CN108129027B - Devitrified glazed tile with surface having golden star stone effect, base glaze and preparation method thereof - Google Patents
Devitrified glazed tile with surface having golden star stone effect, base glaze and preparation method thereof Download PDFInfo
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- CN108129027B CN108129027B CN201810089354.6A CN201810089354A CN108129027B CN 108129027 B CN108129027 B CN 108129027B CN 201810089354 A CN201810089354 A CN 201810089354A CN 108129027 B CN108129027 B CN 108129027B
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- 239000004575 stone Substances 0.000 title claims abstract description 29
- 230000000694 effects Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 241000499895 Bloomeria Species 0.000 title claims abstract description 16
- 238000010304 firing Methods 0.000 claims abstract description 20
- 238000004031 devitrification Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 24
- 239000011787 zinc oxide Substances 0.000 claims description 21
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
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- 238000002425 crystallisation Methods 0.000 claims description 15
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- 230000004927 fusion Effects 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 239000010433 feldspar Substances 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- KKKYJLNWARAYSD-UHFFFAOYSA-N hexacalcium;tetraborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] KKKYJLNWARAYSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 229910052620 chrysotile Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 235000012222 talc Nutrition 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 229910052845 zircon Inorganic materials 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000007688 edging Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 48
- 235000013339 cereals Nutrition 0.000 abstract description 44
- 239000000203 mixture Substances 0.000 abstract description 37
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 8
- 235000009566 rice Nutrition 0.000 abstract description 8
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- 241000209094 Oryza Species 0.000 description 7
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 6
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001914 calming effect Effects 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
-
- 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
-
- 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
-
- 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
- C04B33/00—Clay-wares
- C04B33/32—Burning methods
- C04B33/34—Burning methods combined with glazing
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to a devitrification glazed tile with a golden star stone effect on the surface, a base glaze and a preparation method thereof. On the basis of not making great changes to the existing glazed tile production process, the invention focuses on the formula composition of a frit, the formula composition of a base glaze, the formula composition of a devitrified crystal grain, the formula composition of a cover glaze, the optimization of the granularity of the devitrified crystal grain, the optimization of a firing process and the like, so that the surface of the prepared glazed tile product is matt, the touch glaze of a finger is fine and smooth and has no concave-convex sense, the pattern texture is clear and natural, the imitative stone is vivid, under the irradiation of lamplight, the surface presents a plurality of crystals with different sizes like natural golden star stone, the crystals are transparently embedded in the glaze body of the base glaze, small people like needle points and large people like rice grains, and sparkling brilliant rays are emitted like glowing stars in a night sky, and the glazed tile has unique decoration and artistic quality; meanwhile, the technology has strong universality and is easy to popularize in the industry.
Description
The technical field is as follows:
the invention relates to the technical field of preparation of glazed tiles, in particular to a devitrified glazed tile with a golden star stone effect on the surface, a base glaze and a preparation method thereof.
Background art:
the star stone is slightly silicified argillaceous limestone containing iron sulfide crystals, wherein the big ones are walnuts, the small ones are rice grains, and the shapes of the big ones are different, and the big ones are the same as grains of gems embedded in jasper, so that the star stone looks like a star which is glowed in the night sky. The star stone is also a lucky stone, symbolizes opportunities, contributes to seeking wealth and gathering wealth, and can invisibly attract and hit a designated noble person to arrive. In India legends, the chrysotile is a wish stone, has the function of exorcising evil spirits, has incredible miraculous power after being worn for a long time, has the effects of reducing blood pressure, calming the nerves, arresting convulsion and improving sleep, is one of financial and transportation stones, can promote financial and transportation and gather energy, and therefore the chrysotile is a superior ornamental stone, has high collection value and is deeply loved by people. However, the golden star stone is not produced in a large number of places, has rare stock and high price, so the cost of the golden star stone used as a household decorative material is higher than that of gold, and if the devitrified glazed tile product with the golden star stone effect on the surface can be developed on the large-scale automatic production wall and floor tile technology, the household is rich and elegant, the fortune is good, the health and the longevity are ensured by paving the common wall and floor tiles and matching with the design of indoor lighting, and the functions of the glazed tile are improved to a new border.
The invention content is as follows:
the invention aims to overcome the defects and provides a devitrified glazed tile with a aventurine effect on the surface, a base glaze and a preparation method thereof, on the basis of not making great changes to the existing glazed tile production process, a formula composition of a frit, a formula composition of a base glaze, a formula composition of a devitrified crystal grain, a formula composition of a cover glaze, optimization of the granularity of the devitrified crystal grain, adjustment and optimization of a sintering process and the like are adopted, so that a great number of crystals are precipitated on the surface of the prepared devitrified glazed tile product like natural aventurine, small crystals such as needle points and large crystals such as rice grains are embedded in a glaze body of the base glaze in a transparent manner, the surface of the product is matt, the glossiness of the surface of the product is measured by a WGG60-E4 glossmeter, the glaze is touched by fingers, is smooth and free from concave-convex feeling, and convex and concave-convex feelings are emitted by the crystals under oblique light or lamplight irradiation, the jade is embedded in the jadeite like a fine gem, so that the jade seems to burn and glow in the night sky, has unique decoration and artistry, has strong universality and is easy to popularize in the industry.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a preparation method of a devitrification glazed tile with a aventurine effect on the surface, which comprises the following steps:
A. preparing a frit:
the frit comprises the following components in percentage by weight:
SiO266.8％～67.8％，Al2O38.5％～9.5％，CaO 8.5％～9.5％，MgO 1.5％～2.5％，K2O 3.6％～4.6％，Na2O 2.4％～3.4％，ZrO23.5％～4.5％，B2O30.8 to 1.8 percent, and the sum of all the components is 100 percent;
raw materials containing the components with the particle size smaller than 150 meshes are prepared: quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zircon powder and boric acid are mixed according to the range of the components, mixed by a mixer, melted in a fusion cake tank kiln at the melting temperature of 1520-1540 ℃, quenched in water to form fusion cake particles, and dried to obtain fusion cakes;
B. preparing a base glaze:
the basic glaze comprises the following components in percentage by weight:
SiO240.4％～41.4％，Al2O318％～19％，CaO 9.2％～10.2％，MgO 3％～4％，K2O 1.8％～2.8％，Na2O 0.6％～1.2％，ZrO26.5％～7.5％，B2O30.4-1.2 percent of BaO 2-3 percent of ZnO 7.5-8.5 percent of ZnO and 3-4 percent of ignition loss; the sum of all the components is 100 percent;
selecting the frit, feldspar powder, calcium carbonate, calcined talc, alumina powder, zirconium silicate, barium carbonate, zinc oxide, calcium tetraborate, kaolin and an additional auxiliary raw material with the weight percentage of 0.4-1% according to the weight percentage of the basic glaze components in the step A in a corresponding proportion, adding a proper amount of water, performing ball milling and fine crushing to obtain glaze slurry with the fineness of 325 meshes, the mass percentage of screen residue of 0.3-0.6% and the mass percentage of 28-31%, and performing iron removal and sieving to obtain the basic glaze;
wherein the additional auxiliary raw materials comprise carboxymethyl cellulose, sodium tripolyphosphate and water glass;
C. preparing crystallized grains:
the weight percentage of the components of the crystallization grains is as follows:
SiO265％～66％，Al2O38％～9％，CaO 11％～12％，MgO 0.2％～0.6％，K2O 5％～5.8％，Na2O 1.4％～2.2％，ZnO 4.2％～5.2％，B2O31.4 to 2.4 percent of PbO, 1.8 to 2.6 percent of PbO; the sum of all the components is 100 percent;
raw materials containing the components with the particle size smaller than 150 meshes are prepared: quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zinc oxide, boric acid and red lead powder are mixed according to the range of the components, mixed by a mixer, melted in a fusion block tank kiln, melted at the temperature of 1500-1520 ℃, quenched into particles by water, dried and crushed into fine particles of 40-180 meshes, and crystallized grains are obtained;
D. preparing overglaze according to the following parts by weight:
mixing and stirring uniformly 100 parts of the base glaze prepared in the step B and 1-10 parts of the crystallized grains prepared in the step C to obtain an overglaze;
E. preparation and firing of the product:
and D, applying the overglaze prepared in the step D on a glazed tile blank normally applied with the base glaze, then printing, applying base slurry, entering a roller kiln for glaze firing, ensuring that the firing time in a temperature range of 1020-1080 ℃ accounts for 25% of the total firing time, and edging to obtain a finished product, wherein the maximum firing temperature is 1125-1135 ℃, the firing time is 45-90 minutes.
The invention also relates to a crystallized glazed tile with the surface having the golden star stone effect, which is prepared by the preparation method of the crystallized glazed tile with the surface having the golden star stone effect.
The invention is further optimized as follows:
the surface of the prepared devitrified glazed tile finished product with the surface having the golden star stone effect is like natural golden star stone to precipitate a lot of crystals, small crystals such as needle points and large crystals such as rice grains are transparently embedded in the glaze body of the base glaze, the surface of the finished product is matt, the glossiness of the surface of the finished product is 7-10 measured by a WGG60-E4 glossometer, the glaze surface is fine and smooth when touched by fingers and has no concave-convex feeling, and under oblique light or lamplight irradiation, the crystals emit shining brilliance, and the brilliant rays are embedded in jades like tiny jewels, so that stars which seem to be glowing and glowing in a night sky.
The invention also relates to a preparation method of the basic glaze for preparing the devitrified glazed tile, wherein the preparation method comprises the following steps:
the basic glaze comprises the following components in percentage by weight:
SiO240.4％～41.4％，Al2O318％～19％，CaO 9.2％～10.2％，MgO 3％～4％，K2O 1.8％～2.8％，Na2O 0.6％～1.2％，ZrO26.5％～7.5％，B2O30.4-1.2 percent of BaO 2-3 percent of ZnO 7.5-8.5 percent of ZnO and 3-4 percent of ignition loss; the sum of all the components is 100 percent;
according to the weight percentage content of the basic glaze components, selecting frit, feldspar powder, calcium carbonate, calcined talc, alumina powder, zirconium silicate, barium carbonate, zinc oxide, calcium tetraborate, kaolin and an additional auxiliary raw material with the weight percentage of 0.4-1% according to the corresponding proportion, adding a proper amount of water, performing ball milling and fine crushing to obtain glaze slurry with the fineness of 325 meshes, wherein the glaze slurry contains 0.3-0.6% of screen residue and 28-31% of water by mass percentage, and performing iron removal and sieving to obtain the basic glaze; wherein the additional auxiliary raw materials comprise carboxymethyl cellulose, sodium tripolyphosphate and water glass;
wherein the frit comprises the following components in percentage by weight:
SiO266.8％～67.8％，Al2O38.5％～9.5％，CaO 8.5％～9.5％，MgO 1.5％～2.5％，K2O 3.6％～4.6％，Na2O 2.4％～3.4％，ZrO23.5％～4.5％，B2O30.8 to 1.8 percent, and the sum of all the components is 100 percent;
raw materials containing the components with the particle size smaller than 150 meshes are prepared: quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zircon powder and boric acid are mixed according to the range of the components, mixed by a mixer, melted in a fusion cake tank kiln at the melting temperature of 1520-1540 ℃, quenched in water to form fusion cake particles, and dried to obtain the fusion cake.
The invention also relates to a base glaze for preparing the devitrified glazed tile, which is prepared according to the preparation method of the base glaze for preparing the devitrified glazed tile.
The surface of the finished product prepared by the invention is crystallized into a large number of crystals like iron sulfide in natural aventurine, small crystals such as needle points and large crystals such as rice grains are transparently embedded in the glaze body of the base glaze, the surface of the finished product is matt, the surface glossiness of the finished product is measured to be 7-10 by a WGG60-E4 glossmeter, the glaze surface is touched by fingers, the finished product is exquisite and smooth and has no concave-convex feeling, under the irradiation of oblique light or lamplight, the crystals emit shining brilliance, and are embedded in jades like tiny gemstones, so that the glowing stars in the night sky seem, the technology has unique decoration and artistry, and meanwhile, the technology has stronger universality and is easy to popularize.
The invention relates to a devitrification glazed tile with a golden star stone effect on the surface, a base glaze and a preparation method thereof, which optimize the formula composition of a frit and the formula composition of the base glaze:
on one hand, the base glaze is ensured to be dull and have the gloss of only 7-10 after being sintered at high temperature so as to dry out the dazzling starlight of the devitrified crystal grains; on the other hand, the base glaze melt at high temperature has proper viscosity and melting capacity, the crystallization crystal grains are not melted into a whole to lose crystal precipitation due to excessively low viscosity and excessively high melting capacity, and the crystallization crystal grains cannot sink into the base glaze under the action of gravity to be tightly embedded with the base glaze due to excessively high viscosity and excessively low melting capacity, so that the crystallization crystal grains protrude out of the base glaze surface, the smoothness of the product surface is influenced, and the crystallization crystal grains are easy to fall off even due to infirm bonding. Thus controlling Al in the base glaze formula composition2O3And SiO2The total content of the glaze is 58.4-60.4 percent of the basic glaze composition, and proper silicon-aluminum ratio, and proper K which plays a role in adjusting the viscosity and the melting capacity of a glaze melt is added2O、Na2Oxides such as O, CaO, MgO, and ZnO. Because of K2O and Na2O is univalent network exo oxide, which has strong 'net breaking' function in the glaze melting process and can obviously reduce the melting temperature and high-temperature viscosity of the glaze, CaO and MgO are bivalent network exo oxides and can release free oxygen at high temperature to destroy the network structure, reduce the viscosity of the glaze melt and improve the fluidity of the glaze, and are good high-temperature flux components. ZnO has good melting-assisting effect in the glaze, can play a good role in the mechanical strength, elasticity, melting property and heat resistance of the glaze, can increase the mature temperature range of the glaze, but the using amount is not too large, otherwise the refractoriness and viscosity of the glaze can be improved, and CaO, MgO and ZnO oxides play a role in promoting the formation of matt glaze. In addition, the base glaze formulation is also in the form of raw materialThe addition of a proper amount of calcium tetraborate as a raw material can provide B which is insufficient in frit composition2O3Ingredients; on the other hand, as the calcium tetraborate has low water solubility, the research of the inventor finds that the calcium tetraborate is added into the base glaze in the form of raw material, and after post-processing treatment, slight boron-containing component is separated out, and the separated boron-containing component, carboxymethyl cellulose and water glass form a good suspending agent which can prevent the separated phase precipitation of the crystallization grains and the base glaze due to high specific gravity, so that the crystallization grains are uniformly distributed and dispersed in the base glaze. By optimizing the composition of the formula of the crystallized grains, on one hand, the crystallized grains are guaranteed to be highly transparent after high-temperature calcination, so that the integrity of the surface printed patterns cannot be influenced, otherwise, the printed patterns are covered due to the over-strong opacification capability, and the color development and the integrity of the surface patterns of the product are influenced; on the other hand, the crystal has strong reflection action on light, so that the precipitated crystals can emit sparkling starlight under the irradiation of the product. Therefore, a proper amount of PbO which can effectively promote the transparency and the glossiness of the glaze is added into the formula of the crystallized grains. Meanwhile, the initial melting temperature of the crystallization grains and the base glaze is required to be different properly, otherwise, the crystallization grains are completely melted with the base glaze at a high temperature due to the low initial melting temperature, and the crystals are lost. Therefore, Al is controlled in the formula composition of the crystallized grains2O3With SiO2To ensure the initial melting temperature of the crystallized grains. By optimizing the formula composition of the overglaze and the granularity of the crystallized grains, the large and small crystals precipitated on the surface of the product are ensured to be naturally distributed, the natural effects of small ones such as needle points and large ones such as rice grains are presented, the glowing stars in the night sky are provided, otherwise the glossiness of the surface of the product is influenced by too many crystals, so that the effect of forming strong contrast with the basic glaze is lost, and if the specifications of the crystals are single, the crystals are dull and lose the natural effect. By optimizing the sintering process, the sintering time of a temperature region of 1020-1080 ℃ is ensured to account for 25% of the total sintering time, on one hand, the crystallized grains can be fully fused at high temperature to form a highly transparent glass body, the transparency and the glossiness of the crystallized grains are ensured, and the crystallized grains are not required to be sinteredA flowing liquid phase is formed due to overhigh temperature so as to prevent the liquid phase from being completely melted into the base glaze and losing crystals; on the other hand, the viscosity of the basic glaze melt is ensured, so that the devitrified crystal grains can sink into the basic glaze melt under the action of specific gravity and are naturally embedded, otherwise, the devitrified crystal grains cannot sink into the basic glaze melt and protrude out of the surface to influence the smoothness of the product surface due to insufficient liquid phase amount in the basic glaze melt due to too low temperature; or the crystallization grains are completely melted to lose crystals due to overhigh temperature, excessive liquid phase and over-strong melting capacity; meanwhile, the heat preservation is carried out in the area, which is beneficial to the growth of crystals in the crystallized grains and forms the crystals like the natural auricle internal iron sulfide crystals.
The devitrified glazed tile with the surface having the golden star stone effect, the base glaze and the preparation method thereof have the following advantages that:
1. because the composition of the frits, the formula composition of the basic glaze, the formula composition of the crystallization grains, the formula composition of the overglaze, the optimization of the granularity of the crystallization grains, the adjustment and optimization of the firing process and the like are optimized, thereby separating a plurality of crystals like iron sulfide in natural chrysotile from the surface of the prepared devitrified glazed tile product, the small crystals such as needle points and the large crystals such as rice grains are embedded in the basic glaze body in a transparent state, the surface of the product is dull, the surface glossiness of the finished product is measured to be 7-10 by a WGG60-E4 glossmeter, the surface of the glaze is touched by fingers, the product is fine, smooth and free of concave-convex feeling, the patterns and the textures are clear and natural, the stone imitation is vivid, under the irradiation of oblique light or lamplight, the crystals emit shining light, are embedded in the jadeite like fine gems, seem to burn glowing stars in the night sky, and have unique decoration and artistry.
2. The product has surface flatness, modulus of rupture, breaking strength, acid and alkali resistance, wear resistance, radioactivity and lead and cadmium dissolution rate all reaching the standard requirements of GB/T4100-2015, GB6566-2010 and HJ/T297-2006.
3. The product adopts the existing glazed tile production process, so that the iron sulfide crystal contained in the natural aventurine can emit shining brilliant rays under the special illumination, and the effect can be copied to the glazed tile product, and the industrial scale is easy to realize. Therefore, the glazed tile product has high grade decoration, ornamental performance, collection performance and special functionality of the star stone, and the functions of the glazed tile are improved to a new level.
Description of the drawings:
FIG. 1 is a process flow chart for preparing a devitrified glazed tile with the surface having the effect of a star stone according to the present invention.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
Example 1
A preparation method of a devitrification glazed tile with a chrysotile effect on the surface comprises the following steps:
A. preparing a frit:
the frit has the following chemical composition as shown in table 1:
TABLE 1 chemical composition of frits TABLE (weight%,%)
| Composition of | SiO2 | Al2O3 | CaO | MgO | K2O | Na2O | ZrO2 | B2O3 |
| 1# | 66.8 | 9.5 | 9 | 2.5 | 4.5 | 2.4 | 3.5 | 1.8 |
| 2# | 67.3 | 9 | 9.5 | 1.5 | 4.6 | 2.9 | 3.9 | 1.3 |
| 3# | 67.8 | 8.5 | 8.5 | 2 | 4.5 | 3.4 | 4.5 | 0.8 |
| 4# | 67.8 | 8.7 | 9.2 | 2.2 | 3.6 | 3.2 | 4 | 1.3 |
| 5# | 67.5 | 9.4 | 9.3 | 1.8 | 4.1 | 2.6 | 4.2 | 1.1 |
Preparing a frit: selecting quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zircon powder and boric acid which have the particle sizes less than 150 meshes according to the chemical compositions in the table 1, mixing the raw materials in a mixer, melting the raw materials in a frit tank kiln at the melting temperature of 1520-1540 ℃, then quenching the raw materials into frit particles by water, and drying the frit particles to obtain the frit.
B. Preparing a base glaze:
the chemical composition of the base glaze is shown in the following table 2:
TABLE 2 chemical composition table of base glaze (weight%,%)
| Composition of | SiO2 | Al2O3 | CaO | MgO | K2O | Na2O | ZrO2 | B2O3 | BaO | Zn0 | Loss on ignition |
| 1# | 40.4 | 19 | 9.7 | 4 | 2.3 | 1.2 | 7.2 | 1.2 | 2.5 | 8.5 | 4 |
| 2# | 40.9 | 19 | 10.2 | 3.5 | 2.7 | 0.9 | 7.5 | 0.8 | 2 | 8.5 | 4 |
| 3# | 41.4 | 19 | 9.2 | 3 | 2.8 | 1.2 | 7.5 | 0.4 | 3 | 8.5 | 4 |
| 4# | 41.4 | 18.5 | 10 | 3.8 | 1.8 | 0.6 | 7.5 | 1 | 3 | 8.4 | 4 |
| 5# | 41.3 | 18 | 10.2 | 4 | 2.6 | 1.2 | 7 | 1.2 | 3 | 8 | 3.5 |
| 6# | 40.8 | 19 | 10.2 | 4 | 2.8 | 1.2 | 6.5 | 1.2 | 3 | 7.5 | 3.8 |
| 7# | 40.4 | 18 | 10.2 | 4 | 2.8 | 1.2 | 7.5 | 1.2 | 3 | 8.5 | 3.2 |
| 8# | 41.2 | 19 | 10.2 | 4 | 2.8 | 1 | 7.3 | 0.9 | 2.8 | 7.8 | 3 |
Preparing a base glaze: selecting the frit, feldspar powder, calcium carbonate, calcined talc, alumina powder, zirconium silicate, barium carbonate, zinc oxide, calcium tetraborate, kaolin and an additional auxiliary raw material with the weight percentage of 0.4-1% according to the corresponding proportion in the chemical components shown in the table 2, adding a proper amount of water, performing ball milling and fine crushing to obtain glaze slurry with the fineness of 325 meshes, the screen residue of which is 0.3-0.6% by mass and contains 28-31% by mass of water, and performing iron removal and sieving to obtain base glaze; wherein the additional auxiliary raw materials comprise carboxymethyl cellulose, sodium tripolyphosphate and water glass.
The base glaze is a dull glaze after being fired at a temperature of 1125-1135 ℃, and the surface glossiness of the base glaze is 7-10 measured by a WGG60-E4 glossiness meter.
The basic glaze in the invention can also be matched with various commonly used crystallization grains in the field in a corresponding proportion to obtain the crystallization glazed tiles with different effects.
C. Preparing crystallized grains:
the chemical composition of the crystallized grains is shown in the following table 3:
TABLE 3 chemical composition of the crystallized grains TABLE (% by weight)
| Composition of | SiO2 | Al2O3 | CaO | MgO | K2O | Na2O | Zn0 | B2O3 | PbO |
| 1# | 65 | 9 | 11 | 0.4 | 5 | 2.2 | 4.2 | 1.4 | 1.8 |
| 2# | 65.5 | 8.5 | 11.2 | 0.6 | 5 | 1.8 | 4.2 | 1.4 | 1.8 |
| 3# | 66 | 8 | 11 | 0.2 | 5.8 | 1.4 | 4.2 | 1.4 | 2 |
| 4# | 65 | 8 | 11.5 | 0.2 | 5.2 | 1.4 | 4.2 | 1.9 | 2.6 |
| 5# | 65 | 8 | 11 | 0.2 | 5.4 | 1.4 | 4.4 | 2.4 | 2.2 |
| 6# | 65 | 8.1 | 12 | 0.3 | 5 | 1.5 | 4.7 | 1.5 | 1.9 |
| 7# | 65.2 | 8.1 | 11.2 | 0.3 | 5 | 1.5 | 5.2 | 1.5 | 2 |
Preparing crystallized grains: selecting quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zinc oxide, boric acid and red lead powder which have the particle sizes less than 150 meshes according to the chemical compositions in the table 3, mixing the raw materials in a mixer, melting the raw materials in a fusion block tank kiln at the melting temperature of 1500-1520 ℃, quenching the raw materials in water to obtain particles, drying and crushing the particles to obtain fine particles with the particle sizes of 40-180 meshes, thus obtaining the crystallized grains.
The devitrified crystal grains are transparent after being sintered at the high temperature of 1125-1135 ℃ and are embedded in the glaze body of the basic glaze, and emit sparkling light and glowing under the irradiation of lamplight.
D. Preparing overglaze:
the formulation for preparing the overglaze had the following composition in table 4:
TABLE 4 composition of overglaze composition Table (parts by weight)
Preparing a cover glaze: and C, weighing the base glaze prepared in the step B and the crystallized grains prepared in the step C according to a formula composition table of the overglaze in the table 4, and uniformly mixing and stirring to obtain the overglaze for later use.
E. Preparation of the product:
and D, applying the overglaze prepared in the step D on the surface of the brick blank to which the base glaze is normally applied, printing and decorating by using a silk screen plate or an offset printing roller or an ink jet machine according to the design requirements of the product, applying the base slurry, performing glaze firing in a roller kiln, ensuring that the firing temperature is 1125-1135 ℃ at the highest firing temperature and the firing time is 45-90 minutes, ensuring that the firing time in a temperature range of 1020-1080 ℃ accounts for 25% of the total firing time, and performing edge grinding to obtain the finished product.
The glazed tile product prepared by the preparation method of the devitrified glazed tile with the aventurine effect on the surface is matt, the surface glossiness of the product measured by a WGG60-E4 glossmeter is 7-10, the pattern texture of the product is clear, the stone imitation is vivid, the glaze surface is touched by fingers, the product is fine and smooth and free of concave-convex feeling, a plurality of crystals like iron sulfide in natural aventurine are separated out on the surface, the crystals are embedded in the glaze body of the base glaze in a transparent manner, small persons like tips and big persons like rice grains, and under oblique light or lamplight irradiation, the crystals emit shining brilliance, like fine gemstones embedded in jades, like glowing stars in a night sky, and the glazed tile product has unique decoration and artistry.
The indexes of the detected product are shown in the following table 5.
Table 5: product quality inspection results
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited in any way; those of ordinary skill in the art can readily practice the present invention as described above; however, those skilled in the art should, upon attaining an understanding of the present disclosure, appreciate that many changes, modifications, and equivalents may be made to the invention without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution made to the above embodiments according to the essential technology of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A preparation method of a devitrification glazed tile with a chrysotile effect on the surface is characterized in that:
which comprises the following steps:
A. preparing a frit:
the frit comprises the following components in percentage by weight:
SiO266.8％～67.8％，Al2O38.5％～9.5％，CaO 8.5％～9.5％，MgO 1.5％～2.5％，K2O 3.6％～4.6％，Na2O 2.4％～3.4％，ZrO23.5％～4.5％，B2O30.8 to 1.8 percent, and the sum of all the components is 100 percent;
raw materials containing the components with the particle size smaller than 150 meshes are prepared: quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zircon powder and boric acid are mixed according to the range of the components, mixed by a mixer, melted in a fusion cake tank kiln at the melting temperature of 1520-1540 ℃, quenched in water to form fusion cake particles, and dried to obtain fusion cakes;
B. preparing a base glaze:
the basic glaze comprises the following components in percentage by weight:
SiO240.4％～41.4％，Al2O318％～19％，CaO 9.2％～10.2％，MgO 3％～4％，K2O1.8％～2.8％，Na2O 0.6％～1.2％，ZrO26.5％～7.5％，B2O30.4-1.2 percent of BaO 2-3 percent of ZnO 7.5-8.5 percent of ZnO and 3-4 percent of ignition loss; the sum of all the components is 100 percent;
selecting the frit, feldspar powder, calcium carbonate, calcined talc, alumina powder, zirconium silicate, barium carbonate, zinc oxide, calcium tetraborate, kaolin and an additional auxiliary raw material with the weight percentage of 0.4-1% according to the weight percentage of the basic glaze components in the step A in a corresponding proportion, adding a proper amount of water, performing ball milling and fine crushing to obtain glaze slurry with the fineness of 325 meshes, the mass percentage of screen residue of 0.3-0.6% and the mass percentage of 28-31%, and performing iron removal and sieving to obtain the basic glaze;
wherein the additional auxiliary raw materials comprise carboxymethyl cellulose, sodium tripolyphosphate and water glass;
C. preparing crystallized grains:
the weight percentage of the components of the crystallization grains is as follows:
SiO265％～66％，Al2O38％～9％，CaO 11％～12％，MgO 0.2％～0.6％，K2O 5％～5.8％，Na2O 1.4％～2.2％，ZnO 4.2％～5.2％，B2O31.4 to 2.4 percent of PbO, 1.8 to 2.6 percent of PbO; the sum of all the components is 100 percent;
raw materials containing the components with the particle size smaller than 150 meshes are prepared: quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zinc oxide, boric acid and red lead powder are mixed according to the range of the components, mixed by a mixer, melted in a fusion block tank kiln, melted at the temperature of 1500-1520 ℃, quenched into particles by water, dried and crushed into fine particles of 40-180 meshes, and crystallized grains are obtained;
D. preparing overglaze according to the following parts by weight:
mixing and stirring uniformly 100 parts of the base glaze prepared in the step B and 1-10 parts of the crystallized grains prepared in the step C to obtain an overglaze;
E. preparation and firing of the product:
and D, applying the overglaze prepared in the step D on a glazed tile blank normally applied with the base glaze, then printing, applying base slurry, entering a roller kiln for glaze firing, ensuring that the firing time in a temperature range of 1020-1080 ℃ accounts for 25% of the total firing time, and edging to obtain a finished product, wherein the maximum firing temperature is 1125-1135 ℃, the firing time is 45-90 minutes.
2. A devitrification glazed tile with a golden star stone effect on the surface is characterized in that:
the devitrified glazed tile with the surface having the golden star stone effect as claimed in claim 1 is prepared.
3. The devitrified glazed tile with the surface having the effect of the Venetian stone as claimed in claim 2, wherein:
the surface of the prepared crystallized glazed tile finished product with the chrysotile effect on the surface is measured to be 7-10 by a WGG60-E4 gloss meter.
4. A preparation method of a base glaze for preparing a devitrified glazed tile is characterized by comprising the following steps:
the basic glaze comprises the following components in percentage by weight:
SiO240.4％～41.4％，Al2O318％～19％，CaO 9.2％～10.2％，MgO 3％～4％，K2O1.8％～2.8％，Na2O 0.6％～1.2％，ZrO26.5％～7.5％，B2O30.4-1.2 percent of BaO 2-3 percent of ZnO 7.5-8.5 percent of ZnO and 3-4 percent of ignition loss; the sum of all the components is 100 percent;
according to the weight percentage content of the basic glaze components, selecting frit, feldspar powder, calcium carbonate, calcined talc, alumina powder, zirconium silicate, barium carbonate, zinc oxide, calcium tetraborate, kaolin and an additional auxiliary raw material with the weight percentage of 0.4-1% according to the corresponding proportion, adding a proper amount of water, performing ball milling and fine crushing to obtain glaze slurry with the fineness of 325 meshes, wherein the glaze slurry contains 0.3-0.6% of screen residue and 28-31% of water by mass percentage, and performing iron removal and sieving to obtain the basic glaze; wherein the additional auxiliary raw materials comprise carboxymethyl cellulose, sodium tripolyphosphate and water glass;
wherein the frit comprises the following components in percentage by weight:
SiO266.8％～67.8％，Al2O38.5％～9.5％，CaO 8.5％～9.5％，MgO 1.5％～2.5％，K2O 3.6％～4.6％，Na2O 2.4％～3.4％，ZrO23.5％～4.5％，B2O30.8 to 1.8 percent, and the sum of all the components is 100 percent;
raw materials containing the components with the particle size smaller than 150 meshes are prepared: quartz powder, feldspar powder, alumina powder, calcium carbonate, talcum powder, potassium carbonate, sodium carbonate, zircon powder and boric acid are mixed according to the range of the components, mixed by a mixer, melted in a fusion cake tank kiln at the melting temperature of 1520-1540 ℃, quenched in water to form fusion cake particles, and dried to obtain the fusion cake.
5. A basic glaze for preparing devitrified glazed tiles is characterized in that:
the method for preparing the base glaze for the devitrified glazed tile according to claim 4.
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| CN112500196B (en) * | 2020-11-25 | 2022-05-06 | 蒙娜丽莎集团股份有限公司 | Ceramic tile with stereoscopic gem particle feeling glaze and preparation method thereof |
| CN113387580A (en) * | 2021-07-14 | 2021-09-14 | 佛山市陶莹新型材料有限公司 | Starlight glaze and preparation method thereof |
| CN113651607B (en) * | 2021-08-12 | 2022-12-23 | 广东宏宇新型材料有限公司 | Ceramic tile with night sky and river decoration effect |
| CN114292131B (en) * | 2021-12-28 | 2022-11-11 | 新明珠集团股份有限公司 | Glazed tile with bright star effect on surface and preparation method thereof |
| CN114276121B (en) * | 2021-12-29 | 2023-05-05 | 新明珠集团股份有限公司 | Ceramic tile with starlight stereoscopic effect and preparation method thereof |
| CN114426397B (en) * | 2022-01-10 | 2023-01-24 | 蒙娜丽莎集团股份有限公司 | Preparation method of snow-powder fritted glaze and ceramic tile with snow-powder effect |
| CN114262208A (en) * | 2022-01-17 | 2022-04-01 | 江西富利高新材料有限公司 | Large-particle dry particle superposed matte glaze ceramic plate and preparation method thereof |
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Denomination of invention: Crystalline glazed tiles with Venus stone effect on the surface, basic glaze and their preparation methods Granted publication date: 20200901 Pledgee: Guangdong Qingyuan Rural Commercial Bank Co.,Ltd. Yuantan Branch Pledgor: GUANGDONG HONGHAI CERAMICS INDUSTRIAL Co.,Ltd. Registration number: Y2024980006544 |