CN114853463B - Nitrogen-doped phosphate-based photocatalytic ceramic product and preparation method thereof - Google Patents
Nitrogen-doped phosphate-based photocatalytic ceramic product and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 92
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 29
- 239000010452 phosphate Substances 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000010304 firing Methods 0.000 claims abstract description 23
- 230000012010 growth Effects 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 43
- 239000013078 crystal Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- CRLHSBRULQUYOK-UHFFFAOYSA-N dioxido(dioxo)tungsten;manganese(2+) Chemical compound [Mn+2].[O-][W]([O-])(=O)=O CRLHSBRULQUYOK-UHFFFAOYSA-N 0.000 claims description 23
- 239000004202 carbamide Substances 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000005995 Aluminium silicate Substances 0.000 claims description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims description 13
- 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 13
- 238000007873 sieving Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 229910017119 AlPO Inorganic materials 0.000 claims description 7
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 238000000227 grinding Methods 0.000 description 22
- 238000001035 drying Methods 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
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- 239000004615 ingredient Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 phenyl compound Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 230000009661 flower growth Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- 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
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- 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
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a nitrogen-doped phosphate-based photocatalytic ceramic product and a preparation method thereof. The preparation method comprises the following steps: applying a glaze composition having a phosphate-based component that promotes the growth of the crystalline structure orientation dominance to the surface of the ceramic body; firing the ceramic body after application of the glaze composition; calcining the sintered ceramic body and the nitrogen-containing powder in an inert atmosphere to obtain the nitrogen-doped phosphate-based photocatalytic ceramic product.
Description
Technical Field
The invention belongs to the field of ceramic glaze, and particularly relates to a nitrogen-doped phosphate-based photocatalytic ceramic product and a preparation method thereof.
Background
The traditional building ceramic industry has excessive productivity, the market trend is gradually narrowed, and the surface functionalization of ceramic products becomes an important development direction for improving the value of traditional ceramic materials and developing markets for enterprise innovation. Ceramic products with the functions of heat insulation, heat preservation, luminescence, antibacterial ceramic and the like are expanded by a part of ceramic enterprises in China. At present, the ceramic sanitary ware for building is widely used in engineering construction, capital construction and home decoration in China. In the face of threat to home environment or human health caused by toxic organic matters or gases released by various chemical products, consumers have raised great demands on environment-friendly building ceramics. The development of ceramic products with the function of environmental protection and degradation of toxic organic pollutants is one of the problems to be solved in the ceramic industry of buildings in China. Whether or not the photocatalyst can be reasonably used in the ceramic product with the above functions becomes an important issue for solving the above problems.
Traditional building sanitary and daily ceramic glazes are mainly divided into fritted glaze and raw glaze. The frit glaze has few surface defects and is widely used for more and more ceramic enterprises. The production and research of fritted glazes mainly focus on the following aspects: the use and research of lead-free and cadmium-free nontoxic elements, namely lead-free frit glaze; high-temperature wear-resistant frit glaze; transparent glaze with excellent mirror decoration effect, namely, completely polished glaze; in addition, color-doped glaze, opaque glaze, crystalline glaze, etc. How to obtain ceramic products with both glaze crystallization effect and photocatalysis function is an important technical problem to be solved by the invention.
Disclosure of Invention
The invention provides a nitrogen-doped phosphate-based photocatalytic ceramic product and a preparation method thereof. The glaze composition with phosphate-based components for promoting the dominant growth of crystal structure orientation can preferentially form a high-activity crystal structure and grow in an orientation mode in a glaze layer under the promotion of phosphate system ground coat, promote the dominant distribution of the crystal components on the surface of the glaze layer, and ensure the full exposure of active sites on the surface of ceramic glaze. Meanwhile, manganese tungstate with excellent photocatalytic degradation performance is introduced into the glaze composition, and the glaze composition has good degradation performance on toxic gases such as formaldehyde, phenyl compounds and the like.
In a first aspect, the present invention provides a method for preparing a nitrogen doped phosphate-based photocatalytic ceramic product. The preparation method comprises the following steps:
applying a glaze composition having a phosphate-based component that promotes the growth of the crystalline structure orientation dominance to the surface of the ceramic body; the glaze composition comprises the following raw materials: 80-90% of powder A, 5-10% of manganese tungstate and 5-10% of kaolin in percentage by mass; the powder A comprises the following raw materials: in mass percent, siO 2 15～30％、AlPO 4 6～12％、Mn 3 (PO 4 ) 2 6～10％、Li 3 PO 4 20～54％、Na 3 PO 4 16～21％、K 3 PO 4 20～29％；
Firing the ceramic body after application of the glaze composition;
calcining the sintered ceramic body and the nitrogen-containing powder in an inert atmosphere to obtain the nitrogen-doped phosphate-based photocatalytic ceramic product. In some embodiments, the nitrogen-containing powder is urea.
The traditional glaze composition composed of oxides such as silicon oxide, aluminum oxide, calcium oxide, sodium oxide and the like is difficult to fully expose crystalline components on the surface of the glaze layer, and active ingredients of the glaze are difficult to show good photocatalytic activity. The primer component of the phosphate system has a different melt liquid viscosity and metal ion diffusion rate at high temperatures than the glaze composition of the oxide system, under which conditions the rate of growth of the crystalline glaze component orientation and normal distribution within the bulk crystalline glaze layer will exhibit significant changes. Specifically, under a phosphate-based under-glaze system, the oriented growth of the manganese tungstate-based crystalline glaze can be preferentially distributed on the surface of the glaze layer, and one-dimensional orientation is formed, so that conditions for full exposure and growth of a high-activity crystalline glaze system can be provided. In addition, the sintered ceramic body and the nitrogen-containing powder are calcined in an inert atmosphere, so that nitrogen elements can be embedded into the surface of the glazed glass phase in the form of solid solution, and the surface cations can be stably migrated and kept in an active structure by nitrogen doping in repeated catalytic cycles, thereby improving the degradation efficiency.
Preferably, the powder A is in the form of a frit.
Preferably, the preparation process of the frit comprises the following steps: uniformly mixing the raw materials according to the powder material A, sieving the mixture, preserving heat for 10 to 20 minutes at a first temperature, preserving heat for 10 to 20 minutes at a second temperature, preserving heat for 10 to 20 minutes at a third temperature, quenching and crushing to obtain a frit; wherein the first temperature is 600-900 ℃, the second temperature is 700-1000 ℃, and the third temperature is 1300-1500 ℃; preferably, the second temperature is 50-200 ℃ higher than the first temperature.
Preferably, the mesh number of the sieve is 30-100 mesh.
Preferably, the particle size of the powder A is 100-300 meshes.
Preferably, the glaze composition generates linear crystals growing in scattering orientation under a high-temperature sintering environment.
Preferably, the linear crystal is a manganese tungstate crystal.
Preferably, the highest sintering temperature is 1100-1300 ℃, and the sintering period is 60-170 minutes.
Preferably, the inert atmosphere for calcination is argon.
Preferably, the calcination temperature is 400-800 ℃ and the calcination time is 30-90 minutes.
Preferably, the glaze composition is applied to the surface of the ceramic body in the form of a glaze slip; the glaze slip comprises a dispersing agent and water besides the glaze composition; preferably, the water accounts for 40-60% of the mass of the glaze slip, and the dispersant accounts for 0.1-0.5% of the mass of the glaze slip.
Preferably, the glaze slip forms a crystalline glaze layer of 0.05-0.3 mm on the surface of the ceramic body.
In a second aspect, the invention provides a nitrogen doped phosphate-based photocatalytic ceramic product obtained by the method of any one of the above.
Drawings
FIG. 1 is an XRD pattern for the glaze layer of example 1;
FIG. 2 is a graph of the photocatalytic degradation of formaldehyde for examples 1-3 and comparative example 1;
FIG. 3 is a graph of the performance of examples 1-3 and comparative example 1 in photocatalytic degradation of phenyl compounds;
fig. 4 is a digital photograph of a nitrogen doped phosphate-based photocatalytic ceramic product.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent. The following illustrates the preparation of the nitrogen doped phosphate-based photocatalytic ceramic product according to the present invention.
A glaze composition having a phosphate-based component that promotes the growth of the crystalline structure orientation dominance is applied to the surface of the ceramic body. The composition and specification of the ceramic body are not particularly limited, and a construction ceramic body commonly used in the art may be employed.
The glaze composition comprises the following raw materials: 80-90% of powder A, 5-10% of manganese tungstate and 5-10% of kaolin.
The powder material A is the main component of the glaze composition, plays the role of the ground coat in the glaze composition, and provides a liquid phase environment in a high-temperature melting state. The powder A comprises the following raw materials: in mass percent, siO 2 15～30％、AlPO 4 6～12％、Mn 3 (PO 4 ) 2 6～10％、Li 3 PO 4 20～54％、Na 3 PO 4 16～21％、K 3 PO 4 20-29%. Powder A provides a liquid environment for the nucleation and growth of active manganese tungstate crystals in a high-temperature environment, so that the active manganese tungstate crystals can grow at a faster rate. If the powder A is replaced by the traditional feldspar and clay, the grain size of the crystallized crystal is smaller and even grain growth cannot be promoted, and the formed oriented growth structure is less. This is because the conventional feldspar or clay is used as a primer component of the glaze composition, the nucleation rate of manganese tungstate crystal nuclei is low, and it is difficult to directly nucleate and grow in a short time. The crystal glaze formed by using feldspar or clay has long growth time, and the heat preservation time is generally up to 4-10 hours under the condition of high temperature, and the total sintering period is more than 15 hours. The glaze composition has the advantages of easy control of the crystal pattern morphology, energy saving, heat preservation time of only 5-20 minutes under high temperature condition, and total sintering period of 60-170 minutes.
As previously described, powder A provides an environment for nucleation and growth of crystals, allowing rapid nucleation of manganese tungstate. If the mass percentage of the powder material A in the glaze composition is less than 80%, the crystallization component cannot effectively migrate and crystallize and grow in a high-temperature melting state, the crystallization glaze is not easy to nucleate, the crystal nucleus grows and the size distribution is uneven, and the glaze decoration effect is poor. If the mass ratio of the powder A in the glaze composition is higher than 90%, the crystal flower is easily melted to cause a significant decrease in the number of crystal flowers, and the decorative effect is also deteriorated.
Preferably, the powder a is in the form of a frit. The direct use of powder A in the form of a raw material does not allow crystallization and catalytic effects to be achieved simultaneously with excellent results. The reason is that the frit powder is more uniformly mixed than the raw material, and the distribution of nucleation generated crystal flowers is also more uniform. Meanwhile, the frit powder can also reduce the sintering temperature and expand the sintering range. The melting temperature of the frit is higher, so that various raw materials are fully reacted and melted at high temperature and are converted into glass-shaped substances, and the glass-shaped substances are remelted during the sintering, so that the melting point of the glaze is reduced, the melting range of the glaze is enlarged, and convenience is brought to production control. Moreover, the frit powder improves the glaze quality and reduces the shrinkage of the glaze compared with the raw material. When the frit is manufactured, substances which can be decomposed in the raw materials and certain volatile matters are discharged in advance, and the processes are avoided during glaze firing, so that pinhole defects are reduced. Meanwhile, the glaze after being melted has little loss in firing, hardly contracts, can be better adapted to a green body, and reduces the defects of glaze rolling, glaze shrinkage and the like. Therefore, the glaze composition obtained by the invention has uniform color, improved coloring efficiency, increased glaze stability, suspension property and adhesion with a blank body, and reduced bubbles. Although the raw material can realize crystallization and has a certain catalytic effect, the crystal nucleus growth of the obtained crystal glaze is difficult to control, the repeatability is extremely poor, the size of crystal flowers is limited, and the catalytic effect is obviously limited.
Weighing the raw materials according to the raw material composition of the powder A, mixing, grinding and sieving to obtain a mixture. The mixing means may be dry blending. The mesh number of the sieving is 30-100 meshes. Placing the mixture into a crucible, placing the crucible into an electric furnace, preserving heat at a first temperature for 10-20 minutes, preserving heat at a second temperature for 10-20 minutes, preserving heat at a third temperature for 10-20 minutes, quenching and crushing to obtain a frit; wherein the first temperature is 600-900 ℃, the second temperature is 700-1000 ℃, and the third temperature is 1300-1500 ℃; preferably, the second temperature is 50-200 ℃ higher than the first temperature. And taking out the frit from the water, drying, putting into a ball milling tank, grinding, and drying for later use. During this ball milling process, for example, the frit is controlled: the mass ratio of the grinding balls is 1:6. can be sieved after grinding for 1 to 6 hours.
The particle size of the powder A is 100-300 meshes. The frit is further ground in order to refine it so that the constituents of the frit are substantially uniformly distributed at high temperature. The higher the thinning degree is, the better the uniformity degree of the crystal flower growth is.
Manganese tungstate is used as an active material in the glaze composition to play a photocatalytic role. The mass percentage of the manganese tungstate in the glaze composition is controlled to be 5-10%. The content of manganese tungstate is too much or too little, and the photocatalytic effect is obviously weakened. The manganese tungstate content is low, the crystal flowers are few, the photocatalytic degradation components are reduced, and the catalytic effect is weakened; the manganese tungstate with high content has more nucleation patterns, and the nucleation patterns are overlapped with each other, so that uneven distribution is caused, and the decoration effect and the photocatalysis effect are also affected.
Although the powder material A also contains manganese element, the manganese in the powder material A is formed by taking the manganese element as the element of the ground coat, and the manganese tungstate introduced into the crystal glaze can be taken as a crystallizing agent, and meanwhile, the photocatalytic degradation effect is achieved.
The kaolin contains Al 2 O 3 ·2SiO 2 ·2H 2 O. The kaolin can raise the melting temperature of the glaze and improve suspension property so that the glaze is not easy to settle. If the content of kaolin is too small, the dispersion uniformity and stability of the glaze cannot be effectively ensured; if the kaolin content is too high, the active ingredients of the glaze are easily encapsulated by the kaolin and cannot be exposed, resulting in limited catalytic degradation properties of the glaze composition.
The glaze composition is prepared. Powder A, manganese tungstate and kaolin are uniformly mixed and ground in a ball milling tank. In the ball milling process, controlling materials: grinding ball: the mass ratio of water is 1:1:1, grinding for 1-6 hours, sieving with a 300-mesh sieve, and drying for later use.
Firing the ceramic body after the application of the glaze composition. The kiln is oxidized by a roller kiln and is preferably quick-fired. The highest sintering temperature is 1100-1300 ℃, and the sintering period is 60-170 minutes. The holding time for the highest firing temperature may be 5 to 20 minutes.
The glaze composition may be applied to the surface of the ceramic body in the form of a glaze slip. The glaze slip comprises water and a dispersing agent besides the glaze composition. The mass percentage of water in the glaze slip is 40-60%, and the mass percentage of the dispersing agent is 0.1-0.5%. Such dispersants include, but are not limited to, ammonium polyacrylate salts and the like. The components in the glaze slip are uniformly dispersed by stirring. The glaze slip forms a crystalline glaze layer with the thickness of 0.05-0.3 mm on the surface of the ceramic body. At this time, the ceramic body may be dried prior to firing. For example at 50 to 100 ℃.
And (3) preserving the temperature of the sintered ceramic body and the nitrogen-containing split body for 30-90 min at 400-800 ℃ in an inert atmosphere to obtain the nitrogen-doped phosphate-based photocatalytic ceramic product. The purpose of controlling the temperature and time of nitrogen doping within the above ranges is to control the decomposition rate of the nitrogen-containing split and to control the nitrogen doping. In some technical schemes, the nitrogen source can have a nitrogen mass percentage of 20-70%. For example, urea powder is spread on the surface of the ceramic body after firing. The urea is used in an amount of 100cm 2 0.5-2.0 g urea powder is used on the surface of the ceramic body. The urea powder may also be replaced with melamine.
Urea powder can not be paved on the surface of the glazed ceramic body and then sintered. The nitrogen doping of the present invention needs to be performed under an inert atmosphere. If urea powder is paved on the surface of the ceramic body and then the ceramic body is sintered, the growth of a crystal orientation structure in the glaze layer and the formation of a glass phase structure are affected, and the special solid solution doping effect of nitrogen is lost. The invention also embeds nitrogen element into the glazed glass phase structure in the form of solid solution.
The nitrogen doping can not be realized by directly calcining the glazed ceramic body in a nitrogen atmosphere. Since nitrogen is an inert gas, it is difficult to achieve the above doping due to the poor activity of nitrogen atoms.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The preparation method of the nitrogen doped phosphate-based photocatalytic ceramic product comprises the following steps:
1) And (3) preparing a material A. The ingredients are mixed according to the following mass ratio: siO (SiO) 2 20％、AlPO 4 9％、Mn 3 (PO 4 ) 2 6％、Li 3 PO 4 20％、Na 3 PO 4 16％、K 3 PO 4 29%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, the mixture is put into a crucible, put into an electric furnace, kept at 900 ℃ for 20 minutes, kept at 1000 ℃ for 20 minutes, kept at 1500 ℃ for 20 minutes, taken out and poured into water for quenching to obtain the frit. Taking out the frit from water, drying, putting the frit into a ball milling tank, taking ball stones with the particle diameters of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. Mixing 80% of material A, 10% of manganese tungstate and 10% of kaolin according to the mass ratio, uniformly mixing, putting the mixture into a ball milling tank, taking ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 6 hours, and sieving with a 300-mesh sieve, wherein the material is denoted as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.5mm, drying at 80 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1250 ℃, preserving heat for 20 minutes, and controlling the firing period to be 60 minutes.
5) Spreading urea powder on the surface of the ceramic body after firing every 100cm 2 0.5g of urea powder is used on the surface of the ceramic body,calcining for 90 minutes at 400 ℃ in an inert atmosphere to obtain the nitrogen doped phosphate-based photocatalytic ceramic product.
Example 2
The preparation method of the nitrogen doped phosphate-based photocatalytic ceramic product comprises the following steps:
1) And (3) preparing a material A. The ingredients are mixed according to the following mass ratio: siO (SiO) 2 20％、AlPO 4 9％、Mn 3 (PO 4 ) 2 6％、Li 3 PO 4 20％、Na 3 PO 4 16％、K 3 PO 4 29%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, the mixture is put into a crucible, put into an electric furnace, kept at 900 ℃ for 20 minutes, kept at 1000 ℃ for 20 minutes, kept at 1500 ℃ for 20 minutes, taken out and poured into water for quenching to obtain the frit. Taking out the frit from water, drying, putting the frit into a ball milling tank, taking ball stones with the particle diameters of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. Mixing 80% of material A, 10% of manganese tungstate and 10% of kaolin according to the mass ratio, uniformly mixing, putting the mixture into a ball milling tank, taking ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 6 hours, and sieving with a 300-mesh sieve, wherein the material is denoted as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.5mm, drying at 80 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1250 ℃, preserving heat for 20 minutes, and controlling the firing period to be 60 minutes.
5) Spreading urea powder on the surface of the ceramic body after firing every 100cm 2 1.5g of urea powder is used on the surface of the ceramic body, and the ceramic body is calcined at 600 ℃ for 60 minutes in an inert atmosphere to obtainThe nitrogen doped phosphate-based photocatalytic ceramic product.
Example 3
The preparation method of the nitrogen doped phosphate-based photocatalytic ceramic product comprises the following steps:
1) And (3) preparing a material A. The ingredients are mixed according to the following mass ratio: siO (SiO) 2 20％、AlPO 4 9％、Mn 3 (PO 4 ) 2 6％、Li 3 PO 4 20％、Na 3 PO 4 16％、K 3 PO 4 29%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, the mixture is put into a crucible, put into an electric furnace, kept at 900 ℃ for 20 minutes, kept at 1000 ℃ for 20 minutes, kept at 1500 ℃ for 20 minutes, taken out and poured into water for quenching to obtain the frit. Taking out the frit from water, drying, putting the frit into a ball milling tank, taking ball stones with the particle diameters of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. Mixing 80% of material A, 10% of manganese tungstate and 10% of kaolin according to the mass ratio, uniformly mixing, putting the mixture into a ball milling tank, taking ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 6 hours, and sieving with a 300-mesh sieve, wherein the material is denoted as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.5mm, drying at 80 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1250 ℃, preserving heat for 20 minutes, and controlling the firing period to be 60 minutes.
5) Spreading urea on the surface of the ceramic body after firing in a split manner, wherein each 100cm 2 2.0g of urea powder is used on the surface of the ceramic body, and the ceramic body is calcined at 800 ℃ for 30 minutes in inert atmosphere to obtain the nitrogen doped phosphate-based photocatalytic ceramic product。
Comparative example 1
Preparing a ceramic product:
1) And (3) preparing a material A. The ingredients are mixed according to the following mass ratio: siO (SiO) 2 20％、AlPO 4 9％、Mn 3 (PO 4 ) 2 6％、Li 3 PO 4 20％、Na 3 PO 4 16％、K 3 PO 4 29%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, the mixture is put into a crucible, put into an electric furnace, kept at 900 ℃ for 20 minutes, kept at 1000 ℃ for 20 minutes, kept at 1500 ℃ for 20 minutes, taken out and poured into water for quenching to obtain the frit. Taking out the frit from water, drying, putting the frit into a ball milling tank, taking ball stones with the particle diameters of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. Mixing 80% of material A, 10% of manganese tungstate and 10% of kaolin according to the mass ratio, uniformly mixing, putting the mixture into a ball milling tank, taking ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio of 1/3, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 6 hours, and sieving with a 300-mesh sieve, wherein the material is denoted as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.5mm, drying at 80 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1250 ℃, preserving heat for 20 minutes, and controlling the firing period to be 60 minutes to obtain the ceramic product.
XRD analysis was performed on the glaze of the ceramic product of example 1, and the results are shown in FIG. 1. The comparative PDF card was found to contain manganese tungstate on the surface of the crystallized glaze ceramic product.
The ceramic products containing the crystalline glaze prepared in comparative example 1, example 2 and example 3 were subjected to photocatalytic tests. The photocatalytic performance of the samples was tested using a BL-GHX-V type photocatalyst (Bilang biosciences Co., ltd.).
When the contaminant is formaldehyde, ceramic tiles 6cm long by 1cm wide are placed in a reactor with visible light irradiation (xenon lamp, 500W) and the lamp is turned on for illumination. Formaldehyde enters the reactor by blowing, the inlet formaldehyde concentration is measured by gas chromatography, and the degradation rate is calculated. The formaldehyde sampling time was 20 minutes each time. And measuring the concentration of formaldehyde at different degradation times to obtain a degradation curve. When the contaminant is a phenyl compound, formaldehyde may be replaced with a phenyl compound.
FIG. 2 is every 100cm 2 0g of urea powder (comparative example 1) per 100cm was used on the ceramic body surface of (C) 2 0.5g urea powder (example 1) per 100cm was used on the ceramic body surface of (C) 2 1.5g of urea powder per 100cm of ceramic body surface (example 2) was used 2 Performance profile of photocatalytic degradation of formaldehyde using 2.0g urea powder (example 3) on the ceramic body surface.
FIG. 3 is every 100cm 2 0g of urea powder (comparative example 1) per 100cm was used on the ceramic body surface of (C) 2 0.5g urea powder (example 1) per 100cm was used on the ceramic body surface of (C) 2 1.5g of urea powder per 100cm of ceramic body surface (example 2) was used 2 Performance profile of photocatalytic degradation of phenyl compounds using 2.0g urea powder (example 3) on the ceramic bulk surface.
It can be seen that the residual amount of the ceramic product without nitrogen doping for 4 hours of photocatalytic degradation of formaldehyde and phenyl compounds is about 40%. The residual amount of formaldehyde and phenyl compounds degraded by the photocatalytic ceramic product after nitrogen doping is obviously reduced.
Claims (12)
1. A method for preparing a nitrogen-doped phosphate-based photocatalytic ceramic product, the method comprising the steps of:
applying a glaze composition having a phosphate-based component that promotes the growth of the crystalline structure orientation dominance to the surface of the ceramic body; the glaze composition comprises the following raw materials: 80 to 9 mass percent of powder A0 percent, 5 to 10 percent of manganese tungstate and 5 to 10 percent of kaolin; the powder A comprises the following raw materials: in mass percent, siO 2 15～30%、AlPO 4 6～12%、Mn 3 (PO 4 ) 2 6～10%、Li 3 PO 4 20～54%、Na 3 PO 4 16～21%、K 3 PO 4 20～29%；
Firing the ceramic body after application of the glaze composition;
calcining the sintered ceramic body and the nitrogen-containing powder in an inert atmosphere to obtain the nitrogen-doped phosphate-based photocatalytic ceramic product;
the nitrogen mass percentage of the nitrogen source of the nitrogen-containing powder is 20-70%; the nitrogenous powder is urea powder;
the calcination temperature is 400-800 ℃, and the calcination time is 30-90 minutes.
2. The method of claim 1, wherein the frit a is in the form of a frit.
3. The method of claim 2, wherein the frit is prepared by: uniformly mixing the raw materials according to the powder material A, sieving the mixture, preserving heat for 10 to 20 minutes at a first temperature, preserving heat for 10 to 20 minutes at a second temperature, preserving heat for 10 to 20 minutes at a third temperature, quenching and crushing to obtain a frit; wherein the first temperature is 600-900 ℃, the second temperature is 700-1000 ℃, and the third temperature is 1300-1500 ℃.
4. A method of preparation according to claim 3, wherein the second temperature is 50-200 ℃ higher than the first temperature.
5. The method of producing according to claim 1, wherein the glaze composition forms linear crystals grown in a scattering orientation under a high-temperature firing environment.
6. The method of claim 5, wherein the linear crystals are manganese tungstate crystals.
7. The method according to claim 1, wherein the maximum firing temperature is 1100 to 1300 ℃ and the firing period is 60 to 170 minutes.
8. The method of claim 1, wherein the inert atmosphere for calcination is argon.
9. The method of manufacturing according to claim 1, wherein the glaze composition is applied to the surface of the ceramic body in the form of a glaze slip; the glaze slip comprises a dispersing agent and water in addition to the glaze composition.
10. The preparation method according to claim 9, wherein the water accounts for 40-60% of the mass of the glaze slip, and the dispersant accounts for 0.1-0.5% of the mass of the glaze slip.
11. The method according to claim 9, wherein the glaze slip forms a crystalline glaze layer of 0.05 to 0.3mm on the surface of the ceramic body.
12. Nitrogen doped phosphate-based photocatalytic ceramic product obtained by the method of preparation according to any one of claims 1 to 11.
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