Antibacterial glaze powder with photocatalytic activity and preparation process thereofThe application relates to a divisional application, the application number of the original application is 202211297725.2, the application date is 2022, 10 months and 22 days, and the application is named as antibacterial glaze powder and a preparation process thereof.
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to antibacterial glaze powder with photocatalytic activity and a preparation process thereof.
Background
Bacteria most common in living rooms and most threatening to human health are among the species escherichia coli and staphylococcus aureus. In particular, there is a so-called "human health killer" which, when invaded into a human or animal, causes gastrointestinal tract infections in the human or animal, mainly by infection with specific pilus antigens, pathogenic toxins, etc. Staphylococcus aureus has its trace in air, water and dust. In recent years, when the body is infected with staphylococcus aureus, white blood cells in the body are reduced, thereby causing the body to have reduced resistance and increasing the risk of illness. Especially for places such as home kitchens, toilets and the like, the ceramic surface is provided with tiny pinholes which are invisible to naked eyes, the ceramic tile has long service time, bacteria are easy to accumulate and breed and even infect, and the health is seriously affected. How to endow ceramic surfaces with excellent antibacterial properties becomes a key problem of concern in the field of architectural ceramics. The need for antimicrobial ceramics is becoming more and more acute.
Because the ceramic is generally required to be sintered at high temperature, the antibacterial agent applied to the antibacterial ceramic has good antibacterial capability and antibacterial durability, and also has excellent high-temperature stability and safety. The preparation of antibacterial ceramics is generally divided into two types, one is to fully mix metal ion-loaded antibacterial agent with glaze slurry, glazing the green body and sintering at high temperature to prepare antibacterial ceramics, and the metal ions on the surface of the ceramics are continuously dissolved out to continuously kill bacteria. The silver ion with the strongest sterilization capability is generally selected as the metal ion, and other antibacterial agents with antibacterial function are needed to be added to save the cost because the cost of the silver ion antibacterial agent is generally high. Another method is to coat the TiO2 film with photocatalysis capability on the ceramic glaze of the finished product, when light or ultraviolet irradiation is applied, tiO2 can generate photocatalytic reaction to generate oxygen free radical and hydroxyl free radical, and react with microorganisms to kill them, but TiO2 can change from anatase structure to rutile structure at high temperature, and rutile titanium dioxide does not have photocatalysis capability, so the heat treatment temperature of the ceramic coated with the TiO2 film cannot be higher than 800 ℃ generally, and thus the combination of TiO2 and the glaze is unstable and easy to fall off. In the process of sintering ceramics at high temperature, how to maintain the stability of the glaze and good photocatalytic capability deserves continuous research and exploration.
Therefore, there is a need to develop an antimicrobial glaze powder with photocatalytic activity to meet the market demand.
Disclosure of Invention
The invention aims to overcome the defects of unstable glaze combination and weak photocatalytic capability of the existing ceramic during high-temperature sintering, and provides antibacterial glaze powder with photocatalytic activity.
The invention also aims to provide a preparation process of the antibacterial glaze powder with photocatalytic activity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The antibacterial glaze powder with photocatalytic activity consists of, 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 talcum, 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 quartz has high liquid phase viscosity at high temperature and strong affinity, can increase the binding capacity of various oxides, and can be melted with potassium feldspar, calcined talcum and calcite to generate transparent quartz glass, so that the glaze is bright, the glossiness of the glaze is improved, meanwhile, the coefficient of thermal expansion of the quartz in the glaze is small, the defects of shrinkage, bending deformation and the like during sintering of the glaze powder can be properly counteracted, the heat resistance of the glaze powder can be improved, and meanwhile, the quartz can increase the mechanical strength of the glaze, improve the hardness of the glaze and enable the porcelain to be wear-resistant.
The potassium feldspar can reduce the melting temperature of powder, is favorable for sintering glaze powder and reducing the sintering temperature, and simultaneously, the potassium feldspar melt is filled among crystal grains, is favorable for compacting the glaze surface and reducing pores, and forms a glass matrix of the glaze surface after being cooled, so that the transparency can be improved, the interaction between Al2O3 and SiO2 in the potassium feldspar liquid phase promotes the nucleation and growth of mullite crystals, and the mechanical strength and chemical stability are endowed to the glaze surface.
Calcite and wollastonite contain more calcium oxide, and the calcium oxide has fluxing effect, so that the viscosity of glaze powder can be reduced at high temperature, and gas generated in the sintering process can be discharged, so that bubbles in a glaze layer are reduced or eliminated, and further, pinholes on the glaze surface are reduced. The calcium oxide has higher refractive index and surface tension, and can improve the surface glossiness and flatness. Wollastonite has good compatibility with quartz, reduces undissolved quartz grains in the glaze layer, and improves the wear resistance of the glaze layer.
The talcum powder can reduce the firing temperature, widen the firing range and promote the formation of an intermediate layer of the blank glaze, thereby improving the thermal stability of the glaze surface and the adaptability of the glaze to atmosphere, providing conditions for high-temperature oxidation and exhaust of the glaze and reducing the possibility of pinholes and glaze bubbles.
The addition of nano zinc oxide can reduce the firing temperature and high-temperature viscosity of the glaze, reduce pinholes on the glaze surface, improve the surface tension of the glaze and be beneficial to forming a smooth glaze surface. In addition, the nano zinc oxide has higher refractive index, and the proper amount of nano zinc oxide is added into the glaze powder, so that the refractive index of the glaze layer is improved, and the glossiness of the glaze surface is improved. The nano zinc oxide in the glaze can improve the elasticity of the glaze, buffer the damage of harmful reaction force to the glaze layer, further improve the thermal stability of the product, reduce the expansion coefficient of the glaze layer and enlarge the melting temperature range of the glaze powder.
Further, nano zinc oxide can automatically decompose self-moving negatively charged electrons in water and air under sunlight, particularly ultraviolet light irradiation, and meanwhile positively charged holes are reserved. The holes can activate oxygen and hydroxyl, so that water and air adsorbed on the holes become active oxygen and hydroxyl, and the active oxygen and hydroxyl have strong oxidation-reduction effect, so that cell membranes of bacteria on the surface of the glaze layer are damaged, and the bacteria are killed.
The modified titanium dioxide is prepared by modifying titanium dioxide powder together with zirconium phosphate and silicon dioxide. The preparation method of the modified titanium dioxide comprises the following steps of mixing butyl titanate and ethanol solution, adding the mixture into deionized water to obtain a mixture, mixing ethyl silicate and ethanol solution, dripping the mixture into the mixture, adding zirconium nitrate, standing for 1 hour, adding phosphoric acid, and drying to obtain the modified titanium dioxide. Specifically, the volume ratio of butyl titanate to ethanol solution to deionized water is 1:5:4, the volume ratio of ethyl silicate to ethanol solution is 1:8, the concentration of zirconium nitrate is 0.5mol/L, and phosphoric acid with the effective content of 10% is selected.
In the prior art, the titanium dioxide photocatalysis film is coated on the glaze of common ceramics, in order to improve the antibacterial performance, the heat treatment temperature is generally below 973K, if the temperature is too high, anatase titanium dioxide can be converted into rutile titanium dioxide, meanwhile, alkali metal, alkaline earth metal and other ions in the glaze can accelerate the phase change of the titanium dioxide from anatase-rutile phase at high temperature, and the titanium dioxide can react with the titanium dioxide to generate titanate, so that the photocatalytic activity of the titanium dioxide is reduced, and even the photocatalytic activity is completely lost. However, the titanium dioxide coating of the coated titanium dioxide photocatalysis antibacterial ceramic after heat treatment at medium and low temperature is not firmly combined with the blank glaze of the base ceramic, the coating is easy to be damaged and fall off under the action of a certain external force in the use process, and meanwhile, the wear resistance of the titanium dioxide coating is poorer than that of the ceramic.
According to the invention, the process of coating the silicon dioxide on the surface of the titanium dioxide is optimized, so that a continuous coating layer is formed on the surface of the titanium dioxide, the interfaces among the titanium dioxide particles are separated, and the diffusion film among the titanium dioxide particles is increased, so that the transition of the titanium dioxide from an anatase phase to a rutile phase and the growth of the anatase phase grains can be effectively inhibited under the high-temperature condition, and the titanium dioxide still exists in an anatase phase with a smaller particle size after the modified powder is calcined at a high temperature of 1273K or more. Meanwhile, due to the porous structure of the silicon dioxide and high transmittance to ultraviolet light, the modified powder after high-temperature calcination still presents better photocatalytic activity. And then, zirconium phosphate with high melting point and good high-temperature stability is utilized to carry out secondary modification on the silicon dioxide coating layer, so that the modified powder can effectively resist the corrosion of alkali metal, alkaline earth metal and other ions in the ceramic glaze at high temperature, and finally, the modified titanium dioxide photocatalyst capable of being directly added into the ceramic glaze is prepared.
Because glaze powder needs to be made into glaze slurry, the titanium dioxide in the partially destroyed modified titanium dioxide is dissolved out, cerium oxide and lanthanum oxide are added in the firing process, and La3+ and Ce4+ are doped into the partially dissolved titanium dioxide crystal lattice, so that the particles show larger activity and larger photocatalytic degradation activity. Since the ionic radii of La3+ and Ce4+ are larger than the ionic radius of Ti4+, la3+、Ce4+ can only enter the gap position of titanium dioxide to form gap ions or be dispersed on the surface of titanium dioxide in the form of LaO and CeO2, when La3+ and Ce4+ enter the titanium dioxide crystal lattice, the crystal lattice is expanded, the crystal lattice volume is increased, the crystal lattice distortion is caused, empty points are generated in the titanium dioxide crystal lattice, and a larger activity space is provided for crystal lattice oxygen, so that the activity and transportation capacity of the crystal lattice oxygen in the catalyst are improved. Oxygen atoms on the surface layer of the titanium dioxide crystal lattice easily escape from the crystal lattice to play a role in capturing holes, so that the probability of recombination of the holes and electrons in the titanium dioxide crystal lattice is reduced, and better activity is shown. In addition, doped cerium ions and lanthanum ions are easy to generate oxidation-reduction reaction on the surface of titanium dioxide crystal grains, and then oxygen vacancies and interstitial titanium are generated through diffusion, so that interaction among different titanium atomic positions is inhibited, phase transformation from anatase phase to rutile phase is prevented, and photocatalytic activity of the titanium dioxide and phase transformation temperature of the anatase-rutile phase can be improved to a certain extent.
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.
The antibacterial agent is a mixture of zinc ammonia complex solution and silver ammonia complex solution.
The zeolite molecule is a three-dimensional space network structure formed by silicon oxygen tetrahedron and aluminum oxygen tetrahedron through sharing oxygen atoms, has a micropore internal network structure, and nano particles are independently separated in discrete holes and channels in the zeolite, so that the agglomeration of the particles can be prevented, larger nano particles or particles with micron size are formed, and the zeolite has excellent ion exchange capability. The zeolite is [ Ag (NH3)2]+ solution, ag+ enters the zeolite through cation exchange with Na+ and is firmly combined, and the silver carrying capacity of the material can be improved by improving the specific surface area of the zeolite and enabling more Ag+ to exchange with Na+ in the zeolite during the ball milling process.
The columnar body surrounded by Ca2+ and OH- in the crystal structure of the hydroxyapatite forms a symmetrical channel parallel to the c axis, so that various metal ions are easy to adsorb, the crystallized hydroxyapatite powder, the silver ammonia complex solution and the zinc ammonia complex solution are subjected to ion exchange reaction, and Ag+、Zn2+ can replace Ca2+、Ag+、Zn2+ in the crystal to enter the structure in an ion exchange mode, so that the leaching amount of silver ions is small, and the antibacterial effect is strong.
The tobermorite is of a layered crystal structure and has good divalent ion exchange performance, a part of A13+ is substituted for Si4+ in the tobermorite, and Na+ is used for carrying out valence balance, so that the tobermorite with monovalent ion exchange capability can be obtained, and the leaching amount of silver ions is smaller.
The bentonite has strong adsorption capacity and ion exchange capacity, and cations such as Ca2+、Na+ and the like adsorbed between crystal layers of the bentonite increase the distance between the crystal layers, so that the adsorbed cations are easier to absorb moisture and expand, and the adsorbed cations are easy to replace, because silver ions in the bentonite are weaker in combination between the layers of the bentonite, the silver ions are easy to release out, the long-term antibacterial property of the antibacterial agent cannot be maintained, and the antibacterial agent is easy to change color to influence the appearance. When silver ammonia, zinc ammonia, silver ammonia and copper ammonia are introduced into bentonite, the complex ion bond strength of [ Ag (NH3)2]+、[Zn(NH3)4]2+ and the like) is more stable than that of Ag-O, ag+ can be prevented from reduction aggregation at high temperature, the complex ion bond strength of [ Ag (NH3)2]+、[Zn(NH3)4]2+ and the like) is more stable than that of Ag-O, and Ag+ can be prevented from reduction aggregation into silver atom clusters at high temperature, so that the antibacterial performance of the bentonite at high temperature is maintained.
The grinding aid comprises lignosulfonate and modified sodium silicate.
Furthermore, the lignosulfonate has certain grinding assisting and dispersing effects on solid particles, and the suspension system is kept stable by reducing the surface chemical energy of the particles, so that the high-solid-content glaze slurry particles are dispersed in an aqueous medium when the glaze powder is prepared into the glaze slurry, and the glaze slurry has better fluidity, thereby achieving the purpose of reducing the water adding amount. Further, the modified sodium silicate is layered crystal sodium disilicate, and the layered crystal sodium disilicate has a good water reducing effect on bentonite slurry. The layered crystalline sodium disilicate forms an infinitely extending planar layer in two dimensions that can combine with metal cations in the particles and connect the upper and lower layers to form a multi-layered overlapping structure. And the addition of the layered crystalline sodium disilicate enables the glaze slip to have good fluidity and thixotropic property.
The deflocculant is polyacrylic acid-maleic anhydride.
Acrylic acid-maleic anhydride can be firmly adsorbed on the surface of particles with a laminate structure in a line-surface combination mode, so that the flocculation structure of the glaze slurry is effectively dispersed, the performance of the ceramic slurry is improved, and the ceramic slurry has a good use effect. The carboxyl functional group of polyacrylic acid-maleic anhydride and the sulfonic acid functional group in lignosulfonate cooperate to play a more effective electrostatic repulsive action, and simultaneously form a steric hindrance effect, so that clay particles in the glaze slip are more effectively dispersed without aggregation and precipitation. Meanwhile, the maleic anhydride has good compatibility and can promote the combination of inorganic matters and organic matters.
The auxiliary agent comprises benzotriazole and PE wax.
Furthermore, the micro-benzotriazole is added into the antibacterial glaze powder, so that the absorption of Ag+ to ultraviolet rays can be effectively reduced, and the oxidation of Ag+ is prevented, thereby achieving the purpose of inhibiting silver discoloration. The PE wax can reduce the surface tension of water on the surface of the particles, so that the water can be better spread on the surface of the particles, the wetting and emulsifying effects are achieved, the water consumption is reduced, the dynamic friction factor and the static friction factor among the particles are reduced through the adsorption of the PE wax, the reverse adsorption of the hydrophobic groups outwards is formed on the surface of the particles, and the lubricity among the particles is improved.
The coating agent is one or two of titanate coupling agent and silane coupling agent.
Furthermore, the titanate coupling agent and the silane coupling agent provide high molecular polymers with enough chain length to bridge among particles, generate a crosslinking effect to form an irregular network structure and form condensation, tightly wrap glaze particles, and simultaneously form a film after curing to increase the surface strength of the glaze, so that the glaze is prevented from absorbing moisture and deteriorating.
A preparation process of antibacterial glaze powder with photocatalytic activity comprises the following steps:
1) Respectively weighing the following raw materials, 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 an antibacterial agent, 5-10 parts of a grinding aid, 1-2 parts of a deflocculant, 1-2 parts of an auxiliary agent and 3-8 parts of a coating agent;
2) Sequentially placing quartz, potassium feldspar, calcite, wollastonite, calcined talcum, nano zinc oxide, cerium oxide and lanthanum oxide into a ball mill, grinding for 15min, grinding to 200-250 meshes, and discharging to obtain a first component;
3) Firstly, mixing hydroxyapatite, zeolite, tobermorite, bentonite, an auxiliary agent and a deflocculant, putting the mixture into a stirred ball mill, adding water accounting for 50% of the weight of the materials in the step 3, performing wet ball milling, adding an antibacterial agent for multiple times, putting into the stirred ball mill, grinding for 30min, and drying to obtain a second component;
4) The first component, the second component, the modified titanium dioxide and the coating agent are put into powder coating modification equipment, stirred, heated and solidified to prepare the antibacterial glaze powder.
And 2, preparing basic powder which contains nano zinc oxide and has sterilizing capability and proper particle size, preparing a porous material with silver-carrying ions in step 3, and curing the basic powder, the porous material and the modified titanium dioxide into a film in 120-140 ℃ after mixing by utilizing a coating agent to improve compatibility in step 4, so as to obtain the antibacterial glaze powder.
The preparation process can improve silver loading of the porous material, improves preservation effect of the glaze powder through a coating process, avoids damaging the structure of modified titanium dioxide through a proper preparation process, and improves antibacterial effect of the antibacterial glaze powder.
Compared with the prior art, the invention has the following advantages:
1. According to the antibacterial glaze powder with photocatalytic activity, the silver-containing antibacterial agent and the nano zinc oxide can improve surface contact bacteria to kill, the modified titanium dioxide can improve the effect of photocatalysis to kill bacteria, multiple antibacterial layers are formed on the surface of a fired glaze layer through the combination of the silver-containing antibacterial agent, the nano zinc oxide and the modified titanium dioxide, the excellent sterilizing effect is achieved, and meanwhile, the cost of independently using the silver-containing antibacterial agent can be reduced through the collocation of multiple antibacterial materials.
2. According to the invention, through the porous material with ion exchange capability and multiple through holes, the silver carrying capacity of the antibacterial glaze powder is improved by adding the silver ammonia complex solution and the zinc ammonia complex solution for metal replacement, and meanwhile, the dissolution rate of silver is reduced by combining the powder with silver ions, so that the antibacterial effect is improved and the antibacterial service life of the glaze powder is prolonged;
3. according to the invention, the temperature of converting anatase into rutile is improved by modifying the titanium dioxide, so that the failure of the titanium dioxide in the high-temperature firing process is avoided, and the photocatalytic disinfection effect of the titanium dioxide is improved.
4. The preparation process can improve silver loading of the porous material, improves preservation effect of the glaze powder through a coating process, avoids damaging the structure of modified titanium dioxide through a proper preparation process, and improves antibacterial effect of the antibacterial glaze powder.
Detailed Description
In order to make the technical solution of the present invention more apparent to those skilled in the art, the following examples are now given, and the raw materials, reagents or apparatuses used in the following embodiments are commercially available or may be obtained by known methods unless otherwise specified.
The invention is further described with reference to the following specific examples:
TABLE 1 weight ratio of the formulations
Example 1
The preparation method of the modified titanium dioxide comprises the steps of mixing 20g of butyl titanate with 100g of ethanol solution, adding into 80ml of deionized water to obtain a mixture, mixing 10g of ethyl silicate with 80g of ethanol solution, dripping into the mixture, adding 20ml of 0.5mol/L zirconium nitrate, standing for 1 hour, adding 5g of 10% phosphoric acid, and drying to obtain the modified titanium dioxide.
The preparation process of the antibacterial glaze powder with photocatalytic activity in the embodiment 1 comprises the following steps of:
1) Weighing 25 parts of quartz, 10 parts of potassium feldspar, 3 parts of calcite, 5 parts of wollastonite, 2 parts of calcined talcum, 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 an antibacterial agent, 5 parts of a grinding aid, 1 part of a deflocculant, 1 part of an auxiliary agent and 3 parts of a coating agent;
2) Sequentially placing quartz, potassium feldspar, calcite, wollastonite, calcined talcum, nano zinc oxide, cerium oxide and lanthanum oxide into a ball mill, grinding for 15min, grinding to 250 meshes, and discharging to obtain a first component;
3) Firstly, mixing hydroxyapatite, zeolite, tobermorite, bentonite, an auxiliary agent and a deflocculant, putting the mixture into a stirred ball mill, adding water accounting for 50% of the weight of the materials in the step 3, performing wet ball milling, adding an antibacterial agent for multiple times, putting into the stirred ball mill, grinding for 30min, and drying to obtain a second component;
4) The first component, the second component, the modified titanium dioxide and the coating agent are put into powder coating modification equipment, stirred, heated and solidified to prepare the antibacterial glaze powder.
Example 2
The preparation method of the modified titanium dioxide comprises the steps of mixing 20g of butyl titanate with 100g of ethanol solution, adding into 80ml of deionized water to obtain a mixture, mixing 10g of ethyl silicate with 80g of ethanol solution, dripping into the mixture, adding 20ml of 0.5mol/L zirconium nitrate, standing for 1 hour, adding 5g of 10% phosphoric acid, and drying to obtain the modified titanium dioxide.
The preparation process of the antibacterial glaze powder with photocatalytic activity in the embodiment 2 comprises the following steps:
1) 35 parts of quartz, 20 parts of potassium feldspar, 5 parts of calcite, 8 parts of wollastonite, 3 parts of calcined talcum, 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 an antibacterial agent, 10 parts of a grinding aid, 2 parts of a deflocculant, 2 parts of an auxiliary agent and 8 parts of a coating agent;
2) Sequentially placing quartz, potassium feldspar, calcite, wollastonite, calcined talcum, nano zinc oxide, cerium oxide and lanthanum oxide into a ball mill, grinding for 15min, grinding to 200 meshes, and discharging to obtain a first component;
3) Firstly, mixing hydroxyapatite, zeolite, tobermorite, bentonite, an auxiliary agent and a deflocculant, putting the mixture into a stirred ball mill, adding water accounting for 50% of the weight of the materials in the step 3, performing wet ball milling, adding an antibacterial agent for multiple times, putting into the stirred ball mill, grinding for 30min, and drying to obtain a second component;
4) The first component, the second component, the modified titanium dioxide and the coating agent are put into powder coating modification equipment, stirred, heated and solidified to prepare the antibacterial glaze powder.
Example 3
The preparation method of the modified titanium dioxide comprises the steps of mixing 20g of butyl titanate with 100g of ethanol solution, adding into 80ml of deionized water to obtain a mixture, mixing 10g of ethyl silicate with 80g of ethanol solution, dripping into the mixture, adding 20ml of 0.5mol/L zirconium nitrate, standing for 1 hour, adding 5g of 10% phosphoric acid, and drying to obtain the modified titanium dioxide.
The preparation process of the antibacterial glaze powder with photocatalytic activity in the embodiment 3 comprises the following steps of:
1) 30 parts of quartz, 15 parts of potassium feldspar, 4 parts of calcite, 6 parts of wollastonite, 2 parts of calcined talcum, 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 an antibacterial agent, 7 parts of a grinding aid, 1 part of a deflocculant, 2 parts of an auxiliary agent and 5 parts of a coating agent;
2) Sequentially placing quartz, potassium feldspar, calcite, wollastonite, calcined talcum, nano zinc oxide, cerium oxide and lanthanum oxide into a ball mill, grinding for 15min, grinding to 200-250 meshes, and discharging to obtain a first component;
3) Firstly, mixing hydroxyapatite, zeolite, tobermorite, bentonite, an auxiliary agent and a deflocculant, putting the mixture into a stirred ball mill, adding water accounting for 50% of the weight of the materials in the step 3, performing wet ball milling, adding an antibacterial agent for multiple times, putting into the stirred ball mill, grinding for 30min, and drying to obtain a second component;
4) The first component, the second component, the modified titanium dioxide and the coating agent are put into powder coating modification equipment, stirred, heated and solidified to prepare the antibacterial glaze powder.
Comparative example 1
Comparative example 1 was modified based on example 3, and comparative example 1 was compared with example 3, in which the modified titanium dioxide was replaced with titanium dioxide in comparative example 1, and the other steps were the same.
Comparative example 2
Comparative example 2 is a modification of example 3, and comparative example 2 is a modification of example 3 in which hydroxyapatite, zeolite, tobermorite, bentonite, an auxiliary agent, a deflocculant and modified titanium dioxide are mixed and put into a stirred ball mill, water accounting for 50% of the weight of the materials in step 3 is added for wet ball milling, an antibacterial agent is added for multiple times, the mixture is put into the stirred ball mill, the mixture is ground for 60min and then dried to obtain a second component, and step 4) is a modification of the first component, the second component and the coating agent are put into powder coating modifying equipment, stirred, heated and solidified to prepare the antibacterial glaze powder.
Comparative example 3
Comparative example 3 is a modification of example 3, and comparative example 3 is compared with example 3, wherein no grinding aid or deflocculant is added in comparative example 3, and step 3) is changed to that hydroxyapatite, zeolite, tobermorite and bentonite are firstly mixed and put into a stirred ball mill, water accounting for 50% of the weight of the materials in step 3 is added for wet ball milling, an antibacterial agent is added for multiple times, and the mixture is put into the stirred ball mill, and is dried after being ground for 30min to obtain a second component;
Comparative example 4
Comparative example 4 was modified based on example 3, and comparative example 4 was compared with example 3, and the zinc ammonia complexing solution and the silver ammonia complexing solution were changed to silver nitrate solution in comparative example 4, and the other steps were the same.
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%, ball milling was rapidly performed for 10min, and the water reducing effect was tested according to QB/T1545 2015;
The obtained glaze slip is coated on the surface of a ceramic block with the same specification and the same size, and is fired at 1180 ℃ to form a glaze, the antibacterial effect is tested by adopting a block sterilization rate experiment, specifically, the material is divided into small blocks and then is put into a bacterial suspension with a certain concentration, mixed culture is carried out, the bacterial concentration in the bacterial suspension is calculated by sampling at fixed time, the antibacterial rate is calculated, and the measured results are shown in the following table:
TABLE 2 Performance test Effect of examples 1-3 and comparative examples 1-4
As is clear from the data in Table 2, the glaze powders prepared in examples 1 to 3 and comparative examples 1 to 4, when mixed with water, had suitable flow rates, which indicated that the glaze slips prepared in examples 1 to 3 and comparative examples 1,2 and 4 had good stability, and that in comparative example 3, the water reducing effect was poor due to the absence of the grinding aid and deflocculating agent, the dispersing effect was poor due to the higher viscosity, and the silver loading of the porous material was reduced.
In the antibacterial experiments, the antibacterial rates of the modified titanium dioxide to the titanium dioxide in the comparative example 1 are proved to be over 99 percent, and the photocatalytic effect of the modified titanium dioxide is poor because the modified titanium dioxide is changed to the titanium dioxide and the titanium dioxide is mostly converted to the rutile phase at high temperature. In comparative example 2, since the modified titanium dioxide is ball-milled in the glaze powder for a long time, the crystal structure is destroyed, the coating effect of the silicon dioxide and zirconium phosphate is affected, and a part of the modified titanium dioxide is mostly converted into rutile phase at high temperature, and the photocatalytic effect thereof is deteriorated.
In the appearance comparison experiment, in comparative example 4, the binding ability of Ag+ to the porous material was weak, and free silver ions were accumulated during the high temperature process to cause the appearance to be dark.
According to the antibacterial glaze powder with photocatalytic activity, the silver-containing antibacterial agent and the nano zinc oxide can improve surface contact bacteria to kill, the modified titanium dioxide can improve the effect of photocatalytic bacteria killing, and multiple antibacterial layers are formed on the surface of the fired glaze layer through the combination of the silver-containing antibacterial agent, the nano zinc oxide and the modified titanium dioxide, so that the antibacterial glaze powder has an excellent sterilizing effect.
According to the invention, through the porous material with ion exchange capability and multiple through holes, the silver carrying capacity of the antibacterial glaze powder is improved by adding the silver ammonia complex solution and the zinc ammonia complex solution for metal replacement, and meanwhile, the dissolution rate of silver is reduced by combining the powder with silver ions, so that the antibacterial effect is improved and the antibacterial service life of the glaze powder is prolonged;
According to the invention, the temperature of converting anatase into rutile is improved by modifying the titanium dioxide, so that the failure of the titanium dioxide in the high-temperature firing process is avoided, and the photocatalytic disinfection effect of the titanium dioxide is improved.
The preparation process can improve silver loading of the porous material, improves preservation effect of the glaze powder through a coating process, avoids damaging the structure of modified titanium dioxide through a proper preparation process, and improves antibacterial effect of the antibacterial glaze powder.
The foregoing examples are provided to further illustrate the technical contents of the present invention for the convenience of the reader, but are not intended to limit the embodiments of the present invention thereto, and any technical extension or re-creation according to the present invention is protected by the present invention. The protection scope of the invention is subject to the claims.