth surface or a rubber roll pattern which can be tightly attached to the concave-convex texture of the ceramic tile; printing a pearlescent mica slurry rubber roll on the surface of the marble ceramic tile; the pearlescent mica slurry comprises: 8-13% of pearlescent mica pigment, 6-8.5% of low-temperature glass melt agent powder and 79-86% of rubber roll stamp-pad ink in percentage by mass; and then sintering at low temperature to obtain the metal decorative glaze surface marble ceramic tile.
In summary, the preparation method of the metal decorative glaze marble ceramic tile of the invention is that the pearlescent mica pigment is mixed with low-temperature glass flux powder and then covered on the surface of the marble ceramic tile, and the marble ceramic tile is sintered at low temperature to be firmly bonded with the glaze. The surface of the marble ceramic tile with the requirement of wear resistance is polished, then the local sunken area is attached with the pearlescent mica pigment, and for the wall decoration ceramic tile without the requirement of wear resistance, the pearlescent mica pigment is transferred to the surface of the ceramic tile by adopting a rubber roll printing process, and after low-temperature sintering reaction, the surface of the ceramic tile is decorated with metal texture.
Drawings
FIG. 1 is a surface effect diagram of a metal-glazed marble tile having golden and silver textures prepared in example 1;
fig. 2 is a surface effect diagram of the metal decorated glazed marble tile with golden yellow texture prepared in example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.
The present disclosure provides two ways to prepare the metal decorating glazed marble tile. As the scheme a, the following exemplifies a method for preparing the metal decorated glazed marble tile of the present invention.
Selecting marble tiles with depressions on the surface. The marble tile semi-finished product with the surface provided with the depressions is preferred (the semi-finished product refers to the tile which is not treated after being taken out of the kiln after being sintered at high temperature for one time). The sources of the semi-finished marble tile are not limited. The marble tile with the surface having the depressions includes, but is not limited to, a marble tile with depressions formed by any one of green tile with grooves, carved ink decoration, and depressed glaze decoration. In the specific embodiment, a marble tile having a surface with depressions, which is manufactured by Mona Lisa group Ltd, is used.
Preparing pearlescent mica slurry. The pearlescent mica slurry comprises: by mass percentage, 6-15% of pearlescent mica pigment, 6-10% of low-temperature glass flux powder and 75-88% of sodium carboxymethylcellulose aqueous solution.
The particle size of the pearlescent mica pigment is related to the metallic texture. Preferably, the particle size of the pearlescent mica pigment is 400-800 meshes. The excessive coarse particle size of the pearlescent mica pigment can influence the uniformity of the brick surface accumulation, and the visual effect of smooth and fine metal texture of the brick surface is difficult to obtain; the fine particle size of the pearlescent mica pigment can affect the fluidity of the slurry and the dispersion of the pearlescent mica pigment in the slurry, and finally can also affect the fine and smooth effect of the metal texture of the brick surface.
The low temperature glass flux powder functions to create a glass phase to fix the pearlescent mica pigment on the tile surface, especially at the recessed locations of the tile. The chemical composition of the low-temperature glass flux powder comprises: by mass percent, SiO2 35-45％，Al2O3 2-8％，B2O3 20-35％，ZnO 6-9％，Na2O 10-20％，P2O5 1-4％，Li2And 3-7% of O. In experiments, it is found that when the low-temperature glass flux powder does not contain calcium oxide and magnesium oxide, the pearlescent mica pigment has excellent visual effect of metallic texture on the surface of the brick after being fired, because CaO and MgO components in the glass flux can damage a particle film layer of the pearlescent mica pigment in the process of forming a glass phase by high-temperature melting, the refractive index of the material is reduced, and the metallic texture is influenced. In some embodiments, the chemical composition of the low temperature glass frit powder comprises: SiO 22 35-45％，Al2O3 2-8％，B2O3 20-35％，ZnO 6-9％，Na2O 10-20％，P2O5 1-4％，Li23-7% of O, 0-0.5% of CaO and 0-0.5% of MgO. Preferably, the total amount of CaO and/or MgO is less than 0.5 wt%.
The onset temperature (sintering temperature) of the low temperature glass flux powder affects the adhesion of the pearlescent mica pigment to the tile surface. The initial melting temperature of the low-temperature glass flux powder is preferably controlled to be 500-700 ℃, and preferably 580-650 ℃. If the initial melting temperature of the low-temperature glass flux powder is too high, the pearly mica pigment is not firmly bonded with the surface (glaze surface) of the original marble ceramic tile, so that the metal luster is insufficient. However, the initial melting temperature of the glass flux powder cannot be too low, otherwise the glaze effect is affected.
The sodium carboxymethyl cellulose has the functions of improving the lubricating, flowing and suspending performances of the pearlescent mica slurry, promoting the pearlescent mica pigment to be fully dispersed, and preventing the pearlescent mica pigment from agglomerating to influence the metallic luster and the visual effect. In some embodiments, the sodium carboxymethylcellulose aqueous solution is 0.8-2.5% by weight.
In the process of preparing the pearlescent mica slurry, the adding sequence of the pearlescent mica pigment, the low-temperature glass flux powder and the sodium carboxymethylcellulose aqueous solution is not limited. In some embodiments, the pearlescent mica pigment and the low-temperature glass flux powder are uniformly stirred, and then are added into the sodium carboxymethylcellulose aqueous solution to be continuously stirred. The preparation of the pearlescent mica slurry is not suitable for ball milling or high-speed stirring, because the surface film layer of the pearlescent mica pigment can be damaged by violent collision and friction among particles, and the metal texture of the material is reduced. The stirring speed is suitably controlled to 60-300 rpm. The stirring time may be 8-20 minutes, for example 10 minutes. The mixed solution after stirring is passed through a 120-mesh 250-mesh vibrating screen, such as a 160-mesh vibrating screen, for standby.
The pearlescent mica slurry is applied to the surface of the ceramic tile in a glaze spraying mode. The tile surface may be pre-cleaned prior to glazing to avoid dust or impurities on the tile surface adversely affecting the glazed finish. In some embodiments, the pearlescent mica slurry is sprayed uniformly onto the tile surface with a spray gun. The glaze pouring or screen printing mode is not suitable for the invention, because the glaze pouring can cause the pearlescent mica pigment to be stacked too thickly, which is not economical and influences the glaze effect; screen printing is only suitable for small-sized tiles and also cannot uniformly cover the recessed area with pigments.
The specific gravity of the pearlescent mica slurry is 1.1-1.3g/cm3. The pearlescent mica pigment is of a layered structure, the slurry needs to be stirred slowly during preparation so as to ensure uniformity, the slurry with low specific gravity has good flow property, the pigment is less agglomerated in the slurry, and the distribution is uniform.
The glazing amount of the pearlescent mica slurry is 180-400g/m2. If the glazing amount of the pearlescent mica slurry is too low, the pearlescent mica pigment adhered to the concave position is too little, and the metal decorative effect is poor. However, if the glazing amount of the pearlescent mica slurry is too large, the pigment is excessively accumulated, and the surface is not flat. The matching of the low specific gravity and the glazing amount can ensure the final glazing effect in a wide range.
After glazing is finished, the surface of the marble tile sprayed with the pearlescent mica slurry is extruded by using a flat rubber sheet so as to extrude at least part of the pearlescent mica slurry into the depressions of the marble tile. Specifically, the ceramic tile moves on the glaze line at a constant speed, the glaze is lightly pressed by a fixed straight rubber, the rubber blocks the movement of the tile surface slurry along with the tile, at least part of the pearlescent mica slurry is squeezed into the depression, and the rest pearlescent mica slurry is driven to the edge of the ceramic tile by the rubber. The pearlescent mica slurry driven to the edge of the ceramic tile automatically falls down and flows into a collecting container for recycling. In the extrusion process, the rubber is vertical to the ceramic tile in the movement direction of the glaze line, so that the uniform flow of slurry on the whole tile surface is facilitated, and meanwhile, the redundant slurry can also fall down from the edge of the tile quickly.
The pattern shaping can be completed while the rubber is desized. When the rubber is desized, the pearlescent mica pigment is uniformly attached to the area of the preset concave pattern on the brick surface. The other areas of the brick surface scraped by the rubber still have a little pigment attached, but can be completely removed in the subsequent polishing process without influencing the shaping of the whole pattern.
And (5) firing. And conveying the marble ceramic tiles into a low-temperature decoration firing roller kiln through a glaze line for firing. The firing is preferably low-temperature firing. The marble ceramic tile with the concave surface is sintered at high temperature (about 1200 ℃), namely, crystal phase structures for ensuring various physical and chemical properties of the ceramic tile are formed. The highest sintering temperature of 500-700 ℃ is selected to avoid destroying the original material crystal phase structure during secondary sintering.
In some embodiments, the firing schedule may be: the maximum sintering temperature is 580-650 ℃, and the holding time at the maximum temperature stage (the holding time at the maximum sintering temperature) is 5-8 minutes. The firing period can be adjusted adaptively according to the specification of the marble tile. The specification of the marble ceramic tile is that when the length is 600-; the specification of the marble tile is 1200mm in length, 1200mm in width, 800 mm, 1200mm in thickness and 3-10mm in thickness, and the firing time is 75-105 minutes. The physical and chemical properties of the marble ceramic tile after being fully cooled and taken out of the kiln in the firing process completely meet the national standard.
Polishing the marble ceramic tile sintered at low temperature. For example, the tile after the firing and the removal from the kiln is left to cool for one day and then sent to a polishing line for polishing. The polishing is a conventional operation. The anti-fouling wax can be polished to be ultra-clean and bright after primary grinding, medium grinding and fine grinding. And (5) edging, grading, packaging and warehousing finished products.
The method adopts a secondary sintering process, and uses a low-temperature glass fusing agent to bond the pearlescent mica pigment on the brick surface, thereby solving the problems of temperature resistance and wear resistance of the pearlescent mica pigment in the using process. The preparation method of the metal decorative glaze marble ceramic tile polishes, and the residual pearl mica pigment on the surface of the tile and the original surface glaze layer are polished and removed, so that the original pattern and color of the ceramic tile are reduced, and only the pearl mica pigment at the concave position is left to generate metal texture. Because the pearl mica pigment only exists in the depressed part of the surface of the tile, the marble tile obtained by the method can overcome the use limitation caused by poor wear resistance of the pearl mica pigment.
As the scheme B, the following exemplifies a method for preparing the metal decorated glazed marble tile of the present invention.
And (4) selecting marble tiles. The shape of the marble tile is not particularly limited by the scheme. The surface of the marble ceramic tile is smooth or the rubber roller pattern can be closely attached to the concave-convex texture of the ceramic tile (the semi-finished product refers to the ceramic tile which is not treated after being fired at high temperature and taken out of a kiln). The sources of the semi-finished marble tile are not limited. In the specific embodiment, a flat-glazed marble tile manufactured by Mona Lisa group Ltd is used.
Preparing pearlescent mica slurry. The pearlescent mica slurry comprises: 8-13% of pearlescent mica pigment, 6-8.5% of low-temperature glass melt agent powder and 79-86% of rubber roll stamp-pad ink. The choice of pearlescent mica pigment and low temperature glass flux powder is the same as in the previous embodiment and will not be described further herein. The pearlescent mica pigment has good suspension property and fluidity in the rubber roller stamp-pad ink, and the rubber roller stamp-pad ink can be used as a special medium for rubber roller printing.
In the process of preparing the pearlescent mica slurry, the adding sequence of the pearlescent mica pigment, the low-temperature glass flux powder and the rubber roll stamp-pad ink is not limited. In some embodiments, the pearlescent mica pigment and the low-temperature glass flux powder are added into the rubber roll stamp-pad ink after being uniformly stirred. The preparation of the pearlescent mica slurry is not suitable for ball milling or high-speed stirring, because the surface film layer of the pearlescent mica pigment can be damaged by violent collision and friction among particles, and the metal texture of the material is reduced. The stirring speed is suitably controlled to 60-300 rpm. The stirring time may be 8-20 minutes, for example 10 minutes. The mixed solution after stirring is sieved by a 120-mesh and 250-mesh vibrating screen, such as a 200-mesh vibrating screen, for standby.
And applying the pearlescent mica slurry on the surface of the ceramic tile in a rubber roll printing mode. The tile surface may be pre-cleaned prior to glazing to avoid dust or impurities on the tile surface adversely affecting the glazed finish. In some embodiments, the pearlescent mica slurry is printed on the surface of the tile with a rubber roller. The rubber roller can be engraved with patterns and textures matched with the decorative patterns of the marble ceramic tile finished product, such as an overprinting process, so that the layering sense of surface decoration can be greatly enriched. The printing area of the rubber roller printing process has a wide application range of about 0.1-5m2。
The specific gravity of the pearlescent mica slurry can be adjusted according to the printing thickness of the rubber roller. In some embodiments, the pearlescent mica slurry has a specific gravity of 1.15 to 1.30g/cm3. The glazing amount of the pearlescent mica slurry can be adjusted according to the pattern area of the rubber roll printing process. For example, the pearlescent mica slurry is applied in an amount of 60 to 200g/m2。
And (5) firing. And conveying the marble ceramic tiles into a low-temperature decoration firing roller kiln through a glaze line to be fired. The firing is preferably low-temperature firing. The marble ceramic tile selected by the invention has undergone one-time high-temperature firing (about 1200 ℃), namely, crystal phase structures ensuring various physical and chemical properties of the ceramic tile are formed. The highest sintering temperature of 500-700 ℃ is selected to avoid destroying the original material crystal phase structure during secondary sintering.
In some embodiments, the firing schedule may be: the maximum sintering temperature is 580-650 ℃, and the holding time at the maximum temperature stage (the holding time at the maximum sintering temperature) is 5-8 minutes. The firing period can be adjusted adaptively according to the specification of the marble tile. The specification of the marble ceramic tile is that when the length is 600-; the specification of the marble tile is 1200mm in length, 1200mm in width, 800 mm, 1200mm in thickness and 3-10mm in thickness, and the firing time is 75-105 minutes. After the firing process, the marble ceramic tile after being fully cooled and taken out of the kiln completely meets the national standard in each physical and chemical property.
And (6) edging. For example, the tile after firing and drawing is left to cool for one day and then sent to a edging line for edging. And (4) adding a film on the brick surface after grading, packaging the finished product and warehousing.
The preparation method of the metal decorative glaze marble ceramic tile adopts rubber roll printing, has fine patterns, can be particularly matched with the patterns on the bottom layer of the original ceramic tile, ensures that the glaze has rich hierarchical expression and strong stereoscopic impression, and is more suitable for wall decoration.
In conclusion, the preparation method of the metal decorative glaze marble ceramic tile provided by the invention is a new way for realizing wide application of the pearlescent mica pigment in the decoration of the ceramic tile glaze, can realize automatic production, reduces the comprehensive cost of manpower in the production process, and simultaneously has long-term stable metal texture and color decorative effect of the ceramic tile glaze, and the acid and alkali resistance of the glaze meets the national standard requirements.
Chinese patent CN 107827363A discloses a method for producing golden yellow metal effect on the surface of a ceramic tile by sintering pearlescent mica pigment at 1180-1230 ℃ high temperature. Although the patent tries to improve the temperature resistance by adjusting overglaze and printing basic glaze, the method has extremely strict requirements on the selection of pearl mica raw materials and production conditions, is difficult to realize stable industrial and commercial manufacture, and only one white pearl mica pigment can keep partial metal texture under the high-temperature firing system of 1200 ℃. The invention adopts a low-temperature sintering process, follows the material characteristics of the pearlescent mica pigment, has wide selection range of pearlescent mica raw materials and no limitation on color and texture. The invention makes up the defects of the material in the actual production and use process from the process technology point of view, and can really realize the wide application of the pearlescent mica series pigment in the decoration of the ceramic tile.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The preparation method of the metal decorative glaze marble ceramic tile comprises the following steps:
preparing pearlescent mica slurry. 10 g of pearlescent mica pigment with the fineness of 600 meshes and 8 g of low-temperature glass flux powder with the fineness of 325 meshes are uniformly mixed, added into 100 g of sodium carboxymethylcellulose aqueous solution with the mass fraction of 2 percent and low viscosity, slowly stirred for 10 minutes and then screened by a 160-mesh vibrating screen for later use. The pearlescent mica pigment can be a golden yellow pearlescent mica pigment or a silver pearlescent mica pigment.
Selecting marble tiles with depressions on the surface. The marble tile can be a marble tile with a green brick having a groove, a carved ink decoration, and a sinking glaze decoration. The surface of the ceramic tile is cleaned to avoid the dust or impurities on the surface of the ceramic tile from causing adverse effects on the glaze decoration. And uniformly spraying the prepared pearlescent mica slurry on the surface of the marble ceramic tile by using a spray gun, lightly pressing the glaze surface by using a flat rubber, wherein the rubber is vertical to the ceramic tile in the movement direction of a glaze line, at least part of the pearlescent mica slurry is extruded into a concave position, and the redundant pearlescent mica slurry outside the concave position is driven to the edge of the ceramic tile by the rubber. The redundant pearl mica slurry automatically falls down and flows into a collecting container at the lower part of the glaze line for recycling. The specific gravity of the pearlescent mica slurry is 1.15g/cm3The glazing amount is 350g/m2。
And conveying the marble ceramic tile subjected to the pearlescent mica slurry application into a low-temperature decoration firing roller kiln through a glaze line. The maximum sintering temperature is 580-650 ℃, and the heat preservation time at the maximum sintering temperature is 5-8 minutes. And after sintering, fully cooling, polishing and edging to obtain the metal decorative glaze surface marble ceramic tile.
The low-temperature firing ensures that various physicochemical properties of the metal decorative glaze marble ceramic tile are stable, and the final finished ceramic tile completely meets the national standard. Fig. 1 shows a metal decorative glazed marble tile with golden yellow texture and silver texture. The marble tile only has the pearlescent mica pigment at the depressed part on the surface of the tile, so that the problem of use limitation caused by poor wear resistance of the pearlescent mica pigment can be solved.
Example 2
The preparation method of the metal decorative glaze marble ceramic tile comprises the following steps:
preparing pearlescent mica slurry. Uniformly mixing 12 g of pearlescent mica pigment with the fineness of 600 meshes and 9 g of low-temperature glass flux powder with the fineness of 325 meshes, adding the mixture into 100 g of rubber roll stamp-pad ink, slowly stirring for 15 minutes, and sieving the mixture uniformly through a 200-mesh vibrating screen for later use.
And selecting the marble ceramic tile with smooth glaze or rubber roll patterns which can be tightly attached with concave-convex textures of the glaze of the ceramic tile. The surface of the ceramic tile is cleaned to avoid the dust or impurities on the surface of the ceramic tile from causing adverse effects on the subsequent glaze decoration. And applying the prepared pearlescent mica slurry on the surface of the marble ceramic tile through rubber roll printing. The specific gravity of the pearlescent mica slurry is 1.20g/cm3The glazing amount is 120g/m2。
And conveying the marble ceramic tile subjected to the pearlescent mica slurry application into a low-temperature decoration firing roller kiln through a glaze line. The maximum sintering temperature is 580-650 ℃, and the heat preservation time at the maximum sintering temperature is 5-8 minutes. And fully cooling and edging the ceramic tile after firing to obtain the metal decorative glaze marble ceramic tile.
The low-temperature firing ensures that various physicochemical properties of the metal decorative glaze marble ceramic tile are stable, and the final finished ceramic tile completely meets the national standard. Fig. 2 shows a metal decorated glazed marble tile with a golden yellow color. The marble tile adopts the rubber roller for printing, has fine patterns, can be matched with the patterns on the bottom layer of the original tile, has rich glaze layer expression and strong third dimension, and is more suitable for wall decoration.
Comparative example 1
The preparation method of the metal decorative glaze marble ceramic tile comprises the following steps:
golden yellow metallic luster glaze is prepared. 70 parts of 325-mesh ceramic glaze and 30 parts of 600-mesh golden yellow pearlescent pigment are slowly stirred uniformly at normal temperature for later use. The chemical composition of the ceramic glaze comprises: by mass percent, SiO2 69.7％，Al2O311％，B2O3 12％，K2O 1.5％，Na23.8 percent of O and 2.0 percent of CaO; the chemical composition of the golden pearlescent pigment comprises: by mass percent, SiO2 30.85％，Al2O3 18％，Fe2O3 45％，K2O 5.5％，Na2O 0.4％，CaO 0.05％，MgO 0.2％。
Adding a certain amount of water and stamp-pad ink into the prepared metallic luster glaze, uniformly mixing, applying the mixture on a green brick by a spray gun or a silk screen printing, and sintering at 1100-plus 1200 ℃ to obtain a golden metallic luster glaze ceramic tile product.
Comparative example 1 attempts to improve the temperature resistance and wear resistance of pearlescent mica pigment by adjusting the ceramic glaze formula system, but the practicability and operability are poor.
Comparative example 2
The preparation method of the metal decorative glaze marble ceramic tile comprises the following steps:
and preparing the pearlescent glaze. 6-7 parts of pearlescent mica pigment with the particle size of 10-150um, 3-4 parts of frit with the particle size of less than 400 meshes and 100 parts of stamp-pad ink are uniformly mixed. The chemical composition of the clinker powder comprises: by mass percent, SiO2 65-75％，Al2O3 5-8％，B2O3 13-15％，K2O 1.5-2.2％，Na2O 4-5％，CaO 0-1.0％，MgO 0-0.5％。
And (3) applying the pearlescent glaze on the surface of the ceramic tile blank or the overglaze by using a spray gun or screen printing, drying, and then sintering at the temperature of 1180-1230 ℃ to obtain the golden pearlescent glazed tile. The glazing amount of the pearlescent glaze is 110-250g/m2。
Comparative example 2 attempts to improve the temperature resistance and wear resistance of pearlescent mica pigment by adjusting the glaze formulation of pearlescent glaze, and at the same time increases the screen printing process (small printing area,<1m2) However, the problem of poor practicability and operability when the pearlescent mica pigment is used for preparing the metallic luster ceramic tile is not changed.
Claims (10)
1. The preparation method of the metal decorative glaze marble ceramic tile is characterized by comprising the following steps: selecting a marble tile with a concave surface; spraying the pearlescent mica slurry on the surface of the marble ceramic tile; the pearlescent mica slurry comprises: by mass percentage, 6-15% of pearlescent mica pigment, 6-10% of low-temperature glass flux powder and 75-88% of sodium carboxymethylcellulose aqueous solution; and extruding the surface of the marble ceramic tile sprayed with the pearlescent mica slurry by using a flat rubber sheet to extrude at least part of the pearlescent mica slurry into the depressions of the marble ceramic tile, and then sintering at a low temperature and polishing to obtain the metal decorative glaze marble ceramic tile.
2. The method as claimed in claim 1, wherein the low-temperature glass flux powder has an initial melting temperature of 500-700 ℃, preferably 580-650 ℃.
3. The method of claim 1 or 2, wherein the chemical composition of the low temperature glass frit powder comprises: by mass percent, SiO2 35-45%，Al2O3 2-8%，B2O3 20-35%，ZnO 6-9%，Na2O 10-20%，P2O51-4%，Li2O 3-7%。
4. The production method according to any one of claims 1 to 3, characterized in that the particle size of the pearlescent mica pigment is 400-800 mesh.
5. The preparation method according to any one of claims 1 to 4, characterized in that the maximum firing temperature of the low-temperature firing is 500-700 ℃, preferably 580-650 ℃; the heat preservation time at the highest sintering temperature is 5-8 minutes.
6. The production method according to any one of claims 1 to 5, wherein the specific gravity of the pearlescent mica slurry is 1.1 to 1.3g/cm3The glazing amount is 180-2。
7. The preparation method according to any one of claims 1 to 6, wherein the mass percentage of the sodium carboxymethylcellulose aqueous solution is 0.8-2.5%.
8. The method for preparing according to any one of claims 1 to 7, wherein the marble tile having a surface with depressions is a marble tile having depressions formed by at least one of green tile with grooves, finishing engraving ink decoration, and depressed glaze decoration.
9. The preparation method according to any one of claims 1 to 8, wherein the firing time is 50 to 70 minutes when the specification of the marble tile is 600-1200mm in length, 300-600mm in width, and 5.5 to 10mm in thickness; the specification of the marble tile is 1200mm in length, 1200mm in width, 800 mm, 1200mm in thickness and 3-10mm in thickness, and the firing time is 75-105 minutes.
10. The preparation method of the metal decorative glaze marble ceramic tile is characterized by comprising the following steps: selecting a marble ceramic tile with a smooth surface or a rubber roll pattern which can be tightly attached to the concave-convex texture of the ceramic tile; printing a pearlescent mica slurry rubber roll on the surface of the marble ceramic tile; the pearlescent mica slurry comprises: 8-13% of pearlescent mica pigment, 6-8.5% of low-temperature glass melt agent powder and 79-86% of rubber roll stamp-pad ink in percentage by mass; and then sintering at low temperature to obtain the metal decorative glaze surface marble ceramic tile.
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| CN116535248A (en) * | 2023-05-23 | 2023-08-04 | 广东天弼陶瓷有限公司 | Polished glazed hole stone brick with metallic luster and strong third dimension and preparation method thereof |
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