CN115124244B - Transparent frit, crystalline wear-resistant glaze, glazed brick and preparation method thereof - Google Patents

Transparent frit, crystalline wear-resistant glaze, glazed brick and preparation method thereof Download PDF

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CN115124244B
CN115124244B CN202211051542.2A CN202211051542A CN115124244B CN 115124244 B CN115124244 B CN 115124244B CN 202211051542 A CN202211051542 A CN 202211051542A CN 115124244 B CN115124244 B CN 115124244B
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layer
wear
glaze
transparent frit
resistant
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CN115124244A (en
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何江赞
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Foshan Tang Hong Glaze Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52Multiple 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/89Coating or impregnation for obtaining at least two superposed coatings having different compositions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a transparent frit, a crystalline wear-resistant glaze, a glazed brick and a preparation method thereof, and relates to the field of ceramic tile manufacturing. Wherein, the transparent frit comprises the following chemical components in percentage by mass: siO 2 2 45%~50%、Al 2 O 3 18%~24%、Fe 2 O 3 0.002%~0.05%、TiO 2 0.001%~0.02%、CaO 8%~12%、MgO 4%~6%、K 2 O 5%~7%、Na 2 O 5%~7%、ZnO 3%~5%、B 2 O 3 1 to 3 percent, 0.5 to 2.1 percent of loss on ignition and the balance of impurities. The transparent frit has high transparency and good color development on ink, can be used for preparing crystalline wear-resistant glaze, and can obviously improve the wear resistance of the glaze.

Description

Transparent frit, crystalline wear-resistant glaze, glazed brick and preparation method thereof
Technical Field
The invention relates to the field of ceramic tile manufacturing, in particular to a transparent frit, crystalline wear-resistant glaze, glazed tile and a preparation method thereof.
Background
The glazed polished tile is a tile product with good glossiness, which is obtained by polishing the glaze of the tile, but the glaze of the surface layer of the existing glazed tile is completely destroyed after polishing due to low hardness and poor abrasion resistance of the glaze of the surface layer, so that the finally obtained glazed tile product has the problems of low transparency and easy scratching.
In addition, an increase in the hardness of the glaze often results in a change in color development, making it difficult to achieve both an increase in the hardness of the glaze and a normal color development.
It is seen that improvements and enhancements in the prior art are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a transparent frit, a crystalline wear-resistant glaze, a glazed brick and a preparation method thereof, aiming at improving the hardness, wear resistance and transparency of a glaze layer and ensuring good color development of the glazed brick.
In order to achieve the purpose, the invention adopts the following technical scheme:
a transparent frit having chemical components in mass fractions comprising: siO 2 2 45%~50%、Al 2 O 3 18%~24%、Fe 2 O 3 0.002%~0.05%、TiO 2 0.001%~0.02%、CaO 8%~12%、MgO 4%~6%、K 2 O 5%~7%、Na 2 O 5%~7%、ZnO 3%~5%、B 2 O 3 1 to 3 percent, 0.5 to 2.1 percent of loss on ignition and the balance of impurities.
The transparent frit comprises the following raw materials in percentage by mass: 25-35% of glass powder, 18-25% of magnesia-alumina spinel, 10-20% of anorthite, 2-8% of zinc oxide, 10-20% of potassium feldspar, 5-10% of potassium nitrate, 2-8% of borax and 2-6% of fluorite.
The transparent frit comprises the following raw materials in percentage by mass: 30% of glass powder, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 15% of potassium feldspar, 9% of potassium nitrate, 3% of borax and 5% of fluorite.
A crystalline abrasion-resistant glaze comprising, in mass percent: 6-10% of kaolin, 5-10% of quartz, 1-5% of magnesia-alumina spinel, 15-25% of transparent frit, 25-35% of potassium feldspar, 8-15% of albite, 4-8% of zinc oxide, 8-15% of anorthite, 3-8% of cordierite and 1-5% of corundum; the transparent frit is as described above.
The crystalline wear-resistant glaze comprises the following components in percentage by mass: 8% of kaolin, 8% of quartz, 4% of magnesia-alumina spinel, 20% of transparent frit, 27% of potassium feldspar, 10% of albite, 5% of zinc oxide, 10% of anorthite, 5% of cordierite and 3% of corundum.
A glazed brick comprises a blank layer, a ground glaze layer, an ink-jet layer and a wear-resistant layer which are sequentially arranged from bottom to top; the wear-resistant layer is made of the crystalline wear-resistant glaze material.
The glazed brick is characterized in that a coloring layer is arranged between the ink spraying layer and the wear-resistant layer.
The glazed tile, wherein the coloring layer is made of the transparent frit as described above.
A method for preparing a polished tile, which is used for preparing the polished tile, and comprises the following steps: b01, forming a ground coat on the blank; b02, forming an ink spraying layer on the ground glaze layer; b03, forming a wear-resistant layer on the ink-jet layer; and B04, firing and polishing to obtain the glazed brick.
The preparation method of the glazed brick further comprises the following steps: firstly, forming a color development layer on the ink jet layer, and then forming a wear-resistant layer on the color development layer.
Has the beneficial effects that:
the invention provides a transparent frit which adopts a formula of high silicon and high potassium and can well improve the color development of ink. The transparent frit has high hardness and good transparency, and can improve the hardness and the wear resistance of a glaze layer when being applied to the preparation of glaze.
The invention also provides a crystalline wear-resistant glaze, which takes mature crystalline anorthite and cordierite as crystal nuclei, adds transparent frit to help the nucleation and growth of crystals, and improves the hardness and wear resistance of the glaze through corundum, magnesia-alumina spinel and the like, so that the formed glaze layer has good hardness and wear resistance and good transparency.
The invention also provides a glazed brick, wherein the wear-resistant layer is made of the crystalline wear-resistant glaze, and the glazed brick not only has the characteristics of high hardness and good wear resistance, but also has good transparency.
The invention also provides a preparation method of the glazed brick, and the wear-resistant layer is sprayed on the coloring layer to promote the separation of the crystal of the wear-resistant layer. The matching of the coloring layer and the wear-resistant layer not only ensures that the glazed tile has good coloring and high transparency, but also ensures that the glazed tile has high hardness and good wear resistance.
Detailed Description
The invention provides a transparent frit, a crystalline wear-resistant glaze, a glazed brick and a preparation method thereof, and the invention is further detailed by the following embodiments in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a transparent frit, which comprises the following chemical components in parts by mass: siO 2 2 45%~50%、Al 2 O 3 18%~24%、Fe 2 O 3 0.002%~0.05%、TiO 2 0.001%~0.02%、CaO 8%~12%、MgO 4%~6%、K 2 O 5%~7%、Na 2 O 5%~7%、ZnO 3%~5%、B 2 O 3 1 to 3 percent, 0.5 to 2.1 percent of ignition loss and the balance of impurities.
In one embodiment, the raw materials for preparing the transparent frit comprise, by mass: 25-35% of glass powder, 18-25% of magnesia-alumina spinel, 10-20% of anorthite, 2-8% of zinc oxide, 10-20% of potassium feldspar, 5-10% of potassium nitrate, 2-8% of borax and 2-6% of fluorite. The magnesium aluminate spinel has the advantages of high hardness and good transparency, is superior to calcined alumina, and can remarkably improve the hardness and the transparency of glaze. Preferably, the magnesium aluminate spinel has a size of 400 meshes. The glass powder can be powder prepared from waste glass, the glass powder is a material obtained by melting, belongs to clinker, is low in melting point, and when secondary melting is carried out under the action of a solvent, part of magnesium-aluminum spinel and glass crystal can be co-melted to form a frit with cordierite crystal, so that the transparency is increased. The zinc oxide, the potassium feldspar and the potassium nitrate can reduce the melting temperature and have good color development on the ink. Borax and fluorite can obviously reduce the high-temperature viscosity of the clinker, and facilitate the blanking of the clinker. The transparent frit adopts a formula of high silicon and high potassium, and can well improve the color development of ink.
Preferably, the transparent frit comprises the following raw materials in percentage by mass: 30% of glass powder, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 15% of potassium feldspar, 9% of potassium nitrate, 3% of borax and 5% of fluorite. In the above-mentioned mixing ratio, the glaze layer made of transparent frit has optimum transparency and optimum coloring effect for red and yellow of ink.
The preparation method of the transparent frit comprises the following steps: step A01, uniformly mixing all the components, and firing for 2 hours at the temperature of 0-500 ℃; step A, firing at the temperature of 02.500-900 ℃ for 2h; step A, firing at 03.900-1500 ℃ for 1.5h; step A04.1500 ℃ firing for 2h. The magnesium aluminate spinel can be partially dissolved into glass at 1500 ℃ for 2h, and cordierite crystal is formed.
A crystalline wear-resistant glaze comprising, in mass percent: 6 to 10 percent of kaolin, 5 to 10 percent of quartz, 1 to 5 percent of magnesia-alumina spinel, 15 to 25 percent of the transparent frit, 25 to 35 percent of potassium feldspar, 8 to 15 percent of albite, 4 to 8 percent of zinc oxide, 8 to 15 percent of anorthite, 3 to 8 percent of cordierite and 1 to 5 percent of corundum. The anorthite and cordierite are mature crystals and play a role of a crystal nucleating agent in the formula, and the corundum and the magnesia-alumina spinel can obviously increase the toughness and the hardness of the glaze, so that the wear resistance of the glaze layer is improved. The potassium feldspar and the albite are used as solvents, and the antifouling performance of the glaze can be improved. The transparent frit is mixed with other components, so that the temperature and high-temperature viscosity of the glaze can be adjusted, and crystal nucleation and growth are facilitated.
Preferably, the crystalline wear-resistant glaze comprises the following components in percentage by mass: 8% of kaolin, 8% of quartz, 4% of magnesia-alumina spinel, 20% of the transparent frit, 27% of potassium feldspar, 10% of albite, 5% of zinc oxide, 10% of anorthite, 5% of cordierite and 3% of corundum. When the ratio of transparent frit (clinker) to other components (raw meal) is 2: when 8, the obtained glaze layer has the best comprehensive performance, highest hardness, best wear resistance and transparency and best antifouling performance.
A glazed brick comprises a body layer, a ground coat layer, an ink-jet layer and a wear-resistant layer which are sequentially arranged from bottom to top. The wear-resistant layer can effectively improve the hardness of the surface of the glazed brick. The wear-resistant layer is made of the crystalline wear-resistant glaze. The wear-resistant layer has the advantages of good transparency, good wear resistance, good antifouling property and high hardness.
In one embodiment, a coloring layer is further disposed between the ink-jet layer and the wear-resistant layer. The color development layer is used for adjusting and protecting the color development of the ink, and the abrasion-resistant layer is prevented from influencing the color development of the original ink.
In one embodiment, the chromonic layer is made from the transparent frit described above. The color development layer has better color development on red and yellow of the ink, so that the color development of the fired glazed brick is closer to that of the existing product.
A preparation method of a glazed brick is used for preparing the glazed brick, and comprises the following steps: b01, forming a ground coat on the blank; b02, forming an ink spraying layer on the ground glaze layer; b03, forming a color forming layer on the ink jet layer; b04, forming a wear-resistant layer on the coloring layer; and B05, firing and polishing to obtain the glazed brick.
The firing method comprises the following specific steps: firing is carried out under the firing temperature curve of the existing production kiln, and the firing temperature is 1180-1230 ℃.
Preferably, in the step B03, spraying is carried outSpraying a coloring glaze on the ink layer to form a coloring layer; the coloring glaze is prepared from transparent frits, and the specific gravity of glaze slip is 1.35-1.4 g/cm 3 (ii) a The fineness of the coloring glaze slip is 325 meshes and the residual is 0.3 to 0.6 percent; the spraying amount is 30-45 g on a tray with the specification of 300 × 600mm.
Preferably, in the step B04, a wear-resistant glaze is sprayed on the coloring layer to form a wear-resistant layer; the wear-resistant glaze is prepared from crystalline wear-resistant glaze material, and the specific gravity of glaze slip is 1.85-1.9 g/cm 3 (ii) a The fineness of the wear-resistant glaze slip is 325 meshes and the residual is 0.1 to 0.4 percent; the glaze pouring amount is 100-120 g of glaze pouring on a tray with the specification of 300 x 600mm.
Example 1
A transparent frit comprising the chemical components in mass fraction: siO 2 2 47.1%、Al 2 O 3 21.5%、Fe 2 O 3 0.012%、TiO 2 0.014%、CaO 9.18%、MgO 4.39%、K 2 O 5.83%、Na 2 O 5.49%、ZnO 3.21%、B 2 O 3 1.21 percent, 0.9 percent loss on ignition and the balance of impurities.
The preparation raw materials of the transparent frit comprise the following components in percentage by mass: 30% of glass powder, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 15% of potassium feldspar, 9% of potassium nitrate, 3% of borax and 5% of fluorite.
The preparation method of the transparent frit comprises the following steps: step A01, uniformly mixing all the components, heating to 500 ℃ from normal temperature, and burning for 2 hours in time; step A02, raising the temperature from 500 ℃ to 900 ℃, and consuming 2 hours; step A03, raising the temperature from 900 ℃ to 1500 ℃, and consuming 1.5h; step A, firing at 04.1500 ℃ for 2h; and (5) quenching with cold water.
A color-developing layer of a tile is obtained by firing a color-developing glaze slip prepared from the transparent frit of this example. The specific gravity of the color development glaze slip is 1.4g/cm 3 (ii) a The fineness of the coloring glaze slip is 0.5 percent of the residue of a 325-mesh screen; the spray amount was 45g (300 x 600mm tray).
Example 2
A transparent frit comprising the chemical components in mass fraction: siO 2 2 46.3%、Al 2 O 3 20.92%、Fe 2 O 3 0.011%、TiO 2 0.014%、CaO 11.5%、MgO 4.28%、K 2 O 5.74%、Na 2 O 5.39%、ZnO 3.19%、B 2 O 3 1.08 percent, 0.99 percent loss on ignition and the balance of impurities.
The transparent frit comprises the following preparation raw materials in percentage by mass: 25% of glass powder, 18% of magnesia-alumina spinel, 18% of anorthite, 3% of zinc oxide, 20% of potassium feldspar, 8% of potassium nitrate, 3% of borax and 5% of fluorite. The transparent frit was prepared in the same manner as in example 1.
A color-developing layer of a tile is obtained by firing a color-developing glaze slip prepared from the transparent frit of this example. The specific gravity of the color development glaze slip is 1.3g/cm 3 (ii) a The fineness of the coloring glaze slip is 0.3 percent of the residue of a 325-mesh screen; the spray amount was 35g (300 x 600mm tray).
Example 3
A transparent frit comprising the chemical components in mass fraction: siO 2 2 48.1%、Al 2 O 3 21.7%、Fe 2 O 3 0.012%、TiO 2 0.012%、CaO 9.24%、MgO 4.31%、K 2 O 5.14%、Na 2 O 5.41%、ZnO 3.09%、B 2 O 3 1.23 percent, loss on ignition 0.81 percent and the balance of impurities.
The transparent frit comprises the following preparation raw materials in percentage by mass: 32% of glass powder, 24% of magnesia-alumina spinel, 16% of anorthite, 3% of zinc oxide, 12% of potassium feldspar, 5% of potassium nitrate, 3% of borax and 5% of fluorite. The transparent frit was prepared in the same manner as in example 1.
A color-developing layer of a tile is obtained by firing a color-developing glaze slip prepared from the transparent frit of this example. The specific gravity of the color development glaze slip is 1.3g/cm 3 (ii) a The fineness of the coloring glaze slip is 0.6 percent of the residue of a 325-mesh screen; the spray amount was 30g (300 x 600mm tray).
Comparative example 1
A ceramic tile colour layer was prepared by a process different from that of example 2 in the formulation of the transparent frit. The transparent frit of the embodiment is prepared from the following raw materials in percentage by mass:
30% of quartz, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 15% of potassium feldspar, 9% of potassium nitrate, 3% of borax and 5% of fluorite.
The preparation method of the transparent frit is the same as example 1.
The transparency of the colored layer of the tiles obtained in examples 1 to 3 and comparative example 1 was measured (test method is described in GB/T2680-94). The specific test method was carried out by forming the colored layer on a green body, firing the green body and then removing the green body, and measuring the visible light linear transmittance of the colored layer having a thickness of 1 mm. The specific test results are as follows:
watch 1
Figure 410626DEST_PATH_IMAGE001
As can be seen from the results in Table I, the color developing layers fired from the frits to which the glass powder was added had better transparency than the color developing layers fired from the frits to which the glass powder was added in examples 1-3 and from the frit to which the glass powder was not added in comparative example 1.
Example 4
A glazed tile is prepared by the following steps: c01, forming a ground coat on the blank; c02, forming an ink spraying layer on the ground glaze layer; c03, forming a color forming layer on the ink jet layer; c04, forming a wear-resistant layer on the coloring layer; and C05, firing and polishing to obtain the glazed brick.
The firing method comprises the following specific steps: firing is carried out under the firing temperature curve of the existing production kiln, and the firing temperature is 1180-1230 ℃.
In the step B03, spraying the coloring glaze on the ink spraying layer to form a coloring layer; the colored glaze is prepared from the transparent frit described in example 2, and the specific gravity of the glaze slip is 1.35g/cm 3 (ii) a The fineness of the coloring glaze slip is 0.3 percent of the residue of a 325-mesh screen; the spray amount was 45g (300 x 600mm trays).
In the step B04, spraying the wear-resistant glaze on the coloring layer to form a wear-resistant layer; the wear-resistant glaze is prepared from a crystalline wear-resistant glaze material, and the specific gravity of glaze slip is 1.85g/cm 3 (ii) a The fineness of the wear-resistant glaze slip is 0.3 percent of the screen residue of 325 meshes; the glaze pouring amount is 110g (300X 600mm torr)A disc).
The crystalline wear-resistant glaze material comprises the following components in percentage by mass: 9% of kaolin, 9% of quartz, 5% of magnesia-alumina spinel, 10% of the transparent frit described in example 2, 29% of potassium feldspar, 11% of albite, 6% of zinc oxide, 11% of anorthite, 6% of cordierite and 4% of corundum.
Example 5
A polished tile, the preparation method of which is different from that of example 4 in the formulation of crystalline wear-resistant glaze.
The crystalline wear-resistant glaze material comprises the following components in percentage by mass: 8.5% of kaolin, 8.5% of quartz, 4% of magnesia-alumina spinel, 15% of transparent frit described in example 2, 28% of potassium feldspar, 10.5% of albite, 5.5% of zinc oxide, 10.5% of anorthite, 5.5% of cordierite and 4% of corundum.
Example 6
A glazed tile, the preparation method of which is different from that of example 4 in that the formulation of the crystalline wear-resistant glaze is different.
The crystalline wear-resistant glaze material of the embodiment comprises the following components in percentage by mass: 8% of kaolin, 8% of quartz, 4% of magnesia-alumina spinel, 20% of the transparent frit described in example 2, 27% of potassium feldspar, 10% of albite, 5% of zinc oxide, 10% of anorthite, 5% of cordierite and 3% of corundum.
Example 7
A glazed tile, the preparation method of which is different from that of example 4 in that the formulation of the crystalline wear-resistant glaze is different.
The crystalline wear-resistant glaze material comprises the following components in percentage by mass: 7.5% of kaolin, 7.5% of quartz, 3.5% of magnesia-alumina spinel, 25% of transparent frit described in example 2, 26% of potassium feldspar, 9.5% of albite, 4.5% of zinc oxide, 9.5% of anorthite, 4.5% of cordierite and 2.5% of corundum.
Comparative example 2
A glazed tile differing from example 6 in the formulation of the crystalline abrasion resistant glaze.
The crystalline wear-resistant glaze material of the embodiment comprises the following components in percentage by mass:
8% of kaolin, 8% of quartz, 4% of magnesia-alumina spinel, 25% of transparent frit, 27% of potassium feldspar, 10% of albite, 5% of zinc oxide, 10% of anorthite and 3% of corundum powder.
Comparative example 3
A glazed tile differing from example 6 in the formulation of the crystalline abrasion resistant glaze.
The crystalline wear-resistant glaze material comprises the following components in percentage by mass:
8% of kaolin, 8% of quartz, 4% of magnesia-alumina spinel, 23% of transparent frit, 27% of potassium feldspar, 10% of albite, 5% of zinc oxide, 10% of anorthite and 5% of cordierite.
The mohs hardness and abrasion resistance rating of the glazed tiles of example 6, comparative example 2 and comparative example 3 were determined by the test method referred to GB/T3810.7-2016 with the following results:
a second table:
Figure 390083DEST_PATH_IMAGE002
the crystalline abrasion-resistant glaze of example 6 contains cordierite and corundum, the crystalline abrasion-resistant glaze of comparative example 2 does not contain cordierite, and the crystalline abrasion-resistant glaze of comparative example 3 does not contain corundum, and as can be seen from the test results in table two, the mohs hardness and the abrasion resistance of the abrasion-resistant layer are both different from those of example 6 in the absence of cordierite or corundum.
The polished tiles of examples 4-7 were tested for mohs hardness, abrasion resistance rating, transparency and stain resistance, with the following results:
a third table:
Figure 966558DEST_PATH_IMAGE003
in table three, the green material refers to the sum of the other components except the transparent frit in the crystalline wear-resistant glaze.
From the results of table three, it can be seen that each performance of example 6 is the best, and when the content of the transparent frit in the crystalline wear-resistant glaze is 15% -25%, the overall performance of the glazed brick is the best.
Example 8
A glazed tile produced by the method of example 6 which differs from that of example 6 in that the colour layer is not included and the abrasion resistant layer is formed directly on the ink-jet layer.
Comparative example 4
A glazed tile is prepared by the following steps: b01, forming a ground coat on the blank; b02, forming an ink spraying layer on the ground glaze layer; b03, forming a surface glaze layer on the ink spraying layer; and B04, firing and polishing to obtain the polished glazed brick.
The firing method comprises the following specific steps: firing is carried out under the firing temperature curve of the existing production kiln, and the firing temperature is 1180-1230 ℃.
The glaze material of the overglaze layer comprises the following components in percentage by mass: 7% of kaolin, 10% of calcined kaolin, 5% of dolomite, 10% of wollastonite, 10% of quartz, 5% of calcined talc, 35% of potassium feldspar, 15% of albite and 3% of barium carbonate.
The prior art product of comparative example 4 was tested for mohs hardness, clarity and color development and compared to examples 8 and 6 as follows:
table four:
Figure 142193DEST_PATH_IMAGE004
the comparative example 4 is a glazed brick with proper color development and good overall color effect in the existing products, the brightness is moderate, and the glazed brick is reddish and yellowish in color, but the existing products obviously have the defect of insufficient hardness.
The result of table four shows that the polished tile of example 8 has a significantly improved hardness and improved transparency, but the color of example 8 is whiter, greener and bluer, and is not satisfactory for color development.
The mohs hardness and clarity of example 6 are superior to the existing product. On the other hand, the color of example 6 was reddish to yellowish, similar to that of the conventional product, and the color was black, and after neutralization of the reddish to yellowish color, the product had the same visual effect as that of the conventional product (comparative example 4).
Example 9
A ceramic tile is prepared by the following steps: b01, forming a ground coat on the blank; b02, forming an ink spraying layer on the ground glaze layer; b03, forming a color forming layer on the ink jet layer; and B04, firing and polishing to obtain the ceramic tile.
Wherein the ground glaze layer is made of white glaze. The coloring layer is obtained by firing a coloring glaze slip prepared from the transparent frit of example 2. The specific gravity of the color development glaze slip is 1.3g/cm 3 (ii) a The fineness of the color glaze slip is 0.3 percent of the screen residue of 325 meshes; the spray amount was 35g (300 x 600mm tray).
Comparative example 5
A ceramic tile was prepared according to a method different from that of example 9 in the formulation of the transparent frit. The transparent frit of the present embodiment includes, by mass:
54% of glass powder, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 3% of borax and 5% of fluorite.
The preparation method of the transparent frit is the same as example 1.
Comparative example 6
A ceramic tile was prepared according to a method different from that of example 9 in the formulation of the transparent frit. The transparent frit of the present embodiment includes, by mass:
30% of glass powder, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 24% of potassium feldspar, 3% of borax and 5% of fluorite.
The preparation method of the transparent frit is the same as example 1.
Comparative example 7
A ceramic tile was prepared according to a method different from that of example 9 in the formulation of the transparent frit. The transparent frit described in this embodiment comprises, by mass:
30% of glass powder, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 24% of potassium nitrate, 3% of borax and 5% of fluorite.
The transparent frit was prepared in the same manner as in example 1.
The color development of the tiles prepared in example 9 and comparative examples 4 to 7 was measured, and the test results were as follows:
table five:
Figure 222145DEST_PATH_IMAGE005
in comparative example 5, the transparent frit is not added with potassium feldspar and potassium nitrate, and has a whitish color compared with that of comparative example 4 and is greenish and blue; the transparent frit of comparative example 6, with the addition of potassium feldspar, developed a whiter and greener color than comparative example 4; the transparent frit of comparative example 7, to which potassium nitrate was added, had darker color than that of comparative example 4, but too reddish to yellowish, where the color development of red was very noticeable. In example 9, potassium feldspar and potassium nitrate were added to the transparent frit, and the use of the potassium feldspar and potassium nitrate in a reasonable combination makes the tile more gentle to the red and yellow color.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.

Claims (9)

1. A transparent frit is characterized by comprising the following chemical components in percentage by mass: siO 2 2 45%~50%、Al 2 O 3 18%~24%、Fe 2 O 3 0.002%~0.05%、TiO 2 0.001%~0.02%、CaO 8%~12%、MgO 4%~6%、K 2 O 5%~7%、Na 2 O 5%~7%、ZnO 3%~5%、B 2 O 3 1 to 3 percent of the total weight of the alloy, 0.5 to 2.1 percent of the loss on ignition and the balance of impurities; the preparation raw materials of the transparent frit comprise the following components in percentage by mass: 25-35% of glass powder, 18-25% of magnesia-alumina spinel, 10-20% of anorthite, 2-8% of zinc oxide, 10-20% of potassium feldspar, 5-10% of potassium nitrate, 2-8% of borax and 2-6% of fluorite.
2. The transparent frit according to claim 1, wherein the raw materials for preparing the transparent frit comprise, in mass percent: 30% of glass powder, 20% of magnesia-alumina spinel, 15% of anorthite, 3% of zinc oxide, 15% of potassium feldspar, 9% of potassium nitrate, 3% of borax and 5% of fluorite.
3. A crystalline wear-resistant glaze is characterized by comprising the following components in percentage by mass: 6-10% of kaolin, 5-10% of quartz, 1-5% of magnesia-alumina spinel, 15-25% of transparent frit, 25-35% of potassium feldspar, 8-15% of albite, 4-8% of zinc oxide, 8-15% of anorthite, 3-8% of cordierite and 1-5% of corundum; the transparent frit of any of claims 1-2.
4. The crystalline wear-resistant glaze according to claim 3, comprising, in mass percent: 8% of kaolin, 8% of quartz, 4% of magnesia-alumina spinel, 20% of transparent frit, 27% of potassium feldspar, 10% of albite, 5% of zinc oxide, 10% of anorthite, 5% of cordierite and 3% of corundum.
5. A glazed brick is characterized by comprising a body layer, a ground coat layer, an ink-jet layer and a wear-resistant layer which are sequentially arranged from bottom to top; the wear resistant layer is made of a crystalline wear resistant glaze according to any one of claims 3 to 4.
6. A glazed brick is characterized by comprising a blank layer, a ground glaze layer, an ink spraying layer, a color development layer and a wear-resistant layer which are sequentially arranged from bottom to top; the wear resistant layer is made of a crystalline wear resistant glaze according to any one of claims 3 to 4.
7. The glazed tile of claim 6, wherein the colour layer is made from the transparent frit of any one of claims 1-2.
8. A method for preparing a glazed tile according to claim 5, comprising the steps of: b01, forming a ground coat on the blank; b02, forming an ink spraying layer on the ground glaze layer; b03, forming a wear-resistant layer on the ink-jet layer; and B04, firing and polishing to obtain the polished glazed brick.
9. A process for the preparation of a glazed tile according to any one of claims 6 to 7, comprising the steps of: firstly, forming an ink-jet layer on the ground glaze layer, then forming a color-developing layer on the ink-jet layer, then forming a wear-resistant layer on the color-developing layer, firing and polishing to obtain the glazed brick.
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