A flash glaze anti-fouling glaze and its preparation method
By constructing a polyphosphazene-borosilicate hybrid layer on the surface of zinc oxide, the problems of zinc oxide agglomeration and insufficient bonding in the glaze are solved, thereby achieving a delicate shimmering effect, improved anti-fouling performance and wear resistance of the glaze.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUANGDONG SANFI CERAMICS GRP CO LTD
- Filing Date
- 2026-05-25
- Publication Date
- 2026-06-19
AI Technical Summary
The zinc oxide particles in existing glazes have high surface energy, making them prone to agglomeration and resulting in uneven crystal size. Micropores and microcracks are easily formed at the grain boundaries, affecting the anti-fouling performance and wear resistance of the glaze. Furthermore, the crystals are not well bonded to the glass, making them prone to detachment and reducing long-term stability.
A polyphosphazene-borosilicate hybrid layer is constructed on the zinc oxide surface to form an organic-inorganic hybrid interface layer containing a P=N framework, a Si-O-Si network, and a Si-OB structure. This enhances the bonding strength and interfacial compatibility between zinc oxide and the glaze glass phase, and promotes the precipitation of fine and uniform crystals.
It enhances the shimmering and delicate effect of the glaze, reduces stain penetration, improves wear resistance and long-term stability, prevents crystals from falling off, and makes the glaze more stain-resistant and easier to clean.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of glaze technology, specifically to a flash-cleaning antifouling glaze and its preparation method. Background Technology
[0002] With the development of the building ceramics and home decoration industries, consumers have placed higher demands on the decorative effect, stain resistance, and long-term stability of ceramic glazes. Among them, crystalline glazes with a delicate shimmering effect have attracted widespread attention due to their ability to create a soft and transparent decorative texture. In existing technologies, the shimmering or crystalline effect is usually achieved by adding nucleating agents such as zinc oxide to the glaze to promote the precipitation of crystals such as zinc siliceous minerals.
[0003] However, ordinary zinc oxide still has many drawbacks in practical applications. Due to the high surface energy of zinc oxide particles, they are prone to agglomeration in the glaze slurry system, leading to localized enrichment of zinc ions during firing. This results in uneven crystal size, easily forming coarse grains and localized dark spots, affecting the smooth and clean finish of the glaze. Simultaneously, the bonding between the crystals precipitated from ordinary zinc oxide and the glassy phase of the glaze is weak, easily forming micropores and microcracks in the grain boundary regions. Stains can easily penetrate along the grain boundaries and open pores, leading to a decrease in the glaze's anti-fouling performance.
[0004] Furthermore, during long-term friction, scrubbing, or use, insufficient bonding between the crystals and the glass phase interface can cause precipitated crystals to easily detach, increasing the roughness and reducing the gloss of the glaze surface, and further diminishing its wear resistance and long-term stability. Therefore, improving the dispersion stability of zinc oxide in the glaze slurry, enhancing the interfacial bonding between the crystals and the glass phase, and further improving the glaze's flash-cleaning effect, anti-fouling properties, and long-term stability have become pressing technical problems that need to be solved in this field. Summary of the Invention
[0005] To address the shortcomings of the existing technology, this invention provides a flash-cleaning antifouling glaze and its preparation method.
[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: A flash-clean anti-fouling glaze comprises the following raw materials in parts by weight: 25-45 parts feldspar, 22-35 parts quartz, 10-18 parts calcite, 3-7 parts dolomite, 1-4 parts talc, 5-12 parts kaolin, 8-15 parts strontium carbonate, and 3-10 parts modified zinc oxide. The modified zinc oxide is zinc oxide particles with a polyphosphazene-borosilicate hybrid layer bonded to their surface.
[0007] This invention does not directly use ordinary zinc oxide as a nucleating agent. The reason is that while ordinary zinc oxide can promote the precipitation of crystals such as zinc siliceous minerals in crystalline glazes, it is prone to agglomeration in the glaze slurry and localized enrichment during firing, leading to uneven crystal size and the formation of micropores and microcracks at grain boundaries. This reduces the glaze's stain resistance and abrasion resistance. Furthermore, the bonding between the crystals precipitated from ordinary zinc oxide and the glassy phase of the glaze is weak, making them prone to detachment during long-term friction or washing, resulting in increased glaze roughness and decreased gloss.
[0008] This invention constructs a polyphosphazene-borosilicate hybrid layer on the surface of zinc oxide, thereby forming an organic-inorganic hybrid interface layer containing a P=N framework, a Si-O-Si network, and a Si-OB structure. The polyphosphazene structure improves the flexibility and thermal stability of the modified layer, while the borosilicate network enhances the interfacial compatibility between zinc oxide and aluminosilicate components such as feldspar, quartz, and kaolin.
[0009] During firing, modified zinc oxide releases zinc ions more uniformly, promoting the precipitation of fine, uniform crystals and reducing coarse grains and grain boundary defects. Simultaneously, the polyphosphazene-borosilicate hybrid layer further transforms at high temperatures to form a BO-Si-P hybrid interface structure. This structure enhances the bonding strength between the crystals and the glassy phase of the glaze, reducing interfacial stress concentration caused by thermal expansion mismatch, thereby reducing grain boundary microcracks and open pores. Therefore, this invention not only improves the glaze's shimmering and delicate effect but also reduces the penetration of stains along grain boundaries and micropores, enhancing the glaze's anti-fouling properties. Furthermore, because the crystals are more firmly bonded to the glass, they are less prone to detachment under long-term friction, further improving the glaze's wear resistance and long-term stability.
[0010] Preferably, it is composed of the following raw materials in parts by weight: 30-40 parts feldspar, 25-30 parts quartz, 12-16 parts calcite, 4-6 parts dolomite, 2-3 parts talc, 7-10 parts kaolin, 10-13 parts strontium carbonate, and 4-8 parts modified zinc oxide.
[0011] Preferably, it is composed of the following raw materials in parts by weight: 36 parts feldspar, 28 parts quartz, 14 parts calcite, 5 parts dolomite, 2.5 parts talc, 8 parts kaolin, 12 parts strontium carbonate, and 6 parts modified zinc oxide.
[0012] Preferably, the modified zinc oxide is prepared by the following method: first, zinc oxide is hydroxylated to obtain hydroxylated zinc oxide; then, hexachlorocyclotriphosphazene is reacted with an aminosilane coupling agent containing alkoxysilane groups to generate a polyphosphazene prepolymer containing siloxane groups, which is then hydrolyzed and condensed with borate ester to obtain a polyphosphazene-borosilicate hybrid sol; finally, the hydroxylated zinc oxide is mixed and reacted with the hybrid sol, and then cured and ground to obtain the final product.
[0013] Preferably, the preparation conditions for the hydroxylated zinc oxide are as follows: zinc oxide is dispersed in a 60-80 wt% ethanol-water mixed solvent, the pH is adjusted to 8.5-9.5, and the reaction is carried out by stirring at 50-60°C; the aminosilane coupling agent containing alkoxysilyl groups is N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane; and the borate ester is triethyl borate.
[0014] Preferably, in the preparation of the polyphosphazene-borosilicate hybrid sol: the mass ratio of hexachlorocyclotriphosphazene to N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane is (0.5-2):(2-5); the amount of triethyl borate added is 1-5% of the mass of the polyphosphazene prepolymer solution; the pH of the hydrolysis condensation is 4.0-5.0, and the temperature is 45-60℃.
[0015] Preferably, the hydroxylated zinc oxide is mixed and reacted with the polyphosphazene-borosilicate hybrid sol, then cured at 130-150°C, and then ground and sieved.
[0016] The preparation method of the flash-clean antifouling glaze includes the following steps: mixing the feldspar, quartz, calcite, dolomite, talc, kaolin, strontium carbonate and modified zinc oxide in the specified weight parts evenly, and ball milling to obtain the flash-clean antifouling glaze.
[0017] The ball-to-material ratio is 1:(1.5-2.5), and the ball mill speed is 250-400 rpm.
[0018] Preferably, the modified zinc oxide is prepared by a method comprising the following steps: S1. Disperse zinc oxide in an alcohol-water mixed solvent, adjust the pH to alkaline, stir the reaction to obtain a hydroxylated zinc oxide dispersion; S2. Under a protective atmosphere, hexachlorocyclotriphosphazene is dissolved in an organic solvent. Separately, an aminosilane coupling agent containing alkoxysilane groups and an acid-binding agent are dissolved in the organic solvent. These are added dropwise to the hexachlorocyclotriphosphazene solution at low temperature, and the reaction is carried out by heating. After filtration, a polyphosphazene prepolymer solution containing siloxane groups is obtained. Boronate is added to the prepolymer solution to adjust the pH to acidic, and hydrolysis and condensation are carried out to obtain a polyphosphazene-borosilicate hybrid sol. S3. The hydroxylated zinc oxide dispersion from step S1 is mixed with the polyphosphazene-borosiloxane hybrid sol from step S2, stirred and reacted, and then centrifuged, washed, dried, cured and ground to obtain modified zinc oxide.
[0019] The reaction mechanism of this invention is as follows: S1 involves hydroxylation of zinc oxide under alkaline conditions: the surface of zinc oxide particles interacts with water molecules in an ethanol-water system, and forms more surface hydroxyl groups under ammonia conditions, thereby improving the reactivity of the zinc oxide surface and its subsequent interfacial bonding ability. Hydroxylated zinc oxide not only improves its dispersibility in solvent systems but also provides active sites for the subsequent chemical grafting of hybrid layers.
[0020] Under nitrogen protection, hexachlorocyclotriphosphazene (S2) undergoes a nucleophilic substitution reaction with N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane. N-(2-aminoethyl)-3-aminopropyltrimethoxysilane contains primary and secondary amino groups, which can undergo nucleophilic substitution with the P-Cl bond in hexachlorocyclotriphosphazene, introducing alkoxysilane-containing side chains onto the polyphosphazene backbone. Its trimethoxysilane group further hydrolyzes under weakly acidic conditions to form Si-OH, which condenses with B-OH formed from the hydrolysis of triethyl borate to generate a Si-OB structure, thus forming a polyphosphazene-borosilicate hybrid sol.
[0021] S3 involves reacting hydroxylated zinc oxide with a polyphosphazene-borosilicate hybrid sol. The Si-OH and B-OH groups in the hybrid sol undergo condensation reactions with the Zn-OH groups on the zinc oxide surface, forming interfacial chemical bonds such as Zn-O-Si and Zn-OB. This ensures the stable bonding of the polyphosphazene-borosilicate hybrid layer to the zinc oxide particles. Subsequent low-temperature curing further cross-links and densifies the hybrid layer, resulting in a modified zinc oxide composite nucleating agent with a polyphosphazene-borosilicate hybrid layer bonded to its surface.
[0022] Furthermore, the preparation method of the modified zinc oxide is as follows: S1. Add 7-14 parts by weight of zinc oxide to 240-400 parts by weight of 60-80 wt% ethanol-water mixed solvent, and ultrasonically disperse for 20-50 min; add ammonia water to adjust the pH to 8.5-9.5, and stir at 50-60℃ and 300-600 rpm for 1-3 h to obtain hydroxylated zinc oxide dispersion. S2. Under nitrogen protection, 0.5-2 parts by weight of hexachlorocyclotriphosphazene are added to 20-50 parts by weight of anhydrous tetrahydrofuran and stirred to dissolve, obtaining a hexachlorocyclotriphosphazene solution; separately, 2-5 parts by weight of N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane and 1-3 parts by weight of triethylamine are added to 30-60 parts by weight of anhydrous tetrahydrofuran, stirred evenly, and then added dropwise to the hexachlorocyclotriphosphazene solution at 2-6℃; after the addition is complete, the temperature is raised to 50-70℃ and reacted for 4-10 hours, filtered, and a polyphosphazene prepolymer solution containing siloxane groups is obtained; 0.3-1 parts by weight of triethyl borate are added to the polyphosphazene prepolymer solution, the pH is adjusted to 4-5, and hydrolysis and condensation are carried out at 44-60℃ for 2-5 hours to obtain a polyphosphazene-borosilicate hybrid sol; S3. Add 200-400 parts by weight of hydroxylated zinc oxide dispersion to 10-20 parts by weight of polyphosphazene-borosiloxane hybrid sol, stir at 50-65℃ and 300-500rpm for 2-6 hours, centrifuge, wash, dry, cure at 130-150℃ for 1-3 hours, and grind through a 100-300 mesh sieve after natural cooling to obtain modified zinc oxide.
[0023] The beneficial effects of this invention are: This invention provides a flash-cleaning antifouling glaze and its preparation method. By constructing a polyphosphazene-borosilicate hybrid layer on the surface of zinc oxide, an organic-inorganic hybrid interface layer containing a P=N framework, a Si-O-Si network, and a Si-OB structure is formed on the zinc oxide surface. The polyphosphazene structure improves the flexibility and thermal stability of the modified layer, while the borosilicate network enhances the interfacial compatibility between zinc oxide and aluminosilicate components such as feldspar, quartz, and kaolinite. This effectively improves the dispersion stability of zinc oxide in the glaze slurry and reduces the problem of local enrichment and agglomeration of ordinary zinc oxide during firing.
[0024] 2. The modified zinc oxide in this invention can release zinc ions more uniformly during firing, promoting the precipitation of fine and uniform crystals and reducing the formation of coarse grains and local dark spots. Simultaneously, the polyphosphazene-borosilicate hybrid layer further transforms at high temperature to form a BO-Si-P hybrid interface structure. This structure enhances the bonding strength between the crystals and the glaze glass phase, reducing interfacial stress concentration caused by thermal expansion mismatch, thereby reducing grain boundary microcracks and open pores. Therefore, the glaze crystals prepared by this invention are more delicate and uniform, resulting in a soft and transparent sparkling effect.
[0025] 3. The glaze of the present invention can effectively reduce grain boundary defects and open pores, and stains are not easy to penetrate along grain boundaries and micropores, thus significantly improving the anti-fouling performance and easy cleaning performance of the glaze surface; at the same time, the bond between the crystal and the glass phase is stronger, and the crystal is not easy to fall off during long-term friction and scrubbing, thereby further improving the wear resistance and long-term stability of the glaze surface, and has good application prospects. Detailed Implementation
[0026] The invention will now be described in further detail with reference to specific embodiments, but it should not be construed as limiting the scope of the invention to the following embodiments.
[0027] The raw materials described in this application are partially described; all other raw materials not described are commercially available. Feldspar, 200 mesh, was purchased from Shengfei Mineral Products Processing Plant in Lingshou County.
[0028] N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane, CAS No. 1760-24-3.
[0029] Example 1
[0030] A flash-clean anti-fouling glaze is composed of the following raw materials in parts by weight: 36 parts feldspar, 28 parts quartz, 14 parts calcite, 5 parts dolomite, 2.5 parts talc, 8 parts kaolin, 12 parts strontium carbonate, and 6 parts modified zinc oxide.
[0031] The method for preparing the modified zinc oxide is as follows: S1. Add 10 parts by weight of zinc oxide to 300 parts by weight of 75 wt% ethanol-water mixed solvent and ultrasonically disperse for 30 min; add ammonia water to adjust the pH to 9.0, and stir at 55℃ and 400 rpm for 1.5 h to obtain hydroxylated zinc oxide dispersion. S2. Under nitrogen protection, 1.0 parts by weight of hexachlorocyclotriphosphazene were added to 30 parts by weight of anhydrous tetrahydrofuran and stirred until dissolved to obtain a hexachlorocyclotriphosphazene solution. Separately, 3 parts by weight of N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane and 1.5 parts by weight of triethylamine were added to 40 parts by weight of anhydrous tetrahydrofuran and stirred until homogeneous. The mixture was then added dropwise to the hexachlorocyclotriphosphazene solution at 4°C. After the addition was complete, the temperature was raised to 60°C and reacted for 8 hours. The mixture was then filtered to obtain a polyphosphazene prepolymer solution containing siloxane groups. 0.6 parts by weight of triethyl borate were added to the polyphosphazene prepolymer solution to adjust the pH to 4.5. The solution was then hydrolyzed and condensed at 50°C for 3 hours to obtain a polyphosphazene-borosilicate hybrid sol. S3. Add 300 parts by weight of hydroxylated zinc oxide dispersion to 16 parts by weight of polyphosphazene-borosilicate hybrid sol, stir at 55℃ and 400 rpm for 4 h, centrifuge, wash, dry, cure at 140℃ for 2 h, and grind through a 200 mesh sieve after natural cooling to obtain modified zinc oxide.
[0032] The preparation method of the flash-clean antifouling glaze is as follows: 36 parts by weight of feldspar, 28 parts by weight of quartz, 14 parts by weight of calcite, 5 parts by weight of dolomite, 2.5 parts by weight of talc, 8 parts by weight of kaolin, 12 parts by weight of strontium carbonate, and 6 parts by weight of modified zinc oxide are mixed evenly and ball-milled for 4 hours. The ball-to-material ratio is 1:2, the ball milling speed is 300 rpm, and the mixture is evenly dispersed to obtain the flash-clean antifouling glaze.
[0033] Example 2
[0034] This is essentially the same as Example 1, except that the amount of modified zinc oxide added is 4 parts by weight. Other raw materials, dosages, and preparation methods are the same as in Example 1.
[0035] Example 3
[0036] This is essentially the same as Example 1, except that the amount of modified zinc oxide added is 8 parts by weight. Other raw materials, dosages, and preparation methods are the same as in Example 1.
[0037] Example 4
[0038] The method is essentially the same as in Example 1, except that in step S3 of the modified zinc oxide preparation method, the weight ratio of the hydroxylated zinc oxide dispersion to the polyphosphazene-borosiloxane hybrid sol is 300:10. Other raw materials, amounts, and preparation methods are the same as in Example 1.
[0039] Example 5
[0040] The method is essentially the same as in Example 1, except that in step S3 of the modified zinc oxide preparation method, the weight ratio of the hydroxylated zinc oxide dispersion to the polyphosphazene-borosiloxane hybrid sol is 300:20. Other raw materials, amounts, and preparation methods are the same as in Example 1.
[0041] Comparative Example 1
[0042] This is basically the same as Example 1, except that 6 parts by weight of modified zinc oxide is replaced with 6 parts by weight of ordinary zinc oxide. Other raw materials, dosages and preparation methods are the same as in Example 1.
[0043] Comparative Example 2
[0044] This is basically the same as Example 1, except that 6 parts by weight of modified zinc oxide is replaced with 6 parts by weight of hydroxylated zinc oxide. Other raw materials, dosages and preparation methods are the same as in Example 1.
[0045] Comparative Example 3
[0046] The method is basically the same as in Example 1, except that triethyl borate is not added in the preparation of the modified zinc oxide. The preparation method of the modified zinc oxide is as follows: S1. Add 10 parts by weight of zinc oxide to 300 parts by weight of 75 wt% ethanol-water mixed solvent and ultrasonically disperse for 30 min; add ammonia water to adjust the pH to 9.0, and stir at 55℃ and 400 rpm for 1.5 h to obtain hydroxylated zinc oxide dispersion. S2. Under nitrogen protection, 1.0 part by weight of hexachlorocyclotriphosphazene was added to 30 parts by weight of anhydrous tetrahydrofuran and stirred until dissolved to obtain a hexachlorocyclotriphosphazene solution; separately, 3 parts by weight of N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane and 1.5 parts by weight of triethylamine were added to 40 parts by weight of anhydrous tetrahydrofuran and stirred until homogeneous. Then, the mixture was added dropwise to the hexachlorocyclotriphosphazene solution at 4°C; after the addition was completed, the temperature was raised to 60°C and reacted for 8 hours. The mixture was then filtered to obtain a polyphosphazene prepolymer solution containing siloxane groups. S3. Add 300 parts by weight of hydroxylated zinc oxide dispersion to 16 parts by weight of the above polyphosphazene prepolymer solution containing siloxane groups, stir at 55°C and 400 rpm for 4 h, centrifuge, wash, dry, cure at 140°C for 2 h, and grind through a 200-mesh sieve after natural cooling to obtain modified zinc oxide.
[0047] Comparative Example 4
[0048] The method is basically the same as in Example 1, except that hexachlorocyclotriphosphazene is not added in the preparation of the modified zinc oxide. The preparation method of the modified zinc oxide is as follows: S1. Add 10 parts by weight of zinc oxide to 300 parts by weight of 75 wt% ethanol-water mixed solvent and ultrasonically disperse for 30 min; add ammonia water to adjust the pH to 9.0, and stir at 55℃ and 400 rpm for 1.5 h to obtain hydroxylated zinc oxide dispersion. S2. Under nitrogen protection, 3 parts by weight of N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane and 1.5 parts by weight of triethylamine were added to 40 parts by weight of anhydrous tetrahydrofuran. After stirring evenly, an aminosilane precursor solution was obtained. 0.6 parts by weight of triethyl borate were added to the solution to adjust the pH to 4.5. The solution was then hydrolyzed and condensed at 50°C for 3 hours to obtain a borosilicate hybrid sol. S3. Add 300 parts by weight of hydroxylated zinc oxide dispersion to 16 parts by weight of borosilicate hybrid sol, stir at 55°C and 400 rpm for 4 hours, centrifuge, wash, dry, cure at 140°C for 2 hours, and grind through a 200-mesh sieve after natural cooling to obtain modified zinc oxide.
[0049] Comparative Example 5
[0050] Similar to Example 1, except that instead of preparing polyphosphazene-borosilicate hybrid modified zinc oxide in advance, ordinary zinc oxide, hexachlorocyclotriphosphazene, N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane, and triethyl borate are directly added to the glaze in the corresponding proportions and mixed and ball-milled.
[0051] Test Example 1
[0052] Sample preparation: The flash-cleaning anti-fouling glazes obtained in Examples 1-5 and Comparative Examples 1-5 were respectively mixed with water to prepare glaze slurries. The solid content of the glaze slurry was controlled to be 35wt%. After ball milling for 4 hours, the glazes were passed through a 325-mesh sieve and allowed to stand for 30 minutes to remove bubbles.
[0053] The glaze slurry was applied to the surface of the ceramic body by spraying glaze, with an application rate of 95 g / m². After drying, the body was placed in a roller kiln for firing at a maximum temperature of 1200℃ for 60 min. After the firing was completed, the temperature was lowered to 650℃ at a rate of 120℃ / h, and then further lowered to below 120℃ at a rate of 300℃ / h. The body was then allowed to cool naturally after being removed from the kiln to obtain the test sample.
[0054] The samples obtained in Examples 1-5 and Comparative Examples 1-5 were subjected to appearance observation, 60° gloss test, surface roughness test, and crystal uniformity observation. Crystal uniformity was observed using a metallographic microscope at a magnification of 200x. The crystal uniformity of the glaze was evaluated by observing the crystal size, uniformity of crystal distribution, and the presence of obvious coarse grains, local dark spots, and grain boundary defects.
[0055] Among them, the 60° gloss was tested using a gloss meter, with 5 locations randomly selected for each sample and the average value taken; the surface roughness Ra was tested using a roughness meter; and the crystal uniformity was observed under a microscope, and evaluated according to whether the crystal distribution was uniform and whether there were obvious coarse grains and local dark spots.
[0056] Table 1 Flash Cleaning Effect and Glaze Structure Test
[0057] Test Example 2 The tests were conducted in accordance with GB / T 3810.14-2016, "Test Methods for Ceramic Tiles - Part 14: Determination of Stain Resistance". Soy sauce, coffee, and oil-based markers were used as contaminants. These contaminants were applied or coated onto the sample surface and allowed to stand for 24 hours. The samples were then cleaned sequentially with water, a damp cloth, and a neutral detergent. The stain resistance level was determined based on the residue remaining; a higher level indicates better stain resistance. A "wiping count" was also used to evaluate the effectiveness of the quick-cleaning method: the wiping endpoint was defined as when the stain was essentially invisible to the naked eye; one wiping with a damp cloth was counted as one wipe, and the number of wipes required to remove the contaminant was recorded. Each sample group was tested in triplicate, and the average value was used as the final result.
[0058] Table 2. Results of stain resistance and easy cleaning tests
[0059] The results above show that the samples prepared by this invention have good flash-cleaning effect, anti-fouling performance, and easy-to-clean properties. In Example 1, the crystals are fine and uniform, and the glaze exhibits a delicate and soft flash effect; simultaneously, its stain resistance level reaches level 5, and oil-based pens can be basically removed with only 5.3 wipes, indicating that the polyphosphazene-borosilicate hybrid modified zinc oxide used in this invention can significantly improve the flash-cleaning effect and anti-fouling performance of the glaze. In Example 2, the amount of modified zinc oxide added is relatively low, resulting in slightly fewer crystals, thus the flash effect is slightly weaker than in Example 1, but it still maintains good crystal uniformity and anti-fouling performance. In Example 3, with the increase in the amount of modified zinc oxide added, the number of crystals further increases, thus the flash effect is more obvious, and the 60° gloss increases to 38.2 GU, but due to the increase in local crystal density, the surface roughness slightly increases. This indicates that the amount of modified zinc oxide added affects the degree of crystallization and the microstructure of the glaze, and within a suitable range, it can balance the flash-cleaning effect and the density of the glaze. Examples 4 and 5 mainly investigated the effect of the coating amount of the polyphosphazene-borosilicate hybrid layer on the performance. When the coating amount of the hybrid sol was low, the degree of interfacial modification of the zinc oxide surface was limited, so the crystal uniformity and anti-fouling performance were slightly lower than those in Example 1. However, after the coating amount was increased, the interfacial compatibility between zinc oxide and the glass phase of the glaze was further improved, and the crystallization was more complete, thus enhancing the flashing effect. However, due to the increase in crystal precipitation, the roughness increased slightly, indicating that the polyphosphazene-borosilicate hybrid layer can effectively improve the dispersion of zinc oxide in the glaze slurry and the interfacial bonding performance after firing.
[0060] Comparative Example 1, using ordinary zinc oxide, had a 60° gloss of only 19.6 GU and a stain resistance level of only 3. This is because ordinary zinc oxide tends to agglomerate in the glaze slurry, leading to localized enrichment during firing, resulting in insufficient or uneven crystallization. Micropores and microcracks easily form at grain boundaries, thus reducing the glaze's sparkle-cleaning effect and stain resistance. Comparative Example 2, using hydroxylated zinc oxide, showed improved performance compared to ordinary zinc oxide, indicating that hydroxylation can improve the dispersibility of zinc oxide to some extent. However, due to the lack of a stable organic-inorganic hybrid interface layer, the bond between zinc oxide and the glaze's glass phase remained weak, thus still exhibiting problems of uneven crystal size and localized staining residue. Comparative Example 3, without the addition of triethyl borate (i.e., without the formation of a Si-OB borosilicate network structure), showed a significant decrease in crystal uniformity and stain resistance, indicating that the borosilicate network can improve the density of the hybrid layer and the interfacial bonding ability, thereby reducing grain boundary defects and stain penetration. Comparative Example 4, without the addition of hexachlorocyclotriphosphazene, only formed a borosilicate structure. While its performance was superior to ordinary zinc oxide, it was still inferior to Example 1. This indicates that the P=N flexible framework in polyphosphazene can improve the stability and toughness of the hybrid layer, thereby further improving the bonding strength between the crystal and the glass phase. In Comparative Example 5, hexachlorocyclotriphosphazene, N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane, and triethyl borate were directly added to the glaze without pre-constructing a polyphosphazene-borosilicate hybrid layer on the zinc oxide surface. The surface roughness reached 0.42 μm, and contaminants were difficult to remove. This demonstrates that the key to this invention is not simply adding P, Si, and B components, but rather constructing a stable polyphosphazene-borosilicate hybrid interface layer in situ on the zinc oxide surface, thereby achieving a stable interfacial bond between zinc oxide and the glaze glass phase and promoting the formation of fine, uniform crystals.
Claims
1. A flash-cleaning anti-fouling glaze, characterized in that, The raw materials include the following parts by weight: 25-45 parts feldspar, 22-35 parts quartz, 10-18 parts calcite, 3-7 parts dolomite, 1-4 parts talc, 5-12 parts kaolinite, 8-15 parts strontium carbonate, and 3-10 parts modified zinc oxide. The modified zinc oxide is zinc oxide particles with a polyphosphazene-borosilicate hybrid layer bonded to their surface.
2. The flash-cleaning antifouling glaze according to claim 1, characterized in that, It is composed of the following raw materials in parts by weight: 30-40 parts feldspar, 25-30 parts quartz, 12-16 parts calcite, 4-6 parts dolomite, 2-3 parts talc, 7-10 parts kaolinite, 10-13 parts strontium carbonate, and 4-8 parts modified zinc oxide.
3. The flash-cleaning antifouling glaze according to claim 1, characterized in that, It is composed of the following raw materials in parts by weight: 36 parts feldspar, 28 parts quartz, 14 parts calcite, 5 parts dolomite, 2.5 parts talc, 8 parts kaolin, 12 parts strontium carbonate, and 6 parts modified zinc oxide.
4. The flash-cleaning antifouling glaze according to any one of claims 1-3, characterized in that, The modified zinc oxide is prepared by the following method: first, zinc oxide is hydroxylated to obtain hydroxylated zinc oxide; then, hexachlorocyclotriphosphazene is reacted with an aminosilane coupling agent containing alkoxysilane groups to generate a polyphosphazene prepolymer containing siloxane groups, which is then hydrolyzed and condensed with borate ester to obtain a polyphosphazene-borosilicate hybrid sol; finally, the hydroxylated zinc oxide is mixed and reacted with the hybrid sol, and then cured and ground to obtain the final product.
5. The flash-cleaning antifouling glaze according to claim 4, characterized in that, The preparation conditions for the hydroxylated zinc oxide are as follows: zinc oxide is dispersed in a 60-80 wt% ethanol-water mixed solvent, the pH is adjusted to 8.5-9.5, and the reaction is carried out by stirring at 50-60℃; the aminosilane coupling agent containing alkoxysilyl groups is N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane; and the borate ester is triethyl borate.
6. The flash-cleaning antifouling glaze according to claim 5, characterized in that, In the preparation of the polyphosphazene-borosilicate hybrid sol: the mass ratio of hexachlorocyclotriphosphazene to N-(beta-aminoethyl)-gama-aminopropyltrimethoxysilane is (0.5-2):(2-5); the amount of triethyl borate added is 1-5% of the mass of the polyphosphazene prepolymer solution; the pH of hydrolysis and condensation is 4.0-5.0, and the temperature is 45-60℃.
7. The flash-cleaning antifouling glaze according to claim 4, characterized in that, The hydroxylated zinc oxide is mixed and reacted with the polyphosphazene-borosilicate hybrid sol, then cured at 130-150℃, and finally ground and sieved.
8. A method for preparing a flash-cleaning antifouling glaze as described in any one of claims 1-7, characterized in that, The process includes the following steps: mixing the specified weight proportions of feldspar, quartz, calcite, dolomite, talc, kaolin, strontium carbonate, and modified zinc oxide evenly, and ball milling to obtain a flash-clean anti-fouling glaze.
9. The preparation method according to claim 8, characterized in that, The modified zinc oxide is prepared by a method comprising the following steps: S1. Disperse zinc oxide in an alcohol-water mixed solvent, adjust the pH to alkaline, stir the reaction to obtain a hydroxylated zinc oxide dispersion; S2. Under a protective atmosphere, hexachlorocyclotriphosphazene is dissolved in an organic solvent, and an aminosilane coupling agent and an acid-binding agent containing alkoxysilyl groups are dissolved in the organic solvent. The solutions are added dropwise to the hexachlorocyclotriphosphazene solution at low temperature, and the reaction is carried out by heating. After filtration, a polyphosphazene prepolymer solution containing siloxyalkyl groups is obtained. Boronate ester was added to the prepolymer solution, the pH was adjusted to acidic, and hydrolysis and condensation were carried out to obtain polyphosphazene-borosilicate hybrid sol; S3. The hydroxylated zinc oxide dispersion from step S1 is mixed with the polyphosphazene-borosiloxane hybrid sol from step S2, stirred and reacted, and then centrifuged, washed, dried, cured and ground to obtain modified zinc oxide.