CN111548016A - Matt protection glaze with glossiness of below 3 degrees for thin ceramic tile, thin ceramic tile and preparation method thereof - Google Patents
Matt protection glaze with glossiness of below 3 degrees for thin ceramic tile, thin ceramic tile and preparation method thereof Download PDFInfo
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- CN111548016A CN111548016A CN202010429731.3A CN202010429731A CN111548016A CN 111548016 A CN111548016 A CN 111548016A CN 202010429731 A CN202010429731 A CN 202010429731A CN 111548016 A CN111548016 A CN 111548016A
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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
- C04B41/80—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 matt protection glaze with the glossiness of less than 3 degrees for a thin ceramic tile, the thin ceramic tile and a preparation method thereof. The chemical composition of the non-light protection glaze comprises: by mass percent, SiO2：55.0～60.0%、Al2O3：16.0～20.0%、Fe2O3：0.1～0.5%、TiO2：0.01～0.2%、CaO：0.5～2.5%、MgO：0.5～2.0%、K2O：2.5～4.0%、Na2O: 1.5-3.0%, BaO: 8.0-10.0%, SrO: 0.5-2.5%, ZnO: 0.5-2.0%, loss on ignition: 4.0 to 6.0 percent.
Description
Technical Field
The invention relates to a matt protection glaze with the glossiness of less than 3 degrees for a thin ceramic tile, the thin ceramic tile using the matt protection glaze and a preparation method thereof, belonging to the technical field of ceramic tile production and manufacturing.
Background
The ceramic tile is a general name of various products prepared by using various natural silicate minerals such as natural clay, feldspar, quartz and the like as main raw materials through crushing, mixing, molding and calcining, and belongs to one of the most widely used ceramic products. With the rapid development of recent decades, the yield of ceramic tiles is continuously and stably kept in the world for many years, so that a plurality of ceramic raw materials such as clay silicate minerals face the problems of over-exploitation and resource exhaustion, meanwhile, the contradiction between development and resource, energy and waste discharge also exists, and the development of green and environment-friendly architectural ceramics becomes the target of the whole industry. The thinning of the ceramic tile is one of the important ways for realizing resource saving, energy conservation and emission reduction in the building ceramic industry. The thin ceramic tile is a novel building ceramic with large specification and small thickness, can reduce the consumption of raw materials such as kaolin and the like, can be quickly fired, saves energy, and is the future development direction of the building ceramic.
At present, ceramic tiles with the thickness of 5.5-7.5 mm are popularized and used in the market, along with the rapid development of ceramic technology, the technology for producing the ceramic tiles with the thickness of 5.5-7.5 mm is more and more mature, but at present, ceramic tile series products with the thickness of 2.5-3.5 mm are not available in the market. The 2.5-3.5 mm-thick series thin ceramic tiles need relatively less glazing amount, and can be produced in batch. In addition, if the indoor wall surface and the floor are decorated by ceramic products with high glossiness, the light reflection coefficient reaches 90 percent, and the light reflection can greatly exceed the application range which can be borne by a human body and even damage the health of the human body if the indoor wall surface and the floor are in the environment for a long time.
Disclosure of Invention
Aiming at the problem of serious light pollution of high-gloss ceramic products in the prior art, the invention provides a matt protection glaze with the gloss of less than 3 degrees for thin ceramic tiles, the thin ceramic tiles and a preparation method thereof.
In a first aspect, the present invention provides a matte protective glaze for thin ceramic tiles having a gloss level of less than 3 degrees, the matte protective glaze having a chemical composition comprising: by mass percent, SiO2：55.0～60.0％、Al2O3：16.0～20.0％、Fe2O3：0.1～0.5％、TiO2：0.01～0.2％、CaO：0.5～2.5％、MgO：0.5～2.0％、K2O：2.5～4.0％、Na2O: 1.5-3.0%, BaO: 8.0-10.0%, SrO: 0.5-2.5%, ZnO: 0.5-2.0%, loss on ignition: 4.0 to 6.0 percent.
Preferably, the silicon-aluminum ratio of the non-light protection glaze is controlled to be 5.0-6.0. The silicon-aluminum ratio refers to the ratio of the amounts of silicon oxide and aluminum oxide species. If the silicon-aluminum ratio of the matte protective glaze is lower than 5.0, the glossiness of the glaze surface after firing is below 3 ℃, but the pollution resistance is poor; if the silicon-aluminum ratio of the matte protective glaze is higher than 6.0, the fired glaze has excellent pollution resistance, but the glossiness is far higher than 3 degrees, and the wear resistance is reduced.
Preferably, K in the non-light protection glaze2O and Na2The mass ratio of O is 1: 1-2.1: 1, so that the matt protective glaze has high transparency. If K is in the matt protective glaze2O and Na2The mass ratio of O is lower than 1:1, so that the high-temperature viscosity of the glaze is low, strontium feldspar and celsian crystals with larger grain sizes are easy to separate out from the glaze layer, and the transparency of the glaze is greatly reduced; if K is in the matt protective glaze2O and Na2The mass ratio of O is higher than 2.1:1, so that the glaze material has too high-temperature viscosity, poor melting capability and raw firing, and the glaze layer has less content of glass phase, thereby reducing the transparency of the glaze.
Preferably, the mineral composition of the matte protective glaze comprises: by mass percentage, 16.0-20.0% of potassium feldspar, 4.0-10.0% of albite, 20.0-28.0% of washing kaolin, 14.0-18.0% of quartz, 7.0-9.0% of barium carbonate, and strontium carbonate: 0.5-2.5% of sintered talc, 0.5-2.5% of high-temperature dull frit and 20.0-28.0% of high-temperature dull frit; wherein the chemical composition of the high temperature matte frit comprises: by mass percent, SiO2：45.0～50.0％、Al2O3：16.0～20.0％、Fe2O3：0.05～0.15％、TiO2：0.01～0.10％、CaO：5.5～7.5％、MgO：1.0～3.0％、K2O：4.0～6.0％、Na2O：1.5～2.5％、BaO：9.0～13.0％，SrO：1.0～3.0％，ZnO：4.0～7.0％Loss on ignition: 0.5 to 1.0 percent.
The gloss of the glaze surface of the product is controlled to be below 3 ℃ by the matte protective glaze, so that the matte protective glaze has no light pollution, and has good antifouling performance and high wear resistance. The common high-white overglaze usually controls the silicon-aluminum ratio to be below 4.0, the glaze layer is not completely fired to achieve the firing effect, and although the glaze surface glossiness is controlled to be below 3 degrees, the matt glaze is formed, but the glass phase formed in the glaze layer in the high-temperature firing process of the matt glaze is less, so that the matt glaze system does not have the pollution resistance. While the glossiness of the normally used matte protective glaze is more than 5 degrees, the adjustment of the glossiness is realized by introducing alumina to adjust the aluminum-silicon ratio and introducing barium carbonate to precipitate celsian crystals, when the glossiness is adjusted to be less than 5 degrees by using the alumina and the barium carbonate, although the celsian crystals are precipitated in the glaze layer and have high wear resistance, the glass phase in the glaze layer after being fired is too little and is easy to be fired, so that the stain resistance of the glaze layer after being fired is poor.
Therefore, after the matte protective glaze is fired at a high temperature, more glass phases are formed in the glaze layer, so that the glaze layer has good pollution resistance, but more glass phases are formed in the glaze layer, so that the glossiness of the glaze layer is greatly improved, namely, the matte protective glaze simultaneously has good pollution resistance and low glossiness which are contradictory, and a technical bottleneck needs to be broken through. According to the matte protective glaze, the silicon-aluminum ratio is controlled within the range of 5.0-6.0, 100% of glass phase and high-pollution-resistance high-temperature matte frit are introduced, and a glaze layer after high-temperature firing has more glass phases, so that the matte protective glaze has excellent pollution resistance; meanwhile, high-temperature dull frit, washing kaolin, strontium carbonate, barium carbonate and other dull components are introduced into the ceramic glaze, and a large amount of strontium feldspar and barium feldspar crystals are separated out after the ceramic glaze is fired, so that the glossiness of the glaze surface is reduced to be below 3 ℃.
In a second aspect, the present invention provides a method for preparing a thin ceramic tile, comprising the steps of:
step (1), pressing and molding blank powder to form a high-white blank;
step (2), ink-jet printing a design pattern on the surface of the high-white blank, wherein the texture and the color of the ink-jet printing design pattern are adaptively changed according to the layout design effect;
step (3) of applying the matte protective glaze with the glossiness of less than 3 degrees for the thin ceramic tile according to claim 1 on the surface of the high-white blank after the design pattern is printed by ink jet;
and (4) drying and sintering the high-white blank body after the matte protective glaze is applied to obtain the thin ceramic tile.
Preferably, the glazing mode of the matt protective glaze is glaze spraying, and the specific gravity is 1.25-1.35 g/cm3The glazing amount is 100-140 g/m2。
Preferably, the chemical composition of the high-white body comprises: by mass percent, SiO2：40.0～68.0％、Al2O3：20.0～50.0％、Fe2O3：0.15～0.5％、TiO2：0.05～0.30％、CaO：0.1～0.5％、MgO：0.5～1.5％、K2O：2.0～3.5％、Na2O: 1.5-4.0%, loss on ignition: 3.5 to 5.5 percent. The high-white blank body formed by the chemical composition can reduce the glazing amount of the overglaze, reduce the moisture of the thin ceramic tile and effectively reduce the breakage rate of the thin ceramic tile in the glaze line running process.
Preferably, the maximum firing temperature is 1180-1220 ℃, and the firing period is 40-80 min.
Preferably, in the step (2), before the design pattern is printed by ink-jet printing, the high-white blank is dried, and the moisture content of the dried high-white blank is controlled within 0.5 wt%.
Preferably, in the step (2), before the design pattern is printed by ink-jet printing, the surface of the dried high-white blank is glazed.
In a third aspect, the invention also provides a thin ceramic tile obtained by any one of the preparation methods, wherein the thickness of the thin ceramic tile is 2.5-3.5 mm.
The matt protective glaze has good transparency and bright color, and realizes the matt effect on the surface of the fired brick under the condition that the glazing amount of the matt protective glaze is only 55-75% of that of the common protective glaze. Meanwhile, the problem that thin ceramic tiles with the thickness of 2.5-3.5 mm cannot be produced in batch due to high moisture content caused by large glazing amount is effectively solved by using the matt protection glaze, and customized batch production of the thin ceramic tiles with the thickness of 2.5-3.5 mm is realized. The thin ceramic tile with the thickness of 2.5-3.5 mm, which is obtained by the preparation method, has the advantages of fine glaze texture, glossiness below 3 degrees, no light pollution and good antifouling performance.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive. Unless otherwise specified, each percentage means a mass percentage.
And pressing and molding the blank powder to form a high-white blank. As an example, the chemical composition of the high-white body comprises, in mass percent, SiO2：40.0～68.0％、Al2O3：20.0～50.0％、Fe2O3：0.15～0.5％、TiO2：0.05～0.30％、CaO：0.1～0.5％、MgO：0.5～1.5％、K2O：2.0～3.5％、Na2O: 1.5-4.0%, loss on ignition: 3.5 to 5.5 percent.
And drying the high-white blank at high temperature. The drying time can be 15-30 min. The moisture of the dried green body is controlled within 0.5 wt%.
And printing a design pattern on the surface of the dried high-white blank in an ink-jet mode. The pattern and color of the ink-jet printing are adaptively changed according to the pattern effect of the layout design. In addition, before the design pattern is printed by ink-jet printing, the digital overglaze can be applied by a digital glaze spraying machine according to the texture and the design color of the design pattern.
Drying the high white blank after the design pattern is printed by ink-jet printing, and applying a matte protective glaze.
The chemical composition of the above-mentioned matte protective glaze may include: by mass percent, SiO2：55.0～60.0％、Al2O3：16.0～20.0％、Fe2O3：0.1～0.5％、TiO2：0.01～0.2％、CaO：0.5～2.5％、MgO：0.5～2.0％、K2O：2.5～4.0％、Na2O: 1.5-3.0%, BaO: 8.0-10.0%, SrO: 0.5-2.5%, ZnO: 0.5-2.0%, loss on ignition: 4.0 &6.0％。
In some embodiments, the mineral composition of the above-described matte protective glaze may include: 16.0-20.0% of potassium feldspar, 4.0-10.0% of albite, 20.0-28.0% of washing kaolin, 14.0-18.0% of quartz, 7.0-9.0% of barium carbonate, and strontium carbonate: 0.5-2.5%, 0.5-2.5% of calcined talc and 20.0-28.0% of high-temperature matt frit.
The high-temperature matt frit is 100% of amorphous phase (glass phase), has excellent pollution resistance, and can improve the pollution resistance of the matt protective glaze; meanwhile, the frit has low high-temperature viscosity and contains components such as strontium, barium and the like, and strontium feldspar and barium feldspar crystals are easy to separate out from the glaze layer in the firing process, so that the effect of dull glaze surface after firing is achieved, and the glossiness of the dull protective glaze can be reduced. The chemical composition of the high temperature matte frit may include: by mass percent, SiO2：45.0～50.0％、Al2O3：16.0～20.0％、Fe2O3：0.05～0.15％、TiO2：0.01～0.10％、CaO：5.5～7.5％、MgO：1.0～3.0％、K2O：4.0～6.0％、Na2O: 1.5-2.5%, BaO: 9.0-13.0%, SrO: 1.0-3.0%, ZnO: 4.0-7.0%, loss on ignition: 0.5 to 1.0 percent.
In some embodiments, the mineral composition of the high temperature matte frit may comprise: by mass percent, potassium feldspar: 36.0-44.0%, albite: 6.0-14.0%, quartz 6.0-8.0%, calcite: 4.5-6.5%, dolomite: 7.0-9.0%, alumina: 8.0-10.0%, strontium carbonate: 1.5-3.5%, barium carbonate: 11.0-15.0%, zinc oxide: 4.0 to 6.0 percent. The high temperature matte frit is prepared by: weighing the raw materials according to the formula proportion, mixing; melting the mixed raw materials into molten glass; water quenching the molten glass, and cooling to obtain frit particles; and drying the frit particles, crushing and sieving to obtain the high-temperature matt frit.
The melting temperature in the preparation process of the high-temperature matt frit is 1350-1450 ℃. In some embodiments, the high temperature matte frit has a particle size of 2 to 5 mm.
Preparing the matt protective glaze. Weighing raw materials according to the mineral composition of the matt protection glaze, and ball-milling the raw materials to ensure that the fineness of the glaze slip is 0.3-0.5 wt% of the residue of the 325-mesh screen, thereby obtaining the matt protection glaze.
In the matt protection glaze, the glossiness of the protection glaze is adjusted by adjusting the silicon-aluminum ratio in the formula and the chemical composition, replacing washed kaolin with high-temperature matt frit, replacing part of potassium feldspar with albite, replacing part of strontium carbonate with calcined talc and the like, and the glossiness is below 3 degrees.
In addition, the matte protection glaze of the present invention has good contamination resistance by replacing a part of the water-washed kaolin having poor contamination resistance with a high-temperature matte frit of 100% glass phase which itself has good contamination resistance; while adjusting K in the formula2O and Na2The proportion of O increases the quantity of the glass phase after sintering, inhibits the formation of strontium feldspar crystals and barium feldspar crystals with large grain size, and has good pollution resistance; the burning talc is used to replace partial strontium carbonate, increase the amount of glass phase after burning and control the amount of strontium feldspar and celsian crystal, so that it has excellent pollution resistance. The invention mainly combines the three modes, can realize that the gloss of the matt protection glaze is below 3 degrees, and still has good pollution resistance. In some embodiments, the ceramic tile to which the matte protective glaze is applied may have a stain resistance of grade 5.
The glossiness of the matte protection glaze is consistent with that of the traditional high-whiteness covering glaze, and is below 3 degrees, but the traditional high-whiteness covering glaze has no antifouling capacity, but the matte protection glaze with the glossiness below 3 degrees has excellent pollution resistance. Meanwhile, the matt glaze used by ceramic manufacturers is usually controlled to be more than 5 ℃ in terms of antifouling performance, and when the glossiness is lower than 3 ℃, dirt is easily absorbed, so that the pollution resistance is poor, and the matt protection glaze provided by the invention is excellent in pollution resistance. After the matte protective glaze is fired at a high temperature, more glass phases are formed in the glaze layer, so that the glaze layer has good pollution resistance, but more glass phases are formed in the glaze layer, so that the glossiness of the glaze layer is greatly improved, namely the matte protective glaze has good pollution resistance and low glossiness which are mutually contradictory. The silicon-aluminum ratio of the matte protective glaze is controlled within the range of 5.0-6.0, 100% of glass phase and high-pollution-resistance high-temperature matte frit are introduced, and a glaze layer after high-temperature sintering has more glass phases so as to have excellent pollution resistance; meanwhile, high-temperature dull frit, washing kaolin, strontium carbonate, barium carbonate and other dull components are introduced, so that a large amount of strontium feldspar and barium feldspar crystals are separated out after sintering, and the glossiness of the glaze surface can be reduced to be below 3 ℃.
The matt protective glaze has good transparency and bright color. The silicon-aluminum ratio is controlled within the range of 5.0-6.0 by introducing a large amount of quartz, high-temperature dull frit, washed kaolin and other components, and K in the formula is controlled2O and Na2The proportion of O causes a great amount of glass phase to exist in the fired glaze layer, so that the matt protective glaze has higher transparency. In addition, the invention introduces a large amount of quartz, strontium carbonate and high-temperature dull frit with good own color development, so that the protective glaze has bright color development and good color development effect.
The matt protective glaze also has high wear resistance. Strontium feldspar and celsian crystals are separated out from the fired glaze layer by introducing high-temperature dull frit, strontium carbonate and barium carbonate, so that the glaze has high wear resistance.
The matt protective glaze has good transparency and bright color, and realizes the matt effect on the surface of the fired brick under the condition that the glazing amount of the matt protective glaze is only 55-75% of that of the common protective glaze. The invention introduces high-temperature dull frit, strontium carbonate and barium carbonate to ensure that the high-temperature viscosity of the glaze is smaller, and a certain amount of strontium feldspar crystals and barium feldspar crystals with small grain size are separated out from the glaze layer in the firing process, so that the thickness of the glaze layer can be properly reduced, and the glaze layer still has the effect of dull glaze. In some embodiments, the phase composition of the matte protective glaze comprises: the glass phase comprises the following components in percentage by mass: 38.0-48.0%, strontium feldspar: 1.0-5.0%, celsian: 18.0-24.0%, quartz: 13.0-17.0%, microcline feldspar: 16.0 to 20.0 percent.
The matte protective glaze can be applied by spraying glaze. Swing arm type sprayer capable of adopting inletAnd glazing by using a glazing machine. The specific gravity of the protective glaze can be 1.25-1.35 g/cm3The glazing amount can be 100-140 g/m2. The thickness of the glaze layer of the non-light protection glaze after firing is 0.02-0.04 mm.
And drying the high white blank body applied with the matte protective glaze, quickly firing, edging, grading and packaging. The highest firing temperature can be 1180-1220 ℃, and the firing period can be 40-80 min.
The matte protective glaze with the glossiness of less than 3 degrees has the characteristics of no dirt absorption, easy cleaning, extremely low glossiness, difficult visual discrimination, matte reflection effect, environmental protection, health and convenient maintenance, and can avoid the phenomenon of light pollution. Meanwhile, the matte protective glaze with the glossiness of less than 3 degrees also has high wear resistance, and can keep bright decorative effect of the pattern color of the brick surface for a long time. It is worth noting that the method is only applied to thin ceramic tiles with the thickness of 2.5-3.5 mm at present, the thin ceramic tiles can only adopt a simple glaze glazing process with a very small glazing amount, and the use of dry granular glaze with a complex process can increase the glazing amount, so that thin semi-finished products are greatly damaged in the glaze line operation process, the excellent rate is low, the production cost is greatly improved, and the batch production of the thin ceramic tiles cannot be realized.
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 method comprises the following steps: and pressing and molding the blank powder to form a high-white blank.
Step two: and (3) drying the high-white blank at high temperature for 15-30 min, and controlling the moisture of the dried blank to be within 0.5 wt%.
Step three: and printing a design pattern on the surface of the dried high-white blank in an ink-jet mode.
Step four: preparing the matt protective glaze according to the mixture ratio. The mineral composition of the matte protective glaze is as follows: by mass percent, 18.0 percent of potash feldspar, 7.0 percent of albite, 24.0 percent of washing kaolin, 16.0 percent of quartz, 8.0 percent of barium carbonate, 1.5 percent of calcined talc, and strontium carbonate: 1.5% and high-temperature matt frit 24.0%. The chemical composition of the non-light protection glaze is as follows: in mass percent, SiO2：57.08％、Al2O3：17.33％、Fe2O3：0.36％、TiO2：0.04％、CaO：1.77％、MgO：1.09％、K2O：3.33％、Na2O: 1.94%, BaO: 8.95%, SrO: 1.50%, ZnO: 1.34%, loss on ignition: 5.13 percent.
Step five: applying a matte protective glaze on the surface of the high white blank after ink-jet printing of the design pattern, wherein the specific gravity of the matte protective glaze is 1.25g/cm3The glazing amount is 140g/m2。
Step six: and drying the high white blank body applied with the matte protective glaze at high temperature, and quickly firing the high white blank body in a roller kiln. The maximum firing temperature is 1220 ℃, and the firing period is 40 min.
Step seven: and (5) edging, grading, packaging and warehousing.
The glaze glossiness is tested by adopting a test method of GB/T13891 plus 2008 & ltdetermination of mirror-oriented glossiness of building decorative materials & gt, the pollution resistance of the glaze is tested by adopting a test method of GB/T3810.14-2016 & ltdetermination of pollution resistance & gt, and the wear resistance of the glaze is tested by adopting a test method of GB/T3810.7-2016 & ltdetermination of wear resistance of glazed tile surfaces & gt.
The glaze glossiness of the thin ceramic tile obtained in example 1 is 2.5 degrees, the pollution resistance is 5 grades, and the glaze abrasion resistance is 2100 revolutions and 4 grades.
Example 2
The method comprises the following steps: and pressing and molding the blank powder to form a high-white blank.
Step two: and (3) drying the high-white blank at high temperature for 15-30 min, and controlling the moisture of the dried blank to be within 0.5 wt%.
Step three: and printing a design pattern on the surface of the dried high-white blank in an ink-jet mode.
Step four: preparing the matt protective glaze according to the mixture ratio. The mineral composition of the matte protective glaze is as follows: by mass percentage, 16.0% of potassium feldspar, 10.0% of albite, 28.0% of water-washed kaolin, 14.0% of quartz, 9.0% of barium carbonate, and strontium carbonate: 0.5%, calcined talc: 2.5% and high-temperature matt frit 20.0%. The chemical composition of the non-light protection glaze is as follows: by mass percent, SiO2：56.40％、Al2O3：18.28％、Fe2O3：0.40％、TiO2：0.04％、CaO：1.53％、MgO：1.34％、K2O：3.07％、Na2O: 2.15%, BaO: 9.29%, SrO: 0.73%, ZnO: 1.11%, loss on ignition: 5.51 percent.
Step five: spraying a matte protective glaze on the surface of the high-white blank after ink-jet printing of the design pattern, wherein the specific gravity of the matte protective glaze is 1.35g/cm3Glazing amount of 100g/m2。
Step six: and drying the high white blank body applied with the matte protective glaze at high temperature, and quickly firing the high white blank body in a roller kiln. The highest firing temperature is 1180 ℃, and the firing period is 80 min.
Step seven: and (5) edging, grading, packaging and warehousing.
The glaze glossiness is tested by adopting a test method of GB/T13891 plus 2008 & ltdetermination of mirror-oriented glossiness of building decorative materials & gt, the pollution resistance of the glaze is tested by adopting a test method of GB/T3810.14-2016 & ltdetermination of pollution resistance & gt, and the wear resistance of the glaze is tested by adopting a test method of GB/T3810.7-2016 & ltdetermination of wear resistance of glazed tile surfaces & gt.
The glaze glossiness of the thin ceramic tile obtained in example 2 is 2 degrees, the pollution resistance is 5 grades, and the glaze abrasion resistance is 2100 revolutions and 4 grades.
Example 3
The method comprises the following steps: and pressing and molding the blank powder to form a high-white blank.
Step two: and (3) drying the high-white blank at high temperature for 15-30 min, and controlling the moisture of the dried blank to be within 0.5 wt%.
Step three: and printing a design pattern on the surface of the dried high-white blank in an ink-jet mode.
Step four: preparing the matt protective glaze according to the mixture ratio. The mineral composition of the matte protective glaze is as follows: by mass percent, potassium feldspar: 20.0%, albite: 4.0%, water-washed kaolin: 20.0%, quartz: 18.0%, barium carbonate: 7.0%, strontium carbonate: 2.5%, calcined talc: 0.5%, high temperature matte frit: 28.0 percent. The chemical composition of the non-light protection glaze is as follows: by mass percent, SiO2：57.77％、Al2O3：16.38％、Fe2O3：0.32％、TiO2：0.03％、CaO：2.00％、MgO：0.84％、K2O：3.59％、Na2O: 1.74%, BaO: 8.60%, SrO: 2.28%, ZnO: 1.56%, loss on ignition: 4.74 percent.
Step five: spraying a matte protective glaze on the surface of the high-white blank after ink-jet printing of the design pattern, wherein the specific gravity of the matte protective glaze is 1.30g/cm3And the glazing amount is 120g/m2。
Step six: and drying the high white blank body applied with the matte protective glaze at high temperature, and quickly firing the high white blank body in a roller kiln. The maximum firing temperature is 1200 ℃, and the firing period is 60 min.
Step seven: and (5) edging, grading, packaging and warehousing.
The glaze glossiness is tested by adopting a test method of GB/T13891 plus 2008 & ltdetermination of mirror-oriented glossiness of building decorative materials & gt, the pollution resistance of the glaze is tested by adopting a test method of GB/T3810.14-2016 & ltdetermination of pollution resistance & gt, and the wear resistance of the glaze is tested by adopting a test method of GB/T3810.7-2016 & ltdetermination of wear resistance of glazed tile surfaces & gt.
The glaze glossiness of the thin ceramic tile obtained in example 3 is 3 degrees, the pollution resistance is 5 grades, and the glaze abrasion resistance is 2100 revolutions and 4 grades.
Comparative example 1
Essentially the same as example 3, except that:
step four: preparing the common high-white overglaze according to the mixture ratio. The mineral composition of a conventional high-white overglaze does not include strontium carbonate, barium carbonate and high temperature matte frits. The mineral composition of the common high-white overglaze is as follows: in percentage by massAnd potassium feldspar: 40.0%, albite: 20.0%, water-washed kaolin: 24.0%, alumina: 6%, zirconium silicate: 10 percent. The chemical composition of the common high-white overglaze is as follows: by mass percent, SiO2：56.25％、Al2O3：25.19％、Fe2O3：0.29％、TiO2：0.12％、CaO：0.25％、MgO：0.18％、K2O：4.62％、Na2O：2.95％、ZrO2: 6.10%, loss on ignition: 3.53 percent.
The glaze glossiness is tested by adopting a test method of GB/T13891 plus 2008 & ltdetermination of mirror-oriented glossiness of building decorative materials & gt, the pollution resistance of the glaze is tested by adopting a test method of GB/T3810.14-2016 & ltdetermination of pollution resistance & gt, and the wear resistance of the glaze is tested by adopting a test method of GB/T3810.7-2016 & ltdetermination of wear resistance of glazed tile surfaces & gt.
The ceramic tile obtained in the comparative example 3 has the glaze glossiness of 2.5, the pollution resistance of 1 grade, and the glaze abrasion resistance of 2100 turns and 4 grades.
Comparative example 2
Essentially the same as example 3, except that: the silicon-aluminum ratio of the matte protective glaze is 6.86.
Step four: preparing the matt protective glaze according to the mixture ratio. The mineral composition of the matte protective glaze is as follows: by mass percent, potassium feldspar: 20.0%, albite: 4.0%, water-washed kaolin: 15.0%, quartz: 22.0%, barium carbonate: 7.0%, strontium carbonate: 2.5%, calcined talc: 0.5%, high temperature matte frit: 29.0 percent. The chemical composition of the non-light protection glaze is as follows: by mass percent, SiO2：59.80％、Al2O3：14.81％、Fe2O3：0.26％、TiO2：0.03％、CaO：2.07％、MgO：0.84％、K2O：3.51％、Na2O: 1.72%, BaO: 8.70%, SrO: 2.30%, ZnO: 1.62%, loss on ignition: 4.19 percent.
The glaze glossiness is tested by adopting a test method of GB/T13891 plus 2008 & ltdetermination of mirror-oriented glossiness of building decorative materials & gt, the pollution resistance of the glaze is tested by adopting a test method of GB/T3810.14-2016 & ltdetermination of pollution resistance & gt, and the wear resistance of the glaze is tested by adopting a test method of GB/T3810.7-2016 & ltdetermination of wear resistance of glazed tile surfaces & gt.
The ceramic tile obtained in the comparative example 3 has the glaze glossiness of 18 degrees, the pollution resistance of 5 grades, and the glaze abrasion resistance of 1500 turns and 3 grades.
Comparative example 3
Essentially the same as example 3, except that: in the chemical composition of the matt protective glaze, K2O and Na2The mass ratio of O is 1: 1.77.
Step four: preparing the matt protective glaze according to the mixture ratio. The mineral composition of the matte protective glaze is as follows: by mass percent, albite: 24.0%, water-washed kaolin: 20.0%, quartz: 18.0%, barium carbonate: 7.0%, strontium carbonate: 2.5%, calcined talc: 0.5%, high temperature matte frit: 28.0 percent. The chemical composition of the non-light protection glaze is as follows: by mass percent, SiO2：57.20％、Al2O3：17.11％、Fe2O3：0.30％、TiO2：0.03％、CaO：1.97％、MgO：0.84％、K2O：1.86％、Na2O: 3.30%, BaO: 8.60%, SrO: 2.28%, ZnO: 1.56%, loss on ignition: 4.76 percent.
The glaze glossiness is tested by adopting a test method of GB/T13891 plus 2008 & ltdetermination of mirror-oriented glossiness of building decorative materials & gt, the pollution resistance of the glaze is tested by adopting a test method of GB/T3810.14-2016 & ltdetermination of pollution resistance & gt, and the wear resistance of the glaze is tested by adopting a test method of GB/T3810.7-2016 & ltdetermination of wear resistance of glazed tile surfaces & gt.
The ceramic tile obtained in the comparative example 3 has the glaze glossiness of 2 degrees, the pollution resistance of 1 grade, and the glaze abrasion resistance of 2100 turns and 4 grades.
Comparative example 4
Essentially the same as example 3, except that: the silica to alumina ratio of the matte protective glaze was 4.66.
Step four: preparing the matt protective glaze according to the mixture ratio. The mineral composition of the matte protective glaze is as follows: 16% of potassium feldspar, 16% of albite: 4.0%, water-washed kaolin: 28.0%, quartz: 10.0%, barium carbonate: 10.0%, strontium carbonate: 3.5%, calcined talc:0.5%, high temperature matte frit: 24.0 percent. The chemical composition of the non-light protection glaze is as follows: by mass percent, SiO2：50.86％、Al2O3：18.54％、Fe2O3：0.40％、TiO2：0.04％、CaO：1.99％、MgO：0.86％、K2O：3.44％、Na2O: 1.64%, BaO: 10.96%, SrO: 2.98%, ZnO: 1.56%, loss on ignition: 6.57 percent.
The glaze glossiness is tested by adopting a test method of GB/T13891 plus 2008 & ltdetermination of mirror-oriented glossiness of building decorative materials & gt, the pollution resistance of the glaze is tested by adopting a test method of GB/T3810.14-2016 & ltdetermination of pollution resistance & gt, and the wear resistance of the glaze is tested by adopting a test method of GB/T3810.7-2016 & ltdetermination of wear resistance of glazed tile surfaces & gt.
The ceramic tile obtained in the comparative example 3 has the glaze glossiness of 2 degrees, the pollution resistance of 1 level, the glaze abrasion resistance of 750 turns and 3 levels.
Claims (9)
1. A matte protective glaze for thin ceramic tiles having a gloss level of less than 3 degrees, wherein the chemical composition of the matte protective glaze comprises: by mass percent, SiO2：55.0～60.0%、Al2O3：16.0～20.0%、Fe2O3：0.1～0.5%、TiO2：0.01～0.2%、CaO：0.5～2.5%、MgO：0.5～2.0%、K2O：2.5～4.0%、Na2O: 1.5-3.0%, BaO: 8.0-10.0%, SrO: 0.5-2.5%, ZnO: 0.5-2.0%, loss on ignition: 4.0 to 6.0 percent.
2. A matte-protective glaze according to claim 1, wherein the mineral composition of the matte-protective glaze comprises: by mass percentage, 16.0-20.0% of potassium feldspar, 4.0-10.0% of albite, 20.0-28.0% of washing kaolin, 14.0-18.0% of quartz, 7.0-9.0% of barium carbonate, and strontium carbonate: 0.5-2.5% of sintered talc, 0.5-2.5% of high-temperature dull frit and 20.0-28.0% of high-temperature dull frit; wherein the chemical composition of the high temperature matte frit comprises: by mass percent, SiO2：45.0～50.0%、Al2O3：16.0～20.0%、Fe2O3：0.05～0.15%、TiO2：0.01～0.10%、CaO：5.5～7.5%、MgO：1.0～3.0%、K2O：4.0～6.0%、Na2O: 1.5-2.5%, BaO: 9.0-13.0%, SrO: 1.0-3.0%, ZnO: 4.0-7.0%, loss on ignition: 0.5 to 1.0 percent.
3. The preparation method of the thin ceramic tile is characterized by comprising the following steps:
step (1), pressing and forming blank powder to form a high-white blank;
step (2), ink-jet printing a design pattern on the surface of the high-white blank, wherein the texture and the color of the ink-jet printing design pattern are adaptively changed according to the layout design effect;
step (3) of applying the matte protective glaze with the glossiness of less than 3 degrees for the thin ceramic tile according to claim 1 on the surface of the high-white blank after the design pattern is printed by ink jet;
and (4) drying and sintering the high-white blank body after the matte protective glaze is applied to obtain the thin ceramic tile.
4. The preparation method according to claim 3, wherein the glazing mode of the matt protective glaze is glaze spraying, and the specific gravity is 1.25-1.35 g/cm3The glazing amount is 100-140 g/m2。
5. The preparation method according to claim 3, wherein the chemical composition of the high-white body comprises: by mass percent, SiO2：40.0～68.0%、Al2O3：20.0～50.0%、Fe2O3：0.15～0.5%、TiO2：0.05～0.30%、CaO：0.1～0.5%、MgO：0.5～1.5%、K2O：2.0～3.5%、Na2O: 1.5-4.0%, loss on ignition: 3.5 to 5.5 percent.
6. The production method according to claim 3, wherein the maximum firing temperature is 1180 to 1220 ℃ and the firing period is 40 to 80 min.
7. The manufacturing method according to claim 3, wherein in the step (2), the high-white body is dried before the design pattern is printed by ink-jet printing, and the moisture of the dried high-white body is controlled within 0.5 wt%.
8. The method according to claim 7, wherein in the step (2), before the design pattern is printed by ink-jet printing, the surface of the dried high-white blank is glazed.
9. The thin ceramic tile obtained by the method of preparation according to any one of claims 3 to 8, characterized in that it has a thickness of 2.5-3.5 mm.
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| CN114163225A (en) * | 2021-12-23 | 2022-03-11 | 广西蒙娜丽莎新材料有限公司 | Preparation method of ceramic tile with super matte effect |
| CN115872782A (en) * | 2022-12-23 | 2023-03-31 | 广东金牌陶瓷有限公司 | Terrazzo surface texture imitated ceramic rock plate and preparation method thereof |
| CN115872782B (en) * | 2022-12-23 | 2024-01-05 | 广东金牌陶瓷有限公司 | Ceramic rock plate imitating terrazzo surface texture and preparation method thereof |
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