CN108545946A - A kind of anti-skid brick and preparation method thereof - Google Patents

A kind of anti-skid brick and preparation method thereof Download PDF

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Publication number
CN108545946A
CN108545946A CN201810712929.5A CN201810712929A CN108545946A CN 108545946 A CN108545946 A CN 108545946A CN 201810712929 A CN201810712929 A CN 201810712929A CN 108545946 A CN108545946 A CN 108545946A
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ground
glaze
overglaze
skidding
additive
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CN108545946B (en
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林伟
范新晖
吴志坚
李丽芳
邓荣
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FOSHAN SHIWAN EAGLE BRAND CERAMIC Co Ltd
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FOSHAN SHIWAN EAGLE BRAND CERAMIC 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
    • C03C8/14Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • C04B33/00Clay-wares
    • C04B33/32Burning methods
    • C04B33/34Burning methods combined with glazing
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating 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
    • C04B41/89Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • 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
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562Heating rate
    • 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
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567Treatment time
    • 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
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661Multi-step sintering

Abstract

A kind of anti-skid brick of the application offer and preparation method thereof, anti-skid brick includes green body, ground glaze layer, cover coat and anti-skidding glaze layer;Ground glaze layer is arranged between green body and cover coat, and cover coat is arranged between ground glaze layer and anti-skidding glaze layer;The ground-coat enamel that ground glaze layer uses includes ground-coat enamel additive;Ground-coat enamel additive is the toluene solution of compound A, and mass concentration is 1 2%;The structural formula of compound A is as follows:

Description

A kind of anti-skid brick and preparation method thereof
Technical field
The present invention relates to ceramic fields, in particular to a kind of anti-skid brick and preparation method thereof.
Background technology
As the improvement of people's living standards, the requirement for the inherent decoration of building is also higher and higher.Floor tile is as common Architectural constructional materials, assigned in more functions, especially top-grade building object by people, to the requirement of the various aspects of performance of floor tile All highers, and taking place frequently with the tumble injury event that slips, people increasingly pay close attention to the non-skid property of floor tile.
There is the scheme of some ship-and-galley tiles in the prior art, but mostly there are while non-skid property promotion, it is decorative, anti- The defect that folding endurance energy, thermal shock resistance decline is especially more prominent in thin layer skid resistant course product.How skid resistance is being ensured The stabilization that other performances are taken into account while energy, becomes urgent problem to be solved.
In view of this, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of anti-skid brick, and the anti-skid brick has non-skid property good, stable structure Property it is strong, it is decorative, thermal shock resistance and fracture resistance are good the advantages that.
The second object of the present invention is to provide a kind of preparation method of the anti-skid brick, by preventing made from the method Sliding brick can obtain the above advantage.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme:
A kind of anti-skid brick, including green body, ground glaze layer, cover coat and anti-skidding glaze layer, the ground glaze layer are arranged in the green body Between the cover coat, the cover coat is arranged between the ground glaze layer and the anti-skidding glaze layer;
The ground-coat enamel that the ground glaze layer uses includes ground-coat enamel additive;The ground-coat enamel additive is the toluene solution of compound A, Its mass concentration is 1-2%;The ground-coat enamel additive accounts for the 0.5-2% of the ground-coat enamel gross mass;The structural formula of the compound A It is as follows:
The overglaze that the cover coat uses includes overglaze additive, and the overglaze additive is tungsten oxide, molybdenum oxide and oxygen Change the mixture of nickel, the mass ratio of the tungsten oxide, the molybdenum oxide and the nickel oxide is 2:2:1;The overglaze additive Account for the 0.05-0.1% of the overglaze gross mass;
The anti-skidding glaze that the anti-skidding glaze layer uses includes anti-skidding glaze additive, and the anti-skidding glaze additive is sodium chloride, chlorine Change aluminium, aluminum sulfate and 12 hydrazine aluminum sulfate potassium, the sodium chloride, the aluminium chloride, the aluminum sulfate and 12 hydration The mass ratio of alum is 4:3:2:1;The anti-skidding glaze additive accounts for the 2-5% of the anti-skidding glaze gross mass.
The use of ground-coat enamel additive, overglaze additive, anti-skidding glaze additive, in addition to making the microstructure of each layer itself occur Change and then improve except the accordingly intensity of each layer and bonding force, also plays a role between the faying face of each layer, improve each layer Between conjugation, to improve the anti-skidding of structural strength, flexural strength, non-skid property and thermal shock resistance etc. on the whole Brick performance.Anti-skidding glaze additive can improve the microstructure on anti-skidding glaze surface, make it while ensureing finish, improve it Non-skid property.
Preferably, the ground-coat enamel further includes ground-coat enamel raw material and ground-coat enamel frit, and the ground-coat enamel raw material by percentage to the quality, wraps It includes:Marble 10%, quartz 8%, boron oxide 10%, zirconium silicate 10%, middle aluminium powder 6%, kaolin 8%, take off albite 23% Aluminum silicon powder 3%, calcite 3%, dolomite 10%, raw talcum 9%;The ground-coat enamel frit by percentage to the quality, including:SiO2 65%, Al2O3 10%, Fe2O31%, CaO 10%, MgO 5%, K2O 2%, Na2O 7%.
It is further preferred that it is 0.3-0.5% that the fineness of the glaze slip of the ground-coat enamel, which is 300 mesh screen residues,.
The ingredient and dosage for optimizing ground-coat enamel and ground-coat enamel frit, control tailing over for glaze slip, can preferably optimize ground glaze layer Performance.Wherein the addition of marble, raw talcum reinforces the stabilization of ground-coat enamel primarily to change the whole component distributing of ground-coat enamel Property.And the use of ground-coat enamel frit, it can be effectively improved the microcosmic composition of ground-coat enamel, optimize properties.
Preferably, the overglaze further includes overglaze material and overglaze frit;The overglaze material is wrapped by percentage to the quality It includes:SiO258%, Al2O315%, Fe2O32%, TiO20.5%, CaO8%, NiO0.5%, K2O4%, Cr2O31.5%, ZnO8%, BaO2.5%;The overglaze frit by percentage to the quality, including:SiO2 55%, Al2O3 15%, Fe2O31%, CaO 8%, MgO 5%, K2O 1%, Na2O 7%, B2O3 8%.
It is further preferred that it is 0.2-0.4% that the fineness of the glaze slip of the overglaze, which is 200 mesh screen residues,.
The ingredient and dosage for optimizing overglaze and overglaze frit, control tailing over for glaze slip, can preferably optimize cover coat Performance.Wherein, the use of the silica of high-content and titanium oxide, chromium oxide optimizes each component particle in sintering procedure Between package situation and interaction, further improve the intensity of cover coat, optimize with ground glaze layer, anti-skidding glaze layer knot It closes.
Preferably, the anti-skidding glaze further includes anti-skidding glaze raw material and anti-skidding glaze frit;The anti-skidding glaze raw material is prevented with described The mass ratio of sliding glaze frit is 25:1;
The anti-skidding glaze raw material includes based on mass fraction:SiO249%, Al2O315%, Fe2O30.6%, TiO20.1%, CaO8%, MgO7%, K2O4.2%, Na2O5%, ZnO10%, BaO1.1%;
The anti-skidding glaze frit includes basic dry granular, cooperation dry granular and function dry granular, and the basis dry granular, the cooperation are dry The mass ratio of grain and the function dry granular is 3:1:1;
It is described basis dry granular include based on mass fraction:SiO252%, Al2O319%, Fe2O30.05%, CaO11%, MgO3.3%, K2O5.9%, Na2O5.55%, ZnO3.2%;
The cooperation dry granular includes based on mass fraction:SiO254.5%, Al2O315%, Fe2O30.1%, CaO8.2%, MgO2.5%, K2O7.5%, Na2O9%, ZnO2.5%, CuO0.5%, CoO0.2%;
The function dry granular based on mass fraction include SiO251.5%, Al2O323%, Fe2O30.3%, CaO13.5%, MgO3.3%, K2O3%, Na2O2.6%, ZnO2.2%, Pr6O110.3%, La2O30.2%, Ce2O30.1%.
It is further preferred that it is 0.2-0.5% that the fineness of the glaze slip of the anti-skidding glaze, which is 325 mesh screen residues,.
Anti-skidding glaze optimizing components are coordinated at split-phase with anti-skidding glaze frit, and a part of material is completely molten in sintering procedure Melt, branch material parts melting, forms package appropriate and rational structure;The granularity control of dry granular is to allow three kinds to do Material distribution between grain, between dry granular and anti-skidding glaze raw material is more reasonable.The control tailed over also for obtain performance more The microstructure of optimization.
A kind of preparation method of the anti-skid brick, includes the following steps:
A. blank forming carries out first time drying process, and then on the surface of the green body, leaching ground-coat enamel obtains the ground-coat enamel Layer, and carry out second and be dried;On the surface of the ground glaze layer, leaching overglaze obtains the cover coat again, then carries out ink-jet Stamp, and carry out third time drying process;
B. anti-skidding glaze is sprayed, the anti-skidding glaze layer is obtained, and carries out the 4th drying process, preparation is obtained and fires brick body;
C. brick body is fired into preparation and is put into kiln progress first time firing, by first time temperature programming to 400 DEG C of firings; Then the first secondary program cooling is carried out, after being down to 80 DEG C, kiln is put into and carries out second of firing, extremely by second of temperature programming 1200 DEG C of firings;
D. the second secondary program cooling is then carried out, after being down to 80 DEG C, is put into the argon atmosphere containing carbon dioxide cooling To room temperature, semi-finished product are obtained, the semi-finished product are post-treated to obtain finished product.
Preferably, the first time temperature programming is:150 DEG C first are risen to 10min, maintains 5min, then risen to 15min 300 DEG C, 15min is maintained, then rises to 400 DEG C with 5min, maintains 30min;Second of temperature programming be:First stage is used 10min rises to 300 DEG C, maintains 5min, second stage to rise to 600 DEG C with 5min, 20min, phase III is maintained to be risen to 30min 1200 DEG C, maintain 2h.
It is further preferred that the first secondary program cooling is:350 DEG C first are down to 10min, is then down to 300 with 30min DEG C, then 150 DEG C are down to 50min, 80 DEG C are finally down in 70min;Second secondary program cools down:First dropped with 60min To 1000 DEG C, 700 DEG C then is down to 60min, then 300 DEG C are down to 60min, is finally down to 80 DEG C with 60min.
Temperature programming, program cooling and the use of secondary burning process, can effectively control the release of internal stress, carry Rise the structural behaviour of anti-skid brick;Finally be placed in the argon atmosphere of carbon dioxide it is cooling, be in order to surface micro-oxidation lanthanum with Carbon dioxide acts on, while ar gas environment ensures the stability that surface changes in cooling procedure.
Compared with prior art, beneficial effects of the present invention are:
(1) by optimizing the ingredient and dosage of each layer, the use of especially each layer additive so that anti-skid brick has anti-skidding The all preferable advantage such as performance, structural stability, dicoration, thermal shock resistance and fracture resistance;
(2) by the method for repeatedly dry, temperature programming and program cooling, sintering procedure inside brick body can be released effectively The stress of middle generation improves the bond strength between each layer, to reach raising overall construction intensity, promotes flexural strength, resists The purpose of thermal shock performance;
(3) rare-earth oxide is added in cover coat, improves surface and internal microstructure, improve intensity and skid resistance Energy;By being cooled to room temperature change surface texture in certain circumstances so that non-skid property, while finish etc. decorates performance It can be guaranteed.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.
Embodiment 1
A kind of anti-skid brick, including green body, ground glaze layer, cover coat and anti-skidding glaze layer, ground glaze layer are arranged in green body and cover coat Between, cover coat is arranged between ground glaze layer and anti-skidding glaze layer;
The ground-coat enamel that ground glaze layer uses includes ground-coat enamel raw material, ground-coat enamel frit and ground-coat enamel additive, and the fineness of the glaze slip of ground-coat enamel is 300 mesh screen residues are 0.3%;Ground-coat enamel raw material by percentage to the quality, including:Marble 10%, quartz 8%, boron oxide 10%, silicon Sour zirconium 10%, middle aluminium powder 6%, albite 23%, kaolin 8%, desiliconization aluminium powder 3%, calcite 3%, dolomite 10%, raw cunning Stone 9%;Ground-coat enamel frit by percentage to the quality, including:SiO2 65%, Al2O3 10%, Fe2O31%, CaO 10%, MgO 5%, K2O 2%, Na2O 7%;Ground-coat enamel additive is the toluene solution of compound A, mass concentration 2%;Ground-coat enamel additive Account for the 0.5% of ground-coat enamel gross mass;The structural formula of compound A is as follows:
;The mass ratio of ground-coat enamel raw material and ground-coat enamel frit is 10:1.
The overglaze that cover coat uses includes overglaze material, overglaze frit and overglaze additive, and the fineness of the glaze slip of overglaze is 200 mesh screen residues are 0.4%;Overglaze material includes by percentage to the quality:SiO258%, Al2O315%, Fe2O32%, TiO20.5%, CaO8%, NiO0.5%, K2O4%, Cr2O31.5%, ZnO8%, BaO2.5%;The overglaze frit is with matter Percentages are measured, including:SiO2 55%, Al2O3 15%, Fe2O31%, CaO 8%, MgO 5%, K2O 1%, Na2O 7%, B2O3 8%;Overglaze additive is the mixture of tungsten oxide, molybdenum oxide and nickel oxide, tungsten oxide, molybdenum oxide and nickel oxide Mass ratio be 2:2:1;Overglaze additive accounts for the 0.1% of overglaze gross mass;The mass ratio of overglaze material and overglaze frit is 15: 1;
The anti-skidding glaze that anti-skidding glaze layer uses includes anti-skidding glaze raw material, anti-skidding glaze frit and anti-skidding glaze additive, anti-skidding glaze The fineness of glaze slip is that 325 mesh screen residues are 0.3%;Anti-skidding glaze raw material includes based on mass fraction:SiO249%, Al2O315%, Fe2O30.6%, TiO20.1%, CaO8%, MgO7%, K2O4.2%, Na2O5%, ZnO10%, BaO1.1%;Anti-skidding glaze is molten Block includes basic dry granular, cooperation dry granular and function dry granular, and the mass ratio of basic dry granular, cooperation dry granular and function dry granular is 3:1:1; Basic dry granular includes based on mass fraction:SiO252%, Al2O319%, Fe2O30.05%, CaO11%, MgO3.3%, K2O5.9%, Na2O5.55%, ZnO3.2%;Cooperation dry granular include based on mass fraction:SiO254.5%, Al2O315%, Fe2O30.1%, CaO8.2%, MgO2.5%, K2O7.5%, Na2O9%, ZnO2.5%, CuO0.5%, CoO0.2%;Function Dry granular based on mass fraction include SiO251.5%, Al2O323%, Fe2O30.3%, CaO13.5%, MgO3.3%, K2O3%, Na2O2.6%, ZnO2.2%, Pr6O110.3%, La2O30.2%, Ce2O30.1%.Anti-skidding glaze additive is chlorine Change sodium, aluminium chloride, aluminum sulfate and 12 hydrazine aluminum sulfate potassium, sodium chloride, aluminium chloride, aluminum sulfate and 12 hydrazine aluminum sulfate potassium Mass ratio is 4:3:2:1;Anti-skidding glaze additive accounts for the 4% of anti-skidding glaze gross mass;The thickness of anti-skidding glaze layer is 0.5mm;Anti-skidding glaze The mass ratio of raw material and anti-skidding glaze frit is 25:1.
Anti-skid brick manufacture is carried out in accordance with the following methods:
The first step carries out blank forming, is dried by first time, and then on the surface of green body, leaching ground-coat enamel obtains ground-coat enamel Layer, and carry out second and be dried;Again the surface of ground glaze layer leaching overglaze obtain cover coat, then carry out it is ink-jet printed, and Carry out third time drying process;
Second step sprays anti-skidding glaze, obtains anti-skidding glaze layer, and carries out the 4th drying process, obtains preparation and fires brick body;
Third walks, and brick body is fired in preparation is put into kiln progress first time firing, by first time temperature programming to 400 DEG C It fires, first time temperature programming is:150 DEG C first are risen to 10min, 5min is maintained, then 300 DEG C are risen to 15min, maintains Then 15min rises to 400 DEG C with 5min, maintain 30min;Then the first secondary program cooling is carried out, the cooling of the first secondary program is: 350 DEG C first are down to 10min, then 300 DEG C is down to 30min, then 150 DEG C are down to 50min, is finally down in 70min 80℃;It is then placed in kiln and carries out second of firing, by second of temperature programming to 1200 DEG C of firings, second of temperature programming For:First stage rises to 300 DEG C with 10min, maintains 5min, second stage to rise to 600 DEG C with 5min, maintains 20min, third rank Section rises to 1200 DEG C with 30min, maintains 2h;
4th step, carries out the second secondary program cooling, and the cooling of the second secondary program is:1000 DEG C first are down to 60min, is then used 60min is down to 700 DEG C, then is down to 300 DEG C with 60min, is finally down to 80 DEG C with 60min;It is then placed in containing carbon dioxide It is cooled to room temperature in argon atmosphere, obtains semi-finished product, semi-finished product are post-treated to obtain finished product.
It should be noted that the preparation method of compound A approximately as:O-phenylenediamine and BOC acid anhydrides (two dimethyl dicarbonate fourths Ester) it reacts, product is reacted with dimethyl propylene diacid chloride, is then reacted with oxalyl chloride after progress degreasing reaction and be can be obtained chemical combination Object A.
Embodiment 2
A kind of anti-skid brick, including green body, ground glaze layer, cover coat and anti-skidding glaze layer, ground glaze layer are arranged in green body and cover coat Between, cover coat is arranged between ground glaze layer and anti-skidding glaze layer;
The ground-coat enamel that ground glaze layer uses includes ground-coat enamel raw material, ground-coat enamel frit and ground-coat enamel additive, and the fineness of the glaze slip of ground-coat enamel is 300 mesh screen residues are 0.5%;Ground-coat enamel raw material, ground-coat enamel frit, ground-coat enamel additive are same as Example 1;The quality of ground-coat enamel additive is dense Degree is 1%;Ground-coat enamel additive accounts for the 2% of ground-coat enamel gross mass;The mass ratio of ground-coat enamel raw material and ground-coat enamel frit is 15:1.
The overglaze that cover coat uses includes overglaze material, overglaze frit and overglaze additive, and the fineness of the glaze slip of overglaze is 200 mesh screen residues are 0.2%;Overglaze material, overglaze frit, overglaze additive component are same as Example 1, tungsten oxide, molybdenum oxide Mass ratio with nickel oxide is 2:2:1;Overglaze additive accounts for the 0.05% of overglaze gross mass;The matter of overglaze material and overglaze frit Amount is than being 10:1.
The anti-skidding glaze that anti-skidding glaze layer uses includes anti-skidding glaze raw material, anti-skidding glaze frit and anti-skidding glaze additive, anti-skidding glaze The fineness of glaze slip is that 325 mesh screen residues are 0.2%;Anti-skidding glaze raw material, anti-skidding glaze frit, anti-skidding glaze additive component and embodiment 1 It is identical;Sodium chloride, aluminium chloride, aluminum sulfate and 12 hydrazine aluminum sulfate potassium mass ratio be 4:3:2:1;Anti-skidding glaze additive accounts for anti- The 2% of sliding glaze gross mass;The thickness of anti-skidding glaze layer is 2mm;The mass ratio of anti-skidding glaze raw material and anti-skidding glaze frit is 20:1.
The preparation method is the same as that of Example 1.
Embodiment 3
A kind of anti-skid brick, including green body, ground glaze layer, cover coat and anti-skidding glaze layer, ground glaze layer are arranged in green body and cover coat Between, cover coat is arranged between ground glaze layer and anti-skidding glaze layer;
The ground-coat enamel that ground glaze layer uses includes ground-coat enamel raw material, ground-coat enamel frit and ground-coat enamel additive, and the fineness of the glaze slip of ground-coat enamel is 300 mesh screen residues are 0.4%;Ground-coat enamel raw material, ground-coat enamel frit, ground-coat enamel additive are same as Example 1;The quality of ground-coat enamel additive is dense Degree is 1.5%;Ground-coat enamel additive accounts for the 1% of ground-coat enamel gross mass;The mass ratio of ground-coat enamel raw material and ground-coat enamel frit is 20:1.
The overglaze that cover coat uses includes overglaze material, overglaze frit and overglaze additive, and the fineness of the glaze slip of overglaze is 200 mesh screen residues are 0.3%;Overglaze material, overglaze frit, overglaze additive component are same as Example 1, tungsten oxide, molybdenum oxide Mass ratio with nickel oxide is 2:2:1;Overglaze additive accounts for the 0.08% of overglaze gross mass;The matter of overglaze material and overglaze frit Amount is than being 20:1.
The anti-skidding glaze that anti-skidding glaze layer uses includes anti-skidding glaze raw material, anti-skidding glaze frit and anti-skidding glaze additive, anti-skidding glaze The fineness of glaze slip is that 325 mesh screen residues are 0.5%;Anti-skidding glaze raw material, anti-skidding glaze frit, anti-skidding glaze additive component and embodiment 1 It is identical;Sodium chloride, aluminium chloride, aluminum sulfate and 12 hydrazine aluminum sulfate potassium mass ratio be 4:3:2:1;Anti-skidding glaze additive accounts for anti- The 5% of sliding glaze gross mass;The thickness of anti-skidding glaze layer is 5mm;The mass ratio of anti-skidding glaze raw material and anti-skidding glaze frit is 15:1.
The preparation method is the same as that of Example 1.
It should be strongly noted that also containing necessary water in ground-coat enamel, overglaze and anti-skidding glaze, the dosage of water can be according to reality It needs to be adjusted.
Comparative example 1
Compared with Example 1, difference lies in do not add ground-coat enamel additive, overglaze additive and anti-skidding glaze additive.
Comparative example 2
Compared with Example 2, difference lies in ground-coat enamel raw material is without marble and raw talcum.
Comparative example 3
Compared with Example 3, difference lies in overglaze material is free of titanium oxide, nickel oxide and chromium oxide.
Comparative example 4
Compared with Example 1, difference lies in cooperation dry granular is free of CuO, CoO, and function dry granular is free of La2O3, Ce2O3 And Pr6O11.
Comparative example 5
Compared with Example 1, difference lies in cooling down without temperature programming and program when, manufacture, in atmospheric environment It is cooled to room temperature.
Finished product anti-skid brick made from embodiment 1-3, comparative example 1-5, is tested for the property, and as a result see the table below shown in 1.
1 the performance test results of table
As seen from the above table, the use of ground-coat enamel ingredient, overglaze ingredient and additive has the structural strength of anti-skid brick larger It influences, the ingredient of the ingredient especially frit of anti-skidding glaze has larger impact for the non-skid property of anti-skid brick;Manufacturing process for The structural strength and non-skid property of anti-skid brick have larger impact.It is formulated using anti-skid brick provided by the present application and manufacturer Method can change the interacting state between multilayered structure, change microstructure and surface micro-structure, optimize product structure strong Degree and non-skid property.
For those skilled in the art, the application can have various modifications and variations.It is all in spirit herein Within principle, any modification, equivalent replacement, improvement and so on should be included within the protection domain of the application.Although The present invention is illustrate and described with specific embodiment, however will be appreciated that without departing substantially from the spirit and scope of the present invention In the case of can make many other change and modification.It is, therefore, intended that including belonging to this hair in the following claims All such changes and modifications in bright range.

Claims (10)

1. a kind of anti-skid brick, which is characterized in that including green body, ground glaze layer, cover coat and anti-skidding glaze layer, the ground glaze layer setting exists Between the green body and the cover coat, the cover coat is arranged between the ground glaze layer and the anti-skidding glaze layer;
The ground-coat enamel that the ground glaze layer uses includes ground-coat enamel additive;The ground-coat enamel additive is the toluene solution of compound A, matter Measure a concentration of 1-2%;The ground-coat enamel additive accounts for the 0.5-2% of the ground-coat enamel gross mass;The structural formula of the compound A is such as Under:
The overglaze that the cover coat uses includes overglaze additive, and the overglaze additive is tungsten oxide, molybdenum oxide and nickel oxide Mixture, the mass ratio of the tungsten oxide, the molybdenum oxide and the nickel oxide is 2:2:1;The overglaze additive accounts for institute State the 0.05-0.1% of overglaze gross mass;
The anti-skidding glaze that the anti-skidding glaze layer uses includes anti-skidding glaze additive, the anti-skidding glaze additive be sodium chloride, aluminium chloride, Aluminum sulfate and 12 hydrazine aluminum sulfate potassium, the sodium chloride, the aluminium chloride, the aluminum sulfate and 12 hydrazine aluminum sulfate The mass ratio of potassium is 4:3:2:1;The anti-skidding glaze additive accounts for the 2-5% of the anti-skidding glaze gross mass.
2. anti-skid brick according to claim 1, which is characterized in that the ground-coat enamel further includes ground-coat enamel raw material and ground-coat enamel frit, The ground-coat enamel raw material by percentage to the quality, including:Marble 10%, quartz 8%, boron oxide 10%, zirconium silicate 10%, middle aluminium Powder 6%, albite 23%, kaolin 8%, desiliconization aluminium powder 3%, calcite 3%, dolomite 10%, raw talcum 9%;The bottom Glaze frit by percentage to the quality, including:SiO2 65%, Al2O3 10%, Fe2O31%, CaO 10%, MgO 5%, K2O 2%, Na2O 7%.
3. anti-skid brick according to claim 2, which is characterized in that the fineness of the glaze slip of the ground-coat enamel is that 300 mesh screen residues are 0.3-0.5%.
4. anti-skid brick according to claim 1, which is characterized in that the overglaze further includes overglaze material and overglaze frit; The overglaze material includes by percentage to the quality:SiO258%, Al2O315%, Fe2O32%, TiO20.5%, CaO8%, NiO0.5%, K2O4%, Cr2O31.5%, ZnO8%, BaO2.5%;The overglaze frit by percentage to the quality, including: SiO2 55%, Al2O3 15%, Fe2O31%, CaO 8%, MgO 5%, K2O 1%, Na2O 7%, B2O3 8%.
5. anti-skid brick according to claim 4, which is characterized in that the fineness of the glaze slip of the overglaze is that 200 mesh screen residues are 0.2-0.4%.
6. anti-skid brick according to claim 1, which is characterized in that the anti-skidding glaze further includes anti-skidding glaze raw material and anti-skidding glaze Frit;The mass ratio of the anti-skidding glaze raw material and the anti-skidding glaze frit is 25:1;
The anti-skidding glaze raw material includes based on mass fraction:SiO249%, Al2O315%, Fe2O30.6%, TiO20.1%, CaO8%, MgO7%, K2O4.2%, Na2O5%, ZnO10%, BaO1.1%;
The anti-skidding glaze frit includes basic dry granular, cooperation dry granular and function dry granular, the basis dry granular, the cooperation dry granular and The mass ratio of the function dry granular is 3:1:1;
It is described basis dry granular include based on mass fraction:SiO252%, Al2O319%, Fe2O30.05%, CaO11%, MgO3.3%, K2O5.9%, Na2O5.55%, ZnO3.2%;
The cooperation dry granular includes based on mass fraction:SiO254.5%, Al2O315%, Fe2O30.1%, CaO8.2%, MgO2.5%, K2O7.5%, Na2O9%, ZnO2.5%, CuO0.5%, CoO0.2%;
The function dry granular based on mass fraction include SiO251.5%, Al2O323%, Fe2O30.3%, CaO13.5%, MgO3.3%, K2O3%, Na2O2.6%, ZnO2.2%, Pr6O110.3%, La2O30.2%, Ce2O30.1%.
7. anti-skid brick according to claim 6, which is characterized in that the fineness of the glaze slip of the anti-skidding glaze is 325 mesh screen residues For 0.2-0.5%.
8. a kind of preparation method of any one of claim 1-7 anti-skid bricks, which is characterized in that include the following steps:
A. blank forming carries out first time drying process, and then on the surface of the green body, leaching ground-coat enamel obtains the ground glaze layer, and Second is carried out to be dried;Again the surface of the ground glaze layer leaching overglaze obtain the cover coat, then carry out it is ink-jet printed, And carry out third time drying process;
B. anti-skidding glaze is sprayed, the anti-skidding glaze layer is obtained, and carries out the 4th drying process, preparation is obtained and fires brick body;
C. brick body is fired into the preparation and is put into kiln progress first time firing, by first time temperature programming to 400 DEG C of firings; Then the first secondary program cooling is carried out, after being down to 80 DEG C, kiln is put into and carries out second of firing, extremely by second of temperature programming 1200 DEG C of firings;
D. the second secondary program cooling is then carried out, after being down to 80 DEG C, is put into the argon atmosphere containing carbon dioxide and is cooled to often Temperature obtains semi-finished product, and the semi-finished product are post-treated to obtain finished product.
9. preparation method according to claim 8, which is characterized in that the first time temperature programming is:First with 10min liters To 150 DEG C, 5min is maintained, then 300 DEG C are risen to 15min, maintain 15min, then rise to 400 DEG C with 5min, maintain 30min; Second of temperature programming be:First stage rises to 300 DEG C with 10min, and 5min, second stage is maintained to rise to 600 with 5min DEG C, it maintains 20min, phase III to rise to 1200 DEG C with 30min, maintains 2h.
10. preparation method according to claim 9, which is characterized in that first secondary program, which cools down, is:First use 10min 350 DEG C are down to, then 300 DEG C is down to 30min, then 150 DEG C are down to 50min, 80 DEG C is finally down in 70min;It is described Second secondary program cools down:1000 DEG C first are down to 60min, is then down to 700 DEG C with 60min, then 300 DEG C are down to 60min, Finally 80 DEG C are down to 60min.
CN201810712929.5A 2018-06-29 Anti-slip brick and preparation method thereof Active CN108545946B (en)

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CN203568981U (en) * 2013-11-28 2014-04-30 广东金牌陶瓷有限公司 Antiskid glazed tile
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CN105837172A (en) * 2016-03-23 2016-08-10 广东宏陶陶瓷有限公司 Resource-saving glazed ceramic tile having antiskid effect on surface and preparation method thereof
CN106348791A (en) * 2016-08-26 2017-01-25 高名胜 Non-slip ceramic tile manufacturing method
CN107417121A (en) * 2017-08-18 2017-12-01 佛山市石湾裕龙陶瓷有限公司 A kind of ceramics with anti-skidding glaze
CN107417115A (en) * 2017-07-17 2017-12-01 佛山市简陶瓷有限公司 A kind of preparation method of high-hardness, wearable glaze
CN107963814A (en) * 2017-11-16 2018-04-27 蒙娜丽莎集团股份有限公司 Compound glaze, the wear-resisting porcelain Antique Imitation Tiles of compound glaze slip and the soft face of 4-8 degree

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011113305A1 (en) * 2010-03-18 2011-09-22 Yang Dening Plate glass with colorful glaze layer and manufacuring process thereof
CN203568981U (en) * 2013-11-28 2014-04-30 广东金牌陶瓷有限公司 Antiskid glazed tile
CN104261897A (en) * 2014-09-25 2015-01-07 佛山市三水新明珠建陶工业有限公司 Ceramic tile having antiskid effect and manufacturing method thereof
CN105837172A (en) * 2016-03-23 2016-08-10 广东宏陶陶瓷有限公司 Resource-saving glazed ceramic tile having antiskid effect on surface and preparation method thereof
CN106348791A (en) * 2016-08-26 2017-01-25 高名胜 Non-slip ceramic tile manufacturing method
CN107417115A (en) * 2017-07-17 2017-12-01 佛山市简陶瓷有限公司 A kind of preparation method of high-hardness, wearable glaze
CN107417121A (en) * 2017-08-18 2017-12-01 佛山市石湾裕龙陶瓷有限公司 A kind of ceramics with anti-skidding glaze
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