CN113248150B - Engraving protection glaze and ceramic tile capable of improving engraving depth and preparation method thereof - Google Patents
Engraving protection glaze and ceramic tile capable of improving engraving depth and preparation method thereof Download PDFInfo
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- CN113248150B CN113248150B CN202110688307.5A CN202110688307A CN113248150B CN 113248150 B CN113248150 B CN 113248150B CN 202110688307 A CN202110688307 A CN 202110688307A CN 113248150 B CN113248150 B CN 113248150B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/001—Applying decorations on shaped articles, e.g. by painting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
- B28B11/044—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers with glaze or engobe or enamel or varnish
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F9/00—Designs imitating natural patterns
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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
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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Abstract
The invention discloses a finishing carving protective glaze capable of improving carving depth, a ceramic tile and a preparation method thereof, wherein the finishing carving protective glaze comprises glaze slip and a suspending agent, the glaze formula of the glaze slip is a formula with high temperature and high viscosity, the suspending agent comprises a wetting agent, a dispersing agent, a thickening agent, a defoaming agent and an antifreezing agent, the finishing carving protective glaze is sprayed on the surface of the ceramic tile, the ceramic tile with clear carving texture can be prepared, and the preparation method of the ceramic tile comprises the following steps: preparing a finishing impression protective glaze; coating a cover glaze on the green brick; carrying out ink-jet printing on the surface of the overglaze, and then spraying the finishing carving protective glaze on the surface of the green brick applied with the finishing carving ink to obtain a finishing carving texture layer; and (4) firing the green brick with the carved texture layer in a kiln to obtain the ceramic tile with clear carved texture. The carving protective glaze disclosed by the invention can maximize the fall of the carving protective glaze by adopting the combination of the glaze slip with high temperature and high viscosity and the suspending agent, so that the carving depth is effectively improved, and the carving protective glaze has clear concave-convex textures by being sprayed on the surface of the ceramic tile.
Description
Technical Field
The invention relates to the field of ceramic glaze and architectural ceramics, in particular to a finishing carving protective glaze and a ceramic tile capable of improving carving depth and a preparation method thereof.
Background
With the improvement of living standard of people, in modern decorative plates, people have higher requirements on the decoration, environmental protection and durability, surface impression and fine concave-convex texture engraving effect similar to wood grains and cloth grains. The ceramic tile with excellent physicochemical property is the preferable of people for the durable decorative material which is good for household decoration enjoyment, and especially the ceramic tile which generates surface effects such as real wood, cloth and the like is favored by consumers, and furthermore, the ceramic tile process is adopted to manufacture the wood grain, the cloth grain and the like which have vivid colors and the carved effect of three-dimensional concave-convex sense, so that the ceramic tile greatly saves high-quality natural resources.
The preparation method of the ceramic tile with carved textures manufactured at the present stage generally comprises the following two methods:
1. the method adopts a die with fixed texture to press the green body, only one carved texture can be presented, when various carved textures are prepared, dies with various effects are needed, but the die effect and the pattern texture are difficult to coincide and are not vivid enough, and the effect difference becomes large after the dies are used for a period of time.
2. The protective glaze layer is distributed on the ceramic tile blank with the ink pattern layer, and the ink with the texture pattern can physically discharge the subsequently sprayed water-based glaze by utilizing the characteristic that the ink is separated between the oiliness of the ink and the water-based property of the transparent glaze, so that the carved effect of the ceramic tile with the ink texture pattern position as the depression is formed. The carved ceramic tile prepared by the method has diversified carving effects, and is more popular in the market than the carved products of the traditional die products. But use traditional finishing impression protective glaze effect can't make glaze slip and finishing impression ink obtain abundant separation on the finishing impression ink, and partial glaze slip covers on the finishing impression ink, leads to the fall to reduce between glaze and the ink, thereby makes glyptic degree of depth shallow, makes the three-dimensional unsmooth sense of the ceramic tile surface texture of preparing not strong enough, and the wood grain that the finishing impression made is lifelike inadequately with cloth line and stone line, and uses the sculpture degree of depth that traditional finishing impression protective glaze obtained to can't reach the design demand, has restricted the subject matter variety of this type of product.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a finishing carving protective glaze capable of improving the carving depth.
The invention also aims to provide a ceramic tile with clear carving textures, wherein the carved protective glaze is sprayed on the surface of the ceramic tile, so that the glaze surface of the ceramic tile presents concave-convex carved textures, the carving depth of the textures is deep, and the carving effect is good.
The invention aims to provide a preparation method of a ceramic tile with clear carving textures, which can solve the problems of glaze shortage, glaze wrinkling and non-uniform glazing behind the ceramic tile by setting the number and the positions of spray guns.
In order to achieve the purpose, the invention adopts the following technical scheme:
a precise carving protective glaze capable of improving carving depth comprises glaze slip and suspending agent;
the glaze slip comprises, by weight, 15-18 parts of potassium feldspar, 20-24 parts of albite, 9-12 parts of kaolin, 12-14 parts of barium carbonate, 5-7 parts of wollastonite, 4-6 parts of zinc oxide, 5-7 parts of quartz, 30-34 parts of matte frit, 40-46 parts of water, 0.12-0.18 part of carboxymethyl cellulose and 0.3-0.38 part of sodium tripolyphosphate;
the suspending agent comprises, by mass, 0.3-1% of a wetting agent, 0.3-3% of a dispersing agent, 0.2-5% of a thickening agent, 5-13% of a defoaming agent, 5-10% of an antifreezing agent and the balance of water.
Further, the weight ratio of the glaze slip to the suspending agent is 100: 10 to 15.
Further, the weight ratio of the carved protective glaze is 1.35-1.45g/cm for carrying out high-speed flowering.
Further, the flow rate of the suspending agent is 70-90 seconds, and the viscosity is 300-400 Pa.s.
Further, the glaze slip is obtained by carrying out heavy planting at the specific gravity of 1.86-1.90g/cm and carrying out fineness of 325 meshes and the balance of 0.4-0.6%.
Further, in the suspending agent, the wetting agent is a polyoxyethylene alkylating ether wetting agent;
the dispersing agent is one or more of alkali metal phosphate, triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum or fatty acid polyglycol ester;
the thickening agent is one or more of xanthan gum, carboxymethyl cellulose, sodium polyacrylate, gaseous silicon dioxide, bentonite or magnesium aluminum silicate;
the defoaming agent is of an organic silicone type and/or an ester-ether type;
the antifreezing agent is ethylene glycol and/or propylene glycol.
Further, the chemical composition of the matte frit comprises 17.05% of Al2O3、47.23%SiO2、6.76%CaO、2.35%MgO、12.28%BaO、5.72%ZnO、2.10%SrO、4.64%K2O、1.33%Na2O and0.25% loss on ignition.
A ceramic tile with clear carving textures comprises a tile blank, a surface glaze layer and a carved texture layer, wherein the carved texture layer is composed of a carved ink and a carved protective glaze, and the carved protective glaze adopts the carved protective glaze;
the finishing impression ink with the combined action of finishing impression protection glaze the overglaze layer top forms with the finishing impression ink is sunken the finishing impression protection glaze is bellied unsmooth finishing impression texture.
A preparation method of ceramic tiles with clear carving textures is used for preparing the ceramic tiles with clear carving textures, and comprises the following steps:
(1) mixing the raw materials of the glaze slip, performing ball milling to obtain the glaze slip, and uniformly mixing the glaze slip and a suspending agent to obtain the engraving protective glaze;
(2) spraying a cover glaze on the green brick to obtain a cover glaze layer;
(3) carrying out ink-jet printing on the surface of the overglaze layer and applying the finishing carving ink, and then spraying the finishing carving protective glaze on the surface of the brick blank applied with the finishing carving ink by adopting a spray gun glaze spraying process to obtain a finishing carving texture layer;
(4) and (4) firing the green brick with the carved texture layer obtained in the step (3) in a kiln to obtain the ceramic tile with clear carved texture.
Further, in the step (3), when the finishing carving protective glaze is sprayed, the glaze spraying is performed by adopting a combination of two groups of spray guns A with the caliber of 0.43mm and three groups of spray guns B with the caliber of 0.52mm, and the installation sequence of the five groups of spray guns is respectively spray gun A → spray gun B → spray gun A;
the distance between the spray gun A and the spray gun B is 30cm-40cm, and the distance between the spray gun B and the spray gun B is 15 cm;
the height of the nozzle of the spray gun from the surface of the green brick is 70 cm-80 cm, and the spray gun is perpendicular to the surface of the green brick.
The technical scheme has the following beneficial effects:
1. this technical scheme is through adding the suspending agent in the finishing impression protection glaze, reduces the mobility of finishing impression protection glaze, makes the finishing impression protection glaze viscosity promote and the suspending agent can carry out abundant wetting with the solid particle in the glaze slip, at the in-process of glazing porcelain, and the finishing impression protection glaze can form drop-shaped glaze layer and does not collapse, makes the finishing impression protection glaze and the maximization of finishing impression ink fall, can effectively promote the sculpture degree of depth, makes the sculpture effect show the promotion.
2. The glaze slip among this technical scheme is high temperature high viscosity formula, and the frit has high viscosity at high temperature firing in-process, and mobility is relatively poor, can furthest keep the sculpture effect that demonstrates when glazing porcelain to strengthen the unsmooth sense on ceramic tile surface, form darker sculpture texture, further promote the sculpture degree of depth, satisfy the design demand of various types of finishing impression subject matter.
Drawings
FIG. 1 is a schematic view showing the distribution of an engraving protective glaze and an engraving ink when no suspending agent is added;
FIG. 2 is a schematic diagram of the distribution of the finishing carving protective glaze and the finishing carving ink in one embodiment of the invention (the finishing carving protective glaze adopts a high-temperature and high-viscosity glaze formula and is added with a suspending agent);
FIG. 3 is a view of the glazed surface after glazing without adding a suspending agent to the finishing glaze;
FIG. 4 is a diagram of the glaze surface of a ceramic tile after spraying the finishing carving protective glaze (the finishing carving protective glaze adopts a high-temperature high-viscosity glaze formula and is added with a suspending agent);
FIG. 5 is a diagram showing the finished product of a tile made according to a comparative example of the present invention using a high temperature low viscosity glaze formulation;
FIG. 6 is a finished display of a tile with clear carved texture (using a high temperature, high viscosity glaze formulation with the addition of a suspending agent) according to one embodiment of the present invention;
wherein, the engraving protective glaze 1' without the addition of the suspending agent, the engraving protective glaze 1 adopting a high-temperature high-viscosity glaze formula and the suspending agent and the engraving ink 2.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and the detailed description.
A precise carving protective glaze capable of improving carving depth comprises glaze slip and suspending agent;
the glaze slip comprises, by weight, 15-18 parts of potassium feldspar, 20-24 parts of albite, 9-12 parts of kaolin, 12-14 parts of barium carbonate, 5-7 parts of wollastonite, 4-6 parts of zinc oxide, 5-7 parts of quartz, 30-34 parts of matte frit, 40-46 parts of water, 0.12-0.18 part of carboxymethyl cellulose and 0.3-0.38 part of sodium tripolyphosphate;
the suspending agent comprises, by mass, 0.3-1% of a wetting agent, 0.3-3% of a dispersing agent, 0.2-5% of a thickening agent, 5-13% of a defoaming agent, 5-10% of an antifreezing agent and the balance of water.
It is worth mentioning that when the ceramic tile with the carved texture is prepared, a layer of finishing carving ink is firstly printed on the surface of a tile blank in an ink jet mode, then a layer of finishing carving protective glaze is sprayed, the finishing carving ink is oily, the finishing carving protective glaze is water-based, according to the principle that water and oil are incompatible, the finishing carving ink and the finishing carving protective glaze act together to form concave and convex finishing carving texture taking the finishing carving ink as concave and the finishing carving protective glaze as convex on the surface of the tile blank, but because the existing finishing carving protective glaze does not contain a suspending agent, when glazing, the finishing carving protective glaze is easy to diffuse due to large glazing amount, thick glaze layer and low specific gravity, the fluidity of the glaze is strong, so that part of the finishing carving protective glaze can cover the finishing carving ink, the structure taking the finishing carving ink as concave and the finishing carving protective glaze as convex is destroyed, and the fall between the finishing carving protective glaze and the finishing carving ink is reduced, thereby deteriorating the engraving effect as shown in fig. 1. In order to improve the engraving depth, the technical scheme reduces the fluidity of the carved protective glaze by adding a proper amount of suspending agent into the carved protective glaze, so that the viscosity of the carved protective glaze is improved, and the suspending agent can fully wet solid particles in the glaze slurry, as shown in figure 2, in the glazing process, the carved protective glaze can form a bead-shaped glaze layer without collapse, so that the fall between the carved protective glaze and the carved ink is maximized, and the engraving effect is obviously improved.
Moreover, the glaze slip in the technical scheme is a high-temperature high-viscosity formula, the glaze surface has high viscosity and poor fluidity in the high-temperature sintering process, and the carving effect presented in the glazing process can be kept to the maximum extent, so that the concave-convex feeling of the surface of the ceramic tile is enhanced, deeper carving textures are formed, and the design requirements of various types of finishing carving subject matters are met. If the high-temperature viscosity of the glaze formula is smaller, the fine carving protective glaze collapses due to good high-temperature fluidity of the glaze surface in the firing process, so that the carving depth is reduced.
Specifically, by adopting the glaze slip formula of the technical scheme, Al in the chemical composition of the glaze slip2O3、SiO2The mass percent of the component (A) is increased, and CaO, MgO, BaO, ZnO, SrO and K2O、Na2The mass percentage of the chemical components O is reduced, and the viscosity of the glaze slip caused by high temperature can be effectively improved. The glaze slip comprises the following chemical components in percentage by mass: al (Al)2O3：13.76-14%、SiO2：50.98-51%、CaO：4.1-4.25%、MgO：0.74-0.8%、BaO：12.32-12.98%、ZnO：5.66-6.46%、SrO：0.29-0.36%、K2O: 3.0-3.04%, Na 2O: 2.95-3.02% and loss on ignition: 3.4-3.45%, the high-temperature viscosity of the glaze slip formula is along with Al2O3、SiO2The content increases with the increase of CaO, MgO, BaO, ZnO, SrO and K2O、Na2The content of O is increased and reduced, when the glaze slurry in the technical scheme is fired at the temperature of 1150 ℃, the high-temperature viscosity of the glaze slurry is 395-419Pa.S, the lg high-temperature viscosity value is within the range of 2.6-2.62, and the sintering state and the carving effect of the glaze surface are optimal. If the high-temperature viscosity of the glaze slip is too large, the blank is not easy to oxidize and exhaust, the glaze surface is easy to form pinhole miliaria, if the high-temperature viscosity is too small, the high-temperature fluidity of the glaze surface is improved, and the glaze surface can collapse in the firing process to reduce the carving effect. If the lg value is more than 4, the glaze slip is in a raw burning state, if the lg value is 3-4, the glaze slip is in a semi-raw burning state, if the lg value is 1.6-3, the glaze slip is in a fully sintering state, and if the lg value is less than 1.6, the glaze is over-burnt; the larger the lg value, the higher the kiln firing temperature requirement.
Further, the glaze slip adopts the matte frit, and the surface of the ceramic tile presents a matte effect after being fired, so that the carved texture is clearer and more obvious.
Therefore, the combination of the high-temperature and high-viscosity glaze formula and the suspending agent of the engraving protection glaze in the technical scheme can separate the engraving protection glaze from the engraving ink to the greatest extent, so that the fall of the engraving protection glaze and the engraving ink is maximized, the engraving depth is improved, and the engraving protection glaze has clear concave-convex textures by spraying on the surface of the ceramic tile.
Preferably, the raw materials of the glaze slip comprise, by weight, 15 parts of potassium feldspar, 20 parts of albite, 10 parts of kaolin, 12 parts of barium carbonate, 5 parts of wollastonite, 4 parts of zinc oxide, 5 parts of quartz, 30 parts of matte frit, 42 parts of water, 0.14 part of carboxymethyl cellulose and 0.32 part of sodium tripolyphosphate.
Further, the weight ratio of the glaze slip to the suspending agent is 100: 10 to 15.
It is worth to be noted that, the engraving ink is oily, the engraving protective glaze is aqueous and utilizes the principle of water-oil incompatibility, the engraving ink can pull the engraving protective glaze open to form the engraving effect, but the engraving protective glaze has large glazing amount, thick glaze layer, low specific gravity and strong fluidity, so that the glaze layer collapses and diffuses, part of the glaze slip still covers the engraving protective glaze, so that the fall between the glaze layer and the engraving ink is reduced, the engraving effect is deteriorated, a proper amount of suspending agent is added into the engraving protective glaze to reduce the fluidity of the glaze slip, so that the viscosity of the glaze slip is increased, the suspending agent can fully wet solid particles in the glaze slip, a bead-shaped glaze layer can be formed in the glazing process without collapsing, the fall between the glaze layer and the engraving ink is maximized, and the engraving effect is remarkably improved.
If the addition amount of the suspending agent is too small, the glaze surface has poor carving effect after glazing; if the addition amount of the suspending agent is too high, the defect of glazing and recessed glaze is easily caused, and if the addition amount of the suspending agent is too high, the evaporation speed of glaze water is slow, so that the water content in a kiln is increased, and the defect of brick explosion is easily caused, so that the weight ratio of the glaze slip to the suspending agent is preferably 100: 10 to 15.
Further, the specific gravity of the carved protective glaze is 1.35-1.45g/cm for carrying out high-speed cultivation.
Specifically, if the specific gravity of the finishing carving protective glaze is less than 1.35g/cm, the flowability of the finishing carving protective glaze is high, the carving depth is reduced, and the concave-convex finishing carving texture on the surface of the ceramic tile is unclear; if the specific gravity of the carved protective glaze exceeds 1.45g/cm for high-viscosity cultivation, spraying by a spray gun is not facilitated.
Further, the flow rate of the suspending agent is 70-90 seconds, and the viscosity is 300-400 Pa.s.
The suspending agent in the technical scheme is a low-bubble suspending agent, so that the defects of glazing can be reduced in the glazing process, and the influence on the attractiveness of the glaze due to bubbles generated on the glaze is avoided. If the flow rate of the suspending agent is too high or the viscosity of the suspending agent is too low, the fluidity of the finishing carving protective glaze is increased to a certain extent, so that the carving depth is reduced; if the flow rate of the suspending agent is too low or the viscosity is too high, the suspending agent is not beneficial to mixing with the glaze slip and glazing, and the glaze surface is easy to have glazing defects.
Further, the glaze slip has a specific gravity of 1.86-1.90g/cm for cultivating fruit and has a fineness of 325 meshes and a residual amount of 0.4-0.6%.
It is worth to say that when the fineness of the glaze slip is 325 meshes and the residual amount is 0.4-0.6%, the glaze is easy to apply, the situation of blocking a spray gun cannot occur in the process of applying the glaze, and the glaze is easy to fire. If the specific gravity of the glaze slip is too large, the glaze slip is not favorable for ball discharging and the mixing of the suspending agent; the prepared carved protective glaze needs to be stored and aged due to production requirements, and if the specific gravity of the glaze slip is too low, the glaze slip is easy to deposit in a storage cylinder.
Further, in the suspending agent, the wetting agent is a polyoxyethylene alkyl ether wetting agent;
the dispersant is one or more of alkali metal phosphate, triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivative, polyacrylamide, guar gum or fatty acid polyglycol ester;
the thickener is one or more of xanthan gum, carboxymethyl cellulose, sodium polyacrylate, gaseous silicon dioxide, bentonite or magnesium aluminum silicate;
the defoaming agent is organic silicone and/or ester-ether type;
the antifreezing agent is ethylene glycol and/or propylene glycol.
It is worth explaining that the wetting agent in the suspending agent plays a role in wetting the glaze slip particles, and the glaze slip particles are incompatible with the oil-based engraving ink in the glazing process to generate the engraving effect; the dispersant can prevent glaze particles in the glaze slurry from being adhered to each other, so that the glaze particles are uniformly distributed and fully wetted; the thickening agent can increase the viscosity of the glaze slurry and reduce the fluidity, and a bead-shaped glaze layer is formed in the glazing process; the defoaming agent can reduce bubbles in the glaze slip and prevent the glaze surface defect caused by the bubbles in the glazing process.
Specifically, the suspending agent in the technical scheme is mainly made of organic compounds, the organic compounds are added into the engraving and protecting glaze, and the organic compounds are decomposed and volatilized during firing, so that the chemical reaction of the formula is not participated in, and the structure of the formula is not influenced.
Further, the chemical composition of the matte frit comprises Al2O317.05%、SiO247.23%、CaO6.76%、MgO2.35%、BaO12.28%、ZnO5.72%、SrO2.10%、K2O4.64%、Na2O1.33% and ignition loss 0.25%.
Particularly, the matte frit can widen the sintering range and reduce the loss of glaze material after sintering, meanwhile, the matte frit in the scheme has the characteristic of high silicon aluminum content, and the introduction of the matte frit into the glaze slurry can further improve the viscosity of the glaze slurry at high temperature.
A ceramic tile with clear carving textures comprises a tile blank, a surface glaze layer and a carved texture layer, wherein the carved texture layer consists of carved ink and a carved protective glaze, and the carved protective glaze adopts the carved protective glaze;
the combined action of the finishing carving ink and the finishing carving protective glaze forms concave-convex finishing carving textures which take the finishing carving ink as a recess and the finishing carving protective glaze as a protrusion on the top of the overglaze layer.
As shown in fig. 6, the ceramic tile with clear carving texture has the advantages of deep carving depth, clear concave-convex precise carving texture, strong third dimension and vivid wood grain made by precise carving effect.
A preparation method of ceramic tiles with clear carving textures is used for preparing the ceramic tiles with clear carving textures, and comprises the following steps:
(1) mixing the raw materials of the glaze slip, performing ball milling to obtain the glaze slip, and uniformly mixing the glaze slip and a suspending agent to obtain the engraving protective glaze;
(2) spraying a cover glaze on the green brick to obtain a cover glaze layer;
(3) carrying out ink-jet printing on the surface of the overglaze layer and applying the finishing carving ink, and then spraying the finishing carving protective glaze on the surface of the brick blank applied with the finishing carving ink by adopting a spray gun glaze spraying process to obtain a finishing carving texture layer;
(4) and (4) firing the green brick with the carved texture layer obtained in the step (3) in a kiln to obtain the ceramic tile with clear carved texture.
Specifically, in the step (1), the raw materials of the glaze slurry are weighed according to the weight parts, mixed uniformly, and put into a ball mill for ball milling for 8-10 hours to ensure that the fineness is 0.4-0.6% of the rest of a 325-mesh sieve, so as to obtain the glaze slurry. In the step (3), the pattern to be designed and the finishing carving effect are printed on the overglaze layer by an ink jet printer, then the prepared finishing carving protective glaze is uniformly sprayed on the ink jet design pattern by adopting a glaze spraying process, as shown in fig. 4, after the finishing carving protective glaze is sprayed, the finishing carving texture on the surface of the ceramic tile is clear, preferably, the amount of the finishing carving protective glaze per square is 300-500g, and finally, the green brick with the finishing carving texture is put into a kiln to be fired at the firing temperature of 1143-1153 ℃.
Further, in the step (3), when the finishing carving protective glaze is sprayed, the glaze spraying is carried out by adopting the combination of two groups of spray guns A with the caliber of 0.43mm and three groups of spray guns B with the caliber of 0.52mm, and the installation sequence of the five groups of spray guns is respectively spray gun A → spray gun B → spray gun A;
the distance between the spray gun A and the spray gun B is 30cm-40cm, and the distance between the spray gun B and the spray gun B is 15 cm;
the height of the nozzle of the spray gun from the surface of the green brick is 70 cm-80 cm, and the spray gun is perpendicular to the surface of the green brick.
In the process of applying the finishing impression protective glaze, if the size and the position of the spray gun are not properly arranged, the problems of glaze shortage, glaze wrinkling, glazing unevenness and the like on the back of a finished product can be caused.
According to the technical scheme, the problems of glaze shortage and glaze wrinkling behind finished products can be solved by limiting the caliber size of the spray gun and arranging and combining the spray gun A → the spray gun B → the spray gun A. Specifically, a spray gun B with the caliber of 0.52mm is used for ensuring that the glazing amount requirement can be met, but the atomization effect of the spray gun B is easy to cause the defect of rainflower point shape; therefore, a spray gun A with the caliber of 0.43mm is matched to ensure the atomization effect, so that the glaze surface is smooth and does not wrinkle after the glaze surface is sprayed with the engraving protection glaze. The distance between the spray gun B and the spray gun B is set to be 15cm, the smaller the distance between the spray gun B and the spray gun B is, the better the glazing flatness is, but when the distance is smaller, the condition that the atomizing spray gun is stained with atomizing engraving protective glaze to generate glaze dripping exists, so the distance of 15cm is the best. Because the 15cm gun distance is short, the glaze surface is difficult to dry, and the engraving protective glaze can be blown away to cause glaze shortage due to atomization pressure at the back, the distance between the front and back groups of spray guns A and B is increased to supplement the glaze behind the glaze shortage, and the glaze shortage is avoided.
The height of the nozzle and the surface of the green brick is set to be 70 cm-80 cm, the spray gun is perpendicular to the surface of the green brick, the nozzle is located on the same horizontal plane and is located at the center of the surface of the green brick, the spray gun is set to be located in the position, the surface of the green brick and the atomization position of the spray gun can reach the best contact surface, and the glazing uniformity is best. When the carved protective glaze is sprayed, the pressure of the glaze spraying cabinet is set to be 4.5-5 mpa, the glaze layer is easy to hit out of the glaze pit due to overlarge pressure, and the problem of glaze dripping can occur due to undersize pressure.
The technical scheme of the invention is further illustrated by combining specific examples and comparative examples.
Examples 1 to 5
In the embodiments 1-5, before preparing the engraving protection glaze capable of increasing the engraving depth, the most preferable glaze slurry formula needs to be determined, and the specific operation of determining the most preferable glaze slurry formula is as follows:
the raw materials of the glaze slip in the carved protective glaze comprise potash feldspar, albite, kaolin, barium carbonate, wollastonite, zinc oxide, quartz, matte frit, water, carboxymethyl cellulose and sodium tripolyphosphate, wherein the specific gravity of the glaze slip is 1.88g/cm, and the fineness is 325 meshes and the balance is less than or equal to 0.5%.
Specifically, the formula ratio and the high-temperature viscosity of each raw material in the glaze slip are shown in the following table 1:
specifically, glaze slip is prepared according to the formula ratio shown in table 1, the obtained glaze slip is sprayed on the surface of the ceramic tile printed with the engraving ink by ink-jet printing, and the ceramic tile with the engraved texture is obtained, wherein the preparation method comprises the following detailed steps:
(1) mixing the raw materials of the glaze slip, ball-milling for 10 hours, and sieving with a 325-mesh sieve to obtain the glaze slip;
(2) spraying a cover glaze on the green brick to obtain a cover glaze layer;
(3) performing ink-jet printing on the surface of the overglaze layer, applying finishing carving ink, and then spraying glaze slurry on the surface of the brick blank applied with the finishing carving ink by adopting a spray gun glaze spraying process to obtain a finishing carving texture layer, wherein the amount of the finishing carving protective glaze is 300-500 g/m-2(ii) a Specifically, when glaze slurry is sprayed, glaze spraying is carried out by adopting the combination of two groups of spray guns A with the caliber of 0.43mm and three groups of spray guns B with the caliber of 0.52mm, the five groups of spray guns are respectively arranged in the sequence of spray gun A → spray gun B → spray gun A, the distance between the spray gun A and the spray gun B is 35cm, and the distance between the spray gun B and the spray gun B is 15 cm;
the height of the nozzle of the spray gun from the surface of the green brick is 75cm, and the spray gun is vertical to the surface of the green brick.
(4) And (4) firing the green brick with the carved texture layer obtained in the step (3) in a kiln at the firing temperature of 1150 ℃ to obtain the carved texture ceramic tile.
The glaze slip prepared according to the formula ratio of the raw materials in Table 1 and the preparation method are adopted to obtain the ceramic tile with the carved texture, the glaze effect of the ceramic tile with the clear carved texture is observed, the carving depth of the ceramic tile is measured, and the observation and detection results are shown in the following table 2:
as can be seen from table 2, when the finishing impression protective glaze does not contain a suspending agent and only includes a glaze slip with high temperature and high viscosity, the prepared ceramic tile has a certain engraving effect, as shown in fig. 3, the glaze surface of the green tile which is just sprayed with the glaze slip with high temperature and high viscosity has a certain engraving depth, the deepest engraving depth of the fired finished product is 1.0-1.8 mm, the average value of the engraving depth is 0.7-1.5, the raw material proportioning scheme of the glaze slip with better engraving effect is preferably selected from a1-a5, which is respectively a1, a2 and A3, wherein the high temperature viscosity of a1, a2 and A3 is in the region of 395-419pa.s, and the lg high temperature viscosity value is in the region of 2.6-2.62, the finishing impression effect is better, and the engraving depth of the prepared ceramic tile is reduced when the engraving depth of the ceramic tile exceeds the region, particularly, the formula of the glaze slip of a1 is adopted, and the ceramic tile is not added with suspending agent, and the prepared ceramic tile is carved with clear texture of high temperature and high viscosity, The concave-convex stereoscopic impression is strong, and the engraving effect is good.
Selecting the optimal formula A1 of the glaze slip, and adding a suspension agent to prepare the engraving protective glaze so as to prepare the ceramic tile, wherein the suspension agent comprises a wetting agent, a dispersing agent, a thickening agent, a defoaming agent, an antifreezing agent and the balance of water, the flow rate of the suspension agent is 70-90 seconds, the viscosity is 300-400Pa.s, and the formula of each raw material in the suspension agent is shown in the following table.
The formula of the glaze slip in A1 and the formula of the suspending agent are compared to obtain the carved protective glaze, the preparation method is adopted to prepare the ceramic tile with clear carved texture, the glaze effect of the ceramic tile with clear carved texture is observed, the carving depth is measured, and the observation and detection results are shown in the following table 4:
from the observation and detection results in table 4, it can be seen that the engraving depth of the prepared ceramic tile is obviously increased after the glaze slip formula of a1 and the suspending agent in the formula ratio are adopted, and the engraving depth is increased along with the gradual increase of the effective components of the wetting agent, the dispersing agent, the thickening agent, the defoaming agent and the antifreezing agent in the suspending agent.
Comparative example
The finishing carving protective glaze in the comparative example comprises glaze slip and suspending agent, wherein the formula of the suspending agent is the same as that of the embodiment 1, except that the glaze slip in the finishing carving protective glaze in the comparative example is high-temperature low-viscosity glaze slip, and the raw materials of the finishing carving protective glaze in the comparative example comprise 26 parts of nepheline, 7 parts of kaolin, 4 parts of zinc oxide, 8 parts of calcined talc, 11 parts of wollastonite, 8 parts of dolomite, 16 parts of low-temperature frit, 10 parts of medium-temperature frit and 10 parts of high-temperature frit.
Specifically, the carved protective glaze of the comparative example is adopted, the ceramic tile is prepared according to the preparation method of the embodiment, the glaze effect of the ceramic tile prepared by the comparative example is observed, the depth of the carved texture of the ceramic tile is measured, the glaze effect is shown in fig. 5, and as can be seen from fig. 5, the glaze slip of the carved protective glaze of the comparative example is a high-temperature low-viscosity glaze slip formula, and the glaze slip becomes low in viscosity and high in fluidity when being fired at high temperature, so that the glaze slip diffuses around and covers the surface of the carved ink, the carving depth becomes low, and the carved texture is unclear.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. A finishing impression protective glaze capable of improving the engraving depth is characterized by comprising glaze slip and a suspending agent;
the glaze slip comprises, by weight, 15-18 parts of potassium feldspar, 20-24 parts of albite, 9-12 parts of kaolin, 12-14 parts of barium carbonate, 5-7 parts of wollastonite, 4-6 parts of zinc oxide, 5-7 parts of quartz, 30-34 parts of matte frit, 40-46 parts of water, 0.12-0.18 part of carboxymethyl cellulose and 0.3-0.38 part of sodium tripolyphosphate;
the glaze slip comprises the following chemical components in percentage by mass: al (Al)2O3：13.76-14%、SiO2：50.98-51%、CaO：4.1-4.25%、MgO：0.74-0.8%、BaO：12.32-12.98%、ZnO：5.66-6.46%、SrO：0.29-0.36%、K2O：3.0-3.04%、Na2O: 2.95-3.02% and loss on ignition: 3.4-3.45%;
according to the mass percentage, the raw materials of the suspending agent comprise 0.3-1% of wetting agent, 0.3-3% of dispersing agent, 0.2-5% of thickening agent, 5-13% of defoaming agent, 5-10% of antifreezing agent and the balance of water;
the weight ratio of the glaze slip to the suspending agent is 100: 10 to 15.
2. The finishing carving protection glaze of claim 1, wherein the specific gravity of the finishing carving protection glaze is from 1.35 to 1.45g/cm for high harvest.
3. The finishing glaze of claim 1, wherein the flow rate of the suspending agent is 70-90 seconds, and the viscosity is 300-400 Pa.s.
4. The finishing carving protection glaze of claim 1, wherein the glaze slip has a specific gravity of 1.86-1.90g/cm for high speed cultivation, and has a fineness of 325 mesh with the balance of 0.4-0.6%.
5. The finishing glaze according to claim 1, wherein in the suspending agent, the wetting agent is a polyoxyethylene alkylated ether type wetting agent;
the dispersing agent is one or more of alkali metal phosphate, triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum or fatty acid polyglycol ester;
the thickening agent is one or more of xanthan gum, carboxymethyl cellulose, sodium polyacrylate, gaseous silicon dioxide, bentonite or magnesium aluminum silicate;
the defoaming agent is of an organic silicone type and/or an ester-ether type;
the antifreezing agent is ethylene glycol and/or propylene glycol.
6. The finishing glaze of claim 1, wherein the matte frit has a chemical composition comprising, in mass percent, 17.05% Al2O3、47.23%SiO2、6.76%CaO、2.35%MgO、12.28%BaO、5.72%ZnO、2.10%SrO、4.64%K2O、1.33%Na2O and 0.25% loss on ignition.
7. A ceramic tile with clear carved textures comprises a tile blank, a surface glaze layer and a carved texture layer, wherein the carved texture layer consists of a carved ink and a carved protective glaze, and the carved protective glaze adopts the carved protective glaze of any one of claims 1 to 6;
the finishing impression ink with the combined action of finishing impression protection glaze the overglaze layer top forms with the finishing impression ink is sunken the finishing impression protection glaze is bellied unsmooth finishing impression texture.
8. A method for preparing a tile with clear carved texture, which is used for preparing the tile with clear carved texture of claim 7, and comprises the following steps:
(1) mixing the raw materials of the glaze slip, performing ball milling to obtain the glaze slip, and uniformly mixing the glaze slip and a suspending agent to obtain the engraving protective glaze;
(2) spraying a cover glaze on the green brick to obtain a cover glaze layer;
(3) carrying out ink-jet printing on the surface of the overglaze layer and applying the finishing carving ink, and then spraying the finishing carving protective glaze on the surface of the brick blank applied with the finishing carving ink by adopting a spray gun glaze spraying process to obtain a finishing carving texture layer;
(4) and (4) firing the green brick with the carved texture layer obtained in the step (3) in a kiln to obtain the ceramic tile with clear carved texture.
9. The method for preparing a ceramic tile with clear carved textures as claimed in claim 8, wherein in the step (3), when spraying the finishing carving protective glaze, the glaze spraying is performed by using a combination of two sets of spray guns A with an aperture of 0.43mm and three sets of spray guns B with an aperture of 0.52mm, and the five sets of spray guns are respectively installed in the order of spray gun A → spray gun B → spray gun A;
the distance between the spray gun A and the spray gun B is 30cm-40cm, and the distance between the spray gun B and the spray gun B is 15 cm;
the height of the nozzle of the spray gun from the surface of the green brick is 70 cm-80 cm, and the spray gun is perpendicular to the surface of the green brick.
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| CN114426430A (en) * | 2022-01-06 | 2022-05-03 | 广东中宏创展陶瓷有限公司 | Production process of ceramic tile with carved jade effect |
| CN114478072B (en) * | 2022-04-15 | 2022-07-05 | 广东简一(集团)陶瓷有限公司 | Ceramic tile with concave-convex frosted decoration effect and preparation method thereof |
| CN115784780B (en) * | 2022-12-02 | 2023-12-05 | 佛山碧虎大理石瓷砖有限公司 | Anti-skid and anti-fouling ceramic tile and preparation method thereof |
| CN116813385B (en) * | 2023-06-27 | 2024-06-07 | 蒙娜丽莎集团股份有限公司 | Composite three-dimensional ceramic plate with natural gloss touch glaze and preparation method thereof |
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| KR101798885B1 (en) * | 2017-05-12 | 2017-11-17 | 대동산업 주식회사 | Glaze composition for inkjet printing ceramic tile and manufacturing method of inkjet printing ceramic tile using the glaze |
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