CN112299718B - Magnesium aluminate spinel wear-resistant printing glaze and preparation method and application thereof - Google Patents

Magnesium aluminate spinel wear-resistant printing glaze and preparation method and application thereof Download PDF

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CN112299718B
CN112299718B CN202011107530.8A CN202011107530A CN112299718B CN 112299718 B CN112299718 B CN 112299718B CN 202011107530 A CN202011107530 A CN 202011107530A CN 112299718 B CN112299718 B CN 112299718B
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wear
glaze
magnesia
resistant
resistant printing
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CN112299718A (en
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潘利敏
况学成
邓来福
陈鹏程
郑贵友
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Monalisa Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • 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
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Geochemistry & Mineralogy (AREA)
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Abstract

The invention discloses a magnesia-alumina spinel wear-resistant printing glaze as well as a preparation method and application thereof. The magnesium aluminate spinel wear-resistant printing glaze comprises the following raw materials: the mass percentage of the electric melting magnesia-alumina spinel is as follows: 35-55 percent. The magnesia-alumina spinel wear-resistant printing glaze improves the alumina content in glaze in the form of magnesia-alumina spinel, and compared with the traditional mode of introducing higher alumina content (directly adding alumina or corundum), magnesia-alumina spinel (MgO. Al)2O3) As the combination of the aluminum oxide and the magnesium oxide, the glaze surface has better hardness and wear resistance, and simultaneously has more flux, and the glaze surface can not be burnt.

Description

Magnesium aluminate spinel wear-resistant printing glaze and preparation method and application thereof
Technical Field
The invention relates to a magnesia-alumina spinel wear-resistant printing glaze as well as a preparation method and application thereof, belonging to the technical field of ceramic tile production and manufacturing.
Background
The full-glazed series products are popular with consumers due to rich design patterns, simple process and easy operation, thereby replacing the market of the traditional polished tiles in a large proportion. However, with the increase of the service life, the scratches and the abrasion degree of the surfaces of the full-glazed series products are more obvious than those of polished tiles, and even in some public places, the glaze is over-worn, and the tiles are deficient, so that the products have to be re-decorated. Due to the consideration of wear resistance, the proportion of the full-glazed series products applied in market engineering is reduced. Therefore, the wear resistance of the full-polished glaze is improved, and the market engineering application proportion is enlarged.
In the existing wear-resistant ceramic tiles, the wear resistance of the glaze surface is improved mainly by increasing the content of alumina (such as marble glaze). However, simply increasing the alumina content of the glaze results in poor glaze transparency. In order to ensure the color and transparency of the glaze, the glazing amount needs to be reduced and the polishing amount needs to be correspondingly reduced, but the water ripple of the brick surface is obviously increased, so that the texture of the brick surface is influenced. The wear resistance of the glaze surface can also be improved by crystallization (such as common celsian and strontium feldspar crystallization). However, the Mohs hardness of the celsian is 6-6.5, and the celsian cannot be used in some occasions with extremely high requirements on the hardness of the brick surface.
Disclosure of Invention
Aiming at the problems, the invention provides a magnesia-alumina spinel wear-resistant printing glaze and a preparation method and application thereof, wherein the magnesia-alumina spinel is used for increasing the content of alumina in glaze, and compared with the traditional mode of introducing higher content of alumina (directly adding alumina or corundum), magnesia-alumina spinel (MgO. Al)2O3) As the combination of the aluminum oxide and the magnesium oxide, the glaze surface has better hardness and wear resistance, and simultaneously has more flux, and the glaze surface can not be burnt.
In a first aspect, the invention provides a magnesia-alumina spinel wear-resistant printing glaze. The magnesium aluminate spinel wear-resistant printing glaze comprises the following raw materials: the mass percentage of the electric melting magnesia-alumina spinel is as follows: 35-55 percent. The content of the electric melting magnesia-alumina spinel in the wear-resistant printing glaze is controlled to be 35-55%, and the phenomenon that the antifouling performance is reduced due to the fact that the content of the magnesia-alumina spinel is too high is avoided. Too high a content of magnesium aluminate spinel results in a lower content of vitreous phase in the enamel, which leads to the gaps between the crystals not being filled and to poor contamination resistance. Likewise, too low a magnesium aluminate spinel content may result in less than ideal post-polishing hardness.
Preferably, the chemical composition of the magnesia-alumina spinel wear-resistant printing glaze comprises: by mass percent, SiO2：30～45％、Al2O3: 35-55%, alkali metal oxide 2-5%, alkaline earth metal10.0 to 24% of an oxide. Alkali metal elements such as potassium and sodium have low valence, large distance with oxygen ions, small attraction, small field strength and small single bond energy, and are not beneficial to improving the hardness. In the chemical composition of the wear-resistant printing glaze, the content of alkali metal oxide is controlled as much as possible, the content of high-valence ions such as silicon, aluminum and the like is increased, and the high-valence ions have small distance from oxygen ions, large attraction, large field strength and large single bond energy, so that the hardness is increased.
Preferably, Na in the wear-resistant printing glaze2O (sodium flux) is controlled within 1 wt%. So as to further improve the hardness and wear resistance of the glaze.
Preferably, the magnesium aluminate spinel wear-resistant printing glaze further comprises the following raw materials: burning talc: 15-25% of potassium feldspar: 15-25% of high-boron strontium frit and 5-15% of high-boron strontium frit. Under the condition of not influencing the glaze quality (pores and poor antifouling performance), the boron oxide is properly introduced to replace other alkali metal oxides to be used as a flux, so that the hardness of a glass phase can be improved. Preferably, the chemical composition of the high-boron strontium frit comprises: by mass percent, SiO2：50.0～60.0％、Al2O3：15.0～20.0％、CaO：3.0～5.0％、MgO：3.0～5.0％、SrO：8.0～12.0％、B2O3：5.0～10.0％。
In a second aspect, the invention further provides a preparation method of the magnesia-alumina spinel wear-resistant printing glaze. Weighing raw materials of the magnesia-alumina spinel wear-resistant printing glaze according to the formula ratio, crushing the raw materials and sieving to obtain granular raw materials; mixing the particle raw materials with water and then ball-milling until the particle diameter of the slurry is D90≤10μm。
In a third aspect, the invention further provides application of the magnesia-alumina spinel wear-resistant printing glaze in ceramic tiles.
Preferably, the application mode of the magnesia-alumina spinel wear-resistant printing glaze is glaze pouring or glaze spraying; when the glaze is sprayed, the specific gravity of the wear-resistant printing glaze is 1.83-1.88 g/cm3The glazing amount is 350-500 g/m2。
Preferably, the magnesium aluminate spinel wear-resistant printing glaze is applied by screen printingBrushing; the specific gravity of the wear-resistant printing glaze in the silk-screen printing is 1.40-1.50 g/cm3The glazing amount is 100-180 g/m2。
Preferably, the magnesia-alumina spinel wear-resistant printing glaze is applied to the surface of the green brick, and then the green brick is sintered and polished to obtain the magnesia-alumina spinel wear-resistant full-glazed ceramic brick. The sintered brick surface phase of the obtained magnesia-alumina spinel wear-resistant full-glazed ceramic brick comprises the following components in parts by weight: the mass percentage of the magnesium aluminate spinel phase is 25 percent to 55 percent and the mass percentage of the amorphous phase is 10 percent to 30 percent.
Preferably, before the magnesium aluminate spinel wear-resistant printing glaze is applied to the surface of the brick blank, overglaze can be applied to the surface of the brick blank and a pattern can be printed by ink jet.
Drawings
FIG. 1 is a surface XRD of a magnesia-alumina spinel abrasion-resistant fully glazed ceramic tile in accordance with example 1 of the present invention;
FIG. 2 is a SEM image of the surface of a magnesia alumina spinel abrasion-resistant fully glazed ceramic tile in accordance with example 1 of the present invention;
FIG. 3 is a XRD pattern of the tile surface of a magnesia alumina spinel abrasion-resistant fully glazed ceramic tile in accordance with example 2 of the present invention;
FIG. 4 is a SEM image of the tile surface of a magnesia alumina spinel abrasion-resistant fully glazed ceramic tile in accordance with example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage refers to a mass percentage. The loss on ignition refers to CO decomposed from crystal water and carbonate discharged in the process of burning the detected material2SO of sulfate decomposition2And the loss of the quality of the rest materials of other organic impurities caused by burning and gasifying. "magnesia alumina spinel" may also be referred to as "fused magnesia alumina spinel". The wear-resistant printing glaze can also be called as the wear-resistant printing glaze of magnesium aluminate spinel.
The preparation method of the magnesia-alumina spinel wear-resistant full-glazed ceramic tile is exemplarily described below in combination with the magnesia-alumina spinel wear-resistant printing glaze.
And forming the green body powder to obtain a green brick. Can be dry-pressed by a press to formForming a green brick. The composition of the green body powder is not limited, and the conventional ceramic tile green body powder in the field can be adopted. For example, the chemical composition of the green body powder comprises, in mass percent, SiO2：60.0～70.0％、Al2O3：19.0～25.0％、Fe2O3：0.5～1.5％、TiO2：0.2～0.5％、CaO：0.2～0.8％、MgO：0.3～0.8％、K2O：2.0～4.0％、Na2O: 1.50-3.5%, loss on ignition: 4.0 to 6.0 percent.
And drying the green brick. And controlling the moisture of the dried green brick to be 0.3-0.5 wt%. The drying time can be 1-1.5 h.
And applying surface glaze on the surface of the dried green brick. The overglaze mainly plays a role in covering the ground color and flaws of the blank, facilitating the exhaust of glaze polishing and reducing pores after polishing.
In some embodiments, the chemical composition of the overglaze may include: by mass percent, SiO2：55～60％、Al2O3：21～24％、Fe2O3：0.16～0.46％、TiO2：0.15～0.25％、CaO：0.1～0.3％、MgO：0.1～0.3％、K2O：4.0～5.0％、Na2O：2.0～3.0％、ZrO2: 6.0-10.0%, loss on ignition: 3.0 to 4.0 percent.
The overglaze may be applied by spraying glaze. For example, the specific gravity of the overglaze can be 1.40-1.45 g/cm3The glazing amount can be 400-550 g/m2。
And (4) ink-jet printing a pattern on the surface of the green brick after the overglaze is applied. The color and pattern of the inkjet printed pattern vary according to the layout effect.
And applying wear-resistant printing glaze on the surface of the green brick after the pattern is printed by ink jet. The function of applying the wear-resistant printing glaze is to further improve the hardness and wear resistance of the glaze.
The chemical composition of the wear-resistant printing glaze can comprise: by mass percent, SiO2：30～45％、Al2O3: 35-55%, 2-5% of alkali metal oxide and 10.0-24% of alkaline earth metal oxide.
As an example, the chemical composition of the wear-resistant printing glaze may comprise: in terms of mass percent, SiO2：30～45％、Al2O3：35～55％、Fe2O3：0.1～0.5％、TiO2：0.1～0.5％、CaO：0.1～2.0％、MgO：12.0～20.0％、K2O：2.0～4.0％、Na2O：0.1～1.0％、SrO：0.5～1.5％、B2O3: 0.5-1.5%, loss on ignition: 1.0-3.0%.
In some embodiments, the raw material composition of the abrasion-resistant printing glaze can comprise: burning talc: 15-25% of potassium feldspar: 15-25%, fused magnesia-alumina spinel: 35-55% of high-boron strontium frit: 5 to 15 percent.
The chemical composition of the high-boron strontium frit may include: by mass percent, SiO2：50.0～60.0％、Al2O3：15.0～20.0％、CaO：3.0～5.0％、MgO：3.0～5.0％、SrO：8.0～12.0％、B2O3：5.0～10.0％。
In the development process of the wear-resistant printing glaze, other systems, such as a eucryptite system, are tried, and the hardness is poor due to the high content of the potassium-sodium flux; for example, high silicon systems, which have a relatively high free quartz content, cause higher expansion coefficients and cause cracking problems; for example, the anorthite, albite and celsian crystallization systems have relatively high glass phase content, so that the hardness of the brick surface cannot achieve the ideal effect; for example, cordierite systems have a large overall increase in the hardness of the glaze, but require high synthesis temperatures and are difficult to precipitate in the glaze.
In some embodiments, the method of preparing the abrasion-resistant printing glaze may comprise: weighing the wear-resistant printing glaze raw material according to the formula ratio, crushing the raw material, and screening the crushed raw material through a standard sieve of 100-325 meshes to obtain a granular raw material; ball-milling the granular raw material and water until the granularity of the slurry is D90Less than or equal to 10 mu m. The ratio of particulate material to water may be 1: 0.40. the flow rate of the wear-resistant printing glaze can be 40-90 seconds.
Because the wear-resistant printing glaze contains higher content of magnesium aluminate spinel, the wear-resistant printing glaze needs to be addedSubmicron ball milling to D90Less than or equal to 10 mu m. The submicron grinding method is adopted to reduce the fineness of slurry particles of the wear-resistant printing glaze, particularly the fineness of introduced high-hardness wear-resistant particles, so that the hardness and the permeability of the glaze can be improved. The fineness can make the specific surface area of particles in the glaze material larger, so that the glaze material fully reacts to form a more compact glaze layer, thereby improving the antifouling performance.
The application mode of the wear-resistant printing glaze is not limited, and screen printing, glaze pouring or glaze spraying can be used. Can obtain good glaze hardness and wear resistance.
In some embodiments, the wear-resistant printing glaze is applied by way of pouring or spraying glaze. When the glaze is sprayed, the specific gravity of the wear-resistant printing glaze is 1.83-1.88 g/cm3The glazing amount is 350-500 g/m2. The glaze spraying and applying amount can be converted according to the using amount of the glaze spraying dry material. However, the glazing amount of the wear-resistant printing glaze is relatively large during glaze pouring or glaze spraying, and the higher the glazing amount is, the poorer the transparency and color development of the glaze surface is caused because the wear-resistant printing glaze contains higher content of magnesia-alumina spinel.
In some embodiments, the wear-resistant printing glaze is applied by screen printing, and the amount of wear-resistant printing glaze applied can be maintained within a suitable range. At the moment, the specific gravity of the wear-resistant printing glaze is 1.40-1.50 g/cm3The glazing amount is 100-180 g/m2. The wear-resistant printing glaze is applied by adopting a screen printing mode, so that better uniformity can be ensured under less glazing amount, and the problems of poor transparency and color development are solved. The mesh number of the screen can be 80-160 meshes.
And drying the green brick subjected to the wear-resistant printing glaze. The drying temperature can be 100-150 ℃, and the moisture after drying is controlled within 0.9 wt%.
And sintering the dried green body. The sintering period can be adjusted adaptively according to the specification and the specific oxidation condition of the ceramic tile. For example, the maximum firing temperature is 1180 to 1220 ℃, and the firing period is 60 to 180 minutes.
And polishing the fired ceramic tile, edging and grading to obtain the magnesia-alumina spinel wear-resistant fully-glazed ceramic tile.
As can be seen from fig. 1, the composition of the fired tile surface phase of the magnesia alumina spinel abrasion-resistant fully-glazed ceramic tile (with abrasion-resistant fully-glazed ceramic applied) comprises: the magnesium aluminate spinel phase accounts for 25-55% of the mass percent, and the amorphous phase accounts for 10-30%. As can be seen from fig. 2, a large amount of magnesium aluminate spinel crystals are present in the glaze. After the magnesia-alumina spinel wear-resistant printing glaze is fired, magnesia-alumina spinel is used as a main crystal phase, and the Mohs hardness of the magnesia-alumina spinel can reach 8-9, so that the hardness of the glaze surface can be better improved to a certain extent by introducing the magnesia-alumina spinel.
In some embodiments, the wear-resistant full-polishing glaze can be applied on the surface of the green brick after the pattern is printed by ink jet before the wear-resistant printing glaze is applied. The function of applying the wear-resistant full-polished glaze is mainly to increase the transparent color development, hardness and wear resistance of the glaze layer.
The wear-resistant full-polished glaze comprises the following chemical components: by mass percent, SiO2：40.0～50.0％、Al2O3：18.0～35.0％、ZnO: 2.0 to 10.0%, 2 to 6% of an alkali metal oxide, and 14.0 to 38% of an alkaline earth metal oxide.
The control principle of the alkali metal oxide in the wear-resistant full-polished glaze is basically the same as that of the wear-resistant printing glaze. Preferably, Na in the wear-resistant fully-polished glaze2The content of O (sodium flux) is controlled below 2 wt%, so that the hardness of the glaze surface is not influenced under the condition of improving the color development and the transparency of the glaze surface.
Silica is a glass former and its melt has a high temperature viscosity which is detrimental to the precipitation and formation of crystals. Multiple divalent metal oxides are used as fluxing agents, and the multiple metal oxides are mutually subjected to solid solution to form a solid solution. Solid solution is a defect, and the more the content of solid solution is, the lower the hardness of crystalline solid solution is to cause the lowering of the hardness of the glaze.
The invention introduces aluminum in the form of magnesium aluminate spinel instead of introducing aluminum in the form of alumina (such as corundum) conventionally, reduces the content of silicon oxide, and promotes the integral crystallization of the glaze under the condition that the glaze has enough permeability. In addition, the transparency and the color development of the glaze surface can be influenced by the excessively high content of the magnesia-alumina spinel in the wear-resistant full-polished glaze, so that the gradient glazing process is introduced, namely the content of the magnesia-alumina spinel in the wear-resistant full-polished glaze is lower than that of the subsequently applied wear-resistant printing glaze, and the content of the alkaline earth metal oxide in the wear-resistant full-polished glaze is higher than that of the wear-resistant printing glaze, so that the high-hardness wear-resistant full-polished glazed ceramic tile with high mirror surface degree, good transparency and excellent color development performance is obtained.
Moreover, the total content of the alkaline earth metal oxides of the wear-resistant full-polished glaze is properly controlled, the content of a single alkaline earth metal oxide is increased as much as possible, the wear resistance and the hardness of the glaze are further improved, the multiple alkaline earth metal oxides are prevented from being fused together at low price, multiple crystals are mutually inhibited, and the hardness of the glaze is reduced.
In some embodiments, the chemical composition of the abrasion-resistant full-polished glaze comprises: by mass percent, SiO2：40.0～50.0％、Al2O3：18.0～35.0％、Fe2O3：0.1～0.5％、TiO2：0.1～0.5％、CaO：4.0～8.0％、MgO：5.0～10.0％、K2O：2.0～4.0％、Na2O: 0.5-2.0%, ZnO: 2.0-10.0%, BaO: 5.0-10.0%, loss on ignition: 5.0-8.0%.
The wear-resistant full-polished glaze comprises the following raw materials: magnesium aluminate spinel: 10-35%, 15-30% of divalent metal silicate mineral and 35-55% of monovalent metal silicate mineral. The divalent metal silicate mineral refers to a silicate mineral into which a divalent metal oxide can be introduced. Likewise, a monovalent metal silicate mineral refers to a silicate mineral into which a monovalent metal oxide can be introduced.
A large amount of fused magnesia-alumina spinel is introduced into the wear-resistant full-polished glaze, the fused magnesia-alumina spinel is matched with a proper flux, and a high-hardness magnesia-alumina spinel phase is introduced into the wear-resistant full-polished glaze and is kept in the glaze as far as possible without being melted by the flux, so that a large amount of magnesia-alumina spinel crystals are uniformly distributed on a glaze layer. The content of the wear-resistant full-polished in-glaze magnesia-alumina spinel is controlled to be 10-35%, the phenomenon that the hardness of a glaze surface is reduced and the wear resistance is caused due to the fact that the content of the magnesia-alumina spinel is too low is avoided, and the phenomenon that the content of the magnesia-alumina spinel is too high and the crystal content of the in-glaze magnesia-alumina spinel is too high to cause devitrification is avoided, so that the transparency and the color development of a glaze layer are poor.
For example, the raw material composition of the wear-resistant full-polished glaze comprises: and (2) wollastonite: 5-10% of fused magnesia alumina spinel: 10-35%, 10-20% of calcined talc, 25-35% of potassium feldspar, 10-20% of albite, and barium carbonate: 5E &
15% of kaolin, 5-10% of kaolin and 2-10% of zinc oxide.
The chemical composition of the fused magnesia-alumina spinel may include: SiO in mass percent2：0.1～1.0％、Al2O3：70.0～80.0％、Fe2O3：0.0～0.5％、TiO2：0.0～0.5％、CaO：0.0～0.5％、MgO：15.0～25.0％、K2O：0.0～0.5％、Na2O: 0.0-1.0%, loss on ignition: 1.0 to 5.0 percent.
In some embodiments, the method for preparing the wear-resistant full-polished glaze can comprise the following steps: weighing the wear-resistant full-glazed raw material according to the formula ratio, crushing the raw material, and screening the crushed raw material through a standard sieve of 100-325 meshes to obtain a granular raw material; and (4) ball-milling the granular raw materials and water, and sieving to obtain the glaze slip. The ratio of particulate material to water may be 1: 0.40. ball-milling until the wear-resistant fully-polished glaze with 325 meshes is 0.6-0.8 wt%. The flow rate of the wear-resistant full-polishing glaze can be 40-90 seconds. The wear-resistant full-polished glaze only needs to be ball-milled to the conventional polished glaze fineness because the content of the magnesium aluminate spinel is relatively low.
The application mode of the wear-resistant full-polished glaze can be glaze pouring. In some embodiments, the specific gravity of the wear-resistant full-polished glaze is 1.80-1.88 g/cm3The glazing amount is 450-600 g/m2. The glazing parameters can enable polishing to have more polishing amount and enable the mirror surface degree of the glaze surface to be better.
Comparing fig. 2 and fig. 4, it can be seen that the content of the magnesia-alumina spinel in the printed glaze applied alone is not much different from that in the glaze applied by the gradient glazing method.
As can be seen from fig. 3, the composition of the tile surface phase after firing of the magnesia-alumina spinel wear-resistant fully-glazed ceramic tile (applying wear-resistant fully-glazed and wear-resistant printing glaze) comprises: the magnesium aluminate spinel phase accounts for 25-55% of the mass percent, and the amorphous phase accounts for 10-30%. Namely, the phase composition of the ceramic tile after firing, which is applied with the wear-resistant printing glaze, sequentially applied with the wear-resistant printing glaze and the wear-resistant full-polishing glaze, has little difference. As can be seen from fig. 4, the glaze surface adopting the gradient glazing process also has a large amount of magnesia-alumina spinel crystals.
The preparation method of the invention introduces the magnesia-alumina spinel as a main crystal phase by adjusting the formula of the wear-resistant full-polished glaze and/or the wear-resistant printing glaze, and because the magnesia-alumina spinel has stable chemical properties and high melting point, only a small amount of the magnesia-alumina spinel can participate in reaction and dissolution in the firing process, but the dissolved part can be separated out again in the form of crystals in the cooling process, so that a large amount of uniformly distributed magnesia-alumina spinel crystals exist on the glaze surface. In the technical scheme of the invention, the hardness of the magnesium aluminate spinel is higher than that of a celsian system and a strontium feldspar system, and the crystal quantity of the magnesium aluminate spinel is also higher than that of the celsian system and the strontium feldspar system, so that the ceramic tile with high wear resistance and full-glazed effect can be obtained.
The initial melting temperature of the wear-resistant full-polished glaze can be 1050-1100 ℃, and the initial melting temperature of the wear-resistant printing glaze can be 1110-1150 ℃. The initial melting temperature of the wear-resistant full-polished glaze is preferably 20-50 ℃ lower than that of the wear-resistant printing glaze, so that the flatness of the fired glaze and the quality of the polished glaze can be ensured.
The invention adopts a gradient glazing process, wherein the gradient and the gradient refer to the process from wear-resistant full-polishing glaze to wear-resistant printing glaze, wherein the content of magnesia-alumina spinel is gradually increased, the content of alkaline earth metal is gradually reduced, and the components of glaze are gradually changed. Because the wear-resistant printing glaze has less glazing amount, a thin wear-resistant protective layer is arranged on the glaze surface after firing and polishing, the influence of the thin wear-resistant protective layer on color development and transparency is less, and meanwhile, the protective layer has very high hardness, so that the hardness and wear resistance of the glaze surface can be well improved. Therefore, the glaze surface after polishing has good wear resistance and hardness while ensuring the transparency and color development of the glaze surface. Preferably, the content of magnesium aluminate spinel in the wear-resistant printing glaze is 10-45% higher than that of the wear-resistant full-polished glaze, and the content of alkaline earth metal oxide in the wear-resistant printing glaze is 4-15% lower than that of the wear-resistant full-polished glaze.
The wear resistance test method is to carry out the test according to GB/T3810.6-2016; the hardness was measured using a Mohs hardness pen and a microhardness tester. The fully polished glazed ceramic tile prepared by the method has the characteristics of good transparency, high hardness and excellent wear resistance. For example, the Mohs hardness of the product after polishing can reach 6 grades, the Vickers hardness can reach 1026MPa, and the product can resist 12000 turns of wear.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) Dry pressing the blank powder by a press to form a blank;
(2) drying the blank for 1-1.5 h, wherein the water content of the dried blank is 0.3-0.5 wt%;
(3) spraying surface glaze on the surface of the blank body, wherein the specific gravity of the surface glaze is 1.40-1.45 g/cm3The glazing amount is 400-550 g/m2；
(4) Printing a pattern on the surface of the blank sprayed with the glaze by ink jet;
(5) spraying wear-resistant printing glaze on the surface of the blank after the pattern is printed by ink jet; the chemical composition of the wear-resistant printing glaze comprises: by mass percent, SiO2：30～45％、Al2O3：35～55％、Fe2O3：0.1～0.5％、TiO2：0.1～0.5％、CaO：0.1～2.0％、MgO：12.0～20.0％、K2O：2.0～4.0％、Na2O：0.1～1.0％、SrO：0.5～1.5％、B2O3: 0.5-1.5%, loss on ignition: 1.0-3.0%; the specific gravity of the wear-resistant printing glaze is 1.83-1.88 g/cm3The glazing amount is 350-500 g/m2；
(6) Drying the blank body printed with the wear-resistant printing glaze at the drying temperature of 100-150 ℃, and controlling the water content within 0.9 wt% after drying;
(7) and sintering the dried green body at the maximum sintering temperature of 1220 ℃ for 60 minutes in a sintering period.
(8) Polishing, edging and grading;
(9) and (5) packaging and warehousing.
According to the scheme, the Mohs hardness of the brick surface reaches 6-6.5 grades, the Vickers hardness can reach 1026MPa, the brick is wear-resistant and 12000-turn, and the antifouling property is good.
Example 2
(1) Dry pressing the blank powder by a press to form a blank;
(2) drying the blank for 1-1.5 h, wherein the water content of the dried blank is 0.3-0.5 wt%;
(3) spraying surface glaze on the surface of the blank body, wherein the specific gravity of the surface glaze is 1.40-1.45 g/cm3The glazing amount is 400-550 g/m2；
(4) Printing a pattern on the surface of the blank sprayed with the glaze by ink jet;
(5) spraying wear-resistant full-polished glaze on the surface of the blank after the pattern is printed by ink jet; the wear-resistant full-polished glaze comprises the following chemical components: by mass percent, SiO2：40.0～50.0％、Al2O3：18.0～35.0％、Fe2O3：0.1～0.5％、TiO2：0.1～0.5％、CaO：4.0～8.0％、MgO：5.0～10.0％、K2O：2.0～4.0％、Na2O: 0.5-2.0%, ZnO: 2.0 to 10.0%, BaO: 5.0-10.0%, loss on ignition: 5.0-8.0%; the specific gravity of the wear-resistant full-polished glaze is 1.80-1.88 g/cm3The glazing amount is 450-600 g/m2；
(6) Using 100-mesh thickened secondary silk-screen printing wear-resistant printing glaze on the surface of the blank after the wear-resistant full-polishing glaze is sprayed; the chemical composition of the wear-resistant printing glaze comprises: by mass percent, SiO2：30～45％、Al2O3：35～55％、Fe2O3：0.1～0.5％、TiO2：0.1～0.5％、CaO：0.1～2.0％、MgO：12.0～20.0％、K2O：2.0～4.0％、Na2O：0.1～1.0％、SrO：0.5～1.5％、B2O3: 0.5-1.5%, loss on ignition: 1.0-3.0%; the specific gravity of the wear-resistant printing glaze is 1.40-1.50 g/cm3The glazing amount is 100-180 g/m2；
(7) Drying the blank body printed with the wear-resistant printing glaze at the drying temperature of 100-150 ℃, and controlling the water content within 0.9 wt% after drying;
(8) and sintering the dried green body at the maximum sintering temperature of 1220 ℃ for 60 minutes in a sintering period.
(9) Polishing, edging and grading;
(10) and (6) packaging and warehousing.
The magnesia-alumina spinel abrasion-resistant fully-glazed ceramic tile prepared in the example 2 has good glaze transparency and good color development. In addition, the fully-glazed ceramic tile prepared by the embodiment has high hardness (Mohs hardness is 6-6.5), Vickers hardness can reach 1004MPa, and wear resistance is 12000-grade at 4. The wear-resistant full-polished glaze contains magnesia-alumina spinel which is lower than that of the wear-resistant printing glaze, and the flux content is higher than that of the wear-resistant printing glaze, so that the wear-resistant full-polished glaze has better penetrating feeling and color development compared with the drenched wear-resistant printing glaze.
Comparative example 1
(1) Dry pressing the blank powder by a press to form a blank;
(2) drying the blank for 1-1.5 h, wherein the water content of the dried blank is 0.3-0.5 wt%;
(3) spraying surface glaze on the surface of the blank body, wherein the specific gravity of the surface glaze is 1.40-1.45 g/cm3The glazing amount is 400-550 g/m2；
(4) Printing a pattern on the surface of the blank sprayed with the glaze by ink jet;
(5) spraying wear-resistant printing glaze on the surface of the blank after the pattern is printed by ink jet; the chemical composition of the wear-resistant printing glaze comprises: by mass percent, SiO2：40～50％、Al2O3：25～35％、Fe2O3：0.1～0.5％、TiO2：0.1～0.5％、CaO：0.1～2.0％、MgO：6.0～8.0％、K2O：3.5～4.5％、Na2O: 2.0-3.0%, loss on ignition: 1.0-3.0%; the wear-resistant printing glaze comprises the following raw materials: 24% of magnesium aluminate spinel, 6% of kaolin, 40% of potassium feldspar, 10% of calcined talc, 15% of albite and 5% of zinc oxide; the specific gravity of the wear-resistant printing glaze is 1.83-1.88 g/cm3The glazing amount is 350-500 g/m2；
(6) Drying the blank body printed with the wear-resistant printing glaze at the drying temperature of 100-150 ℃, and controlling the water content within 0.9 wt% after drying;
(7) and sintering the dried green body at the maximum sintering temperature of 1220 ℃ for 60 minutes in a sintering period.
(8) Polishing, edging and grading;
(9) and (6) packaging and warehousing.
Although the wear-resistant printing glaze of comparative example 1 uses magnesium aluminate spinel as one of the raw materials, the content of alkali metal oxide and alkaline earth metal oxide in the glaze exceeds the range defined by the wear-resistant printing glaze of the invention (2-5% of alkali metal oxide and 10.0-24% of alkaline earth metal oxide). In particular, Na in the abrasion-resistant printing glaze of comparative example 12The O content is too high, obviously exceeding 1%. The above factors are combined with the Mohs hardness of 5 grade and the abrasion resistance of 4 grade 12000 r of the polished product of the comparative example 1.
Comparative example 2
Essentially the same as example 1, except that: the wear-resistant printing glaze comprises the following raw materials: according to mass percentage, corundum: 10-15% of kaolin: 5-15% of quartz: 5-15%, wollastonite: 15-25%, calcined talc: 3-8% of potassium feldspar: 10-20%, albite: 5-10%, 3-8% of zinc oxide and 5-15% of barium carbonate. All the raw materials of the wear-resistant printing glaze are mixed and ball-milled until the fineness is 325 meshes and the screen residue is 0.6-0.8 wt%, thus obtaining the wear-resistant printing glaze. The specific gravity of the wear-resistant printing glaze is 1.80-1.88 g/cm3The glazing amount is 450-600 g/m2。
The corundum system is adopted in the comparative example 2, although the abrasion resistance can reach 12000 r, the Mohs hardness after polishing is 5.5-6 grade, which is obviously lower than that of the corundum polishing agent.
Comparative example 3
Essentially the same as example 1, except that: the wear-resistant printing glaze comprises the following raw materials: by mass percentage, quartz: 20-30% and nepheline: 70-80%. All the raw materials of the wear-resistant printing glaze are mixed and then ball-milled until the fineness is 325 meshes and the screen residue is 0.6-0.8 wt%, and the wear-resistant printing glaze is obtained. The specific gravity of the wear-resistant full-polished glaze is 1.80-1.88g/cm3The glazing amount is 450-600 g/m2。
The wear-resistant printing glaze of the comparative example 3 has a larger difference of expansion coefficient relative to the overglaze and the blank body due to the higher content of free quartz in the glaze material, and has the effect of crack glaze. This is obviously not beneficial to improving the Mohs hardness and the wear resistance of the glaze.

Claims (6)

1. The magnesia-alumina spinel wear-resistant printing glaze for the magnesia-alumina spinel wear-resistant full-glazed ceramic tile is characterized by comprising the following raw materials: the mass percentage of the electric melting magnesia-alumina spinel is as follows: 35-55%, burnt talc: 15-25% of potassium feldspar: 15-25% of high-boron strontium frit and 5-15% of high-boron strontium frit; the chemical composition of the high-boron strontium frit comprises: by mass percent, SiO2：50.0～60.0%、Al2O3：15.0～20.0%、CaO：3.0～5.0%、MgO：3.0～5.0%、SrO：8.0～12.0%、B2O3: 5.0-10.0%; the magnesium aluminate spinel wear-resistant printing glaze comprises the following chemical components: by mass percent, SiO2：30～45%、Al2O3: 35-55%, 2-5% of alkali metal oxide and 10.0-24% of alkaline earth metal oxide; the sintered brick surface phase of the magnesia-alumina spinel wear-resistant full-glazed ceramic brick comprises the following components: the mass percentage of the magnesium aluminate spinel phase is 25 percent to 55 percent and the mass percentage of the amorphous phase is 10 percent to 30 percent.
2. The magnesia alumina spinel wear-resistant printing glaze according to claim 1, wherein the magnesia alumina spinel wear-resistant printing glaze contains Na2The content of O is controlled within 1 wt%.
3. The magnesium aluminate spinel wear-resistant printing glaze according to claim 1, wherein the magnesium aluminate spinel wear-resistant printing glaze is applied by glaze pouring or glaze spraying; when the glaze is sprayed, the specific gravity of the wear-resistant printing glaze is 1.83-1.88 g/cm3The glazing amount is 350-500 g/m2。
4. The method of claim 1The magnesia-alumina spinel wear-resistant printing glaze is characterized in that the application mode of the magnesia-alumina spinel wear-resistant printing glaze is screen printing; the specific gravity of the wear-resistant printing glaze in the silk-screen printing is 1.40-1.50 g/cm3The glazing amount is 100-180 g/m2。
5. The magnesia-alumina spinel wear-resistant printing glaze according to claim 1, wherein the magnesia-alumina spinel wear-resistant printing glaze is applied on the surface of a green brick, and then the green brick is sintered and polished to obtain the magnesia-alumina spinel wear-resistant full-glazed ceramic tile.
6. The preparation method of the magnesia-alumina spinel wear-resistant printing glaze according to claim 1, wherein the raw materials of the magnesia-alumina spinel wear-resistant printing glaze with the formula amount are weighed, crushed and sieved to obtain granular raw materials; mixing the particle raw materials with water and then ball-milling until the particle diameter of the slurry is D90≤10μm。
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