CN111039570B - Zirconium-free anorthite-based opaque glaze and preparation method thereof - Google Patents

Zirconium-free anorthite-based opaque glaze and preparation method thereof Download PDF

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Publication number
CN111039570B
CN111039570B CN202010020266.8A CN202010020266A CN111039570B CN 111039570 B CN111039570 B CN 111039570B CN 202010020266 A CN202010020266 A CN 202010020266A CN 111039570 B CN111039570 B CN 111039570B
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glaze
anorthite
zirconium
free
opaque
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CN111039570A (en
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王少华
汪永清
李小女
汪超
张小珍
常启兵
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Jingdezhen Ceramic Institute
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Jingdezhen Ceramic Institute
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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
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • 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
    • C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
    • C03C2205/02—Compositions applicable for the manufacture of vitreous enamels or glazes for opaque enamels or glazes

Abstract

The invention discloses a zirconium-free anorthite-based opaque glaze which comprises the following raw materials: 5-10 wt% of clay, 0-10 wt% of potassium feldspar, 20-40 wt% of albite, 5-20 wt% of quartz, 10-25 wt% of calcite, 0-10 wt% of wollastonite, 8-15 wt% of aluminum oxide, 1-10 wt% of zinc oxide, 3-8 wt% of calcined talc, 1-15 wt% of glass powder and 0.5-1.5 wt% of nucleating agent. In addition, a preparation method of the zirconium-free anorthite-based opaque glaze is also disclosed. According to the invention, through using the raw materials with low cost and optimizing a formula system, flaky or blocky anorthite crystals are separated out from the interior of the glaze layer, and three-dimensional crystallization is combined, so that a good glaze opacifying effect is realized, meanwhile, the whiteness and hardness of the glaze are improved, and the product performance is effectively improved. The raw materials of the invention do not contain radioactive elements and are harmless to the environment and human body; and the opaque glaze has wide application range and is beneficial to popularization and application.

Description

Zirconium-free anorthite-based opaque glaze and preparation method thereof
Technical Field
The invention relates to the technical field of ceramic glaze materials, in particular to anorthite-based opaque glaze and a preparation method thereof.
Background
In order to cover the bad coloring and defect of the blank and expand the source of raw materials, the opaque glaze with good decorative effect is widely applied to the surfaces of building ceramics and sanitary ceramics.
The opacification mechanism of the opacified glaze is that when a second phase (or multiple phases) different from the base glass in properties exists in the glaze layer, incident light passes through the glaze layer and reflects, refracts and diffusely reflects on the interfaces of the multiple phases, so that the glaze layer is devitrified to obtain an opacification effect. Commonly used in ceramics industryThe opaque glaze is tin oxide opaque glaze, titanium oxide opaque glaze and zirconium silicate opaque glaze. The tin oxide opaque glaze has good opacifying effect, but has the disadvantages of high cost and sensitivity to atmosphere, such as firing in a reducing atmosphere to obtain a transparent glaze. TiO in titanium oxide opaque glaze2The devitrification ensures that the glaze has good opacifying effect, but is mainly suitable for low-temperature enamel glaze with the firing temperature of 750-850 ℃, and the glaze is easy to yellow when the firing temperature is more than or equal to 1000 ℃. The zirconium silicate opaque glaze is the most widely used opaque glaze at present, and has the advantages that the whiteness of the glaze is high, the glaze is insensitive to atmosphere, but the zirconium silicate is partially melted at high temperature, so that the required opacifying effect can be realized only by adding 10-20 wt%, and the cost is increased. In addition, Ra is often associated with raw ore of zirconium silicate226、Th232、K40When a large amount of zirconium silicate is added into the glaze, the radioactivity of the product exceeds the standard, and the health of consumers is damaged. Therefore, the development of the zirconium-free opaque glaze with low cost, environmental protection and good opacifying effect has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the zirconium-free anorthite-based opaque glaze, and the preparation method is characterized in that the raw materials with low cost and environmental protection are used, the formula system is optimized, so that flaky or blocky anorthite crystals are separated out from the interior of the glaze layer, and meanwhile, the nucleating agent is introduced to control the three-dimensional crystallization of the anorthite in the interior of the glaze layer, so that the light scattering is increased, the good glaze opacifying effect is realized, the whiteness and hardness of the glaze are improved, and the service life of a product is prolonged. The invention also aims to provide a preparation method of the zirconium-free anorthite-based opaque glaze.
The purpose of the invention is realized by the following technical scheme:
the invention provides a zirconium-free anorthite-based opaque glaze which comprises the following raw materials: 5-10 wt% of clay, 0-10 wt% of potassium feldspar, 20-40 wt% of albite, 5-20 wt% of quartz, 10-25 wt% of calcite, 0-10 wt% of wollastonite, 8-15 wt% of aluminum oxide, 1-10 wt% of zinc oxide, 3-8 wt% of calcined talc, 1-15 wt% of glass powder and 0.5-1.5 wt% of nucleating agent; the above-mentionedThe nucleating agent is TiO2、P2O5、B2O3One or a combination thereof.
Furthermore, the raw material composition of the glass powder is SiO256～70wt％、Al2O32～8wt％、CaO 5～10wt％、MgO 1～5wt％、K2O 1～5wt％、Na2O 8～16wt％。
In the scheme, the anorthite crystals precipitated from the opaque glaze are flaky or blocky and have the size of 1-12 mu m.
The other purpose of the invention is realized by the following technical scheme:
the preparation method of the zirconium-free anorthite-based opaque glaze provided by the invention comprises the following steps:
(1) preparing materials according to the raw material composition of the opaque glaze, and performing wet ball milling and mixing to obtain glaze slurry;
(2) applying glaze slurry on the surface of the blank body in a glaze spraying or glaze pouring mode;
(3) and firing the dried glazed blank to obtain the zirconium-free anorthite-based opaque glaze.
Further, the glaze slurry in the step (1) of the preparation method has the particle size D90 of 8-15 mu m and the specific gravity of 1.40-1.85 g/cm3. When the glaze spraying mode is adopted in the step (2), the specific gravity of the glaze slip is 1.40-1.55 g/cm3The flow rate is 3-20 s/100 mL; when the glaze pouring mode is adopted, the specific gravity of the glaze slip is 1.70-1.85 g/cm3The flow rate is 20-35 s/100 mL. In the step (3), the firing temperature is 1180-1250 ℃, and the firing time is 50-70 min.
The invention has the following beneficial effects:
(1) the raw materials of the invention have wide sources and low cost, and flaky or blocky anorthite crystals are separated out from the glaze layer by optimizing the formula composition; and the nucleating agent is introduced to realize three-dimensional crystallization in the glaze layer, so that light scattering is increased, a good opacifying effect is obtained, the glaze surface has high whiteness (whiteness is 65-75) and high hardness (Mohs hardness is 6-8), and a good matte effect (glossiness is 8-20 degrees) is achieved, and the product performance is effectively improved.
(2) The raw materials of the invention do not contain radioactive elements and are harmless to the environment and human body; the opaque glaze has wide application range and is beneficial to popularization and application.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
FIG. 1 is an XRD pattern of a zirconium-free anorthite-based opaque glaze prepared by an example of the present invention;
FIG. 2 is an SEM image of an anorthite-based opaque glaze prepared by the method.
Detailed Description
The first embodiment is as follows:
1. the zirconium-free anorthite-based opaque glaze comprises the following raw materials: 8 wt% of clay, 10 wt% of potassium feldspar, 20 wt% of albite, 15 wt% of quartz, 15 wt% of calcite, 5 wt% of wollastonite, 8 wt% of alumina, 3 wt% of zinc oxide, 5 wt% of calcined talc, 10 wt% of glass powder and 1 wt% of nucleating agent (TiO)20.5 wt％+B2O30.5 wt%). Wherein the raw material composition of the glass powder is SiO265 wt％、Al2O34 wt％、CaO 8wt％、MgO 3wt％、K2O 5wt％、Na2O 15wt％。
2. The preparation method of the zirconium-free anorthite-based opaque glaze of the embodiment comprises the following steps:
(1) mixing the materials according to the composition of the opacified glaze, adding water, and performing wet ball milling (the mass ratio of the materials, the ball stone and the water is 1: 2: 0.5) for 8 hours to obtain glaze slip with the particle size D90 of 8.3 mu m;
(2) adding water to adjust the specific gravity of the glaze slip to 1.75g/cm3Applying the glaze slurry on the surface of the blank body in a glaze pouring mode at the flow rate of 25s/100 mL;
(3) and (3) firing the dried glazed green body in a roller kiln at the firing temperature of 1200 ℃ for 58min to obtain the zirconium-free anorthite-based opaque glaze with the surface glossiness of 15 degrees, the whiteness of 70 degrees and the Mohs hardness of 7 grades.
Example two:
1. the zirconium-free anorthite-based opaque glaze comprises the following raw materials: 8 wt% of clay, 30 wt% of albite, 15 wt% of quartz, 20 wt% of calcite, 8.5 wt% of alumina, 3 wt% of zinc oxide, 6 wt% of calcined talc, 9 wt% of glass powder and nucleating agent P2O50.5 wt%. Wherein the raw material composition of the glass powder is SiO270 wt％、Al2O33wt％、CaO 8wt％、MgO 2wt％、K2O 4wt％、Na2O 13wt％。
2. The preparation method of the zirconium-free anorthite-based opaque glaze of the embodiment comprises the following steps:
(1) mixing the materials according to the composition of the opacified glaze, adding water, and performing wet ball milling (the mass ratio of the materials, the ball stone and the water is 1: 2: 0.5) for 6 hours to obtain glaze slip with the particle size D90 of 9.5 mu m;
(2) adding water to adjust the specific gravity of the glaze slip to 1.50g/cm3Applying glaze slurry on the surface of the blank body in a glaze spraying mode at the flow rate of 20s/100 mL;
(3) and (3) firing the dried glazed blank in a roller kiln at the firing temperature of 1220 ℃ for 60min to obtain the zirconium-free anorthite-based opaque glaze with the surface glossiness of 13 degrees, the whiteness of 68 and the Mohs hardness of 6.
As shown in figure 1, the zirconium-free anorthite-based opaque glaze prepared by the embodiment of the invention has the unique precipitated crystal phase of anorthite. The precipitated anorthite crystals had a plate-like morphology and a size of about 10 μm (see FIG. 2).

Claims (5)

1. The zirconium-free anorthite-based opaque glaze is characterized by comprising the following raw materials: 5-10 wt% of clay, 0-10 wt% of potassium feldspar, 20-40 wt% of albite, 5-20 wt% of quartz, 10-25 wt% of calcite, 0-10 wt% of wollastonite, 8-15 wt% of aluminum oxide, 1-10 wt% of zinc oxide, 3-8 wt% of calcined talc, 1-15 wt% of glass powder and 0.5-1.5 wt% of nucleating agent; the raw material composition of the glass powder is SiO2 56～70 wt%、Al2O3 2～8 wt%、CaO 5～10 wt%、MgO 1～5 wt%、K2O 1～5 wt%、Na28-16 wt% of O; the nucleating agent is TiO2、P2O5、B2O3One or a combination thereof; under the conditions that the firing temperature of the opaque glaze is 1180-1250 ℃ and the firing time is 50-70 min, anorthite crystals precipitated inside the glaze layer are flaky or blocky and have the size of 1-12 mu m, and three-dimensional crystallization inside the glaze layer is realized.
2. The method for preparing the zirconium-free anorthite-based opacified glaze according to claim 1, which is characterized by comprising the following steps:
(1) preparing materials according to the raw material composition of the opaque glaze, and performing wet ball milling and mixing to obtain glaze slurry;
(2) applying glaze slurry on the surface of the blank body in a glaze spraying or glaze pouring mode;
(3) and firing the dried glazed blank to obtain the zirconium-free anorthite-based opaque glaze.
3. The method for preparing the zirconium-free anorthite-based opaque glaze according to claim 2, wherein the method comprises the following steps: the particle size D90 of the glaze slurry in the step (1) is 8-15 mu m, and the specific gravity is 1.40-1.85.
4. The method for preparing the zirconium-free anorthite-based opaque glaze according to claim 2, wherein the method comprises the following steps: when the glaze spraying mode is adopted in the step (2), the specific gravity of the glaze slip is 1.40-1.55, and the flow rate is 3-20 s/100 mL; when the glaze pouring mode is adopted, the specific gravity of the glaze slip is 1.70-1.85, and the flow rate is 20-35 s/100 mL.
5. The method for preparing the zirconium-free anorthite-based opaque glaze according to claim 2, wherein the method comprises the following steps: in the step (3), the firing temperature is 1180-1250 ℃, and the firing time is 50-70 min.
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CN111439931B (en) * 2020-06-17 2020-12-01 佛山市东鹏陶瓷有限公司 Low-cost zirconium-free white glaze suitable for sanitary ceramics and domestic porcelain and preparation method thereof
CN112851120B (en) * 2021-01-21 2022-08-23 景德镇陶瓷大学 Microcrystalline wear-resistant transparent glaze and preparation method and application of glaze slip thereof
CN113336575B (en) * 2021-07-03 2022-08-05 江西省萍乡市华东出口电瓷有限公司 Porcelain insulator with phase electricity identification function
CN114409387B (en) * 2022-01-10 2023-04-18 蒙娜丽莎集团股份有限公司 Ultra-white rock plate and preparation method thereof
CN115521073B (en) * 2022-09-09 2023-08-25 杭州诺贝尔陶瓷有限公司 Nano-calcium feldspar powder, anorthite microcrystalline frit and transparent microcrystalline glaze ceramic tile

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