CN116535246A - High-skid-resistance transparent dry particles, skid-resistance glaze using same, high-skid-resistance ceramic tile with water-repellent function and preparation method - Google Patents
High-skid-resistance transparent dry particles, skid-resistance glaze using same, high-skid-resistance ceramic tile with water-repellent function and preparation method Download PDFInfo
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- CN116535246A CN116535246A CN202310539311.4A CN202310539311A CN116535246A CN 116535246 A CN116535246 A CN 116535246A CN 202310539311 A CN202310539311 A CN 202310539311A CN 116535246 A CN116535246 A CN 116535246A
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- slip
- skid
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- 239000000919 ceramic Substances 0.000 title claims abstract description 130
- 239000002245 particle Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000005871 repellent Substances 0.000 title description 2
- 239000002994 raw material Substances 0.000 claims abstract description 53
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011449 brick Substances 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 39
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 34
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 33
- 239000011029 spinel Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001610 cryolite Inorganic materials 0.000 claims abstract description 26
- 239000011787 zinc oxide Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 15
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 15
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 15
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000013461 design Methods 0.000 claims description 32
- 239000004579 marble Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 27
- 238000005507 spraying Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- 238000010304 firing Methods 0.000 claims description 21
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 18
- 239000010459 dolomite Substances 0.000 claims description 18
- 229910000514 dolomite Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 239000010431 corundum Substances 0.000 claims description 14
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052664 nepheline Inorganic materials 0.000 claims description 10
- 239000010434 nepheline Substances 0.000 claims description 10
- 239000004328 sodium tetraborate Substances 0.000 claims description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 17
- 239000013078 crystal Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000000976 ink Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 27
- 238000011161 development Methods 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000006184 cosolvent Substances 0.000 description 6
- 238000007688 edging Methods 0.000 description 6
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 5
- 210000003298 dental enamel Anatomy 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 240000001085 Trapa natans Species 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052656 albite Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- -1 magnesium aluminate Chemical class 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 235000009165 saligot Nutrition 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 101150039167 Bex3 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—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
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- 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
Abstract
The invention relates to the technical field of ceramic tiles, in particular to a high-skid-resistance transparent dry particle, an anti-skid glaze using the same, a high-skid-resistance ceramic tile with a hydrophobic function and a preparation method thereof. The high-skid-resistance transparent dry particle is prepared from the following raw materials in percentage by mass: 20-30% of magnesite, 35-45% of alumina, 2-10% of zinc oxide, 15-30% of fluxing agent and 2-8% of catalyst. Cryolite and high-slip transparent dry particles containing magnesia-alumina spinel structures are introduced into the slip-resistant glaze as crystal nuclei, so that ceramic bricks with high hardness and high wear resistance can be obtained; as the serrated octahedral spinel bulges are densely distributed on the brick surface of the ceramic brick, the ceramic brick has higher anti-slip property when wetted, and the octahedral spinel bulges are smaller, so that stains scattered on the surface can be erased by adopting a common wet towel. The anti-slip glaze can be combined with deep ink to achieve stripping effect when the ceramic tile is prepared, linear grooves are formed on the surface of the ceramic tile, liquid can be dispersed along the grooves, accumulated water area is diffused, quick drying is easy, and better anti-slip effect is achieved.
Description
Technical Field
The invention relates to the technical field of ceramic tiles, in particular to a high-skid-resistance transparent dry particle, an anti-skid glaze using the same, a high-skid-resistance ceramic tile with a hydrophobic function and a preparation method thereof.
Background
With the continuous improvement of the living standard of people, consumers have increasingly demanded the functionality of ceramic tile products. At home, the kitchen and bathroom is inevitably scattered with domestic water, oil stain and the like, and the living room bedroom can also generate ponding phenomenon due to daily cleaning, so that at present, the anti-skid performance of common ceramic tiles used in families is obviously reduced after meeting water, and the safety is deteriorated.
In order to solve the problem of poor water-contact skid resistance of the ceramic tile, a method is provided for a plurality of manufacturers to adopt wax water to corrode the glaze after the ceramic tile is fired, and pits are generated to increase the friction coefficient of the glaze so as to improve the skid resistance; and manufacturers adopt large-particle anti-slip dry particles to be attached to the surface of the ceramic tile to form protrusions, and increase the roughness to improve the anti-slip effect. However, by adopting a method of corroding the glaze surface by using wax water, as the porcelain protective layer on the surface of the ceramic tile is destroyed, capillary holes generated by exhaust gas on the surface of the ceramic tile in the firing process are exposed, dirt is easily absorbed, and the dirt cannot be easily cleaned after entering the capillary holes, so that the service performance of the ceramic tile is greatly influenced; when large-particle anti-slip dry particles are adopted to be attached to the surface of the ceramic tile, the particles of the dry particles are large, the hand feeling is rough, dirt is easy to be hidden, gaps exist between the anti-slip dry particles, dirt is easy to clamp at the bottoms of the gaps of the dry particles after falling, the bottoms of the gaps are difficult to clean during cleaning, and the phenomenon of dirt blocking and dirt hiding is formed.
In order to solve the problem of the anti-slip dry particles, some manufacturers try to break the anti-slip dry particles with large particles into anti-slip dry particles with smaller particles, but in the firing process, the anti-slip dry particles with small particles have smaller granularity, irregular broken fracture with the anti-slip effect on the surface starts to melt under the high temperature condition, and the anti-slip dry particles on the surface of the ceramic tile become a round state from sharp, so that the anti-slip dry particles on the surface of the ceramic tile become smooth, the friction resistance becomes small, and the good anti-slip effect cannot be achieved. Therefore, the development of the high-slip-resistance ceramic tile product which can not only resist slipping when meeting water, but also is convenient to manage and not absorb and store dirt is important for life of people.
Disclosure of Invention
The invention mainly aims to provide a high-anti-skid transparent dry particle, an anti-skid glaze using the same, a high-anti-skid ceramic tile with a hydrophobic function and a preparation method thereof, and aims to solve the technical problem that the existing anti-skid ceramic tile is poor in antifouling performance.
In order to achieve the above purpose, the invention provides a high anti-skid transparent dry granule which is prepared from the following raw materials: 20-30% of magnesite, 35-45% of alumina, 2-10% of zinc oxide, 15-30% of fluxing agent and 2-8% of catalyst.
The raw materials used for the transparent dry granule with high skid resistance in the scheme mainly comprise three parts: 1. magnesium source is mainly magnesite; 2. the aluminum source is mainly alumina; 3. the additive mainly comprises a cosolvent and a catalyst, wherein the fluxing agent comprises minerals containing divalent alkaline earth metals and borax; the catalyst comprises one or more of cryolite, aluminum fluoride and ammonium fluoride.
The high-anti-slip transparent dry particles prepared by the raw materials contain an octahedral structure of magnesia-alumina spinel, and the generated spinel structure has the characteristics of good crystal development, uniform structure, stable quality and high hardness, and the Mohs hardness of the ceramic tile prepared under the preferable formula can reach 7 levels and can be used as crystal nucleus of anti-slip glaze in the ceramic tile firing process. In addition, the raw materials are added with fluxing agents such as dolomite, strontium carbonate and the like, and alkaline earth metal elements such as calcium, magnesium, strontium and the like can increase the penetration of the frit under the action of high temperature in the calcination process, and the frit is crushed for the second time to form transparent dry powder.
Preferably, the preparation steps of the high anti-skid transparent dry particles comprise:
s1, uniformly mixing the raw materials of the high-skid-resistance transparent dry particles, and calcining; the calcination curve is that the temperature is raised to 700 ℃ from normal temperature to fire for 30-45min, fire for 45-60min at 700-1100 ℃, fire for 30-60min at 1100-1280 ℃, fire for 60-90min at 1280-1480 ℃ and keep the temperature for 60-90min at 1480 ℃; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 15-18 ℃/min, and preserving heat for 20-30min at 1300 ℃ to obtain frit slurry;
s2, cooling the frit slurry through water quenching, and drying at 200-250 ℃ for 1-2h, and crushing for the second time to obtain the high-skid-resistance transparent dry particles.
The fineness of the raw materials for preparing the high-skid-resistance transparent dry particles is controlled to be 200-250 meshes, and the raw materials are uniformly mixed according to a proportion; placing the mixed raw materials into a high-temperature frit furnace, heating to 1480 ℃ according to the calcination curve, and preserving heat for 60-90 minutes; cooling to 1300 ℃ and preserving heat for 20-30 minutes; and then carrying out water quenching and cooling on the frit slurry, filtering the obtained frit, putting the filtered frit into a baking oven, drying the dried frit at 200 ℃ for 1-2 hours, and crushing the dried frit to obtain the high-skid-resistance transparent dry particles with the magnesia-alumina spinel octahedral structure.
Preferably, the high slip transparent dry particles contain an octahedral structure of magnesium aluminate spinel. After the high anti-slip transparent dry particles with the octahedral structure are used for anti-slip glaze and ceramic tiles, octahedral crystal nuclei can be continuously gathered and naturally grow to form protrusions with microscopic sawtooth-shaped octahedral structures in the firing process, the protrusions are distributed on the surfaces of the ceramic tiles, and the protruding octahedral spinel sawtooth structures have high biting force, so that the anti-slip performance of the ceramic tiles can be improved.
Preferably, the fluxing agent comprises borax and a fluxing agent containing alkaline earth metal oxides; the catalyst is at least one of cryolite, aluminum fluoride and ammonium fluoride. The fluxing agent in the scheme can be borax, dolomite, strontium carbonate and the like; cryolite is preferably used as the catalyst.
The main components of the high anti-skid transparent dry granule are magnesite, alumina, cosolvent and other additives, and the above raw materials are calcined at high temperature to obtain a fused block with spinel structure, wherein dolomite is decomposed at 700-900 ℃ to discharge CO 2 Gas, generating calcium oxide and magnesium oxide; CO of magnesite at around 1100 DEG C 2 The gas is discharged to generate MgO simple substance, the alumina is converted into alpha-Al after completing the crystal form conversion at 1200 DEG C 2 O 3 Continuously firing MgO and alpha-Al at high temperature 2 O 3 The magnesia-alumina spinel octahedral structure produced by the combination reaction has the advantages of good spinel structure development, uniform structure, stable quality and high hardness, the Mohs hardness of the ceramic tile prepared under the preferable formula can reach 7 levels, and the spinel structure crystal also has the characteristics of high temperature resistance and good thermal stability, and the structure of the spinel crystal can not be damaged after the spinel crystal is subjected to secondary sintering in the subsequent high-temperature ceramic tile sintering process. The zinc oxide in the high-anti-slip transparent dry particle raw material can improve the transparent feeling and the color development of the dry particle, the alkaline earth metal and the borax can further increase the transparent feeling of the glass of the high-anti-slip transparent dry particle and reduce the reaction temperature of spinel conversion, and softening reaction is started at an earlier temperature to generate a spinel structure. The temperature is reduced to 1300 ℃ after 1480 ℃ high-temperature calcination, and the heat preservation procedure is carried out, so that the catalysis of the catalyst, i.e. cryolite, aluminum fluoride or ammonium fluoride, can promote the firm bonding of spinel magnesium-aluminum bonds, and fluoride ions accelerate the crystallization of spinel octahedron to form granular crystals.
Preferably, the high anti-skid transparent dry particle fineness formed by secondary crushing of the frit is 200-250 meshes. The frit particles obtained after water quenching and drying are larger, and the frit particles are required to be subjected to secondary crushing to obtain dry particle powder with the fineness of 200-250 meshes, wherein the dried frit is crushed into 8-16 meshes in the primary crushing, and is further crushed into 200-250 meshes of transparent dry particle powder in the secondary crushing. After the high anti-slip transparent dry particles are crushed into powder, the raw materials of the anti-slip glaze are subjected to ball milling, so that the anti-slip glaze and other raw materials can reach required fineness synchronously, and then the anti-slip glaze is uniformly applied to the surface of a green brick through a glaze spraying cabinet.
Besides, the invention also provides an anti-slip glaze which is prepared by mixing and ball milling the following raw materials in percentage by mass: 12-22% of potassium feldspar, 10-18% of nepheline, 4-8% of kaolin, 6-14% of dolomite, 2-10% of zinc oxide, 8-18% of corundum, 4-10% of quartz, 10-24% of high anti-skid transparent dry particles as described in any one of the above, 2-8% of cryolite and 4-8% of barium carbonate. Besides the raw materials, a small amount of additives can be added into the anti-slip glaze to improve the glaze slip performance of the anti-slip glaze, such as sodium tripolyphosphate and sodium carboxymethyl cellulose.
The raw materials in the anti-slip glaze are uniformly mixed and then ball-milled, and then the anti-slip glaze is obtained after slurry discharge, iron removal and sieving. Because the high-anti-slip transparent dry powder containing the magnesia-alumina spinel octahedral structure is added into the anti-slip glaze, the anti-slip glaze prepared by the dry powder can be continuously gathered and naturally grown to form the projections of the microscopic saw-tooth octahedral structure after being uniformly applied to the surface of the ceramic tile due to the high-temperature heat movement and the affinity effect of a catalyst and a chemical bond in the firing process, and the projections are tiny and sharp and are distributed on the surface of the ceramic tile. The high-slip-resistance ceramic tile prepared by the slip-resistance glaze has high biting force of the octahedral spinel sawtooth structure with the raised surface under the condition that water stains exist on the surface of the ceramic tile, can improve the slip-resistance performance of the ceramic tile, is suitable for mass production of the ceramic tile, and has stable performance and good product quality consistency.
The anti-slip glaze takes alkaline earth metal oxide as a main additive, and calcium oxide and magnesium oxide decomposed from dolomite have dissolution assisting effect; under the catalysis of cryolite mineralizer, quartz and corundum in the raw materials have whisker-shaped mullite generated at about 1100 ℃ during firing, and the crystal reaction is completed at 1200 ℃. As the surface of the ceramic tile is provided with the protrusions of the octahedral spinel structure, corundum-mullite crystal phase is generated at the same time, the ceramic tile has better protection effect on the glaze layer, the hardness and the wear resistance of the ceramic tile can be improved, and meanwhile, the ceramic tile has better long-term anti-skid performance and can be kept undamaged for about 30 years.
In addition, the invention also provides a preparation method of the high anti-slip ceramic tile with the hydrophobic function, which comprises the following preparation steps: s01, pressing the green body powder to obtain a green brick, applying a ground glaze on the green brick, and then spraying and printing a marble design pattern;
s02, further jet printing deep ink, and jet printing the set marble stripe deep ink on the surface of the green brick according to aesthetic characteristics and use function requirements of the product;
s03, further applying the anti-slip glaze, namely applying the anti-slip glaze on the green bricks sprayed with marble design patterns and deep ink, and baking and firing to obtain the high anti-slip ceramic bricks with the hydrophobic function.
In the scheme, the ground glaze is sprayed and printed on the green bricks in sequence, and marble design patterns are sprayed and printed on the green bricks, so that the surfaces of the ceramic bricks have rich stone texture; then spraying functional ink-deep ink, wherein the spraying area of the deep ink is the area where the marble design pattern is located, and the deep ink can be used for spraying all the areas where the marble design pattern is located and can be used for spraying only the local area where the marble design pattern is located, so that the width and depth of the line pattern of the marble stripe-shaped deep ink are required to be adjusted according to aesthetic design and functional design; then spraying the anti-slip glaze in the scheme, wherein the anti-slip glaze is sprayed on the whole layout of the green brick, the anti-slip glaze can play a stripping effect when being overlapped at the position where deep ink is sprayed, after firing, linear grooves with different widths and depths are formed, water stains or other liquid on the surface of the ceramic tile can be dispersed along the grooves, so that the diffusion area of the ceramic tile is larger, the ceramic tile plays a role in dewatering, is easy to dry quickly, and reduces the wet sliding degree of the surface of the ceramic tile; meanwhile, the contact area between the sole and the surface of the ceramic tile can be reduced due to the existence of the linear grooves, the pressure intensity is increased under the condition of constant weight, the occlusion degree between the sole and the ceramic tile is improved, and the anti-skid performance of the ceramic tile is further improved.
In addition, the existence of the anti-slip glaze can also lead the ceramic tile to have better wear-resistant and high-hardness effects, the synthesized powder containing magnesia-alumina spinel clinker is introduced into the anti-slip glaze as crystal nucleus and is adhered to the surface of the ceramic tile in the firing process of the ceramic tile, and the cryolite mineralizer is added to promote the spinel powder to continuously gather and grow into an octahedral protruding structure with water caltrop in the firing process of the ceramic tile, and the cryolite mineralizer can also promote the quartz and corundum in the glaze to react to generate mullite crystal phase to form a high-hardness and high-wear-resistant protective layer so as to protect the surface pattern of the ceramic tile from being damaged. The hardness of the surface of the ceramic tile prepared under the preferable formula can reach more than 7 grades, and in daily life, the hardness of quartz sand is 6 grades, so that the surface of the ceramic tile is not damaged; the ceramic tile has small surface abrasion and the anti-skid performance can be kept from being damaged for 30 years.
Preferably, in step S03, the firing temperature is 1200-1220 ℃ and the firing period is 65-75min.
Preferably, in step S03, the mixture is dried at 120-180 ℃ for 30-60min. The moisture in the green bricks and each glaze layer can be removed by pre-drying, so that the ceramic bricks have better quality.
Preferably, the specific gravity of the anti-slip glaze is 1.30-1.50g/ml, and the glazing amount is 180-280g/m 2 . The anti-slip glaze is controlled to improve the hardness, anti-slip effect and hydrophobic effect of the ceramic tile optimally when the application amount is controlled.
In addition, the invention also provides the high-slip-resistance ceramic tile with the hydrophobic function, which is prepared by the preparation method of the high-slip-resistance ceramic tile with the hydrophobic function. The high anti-slip ceramic tile with the hydrophobic function has the same beneficial effects as the preparation method, and is not described in detail herein.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. toxic cosolvent raw materials which are easy to generate gas and react with water are introduced into the anti-slip glaze in a way of presintering the toxic cosolvent raw materials into fusion cakes (dry grains), so that the compactness, the formula stability and the production safety of the anti-slip glaze are ensured.
2. The main components of the high anti-skid transparent dry particles are magnesite, alumina, a cosolvent and a catalyst, the high anti-skid transparent dry particles are firstly prepared into the frit through 1480 ℃ high-temperature calcination, and the cosolvent can increase the transparency and the color development of the frit, and the catalyst can reduce the reaction temperature of spinel, so that the magnesite and the alumina generate octahedral structure spinel through decomposition and catalysis, and the prepared frit can obtain the high anti-skid transparent dry particles with better transparency and good color development and containing magnesia-alumina spinel octahedral structure after being crushed.
3. In the firing process of the ceramic tile, the high anti-slip transparent dry powder containing the magnesia-alumina spinel structure is introduced into the anti-slip glaze as crystal nucleus and is adhered to the surface of the ceramic tile, and the cryolite mineralizer is also added into the anti-slip glaze, so that spinel powder on the surface of the ceramic tile can be promoted to be continuously gathered and grown into an octahedral protruding structure with water caltrop in the firing process of the ceramic tile, and meanwhile, the cryolite can promote quartz and corundum in the glaze to react to generate mullite crystal phase, so that a high-hardness and high-wear-resistant protective layer is obtained, and the surface pattern of the ceramic tile is protected from being damaged.
4. The ceramic tile has a good anti-skid function, and after meeting water, the tile surface is densely provided with the sawtooth-shaped octahedral spinel protruding structures, and each square meter is provided with about 9 ten thousand protrusions, so that the ceramic tile has high anti-skid performance even under the conditions of water stains and oil stains. And as the surface crystals are gathered, the protrusions of the octahedral spinel are smaller, the pits between adjacent protruding particles are shallower, the glaze is in a sintered state, the ceramic tile is not polished and polished, pores are avoided, the ceramic tile prepared under the preferred formula can not absorb dirt and store dirt, and dirt scattered on the surface can be erased by adopting a common wet towel.
5. The ceramic tile provided by the invention also has a good hydrophobic function, the deep ink is added to the anti-slip glaze to achieve a stripping effect in the preparation process, grooves with different widths and depths are formed, the contact area between the grooves and soles can be reduced, the pressure intensity is increased, and the anti-slip performance of the ceramic tile is improved; meanwhile, the grooves extend along the grain trend of the marble design pattern, the ceramic tile has a hydrophobic function while playing a decorative role, water stains or other liquid on the surface of the ceramic tile can be dispersed along the grooves, the diffusion area is larger, quick drying is easy, the wet and slippery degree of the surface of the ceramic tile is reduced, and the anti-skid performance of the ceramic tile is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a partial schematic view of a high slip ceramic tile with hydrophobic functionality in this embodiment;
fig. 2 is a partial groove display of a high slip ceramic tile with hydrophobic function in this solution.
Wherein: 1-blank layer, 2-ground coat layer, 3-marble design pattern layer, 4-deep ink layer, 41-groove and 5-anti-slip coat.
The realization, functional characteristics and advantages of the present application will be further described with reference to the embodiments, referring to the attached drawings.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The preparation method of the high anti-slip ceramic tile with the hydrophobic function comprises the following preparation steps:
s01, pressing and forming the green body powder by a constant force Tai press to obtain a green brick, drying the green brick by a drying kiln, controlling the moisture to be 0.3-0.5%, spraying ground coat, and then adopting a high-definition digital ink-jet machine to spray-print marble design patterns, so that the surface of the ceramic brick has rich stone texture;
s02, continuously adopting a high-definition digital ink-jet machine to jet and print linear deep ink, wherein the deep ink watermark is positioned in the area where the marble design pattern is positioned; the deep ink is selected from deep functional inks produced by Idagay corporation.
S03, spraying anti-slip glaze by using a new cloisonne glaze spraying cabinet, wherein the anti-slip glaze is applied to green bricks sprayed with marble design patterns and deep ink, and the anti-slip glaze at the position with the deep ink can show stripping effects with different sizes; drying in a drying box at 120-180 ℃ for 30-60min, then placing in a kiln, firing at 1200-1220 ℃ for 65-75min, and edging to obtain the high anti-slip ceramic tile with the hydrophobic function.
The anti-slip glaze is prepared by mixing and ball milling the following raw materials in percentage by mass: 12-22% of potassium feldspar, 10-18% of nepheline, 4-8% of kaolin, 6-14% of dolomite, 2-10% of zinc oxide, 8-18% of corundum, 4-10% of quartz, 10-24% of high-skid-resistance transparent dry particles, 2-8% of cryolite and 4-8% of barium carbonate. Adding water to adjust the specific gravity to 1.30-1.50g/ml after ball milling of the anti-slip glaze, and applying the glaze with the glazing quantity of 180-280g/m 2 。
The high-skid-resistance transparent dry particles are prepared from the following raw materials in percentage by mass: 20-30% of magnesite, 35-45% of alumina, 2-10% of zinc oxide, 15-30% of fluxing agent and 2-8% of catalyst; the fluxing agent comprises borax and a fluxing agent containing divalent alkaline earth metals; the catalyst is at least one of cryolite, aluminum fluoride and ammonium fluoride.
The preparation method of the high-skid-resistance transparent dry particles comprises the following steps: s1, uniformly mixing the raw materials, and calcining, wherein the fineness of each raw material is 200-250 meshes; the calcination curve is that the temperature is raised to 700 ℃ from normal temperature to fire for 30-45min, fire for 45-60min at 700-1100 ℃, fire for 30-60min at 1100-1280 ℃, fire for 60-90min at 1280-1480 ℃ and keep the temperature for 60-90min at 1480 ℃; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 15-18 ℃/min, and preserving heat for 20-30min at 1300 ℃ to obtain frit slurry; s2, after the frit slurry is quenched and cooled by water, drying the frit slurry for 1-2 hours at 200-250 ℃ and crushing the frit slurry twice to obtain the high-skid-resistance transparent dry powder with the fineness of 200-250 meshes.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
The blanks in this embodiment can be made by pressing any conventional blank on the market, and in various embodiments, the raw materials of the blanks can be adapted, and a set of blanks is provided herein for use in the preparation of ceramic tiles in the following examples: the chemical composition of the green body powder comprises the following components in percentage by mass: si0 2 65.88％、Al 2 O 3 20.32％、Fe 2 O 3 0.7％、TiO 2 0.16％、CaO 0.51％、MgO 0.91％、K 2 O 3.73％、Na 2 O2.65% and loss on ignition 4.83%.
Similarly, the ground glaze can be any ground glaze in the market, the fineness of the ground glaze can be 325 mesh screen residue less than 0.6%, the specific gravity is 1.80-1.87g/ml (1.83 g/ml in each embodiment below), and the glazing amount is 300-380g/m 2 (Each of the following examples is 350 g/m) 2 ) A set of base enamels is provided herein for use in the preparation of ceramic tiles in the following examples: the chemical composition of the base coat comprises the following components in percentage by mass: si0 2 49.32％、Al 2 O 3 20.53％、Fe 2 O 3 0.15％、TiO 2 0.08％、ZnO 2.32％、CaO 4.21％、MgO 3.65％、K 2 O 3.53％、Na 2 O 2.76％、BaO 3.24％、ZrO 2 5.74% and loss on ignition 4.36%.
Example 1
The preparation method of the anti-slip ceramic tile comprises the following preparation steps:
s01, pressing and forming the green body powder by a constant force Tai press to obtain a green brick, drying the green brick by a drying kiln, spraying ground enamel, and then adopting a high-definition digital ink-jet machine to spray-print marble design patterns;
s02, continuously adopting a high-definition digital ink-jet machine to jet and print linear deep ink, wherein the deep ink watermark is positioned in the area where the marble design pattern is positioned;
s03, spraying common protective glaze containing high-skid-resistance transparent dry particles by using a new cloisonne glaze spraying cabinet, wherein the glaze is applied to green bricks sprayed with marble design patterns; oven-drying at 150deg.C for 30min, baking at 1210 deg.C for 65min, and edging to obtain the final product.
The common protective glaze containing high-skid-resistance transparent dry particles is prepared by mixing and ball milling the following raw materials in percentage by mass: 12% of albite, 15% of potassium feldspar, 4% of zinc oxide, 13% of barium carbonate, 7% of kaolin, 15% of wollastonite, 6% of alumina, 20% of high-skid-resistance transparent dry particle powder and 8% of calcined clay; the glaze is ball milled, then added with water to adjust the specific gravity to 1.4g/ml, and the glazing quantity is 200g/m 2 。
The high-skid-resistance transparent dry particles are prepared from the following raw materials in percentage by mass: 27% of magnesite, 40% of alumina, 7% of zinc oxide, 20% of flux-dolomite and 6% of cryolite.
The preparation method of the high-skid-resistance transparent dry particles comprises the following steps: s1, uniformly mixing the raw materials, and calcining, wherein the fineness of each raw material is 200-250 meshes; the calcination curve is that the temperature is raised to 700 ℃ from normal temperature to fire for 35min, fire for 50min at 700-1100 ℃, fire for 40min at 1100-1280 ℃, fire for 65min at 1280-1480 ℃ and keep the temperature for 70min at 1480 ℃; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 16 ℃/min, and preserving heat for 20min at 1300 ℃ to obtain frit slurry; s2, cooling the frit slurry through water quenching, drying at 200 ℃ for 1h, and crushing to obtain the high-skid-resistance transparent dry particles with the fineness of 200-250 meshes.
Comparative example 1
The conditions in this comparative example were the same as in example 1, except that: the protective glaze applied in the step S03 does not contain high anti-skid transparent dry powder, the dosage of potassium feldspar in other raw materials is adjusted to 25 percent, and the dosage of albite is adjusted to 22 percent, namely, the marble design pattern is printed by ink jet after the ground glaze is applied on the green brick, the deep ink is printed, and then the protective glaze is sprayed, dried and burned to obtain the ceramic tile.
The ceramic tiles prepared in example 1 and comparative example 1 were subjected to performance test, and specific test results are shown in the following table:
note that: the static friction coefficient is detected under the condition of the surface drying of the ceramic tile by adopting national standard GBT4100-2015, and the anti-skid performance is detected under the condition of water or oil on the sole by adopting Debiao inclined platform method DIN51130:2014 standard.
Stain resistance test: 1. cleaning the surface of the ceramic tile, putting the ceramic tile into a drying oven at 200 ℃ for drying for 20 minutes, and taking out; 2. coating pattern marks on the surface of the dried ceramic tile by using a blue oily mark pen; 3. scrubbing the blue pattern mark with a wet towel, and observing whether a stain is remained or not at a distance of 50 cm; 4. and repeating the test for 3 times and observing at 50cm, judging that the test is qualified when no stain is left for 3 times, wherein a small amount of residual stains are slightly hidden, and a large amount of residual stains are hidden.
As shown by the test results of the embodiment 1 and the comparative example 1 in the table, compared with the conventional ceramic tile, the high anti-slip transparent dry powder can improve the hardness and the wear resistance of the ceramic tile and can still maintain better anti-fouling performance and the color development effect of the texture pattern of the ceramic tile after being added into the protective glaze.
Example 2
The preparation steps and parameters in this example are the same as in example 1, except that: the preferred slip-resistant glaze is adopted in the embodiment, and the raw materials are different from the conventional protective glaze. The anti-slip glaze is prepared by mixing and ball milling the following raw materials in percentage by mass: 16% of potassium feldspar, 14% of nepheline, 6% of kaolin, 8% of dolomite, 6% of zinc oxide, 16% of corundum, 7% of quartz, 17% of high-skid-resistance transparent dry granular powder, 5% of cryolite and 5% of barium carbonate. Adding water to adjust the specific gravity to 1.40g/ml after ball milling of the anti-slip glaze, and glazing the glaze with the glazing quantity of 200g/m 2 。
Example 3
The preparation method of the high anti-slip ceramic tile with the hydrophobic function comprises the following preparation steps:
s01, pressing and forming the green body powder by a constant force Tai press to obtain a green brick, drying the green brick by a drying kiln, spraying ground enamel, and then adopting a high-definition digital ink-jet machine to spray-print marble design patterns;
s02, continuously adopting a high-definition digital ink jet machine to jet and print linear deep ink, wherein the deep ink watermark is positioned in the area where the marble design pattern is positioned.
S03, spraying anti-slip glaze by using a new cloisonne glaze spraying cabinet, wherein the anti-slip glaze is applied to green bricks sprayed with marble design patterns and deep ink; drying in a 160 ℃ drying box for 40min, then placing in a kiln and firing for 65min at 1200 ℃, and edging to obtain the high anti-slip ceramic tile with the hydrophobic function.
The anti-slip glaze is prepared by mixing and ball milling the following raw materials in percentage by mass: 20% of potassium feldspar, 16% of nepheline, 8% of kaolin, 10% of dolomite, 5% of zinc oxide, 12% of corundum, 9% of quartz, 12% of high-skid-resistance transparent dry granular powder, 3% of cryolite and 5% of barium carbonate. Adding water to adjust specific gravity to 1.35g/ml after ball milling of the anti-slip glaze, and glazing the glaze with the glazing quantity of 180g/m 2 。
The high-skid-resistance transparent dry particles are prepared from the following raw materials in percentage by mass: 20% of magnesite, 45% of alumina, 5% of dolomite, 9% of zinc oxide, 10% of borax, 4% of strontium carbonate and 7% of cryolite.
The preparation method of the high-skid-resistance transparent dry particles comprises the following steps: s1, uniformly mixing the raw materials, and calcining, wherein the fineness of each raw material is 200-250 meshes; the calcination curve is that the temperature is raised to 700 ℃ from normal temperature to fire for 40min, fire for 60min at 700-1100 ℃, fire for 55min at 1100-1280 ℃, fire for 80min at 1280-1480 ℃ and keep the temperature for 80min at 1480 ℃; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 18 ℃/min, and preserving heat for 20min at 1300 ℃ to obtain frit slurry; s2, after the frit slurry is quenched and cooled by water, drying the frit slurry for 1.5 hours at 230 ℃, and crushing the frit slurry to obtain the high-skid-resistance transparent dry particles with the fineness of 200-250 meshes.
Example 4
The preparation method of the high anti-slip ceramic tile with the hydrophobic function comprises the following preparation steps:
s01, pressing and forming the green body powder by a constant force Tai press to obtain a green brick, drying the green brick by a drying kiln, spraying ground enamel, and then adopting a high-definition digital ink-jet machine to spray-print marble design patterns;
s02, continuously adopting a high-definition digital ink jet machine to jet and print linear deep ink, wherein the deep ink watermark is positioned in the area where the marble design pattern is positioned.
S03, spraying anti-slip glaze by using a new cloisonne glaze spraying cabinet, wherein the anti-slip glaze is applied to green bricks sprayed with marble design patterns and deep ink; drying for 35min in a drying box at 180 ℃, then placing in a kiln to fire for 70min at 1220 ℃, and edging to obtain the high anti-slip ceramic tile with the hydrophobic function.
The anti-slip glaze is prepared by mixing and ball milling the following raw materials in percentage by mass: 20% of potassium feldspar, 14% of nepheline, 5% of kaolin, 7% of dolomite, 6% of zinc oxide, 15% of corundum, 8% of quartz, 17% of high-skid-resistance transparent dry granular powder, 4% of cryolite and 4% of barium carbonate. Adding water to adjust specific gravity to 1.35g/ml after ball milling of the anti-slip glaze, and glazing the glaze with the glazing quantity of 230g/m 2 。
The high-skid-resistance transparent dry particles are prepared from the following raw materials in percentage by mass: 27% of magnesite, 41% of alumina, 10% of dolomite, 6% of zinc oxide, 6% of borax, 4% of strontium carbonate and 6% of cryolite.
The preparation method of the high-skid-resistance transparent dry particles comprises the following steps: s1, uniformly mixing the raw materials, and calcining, wherein the fineness of each raw material is 200-250 meshes; the calcination curve is that the temperature is raised to 700 ℃ from normal temperature to fire for 30min, fire for 45min at 700-1100 ℃, fire for 30min at 1100-1280 ℃, fire for 60min at 1280-1480 ℃ and keep the temperature for 60min at 1480 ℃; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 18 ℃/min, and preserving heat for 25min at 1300 ℃ to obtain frit slurry; s2, cooling the frit slurry through water quenching, drying at 220 ℃ for 2 hours, and crushing to obtain the high-skid-resistance transparent dry powder with the fineness of 200-250 meshes.
Example 5
The preparation method of the high anti-slip ceramic tile with the hydrophobic function comprises the following preparation steps:
s01, pressing and forming the green body powder by a constant force Tai press to obtain a green brick, drying the green brick by a drying kiln, spraying ground enamel, and then adopting a high-definition digital ink-jet machine to spray-print marble design patterns;
s02, continuously adopting a high-definition digital ink jet machine to jet and print linear deep ink, wherein the deep ink watermark is positioned in the area where the marble design pattern is positioned.
S03, spraying anti-slip glaze by using a new cloisonne glaze spraying cabinet, wherein the anti-slip glaze is applied to green bricks sprayed with marble design patterns and deep ink; drying in a drying box at 150 ℃ for 30min, then placing in a kiln and firing at 1213 ℃ for 68min, and edging to obtain the high-slip-resistance ceramic tile with the hydrophobic function.
The anti-slip glaze is prepared by mixing and ball milling the following raw materials in percentage by mass: 17% of potassium feldspar, 15% of nepheline, 5% of kaolin, 10% of dolomite, 7% of zinc oxide, 8% of corundum, 6% of quartz, 22% of high-skid-resistance transparent dry granular powder, 6% of cryolite and 4% of barium carbonate. Adding water to adjust specific gravity to 1.35g/ml after ball milling of the anti-slip glaze, and glazing the glaze with the glazing quantity of 280g/m 2 。
The high-skid-resistance transparent dry particles are prepared from the following raw materials in percentage by mass: 30% of magnesite, 35% of alumina, 15% of dolomite, 6% of zinc oxide, 8% of borax, 4% of strontium carbonate and 2% of cryolite.
The preparation method of the high-skid-resistance transparent dry particles comprises the following steps: s1, uniformly mixing the raw materials, and calcining, wherein the fineness of each raw material is 200-250 meshes; the calcination curve is that the temperature is raised to 700 ℃ from normal temperature to fire for 30min, fire for 45min at 700-1100 ℃, fire for 30min at 1100-1280 ℃, fire for 60min at 1280-1480 ℃ and keep the temperature for 60min at 1480 ℃; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 18 ℃/min, and preserving heat for 20min at 1300 ℃ to obtain frit slurry; s2, cooling the frit slurry through water quenching, drying at 200 ℃ for 2 hours, and crushing to obtain the high-skid-resistance transparent dry powder with the fineness of 200-250 meshes.
Comparative example 2
The preparation steps and parameters of this comparative example are the same as those of comparative example 1, except that: the anti-slip brick is obtained by adopting a method of corroding the glaze surface in the comparative example. The method comprises the following specific steps: directly polishing the surface of the ceramic tile obtained in comparative example 1 with a wax polishing machine at a speed of 100-150r/min to polish the surface of the ceramic tile, and polishing the surface of the ceramic tile with waxThe water adopts corrosion wax water of Nade chemical industry, and the dosage is 5-10g/m 2 。
Comparative example 3
The preparation steps and parameters of this comparative example are the same as those of comparative example 1, except that: the comparative example adopts a method of applying large dry grains to obtain the anti-slip brick. Wherein, the large-particle anti-slip dry particles adopt GFRK-486 dry particles of Carmobia glaze company, and the specific application steps are as follows: after the marble design pattern is sprayed and printed, a slip-resistant dry particle suspension liquid is sprayed on the green bricks by a glaze spraying cabinet, the common protective glaze is replaced by the slip-resistant dry particle suspension liquid, the slip-resistant dry particle suspension liquid is prepared by uniformly stirring 40% of slip-resistant dry particles, 50% of suspending agent and 10% of protective glaze, wherein the specific gravity of the dry particle suspension liquid is 1.45g/ml, and the glazing quantity is 180g/m 2 。
Comparative example 4
The preparation steps and parameters of this comparative example were the same as in example 2, except that: the comparative example does not spray deep ink, namely, the step S02 is canceled, and the anti-slip glaze is directly sprayed after the marble design pattern is sprayed.
Comparative example 5
The preparation steps and parameters of this comparative example were the same as in example 2, except that: zinc oxide is not added into the anti-slip glaze in the comparative example, and the dosage of potassium feldspar in other raw materials is adjusted to be 22 percent.
Comparative example 6
The preparation steps and parameters of this comparative example were the same as in example 2, except that: corundum is not added to the anti-slip glaze in the comparative example, and the amount of potassium feldspar in other raw materials is adjusted to 24% and the amount of nepheline is adjusted to 22%.
The anti-slip ceramic bricks prepared in examples 2 to 5 and comparative examples 2 to 6 were subjected to performance tests, and specific test results are shown in the following table:
as can be seen from the detection results of examples 1-2, the hardness and wear resistance of the ceramic tile are improved after the conventional protective glaze in the market is replaced by the anti-slip glaze raw material in the scheme.
The high-anti-slip ceramic tile with the hydrophobic function prepared by the anti-slip glaze in the embodiment 2-5 can reach more than R11, the hardness can reach more than 5, the wear-resistant grade can reach more than 4, and the anti-fouling performance and the color development effect are good.
As can be seen from the detection results of the embodiment 2 and the comparative examples 2-3, the high anti-slip ceramic tile with the hydrophobic function in the scheme has the advantages of high hardness, high wear resistance and good antifouling property compared with the existing anti-slip ceramic tile. From the test results of example 2 and comparative example 4, it is understood that the deep ink and the anti-slip glaze have a combined effect, and that the dry static friction coefficient and the de-mark inclined platform method test anti-slip performance of the high anti-slip tile are reduced when the deep ink is not applied. As can be seen from the detection results of the example 2 and the comparative example 5, the zinc oxide in the anti-slip glaze can lead the ceramic tile to have better color development effect. From the detection results of example 2 and comparative example 6, it is known that the addition of corundum in the slip-resistant glaze can further improve the slip resistance, hardness and wear resistance of the ceramic tile.
Example 6
The preparation steps and parameters in this example are the same as in example 2, except that: the calcination process of the high anti-slip transparent dry particles does not carry out a heat preservation step at 1300 ℃.
Performance detection is carried out on the high-slip-resistance ceramic tile with the hydrophobic function prepared in the embodiment 6, and specific detection results are shown in the following table:
it is noted that at present, the use of spinel structures in ceramic tiles is generally used to improve the wear resistance, fire resistance of ceramic tiles. In the scheme, the ceramic tile has better anti-slip performance, transparency and color development by using the high anti-slip transparent dry particles with the magnesia-alumina spinel octahedral structure, and besides the special limit of the preparation formula, it is particularly important that a heat preservation process is required to be arranged at 1300 ℃ in the cooling process, just like the detection results of the embodiment 2 and the embodiment 6, when the heat preservation process is cancelled, the anti-slip performance of the ceramic tile is obviously reduced.
Example 7
The preparation method of the high anti-slip ceramic tile with the hydrophobic function comprises the following preparation steps:
s01, pressing and forming the green body powder by a constant force Tai press to obtain a green brick, drying the green brick by a drying kiln, and then adopting a high-definition digital ink-jet machine to spray-print marble design patterns;
s02, continuously adopting a high-definition digital ink jet machine to jet and print linear deep ink, wherein the deep ink watermark is positioned in the area where the marble design pattern is positioned.
S03, spraying anti-slip glaze by using a new cloisonne glaze spraying cabinet, wherein the anti-slip glaze is applied to green bricks sprayed with marble design patterns and deep ink; and (3) drying for 30min in a drying box at 150 ℃, then placing in a kiln, firing for 70min at 1220 ℃, and edging to obtain the high-anti-slip ceramic tile with the hydrophobic function.
The anti-slip glaze is prepared by mixing and ball milling the following raw materials in percentage by mass: 16% of potassium feldspar, 12% of nepheline, 5% of kaolin, 8% of dolomite, 8% of zinc oxide, 15% of corundum, 6% of quartz, 21% of high-skid-resistance transparent dry particle powder, 5% of cryolite and 4% of barium carbonate. Adding water to adjust the specific gravity to 1.35g/ml after ball milling of the anti-slip glaze, and glazing the glaze with the glazing quantity of 240g/m 2 。
The high-skid-resistance transparent dry particles are prepared from the following raw materials in percentage by mass: 25% of magnesite, 39% of alumina, 8% of zinc oxide, 8% of borax, 8% of dolomite, 6% of strontium carbonate and 6% of cryolite.
The preparation method of the high-skid-resistance transparent dry particles comprises the following steps: s1, uniformly mixing the raw materials, and calcining, wherein the fineness of each raw material is 200-250 meshes; the calcination curve is that the temperature is raised to 700 ℃ from normal temperature to fire for 30min, fire for 45min at 700-1100 ℃, fire for 30min at 1100-1280 ℃, fire for 60min at 1280-1480 ℃ and keep the temperature for 60min at 1480 ℃; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 18 ℃/min, and preserving heat for 25min at 1300 ℃ to obtain frit slurry; s2, cooling the frit slurry through water quenching, drying at 200 ℃ for 2 hours, and crushing to obtain the high-skid-resistance transparent dry powder with the fineness of 200-250 meshes.
Performance detection is carried out on the high-slip-resistance ceramic tile with the hydrophobic function prepared in the embodiment 7, and specific detection results are shown in the following table:
as shown by the test results of the table, after the high anti-slip transparent dry particle component amount, the calcination parameters, the anti-slip glaze component amount and the like of the high anti-slip transparent dry particles are further optimized, the anti-slip grade of the high anti-slip ceramic tile with the hydrophobic function can reach R12, the hardness can reach 7, the wear-resistant grade can reach 4, and the ceramic tile has excellent anti-fouling performance and color development effect.
Wherein, the preferable high anti-skid transparent dry granule formula and the dosage of the ceramic tile with better performance are as follows: 23-27% of magnesite, 37-41% of alumina, 7-10% of zinc oxide, 22-30% of fluxing agent and 4-8% of catalyst; the formula and the dosage of the preferred anti-slip glaze are as follows: 15-20% of potassium feldspar, 12-16% of nepheline, 4-6% of kaolin, 6-12% of dolomite, 6-10% of zinc oxide, 14-18% of corundum, 5-9% of quartz, 16-24% of high-skid-resistance transparent dry granular powder, 3-7% of cryolite and 4-8% of barium carbonate.
The preferred high slip transparent dry particle calcination profile is: heating from room temperature to 700 deg.C for 30-40min, heating at 700-1100 deg.C for 45-60min, heating at 1100-1280 deg.C for 30-45min, heating at 1280-1480 deg.C for 60-70min, and maintaining at 1480 deg.C for 60-70min; cooling from 1480deg.C to 1300deg.C at a cooling rate of 15-18deg.C/min, and maintaining at 1300deg.C for 20-30min.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The high-skid-resistance transparent dry particle is characterized by comprising the following raw materials in percentage by mass: 20-30% of magnesite, 35-45% of alumina, 2-10% of zinc oxide, 15-30% of fluxing agent and 2-8% of catalyst.
2. The high anti-slip transparent dry particle according to claim 1, wherein the preparing step of the high anti-slip transparent dry particle comprises:
s1, uniformly mixing the raw materials of the high-skid-resistance transparent dry particles, and calcining;
the calcination curve is: heating from room temperature to 700 deg.C for 30-45min, heating at 700-1100 deg.C for 45-60min, heating at 1100-1280 deg.C for 30-60min, heating at 1280-1480 deg.C for 60-90min, and maintaining at 1480 deg.C for 60-90min; cooling from 1480 ℃ to 1300 ℃, wherein the cooling rate is 15-18 ℃/min, and preserving heat for 20-30min at 1300 ℃ to obtain frit slurry;
s2, cooling the frit slurry through water quenching, drying at 200-250 ℃ for 1-2h, and crushing to obtain the high-skid-resistance transparent dry particles.
3. The high slip transparent dry particle of claim 1 wherein the high slip transparent dry particle comprises a magnesia alumina spinel octahedral structure.
4. A high slip transparent dry particle according to claim 1 wherein the fluxing agent comprises borax and a divalent alkaline earth metal-containing fluxing agent; the catalyst is at least one of cryolite, aluminum fluoride and ammonium fluoride.
5. The high anti-skid transparent dry granule according to claim 2, wherein the fineness of the crushed high anti-skid transparent dry granule is 200-250 mesh.
6. The anti-slip glaze is characterized by being prepared by mixing and ball milling the following raw materials in percentage by mass: 12-22% of potassium feldspar, 10-18% of nepheline, 4-8% of kaolin, 6-14% of dolomite, 2-10% of zinc oxide, 8-18% of corundum, 4-10% of quartz, 10-24% of high anti-slip transparent dry granules according to any of claims 1-5, 2-8% of cryolite and 4-8% of barium carbonate.
7. The preparation method of the high anti-slip ceramic tile with the hydrophobic function is characterized by comprising the following preparation steps:
s01, pressing the green body powder to obtain a green brick, applying a ground glaze on the green brick, and then spraying and printing a marble design pattern;
s02, continuously spraying deep ink on the surface of the green brick according to the set pattern;
s03, continuously applying the anti-slip glaze as claimed in claim 6, and baking after drying to obtain the high anti-slip ceramic tile with the hydrophobic function.
8. The method for preparing a ceramic tile with high slip resistance and hydrophobic property according to claim 7, wherein in step S03, the firing temperature is 1200-1220 ℃ and the firing period is 65-75min.
9. The method for preparing the high anti-slip ceramic tile with the hydrophobic function according to claim 7, wherein the specific gravity of the anti-slip glaze is 1.30-1.50g/ml, and the glazing amount is 180-280g/m 2 。
10. The high anti-slip ceramic tile with a hydrophobic function, which is characterized by being prepared by the preparation method of the high anti-slip ceramic tile with the hydrophobic function according to any one of claims 7 to 9.
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