Antibacterial glaze powder with photocatalytic activity and preparation process thereof

Abstract

The present application is a divisional application of application number 202211297725.2. The present invention belongs to the field of ceramic technology, and specifically relates to an antibacterial glaze powder with photocatalytic activity and a preparation process thereof. The antibacterial glaze powder with photocatalytic activity is composed of the following components in parts by weight: 25-35 parts of quartz, 10-20 parts of potassium feldspar, 3-5 parts of calcite, 5-8 parts of wollastonite, 2-3 parts of calcined talc, 1-3 parts of nano zinc oxide, 1-2 parts of cerium oxide, 1-2 parts of lanthanum oxide, 20-30 parts of porous material, 5-8 parts of modified titanium dioxide, 5-10 parts of antibacterial agent, 5-10 parts of grinding aid, 1-2 parts of deflocculant, 1-2 parts of auxiliary agent, and 3-8 parts of coating agent. The present invention provides an antibacterial glaze powder with photocatalytic activity. The silver-containing antibacterial agent and nano-zinc oxide can improve the killing of surface contact bacteria, and the modified titanium dioxide can improve the photocatalytic killing effect of bacteria. Through the combination of the silver-containing antibacterial agent, nano-zinc oxide and modified titanium dioxide, multiple antibacterial layers are formed on the surface of the fired glaze layer, which has an excellent bactericidal effect.

Description

[0001] This application is a divisional application. The application number of the original application is 202211297725.2, the application date is October 22, 2022, and the name of the invention is "An antibacterial glaze powder and its preparation process". Technical Field

[0002] The invention belongs to the technical field of ceramics, and in particular relates to an antibacterial glaze powder with photocatalytic activity and a preparation process thereof. Background Art

[0003] The most common bacteria in homes, and the ones that pose the greatest threat to human health, are Escherichia coli and Staphylococcus aureus. E. coli, known as the "number one killer of human health," can cause gastrointestinal infections in humans or animals when it invades certain parts of the body, primarily through the production of specific fimbriae antigens and pathogenic toxins. Staphylococcus aureus can be found in air, water, and dust. In recent years, infection with Staphylococcus aureus has been linked to a decrease in white blood cell counts, weakening the body's immune system and increasing the risk of illness. Ceramic surfaces, particularly in kitchens and bathrooms, have tiny pores invisible to the naked eye. Over time, these tiles can easily accumulate and breed bacteria, potentially causing infection and serious health risks. Imparting excellent antimicrobial properties to ceramic surfaces has become a key concern in the architectural ceramics industry, leading to an increasingly urgent demand for antimicrobial ceramics.

[0004] Since ceramics generally need to be sintered at high temperatures, the antibacterial agents used in antibacterial ceramics must not only have good antibacterial ability and antibacterial durability, but also excellent high-temperature stability and safety. The preparation of antibacterial ceramics is generally divided into two types. One is to directly mix the metal ion-loaded antibacterial agent with the glaze slurry, then glaze the body and sinter it at high temperature to make antibacterial ceramics. The metal ions on the surface of the ceramic are continuously dissolved, thereby continuously killing bacteria. The metal ion is generally silver ion with the strongest bactericidal ability. Since the cost of silver ion antibacterial agents is generally very high, other antibacterial agents with antibacterial functions need to be added to save costs. Another method is to coat a thin film of photocatalytic TiO2 on the finished ceramic glaze. When exposed to light or ultraviolet radiation, the TiO2 undergoes a photocatalytic reaction to produce oxygen and hydroxyl radicals, which react with microorganisms and kill them. However, at high temperatures, TiO2 changes from anatase to rutile, and rutile titanium dioxide does not have photocatalytic properties. Therefore, the heat treatment temperature of ceramics coated with TiO2 film cannot generally exceed 800°C. This will cause the TiO2 to bond with the glaze to be unstable and easily fall off. How to maintain the stability of the glaze and good photocatalytic properties during the high-temperature sintering process of ceramics deserves further research and exploration.

[0005] Therefore, it is very necessary to continue to develop an antibacterial glaze powder with photocatalytic activity to meet market demand. Summary of the Invention

[0006] The purpose of the present invention is to overcome the defects of existing ceramics that the glaze bonding is unstable and the photocatalytic ability is weakened during high-temperature sintering, and to provide an antibacterial glaze powder with photocatalytic activity.

[0007] Another object of the present invention is to provide a process for preparing antibacterial glaze powder with photocatalytic activity.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] The invention discloses an antibacterial glaze powder with photocatalytic activity, which is composed of the following components in parts by weight: 25-35 parts of quartz, 10-20 parts of potassium feldspar, 3-5 parts of calcite, 5-8 parts of wollastonite, 2-3 parts of calcined talc, 1-3 parts of nano zinc oxide, 1-2 parts of cerium oxide, 1-2 parts of lanthanum oxide, 20-30 parts of porous material, 5-8 parts of modified titanium dioxide, 5-10 parts of antibacterial agent, 5-10 parts of grinding aid, 1-2 parts of deflocculating agent, 1-2 parts of auxiliary agent, and 3-8 parts of coating agent.

[0010] Quartz has high liquid viscosity and strong affinity at high temperatures, which can increase the binding ability of various oxides. It can fuse with potassium feldspar, talc, and calcite to form transparent quartz glass, which can make the glaze surface bright and improve its gloss. At the same time, the thermal expansion coefficient of quartz in the glaze is small, which can appropriately offset the defects such as shrinkage and bending deformation during firing of the glaze powder, and can improve the heat resistance of the glaze powder. At the same time, quartz can increase the mechanical strength of the glaze surface, improve the glaze hardness, and make the porcelain wear-resistant.

[0011] Potassium feldspar can lower the melting temperature of the powder, which is beneficial to the firing of glaze powder and reduces the firing temperature. At the same time, the potassium feldspar melt fills the space between the grains, which helps to densify the glaze and reduce porosity. After cooling, the potassium feldspar melt forms the glass matrix of the glaze, which can improve transparency. The Al2O3 and SiO2 in the potassium feldspar liquid phase interact with each other, promoting the nucleation and growth of mullite crystals, giving the glaze mechanical strength and chemical stability.

[0012] Calcite and wollastonite contain high levels of calcium oxide, which acts as a flux, reducing glaze viscosity at high temperatures. This allows gases generated during firing to escape, reducing or eliminating bubbles in the glaze and minimizing pinholes. Calcium oxide has a high refractive index and surface tension, improving surface gloss and smoothness. Wollastonite is highly compatible with quartz, reducing undissolved quartz grains in the glaze and improving its wear resistance.

[0013] Burning talc can reduce the firing temperature, widen the firing range, and promote the formation of the intermediate layer between the body and the glaze, thereby improving the thermal stability of the glaze and the glaze's adaptability to the atmosphere, providing conditions for the high-temperature oxidation and exhaust of the glaze, and reducing the possibility of pinholes and glaze bubbles.

[0014] The addition of nano-zinc oxide not only reduces the glaze's firing temperature and high-temperature viscosity, thus reducing pinholes on the glaze surface, but also increases the glaze's surface tension, contributing to a smoother glaze surface. Furthermore, nano-zinc oxide has a high refractive index. Adding an appropriate amount of nano-zinc oxide to the glaze powder increases the glaze's refractive index, thereby enhancing its gloss. Nano-zinc oxide in the glaze enhances its elasticity and buffers the damage caused by harmful reactions. This, in turn, improves the product's thermal stability, reduces the glaze's coefficient of expansion, and expands the glaze powder's melting temperature range.

[0015] Furthermore, when exposed to sunlight, especially ultraviolet light, in water and air, nano-zinc oxide can spontaneously decompose to release free-moving negatively charged electrons, while leaving behind positively charged holes. These holes can activate oxygen and hydroxide, turning the water and air adsorbed on them into active oxygen and hydroxide. These have strong redox effects, damaging the cell membranes of bacteria on the enamel surface and killing them.

[0016] The modified titanium dioxide is titanium dioxide powder modified with zirconium phosphate and silicon dioxide. The modified titanium dioxide is produced by the following steps: mixing butyl titanate with an ethanol solution and adding it to deionized water to obtain a mixture; mixing ethyl silicate with an ethanol solution and adding it dropwise to the mixture; adding zirconium nitrate; standing for 1 hour; then adding phosphoric acid; and drying to obtain the modified titanium dioxide. Specifically, the volume ratio of butyl titanate, ethanol solution, and deionized water is 1:5:4, the volume ratio of ethyl silicate to ethanol solution is 1:8, the concentration of zirconium nitrate is 0.5 mol / L, and a 10% effective content of phosphoric acid is selected.

[0017] In existing technology, titanium dioxide photocatalytic films are applied to the glaze of ordinary ceramics. To improve their antibacterial properties, they are heat-treated at temperatures generally below 973K. Excessively high temperatures convert anatase titanium dioxide into rutile titanium dioxide. Furthermore, alkali metal and alkaline earth metal ions in the glaze not only accelerate the anatase-rutile phase transition of titanium dioxide at high temperatures but may also react with titanium dioxide to form titanates, thereby reducing or even completely eliminating the photocatalytic activity of titanium dioxide. However, the titanium dioxide coating of titanium dioxide-coated photocatalytic antibacterial ceramics heat-treated at medium to low temperatures does not bond firmly to the base ceramic glaze. During use, the coating is susceptible to damage and detachment due to certain external forces. Furthermore, the wear resistance of the titanium dioxide coating itself is inferior to that of the ceramic glaze.

[0018] The present invention optimizes the process of coating titanium dioxide on the surface of titanium dioxide with silicon dioxide, so that silicon dioxide forms a continuous coating on the surface of titanium dioxide, separates the interface between titanium dioxide particles, and increases the diffusion film between titanium dioxide particles. This effectively inhibits the transformation of titanium dioxide from anatase phase to rutile phase and the growth of anatase phase grains under high temperature conditions, and ensures that after the modified powder is calcined at a high temperature of more than 1273K, titanium dioxide still exists in anatase phase with a smaller particle size. At the same time, due to the porous structure of silicon dioxide and its high transmittance to ultraviolet light, the modified powder after high temperature calcination still shows good photocatalytic activity. Then, zirconium phosphate with a high melting point and good high temperature stability is used to perform secondary modification on the silicon dioxide coating layer, so that the modified powder can effectively resist the erosion of alkali metal and alkaline earth metal ions in ceramic glaze at high temperature, and finally prepares a modified titanium dioxide photocatalyst that can be directly added to ceramic glaze.

[0019] Since the glaze powder needs to be made into glaze slurry, it will cause the titanium dioxide in the partially destroyed modified titanium dioxide to dissolve. During the firing process, cerium oxide, lanthanum oxide, La 3+ With Ce 4+ After being doped into the partially dissolved titanium dioxide lattice, the particles showed greater activity and photocatalytic degradation activity. 3+ With Ce 4+ The ionic radius is larger than that of Ti 4+ The ionic radius, La 3+ 、Ce 4+ It can only enter the interstitial position of titanium dioxide to form interstitial ions or disperse on the surface of titanium dioxide in the form of LaO and CeO2. 3+ With Ce 4+ Upon entering the titanium dioxide lattice, cerium ions cause lattice expansion, increasing lattice volume and causing lattice distortion. This creates vacancies within the titanium dioxide lattice, providing a larger active space for lattice oxygen, thereby enhancing the mobility and transport of lattice oxygen in the catalyst. Oxygen atoms on the titanium dioxide surface readily escape the lattice, acting as hole traps, reducing the probability of hole-electron recombination within the titanium dioxide lattice, leading to enhanced photocatalytic activity. CeO2 and LaO, dispersed within the titanium dioxide crystallite surfaces, form Ti-O-Ce and Ti-O-La bonds, respectively, at the anatase interface during heat treatment, effectively hindering grain growth. Furthermore, the doped cerium and lanthanum ions readily undergo redox reactions on the titanium dioxide grain surface, generating oxygen vacancies and interstitial titanium through diffusion. This inhibits interactions between different titanium atomic sites, preventing the anatase to rutile phase transition and, to a certain extent, enhancing the photocatalytic activity and anatase-rutile phase transition temperature of titanium dioxide.

[0020] The porous material comprises 3-5 parts of hydroxyapatite, 3-5 parts of zeolite, 2-5 parts of tobermorite and 12-15 parts of bentonite.

[0021] The antibacterial agent is a mixture of zinc ammonia complex solution and silver ammonia complex solution.

[0022] Zeolite molecules are composed of three-dimensional spatial network structures composed of silicon-oxygen tetrahedrons and aluminum-oxygen tetrahedrons through shared oxygen atoms. They have a microporous internal network structure. Nanoparticles are individually separated in discrete pores and channels within the zeolite, which can prevent particle agglomeration and form larger nanoparticles or micron-sized particles. Zeolite has excellent ion exchange capacity. Zeolite in [Ag(NH3)2] + In solution, Ag + By + The cation exchange enters the zeolite and is firmly bonded. During the ball milling process, the specific surface area of ​​the zeolite is improved to make more Ag + With Na in zeolite + Exchange can increase the silver loading capacity of the material.

[0023] Ca in the hydroxyapatite crystal structure 2+ and OH - The enclosed column forms a symmetrical channel parallel to the c-axis, so it is easy to adsorb various metal ions. The crystallized hydroxyapatite powder is subjected to ion exchange reaction with silver ammonia complex solution and zinc ammonia complex solution. Ag + 、Zn 2+ Will replace Ca in the crystal 2+ 、Ag + 、Zn 2+ The silver ions enter its structure in the form of ion exchange, so the amount of silver ions dissolved is very small and the antibacterial effect is strong.

[0024] Tobermorite is a layered crystal structure with good divalent ion exchange properties. 4+ Use part of A1 3+ Replaced with Na + By carrying out electrovalence balance, tobermorite with monovalent ion exchange capacity can be obtained, and the dissolution amount of silver ions is small.

[0025] Bentonite has strong adsorption and ion exchange capacity. The Ca2+ adsorbed between its crystal layers 2+ 、Na +The cations increase the distance between the crystal layers, making it easier to absorb water and expand. These adsorbed cations are easily replaced because the silver ions in the bentonite are weakly bound between the layers and are easily released, which cannot maintain the long-term antibacterial effect of the antibacterial agent and causes the antibacterial agent to change color and affect the appearance. The metal ions in the bentonite combine with the oxygen in it. When silver ammonia, zinc ammonia, silver ammonia, and copper ammonia are introduced into the bentonite, [Ag(NH3)2] + 、[Zn(NH3)4] 2+ The complex ion bond is stronger than Ag-O and can prevent Ag from + Reductive aggregation, [Ag(NH3)2] + 、[Zn(NH3)4] 2+ The complex ion bond is stronger than Ag-O and can prevent Ag from + The silver atoms are reduced and aggregated into silver atom clusters, thus maintaining their antibacterial properties at high temperatures.

[0026] The grinding aids include lignin sulfonate and modified sodium silicate.

[0027] Furthermore, lignin sulfonate has a certain grinding aid and dispersing effect on solid particles. By reducing the surface chemical energy of the particles, reducing repulsion, and maintaining the stability of the suspension system, when the glaze powder is made into a glaze slurry, the high-solid content glaze slurry particles are dispersed in the aqueous medium, thereby giving the glaze slurry better fluidity and achieving the purpose of reducing the amount of water added. Furthermore, the modified sodium silicate is layered crystalline sodium disilicate, which has a good water-reducing effect on bentonite slurry. Layered crystalline sodium disilicate forms an infinitely extended planar layer in two-dimensional space, which can combine with the metal cations in the particles and connect the upper and lower layers to form a multi-layer overlapping structure. The addition of layered crystalline sodium disilicate gives the glaze slurry good fluidity and thixotropy.

[0028] The deflocculating agent is polyacrylic acid-maleic anhydride.

[0029] Acrylic acid-maleic anhydride securely adsorbs onto the surface of lamellar particles through a line-surface bonding process, effectively dispersing the flocculated structure of the glaze slurry, improving the performance of the ceramic slurry, and delivering superior results. The carboxyl groups of polyacrylic acid-maleic anhydride and the sulfonic acid groups of lignin sulfonate synergistically provide more effective electrostatic repulsion and steric hindrance, effectively dispersing the clay particles in the glaze slurry without aggregation or precipitation. Maleic anhydride also exhibits excellent compatibility, promoting the bonding of inorganic and organic materials.

[0030] The auxiliary agents include benzotriazole and PE wax.

[0031] Furthermore, adding a small amount of benzotriazole to the antibacterial glaze powder can effectively reduce the Ag+ Absorption of ultraviolet rays to prevent Ag + Oxidation, thereby achieving the purpose of inhibiting silver discoloration. PE wax can reduce the surface tension of water on the surface of the particles, allowing water to spread better on the surface of the particles, playing a wetting and emulsifying role, reducing water consumption, and through the adsorption of PE wax, reducing the dynamic and static friction coefficients between particles, forming a hydrophobic group on the surface of the particles. The reverse adsorption outward increases the lubricity between them.

[0032] The coating agent is one or both of a titanate coupling agent and a silane coupling agent.

[0033] Furthermore, the titanate coupling agent and the silane coupling agent provide high molecular polymers with sufficient chain length to bridge between the particles, generate cross-linking to form an irregular network structure, and form agglomeration to tightly wrap the glaze powder particles. At the same time, the titanate coupling agent and the silane coupling agent increase the surface strength of the glaze powder by forming a film after curing, thereby preventing the glaze powder from absorbing moisture and deteriorating.

[0034] A process for preparing antibacterial glaze powder with photocatalytic activity comprises the following steps:

[0035] 1) Weigh the following raw materials in parts by mass: 25-35 parts of quartz, 10-20 parts of potassium feldspar, 3-5 parts of calcite, 5-8 parts of wollastonite, 2-3 parts of calcined talc, 1-3 parts of nano zinc oxide, 1-2 parts of cerium oxide, 1-2 parts of lanthanum oxide, 3-5 parts of hydroxyapatite, 2-3 parts of zeolite, 2-3 parts of tobermorite, 10-15 parts of bentonite, 5-8 parts of modified titanium dioxide, 5-10 parts of antibacterial agent, 5-10 parts of grinding aid, 1-2 parts of deflocculant, 1-2 parts of additive, and 3-8 parts of coating agent;

[0036] 2) placing quartz, potassium feldspar, calcite, wollastonite, calcined talc, nano zinc oxide, cerium oxide, and lanthanum oxide in a ball mill in sequence and grinding for 15 minutes until the particles are 200-250 mesh, and then releasing the mixture to obtain a first component;

[0037] 3) First, hydroxyapatite, zeolite, tobermorite, bentonite, additives, and deflocculant are mixed in a stirred ball mill, and water accounting for 50% of the weight of the materials in step 3 is added for wet ball milling. The antibacterial agent is added in multiple portions, and the mixture is placed in the stirred ball mill. The mixture is ground for 30 minutes and then dried to obtain the second component;

[0038] 4) The first component, the second component, the modified titanium dioxide, and the coating agent are placed in a powder coating modification device, stirred, heated, and solidified to prepare an antibacterial glaze powder.

[0039] In step 2, a basic powder containing nano zinc oxide, having bactericidal ability and suitable particle size is prepared; in step 3, a porous material carrying silver ions is prepared; and in step 4, a coating agent is used to improve compatibility, and the basic powder, the porous material and the modified titanium dioxide are mixed and solidified at 120-140° C. to form a film to obtain an antibacterial glaze powder.

[0040] This preparation process can increase the silver loading capacity of the porous material, improve the preservation effect of the glaze powder through the coating process, and avoid destroying the structure of the modified titanium dioxide through a suitable preparation process, thereby improving the antibacterial effect of the antibacterial glaze powder.

[0041] Compared with the prior art, the present invention has the following advantages:

[0042] 1. The present invention discloses an antibacterial glaze powder with photocatalytic activity. The silver-containing antibacterial agent and nano-zinc oxide can improve the surface contact bacteria and kill them. The modified titanium dioxide can improve the photocatalytic effect of killing bacteria. Through the combination of the silver-containing antibacterial agent, nano-zinc oxide and modified titanium dioxide, multiple antibacterial layers are formed on the surface of the fired glaze layer, which has an excellent bactericidal effect. At the same time, through the combination of multiple antibacterial materials, the cost of using a single silver-containing antibacterial agent can be reduced.

[0043] 2. The present invention uses a porous material with ion exchange capacity and multiple through-holes, and adds silver ammonia complex solution and zinc ammonia complex solution to perform metal replacement, thereby increasing the silver loading of the antibacterial glaze powder. At the same time, through the combination of the powder and silver ions, the dissolution rate of silver is reduced, thereby improving the antibacterial effect and the antibacterial life of the glaze powder.

[0044] 3. The present invention increases the temperature at which anatase is converted to rutile by modifying titanium dioxide, thereby avoiding the failure of titanium dioxide during high-temperature firing and improving the photocatalytic disinfection effect of titanium dioxide.

[0045] 4. This preparation process can increase the silver loading capacity of porous materials, improve the preservation effect of glaze powder through the coating process, and avoid destroying the structure of modified titanium dioxide through a suitable preparation process, thereby improving the antibacterial effect of antibacterial glaze powder. DETAILED DESCRIPTION

[0046] In order to make those skilled in the art more clearly understand the technical solutions of the present invention, the following examples are given for illustration. Unless otherwise specified, the raw materials, reagents or devices used in the following embodiments can be obtained from conventional commercial channels or can be obtained by existing known methods.

[0047] The present invention will be further described below in conjunction with specific embodiments:

[0048] Table 1: Weight distribution ratio of the formula

[0049]

[0050]

[0051] Example 1

[0052] The steps for preparing modified titanium dioxide are as follows: 20g of butyl titanate and 100g of ethanol solution are mixed and added to 80ml of deionized water to obtain a mixture, 10g of ethyl silicate and 80g of ethanol solution are mixed and added dropwise to the mixture, 20ml of 0.5mol / L zirconium nitrate is added, and after standing for 1 hour, 5g of 10% phosphoric acid is added. After drying, modified titanium dioxide is obtained.

[0053] The preparation process of the antibacterial glaze powder with photocatalytic activity in Example 1 comprises the following steps:

[0054] 1) Weigh 25 parts of quartz, 10 parts of potassium feldspar, 3 parts of calcite, 5 parts of wollastonite, 2 parts of calcined talc, 1 part of nano zinc oxide, 1 part of cerium oxide, 1 part of lanthanum oxide, 3 parts of hydroxyapatite, 2 parts of zeolite, 2 parts of tobermorite, 12 parts of bentonite, 5 parts of modified titanium dioxide, 5 parts of antibacterial agent, 5 parts of grinding aid, 1 part of deflocculant, 1 part of auxiliary agent, and 3 parts of coating agent;

[0055] 2) placing quartz, potassium feldspar, calcite, wollastonite, calcined talc, nano zinc oxide, cerium oxide, and lanthanum oxide in a ball mill in sequence, grinding for 15 minutes until the particle size reaches 250 mesh, and then releasing the mixture to obtain a first component;

[0056] 3) First, hydroxyapatite, zeolite, tobermorite, bentonite, additives, and deflocculant are mixed in a stirred ball mill, and water accounting for 50% of the weight of the materials in step 3 is added for wet ball milling. The antibacterial agent is added in multiple portions, and the mixture is placed in the stirred ball mill. The mixture is ground for 30 minutes and then dried to obtain the second component;

[0057] 4) The first component, the second component, the modified titanium dioxide, and the coating agent are placed in a powder coating modification device, stirred, heated, and solidified to prepare an antibacterial glaze powder.

[0058] Example 2

[0059] The steps for preparing modified titanium dioxide are as follows: 20g of butyl titanate and 100g of ethanol solution are mixed and added to 80ml of deionized water to obtain a mixture, 10g of ethyl silicate and 80g of ethanol solution are mixed and added dropwise to the mixture, 20ml of 0.5mol / L zirconium nitrate is added, and after standing for 1 hour, 5g of 10% phosphoric acid is added. After drying, modified titanium dioxide is obtained.

[0060] The preparation process of an antibacterial glaze powder with photocatalytic activity in Example 2 comprises the following steps:

[0061] 1) Weigh 35 parts of quartz, 20 parts of potassium feldspar, 5 parts of calcite, 8 parts of wollastonite, 3 parts of calcined talc, 3 parts of nano zinc oxide, 2 parts of cerium oxide, 2 parts of lanthanum oxide, 5 parts of hydroxyapatite, 3 parts of zeolite, 3 parts of tobermorite, 15 parts of bentonite, 8 parts of modified titanium dioxide, 10 parts of antibacterial agent, 10 parts of grinding aid, 2 parts of deflocculant, 2 parts of additive, and 8 parts of coating agent;

[0062] 2) placing quartz, potassium feldspar, calcite, wollastonite, calcined talc, nano zinc oxide, cerium oxide, and lanthanum oxide in a ball mill in sequence, grinding for 15 minutes until the particles are 200 mesh, and then releasing the mixture to obtain a first component;

[0063] 3) First, hydroxyapatite, zeolite, tobermorite, bentonite, additives, and deflocculant are mixed in a stirred ball mill, and water accounting for 50% of the weight of the materials in step 3 is added for wet ball milling. The antibacterial agent is added in multiple portions, and the mixture is placed in the stirred ball mill. The mixture is ground for 30 minutes and then dried to obtain the second component;

[0064] 4) The first component, the second component, the modified titanium dioxide, and the coating agent are placed in a powder coating modification device, stirred, heated, and solidified to prepare an antibacterial glaze powder.

[0065] Example 3

[0066] The steps for preparing modified titanium dioxide are as follows: 20g of butyl titanate and 100g of ethanol solution are mixed and added to 80ml of deionized water to obtain a mixture, 10g of ethyl silicate and 80g of ethanol solution are mixed and added dropwise to the mixture, 20ml of 0.5mol / L zirconium nitrate is added, and after standing for 1 hour, 5g of 10% phosphoric acid is added. After drying, modified titanium dioxide is obtained.

[0067] The preparation process of an antibacterial glaze powder with photocatalytic activity in Example 3 comprises the following steps:

[0068] 1) Weigh 30 parts of quartz, 15 parts of potassium feldspar, 4 parts of calcite, 6 parts of wollastonite, 2 parts of calcined talc, 2 parts of nano zinc oxide, 1 part of cerium oxide, 1 part of lanthanum oxide, 5 parts of hydroxyapatite, 5 parts of zeolite, 5 parts of tobermorite, 12 parts of bentonite, 6 parts of modified titanium dioxide, 7 parts of antibacterial agent, 7 parts of grinding aid, 1 part of deflocculant, 2 parts of additives, and 5 parts of coating agent;

[0069] 2) placing quartz, potassium feldspar, calcite, wollastonite, calcined talc, nano zinc oxide, cerium oxide, and lanthanum oxide in a ball mill in sequence and grinding for 15 minutes until the particles are 200-250 mesh, and then releasing the mixture to obtain a first component;

[0070] 3) First, hydroxyapatite, zeolite, tobermorite, bentonite, additives, and deflocculant are mixed in a stirred ball mill, and water accounting for 50% of the weight of the materials in step 3 is added for wet ball milling. The antibacterial agent is added in multiple portions, and the mixture is placed in the stirred ball mill. The mixture is ground for 30 minutes and then dried to obtain the second component;

[0071] 4) The first component, the second component, the modified titanium dioxide, and the coating agent are placed in a powder coating modification device, stirred, heated, and solidified to prepare an antibacterial glaze powder.

[0072] Comparative Example 1

[0073] Comparative Example 1 is a variation of Example 3. Compared with Example 3, Comparative Example 1 replaces the modified titanium dioxide with titanium dioxide, and the remaining steps are the same.

[0074] Comparative Example 2

[0075] Comparative Example 2 is a variation on Example 3. Compared with Example 3, Comparative Example 2 changes step 3) to: first, hydroxyapatite, zeolite, tobermorite, bentonite, additives, deflocculant, and modified titanium dioxide are mixed and placed in a stirred ball mill, and water accounting for 50% by weight of the materials in step 3 is added for wet ball milling. The antibacterial agent is added in multiple portions, placed in a stirred ball mill, and ground for 60 minutes before drying to obtain the second component; step 4) is changed to placing the first component, the second component, and the coating agent into a powder coating modification equipment, stirring, heating, and curing to prepare an antibacterial glaze powder.

[0076] Comparative Example 3

[0077] Comparative Example 3 is a variation of Example 3. Compared with Example 3, Comparative Example 3 does not add a grinding aid and a deflocculant. Step 3) is changed to: first, hydroxyapatite, zeolite, tobermorite, and bentonite are mixed and placed in a stirred ball mill, and water accounting for 50% by weight of the materials in Step 3 is added for wet ball milling. The antibacterial agent is added in multiple portions, and the mixture is placed in a stirred ball mill. After grinding for 30 minutes, the mixture is dried to obtain a second component;

[0078] Comparative Example 4

[0079] Comparative Example 4 is a variation on Example 3. Compared with Example 3, Comparative Example 4 replaces the zinc ammonia complex solution and the silver ammonia complex solution with silver nitrate solution, and the remaining steps are the same.

[0080] The glaze powders prepared in Examples 1-3 and Comparative Examples 1-4 were respectively taken, water was added to make the water content of the glaze slurry 45%, and rapid ball milling was performed for 10 minutes. The water reduction effect was tested according to QB / T1545 2015.

[0081] The glaze slurry obtained above was applied to the surface of ceramic blocks of the same specifications and size, and fired at 1180°C to form a glaze surface. The antibacterial effect was tested using a block sterilization rate experiment. Specifically, the material was divided into small blocks and placed in a bacterial suspension of a certain concentration. Mixed culture was carried out, and samples were taken at regular intervals to calculate the bacterial concentration in the bacterial suspension and the antibacterial rate. The measured results are shown in the following table:

[0082] Table 2: Performance test results of Examples 1-3 and Comparative Examples 1-4

[0083]

[0084] It can be seen from the data in Table 2 that when the glaze powders prepared in Examples 1-3 and Comparative Examples 1-4 are mixed with water, Examples 1-3 and Comparative Examples 1, 2, and 4 have suitable flow rates, indicating that the glaze slurry prepared from the glaze powder of the present invention has good stability. In Comparative Example 3, since no grinding aid and deflocculant are added, its water-reducing effect is poor, and due to the high viscosity, the dispersion effect is poor, and the silver loading of the porous material is reduced.

[0085] In antibacterial experiments, Examples 1-3 achieved inhibition rates against Staphylococcus aureus and Escherichia coli exceeding 99%, demonstrating excellent antibacterial performance. The data from Comparative Example 1 demonstrate that, due to the substitution of modified titanium dioxide for titanium dioxide, the titanium dioxide largely converts to the rutile phase at high temperatures, resulting in a decrease in its photocatalytic effect. In Comparative Example 2, due to the prolonged ball milling time of the modified titanium dioxide in the glaze powder, the crystal structure is destroyed, affecting the coating effect of silica and zirconium phosphate. Consequently, a portion of the modified titanium dioxide converts to the rutile phase at high temperatures, resulting in a decrease in its photocatalytic effect.

[0086] In the appearance comparison experiment, the comparative example 4 has + The bonding ability with porous materials is weak. During high temperature, the free silver ions gather and cause the appearance to be dark.

[0087] The present invention provides an antibacterial glaze powder with photocatalytic activity. The silver-containing antibacterial agent and nano-zinc oxide can improve the killing of surface contact bacteria, and the modified titanium dioxide can improve the photocatalytic killing effect of bacteria. Through the combination of the silver-containing antibacterial agent, nano-zinc oxide and modified titanium dioxide, multiple antibacterial layers are formed on the surface of the fired glaze layer, which has an excellent bactericidal effect.

[0088] The present invention uses a porous material with ion exchange capacity and multiple through-holes, and adds a silver-ammonia complex solution and a zinc-ammonia complex solution to perform metal replacement, thereby increasing the silver loading of the antibacterial glaze powder. At the same time, through the combination of the powder and silver ions, the dissolution rate of silver is reduced, thereby improving the antibacterial effect and the antibacterial life of the glaze powder.

[0089] The present invention improves the temperature at which anatase is converted into rutile by modifying titanium dioxide, avoids the failure of titanium dioxide during high-temperature firing, and improves the photocatalytic disinfection effect of titanium dioxide.

[0090] This preparation process can increase the silver loading capacity of the porous material, improve the preservation effect of the glaze powder through the coating process, and avoid destroying the structure of the modified titanium dioxide through a suitable preparation process, thereby improving the antibacterial effect of the antibacterial glaze powder.

[0091] The above examples are merely provided to further illustrate the technical content of the present invention for easier understanding by the reader, but do not limit the embodiments of the present invention to these examples. Any extension or re-creation of the technology based on the present invention is protected by the present invention. The scope of protection of the present invention shall be determined by the claims.

Claims

1. An antibacterial glaze powder with photocatalytic activity, characterized in that: The invention is composed of the following components by weight: 25-35 parts of quartz, 10-20 parts of potassium feldspar, 3-5 parts of calcite, 5-8 parts of wollastonite, 2-3 parts of calcined talc, 1-3 parts of nano zinc oxide, 1-2 parts of cerium oxide, 1-2 parts of lanthanum oxide, 20-30 parts of porous material, 5-8 parts of modified titanium dioxide, 5-10 parts of antibacterial agent, 5-10 parts of grinding aid, 1-2 parts of deflocculant, 1-2 parts of auxiliary agent, and 3-8 parts of coating agent. The antibacterial agent is a mixture of zinc ammonia complex solution and silver ammonia complex solution; The grinding aid comprises lignin sulfonate and modified sodium silicate, wherein the modified sodium silicate is layered crystalline sodium disilicate; The deflocculating agent is acrylic acid-maleic anhydride; The auxiliary agent includes benzotriazole and PE wax; The modified titanium dioxide is titanium dioxide powder modified with zirconium phosphate and silicon dioxide. The modified titanium dioxide is produced by the following steps: mixing butyl titanate with an ethanol solution and adding the mixture to deionized water to obtain a mixture; mixing ethyl silicate with an ethanol solution and adding the mixture dropwise to the mixture; adding zirconium nitrate; standing for 1 hour; then adding phosphoric acid; and drying to obtain the modified titanium dioxide. The volume ratio of butyl titanate, ethanol solution, and deionized water is 1:5:4, and the volume ratio of ethyl silicate to ethanol solution is 1:

8.

2. The antibacterial glaze powder with photocatalytic activity according to claim 1, characterized in that: In parts by weight, the porous material includes 3-5 parts of hydroxyapatite, 3-5 parts of zeolite, 2-5 parts of tobermorite, and 12-15 parts of bentonite.

3. The antibacterial glaze powder with photocatalytic activity according to claim 1, characterized in that: The coating agent is one or both of a titanate coupling agent and a silane coupling agent.

4. The antibacterial glaze powder with photocatalytic activity according to claim 1, characterized in that: The steps for preparing modified titanium dioxide are as follows: 20g of butyl titanate and 100g of ethanol solution are mixed and added to 80ml of deionized water to obtain a mixture; 10g of ethyl silicate and 80g of ethanol solution are mixed and added dropwise to the mixture; 20ml of 0.5mol / L zirconium nitrate is added; after standing for 1 hour, 5g of 10% phosphoric acid is added; and modified titanium dioxide is obtained after drying.

5. The antibacterial glaze powder with photocatalytic activity according to claim 2, characterized in that: The invention is composed of the following components by weight: 30 parts of quartz, 15 parts of potassium feldspar, 4 parts of calcite, 6 parts of wollastonite, 2 parts of calcined talc, 2 parts of nano zinc oxide, 1 part of cerium oxide, 1 part of lanthanum oxide, 5 parts of hydroxyapatite, 5 parts of zeolite, 5 parts of tobermorite, 12 parts of bentonite, 6 parts of modified titanium dioxide, 7 parts of antibacterial agent, 7 parts of grinding aid, 1 part of deflocculant, 2 parts of auxiliary agent and 5 parts of coating agent.

6. The process for preparing an antibacterial glaze powder with photocatalytic activity according to any one of claims 1 to 5, characterized in that: The steps include: 1) Weigh the following raw materials in parts by weight: 25-35 parts of quartz, 10-20 parts of potassium feldspar, 3-5 parts of calcite, 5-8 parts of wollastonite, 2-3 parts of calcined talc, 1-3 parts of nano zinc oxide, 1-2 parts of cerium oxide, 1-2 parts of lanthanum oxide, 20-30 parts of porous material, 5-8 parts of modified titanium dioxide, 5-10 parts of antibacterial agent, 5-10 parts of grinding aid, 1-2 parts of deflocculant, 1-2 parts of additive, and 3-8 parts of coating agent; 2) placing quartz, potassium feldspar, calcite, wollastonite, calcined talc, nano zinc oxide, cerium oxide, and lanthanum oxide in a ball mill in sequence and grinding for 15 minutes until the particles are 200-250 mesh, and then releasing the mixture to obtain a first component; 3) The porous material, additive, and deflocculant are first mixed and placed in a stirred ball mill. Water accounting for 50% of the weight of the materials in step 3 is added for wet ball milling. The antibacterial agent is added in multiple portions and placed in the stirred ball mill. The mixture is ground for 30 minutes and then dried to obtain the second component. 4) The first component, the second component, the modified titanium dioxide, and the coating agent are placed in a powder coating modification device, stirred, heated, and solidified to prepare an antibacterial glaze powder.

7. The process for preparing an antibacterial glaze powder with photocatalytic activity according to claim 6, characterized in that: The curing temperature in step 4) is 120-140°C.

8. The process for preparing an antibacterial glaze powder with photocatalytic activity according to claim 6, characterized in that: The antibacterial glaze powder is added with water to make the water content of the glaze slurry 45%, and the glaze slurry is rapidly ball-milled for 10 minutes, coated on the surface of the ceramic block, and fired at 1180°C.

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