CN117049890B - Zirconium silicate-based composite ultra-white overglaze, ceramic tile and preparation method thereof - Google Patents

Zirconium silicate-based composite ultra-white overglaze, ceramic tile and preparation method thereof Download PDF

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CN117049890B
CN117049890B CN202311319932.8A CN202311319932A CN117049890B CN 117049890 B CN117049890 B CN 117049890B CN 202311319932 A CN202311319932 A CN 202311319932A CN 117049890 B CN117049890 B CN 117049890B
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composite
overglaze
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zirconium silicate
temperature
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CN117049890A (en
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南顺芝
南嘉栋
况学成
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Guangdong Dajiaolu New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • 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
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/04—Opaque glass, glaze or enamel
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

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

Abstract

The invention belongs to the field of ceramic building, and discloses a zirconium silicate-based composite ultrawhite overglaze, a ceramic tile and a preparation method thereof. The composite ultrawhite overglaze comprises the following raw material components in parts by weight: 5-10 parts of kaolin, 10-15 parts of quartz sand, 25-35 parts of petalite and 40-60 parts of whitening agent; the whitening agent comprises mesoporous silica and composite opacified frit powder, and the composite opacified frit powder is embedded in the pores of the mesoporous silica; the chemical composition of the composite opacified frit powder comprises the following components in percentage by weight: siO (SiO) 2 55‑67%，Al 2 O 3 3‑6%，CaO8‑14%，MgO1‑3%，K 2 O0.5‑2%，Na 2 O1‑4%，P 2 O 5 0.5‑2%，ZrO 2 2‑4%，TiO 2 12‑18%，B 2 O 3 0.5-2%. The whiteness of the composite ultra-white overglaze can reach more than 80 degrees, and the composite ultra-white overglaze has a wider use temperature range.

Description

Zirconium silicate-based composite ultra-white overglaze, ceramic tile and preparation method thereof
Technical Field
The invention belongs to the technical field of building ceramics, and particularly relates to a zirconium silicate-based composite ultra-white overglaze, a ceramic tile and a preparation method thereof.
Background
The glaze is a layer of glassy substance applied to the surface of the ceramic body, and the glazing aims at improving the surface property of the body, improving the service performance of the product and increasing the aesthetic feeling of the product. With the rapid development of the building sanitary ceramic industry and the daily ceramic industry, high-grade raw materials are increasingly exhausted, and a large amount of inferior raw materials or industrial waste residues are widely used in ceramic blanks. Therefore, the opaque overglaze with high opaqueness and strong covering power is generally used to improve the quality of the glaze and the added value of the product.
At present, the opacifying glaze is generally realized by adding a proper amount of opacifying agent, and the opacifying mechanism is to utilize the infusibility, recrystallization or phase separation of the opacifying agent to scatter natural light irradiated to the surface of the opacifying glaze, so as to form an opacifying effect and achieve the purpose of covering the natural color of the blank. The opacifiers commonly used in glazes are mainly tin dioxide, titanium dioxide, zirconium silicate (introduced by zircon sand), antimony compounds, etc., of which zircon sand is the most widely used. Zircon sand (refractive index is 1.9-2.0) has excellent opacifying effect in the glaze layer, and has important effects of improving the thermal stability, whiteness and wear resistance of ceramic products, widening the firing temperature range of the glaze, and the like. However, a small amount of radioactive substances in zircon sand are difficult to separate, the associated ore monazite has radioactivity, and the mineral also contains a very small amount of radioactive decay bodies such as thorium and the like, so that certain radioactive hazard can be generated to human bodies, and the raw material cost of the zircon sand is high. Titanium dioxide comprises two crystal forms, rutile and anatase, wherein the refractive index of the rutile is 2.76, the anatase is 2.52, the titanium dioxide has the highest refractive index in the glaze opacifier from the refractive index, the titanium dioxide is a strong opacifier, crystal grains can be separated out in the glaze, and molten drops can be formed, and the price of the titanium dioxide is much lower than that of tin dioxide and zirconium silicate. Titanium dioxide is an unstable opacifier, and the opacifying effect is greatly influenced by the chemical composition of the glaze, the firing temperature and the kiln atmosphere. At present, the opacified glaze using titanium dioxide as an opacifier has narrow ubiquitous firing temperature range, and anatase titanium dioxide is separated out from the glaze only at a lower firing temperature (below 900 ℃), so that a better opacifying effect can be achieved; at a higher firing temperature (above 900 ℃), rutile titanium dioxide is precipitated in the glaze, and the white yellowing and the poor visual effect of the glaze surface occur.
Therefore, there is a need to develop a ceramic opacifying overglaze, which can realize low cost, high whiteness, wide firing range and good color development effect on the glaze surface on the premise of ensuring the quality of the glaze surface.
Disclosure of Invention
The invention provides a composite ultra-white overglaze (whiteness is more than 80 degrees) based on zirconium silicate, a ceramic tile and a preparation method thereof, which are used for solving one or more technical problems in the prior art and at least providing a beneficial selection or creation condition.
In order to solve the technical problems, the first aspect of the invention provides a zirconium silicate-based composite ultrawhite overglaze, which comprises the following raw materials in parts by weight:
5-10 parts of kaolin, wherein the kaolin comprises,
10-15 parts of quartz sand,
25-35 parts of petalite,
40-60 parts of a brightening agent;
the whitening agent comprises mesoporous silica and composite opacified frit powder, and the composite opacified frit powder is embedded in the pores of the mesoporous silica;
the chemical composition of the composite opacifying frit powder comprises the following components in percentage by weight: siO (SiO) 2 55-67%，Al 2 O 3 3-6%，CaO8-14%，MgO1-3%，K 2 O0.5-2%，Na 2 O1-4%，P 2 O 5 0.5-2%，ZrO 2 2-4%，TiO 2 12-18%，B 2 O 3 0.5-2%。
Specifically, the composite opacifying frit is prepared by mixing CaO-TiO 2 -SiO 2 R with larger practical crystallization area is selected on the basis of a ternary system 2 O（K 2 O，Na 2 O）-RO（CaO，MgO）-TiO 2 -SiO 2 -Al 2 O 3 -P 2 O 5 -B 2 O 3 A multi-element system. With CaO and TiO 2 、SiO 2 Is used as a main crystallization agent to obtain stable titanium sphene grains with high refractive index (refractive index is 1.95), thereby reducing the transmittance of light in the glaze (the refractive index of the glass glaze is about 1.5) and improving the whiteness of the glaze surface. Meanwhile, a certain amount of MgO is introduced, and partial MgO is used for replacing CaO, and mixed crystallization is carried out, so that the use temperature range of the glaze is widened.
Meanwhile, in order to prevent titanium sphene in the composite opacified frit powder from being converted into rutile type titanium dioxide in the process of secondary glaze firing due to titanium dioxide generated by high-temperature (about 1120 ℃) decomposition and partial free titanium dioxide, the phenomenon of yellowing of the glaze surface is caused. According to the invention, the composite opacified frit is embedded in the pores of the mesoporous silica in advance in a solvent swelling mode, and the mesoporous silica with high-temperature stability is utilized to carry out embedded coating on the frit, so that the frit can keep the original function and avoid the transformation of rutile type titanium dioxide, thereby damaging the stability and the basic performance of the frit. Compared with the traditional solid phase mixed coating, the embedded coating of the mesoporous silica has higher coating rate and better frit stability, and the coated silica and the ceramic glaze are integrated at high temperature, so that the performance and the glaze quality of the glaze are not negatively affected. In addition, a certain amount of petalite is added into the glaze material to replace the traditional potash-sodium feldspar flux raw material, so that the sintering temperature is reduced, and meanwhile, the expansion coefficient of the glaze material is reduced. More importantly, the petalite is also beneficial to improving the color of the glaze, and further improving the whiteness of the glaze.
The composite opacifying frit of the invention is also added with a certain amount of K 2 O，Na 2 O，B 2 O 3 、P 2 O 5 And ZrO(s) 2 So as to form a second phase with different refractive index from the basic glaze in the glaze, promote the devitrification of the glaze surface and improve the whiteness of the glaze surface. Wherein: alkali metal ion as R + (including K + And Na (Na) + ) As network modifier for balancing charges, al in glaze melt 3+ Tend to formRadicals, adjacent R + Is attracted by an excess of negatively charged aluminoxy groups to form +.>R complex, such complex and +.>The aluminum-silicon composite material has quite good compatibility, namely, the aluminum-silicon composite material and the aluminum-silicon composite material can be well combined into an aluminum-silicon mixed group, and alkali metal ions are enriched in the aluminum-silicon mixed group to form a continuous matrix phase, so that the phase separation of a glaze melt is promoted. B (B) 2 O 3 As a strong fluxing agent, the method is not only beneficial to reducing the melting temperature of the glaze and expanding the temperature range of glaze firing, thereby improving the technological performance of the glaze; and proper amount of B 2 O 3 The viscosity-temperature characteristics of the glaze melt are improved, the speed of improving the viscosity of the glaze in the cooling process is slowed down, and the development of a phase-splitting structure is promoted. P (P) 2 O 5 In the high-silicon low-aluminum multi-component system of the present invention, on the one hand, the glass former P 2 O 5 And SiO 2 Ion field strength difference [ P ] 5+ =2.1，Si 4+ =1.57］，P 5+ The attraction to oxygen atoms is greater than that of Si 4+ Thus P 5+ The oxygen atoms of the alkali metal or alkaline earth metal oxide are more easily abstracted to obtain the optimal coordination number, so that a phosphorus-oxygen polymer is formed, and a phase-separated structure is formed. On the other hand, P 2 O 5 The surface energy of the phase-separated liquid drop is very small, and the free enthalpy of formation of the phase-separated liquid drop can be reduced in the glaze melt, so that the nucleation growth of the phase-separated liquid drop is promoted. At the same time, the invention controls K 2 O，Na 2 O，B 2 O 3 And P 2 O 5 The dosage relation and the firing system of the glass ceramic material lead to the distribution of a certain amount of spherical liquid drops in the glaze melt, and lead the size of the spherical liquid drops to be similar to the wavelength of visible light, thereby generating Rayleigh scattering and further improving the whiteness of the glaze. ZrO (ZrO) 2 By zirconium silicate incorporation, due to Zr 4+ The ionic potential of the zirconium silicate is larger, and the zirconium silicate has wide immiscible area in the multi-element system of the invention, is favorable for promoting phase separation, and leads the zirconium silicate to be totally made of ZrSiO during the glaze firing process 4 The crystal is separated out, so that the opacifying effect of the glaze can be greatly improved under the condition of adding a small amount of zirconium silicate.
As a further improvement of the above scheme, in the chemical composition of the composite opacifying frit powder, the Na 2 O and K 2 The mass ratio of O is (1.5-2): 1.
in particular, it was found that Na 2 The phase separation capacity of the glaze of O is larger than K 2 The glaze phase separation capability of O, and because the alkali metal oxides are network modifiers, the metal ions of the alkali metal oxides easily weaken Si-O bond force or break Si-O bond, so that the thermal expansion coefficient of the glaze is increased, R is 2 O is sensitive to the expansion coefficient of the glaze, so Na needs to be strictly controlled 2 O and K 2 Relationship of the amount of O used.
As a further improvement of the scheme, the pore diameter of the mesoporous silica is 20-50nm, and the particle diameter of the composite opacifying frit powder is 10-30nm.
Preferably, the particle size of the composite opacifying frit is smaller than the pore size of the mesoporous silica, so as to facilitate embedding of the composite opacifying frit powder into the pores of the silica.
As a further improvement of the above scheme, the mass ratio of the mesoporous silica to the composite opacifying frit powder is (0.2-0.4): 1.
specifically, mesoporous silica is used as a raw material for glaze on one hand and as a cladding material of the composite opacified emulsion temperature frit powder on the other hand, so that not only is the mechanical property of the glaze improved, but also the stability of the composite opacified frit is improved, the use temperature range of the glaze is enlarged, and yellowing of the glaze is prevented.
Preferably, the petalite comprises the following chemical compositions in percentage by weight: siO (SiO) 2 70-80%，Al 2 O 3 10-20%，K 2 O0.5-1%，Na 2 O0.5-1%，CaO1-2%，MgO1-2%，Fe 2 O 3 0.05-0.1%，Li 2 O3-5%. The petalite mainly comprises SiO 2 、Al 2 O 3 And Li (lithium) 2 O and a small amount of CaO are contained, and mullite (Al 6 O 13 Si 2 ) Lithium feldspar (liaalsi) 3 O 8 ) Anorthite (CaAl) 2 Si 2 O 8 ) These aluminosilicate phases help to maintain the mechanical properties of the product and reduce sintering temperatures while improving the color of the glaze.
The second aspect of the invention provides a preparation method of the composite ultrawhite overglaze based on zirconium silicate, which comprises the following steps:
(1) Mixing the raw materials for preparing the composite opacified frit powder, pouring the mixture into water for quenching after melting to obtain frit particles; grinding the frit particles to obtain composite opacified frit powder;
(2) Adding a dispersing agent and a silane coupling agent into a solvent to obtain a mixed solution; then dividing the mixed solution into two parts, and respectively adding the composite opacifying frit powder and mesoporous silica into the two parts to disperse to obtain a suspension A and a suspension B; mixing the suspension A and the suspension B, heating and stirring; cooling to room temperature, centrifuging, washing, and drying to obtain whitening agent;
(3) And mixing the whitening agent with other raw materials for preparing the zirconium silicate-based composite ultrawhite overglaze, and performing wet ball milling to obtain the composite ultrawhite overglaze.
Preferably, in the step (1), the melting temperature is 1400-1500 ℃ and the melting time is 6-8 hours.
Preferably, in the step (2), the dispersant is at least one selected from anionic dispersants, phosphate dispersants, and polyacid homopolymer dispersants. These dispersants all help to prevent agglomeration and sedimentation of the inorganic nano-powder.
Further preferably, the dispersant is at least one selected from the group consisting of dispersant 5040, dispersant BYK, and dispersant Tamol.
Preferably, in step (2), the silane coupling agent is selected from vinyltriethoxysilane.
Preferably, in the step (2), the solvent is at least one selected from ethylene glycol, dipropylene glycol methyl ether acetate, toluene and xylene. The solvents are low-polarity solvents, and the solvents dissolved with the silane coupling agent are beneficial to the penetration of the frit powder into the pores of the porous silica, the swelling increase of the pore diameter of the silica and the further increase of the penetration probability of the frit powder into the porous silica.
Preferably, in the step (2), the concentration of the silane coupling agent in the mixed solution is 1-3wt% and the concentration of the dispersing agent is 0.5-1wt%.
Preferably, in the step (2), the concentration of the compound opacifying frit in the mixed solution is 5-10mg/mL.
Preferably, in the step (2), the concentration of the mesoporous silica and the mixed solution is 1-5mg/mL.
Preferably, in the step (2), the heating temperature is 60-100 ℃;
preferably, in step (2), the stirring is at a speed of 400-1500 rpm for 2-4 hours.
Preferably, in the step (2), the centrifugation is performed at 400-6000 rpm for 5-10 minutes.
Preferably, in step (2), the washing is performed 1 to 5 times with the solvent.
The third aspect of the invention provides a zirconium silicate-based composite ultra-white ceramic tile, which comprises a green body and an ultra-white surface glaze layer arranged on the upper surface of the green body, wherein the ultra-white surface glaze layer is formed by firing the zirconium silicate-based composite ultra-white surface glaze.
As a further improvement of the scheme, the thickness of the ultrawhite overglaze layer is 0.15-0.2mm. The ultra-white surface glaze layer contains a large number of microcrystals and liquid drops, so that the thickness of the glaze layer is controlled, the transmittance of light in the glaze is reduced, and the whiteness of the glaze surface is improved.
As a further improvement of the scheme, the raw material components of the green body comprise, by weight: 15-20 parts of stone powder, 45-55 parts of medium-temperature sand, 3-8 parts of high-temperature sand, 2-4 parts of talcum and 20-28 parts of clay. The expansion coefficient of the blank body is similar to that of the ultra-white surface glaze layer, and the adaptability is good.
The fourth aspect of the invention provides a preparation method of the composite ultra-white ceramic tile based on zirconium silicate, which comprises the following steps:
1) Preparing the ultra-white overglaze according to the preparation method of the composite ultra-white overglaze based on zirconium silicate;
2) And applying the super Bai Mianyou on a blank body to form a super white surface glaze layer, and drying and sintering to obtain the composite super white ceramic tile based on zirconium silicate.
As a further improvement of the above scheme, in step 2), the firing temperature schedule is: firstly, raising the temperature to 700-800 ℃ at a heating rate of 12-15 ℃/min, and preserving the heat for 8-10min; then raising the temperature to 900-1000 ℃ at a heating rate of 12-15 ℃/min, and preserving the heat for 8-10min; then the temperature is raised to 1100-1250 ℃ at the heating rate of 8-10 ℃/min, the temperature is kept for 8-10min, and finally the kiln is taken out for natural cooling.
Specifically, for a frit glaze, the firing process of the glaze can be regarded as a secondary heat treatment process of glass. During this process, the particles migrate within the glaze and the glaze in the region of the metastable immiscible phase composition undergoes one or more phase separations, the structure of which is dependent to a considerable extent on its thermal history due to structural relaxation. The final structure is the result of the combined action of the kinetic factors determined by the corresponding glaze firing regime and the thermodynamic factors determined by the chemical composition of the glaze. In the process of heating, the invention respectively carries out heat preservation for a certain time at the temperature (700-800 ℃) of phase-splitting crystallization and the temperature (900-1000 ℃) of liquid drop and crystal growth, adopts a natural cooling mode to fully precipitate the crystal, and simultaneously controls the sizes of the liquid drop and the crystal through a temperature system to jointly act in a plurality of opacifying modes, thereby obtaining the optimal opacifying effect.
Compared with the prior art, the technical scheme of the invention has at least the following technical effects or advantages:
(1) The composite super white overglaze is prepared by mixing CaO-TiO 2 -SiO 2 Based on the ternary system, titanium sphene is used as the main opacifying agent, and a certain amount of K is added simultaneously 2 O，Na 2 O，B 2 O 3 、P 2 O 5 And ZrO(s) 2 Forming a multi-element system to make zirconium silicate, titanium sphene and second phase micro-liquid drop be separated out from glaze melt. Zirconium silicate and titanium sphene with high refractive index are fully utilized to reduce the transmittance of light in the glaze; and enabling second-phase liquid drops with different refractive indexes from the basic glaze to exist in the glaze, so that the glaze surface is devitrified; in addition, the mixed crystallization of MgO and CaO and the improvement effect of the glaze color of petalite jointly improve the whiteness of the glaze.
(2) According to the invention, the composite opacified frit powder is embedded in the pores of mesoporous silicon dioxide in advance in a solvent swelling manner, and the silicon dioxide with high-temperature stability is used for coating the frit powder, so that the whiteness of the glaze surface is improved, the use temperature range of the glaze is further improved, the precipitation of rutile type titanium dioxide is effectively avoided, the titanium opacified frit cannot turn yellow at a higher sintering temperature, and the use range of the titanium opacified frit is greatly widened.
(3) When the composite ultra-white overglaze based on zirconium silicate is applied to ceramic bricks, the whiteness of the glaze surface can reach more than 80 degrees under the premise of realizing low-content zirconium silicate, the glaze surface can be kept not to be yellow in a wider use temperature range (1100-1250 ℃), and the quality of the glaze surface is good.
Detailed Description
The present invention is described in detail below with reference to examples to facilitate understanding of the present invention by those skilled in the art. It is specifically pointed out that the examples are given solely for the purpose of illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and variations of the invention will be within the scope of the invention, as described above, will become apparent to those skilled in the art. Meanwhile, the raw materials mentioned below are not specified, and are all commercial products; the process steps or preparation methods not mentioned in detail are those known to the person skilled in the art.
The green body used in the examples and the comparative examples of the present invention comprises the following raw materials in parts by weight: 18 parts of stone powder, 50 parts of medium-temperature sand, 5 parts of high-temperature sand, 3 parts of talcum and 24 parts of clay.
Example 1
The composite ultra-white overglaze based on zirconium silicate comprises the following raw material components in parts by weight:
5 parts of kaolin, which is used for preparing the composite material,
10 parts of quartz sand, and the balance of the quartz sand,
25 parts of petalite,
40 parts of whitening agent;
wherein: the whitening agent comprises mesoporous silica (with the aperture of 20-50 nm) and composite opacified frit powder (with the particle diameter of 10-30 nm), wherein the composite opacified frit powder is embedded in the pores of the mesoporous silica; and the mass ratio of the mesoporous silica to the composite opacified frit powder is 0.4:1.
the composite opacifying frit powder comprises the following chemical components in percentage by weight: siO (SiO) 2 58%，Al 2 O 3 6%，CaO10%，MgO2%，K 2 O1.5%，Na 2 O3%，P 2 O 5 1%，ZrO 2 2%，TiO 2 15%，B 2 O 3 1.5%。
The petalite comprises the following chemical compositions in percentage by weight: siO (SiO) 2 75%，Al 2 O 3 16%，K 2 O0.5%，Na 2 O0.5%，CaO1.5%，MgO1.5%，Fe 2 O 3 0.05%，Li 2 O4.95%。
A zirconium silicate based composite ultra white ceramic tile comprising the steps of:
(1) Mixing the raw materials for preparing the composite opacified frit powder according to the raw material proportion, melting for 8 hours at 1450 ℃, pouring into water, and quenching to obtain frit particles; grinding the frit particles to obtain opacified frit powder with the particle size of 10-30 nm;
(2) Adding a dispersing agent 5040 and vinyl triethoxysilane into a solvent glycol to obtain a mixed solution (the concentration of a silane coupling agent in the mixed solution is 2wt%, and the concentration of the dispersing agent is 0.5 wt%); then dividing the mixed solution into two parts, and respectively adding the opacified frit powder (the concentration in the mixed solution is 5 mg/mL) and the mesoporous silica (the concentration in the mixed solution is 2 mg/mL) prepared in the step (1) into the two parts to disperse to obtain a suspension A and a suspension B; and mixing the suspension A and the suspension B according to the volume ratio of 1:1, heating to 70 ℃ and stirring at 1000 revolutions per minute for 3 hours; cooling to room temperature, centrifuging at 4000 rpm for 8min, washing with ethylene glycol for 3 times, and drying to obtain whitening agent;
(3) Mixing the whitening agent prepared in the step (2) with other raw materials for preparing the composite ultrawhite overglaze according to a proportion, adding water for ball milling (the mass ratio of the material to the water is 100:40), and obtaining the composite ultrawhite overglaze with the fineness of 325 meshes and 0.5 weight percent of screen residue;
(4) And (3) spraying the composite ultrawhite overglaze prepared in the step (3) on the green body to form an ultrawhite overglaze layer, and drying and sintering to obtain the composite ultrawhite ceramic tile of the embodiment, wherein the thickness of the ultrawhite overglaze layer is 0.15mm.
The firing temperature system is as follows: firstly, raising the temperature to 750 ℃ at a heating rate of 12 ℃/min, and preserving the temperature for 8min; then the temperature is increased to 950 ℃ at a heating rate of 12 ℃/min, and the temperature is kept for 8min; then the temperature is raised to 1160 ℃ at the heating rate of 10 ℃/min, the heat is preserved for 8min, and finally the kiln is taken out for natural cooling.
Example 2
The composite ultra-white overglaze based on zirconium silicate comprises the following raw material components in parts by weight:
8 parts of kaolin, which is used for preparing the composite material,
12 parts of quartz sand and the balance of the quartz sand,
30 parts of petalite,
50 parts of a whitening agent;
wherein: the whitening agent comprises mesoporous silica (with the aperture of 20-50 nm) and composite opacified frit powder (with the particle diameter of 10-30 nm), wherein the composite opacified frit powder is embedded in the pores of the mesoporous silica; and the mass ratio of the mesoporous silica to the composite opacified frit powder is 0.3:1.
the composite opacifying frit powder comprises the following chemical components in percentage by weight: siO (SiO) 2 60%，Al 2 O 3 4%，CaO11%，MgO1%，K 2 O1%，Na 2 O2%，P 2 O 5 0.5%，ZrO 2 3%，TiO 2 16%，B 2 O 3 1.5%。
The petalite comprises the following chemical compositions in percentage by weight: siO (SiO) 2 76%，Al 2 O 3 15%，K 2 O1%，Na 2 O0.5%，CaO1%，MgO2%，Fe 2 O 3 0.05%，Li 2 O4.45%。
A zirconium silicate based composite ultra white ceramic tile comprising the steps of:
(1) Mixing the raw materials for preparing the composite opacified frit powder according to the raw material proportion, melting for 8 hours at 1450 ℃, pouring into water, and quenching to obtain frit particles; grinding the frit particles to obtain opacified frit powder with the particle size of 10-30 nm;
(2) Adding a dispersing agent BYK and vinyl triethoxysilane into a solvent dipropylene glycol methyl ether acetate to obtain a mixed solution (in the mixed solution, the concentration of a silane coupling agent is 1wt%, and the concentration of the dispersing agent is 1 wt%); then dividing the mixed solution into two parts, and respectively adding the opacified frit powder (the concentration in the mixed solution is 10 mg/mL) and the mesoporous silica (the concentration in the mixed solution is 3 mg/mL) prepared in the step (1) into the two parts to disperse to obtain a suspension A and a suspension B; and mixing the suspension A and the suspension B according to the volume ratio of 1:1, heating to 80 ℃ and stirring at 1200 revolutions per minute for 3 hours; cooling to room temperature, centrifuging at 3000 rpm for 10min, washing with dipropylene glycol methyl ether acetate for 3 times, and drying to obtain whitening agent;
(3) Mixing the whitening agent prepared in the step (2) with other raw materials for preparing the composite ultrawhite overglaze according to a proportion, adding water for ball milling (the mass ratio of the material to the water is 100:40), and obtaining the composite ultrawhite overglaze with the fineness of 325 meshes and 0.4 weight percent of screen residue;
(4) And (3) spraying the composite ultrawhite overglaze prepared in the step (3) on the green body to form an ultrawhite overglaze layer, and drying and sintering to obtain the composite ultrawhite ceramic tile of the embodiment, wherein the thickness of the ultrawhite overglaze layer is 0.15mm.
The firing temperature system is as follows: firstly, heating to 740 ℃ at a heating rate of 13 ℃/min, and preserving heat for 9min; then the temperature is increased to 930 ℃ at the heating rate of 13 ℃/min, and the temperature is kept for 9min; then the temperature is increased to 1150 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 9min, and finally the kiln is taken out for natural cooling.
Example 3
The composite ultra-white overglaze based on zirconium silicate comprises the following raw material components in parts by weight:
5 parts of kaolin, which is used for preparing the composite material,
10 parts of quartz sand, and the balance of the quartz sand,
35 parts of petalite,
40 parts of whitening agent;
wherein: the whitening agent comprises mesoporous silica (with the aperture of 20-50 nm) and composite opacified frit powder (with the particle diameter of 10-30 nm), wherein the composite opacified frit powder is embedded in the pores of the mesoporous silica; and the mass ratio of the mesoporous silica to the composite opacified frit powder is 0.4:1.
the composite opacifying frit powder comprises the following chemical components in percentage by weight: siO (SiO) 2 62%，Al 2 O 3 3%，CaO12%，MgO2%，K 2 O1%，Na 2 O2%，P 2 O 5 1.5%，ZrO 2 2%，TiO 2 14%，B 2 O 3 0.5%。
The petalite comprises the following chemical compositions in percentage by weight: siO (SiO) 2 78%，Al 2 O 3 12%，K 2 O1%，Na 2 O1%，CaO2%，MgO2%，Fe 2 O 3 0.06%，Li 2 O3.94%。
A zirconium silicate based composite ultra white ceramic tile comprising the steps of:
(1) Mixing the raw materials for preparing the composite opacified frit powder according to the raw material proportion, melting for 8 hours at 1450 ℃, pouring into water, and quenching to obtain frit particles; grinding the frit particles to obtain opacified frit powder with the particle size of 10-30 nm;
(2) Adding a dispersing agent 5040 and vinyl triethoxysilane into a solvent dipropylene glycol methyl ether acetate to obtain a mixed solution (in the mixed solution, the concentration of a silane coupling agent is 2wt%, and the concentration of the dispersing agent is 0.5 wt%); then dividing the mixed solution into two parts, and respectively adding the opacified frit powder (the concentration in the mixed solution is 5 mg/mL) and the mesoporous silica (the concentration in the mixed solution is 2 mg/mL) prepared in the step (1) into the two parts to disperse to obtain a suspension A and a suspension B; and mixing the suspension A and the suspension B according to the volume ratio of 1:1, heating to 80 ℃ and stirring at 800 rpm for 3 hours; cooling to room temperature, centrifuging at 5000 rpm for 6 min, washing with dipropylene glycol methyl ether acetate for 3 times, and drying to obtain whitening agent;
(3) Mixing the whitening agent prepared in the step (2) with other raw materials for preparing the composite ultrawhite overglaze according to a proportion, adding water for ball milling (the mass ratio of the material to the water is 100:40), and obtaining the composite ultrawhite overglaze with the fineness of 325 meshes and 0.5 weight percent of screen residue;
(4) And (3) spraying the composite ultrawhite overglaze prepared in the step (3) on the green body to form an ultrawhite overglaze layer, and drying and sintering to obtain the composite ultrawhite ceramic tile of the embodiment, wherein the thickness of the ultrawhite overglaze layer is 0.15mm.
The firing temperature system is as follows: firstly, raising the temperature to 720 ℃ at a heating rate of 12 ℃/min, and preserving the temperature for 10min; then the temperature is increased to 920 ℃ at the heating rate of 12 ℃/min, and the temperature is kept for 10min; then the temperature is increased to 1120 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 10min, and finally the kiln is taken out for natural cooling.
Example 4
The composite ultra-white overglaze based on zirconium silicate comprises the following raw material components in parts by weight:
10 parts of kaolin, which is used for preparing the composite material,
15 parts of quartz sand,
25 parts of petalite,
60 parts of whitening agent;
wherein: the whitening agent comprises mesoporous silica (with the aperture of 20-50 nm) and composite opacified frit powder (with the particle diameter of 10-30 nm), wherein the composite opacified frit powder is embedded in the pores of the mesoporous silica; and the mass ratio of the mesoporous silica to the composite opacified frit powder is 0.4:1.
the composite opacifying frit powder comprises the following chemical components in percentage by weight: siO (SiO) 2 61%，Al 2 O 3 3%，CaO8%，MgO1%，K 2 O2%，Na 2 O3.5%，P 2 O 5 1%，ZrO 2 4%，TiO 2 16%，B 2 O 3 0.5%。
The petalite comprises the following chemical compositions in percentage by weight: siO (SiO) 2 72%，Al 2 O 3 18%，K 2 O1%，Na 2 O1%，CaO1.5%，MgO2%，Fe 2 O 3 0.06%，Li 2 O4.44%。
A zirconium silicate based composite ultra white ceramic tile comprising the steps of:
(1) Mixing the raw materials for preparing the composite opacified frit powder according to the raw material proportion, melting for 8 hours at 1450 ℃, pouring into water, and quenching to obtain frit particles; grinding the frit particles to obtain opacified frit powder with the particle size of 10-30 nm;
(2) Adding a dispersing agent BYK and vinyl triethoxysilane into solvent toluene to obtain a mixed solution (in the mixed solution, the concentration of a silane coupling agent is 2wt%, and the concentration of the dispersing agent is 1 wt%); then dividing the mixed solution into two parts, and respectively adding the opacified frit powder (the concentration in the mixed solution is 5 mg/mL) and the mesoporous silica (the concentration in the mixed solution is 2 mg/mL) prepared in the step (1) into the two parts to disperse to obtain a suspension A and a suspension B; and mixing the suspension A and the suspension B according to the volume ratio of 1:1, heating to 60 ℃ and stirring at 1500 revolutions per minute for 2 hours; cooling to room temperature, centrifuging at 3000 rpm for 10min, washing with toluene for 3 times, and drying to obtain whitening agent;
(3) Mixing the whitening agent prepared in the step (2) with other raw materials for preparing the composite ultrawhite overglaze according to a proportion, adding water for ball milling (the mass ratio of the material to the water is 100:40), and obtaining the composite ultrawhite overglaze with the fineness of 325 meshes and 03 weight percent of screen residue;
(4) And (3) spraying the composite ultrawhite overglaze prepared in the step (3) on the green body to form an ultrawhite overglaze layer, and drying and sintering to obtain the composite ultrawhite ceramic tile of the embodiment, wherein the thickness of the ultrawhite overglaze layer is 0.15mm.
The firing temperature system is as follows: firstly, raising the temperature to 780 ℃ at a heating rate of 15 ℃/min, and preserving the heat for 10min; then the temperature is increased to 980 ℃ at the heating rate of 15 ℃/min, and the temperature is kept for 10min; then the temperature is increased to 1200 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 10min, and finally the kiln is taken out for natural cooling.
Comparative example 1
Comparative example 1 differs from example 1 only in that: the same amount of feldspar was used in the raw material component of the zirconium silicate-based composite ultrawhite overglaze of comparative example 1 instead of petalite in example 1, and the kinds and addition amounts of other raw materials and the preparation method of the zirconium silicate-based composite ultrawhite ceramic tile were the same as those in example 1.
Comparative example 2
Comparative example 2 differs from example 3 only in that: the raw material components of the zirconium silicate-based composite ultra-white overglaze of comparative example 2 are composite opacified frit powder as a whitening agent, and are not coated by mesoporous silica, and meanwhile, the usage amount of quartz sand is increased, so that SiO in the system is realized 2 The kinds and addition amounts of other raw materials were the same as in example 3, except that the content of the zirconium silicate-based composite ultra-white ceramic tile was not changed.
The composite ultra-white overglaze based on zirconium silicate in comparative example 2 comprises the following raw material components in parts by weight:
5 parts of kaolin, which is used for preparing the composite material,
21.4 parts of quartz sand,
35 parts of petalite,
28.6 parts of composite opacified frit powder.
Comparative example 3
Comparative example 3 differs from example 4 only in that: the raw material components of the zirconium silicate-based composite ultra-white overglaze of comparative example 3 are composite opacified frit powder as a whitening agent, and are not coated by mesoporous silica, and meanwhile, the usage amount of quartz sand is increased, so that SiO in the system is realized 2 The kinds and addition amounts of other raw materials were the same as in example 4, except that the content of the zirconium silicate-based composite ultra-white ceramic tile was not changed.
The composite ultra-white overglaze based on zirconium silicate in comparative example 3 comprises the following raw material components in parts by weight:
10 parts of kaolin, which is used for preparing the composite material,
26.5 parts of quartz sand,
25 parts of petalite,
28.6 parts of composite opacified frit powder.
Comparative example 4
The zirconium silicate-based composite ultrawhite overglaze of comparative example 4 differs from example 4 only in that: the raw material components of the zirconium silicate-based composite ultrawhite overglaze of comparative example 4, in which the whitening agent was mixed in a solid manner, include composite opacifying frit powder, and the kinds and addition amounts of other raw materials were the same as those of example 4.
The preparation method of the zirconium silicate-based composite ultra-white ceramic tile of comparative example 4 differs from example 4 only in that: in the step (2), the mass ratio of the silicon dioxide powder to the opacified frit powder is 0.4:1, mixing, adding a dispersing agent BYK and a solvent toluene, and performing ultrasonic dispersion to obtain a suspension (in the suspension, the concentration of the dispersing agent, the concentration of the silicon dioxide powder and the concentration of the opacifying frit powder are the same as those in the example 4); then placing the suspension into a reaction kettle with the temperature of 200 ℃ and the rotating speed of 300r/min for 2 hours, and drying to obtain a drying material; and calcining the dried material at 900 ℃ for 2 hours to obtain the whitening agent. The remaining preparation steps and process parameters were the same as in example 4.
Comparative example 5
Comparative example 5 differs from example 1 only in that: the chemical composition of the composite opacifying frit powder in the raw material components of the zirconium silicate-based composite ultrawhite overglaze of comparative example 5 does not contain P 2 O 5 And B 2 O 3 And K is 2 O is greater than Na 2 O content by weightThe percentages include: siO (SiO) 2 58%，Al 2 O 3 6%，CaO11.5%，MgO3%，K 2 O3%，Na 2 O1.5%，ZrO 2 2%，TiO 2 15% of other raw materials, and the amounts of other raw materials added, the method for producing the zirconium silicate-based composite ultra-white ceramic tile was the same as in example 1.
Comparative example 6
Comparative example 6 differs from example 1 only in that: in the composite ultra-white ceramic tile based on zirconium silicate of comparative example 6, one-time heating firing is adopted, and the specific firing schedule is as follows: raising the temperature to 1160 ℃ at a heating rate of 12 ℃/min, preserving the heat for 30min, and finally discharging from the kiln for natural cooling.
Performance detection
The composite ultra-white ceramic tile samples based on zirconium silicate prepared in examples 1 to 4 and comparative examples 1 to 6 above were subjected to whiteness and color development performance tests, and the glazed quality of the samples was observed, wherein: the whiteness adopts a digital display whiteness instrument; color development was tested using a color difference meter and its color value was determined by L, a, b, where "L" represents the brightness of the object: 0-100 represents from black to white; "a" represents the red and green color of an object: positive values represent red and negative values represent green; "b" represents the yellow-blue color of the object: positive values represent yellow and negative values represent blue, and the test results are shown in table 1.
Table 1: comparative Table of Properties of samples prepared in examples 1 to 4 and comparative examples 1 to 6
As can be seen from Table 1, the whiteness of the ceramic tile samples prepared in examples 1-4 of the invention can reach 80-84 degrees, and the high whiteness standard of the zirconium opacified glaze is achieved; and the white color can be presented in a wider use temperature range without yellowing, and the glaze has good quality and good practical value.
Comparative example 1 since the petalite in example 1 was replaced with conventional feldspar, the color improvement effect of the glaze was reduced, resulting in yellowish glaze and reduced whiteness.
Comparative examples 2 and 3 show some yellowing of the glaze without mesoporous silica coating, compared with examples 3 and 4, respectively; and in comparative example 3, since the firing temperature is higher than that of comparative example 2 and higher than the pyrolysis temperature of titanite, yellowing is more remarkable, and a large number of pinhole defects exist on the glaze, it is shown that the direct use of titanite as an opacifying agent is not suitable for high-temperature firing.
Comparative example 4, in which the composite opacified frit was wrapped with silica by conventional solid-phase hybrid wrapping, was slightly yellowish and had few pinholes due to the fact that the wrapping was inferior to the embedded wrapping of example 4, and there was still some high temperature decomposition of the titanite.
Comparative example 5 compared to example 1, the composite opacifying frit powder does not contain P in its chemical composition 2 O 5 And B 2 O 3 And K is 2 O is greater than Na 2 The content of O is insufficient in phase separation power in the glaze melt, and a second phase cannot be formed, so that the whiteness of the glaze surface is obviously reduced.
In comparative example 6, since the crystals were not sufficiently precipitated by firing at one temperature rise, the second-phase droplets were not sufficiently formed, and the whiteness was far inferior to that of example 1.
It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the inventive concept. Accordingly, it is intended that all such modifications as would be within the scope of this invention be included within the scope of this invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent modifications are intended to fall within the scope of the present invention.

Claims (8)

1. The composite ultrawhite overglaze based on zirconium silicate is characterized by comprising the following raw material components in parts by weight:
5-10 parts of kaolin, wherein the kaolin comprises,
10-15 parts of quartz sand,
25-35 parts of petalite,
40-60 parts of a brightening agent;
the whitening agent comprises mesoporous silica and composite opacified frit powder, and the composite opacified frit powder is embedded in the pores of the mesoporous silica;
the chemical composition of the composite opacifying frit powder comprises the following components in percentage by weight: siO (SiO) 2 55-67%，Al 2 O 3 3-6%，CaO8-14%，MgO1-3%，K 2 O0.5-2%，Na 2 O1-4%，P 2 O 5 0.5-2%，ZrO 2 2-4%，TiO 2 12-18%，B 2 O 3 0.5-2%；
The petalite comprises the following chemical components in percentage by weight: siO (SiO) 2 70-80%，Al 2 O 3 10-20%，K 2 O0.5-1%，Na 2 O0.5-1%，CaO1-2%，MgO1-2%，Fe 2 O 3 0.05-0.1%，Li 2 O3-5%；
The preparation process of the whitening agent comprises the following steps: adding a dispersing agent and a silane coupling agent into a solvent to obtain a mixed solution; then dividing the mixed solution into two parts, and respectively adding the composite opacifying frit powder and mesoporous silica into the two parts to disperse to obtain a suspension A and a suspension B; mixing the suspension A and the suspension B, heating and stirring; cooling to room temperature, centrifuging, washing, and drying to obtain whitening agent;
the solvent is at least one selected from ethylene glycol, dipropylene glycol methyl ether acetate, toluene and xylene; the heating temperature is 60-100 ℃;
the temperature system of the composite ultra-white surface glaze firing is as follows: firstly, raising the temperature to 700-800 ℃ at a heating rate of 12-15 ℃/min, and preserving the heat for 8-10min; then raising the temperature to 900-1000 ℃ at a heating rate of 12-15 ℃/min, and preserving the heat for 8-10min; then the temperature is raised to 1100-1250 ℃ at the heating rate of 8-10 ℃/min, the temperature is kept for 8-10min, and finally the kiln is taken out for natural cooling.
2. The zirconium silicate based composite ultrawhite overglaze of claim 1, wherein the mesoporous silica has a pore size of 20-50nm and the composite opacifying frit powder has a particle size of 10-30nm.
3. The zirconium silicate based composite ultrawhite overglaze according to claim 1 or 2, wherein the mass ratio of the mesoporous silica to the composite opacifying frit powder is (0.2-0.4): 1.
4. a method for preparing a zirconium silicate based composite ultrawhite overglaze according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing the raw materials for preparing the composite opacified frit powder, pouring the mixture into water for quenching after melting to obtain frit particles; grinding the frit particles to obtain composite opacified frit powder;
(2) Adding a dispersing agent and a silane coupling agent into a solvent to obtain a mixed solution; then dividing the mixed solution into two parts, and respectively adding the composite opacifying frit powder and mesoporous silica into the two parts to disperse to obtain a suspension A and a suspension B; mixing the suspension A and the suspension B, heating at 60-100 ℃ and stirring; cooling to room temperature, centrifuging, washing, and drying to obtain whitening agent;
the solvent is at least one selected from ethylene glycol, dipropylene glycol methyl ether acetate, toluene and xylene;
(3) And mixing the whitening agent with other raw materials for preparing the zirconium silicate-based composite ultrawhite overglaze, and performing wet ball milling to obtain the composite ultrawhite overglaze.
5. The method for preparing a zirconium silicate-based composite ultrawhite overglaze according to claim 4, wherein in the step (2), the dispersant is at least one selected from anionic dispersant, phosphate dispersant, polyacid homopolymer dispersant;
and/or, the stirring is stirring at a speed of 400-1500 rpm for 2-4 hours.
6. A composite ultra-white ceramic tile based on zirconium silicate, which comprises a blank and an ultra-white overglaze layer arranged on the upper surface of the blank, wherein the ultra-white overglaze layer is formed by firing the composite ultra-white overglaze based on zirconium silicate according to any one of claims 1 to 3.
7. The zirconium silicate based composite ultra white ceramic tile according to claim 6, wherein the ultra white overglaze layer has a thickness of 0.15-0.2mm.
8. A method for preparing a composite ultra-white ceramic tile based on zirconium silicate according to claim 6 or 7, comprising the steps of:
1) The method for preparing a composite ultrawhite overglaze based on zirconium silicate according to claim 4;
2) Applying the super Bai Mianyou on a green body to form a super white surface glaze layer, and drying and sintering to obtain the composite super white ceramic tile based on zirconium silicate;
the firing temperature system is as follows: firstly, raising the temperature to 700-800 ℃ at a heating rate of 12-15 ℃/min, and preserving the heat for 8-10min; then raising the temperature to 900-1000 ℃ at a heating rate of 12-15 ℃/min, and preserving the heat for 8-10min; then the temperature is raised to 1100-1250 ℃ at the heating rate of 8-10 ℃/min, the temperature is kept for 8-10min, and finally the kiln is taken out for natural cooling.
CN202311319932.8A 2023-10-12 2023-10-12 Zirconium silicate-based composite ultra-white overglaze, ceramic tile and preparation method thereof Active CN117049890B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104909570A (en) * 2015-07-15 2015-09-16 中国地质大学（北京） Opacifier, preparation method thereof and ceramic glaze with the opacifier
CN113185125A (en) * 2021-04-13 2021-07-30 佛山市陶莹新型材料有限公司 Composite whitening environment-friendly glaze, ceramic tile and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104909570A (en) * 2015-07-15 2015-09-16 中国地质大学（北京） Opacifier, preparation method thereof and ceramic glaze with the opacifier
CN113185125A (en) * 2021-04-13 2021-07-30 佛山市陶莹新型材料有限公司 Composite whitening environment-friendly glaze, ceramic tile and preparation method thereof

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