CN111253071B - High-stain-resistance FFC glaze, FFC sanitary ceramic and preparation method thereof - Google Patents

High-stain-resistance FFC glaze, FFC sanitary ceramic and preparation method thereof Download PDF

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CN111253071B
CN111253071B CN202010369840.0A CN202010369840A CN111253071B CN 111253071 B CN111253071 B CN 111253071B CN 202010369840 A CN202010369840 A CN 202010369840A CN 111253071 B CN111253071 B CN 111253071B
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glaze
ffc
parts
sanitary ceramic
ball milling
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CN111253071A (en
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王赞
白静静
薛福勤
钟保民
潘欢欢
陈勇
伍军玲
罗宁
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JIANGMEN DONGPENG INTELLIGENT HOUSEHOLD Co.,Ltd.
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating 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
    • C04B41/5022Coating 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • C04B41/86Glazes; Cold glazes

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  • Glass Compositions (AREA)

Abstract

The invention discloses a high-antifouling FFC glaze, FFC sanitary ceramic and a preparation method thereof, wherein the high-antifouling FFC glaze comprises the following raw materials in parts by weight: 22-29 parts of quartz, 24-28 parts of potassium feldspar, 6-10 parts of wollastonite, 7-8 parts of zirconium silicate, 5-10 parts of kaolin, 0-5 parts of calcite, 5-7 parts of zinc oxide, 5-7 parts of alumina, 2-3 parts of frit, 4-8 parts of dolomite, 5-8 parts of calcined talc, 1-4 parts of barium carbonate and 0.2-0.5 part of sodium carboxymethylcellulose. The high anti-fouling FFC glaze material utilizes the polybase effect, enables a blank to exhaust more smoothly by introducing barium carbonate, increasing the using amount of calcined talc and reducing the using amount of albite so as to reduce the porosity of a glaze surface and reduce microcracks of the glaze surface. In addition, the FFC glaze material with high anti-fouling capability utilizes the similar intermiscibility principle, increases the dosage of alumina and quartz, improves the blank glaze associativity, and relatively further reduces the microcracks of the sanitary ceramic glaze surface.

Description

High-stain-resistance FFC glaze, FFC sanitary ceramic and preparation method thereof
Technical Field
The invention relates to the technical field of sanitary ceramics, in particular to an FFC glaze material with high anti-fouling capability, an FFC sanitary ceramic and a preparation method thereof.
Background
In the prior art, in order to improve the integral regularity of the sanitary ceramics, ensure the original intention of designers to the maximum extent and improve the firing qualification rate, the FFC slurry is generally used for manufacturing a blank body of the sanitary ceramics. FFC is an abbreviation for Fine Fire Clay, a material used to make ceramics. The FFC slurry can be used for preparing a green body of sanitary ceramics through high-pressure grouting, the green body of the sanitary ceramics prepared from the FFC slurry is easy to crack in a drying process or deform in a firing process, most of the conventional ceramic glaze materials contain low-temperature materials such as high-sodalite powder, potash-sodalite and the like, and the high-temperature resistance is low, so that the green body is easy to deform at high temperature, and the glaze layer on the surface of the sanitary ceramics has the glaze defects of tiny pinholes, unevenness, microcracks and the like which cannot be seen by naked eyes.
Sanitary ceramics are inevitably exposed to contaminants such as excrement, scale, urine scale, soap foam, fatty acids, amino acids, etc. during use. Contaminants are easily accumulated in fine cracks formed due to process limitations by various physical or chemical forces such as van der waals force, capillary force, hydrogen bonding, etc. Most of pollutants are organic matters, and after the pollutants are accumulated in fine cracks of the sanitary ware, bacteria are easy to breed, so that the appearance is influenced, and the cleaning difficulty is increased. Also, the detergent used in washing may cause environmental pollution, and components in the detergent may affect human health.
Disclosure of Invention
The invention aims to provide an FFC glaze material with high anti-fouling capability, an FFC sanitary ceramic and a preparation method thereof, so as to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a high-stain-resistance FFC glaze which comprises the following raw materials in parts by weight:
22-29 parts of quartz, 24-28 parts of potassium feldspar, 6-10 parts of wollastonite, 7-8 parts of zirconium silicate, 5-10 parts of kaolin, 0-5 parts of calcite, 5-7 parts of zinc oxide, 5-7 parts of alumina, 2-3 parts of frit, 4-8 parts of dolomite, 5-8 parts of calcined talc, 1-4 parts of barium carbonate and 0.2-0.5 part of sodium carboxymethylcellulose.
In the high-stain-resistance FFC glaze, the high-stain-resistance FFC glaze further comprises 0-3 parts by weight of albite.
In the high-antifouling-capacity FFC glaze, the mass ratio of Si to Al in the high-antifouling-capacity FFC glaze is (5.65-6.19): (1.15-1.48); the mass percentage content of sodium oxide in the high anti-fouling FFC glaze is 1.10-1.34%; the mass ratio of calcium oxide to magnesium oxide in the high-antifouling-capacity FFC glaze is (5.40-6.60): (2.98-3.69).
In the FFC glaze with high anti-fouling capacity, the content of potassium oxide in the potassium feldspar is more than or equal to 10%; the content of sodium oxide in the albite is greater than or equal to 7%; the burned talc has a magnesium oxide content of greater than or equal to 30%.
In the FFC glaze with high anti-fouling capability, the weight of zirconium silicate with the particle size of less than 5 mu m in the zirconium silicate is more than 80 percent of the total weight of the zirconium silicate.
In the FFC glaze with high anti-fouling capacity, the frit is a zinc-free opaque frit which comprises the following components in parts by weight: 66% SiO2、4%Al2O3、8%CaO、12%Na2O, 1.0% MgO and 7.8% B2O3
The invention also provides a preparation method of the FFC sanitary ceramic using the FFC glaze with high anti-fouling capacity, which comprises the following steps:
pre-ball milling of frits: weighing the frits according to the proportion, and performing ball milling treatment on the frits according to the formula amount in advance;
ball milling: weighing other raw materials except for the frit according to a ratio, mixing the other raw materials according to the formula amount with the ball-milled frit obtained in the step of pre-ball milling the frit, and adding water for ball milling to obtain glaze slurry, wherein the addition amount of the water is 40-45% of the total weight of the raw materials;
sieving to remove iron: sieving the glaze slip obtained by ball milling by 160-200 meshes and removing iron;
glazing: glazing the sanitary ceramic blank, wherein the thickness of a glazed layer is 0.8-1.2 mm;
and (3) drying: the glazed sanitary ceramic is firstly placed in a drying chamber at 50 ℃ for drying and then is transferred into a drying kiln for drying;
and (3) firing: and firing the dried sanitary ceramic at a high temperature of 1205-1220 ℃.
In the preparation method of the FFC sanitary ceramic, in the ball milling step, the chemical components of the glaze slip comprise the following components in percentage by mass:
56.5~61.9%SiO2、11.5~14.8%Al2O3、5.0~7.0%CaO、4.8~5.6%ZrO2、4.0~6.0%ZnO、2.0~3.5%K2O、0.5~1.5%Na2O、2.8~4.0%MgO、0.1~0.2%B2O30.77-2.0% BaO and 4.0-7.5% I.L.
In the preparation method of the FFC sanitary ceramic, after the ball milling step, the weight of the raw materials with the particle size of less than 10 mu m in the glaze slip is 58-65% of the total weight of the raw materials.
The invention also provides the FFC sanitary ceramic, wherein a blank body of the FFC sanitary ceramic is formed by high-pressure slip casting, and the surface of the FFC sanitary ceramic is sintered by using the FFC glaze with high anti-fouling capability.
Has the advantages that:
(1) the high anti-fouling FFC glaze material utilizes the polybase effect, reduces the network strong destruction body sodium ions by introducing barium carbonate and increasing the using amount of burning talc and reducing the using amount of albite, improves the burning temperature range, enables the blank body to exhaust more smoothly, and reduces the porosity of the glaze surface; and barium carbonate has the effect of reducing pores and bubbles. In addition, the FFC glaze material with high anti-fouling capability utilizes the similar intermiscibility principle, increases the dosage of alumina and quartz, improves the blank glaze associativity, relatively further reduces the microcracks of the sanitary ceramic glaze surface, and reduces the possibility of the defect of the glaze surface; as the defects of microcracks, open pores and the like are main sources of dirt absorption, the defects of the glaze surface are reduced, and the dirt resistance of the sanitary ceramics prepared by using the glaze material is correspondingly improved.
(2) According to the preparation method of the FFC sanitary ceramic, the frits are subjected to ball-milling pretreatment, so that the ball-milling efficiency and the glaze quality of the whole glaze raw material are improved, the frits are firstly subjected to ball-milling pretreatment, the smoothness, the fineness and the glossiness of the glaze are improved, and the number of pinholes is reduced.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The invention provides a high-stain-resistance FFC glaze which comprises the following raw materials in parts by weight:
22-29 parts of quartz, 24-28 parts of potassium feldspar, 6-10 parts of wollastonite, 7-8 parts of zirconium silicate, 5-10 parts of kaolin, 0-5 parts of calcite, 5-7 parts of zinc oxide, 5-7 parts of alumina, 2-3 parts of frit, 4-8 parts of dolomite, 5-8 parts of calcined talc, 1-4 parts of barium carbonate and 0.2-0.5 part of sodium carboxymethylcellulose.
FFC is an abbreviation for Fine Fire Clay, a material used to make ceramics. The FFC slurry can be used for preparing a green body of the sanitary ceramic through high-pressure grouting. The FFC blank has poor thermal stability and is easy to deform at high temperature, most of the conventional sanitary ceramic glaze materials contain low-temperature materials such as high-sodium stone powder, potash-sodium feldspar and the like, and the high-temperature resistance is low, so that the glaze layer on the surface of the sanitary ceramic has glaze defects such as tiny pinholes, unevenness, microcracks and the like which cannot be seen by naked eyes.
Quartz is adopted as silicon dioxide (SiO) in the high-anti-pollution FFC glaze2) The principal donor of the component, Silica (SiO)2) Is the main component forming the glazed glass phase. Wollastonite is likewise silicon dioxide (SiO)2) The main raw materials for providing the components, potassium feldspar, albite and kaolin, are alumina (Al)2O3) Composition, and providing a minor portion of silicon dioxide (SiO)2)。
The Si/Al mass ratio of the glaze can be effectively reduced by adjusting the use amounts of kaolin, potassium feldspar, albite and wollastonite, the glaze melting temperature is directly influenced, the viscosity of the glaze in a melting state is improved, the glaze slip can be fixed on a blank body and is not easy to flow away, and the surface defects of the glaze are reduced. In addition, under high temperature, the melt with higher viscosity can continue to melt, and the breaking of bubbles generated in the melting process can play a role of stirring, so that the glaze is melted more uniformly, and the purpose of further reducing surface defects is achieved.
The high anti-fouling FFC glaze material utilizes the polybase effect, reduces the network strong destruction body sodium ions by introducing barium carbonate and increasing the using amount of burning talc and reducing the using amount of albite, improves the burning temperature range, enables the blank body to exhaust more smoothly, and reduces the porosity of the glaze surface; and barium carbonate has the effect of reducing pores and bubbles. In addition, the FFC glaze material with high anti-fouling capability utilizes the similar intermiscibility principle, increases the dosage of alumina and quartz, improves the binding property of blank glaze, and relatively further reduces the microcracks of the glaze surface.
The crystal chemical formula of the kaolin is 2SiO2·Al2O3·2H2And O, kaolin mainly improves the melting temperature of the glaze and the suspension property of the glaze, so that the glaze slip is not easy to precipitate.
The zirconium silicate has good chemical stability and is not influenced by the firing atmosphere of the ceramic, and the zirconium silicate mainly plays the roles of an opacifier and a whitening agent. In addition, the zirconium silicate is added into the formula system, and can obviously improve the separation performance of the blank glaze of the ceramic, so that the ceramic glaze surface is more attached to the blank body, and the blank body is prevented from slightly deforming and separating from the glaze surface to form fine cracks.
Calcite and dolomite mainly play a role in fluxing in a formula system, wherein the main chemical component of the dolomite is CaMg (CO)3)2The main chemical component of calcite is CaCO3. By regulating the content of calcium and magnesium and the proportion of the network body and the network intermediate, the optimal fluxing effect can be obtained, so that the glaze has higher high-temperature viscosity and higher high-temperature fluidity.
The zinc oxide mainly plays a role in fluxing in a formula system, is matched with calcite and dolomite for use, plays a larger role in improving the glossiness of a glaze surface, can increase the mechanical elasticity of the glaze and the strength of the glaze within a certain range, has unobvious functions of increasing the mechanical elasticity of the glaze and the strength of the glaze when the content of the zinc oxide is less than 2 percent, and easily causes the phenomenon of low temperature and even crystallization of the glaze surface when the content of the zinc oxide is more than 5 percent.
The sodium carboxymethyl cellulose is used as a binder and added into a formula system of the FFC glaze with high antifouling capacity, so that the adhesion capacity of the glaze can be improved, the breakage rate of a dried blank body is reduced, and the adhesion force of the glaze and the strength of a glaze layer are enhanced.
Preferably, the high-stain-resistance FFC glaze further comprises 0-3 parts by weight of albite. Albite is also mainly used for increasing the content of alumina in glaze ingredients and has a fluxing function, but the albite contains sodium oxide which is a strong network disrupter and can break a glass network, so that the high-antifouling FFC glaze reduces the using amount of the albite.
Specifically, the mass ratio of Si/Al is SiO in the glaze2With Al2O3The mass ratio of (a). The mass ratio of Si to Al in the FFC glaze material with high anti-fouling capacity is (5.65-6.19): (1.15-1.48); the mass percentage content of sodium oxide in the high anti-fouling FFC glaze is 1.10-1.34%; the mass ratio of calcium oxide to magnesium oxide in the high-antifouling-capacity FFC glaze is (5.40-6.60): (2.98-3.69).
Specifically, the content of potassium oxide in the potassium feldspar is greater than or equal to 10%; the content of sodium oxide in the albite is greater than or equal to 7%; the burned talc has a magnesium oxide content of greater than or equal to 30%. The potassium feldspar is mainly used for improving the content of aluminum oxide in the glaze material, is provided with potassium oxide, and can reduce the melting temperature and increase the content of alkali so as to reduce the consumption of the alkali and increase the viscosity of the glaze material in a melting state. The calcined talc is mainly used for providing magnesium oxide, and is matched with calcite for use to achieve the purpose of regulating the content of calcium and magnesium, so that the proportion of the network body and the network intermediate is controlled, and the glaze has high-temperature viscosity and high-temperature fluidity.
Therefore, the content of potassium oxide in the potassium feldspar, the content of sodium oxide in the albite and the content of magnesium oxide in the calcined talc influence the high-temperature viscosity and the high-temperature fluidity of the glaze material, and further influence the compactness of the sanitary ceramic glaze surface. If the content of potassium oxide in the potassium feldspar, the content of sodium oxide in the albite or the content of magnesium oxide in the burnt talc is lower than expected, the use amount of the potassium feldspar, the albite or the burnt talc is increased, the Si/Al mass ratio of the glaze is changed, the mass ratio between the magnesium oxide and the calcium oxide is difficult to control, and the glaze cannot obtain expected physical properties. In order to regulate and control the Si/Al mass ratio, the content of sodium oxide and the proportion of calcium oxide and magnesium oxide in the formula, the content of potassium oxide in the potassium feldspar should be more than or equal to 10 percent, and the content of sodium oxide in the albite should be more than or equal to 7 percent; the content of magnesium oxide in the calcined talc should be greater than or equal to 30%.
Preferably, the weight of zirconium silicate having a particle size below 5 μm among the zirconium silicates is more than 80% of the total zirconium silicate weight. The particle size of the zirconium silicate is less than 5 mu m, which is beneficial to improving the flatness, the fineness and the glossiness of a glaze surface, reducing the number of pinholes, shortening the ball milling time and improving the ball milling efficiency.
Specifically, the frit is a zinc-free opaque frit, and the zinc-free opaque frit comprises the following components in parts by weight: 66% SiO2、4%Al2O3、8%CaO、12%Na2O、1.0%MgO、7.8%B2O3. The frit plays a role of a flux, and the zinc-free opaque frit is preferably selected in the technical scheme, so that the glaze quality can be effectively improved due to high initial melting temperature, wide application range, high blank glaze binding degree and good glossiness after firing, but the use amount needs to be controlled, and if the use amount is too much, the glaze is easy to have the defects of pinholes and the like.
The invention also provides a preparation method of the FFC sanitary ceramic with the high anti-fouling FFC glaze, which comprises the following steps:
pre-ball milling of frits: weighing the frits according to the proportion, and performing ball milling treatment on the frits according to the formula amount in advance;
ball milling: weighing other raw materials except for the frit according to a ratio, mixing the other raw materials according to the formula amount with the ball-milled frit obtained in the step of pre-ball milling the frit, and adding water for ball milling to obtain glaze slurry, wherein the addition amount of the water is 40-45% of the total weight of the raw materials;
sieving to remove iron: sieving the glaze slip obtained by ball milling by 160-200 meshes and removing iron;
glazing: glazing the sanitary ceramic blank, wherein the thickness of a glazed layer is 0.8-1.2 mm;
and (3) drying: the glazed sanitary ceramic is firstly placed in a drying chamber at 50 ℃ for drying and then is transferred into a drying kiln for drying;
and (3) firing: and firing the dried sanitary ceramic at a high temperature of 1205-1220 ℃.
The frit is subjected to pre-ball milling in the step of pre-ball milling of the frit, and the volume of the frit cannot be compared with that of other raw materials, so that the frit is subjected to pre-ball milling firstly in order to improve the ball milling efficiency and glaze quality of the whole glaze raw material, thereby being beneficial to improving the smoothness, fineness and glossiness of the glaze and reducing the number of pinholes.
In addition, the glaze slip passes through a 160-200-mesh sieve and is deironized, the glaze slip is subjected to impurity removal and particle size distribution optimization, the density of the glaze surface can be effectively improved, and the problem of glaze surface defects such as tiny pinholes, concave-convex, microcracks and the like on the glaze layer is further reduced. The glaze slip is obtained by mixing glaze and water and then performing a ball milling step.
Further, in the ball milling step, the chemical components of the glaze slip comprise the following components in percentage by mass:
56.5~61.9%SiO2、11.5~14.8%Al2O3、5.0~7.0%CaO、4.8~5.6%ZrO2、4.0~6.0%ZnO、2.0~3.5%K2O、0.5~1.5%Na2O、2.8~4.0%MgO、0.1~0.2%B2O30.77-2.0% BaO and 4.0-7.5% I.L.
Wherein I.L is loss on ignition. And (3) performing ball milling treatment on the frit, and mixing the frit with water accounting for 40-45% of the total amount of the raw materials and other raw materials subjected to ball milling treatment to obtain the glaze slurry containing the components in percentage by mass. The mass ratio of Si to Al in the glaze slip is (5.65-6.19): (1.15-1.48), and the content of sodium oxide is only 1.10-1.34%, so that the damage to a glass network structure is reduced, the bonding property of blank glaze is improved, the thermal expansion coefficient of a blank body subjected to high-pressure grouting is matched with that of the glaze, and the microcracks of the glaze are reduced; in addition, the high mass ratio of Si to Al also improves the sintering temperature range, reduces the porosity of the glaze surface, improves the smoothness of the glaze surface and improves the melting homogenization degree of the glaze material.
In addition, the mass ratio of CaO to MgO is limited to (5.40-6.60): (2.98 ~ 3.69), when making the frit possess higher high temperature viscosity, have higher high temperature mobility again to make the frit can adapt to the ceramic body of high-pressure slip casting, can effectively improve the glaze reaction density of high-pressure slip casting ceramic body, then reduce the glaze layer and appear the problem of glaze defects such as tiny pinhole, unsmooth and microcrack.
Furthermore, after the ball milling step, the weight of the raw materials with the particle size of less than 10 μm in the glaze slip is 58-65% of the total weight of the raw materials. The glaze slip has a granularity of less than 10 microns, is beneficial to improving the flatness, fineness and glossiness of the glaze surface, reducing the number of pinholes, shortening the ball milling time and improving the ball milling efficiency.
The invention also provides the FFC sanitary ceramic, wherein a blank body of the FFC sanitary ceramic is formed by high-pressure slip casting, and the surface of the FFC sanitary ceramic is sintered by using the FFC glaze with high anti-fouling capability. FFC ceramic sanitary ware glaze surface is smooth exquisite, and the glossiness reaches up to 110 ~ 115GU, and the glaze surface is smooth exquisite, and the glaze compactness is strong, can not appear the glaze defect that naked eyes can't see such as small pinhole, unsmooth and microcrack, has stronger anti-soil ability.
Example group A
A preparation method of sanitary ceramics using the high-antifouling FFC glaze material comprises the following steps:
pre-ball milling of frits: weighing the frits according to the table 1, and performing ball milling treatment on the frits according to the formula amount in advance;
ball milling: weighing other raw materials except for the frit according to table 1, mixing the other raw materials with the formula amount with the ball-milled frit obtained in the frit pre-ball milling step, adding water, and carrying out ball milling to obtain glaze slurry, wherein the addition amount of the water is 40-45% of the total amount of the raw materials;
sieving to remove iron: sieving the ground glaze slip by 160-200 meshes and removing iron;
glazing: glazing the sanitary ceramic blank, wherein the thickness of a glazed layer is 0.8-1.2 mm;
and (3) drying: the glazed sanitary ceramic is firstly placed in a drying chamber at 50 ℃ for drying and then is transferred into a drying kiln for drying;
and (3) firing: and firing the dried sanitary ceramic at a high temperature of 1205-1220 ℃.
In examples 1 to 3, 6 and 7, the amount of water added was 40% of the total amount of the raw materials, the thickness of the glaze layer was 1.0mm by passing through a 200-mesh sieve and applying iron-removing glaze, and the firing temperature was 1215 ℃.
In example 4, the amount of water added was 45% based on the total amount of the raw materials, and the glaze layer was sieved through a 180 mesh sieve to remove iron and glaze was 0.8mm thick and fired at 1205 ℃.
In example 5, the amount of water added was 42% based on the total amount of the raw materials, the glaze layer was sieved with a 160 mesh sieve and iron-removed and glazed to a thickness of 1.2mm, and the firing temperature was 1220 ℃.
Figure 718751DEST_PATH_IMAGE001
The frit comprises the following components in parts by weight: 66% SiO2、4%Al2O3、8%CaO、12%Na2O、1.0%MgO、7.8%B2O3. The content of potassium oxide in the potassium feldspar is 10 percent; the content of sodium oxide in the albite is 7 percent; the content of magnesium oxide in the calcined talc was 30%.
The high anti-fouling FFC glaze materials with different raw material formulas in the table 1 and the preparation method are respectively used for preparing the sanitary ceramic plate, and the sanitary ceramic plate and a sanitary ceramic sample plate in the prior art are subjected to a dirt absorption test and a glossiness test.
The method for testing the dirt absorption test comprises the following steps: smearing red ink or blue ink on a 10 x 10cm sanitary ceramic plate, smearing the ceramic plate for 3-5 minutes by using a rubber glove, washing the ceramic plate by using clear water after the ink is dried in the shade, wiping the ceramic plate dry, and checking the number of dirt-absorbing points in a bright place.
The results are shown in table 2 below:
Figure 585076DEST_PATH_IMAGE002
in example 1, the mass ratio of Si to Al was 5.65:1.24, the content of sodium oxide was 1.20%, and the ratio of calcium oxide to magnesium oxide was 6.6: 2.98;
in example 2, the mass ratio of Si/Al was 5.91:1.18, the content of sodium oxide was 1.34%, and the mass ratio of calcium oxide to magnesium oxide was 5.40: 3.25;
in example 3, the mass ratio of Si/Al was 5.70:1.23, the content of sodium oxide was 1.10%, and the mass ratio of calcium oxide to magnesium oxide was 6.60: 3.29;
in example 4, the mass ratio of Si/Al was 6.19:1.48, the content of sodium oxide was 1.30%, and the mass ratio of calcium oxide to magnesium oxide was 6.60: 3.69;
in example 5, the mass ratio of Si/Al was 6.02:1.34, the content of sodium oxide was 1.17%, and the mass ratio of calcium oxide to magnesium oxide was 6.27: 3.17;
in example 6, the Si/Al mass ratio was 5.99:1.33, the sodium oxide content was 1.17%, and the mass ratio of calcium oxide to magnesium oxide was 8.63: 2.26;
in example 7, the mass ratio of Si/Al was 6.79:1.15, the content of sodium oxide was 1.30%, and the mass ratio of calcium oxide to magnesium oxide was 8.98: 3.13.
As can be seen from table 2, in the embodiments 1 to 5, the FFC glaze with high anti-fouling capability is prepared by using the formula content in the technical scheme, so that the sanitary ceramic plate prepared by using the FFC glaze with high anti-fouling capability has good appearance flatness, the glaze surface is smooth and compact, the number of the dirt suction points in the dirt suction test is 8 to 21, the glossiness reaches the range of 110 to 115GU, and the purposes of reducing the defects of the glaze surface, preventing the attachment of pollutants and improving the glossiness are achieved.
By comparing the examples 6 and 7 with other examples, it can be seen that when the content of the raw material components exceeds the range defined in the technical scheme, the sanitary ceramic plate prepared by using the high anti-fouling FFC glaze material has different loss of appearance flatness and glossiness, and the glaze surface defect is increased, so that the prepared sanitary ceramic plate can not reach the standard required by production.
Example 8
The mixture ratio of the raw materials of the high anti-fouling FFC glaze in example 8 is the same as that in example 1, in the sanitary ceramic process of preparing the high anti-fouling FFC glaze by using the high anti-fouling FFC glaze in example 8, the step of pre-ball milling of the frits is omitted, and other steps are the same as those in example 1. And (3) testing results: gloss 108, number of dirt pickup points 23.
Comparative example group B
The preparation method of the sanitary ceramic using the high anti-fouling FFC glaze is consistent with examples 1-3 in example group A, and the raw material ratio of comparative examples 1-3 is shown in Table 3.
Figure 641894DEST_PATH_IMAGE003
The frit comprises the following components in parts by weight: 66% SiO2、4%Al2O3、8%CaO、12%Na2O、1.0%MgO、7.8%B2O3. The content of potassium oxide in the potassium feldspar is 10 percent; the content of sodium oxide in the albite is 7 percent; the content of magnesium oxide in the calcined talc was 30%.
The FFC glaze with high antifouling capacity and different raw material formulas in the table 3 and the preparation method are respectively used for preparing the sanitary ceramic plate, and the sanitary ceramic plate and an industrial sanitary ceramic sample plate are subjected to a pollution absorption test and a glossiness test.
The method for testing the dirt absorption test comprises the following steps: smearing red ink or blue ink on a 10 x 10cm sanitary ceramic plate, smearing the ceramic plate for 3-5 minutes by using a rubber glove, washing the ceramic plate by using clear water after the ink is dried in the shade, wiping the ceramic plate dry, and checking the number of dirt-absorbing points in a bright place.
The results are shown in table 4 below:
Figure 189550DEST_PATH_IMAGE004
in comparative example 1, the mass ratio of Si to Al was 5.92:1.06, the content of sodium oxide was 1.58%, and the mass ratio of calcium oxide to magnesium oxide was 8.29: 1.88;
in comparative example 2, the mass ratio of Si/Al was 6.61:1.33, the content of sodium oxide was 1.89%, and the mass ratio of calcium oxide to magnesium oxide was 7.45: 2.67;
in comparative example 3, the Si/Al mass ratio was 5.56:1.29, the sodium oxide content was 1.23%, and the mass ratio of calcium oxide to magnesium oxide was 10.67: 2.7.
As can be seen from Table 4, in comparative example 1, the albite usage amount is increased, the usage amounts of aluminum oxide and calcined talc are reduced, barium carbonate is not added, the proportion of calcium oxide is large, and the proportion of magnesium oxide is small, so that the sanitary ceramic plate prepared from the FFC glaze with high stain resistance is poor in appearance flatness, more stain absorption points are used in a stain absorption test, and the glossiness does not reach the sizes of examples 1-5.
In the comparative example 2, the albite consumption is increased, so that the sanitary ceramic plate prepared by the high-antifouling-capacity FFC glaze is poor in appearance flatness, more in number of dirt-absorbing points in a dirt-absorbing test, and poor in glossiness which cannot reach the sizes of the examples 1-5.
In the comparative example 3, the use amounts of calcite and dolomite are changed, and the proportion of calcium oxide and magnesium oxide is changed, so that the sanitary ceramic plate prepared from the high-antifouling-capacity FFC glaze is poor in appearance flatness, more in number of dirt-absorbing points in a dirt-absorbing test, and the glossiness of the sanitary ceramic plate cannot reach the sizes of the examples 1-5.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Other embodiments of the invention will occur to those skilled in the art without the exercise of inventive faculty based on the explanations herein, and such equivalent modifications or substitutions are intended to be included within the scope of the present invention as defined in the appended claims.

Claims (8)

1. The FFC glaze with high anti-fouling capability is characterized in that: the composite material comprises the following raw materials in parts by weight:
22-29 parts of quartz, 24-28 parts of potassium feldspar, 0-3 parts of albite, 6-10 parts of wollastonite, 7-8 parts of zirconium silicate, 5-10 parts of kaolin, 0-5 parts of calcite, 5-7 parts of zinc oxide, 5-7 parts of alumina, 2-3 parts of frit, 4-8 parts of dolomite, 5-8 parts of calcined talc, 1-4 parts of barium carbonate and 0.2-0.5 part of sodium carboxymethylcellulose;
wherein the mass ratio of Si to Al in the FFC glaze material with high anti-fouling capacity is (5.65-6.19): (1.15-1.48); the mass percentage content of sodium oxide in the high anti-fouling FFC glaze is 1.10-1.34%; the mass ratio of calcium oxide to magnesium oxide in the high-antifouling-capacity FFC glaze is (5.40-6.60): (2.98-3.69).
2. The high stain resistance FFC glaze of claim 1 wherein: the content of potassium oxide in the potassium feldspar is more than or equal to 10 percent; the content of sodium oxide in the albite is greater than or equal to 7%; the burned talc has a magnesium oxide content of greater than or equal to 30%.
3. The high stain resistance FFC glaze of claim 1 wherein: the weight of zirconium silicate with the particle size of less than 5 mu m in the zirconium silicate is more than 80 percent of the total weight of the zirconium silicate.
4. The high stain resistance FFC glaze of claim 1 wherein: the frit is a zinc-free opaque frit, and the zinc-free opaque frit comprises the following components in percentage by mass: 66% SiO2、4%Al2O3、8%CaO、12%Na2O, 1.0% MgO and 7.8% B2O3
5. A preparation method of the FFC sanitary ceramic using the high-antifouling-capacity FFC glaze material disclosed by any one of claims 1-4 is characterized by comprising the following steps: the method comprises the following steps:
pre-ball milling of frits: weighing the frits according to the proportion, and performing ball milling treatment on the frits according to the formula amount in advance;
ball milling: weighing other raw materials except for the frit according to a ratio, mixing the other raw materials according to the formula amount with the ball-milled frit obtained in the step of pre-ball milling the frit, and adding water for ball milling to obtain glaze slurry, wherein the addition amount of the water is 40-45% of the total weight of the raw materials;
sieving to remove iron: sieving the glaze slip obtained by ball milling by 160-200 meshes and removing iron;
glazing: glazing the sanitary ceramic blank, wherein the thickness of a glazed layer is 0.8-1.2 mm;
and (3) drying: the glazed sanitary ceramic is firstly placed in a drying chamber at 50 ℃ for drying and then is transferred into a drying kiln for drying;
and (3) firing: and firing the dried sanitary ceramic at a high temperature of 1205-1220 ℃.
6. The method of preparing an FFC sanitary ceramic according to claim 5, wherein: in the ball milling step, the glaze slip comprises the following chemical components in percentage by mass:
56.5~61.9%SiO2、11.5~14.8%Al2O3、5.0~7.0%CaO、4.8~5.6%ZrO2、4.0~6.0%ZnO、2.0~3.5%K2O、0.5~1.5%Na2O、2.8~4.0%MgO、0.1~0.2%B2O30.77-2.0% BaO and 4.0-7.5% I.L.
7. The method of preparing an FFC sanitary ceramic according to claim 5, wherein: after the ball milling step, the weight of the raw materials with the particle size of less than 10 mu m in the glaze slip is 58-65% of the total weight of the raw materials.
8. An FFC sanitary ceramic, characterized in that: the FFC sanitary ceramic blank is formed by high-pressure slip casting, and the surface of the FFC sanitary ceramic is sintered by the FFC glaze material with high anti-fouling capacity according to any one of claims 1-4.
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