Ceramic glaze and preparation method and application thereof

Abstract

The application discloses a kind of ceramic glaze and its preparation method and application, belong to ceramic technical field.The ceramic glaze provided by the application includes base glaze and photocatalyst;The photocatalyst includes graphene and the modified titanium dioxide and modified zinc oxide loaded on the surface of graphene;The modified titanium dioxide is Fe, S co-doped titanium dioxide, and the modified zinc oxide is Cu-doped zinc oxide;The particle size of the modified titanium dioxide and / or modified zinc oxide is 10-30nm;The mass ratio of the photocatalyst and the solid in the base glaze is 0.5-3:100.The ceramic glaze provided by the application can effectively reduce the cleaning difficulty of the glaze surface and improve the antibacterial property of the glaze surface.The application also provides a preparation method and application of the above-mentioned ceramic glaze.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramics, in particular to a ceramic glaze and a preparation method and application thereof. BACKGROUND

[0002] With the increasing improvement of people's living standards, ordinary people pay more and more attention to the cleaning of dirt on the surface of sanitary wares and daily-use ceramics; ceramic materials for building exterior walls also need to be self-cleaning (easy-to-clean performance). Since detergents not only cause water pollution but also have an impact on human health, therefore, it is of great practical significance to develop ceramic materials with anti-fouling performance. From a large number of studies on the anti-fouling property of ceramic glaze, the existing anti-fouling technology on the surface of ceramic products can be roughly divided into the following two kinds. One is to provide a super-hydrophilic surface, so as to remove most of the dirt by water flushing; the other is to provide a super-hydrophobic surface, so as to reduce the adhesion of dirt on the ceramic surface.

[0003] However, according to the existing market products, the effects provided by the above two methods are very limited, and it is still an important research topic in the field to improve the easy-to-clean performance of ceramic products. SUMMARY

[0004] The present application aims to at least solve one of the problems existing in the prior art. To this end, the present application provides a ceramic glaze which can effectively reduce the cleaning difficulty of the glaze and improve the antibacterial property of the glaze.

[0005] The present application also provides a preparation method of the above-mentioned ceramic glaze.

[0006] The present application also provides a ceramic product prepared from the raw material including the above-mentioned ceramic glaze.

[0007] According to the embodiment of the first aspect of the present application, a ceramic glaze is provided, which comprises a base glaze and a photocatalyst;

[0008] The photocatalyst comprises graphene and modified titanium dioxide and modified zinc oxide loaded on the surface of the graphene;

[0009] The modified titanium dioxide is Fe and S co-doped titanium dioxide, and the modified zinc oxide is Cu-doped zinc oxide;

[0010] The particle size of the modified titanium dioxide and / or the modified zinc oxide is 10-30 nm;

[0011] The mass ratio of the photocatalyst to the solid in the base glaze is 0.5-3:100.

[0012] The ceramic glaze according to the embodiment of the present application has at least the following beneficial effects:

[0013] The titanium dioxide and the zinc oxide are common photocatalysts, Fe and S are doped into the former, and Cu is doped into the latter, so that the band gap of the corresponding material is reduced, the response of the material is extended from the ultraviolet light to the visible light, but the spectral response of the two materials is different; therefore, the modified titanium dioxide and the modified zinc oxide are combined, so that the light response range of the photocatalyst is widened.

[0014] In the photocatalyst, the modified titanium dioxide and the modified zinc oxide are loaded on the surface of the graphene, so that the contact between the two is promoted, and even chemical connection is formed; further, a heterojunction is formed between the two, and the photocatalytic activity is further improved. Further, in the subsequent preparation method, the graphene is used as a carrier, and the oxygen-containing groups on the graphene are used as chemical anchor points, so that the particle size of the modified titanium dioxide and the modified zinc oxide can be limited, and smaller particle size exposes more active sites, and the photocatalytic activity is further improved.

[0015] Further, in the photocatalyst, the graphene and other components can have a synergistic effect, and the photocatalytic activity is further improved; the graphene itself can also improve the hardness, wear resistance and toughness of the glaze surface of the ceramic glaze.

[0016] Due to the above-mentioned multi-angle synergistic effect, the ceramic glaze prepared by the application has excellent visible light catalytic activity, and can catalytically decompose organic matter, such as cell membranes of bacteria, etc., on the surface under the condition of visible light. Based on the above reasons, the ceramic glaze provided by the application also has excellent antibacterial performance.

[0017] According to some embodiments of the application, the base glaze comprises transparent glaze.

[0018] According to some embodiments of the application, the base glaze comprises feldspar, quartz, kaolin, calcite and talc. The feldspar comprises at least one of potassium feldspar and sodium feldspar.

[0019] According to some embodiments of the application, the base glaze comprises the following components by mass fraction:

[0020] feldspar 50-60 parts; for example, specifically, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts; or a range value composed of any two point values in the above;

[0021] quartz 15-25 parts; for example, specifically, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts; or a range value composed of any two point values in the above;

[0022] calcite 10-15 parts; for example, specifically, 10 parts, 11 parts, 12 parts, 14 parts, 15 parts; or a range value composed of any two point values in the above;

[0023] kaolin 5~10 parts. For example, it can be specifically 5 parts, 6 parts, 7 parts, 8 parts, 10 parts; or a range value composed of any two of the above point values;

[0024] According to some embodiments of the present application, the base glaze further comprises water.

[0025] According to some embodiments of the present application, the solid content of the base glaze is 20~40%. For example, it can be specifically 20%, 25%, 30%, 35%, 40%; or a range value composed of any two of the above point values. Within this range, the obtained ceramic glaze has appropriate viscosity and density, which is beneficial to improve the uniformity of glazing.

[0026] According to some embodiments of the present application, in the photocatalyst, the number of layers of the graphene is ≤10 layers. For example, it can be specifically 1 layer, 5 layers, 10 layers; or a range value composed of any two of the above point values.

[0027] According to some embodiments of the present application, in the photocatalyst, the flake diameter of the graphene is 0.1~10 μm. For example, it can be specifically 0.1 μm, 0.5 μm, 1 μm, 2 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm; or a range value composed of any two of the above point values.

[0028] According to some embodiments of the present application, the mass ratio of the photocatalyst to the solid in the base glaze is 0.5~3:100. For example, it can be specifically 0.5:100, 0.8:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100; or a range value composed of any two of the above point values.

[0029] According to embodiments of the second aspect of the present application, a preparation method of the ceramic glaze of the first aspect of the present application is provided, and the preparation method comprises the following steps:

[0030] S1. Synthesizing the photocatalyst;

[0031] S1a. After the solvent thermal reaction of the iron source, the titanium source and the graphene, annealing in a hydrogen sulfide-containing atmosphere to obtain an intermediate product; the intermediate product comprises modified titanium dioxide and graphene loaded with the modified titanium dioxide;

[0032] S1b. After mixing the copper source and the zinc source, mixing the mixture with the intermediate product, and continuing to react with the lye to obtain the photocatalyst;

[0033] S2. Mixing the photocatalyst and the base glaze.

[0034] The mechanism of the preparation method is as follows:

[0035] In the solvothermal reaction of step S1a, the iron source and the titanium source are co-precipitated on the graphene surface, and then annealed in a hydrogen sulfide atmosphere to introduce sulfur doping, thereby obtaining a modified titanium dioxide and the graphene loaded with the modified titanium dioxide.

[0036] In step S1b, the copper source and the zinc source are mixed to perform a preliminary reaction, and then the intermediate product is introduced into a crystal site (a subsequent attachment site of the modified zinc oxide deposition), and then the copper source and the zinc source are co-precipitated on the surface of the intermediate product to form the modified zinc oxide loaded on the intermediate product after adding an alkali solution; and the photocatalyst is formed.

[0037] Since the preparation method adopts all the technical solutions of the ceramic glaze in the above embodiments, it at least has all the beneficial effects brought by the technical solutions of the above embodiments. Further,

[0038] In the preparation method, the addition of the intermediate product in step S1b promotes the co-loading of the modified zinc oxide and the modified titanium dioxide on the surface of the graphene, and the latter may wrap or contact the former, and the two are tightly combined to form a heterojunction, thereby improving the photocatalytic performance.

[0039] According to some embodiments of the present application, in step S1a, the iron source includes at least one of ferric chloride, ferric nitrate, ferric acetate, or a hydrate of the above iron source.

[0040] According to some embodiments of the present application, in step S1a, the titanium source includes at least one of tetrabutyl titanate, titanium ethoxide, and titanium butoxide.

[0041] According to some embodiments of the present application, in step S1a, the feeding ratio of the iron source and the titanium source satisfies a molar ratio of Fe / (Fe+Ti) of 0.1-5%. For example, it can be specifically 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or a range value composed of any two of the above point values.

[0042] According to some embodiments of the present application, in step S1a, the addition amount of the graphene satisfies that the designed mass percentage of the graphene in the photocatalyst is 10-40%. For example, it can be specifically 10%, 15%, 20%, 25%, 30%, 35%, or 40%, or a range value composed of any two of the above point values. It should be explained that the design premise of the designed mass percentage is that the iron in the iron source and the titanium in the titanium source are completely reacted in step S1a, and the doping mass of a small amount of S in the modified titanium dioxide is ignored.

[0043] According to some embodiments of the present application, in step S1a, the solvent of the solvothermal reaction includes at least one of an alcohol solvent and dimethyl sulfoxide (DMSO).

[0044] According to some embodiments of the present application, in step S1a, the concentration of the titanium source in the solvothermal reaction system is 10-50 mmol / L. For example, it can be specifically 10 mmol / L, 15 mmol / L, 20 mmol / L, 25 mmol / L, 30 mmol / L, 35 mmol / L, 40 mmol / L, 45 mmol / L, 50 mmol / L; or a range value composed of any two of the above point values.

[0045] According to some embodiments of the present application, in step S1a, the solvothermal reaction atmosphere contains hydrogen sulfide. The volume percentage of hydrogen sulfide is 2-3%. For example, it can be specifically 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%; or a range value composed of any two of the above point values. The remaining amount in the solvothermal reaction atmosphere is an inert gas, for example, nitrogen or argon. Using the above atmosphere, preliminary S doping can be formed.

[0046] According to some embodiments of the present application, in step S1a, the temperature of the solvothermal reaction is 180-230°C. For example, it can be specifically 18°C, 190°C, 200°C, 210°C, 220°C, 230°C; or a range value composed of any two of the above point values.

[0047] According to some embodiments of the present application, in step S1a, the duration of the solvothermal reaction is 20-30 h. For example, it can be specifically 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h, 30 h; or a range value composed of any two of the above point values.

[0048] According to some embodiments of the present application, in step S1a, the obtained solid is washed after the solvothermal reaction. The washing agent used in the washing includes at least one of an alcohol solvent and water.

[0049] According to some embodiments of the present application, in step S1a, the highest temperature of the annealing is 100-110°C. For example, it can be specifically 100°C, 102°C, 104°C, 105°C, 106°C, 108°C, 110°C; or a range value composed of any two of the above point values.

[0050] According to some embodiments of the present application, in step S1a, the annealing mechanism is to stop heating after heating to the highest temperature, and then to cool down in the furnace. In this way, one cycle is one annealing. In step S1a, the number of annealings is 1-3 times. By adjusting the annealing here, the doping amount of S in the modified titanium dioxide is adjusted.

[0051] According to some embodiments of the present application, in step S1a, in the hydrogen sulfide-containing atmosphere, the volume percentage of hydrogen sulfide is 2-3%. For example, it can be specifically 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, or a range value composed of any two of the above point values.

[0052] According to some embodiments of the present application, in step S1b, the copper source includes at least one of copper acetate, copper nitrate, copper sulfate, copper chloride, or a hydrate of the above copper source.

[0053] According to some embodiments of the present application, in step S1b, the zinc source includes at least one of zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, or a hydrate of the above zinc source.

[0054] According to some embodiments of the present application, in step S1b, the feeding ratio of the copper source and the zinc source satisfies that the molar ratio of Cu / (Cu+Zn) is 0.5-1.5%. For example, it can be specifically 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, or a range value composed of any two of the above point values.

[0055] According to some embodiments of the present application, in step S1b, the addition amount of the intermediate product satisfies that in the photocatalyst, the designed mass ratio of the modified titanium dioxide and the modified zinc oxide is 0.2-0.5:1. For example, it can be specifically 0.2:1, 0.3:1, 0.4:1, 0.5:1, or a range value composed of any two of the above point values. Here, as with the mass percentage of graphene, it is a designed value, provided that in step S1a, all iron sources and titanium sources completely react to generate modified titanium dioxide deposited on the graphene to form an intermediate product; in step S1b, the copper source and the zinc source completely react to generate modified zinc oxide deposited on the surface of the intermediate product.

[0056] In actual production, the feeding amount of each raw material in the preparation method can be calculated in combination with the molar ratio of Fe / (Fe+Ti), the molar ratio of Cu / (Cu+Zn), the designed mass ratio of the modified titanium dioxide and the modified zinc oxide, and the designed mass percentage of graphene. For example, the designed mass ratio of the modified titanium dioxide and the modified zinc oxide is 0.5:1, and the designed mass percentage of graphene is 20%. Then, the mass ratio of graphene and the modified titanium dioxide is calculated to be 20:26.7, and the mass ratio of the intermediate product and the modified zinc oxide is calculated to be 46.7:53.3. In combination with the molar ratio of Fe / (Fe+Ti), the feeding amount ratio of graphene, the iron source and the titanium source can be calculated. In combination with the molar ratio of Cu / (Cu+Zn), the feeding amount ratio of the intermediate product, the copper source and the zinc source can be calculated.

[0057] According to some embodiments of the application, in step S1b, the solvent used in the mixed reaction system includes at least one of an alcohol solvent and DMSO.

[0058] According to some embodiments of the application, in step S1b, the concentration of the zinc source in the mixed reaction system is 20-50 mmol / L. For example, it can be specifically 20 mmol / L, 25 mmol / L, 30 mmol / L, 35 mmol / L, 40 mmol / L, 45 mmol / L, 50 mmol / L, or a range value composed of any two of the above point values.

[0059] According to some embodiments of the application, in step S1b, the temperature of the mixed reaction is 60-90℃. For example, it can be specifically 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, or a range value composed of any two of the above point values.

[0060] According to some embodiments of the application, in step S1b, the duration of the mixed reaction is 0.5-2 h. For example, it can be specifically 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, or a range value composed of any two of the above point values.

[0061] According to some embodiments of the application, in step S1b, the solvent of the alkali solution includes an alcohol solvent.

[0062] According to some embodiments of the application, in step S1b, the solute of the alkali solution includes at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.

[0063] According to some embodiments of the present application, in step S1b, the concentration of the alkali solution is 1-5 g / L. For example, it can be specifically 1 g / L, 1.5 g / L, 2 g / L, 2.5 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L, or a range value formed by any two of the above point values.

[0064] According to some embodiments of the present application, in step S1b, the molar ratio of zinc ions in the zinc source to hydroxyl ions in the alkali solution is 1:0.5-4.5. For example, it can be specifically 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or a range value formed by any two of the above point values.

[0065] According to some embodiments of the present application, in step S1b, the temperature of the continued reaction is 20-30℃. For example, it can be specifically 20℃, 25℃, 30℃, or a range value formed by any two of the above point values.

[0066] According to some embodiments of the present application, in step S1b, the duration of the continued reaction is 20-40 min. For example, it can be specifically 20 min, 25 min, 30 min, 35 min, 40 min, or a range value formed by any two of the above point values.

[0067] According to some embodiments of the present application, in step S1b, the obtained solid product is further washed after the continued reaction. The washing method includes water washing.

[0068] According to some embodiments of the present application, in step S2, the average particle size of the solid in the base glaze is 50-100 nm. For example, it can be specifically 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or a range value formed by any two of the above point values. If the incoming material cannot meet the above requirements, ball milling is needed.

[0069] According to some embodiments of the third aspect of the present application, a ceramic product is provided, and the preparation raw material of the ceramic product includes the ceramic glaze according to the first aspect of the present application or the ceramic glaze prepared by the preparation method according to the second aspect of the present application.

[0070] Since the ceramic product adopts the ceramic glaze or the preparation method of the ceramic glaze according to the above embodiments, it at least has all the beneficial effects brought by the technical solutions of the above embodiments.

[0071] According to some embodiments of the present application, the preparation method of the ceramic product includes sintering after applying the ceramic glaze on the surface of the ceramic blank.

[0072] According to some embodiments of the present application, the glazing thickness of the ceramic glaze is 0.3-0.9mm. For example, it can be specifically 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm; or a range value formed by any two of the above point values.

[0073] According to some embodiments of the present application, the sintering temperature is 1150-1250℃. For example, it can be specifically 1150℃, 1160℃, 1170℃, 1180℃, 1190℃, 1200℃, 1210℃, 1220℃, 1230℃, 1240℃, 1250℃; or a range value formed by any two of the above point values.

[0074] According to some embodiments of the present application, the sintering time is 10-80min. For example, it can be specifically 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min; or a range value formed by any two of the above point values.

[0075] According to some embodiments of the present application, the sintering cooling rate is ≥50℃ / h. For example, it can be specifically 50℃ / h, 100℃ / h, 150℃ / h, 200℃ / h, 250℃ / h, 300℃ / h, 350℃ / h, 400℃ / h; or a range value formed by any two of the above point values. A faster cooling rate can maximize the retention of the heterojunction in the photocatalyst.

[0076] According to some embodiments of the present application, the sintering is carried out in an oxygen-free condition. For example, it can be specifically at least one of a nitrogen atmosphere, an argon atmosphere, and a vacuum atmosphere. In this way, the oxidation of the graphene can be avoided, and thus the presence of pores on the obtained glaze surface can be avoided.

[0077] According to some embodiments of the present application, the ceramic product comprises at least one of ceramic tableware, ceramic tiles, and ceramic bathroom products.

[0078] Other features and advantages of the present application will be set forth in the following description, and in part will become apparent from the description, or can be learned by practice of the present application. DETAILED DESCRIPTION

[0079] The concept and the resulting technical effects of the present application will be described below in conjunction with embodiments, so as to fully understand the purposes, features and effects of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0080] Example 1

[0081] A ceramic glaze is prepared in this example, and the specific preparation method is as follows:

[0082] S1. Synthesis of the photocatalyst;

[0083] S1a. After the solvent thermal reaction of the iron source, the titanium source and graphene, annealing in a hydrogen sulfide atmosphere to obtain an intermediate product; wherein,

[0084] The iron source is iron acetate tetrahydrate, CAS: 19807-28-4; the concentration is 1.0 mmol / L;

[0085] The titanium source is titanium ethoxide, CAS: 3087-36-3; the concentration is 30 mmol / L;

[0086] The graphene is customized from Xianfeng Nanometer, with 5-10 layers, a sheet diameter of 0.1-10 μm, and more concentrated around 5 μm;

[0087] The mass ratio of graphene to titanium in the titanium source is about 15:11.5; since the amount of S doped in the modified titanium dioxide is small, the mass is ignored, and the mass ratio of the modified titanium dioxide to graphene is about 15:19.6;

[0088] The solvent for the solvent thermal reaction is ethanol.

[0089] The atmosphere used for the solvent thermal reaction is a mixed atmosphere composed of 2.5% hydrogen sulfide and 97.5% nitrogen; that is, before the solvent thermal reaction, the above mixed atmosphere is used for gas replacement.

[0090] The temperature for the solvent thermal reaction is 190°C, and the time length is 22h.

[0091] After the solvent thermal reaction, the obtained solid is washed with ethanol for 3 times, and then dried at 60°C.

[0092] In the atmosphere used for annealing, the volume percentage of hydrogen sulfide is 2.5%, and the balance is nitrogen; the procedure for single annealing is to raise the temperature to 105°C and then lower the temperature; a total of two annealings are performed.

[0093] S1b. After mixing the copper source and the zinc source, a mixture is obtained by mixing the intermediate product and the mixture, and the mixture is continuously reacted with lye; wherein,

[0094] The copper source is copper acetate monohydrate, CAS: 6046-93-1; the concentration is 0.35 mmol / L.

[0095] The zinc source is zinc acetate dihydrate, CAS: 5970-45-6; the concentration is 35 mmol / L;

[0096] The solvent for the mixing reaction is ethanol;

[0097] The temperature of the mixed reaction is 70°C, and the time length is 1.5h.

[0098] The intermediate product is added according to the mass ratio of the intermediate product to the modified zinc oxide 0.346:0.654, that is, the mass ratio of the intermediate product to zinc in the zinc source is 0.346:0.52; it is calculated that the mass ratio of the modified titanium dioxide to the modified zinc oxide is about 0.3:1; and the mass percentage of graphene is about 15%.

[0099] The alkali solution is a 3g / L sodium hydroxide ethanol solution.

[0100] The amount of the alkali solution is calculated and added according to the molar ratio of zinc ions in the zinc source to hydroxide ions in sodium hydroxide 1:1.

[0101] The temperature of the continued reaction is room temperature, about 25°C; and the time length is 30min.

[0102] After the reaction is completed, the product is washed with water and dried at 60°C, and finally crushed through a 325 mesh sieve.

[0103] S2. Mix the photocatalyst and the base glaze. Among them,

[0104] The mass ratio of the photocatalyst to the solid in the base glaze is 1.5:100;

[0105] The solid composition of the base glaze is as follows:

[0106] Potassium feldspar 55 parts; quartz 20 parts; calcite 12 parts; kaolin 8 parts; and the chemical composition of the finally obtained base glaze is about 0.3K2O·0.7CaO·0.5Al2O3·4.0SiO2.

[0107] The base glaze solid is ball milled with water before use to form a base glaze in the state of glaze slurry with a solid content of 30%, and the average particle size of the solid substance is about 80nm.

[0108] After the base glaze and the photocatalyst are mixed, they are continuously ball milled for 10min and passed through a 325 mesh sieve for use.

[0109] Example 2

[0110] In this example, a ceramic glaze is prepared, which is different from Example 1 in particular as follows:

[0111] In step S1a, the mass percentage of graphene is designed to be 40%; and the mass ratio of graphene to titanium in the titanium source is about 40:8.1; and the mass ratio of the intermediate product to zinc in the zinc source is 53.85:36.75.

[0112] Example 3

[0113] A ceramic glaze is prepared in this example, which is different from example 1 in that:

[0114] In step S1a, the concentration of the iron source is 0.4 mmol / L, and the number of times of annealing in hydrogen sulfide is 1; correspondingly, the mass ratio of titanium in graphene and titanium source is about 15:11.66.

[0115] Comparative example 1

[0116] A ceramic glaze is prepared in this example, which is different from example 1 in that:

[0117] In step S1a, no graphene is added, and an equal amount of graphene is added in step S2.

[0118] Comparative example 2

[0119] A ceramic glaze is prepared in this example, which is different from example 1 in that:

[0120] In step S1b, no intermediate product is added, but an equal amount of product obtained in steps S1a and S1b of example 1 is added together in step S2.

[0121] Comparative example 3

[0122] A ceramic glaze is prepared in this example, which is different from example 1 in that:

[0123] In step S2, the mass ratio of the photocatalyst to the solid in the base glaze is 0.2:100.

[0124] Comparative example 4

[0125] A ceramic glaze is prepared in this example, which is different from example 1 in that:

[0126] In step S2, the mass ratio of the photocatalyst to the solid in the base glaze is 5:100.

[0127] Comparative example 5

[0128] A ceramic glaze is prepared in this example, which is different from example 1 in that:

[0129] In step S1a, an equal amount of graphene is replaced by carbon nanotubes, which are purchased from Xianfeng Nanometer with model number XFD01.

[0130] Application example

[0131] A ceramic product is prepared in this example, which specifically includes the following steps:

[0132] The blank is glazed and dried by dipping glaze, and the dried thickness of the glaze layer is 0.4 mm;

[0133] After glazing, the obtained semi-finished product is sintered under nitrogen protection, the highest temperature of sintering is 1200℃, the constant temperature time at the highest temperature is 60min; after the constant temperature ends, the temperature is first reduced to 650℃ at a speed of 120℃ / h, then reduced to below 120℃ at a speed of 300℃ / h, and then discharged from the furnace.

[0134] In the formula, the blank used in the example is composed of corundum 30%, potassium feldspar 29%, kaolin 30%, ball clay 5%, talc 2%, zinc oxide 1%, and zirconium oxide 3% by mass percentage.

[0135] Test Example

[0136] In the example, the morphology, wear resistance, antibacterial property and easy-to-clean performance of the ceramic product obtained in the application example are tested, wherein,

[0137] The morphology is tested by transmission electron microscopy.

[0138] Wear resistance: refer to GB / T3810.7 Test method in 2016 "Ceramic tile test methods Part 7: determination of glazed tile surface wear resistance", the grinding medium is a 3mm diameter steel ball (52.5g), after 12000 revolutions, rinse with deionized water, dry at 110℃, and record the wear mass.

[0139] Antibacterial property: refer to JC / T897 Test the antibacterial performance of the ceramic sample according to the method disclosed in 2014, record the antibacterial rate, and the bacteria is escherichia coli.

[0140] Easy-to-clean performance: refer to GB / T30447-2013 to test the pure water contact angle. Take 1 sun as a simulation light source, place the ceramic product obtained in the application example in a methylene blue solution with a concentration of 20mg / L, take the supernatant after irradiation for 30min, and measure the degradation rate of methylene blue; in each example and comparative example, the glaze surface area of the added ceramic product is consistent.

[0141] The morphology test results show that the modified titanium dioxide and the modified zinc oxide in the photocatalyst used in the application have no obvious boundary, and the two are overlapped and contacted, and are jointly loaded on the surface of graphene. The particle size of a single cluster is in the range of 10-30nm. In comparative example 1, due to the lack of the effect of graphene, the metal oxide clusters are aggregated, and the particle size can even reach micron level; in comparative example 2, the particle size of the modified zinc oxide is large, and there is no direct contact between the modified titanium oxide.

[0142] The above test results are shown in Table 1.

[0143] Table 1 Performance of ceramic glaze obtained in examples and comparative examples

[0144]

[0145] According to the above results, it can be known that the ceramic products prepared by the ceramic glaze within the parameter range provided by the application have excellent wear resistance, antibacterial property and easy-to-clean property.

[0146] The results of Examples 1-2 show that within a certain range, increasing the amount of graphene can fully exert the role of graphene in improving wear resistance, but in Example 2, the proportion of modified zinc oxide and modified titanium oxide is also reduced, and the light degradation rate and the antibacterial rate are also reduced due to the light shielding effect of graphene. The pure water contact angle is also improved due to the change of the above components.

[0147] The results of Examples 1 and 3 show that within the range provided by the application, increasing the doping amount of iron in titanium oxide to a certain extent is beneficial to improving its catalytic efficiency in visible light.

[0148] The results of Example 1 and Comparative Examples 1-2 show that in the photocatalyst provided by the application, there is a significant synergistic effect between graphene, modified titanium dioxide and modified zinc oxide. Graphene as a carrier can avoid the agglomeration of modified titanium dioxide and modified zinc oxide. The specific preparation method promotes the direct contact of modified titanium dioxide and modified zinc oxide and produces a heterojunction, which can significantly improve the photocatalytic activity and further improve the degradation rate of organic matter and the antibacterial rate. Further, the special form of the photocatalyst used in the application also has the effect of improving the dispersibility of graphene. Therefore, in Comparative Examples 1-2, the dispersibility of graphene is poor, so the wear resistance of the obtained ceramic product is also poor. Further, the dispersibility of modified titanium dioxide and / or modified zinc oxide is poor, so the gain effect on hydrophilicity is greatly reduced.

[0149] The results of Example 1 and Comparative Examples 3-4 show that if the amount of photocatalyst is not within the range required by the application, the photocatalytic performance of the obtained ceramic product will be significantly reduced. The former is due to too little photocatalyst, and the latter is due to serious light shielding by graphene.

[0150] The results of Example 1 and Comparative Example 5 show that although graphene and carbon nanotubes are both commonly used carbon-based materials, the former has a sheet structure and can be uniformly spread in the glaze layer, fully exerting the synergistic effect of the components, while the latter tends to wind and aggregate, and the performance gain of the obtained ceramic glaze is very limited.

[0151] The above embodiments of the application are described in detail, but the application is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the application. In addition, the embodiments of the application and the features in the embodiments can be combined with each other without conflict.

Claims

1. A ceramic glaze, characterized in that, The ceramic glaze includes a base glaze and a photocatalyst; The photocatalyst includes graphene and modified titanium dioxide and modified zinc oxide supported on the surface of the graphene. The modified titanium dioxide is Fe and S co-doped titanium dioxide, and the modified zinc oxide is Cu-doped zinc oxide; The particle size of the modified titanium dioxide and / or modified zinc oxide is 10~30nm; The mass ratio of the solid in the photocatalyst to the solid in the base glaze is 1.5~2.5:100; The photocatalyst is prepared by a method comprising the following steps: S1a. An iron source, a titanium source, and graphene are subjected to a solvothermal reaction, followed by annealing in a hydrogen sulfide atmosphere to obtain an intermediate product; the intermediate product includes modified titanium dioxide and graphene supported on the modified titanium dioxide; the amount of graphene added satisfies the following condition: in the photocatalyst, the mass percentage of graphene is 10-40%; S1b. After mixing and reacting the copper source and zinc source, the mixture is then mixed with the intermediate product to obtain a mixture, which is then reacted with an alkaline solution to obtain the photocatalyst.

2. The ceramic glaze according to claim 1, characterized in that, The base glaze includes a transparent glaze.

3. A method for preparing a ceramic glaze as described in any one of claims 1 to 2, characterized in that, The preparation method includes the following steps: S1. Synthesize the photocatalyst; S1a. An iron source, a titanium source, and graphene are subjected to a solvothermal reaction and then annealed in a hydrogen sulfide atmosphere to obtain an intermediate product; the intermediate product includes modified titanium dioxide and graphene supported on the modified titanium dioxide. S1b. After mixing and reacting the copper source and zinc source, the mixture is then mixed with the intermediate product to obtain a mixture, which is then further reacted with an alkaline solution to obtain the photocatalyst; S2. Mix the photocatalyst and the base glaze.

4. The preparation method according to claim 3, characterized in that, In step S1a, the feeding ratio of the iron source and the titanium source satisfies that the molar ratio of Fe / (Fe+Ti) is 0.1~5%; and / or, in step S1a, the amount of graphene added satisfies that the mass percentage of graphene in the photocatalyst is 10~40%.

5. The preparation method according to claim 3, characterized in that, In step S1a, the temperature of the solvothermal reaction is 180~230℃; and / or, in step S1a, the duration of the solvothermal reaction is 20~30h.

6. The preparation method according to claim 3, characterized in that, In step S1a, the atmosphere of the solvothermal reaction contains hydrogen sulfide.

7. The preparation method according to claim 3, characterized in that, In step S1a, the maximum annealing temperature is 100~110℃; and / or, in step S1a, the volume percentage of hydrogen sulfide in the hydrogen sulfide-containing atmosphere is 2~3%.

8. The preparation method according to claim 3, characterized in that, In step S1b, the feeding ratio of the copper source and the zinc source satisfies that the molar ratio of Cu / (Cu+Zn) is 0.5~1.5%; and / or, in step S1b, the amount of the intermediate product added satisfies that, in the photocatalyst, the mass ratio of the modified titanium dioxide to the modified zinc oxide is 0.2~0.5:

1.

9. The preparation method according to claim 3, characterized in that, In step S1b, the temperature of the mixing reaction is 60~90℃; and / or, in step S1b, the duration of the mixing reaction is 0.5~2h.

10. A ceramic product, characterized in that, The raw materials for preparing the ceramic product include the ceramic glaze as described in any one of claims 1 to 2, or the ceramic glaze prepared by the preparation method described in any one of claims 3 to 9; The method for preparing the ceramic includes applying the ceramic glaze to the surface of the ceramic blank and then sintering it; The sintering cooling rate is ≥50℃ / h.

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