CN115448596A - Zirconia-based bathroom ceramic and preparation method thereof - Google Patents
Zirconia-based bathroom ceramic and preparation method thereof Download PDFInfo
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- CN115448596A CN115448596A CN202210948072.3A CN202210948072A CN115448596A CN 115448596 A CN115448596 A CN 115448596A CN 202210948072 A CN202210948072 A CN 202210948072A CN 115448596 A CN115448596 A CN 115448596A
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- zirconium
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 hafnium nitride Chemical class 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 27
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 27
- 239000011258 core-shell material Substances 0.000 claims abstract description 26
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 20
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 19
- 239000010459 dolomite Substances 0.000 claims abstract description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 19
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 18
- 229910052656 albite Inorganic materials 0.000 claims abstract description 18
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 18
- 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 abstract description 18
- 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 abstract description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000008279 sol Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- POCUPXSSKQAQRY-UHFFFAOYSA-N hydroxylamine;hydrate Chemical compound O.ON POCUPXSSKQAQRY-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920003257 polycarbosilane Polymers 0.000 claims description 2
- 229920001709 polysilazane Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005573 silicon-containing polymer Polymers 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dental Preparations (AREA)
Abstract
The invention relates to the field of ceramic materials, in particular to zirconia-based bathroom ceramic and a preparation method thereof, and the zirconia-based bathroom ceramic comprises a blank body and a glaze layer; the glaze layer comprises the following preparation raw materials in parts by weight: zirconium oxide @ MoS 2 20-30 parts of core-shell particles, 8-12 parts of kaolin, 3-6 parts of potassium feldspar, 1-3 parts of albite, 3-5 parts of nano titanium dioxide, 5-10 parts of dolomite, 2-4 parts of zinc oxide, 4-8 parts of aluminum oxide, 0.5-1 part of hafnium nitride, 1-3 parts of metal powder, 2-4 parts of organic silicon polymer, 3-6 parts of organic zirconium precursor, 20-30 parts of POSS sol, 5-10 parts of ethylene glycol and 50-60 parts of water.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to zirconia-based bathroom ceramic and a preparation method thereof.
Background
In recent years, with the increase of the consumer demand level and the consumption level, the requirements on the surface smoothness and the aesthetic effect of the bathroom ceramic product are improved, and higher requirements on other use characteristics are also provided. Some pollutants, such as feces, urine, scales, soap foams, fatty acids and the like, which are contacted with the sanitary ceramics in the using process are easy to accumulate on the concave and convex parts of the product surface or enter the micropores under the action of various physical or chemical forces, such as van der waals force, capillary force, hydrogen bond and the like, so that the sanitary ceramics are polluted, and the cleaning process is time-consuming and labor-consuming.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides zirconia-based bathroom ceramic and a preparation method thereof.
The adopted technical scheme is as follows:
a zirconia-based bathroom ceramic comprises a blank body and a glaze layer;
the blank body can be made of common ceramic raw materials according to a conventional method;
the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 20-30 parts of core-shell particles, 8-12 parts of kaolin, 3-6 parts of potassium feldspar, 1-3 parts of albite, 3-5 parts of nano titanium dioxide, 5-10 parts of dolomite, 2-4 parts of zinc oxide, 4-8 parts of aluminum oxide, 0.5-1 part of hafnium nitride, 1-3 parts of metal powder, 2-4 parts of organic silicon polymer, 3-6 parts of organic zirconium precursor, 20-30 parts of POSS sol, 5-10 parts of ethylene glycol and 50-60 parts of water.
Further, the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 28 parts of core-shell particles, 8 parts of kaolin, 5 parts of potassium feldspar, 2 parts of albite, 3 parts of nano titanium dioxide, 6 parts of dolomite, 2 parts of zinc oxide, 5 parts of aluminum oxide, 0.5 part of hafnium nitride, 2 parts of metal powder, 4 parts of organic silicon polymer, 5 parts of organic zirconium precursor, 30 parts of POSS sol, 6 parts of ethylene glycol and 50 parts of water.
Further, the zirconia @ MoS 2 The preparation method of the core-shell particles comprises the following steps:
adding ammonium tetrathiomolybdate, hydroxylamine hydrochloride and water into a high-pressure reaction kettle, mixing and stirring uniformly, adjusting the pH to 1 by using dilute hydrochloric acid, adding zirconium oxide, sealing and heating to 180-220 ℃ for reaction for 24-36h, filtering the obtained reaction solution, washing with water, and drying in vacuum.
Further, the molar ratio of the ammonium tetrathiomolybdate to the hydroxylamine hydrochloride is 1.9-2:1.
further, the metal powder comprises nickel powder and molybdenum powder, and the mass ratio of the nickel powder to the molybdenum powder is 1-5:1-5.
Further, the organic silicon polymer is any one or more of polycarbosilane, polysiloxane, polysilazane and polyborosilazane.
Further, the preparation method of the organic poly-zirconium precursor comprises the following steps:
under the protection of nitrogen, after phenol and formaldehyde are mixed uniformly, adjusting the pH value to 8-9 by using a sodium hydroxide solution, installing a condensing reflux device, heating to 70-75 ℃, preserving heat, reacting for 1-1.5h, adding a zirconium oxychloride solution, heating to 85-95 ℃, preserving heat, reacting for 1-2h, and then recovering the room temperature.
Further, the zirconium oxychloride solution comprises zirconium oxychloride, ethanol, acetylacetone and hydrogen peroxide, and the mass ratio of the zirconium oxychloride to the acetylacetone to the hydrogen peroxide is 1:1.5-2:1.5-2.
Further, the preparation method of the POSS sol comprises the following steps:
adding phenyl trimethoxy siloxane into absolute ethyl alcohol, uniformly mixing, slowly adding glacial acetic acid as a catalyst, slowly adding water dropwise after dripping, uniformly mixing, and reacting in a water bath at 30-40 ℃ for 5-10 h.
The invention also provides a preparation method of the zirconia-based bathroom ceramic, which comprises the following steps:
zirconium oxide @ MoS 2 The preparation method comprises the following steps of ball-milling and uniformly mixing core-shell particles, kaolin, potassium feldspar, albite, nano titanium dioxide, dolomite, zinc oxide, aluminum oxide, hafnium nitride and metal powder, mixing the mixture with an organic silicon polymer, an organic poly-zirconium precursor, POSS sol, ethylene glycol and water to obtain a glaze, applying the glaze on the surface of a blank by a high-pressure glaze spraying process, and firing the blank at 1180-1250 ℃ for 50-90min.
The invention has the beneficial effects that:
the invention provides zirconia-based bathroom ceramics, zirconia has high chemical inertia, is used as a base material, a glaze layer has extremely high chemical stability and acid and alkali resistance, and MoS 2 Zirconium oxide @ MoS obtained by coating 2 Compared with the method of directly adding zirconia after the core-shell particles are added, the glaze surface is flatThe degree, the water resistance, the corrosion resistance and the antifouling property are improved to some extent, the potassium and sodium content is adjusted through the components, the moderate viscosity of a glaze melt is ensured during firing, the addition of the nano titanium dioxide can improve the glossiness and the whiteness on the one hand, the glaze can be flatly spread on the surface of a blank, further, pits of the glaze surface are reduced, dolomite can play a role in regulating the calcium and magnesium content, the high-temperature viscosity and the surface tension of the glaze melt are adjusted, the mechanical strength of the glaze surface can be increased by the addition of the zinc oxide and the aluminum oxide, the introduction of the organic silicon polymer is beneficial to reducing bubbles of a glaze layer, the roughness of the glaze surface is reduced, the fired glaze surface is smooth and compact, the glossiness is high, and the hafnium nitride is used as a reinforcing phase, the nickel powder and the molybdenum powder are used as metal phases, so that the bearing capacity of the bathroom ceramic can be improved to a certain extent, the mechanical strength is improved, the ZrC phase can be generated in the sintering process of an organic poly-zirconium precursor, the ZrC particles with the nailing and binding effects can effectively improve the bonding strength among particles in the ceramic, the resistance of the particles to movement is increased, the bathroom ceramic has high hardness and density, the POSS sol is used as an organic-inorganic hybrid material, the film forming property of a glaze material on the surface of a blank can be improved, the glossiness and smoothness of a glaze layer after sintering are improved, and pores for storing dirty and containing dirt are reduced
Drawings
Fig. 1 is an SEM image of a surface of a sanitary ceramic prepared in example 1 of the present invention;
fig. 2 is an SEM image of the surface of the sanitary ceramic prepared in comparative example 4 of the present invention.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Zirconium oxide @ MoS 2 Core-shell particles: self-making;
kaolin: processing factory for mineral products in Qiangdong of Lingshou county;
potassium feldspar: processing factory for mineral products in Qiangdong of Lingshou county;
albite: processing factory for mineral products in Qiangdong of Lingshou county;
nano titanium dioxide: the Shijiazhuang Jiancai has a new material technology;
dolomite: processing factory for mineral products in Qiangdong of Lingshou county;
zinc oxide: technology of new stone house Jiang Jian Kai material;
alumina: technology of new stone house Jiang Jian Kai material;
hafnium nitride: bohuas nanotechnology (Ningbo) Ltd
Nickel powder: tianjin cast letter Metal Material Co Ltd
Molybdenum powder: tianjin cast letter Metal Material Co Ltd
Polysiloxane (dimethicone): formerly Seikagaku science and technology (Wuhan) Co Ltd
Organic poly-zirconium precursor: self-making;
POSS sol: and (4) self-making.
Example 1:
a zirconia-based bathroom ceramic comprises a blank body and a glaze layer;
the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 28 parts of core-shell particles, 8 parts of kaolin, 5 parts of potassium feldspar, 2 parts of albite, 3 parts of nano titanium dioxide, 6 parts of dolomite, 2 parts of zinc oxide, 5 parts of aluminum oxide, 0.5 part of hafnium nitride, 1 part of nickel powder, 1 part of molybdenum powder, 4 parts of polysiloxane, 5 parts of organic poly-zirconium precursor, 30 parts of POSS sol, 6 parts of ethylene glycol and 50 parts of water.
Wherein, zirconium oxide @ MoS 2 The preparation method of the core-shell particles comprises the following steps:
adding 260g of ammonium tetrathiomolybdate, 35g of hydroxylamine hydrochloride and 1.5L of water into a high-pressure reaction kettle, mixing and stirring uniformly, adjusting the pH to 1 by using 2mol/L of dilute hydrochloric acid, adding 320g of zirconium oxide, sealing and heating to 210 ℃, reacting for 24 hours, filtering and washing the obtained reaction solution, and then drying for 15 hours in vacuum at 80 ℃.
The preparation method of the organic poly-zirconium precursor comprises the following steps:
under the protection of nitrogen, mixing the components in a molar ratio of 1:1.2, uniformly mixing phenol and formaldehyde, adjusting the pH value to 8-9 by using a 20wt% sodium hydroxide solution, installing a condensation reflux device, heating to 75 ℃, carrying out heat preservation reaction for 1.5h, adding a zirconium oxychloride solution, wherein the mass ratio of zirconium oxychloride, acetylacetone and hydrogen peroxide in the zirconium oxychloride solution is 1:1.5:1.5, heating to 90 ℃, keeping the temperature for reaction for 2 hours, and then recovering the room temperature.
The preparation method of the POSS sol comprises the following steps:
adding 500mL of phenyltrimethoxysiloxane into 2L of absolute ethanol, uniformly mixing, slowly adding 5mL of acetic acid as a catalyst by ice, slowly adding 50mL of water by dropwise adding, uniformly mixing, and reacting in a water bath at 40 ℃ for 10 hours.
The preparation method of the zirconia-based bathroom ceramic comprises the following steps:
zirconium oxide @ MoS 2 The preparation method comprises the following steps of ball-milling and uniformly mixing core-shell particles, kaolin, potassium feldspar, albite, nano titanium dioxide, dolomite, zinc oxide, aluminum oxide, hafnium nitride, nickel powder and molybdenum powder, mixing the mixture with an organic silicon polymer, an organic poly-zirconium precursor, POSS sol, ethylene glycol and water to obtain a glaze, applying the glaze on the surface of a blank through a high-pressure glaze spraying process, and firing at the temperature of 1220 ℃ for 90min.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5230.
Example 2:
a zirconia-based bathroom ceramic comprises a blank body and a glaze layer;
the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 30 parts of core-shell particles, 12 parts of kaolin, 6 parts of potassium feldspar, 3 parts of albite, 5 parts of nano titanium dioxide, 10 parts of dolomite, 4 parts of zinc oxide, 8 parts of aluminum oxide, 1 part of hafnium nitride, 1.5 parts of nickel powder, 1.5 parts of molybdenum powder, 4 parts of polysiloxane, 6 parts of an organic poly-zirconium precursor, 30 parts of POSS sol, 10 parts of ethylene glycol and 60 parts of water.
Wherein, zirconium oxide @ MoS 2 The preparation methods of the core-shell particles, the organic zirconium precursor and the POSS sol are the same as those of the example 1;
the preparation method of the zirconia-based bathroom ceramic comprises the following steps:
zirconium oxide @ MoS 2 The preparation method comprises the following steps of ball-milling and uniformly mixing core-shell particles, kaolin, potassium feldspar, albite, nano titanium dioxide, dolomite, zinc oxide, aluminum oxide, hafnium nitride, nickel powder and molybdenum powder, mixing the mixture with an organic silicon polymer, an organic poly-zirconium precursor, POSS sol, ethylene glycol and water to obtain a glaze, applying the glaze on the surface of a blank through a high-pressure glaze spraying process, and firing at 1250 ℃ for 90min.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5245.
Example 3:
a zirconia-based bathroom ceramic comprises a blank body and a glaze layer;
the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 20 parts of core-shell particles, 8 parts of kaolin, 3 parts of potassium feldspar, 1 part of albite, 3 parts of nano titanium dioxide, 5 parts of dolomite, 2 parts of zinc oxide, 4 parts of aluminum oxide, 0.5 part of hafnium nitride, 1.5 parts of nickel powder, 1.5 parts of molybdenum powder, 2 parts of polysiloxane, 3 parts of an organic poly-zirconium precursor, 20 parts of POSS sol, 5 parts of ethylene glycol and 50 parts of water.
Wherein, zirconium oxide @ MoS 2 The preparation methods of the core-shell particles, the organic zirconium precursor and the POSS sol are the same as those of the example 1;
the preparation method of the zirconia-based bathroom ceramic comprises the following steps:
zirconium oxide @ MoS 2 The preparation method comprises the following steps of ball-milling and uniformly mixing core-shell particles, kaolin, potassium feldspar, albite, nano titanium dioxide, dolomite, zinc oxide, aluminum oxide, hafnium nitride, nickel powder and molybdenum powder, mixing the mixture with an organic silicon polymer, an organic poly-zirconium precursor, POSS sol, ethylene glycol and water to obtain a glaze, applying the glaze on the surface of a blank through a high-pressure glaze spraying process, and firing at 1180 ℃ for 50min.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5190.
Example 4:
a zirconia-based bathroom ceramic comprises a blank body and a glaze layer;
the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 30 parts of core-shell particles, 8 parts of kaolin, 6 parts of potassium feldspar, 1 part of albite, 5 parts of nano titanium dioxide, 5 parts of dolomite, 4 parts of zinc oxide, 4 parts of aluminum oxide, 1 part of hafnium nitride, 1.5 parts of nickel powder, 1.5 parts of molybdenum powder, 2 parts of polysiloxane, 6 parts of an organic poly-zirconium precursor, 20 parts of POSS sol, 10 parts of ethylene glycol and 50 parts of water.
Wherein, zirconium oxide @ MoS 2 The preparation methods of the core-shell particles, the organic poly-zirconium precursor and the POSS sol are the same as those in example 1;
the preparation method of the zirconia-based bathroom ceramic comprises the following steps:
zirconium oxide @ MoS 2 The preparation method comprises the following steps of ball-milling and uniformly mixing core-shell particles, kaolin, potassium feldspar, albite, nano titanium dioxide, dolomite, zinc oxide, aluminum oxide, hafnium nitride, nickel powder and molybdenum powder, mixing the mixture with an organic silicon polymer, an organic poly-zirconium precursor, POSS sol, ethylene glycol and water to obtain a glaze, applying the glaze on the surface of a blank through a high-pressure glaze spraying process, and firing at 1250 ℃ for 50min.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5107.
Example 5:
a zirconia-based bathroom ceramic comprises a blank body and a glaze layer;
the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 20 parts of core-shell particles, 12 parts of kaolin, 3 parts of potassium feldspar, 3 parts of albite, 3 parts of nano titanium dioxide, 10 parts of dolomite, 2 parts of zinc oxide, 8 parts of aluminum oxide, 0.5 part of hafnium nitride, 1.5 parts of nickel powder, 1.5 parts of molybdenum powder, 4 parts of polysiloxane, 3 parts of an organic poly-zirconium precursor, 30 parts of POSS sol, 5 parts of ethylene glycol and 60 parts of water.
Wherein, zirconium oxide @ MoS 2 The preparation methods of the core-shell particles, the organic zirconium precursor and the POSS sol are the same as those of the example 1;
the preparation method of the zirconia-based bathroom ceramic comprises the following steps:
zirconium oxide @ MoS 2 The preparation method comprises the following steps of ball-milling and uniformly mixing core-shell particles, kaolin, potassium feldspar, albite, nano titanium dioxide, dolomite, zinc oxide, aluminum oxide, hafnium nitride, nickel powder and molybdenum powder, mixing the mixture with an organic silicon polymer, an organic poly-zirconium precursor, POSS sol, ethylene glycol and water to obtain a glaze, applying the glaze on the surface of a blank through a high-pressure glaze spraying process, and firing at 1180 ℃ for 90min.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5242.
Example 6
Essentially the same as in example 1, except that the polysiloxane was replaced with polyborosilazane (Oncung New carbon Material, hezhou Co., ltd.).
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5335.
Comparative example 1:
essentially the same as in example 1, except that the zirconia was added directly.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5182.
Comparative example 2:
basically the same as example 1, except that zirconium oxide and MoS were used 2 Are added separately.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5104.
Comparative example 3:
substantially the same as in example 1 except that hafnium nitride was not added.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 4651.
Comparative example 4:
essentially the same as in example 1, except that no polysiloxane was added.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5053.
Comparative example 5:
essentially the same as example 1, except that no organic zirconium precursor was added.
The Hardness (HV) of the glaze layer was 4887 as measured by an HVS-1000 type digital display microhardness tester.
Comparative example 6:
essentially the same as example 1, except that no POSS sol was added.
The test was carried out using an HVS-1000 type digital display microhardness tester, and the glaze layer Hardness (HV) was 5144.
And (4) performance testing:
the bathroom ceramics in the embodiments 1-6 and the comparative examples 1-4 of the invention are used as samples to carry out performance test;
the method for testing the anti-pollution performance comprises the following steps: smearing carbon ink on a sample of 10 x 10cm, smearing for 3-5min with a rubber glove, drying the ink in the shade for 18h, washing with clear water, wiping to dry, controlling the distance between eyes and the sample to be more than 10cm, and observing the number of dirt-absorbing points adsorbed on the surface of a glaze layer of the sample in a good light environment;
method for testing gloss: the gloss value test of the test specimen at a projection angle of 60 ℃ was carried out using a gloss meter (model: MN 268).
The test results are shown in table 1 below:
table 1:
| number of dirt-absorbing points | Degree of gloss | |
| Example 1 | 11 | 111 |
| Example 2 | 8 | 118 |
| Example 3 | 5 | 120 |
| Example 4 | 10 | 115 |
| Example 5 | 14 | 108 |
| Example 6 | 3 | 122 |
| Comparative example 1 | ＞100 | 105 |
| Comparative example 2 | 82 | 106 |
| Comparative example 3 | 50 | 108 |
| Comparative example 4 | ＞100 | 97 |
As shown in the table 1, the bathroom ceramic prepared by the invention has good pollution resistance and glossiness, and has wide market application prospect.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The zirconia-based bathroom ceramic is characterized by comprising a blank body and a glaze layer;
the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 20-30 parts of core-shell particles, 8-12 parts of kaolin, 3-6 parts of potassium feldspar, 1-3 parts of albite, 3-5 parts of nano titanium dioxide, 5-10 parts of dolomite, 2-4 parts of zinc oxide, 4-8 parts of aluminum oxide, 0.5-1 part of hafnium nitride, 1-3 parts of metal powder, 2-4 parts of organic silicon polymer, 3-6 parts of organic zirconium precursor, 20-30 parts of POSS sol, 5-10 parts of ethylene glycol and 50-60 parts of water.
2. The zirconia-based sanitary ceramic of claim 1, wherein the glaze layer comprises the following preparation raw materials in parts by weight:
zirconium oxide @ MoS 2 28 parts of core-shell particles, 8 parts of kaolin, 5 parts of potassium feldspar, 2 parts of albite, 3 parts of nano titanium dioxide, 6 parts of dolomite, 2 parts of zinc oxide, 5 parts of aluminum oxide, 0.5 part of hafnium nitride, 2 parts of metal powder, 4 parts of organic silicon polymer, 5 parts of organic zirconium precursor, 30 parts of POSS sol, 6 parts of ethylene glycol and 50 parts of water.
3. The zirconia-based sanitary ware ceramic of claim 1 wherein said zirconia @ MoS is 2 The preparation method of the core-shell particles comprises the following steps:
adding ammonium tetrathiomolybdate, hydroxylamine hydrochloride and water into a high-pressure reaction kettle, mixing and stirring uniformly, adjusting the pH value to 1 by using dilute hydrochloric acid, adding zirconium oxide, sealing and heating to 180-220 ℃ for reacting for 24-36h, filtering the obtained reaction solution, washing with water, and drying in vacuum.
4. The zirconia-based sanitary ware ceramic of claim 1 wherein the molar ratio of ammonium tetrathiomolybdate to hydroxylamine hydrochloride is from 1.9 to 2:1.
5. the zirconia-based sanitary ware ceramic according to claim 1, wherein the metal powder comprises nickel powder and molybdenum powder, and the mass ratio of the nickel powder to the molybdenum powder is 1-5:1-5.
6. The zirconia-based sanitary ceramic of claim 1 wherein the silicone polymer is any one or more of polycarbosilanes, polysiloxanes, polysilazanes, polyborosilazanes.
7. The zirconia-based sanitary ware ceramic of claim 1 wherein the organic poly-zirconium precursor is prepared by the following method:
under the protection of nitrogen, uniformly mixing phenol and formaldehyde, adjusting the pH value to 8-9 by using a sodium hydroxide solution, installing a condensation reflux device, heating to 70-75 ℃, carrying out heat preservation reaction for 1-1.5h, adding a zirconium oxychloride solution, heating to 85-95 ℃, carrying out heat preservation reaction for 1-2h, and then recovering the room temperature.
8. The zirconia-based sanitary ware ceramic of claim 7 wherein the zirconium oxychloride solution comprises zirconium oxychloride, ethanol, acetylacetone, and hydrogen peroxide, and the mass ratio of zirconium oxychloride to acetylacetone to hydrogen peroxide is 1:1.5-2:1.5-2.
9. The zirconia-based sanitary ceramic of claim 1 wherein the POSS sol is prepared by the following method:
adding phenyl trimethoxy siloxane into absolute ethyl alcohol, uniformly mixing, slowly adding glacial acetic acid as a catalyst, slowly adding water dropwise after dropwise adding, uniformly mixing, and reacting in a water bath at 30-40 ℃ for 5-10 h.
10. A method of making the zirconia-based sanitary ware ceramic of any one of claims 1-9 wherein zirconia @ MoS is added 2 The preparation method comprises the following steps of ball-milling and uniformly mixing core-shell particles, kaolin, potassium feldspar, albite, nano titanium dioxide, dolomite, zinc oxide, aluminum oxide, hafnium nitride and metal powder, mixing the mixture with an organic silicon polymer, an organic poly-zirconium precursor, POSS sol, ethylene glycol and water to obtain a glaze, applying the glaze on the surface of a blank through a high-pressure glaze spraying process, and firing the blank at 1180-1250 ℃ for 50-90min.
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| KR102354671B1 (en) * | 2021-05-21 | 2022-01-21 | 백승민 | Low gloss ceramic glaze composition with excellent abrasion resistance and texture, and its manufacturing method |
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| CN1826478A (en) * | 2003-06-11 | 2006-08-30 | 石川岛播磨重工业株式会社 | Rotating member, housing, bearing, gearbox, rotating machine, shaft structure, and surface treatment method |
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