CN114671664B

CN114671664B - Bacteriostatic ceramic tile for removing formaldehyde and toluene and preparation method thereof

Info

Publication number: CN114671664B
Application number: CN202210400092.7A
Authority: CN
Inventors: 冼啟薹
Original assignee: Huiya Ceramics Co ltd
Current assignee: Huiya Ceramics Co ltd
Priority date: 2022-04-15
Filing date: 2022-04-15
Publication date: 2022-10-04
Anticipated expiration: 2042-04-15
Also published as: CN114671664A

Abstract

The invention relates to an antibacterial ceramic tile for removing formaldehyde and toluene, which is characterized in that: the ceramic tile comprises an embryo body layer, a ground glaze layer, a negative ion glaze layer and a surface glaze layer, wherein the embryo body layer comprises 18-23 parts of clay, 20-25 parts of kaolin, 5-6 parts of nano hydroxyapatite, 2-3 parts of aluminum hydroxide, 3-6 parts of boron nitride nanosheets, 0.5-1 part of diatomite and 2-3 parts of functional fiber cloth; the ground coat layer comprises clay 12-18, citric acid activated kaolin 15-20, quartz 15-22, zinc oxide 5-6, nano silver 0.05-0.1 and nano bismuth oxysulfide 0.05-0.15; the negative ion glaze layer comprises 2-5 parts of modified tourmaline powder and 20-25 parts of diatomite; the overglaze layer comprises clay 10-12, quartz 15-22, mordenite 10-12, Y-type molecular sieve 5-8, silicon carbide 1-3, nano silver 0.05-0.1 and nano bismuth oxysulfide 0.05-0.15. The components promote the ceramic tile disclosed by the invention to have more excellent adsorption capacity, and the capacity of generating negative ions and inhibiting bacteria, so that the ceramic tile not only can inhibit bacteria or absorb formaldehyde, but also can absorb toluene. Meanwhile, the invention also provides an efficient method for preparing the ceramic tile, which is simple and convenient to operate and suitable for mass production.

Description

Bacteriostatic ceramic tile for removing formaldehyde and toluene and preparation method thereof

Technical Field

The invention belongs to the field of ceramic tiles, and particularly relates to an antibacterial ceramic tile for removing formaldehyde and methylbenzene and a preparation method thereof.

Background

Ceramic tiles have a long history and are prepared from refractory metal oxides and semimetal oxides by means of grinding, mixing, pressing, glazing, sintering and the like.

Formaldehyde is the first killer of indoor environment, its release period is as long as 3 years-15 years, and is serious to human body especially infants, pregnant women, old people and chronic patients. The source of indoor formaldehyde is mainly from a new house, and symptoms such as headache, weakness and the like can be caused by long-term contact with low-concentration formaldehyde steam; formaldehyde can also cause touch, pain and temperature sense disorders, excessive perspiration on one side of the body, unequal skin temperatures on two sides of the body, serious harm to health, long release period of toxic gas in the air and difficult detection of residents when the toxic gas slightly exceeds the standard; when the formaldehyde content exceeds 4-5 times, the resident can smell the odor, so that the formaldehyde detection in the indoor air environment by a detection mechanism becomes an essential procedure for living in a new house. Formaldehyde is listed as a first-class carcinogenic and teratogenic substance by the international cancer research organization (IARC, 2006) and also one of 45 toxic organic pollutants causing serious ecological environment influence. China is the largest formaldehyde producing country and consuming country in the world, and the yield of formaldehyde accounts for 1/3 of the yield of formaldehyde in 2006. With the increasing demand of formaldehyde in China, indoor pollution caused by formaldehyde is not ignored.

Like formaldehyde, the residential environment is also contaminated with toluene. Sources of toluene in indoor environments are mainly tobacco-burning fumes, solvents, perfumes, detergents, wallpaper, adhesives, paints, stains, teletext fax machines, computer terminals and printers, among others. Toluene can be absorbed by respiratory tract, digestive tract and skin, and can cause chronic poisoning due to the phenomenon of overproof toluene pollution caused by indoor decoration caused by the composite wood floor, plate furniture and wall painting which are widely used in the indoor decoration process.

Toluene poisoning has two conditions, the first is acute poisoning, which is characterized by dizziness, headache, nausea, vomiting and confusion after inhalation of higher concentration steam, and serious patients have restlessness, convulsion or coma, accompanied by eye and upper respiratory tract irritation symptoms, and can cause conjunctival congestion and pharyngeal congestion. Second, chronic poisoning may occur with dermatitis, chapped skin, hepatomegaly, female menstrual disorders, neurasthenia syndrome, and the like. After entering the body, 48 percent of toluene is metabolized in the body and finally discharged out of the body through the liver, brain, lung and kidney, and in the process, the toluene harms the nervous system, and when the concentration of the toluene in blood reaches 1250mg/m < 3 >, the short-term memory ability, the attention persistence and the sensorimotor speed of a contact person are obviously reduced. Along with the improvement of the living quality of people, people are more and more concerned about the problems of removing the pollution of formaldehyde, methylbenzene and the like and living safety after the decoration of new living rooms.

On the other hand, the popularization of modern communication technology, the increase of household appliances, the serious electromagnetic radiation, the increase of positive ions in the air, the lack of negative ions, and the pollution of various human living environments are also the core reasons of the current human health conditions.

The ceramic tile is thick and hard in texture and high in wear resistance, and even if other functional substances are added, the ceramic tile is difficult to play a role due to the structure of the ceramic tile, so that the improvement of the structure of the ceramic tile is an important link for matching with the performance enhancement of the ceramic tile.

Disclosure of Invention

The invention designs an antibacterial ceramic tile for removing formaldehyde and toluene and a preparation method thereof, and solves the technical problems that: (1) The ceramic tile with the composite function is provided, so that the ceramic tile can not only be used for singly inhibiting bacteria or absorbing formaldehyde, but also can absorb toluene which is an important pollutant ignored by people. (2) The ceramic tile prepared by the method has three important functions of removing formaldehyde and toluene and inhibiting bacteria. (3) The ceramic tile with a new structure can better promote the adsorption of harmful substances such as formaldehyde, toluene and the like in the ceramic tile.

In order to solve the technical problems, the invention adopts the following scheme:

the utility model provides a remove antibacterial ceramic tile of formaldehyde toluene which characterized in that: comprises an embryo body layer, a ground glaze layer, a negative ion glaze layer and a surface glaze layer;

the embryo layer comprises the following components in percentage by weight: 18-23 parts of clay, 20-25 parts of kaolin, 5-6 parts of nano hydroxyapatite, 2-3 parts of aluminum hydroxide, 3-6 parts of boron nitride nanosheet, 0.5-1 part of diatomite and 2-3 parts of functional fiber cloth;

the ground coat comprises the following components in percentage by weight: 12-18 parts of clay, 15-20 parts of citric acid activated kaolin, 15-22 parts of quartz, 5-6 parts of zinc oxide, 0.05-0.1 part of nano silver and 0.05-0.15 part of nano bismuth oxysulfide;

the negative ion glaze layer comprises the following components in percentage by weight: 2-5 parts of modified tourmaline powder and 20-25 parts of diatomite;

the overglaze layer comprises the following components in percentage by weight: 10-12 parts of clay, 15-22 parts of quartz, 10-12 parts of mordenite, 5-8 parts of Y-type molecular sieve, 1-3 parts of silicon carbide, 0.05-0.1 part of nano silver and 0.05-0.15 part of nano bismuth oxysulfide.

Further, the functional fiber cloth of the embryo body layer is nano silver fiber cloth, nano titanium dioxide fiber cloth and carbon nanotube fiber cloth, and the weight ratio of the nano silver fiber cloth to the nano titanium dioxide fiber cloth to the carbon nanotube fiber cloth is 1.

Further, the modified tourmaline powder in the negative ion glaze layer is obtained by treating calcium carbide gas powder with tetradecene succinic anhydride and then doping nano zirconia therein for modification.

A preparation method of an antibacterial ceramic tile for removing formaldehyde and toluene is characterized by comprising the following steps: the method comprises the following steps:

A. preparing functional fiber cloth: prepared by mixing functional substances and fiber cloth;

B. taking embryo components: crushing clay, kaolin, nano hydroxyapatite, aluminum hydroxide, boron nitride nanosheets and diatom opal, adding a proper amount of water, stirring, adding into a mold while uniformly scattering functional fiber cloth, molding and sintering to obtain a blank; wherein the weight ratio of the components of the embryo body is as follows: 18-23 parts of clay, 20-25 parts of kaolin, 5-6 parts of nano hydroxyapatite, 2-3 parts of aluminum hydroxide, 3-6 parts of boron nitride nanosheet, 0.5-1 part of diatom opal and 2-3 parts of functional fiber cloth;

C. taking a ground coat component: crushing clay, citric acid activated kaolin, quartz and zinc oxide, adding a proper amount of water, stirring, adding nano silver and nano bismuth oxysulfide while stirring to obtain a glaze, spraying glaze on a blank, sintering, and preparing a ground glaze; wherein the ground coat comprises the following components in percentage by weight: 12-18 parts of clay, 15-20 parts of citric acid activated kaolin, 15-22 parts of quartz, 5-6 parts of zinc oxide, 0.05-0.1 part of nano silver and 0.05-0.15 part of nano bismuth oxysulfide;

D. taking negative ion glaze layer components: weighing diatomite and modified tourmaline powder, adding a proper amount of water, mixing, grinding in a quick grinding machine for 20-40 min, and performing vacuum drying treatment on ground negative ion glaze slurry to obtain a negative ion glaze fabric; c, glaze spraying is carried out on the blank obtained in the step C, sintering is carried out, and the preparation of the negative ion glaze layer is finished; wherein, the weight ratio of the negative ion glaze layer is as follows: 2-5 parts of modified tourmaline powder and 20-25 parts of diatomite;

E. taking a surface glaze component: crushing clay, quartz, mordenite, a Y-type molecular sieve and silicon carbide, adding a proper amount of water, stirring, adding nano silver and nano bismuth oxysulfide while stirring to obtain a glaze, spraying glaze on the blank obtained in the step D, sintering and preparing an overglaze; the overglaze comprises the following components in percentage by weight: 10-12 parts of clay, 15-22 parts of quartz, 10-12 parts of mordenite, 5-8 parts of Y-type molecular sieve, 1-3 parts of silicon carbide, 0.05-0.1 part of nano silver and 0.05-0.15 part of nano bismuth oxysulfide.

Further, the modified tourmaline powder in the negative ion glaze layer is prepared by the following method:

(1) crushing tourmaline, adding water, ball-milling until the tourmaline passes through a 100-mesh sieve, drying, and carrying out jet milling to obtain tourmaline powder, wherein the mass of the added water is 1/8 of that of the tourmaline powder during ball milling;

(2) adding 10 parts by weight of the tourmaline powder and 15 parts by weight of tetradecene succinic anhydride into 80 parts by weight of N, N-dimethylformamide, carrying out ultrasonic oscillation for 35min to obtain an ultrasonic mixed solution, heating the ultrasonic mixed solution to 60 ℃, stirring for 3h, and then carrying out reduced pressure distillation to remove the solvent to obtain tourmaline powder A;

(3) according to the weight parts, 10 parts of tourmaline powder A is added into 100 parts of deionized water, the mixture is stirred and heated to 55 ℃, stirred for 50min, 0.5-1 part of nano zirconia is added, the mixture is heated to 75 ℃, stirred for 2h at constant temperature, heated to reflux, refluxed for 3h, stopped to react, filtered residue is taken out, and dried, thus obtaining the modified tourmaline powder.

Further, the citric acid activated kaolin in the ground glaze component is obtained according to the following method: drying and grinding kaolin raw ore, sieving the kaolin raw ore with a 100-mesh sieve, adding the kaolin into citric acid with a certain concentration according to the solid-liquid weight ratio of 1 to 13, carrying out ball milling in a planetary mill for a certain time, wherein the ball-material ratio is 5, the ball milling speed is 300r/min, and drying to obtain the citric acid activated kaolin.

Further, the concentration of the citric acid is 1.5mol/L, and the reaction time is 5-7h.

Further, the specific steps for preparing the nano silver fiber cloth are as follows:

(1) mixing sodium dodecyl benzene sulfonate, polyoxyethylene sorbitan monooleate, sodium silicate and nano silver with the particle size of 20-60nm, placing in purified water, ultrasonically stirring at high speed for dispersing for 1-3h, adding inorganic high-temperature glue, and mixing to obtain a mixed material; wherein the weight ratio of the sodium dodecyl benzene sulfonate, the polyoxyethylene sorbitan monooleate, the sodium silicate, the purified water and the nano silver is as follows: 0.2-0.8:1.5-3:0.3-0.6:100:6;

(2) adding chopped fiber cloth to the mixed material, wherein the area size of the chopped fiber cloth is 1 x 5mm-1 x 8mm;

(3) filtering, and oven drying the fiber cloth.

Further, the specific steps for preparing the nano titanium dioxide fiber cloth are as follows:

(1) placing nanometer titanium dioxide with particle size of 20-40nm in weakly alkaline purified water with pH of 7.8-8.5, stirring for 15min, ultrasonically stirring at high speed for dispersing for 1-2h, adding sodium dodecyl benzene sulfonate, and ultrasonically treating for 30-60min; adding inorganic high-temperature glue, and mixing to obtain a mixed material; wherein the weight ratio of the nano titanium dioxide to the sodium dodecyl benzene sulfonate to the purified water is 20-35:1.5:100, respectively;

(3) filtering, and oven drying the fiber cloth.

The ceramic tile comprises four layers of structures from bottom to top, namely a blank layer, a bottom glaze layer, a negative ion glaze layer and a surface glaze layer; vent structures extending towards the inside of the ceramic tile are arranged at intervals at the positions, close to the peripheral edge, of the bottom of the blank layer; the distance between the vent hole and the edge of the ceramic tile is 0.5-1.5cm, and the aperture of the vent hole is 10-100 mu m.

The appropriate amount of water mentioned above can be set according to the purposes of the prior art formulation, and is well known to those skilled in the art, and will not be described herein in a redundant manner.

The inorganic high-temperature adhesive can reach 500-1750 ℃ generally, is mainly prepared from inorganic nano materials through polycondensation, has neutral pH value, and can be used for bonding ceramics and the like.

The sintering temperature of the above-mentioned ground coat layer is 1000-1100 deg.C, and the sintering temperature of other steps is 1200 deg.C.

The inorganic high-temperature adhesive can be selected from commercially available inorganic high-temperature adhesives, and the nano silver is only adhered to the chopped fiber cloth to be scattered into a mold for preparing a blank, so that factors such as a manufacturer for selecting the inorganic high-temperature adhesive are not limited.

From the perspective of bacteriostasis and antibiosis of the ceramic tile of the invention:

the functional fiber cloth can use nano silver fiber cloth, nano titanium dioxide fiber cloth and carbon nanotube fiber cloth, preferably uses nano silver fiber cloth, nano titanium dioxide fiber cloth and carbon nanotube fiber cloth simultaneously, and the weight ratio is 1:2:3. the functional fiber cloth added with functional substances can be used as a binder/adhesive to enhance the toughness and the bonding capability of the ceramic tile blank.

The nano silver fiber cloth is attached with nano silver, so that the nano silver has strong inhibiting and killing effects on dozens of pathogenic microorganisms such as escherichia coli, gonococcus, chlamydia trachomatis and the like, does not generate drug resistance, and can effectively resist bacteria and sterilize. The nano silver fiber cloth is adhered with nano silver for the fiber cloth, the ceramic tile is in the air and is in contact with substances in the air such as bacteria, or the substances in the air can fall into the holes in the blank body through the gaps, at the moment, the ceramic tile blank body distributed with the nano silver fiber cloth can react with the substances in the air in a large area to destroy the substance structure, so that the substances such as bacteria can be killed. Because the nano silver is treated and is not easy to agglomerate in water, the quality of the nano silver is not easy to be influenced, and the activity can be kept for a long time.

The nanometer titanium dioxide fiber cloth is attached with the nanometer titanium dioxide, and the nanometer titanium dioxide is an antibacterial agent, can also oxidize and decompose harmful substances, and is harmless to human bodies. The nano titanium dioxide fiber cloth is adhered with nano titanium dioxide, the ceramic tile is in contact with substances in the air such as pollutants, bacteria, harmful gas and the like in the air, or the substances in the air can fall into holes in the blank body through gaps, and at the moment, the ceramic tile blank body distributed with the nano titanium dioxide fiber cloth reacts with the substances.

The carbon nanotube fiber cloth formed by dispersing the carbon nanotubes in the resin matrix can play a role in strengthening the interface and the matrix. On one hand, the mechanical property of the matrix can be improved, on the other hand, the bridging effect of the carbon nano tubes at the interface of the fiber and the resin can effectively transfer stress, prevent crack propagation, toughen the interface of the fiber and the resin and improve the performance of the composite material. However, there are many constraints that limit the application of carbon nanotubes, such as the inability to disperse uniformly. The carbon nanotubes are easily stuck together due to the high van der waals force between the carbon nanotubes. And the common use of the fiber cloth with three properties can solve the dispersion problem of the carbon nano tube fiber.

The carbon nano tube has good antibacterial performance, and because the tube diameter is small and the specific surface area is large, the opportunity of contacting with bacteria is increased, so that the carbon nano tube is easy to pierce into cell walls to achieve the antibacterial effect. When bacteria directly contact with the carbon nano tube, the cell morphology of the bacteria is distorted, the integrity of the cell membrane is damaged, and intracellular substances flow out, so that the functions of the bacteria cells are lost, and the antibacterial effect is achieved.

After the nano titanium dioxide absorbs the light energy, electrons on the surface of the particles are activated to generate a positively charged structure, and the positively charged structure can generate active oxygen and hydroxyl radicals when contacting with water vapor, so that pollutants, bacteria and organic matters can be oxidized and decomposed into harmless carbon dioxide and water by the reaction of the nano carbon dioxide fiber cloth and the substances.

In the invention, the water vapor stored in the holes provides water vapor power for the nano titanium dioxide, and the light energy transmitted through the gaps of the ceramic tile provides light energy power for the nano titanium dioxide, so that the nano titanium dioxide reacts with harmful substances to generate harmless substances; meanwhile, the hydroxyl radicals contact with the air to take away positrons of oxygen, and air anions (namely negative oxygen ions) are formed. The anion has the effects of tranquilizing, relieving pain, relieving cough, relieving itching, promoting urination, stimulating appetite and lowering blood pressure, and is easy to make people feel happy.

Bismuth oxysulfide is of great interest because of its typical layered structure. Wherein (Bi) ₂ O ₂ ) ²⁺ The stacking of the layers with the Z-axis results in the formation of ultra-thin nanoplates that can have a larger active surface to form more polar-bonded polymer matrix therewith. In addition, lone pair deformation of the Bi6S orbitals in these semiconductors may result in significant overlap of the O2p and Bi6S orbitals in the valence band, which facilitates the migration of photogenerated charge carriers, thereby improving photocatalytic activity, comparable to, or even higher than, titanium dioxide in catalytic activity and antibacterial performance. Has extremely high degradation rate for organic pollutants such as formaldehyde, toluene and the like. Thus, the addition of oxygen chalcogen compounds to the polymer matrix may be a good choice for increasing the capture efficiency and degrading the contaminants. The component can simultaneously realize auxiliary antibiosis, and absorption, degradation and conversion of formaldehyde and toluene. Therefore, the auxiliary antibacterial function is added into the components of the ground glaze and the overglaze, so that the antibacterial function of each layer of structure can be realized, and the integral antibacterial effect of the upper-lower penetration type is achieved.

The ceramic tile highly combines the properties of nano silver and nano titanium dioxide through the selection of the composite functional fiber cloth The carbon nanotube-containing porous carbon material activated carbon fiber is added, and the addition of the carbon fiber material can further fuse nano-particles The nano-silver and the nano-titanium dioxide act together to make up for deficiencies of each other and complement advantages of each other, and the adsorption and the photocatalysis generate synergistic action to realize inhibition The bacteria, the adsorption and the photocatalysis are perfectly combined. More importantly, the nano-grade glaze is added into the components of the ground glaze and the overglaze in the invention The bismuth oxysulfide component assists in antibiosis, and can actually realize that the whole ceramic tile is from a blank body to a ground coat to a negative ion glaze layer and finally to the surface Each layer of the glaze has bacteriostatic and antibacterial properties, and the integral bacteriostatic effect of the up-to-down penetration type is achieved.

The Hydroxyapatite (HAP) material has a micro-nano structure, not only canThe preparation method is used for repairing enamel in biological hard tissues, can also be used for adsorbing pollutants in the field of environmental management, and can be well coordinated with the environment without causing secondary pollution. The structure is hexagonal system, and the basic characteristics of the crystal structure are that Ca-O polyhedron is in the form of trigonal column, and its edge and vertex are connected to form irregular chain, and said chain is extended along c axis, and the chains are connected by phosphate radical to form channel parallel to c axis, and the added anion Cl is added ^- 、F ^- 、OH ^- The filling in the pore canal is also arranged into chains and has absent disorder-order. F-Ca coordinates the octahedral vertices Ca, also with O at 6 vertices of its adjacent 4 phosphates ^2- Are connected. The Ca-OH groups rich on the surface of the formaldehyde adsorbent play a main role in adsorbing and activating formaldehyde molecules.

Hexagonal boron nitride (h-BN) has excellent thermal stability, barrier property, high temperature resistance and other properties, and is increasingly attracted by researchers in various countries. The h-BN is introduced into the current anticorrosive coating system, which is helpful for improving the performance of various aspects of the matrix. Hexagonal boron nitride (h-BN) has a graphite-like structure, often referred to as "white graphite", and its nanosheets (BNNSs) as "white graphene". In addition, BNNSs have many properties superior to graphene, such as high oxidation resistance, strong insulation, wide band gap, and high chemical stability, and can overcome the defect of "corrosion promotion" of graphene in the current research on graphene anticorrosive coatings to some extent.

BNNSs retain the excellent properties of micron-sized h-BN powder, and have the advantages of high specific surface area, high thermal conductivity (300-360W/(m.K)) and the like which are not possessed by h-BN powder due to the reduction of lamella. And due to the high heat conduction efficiency, assistance and reinforcement are provided for the application of the ceramic material in the field of ceramics.

The nitrogen-series flame retardant mainly meets the flame-retardant requirement on the polymer by carrying out gas-phase flame retardance, and is mainly characterized in that in the combustion and heating process, nitrogen gas or ammonia gas and other flame-retardant gases are generated, a large amount of combustion heat can be directly taken away in the process, the flame-retardant gases can also be rapidly diffused so as to dilute the concentration of a large amount of oxygen and other combustion-supporting gases, and the nitrogen-series flame retardant can also react with a large amount of oxygen to polymerize to obtain a high-valence oxide, so that the flame-retardant property of the polymer is greatly improved.

The boron flame retardant forms a carbon layer on the surface of the boron flame retardant to serve as a barrier layer for protecting the boron flame retardant, so that combustible gases such as heat, oxygen and the like are difficult to contact with a polymer, and the flame retardant property is improved. From the properties, the high thermal conductivity of BNNSs can play a certain role in flame retardancy, and the BNNSs also have flame retardancy in terms of the composition.

Diatom opal is porous amorphous SiO formed by biomineralization of diatom ₂ The diatomite particles also have pores with different sizes of nanometer, submicron and micron, and can be suitable for adsorption of various substances with different sizes.

The components of the embryo body selected by the invention ensure that the embryo body layer has excellent antibacterial property, adsorption property and mechanical property Can be used.The Hydroxyapatite (HAP) material has a micro-nano structure, the BNNSs retains the excellent properties of micron-sized h-BN powder, the number of lamellar layers is reduced, and the specific surface area is high. The use of two components of hexagonal structure has a synergistic effect. The two components respectively have a Ca-O polyhedron which is of a trigonal structure and a high-hardness lamellar structure, and have introduced submicron and micron-level pore channels of the kieselguhr and a hexagonal grid layer structure of the kaolin, so that peculiar smell can be absorbed, and the porous texture of the kieselguhr can also absorb moisture and adjust humidity. The composite components are selected to enable the layer to have rich pore channel types, physical and chemical adsorption and integration are integrated, the layer also has firm and wear-resistant properties, aluminum hydroxide is used as a sintering aid to achieve a more stable structure, the ground glaze layer can further absorb and convert residual pollution gas, peculiar smell, particles and the like entering the lower blank body and absorbed and entered through the upper surface glaze layer and the negative ion glaze layer, and the effect is better.

The ceramic tile also has excellent flame retardant property, and the flame retardant mechanism is as follows：

BNNSs is the dual fire behaviour who has nitrogen system fire retardant and boron system fire retardant itself concurrently, BNNSs's lamellar structure has good thermal-insulated effect, and the hexagonal grid layer structure who arranges of combination kaolin itself again can delay the combustion process in fire-retardant process, uses with aluminium hydroxide ATH complex, can delay the conduction of combustion heat on the one hand, BNNSs's lamellar structure has increased the degree of difficulty of inside gas release on the one hand, make the vapor that ATH was heated and is produced absorb more heats, delay and absorb two aspects combined action and reach fire-retardant purposes. Meanwhile, the nano hydroxyapatite is added in the system components, the porous structure of the HAP can adsorb a large amount of smoke generated during combustion, and the smoke can be further suppressed while the flame is retarded, so that the flame retardant property of the whole ceramic tile is improved. Further, the diatomite in the anion layer in the invention can also provide an auxiliary effect from the upper layer for the flame retardant performance of the ceramic tile. The silicon carbide component added into the overglaze can improve the high thermal conductivity of the whole ceramic tile and provide assistance for the flame retardant property of the ceramic tile.

The negative ions are also called as air vitamins, which can promote the synthesis and storage of vitamins in human bodies, strengthen and activate the physiological activity of the human bodies, are like the vitamins in food, and have very important influence on the life activities of the human bodies and other organisms.

It mainly manifests the following aspects: firstly, the influence on the nervous system can strengthen the function of cerebral cortex and mental activity, improve the working benefit, promote the improvement of sleep quality, promote the enhancement of the oxidation strength of brain tissues and ensure that the brain tissues obtain more oxygen; secondly, the negative ions have the effect of obviously expanding blood vessels and improving the cardiac function and the myocardial nutrition on the cardiovascular system; thirdly, the blood coagulation system is acted, so that the blood coagulation flow rate is slowed down, the blood coagulation time is prolonged, and the oxygen content in the blood is increased; fourthly, the negative ion health care product has the effect on the respiratory system of a human body, can improve the lung capacity of the human body, can increase the oxygen absorption capacity of the lung of the human body by more than 20 percent by inhaling the negative ions in the air for more than 30 minutes, and also has the functions of calming, hypnotizing and purifying the air.

The negative ion glaze layer has more excellent negative ion release performance, and the action mechanism is as follows：

Tourmaline is a silicate mineral with a ring structure containing boron mainly including Li, na, fe, mg and Al, and has certain adsorption to gas molecules. The adsorption of the tourmaline mineral surface is mainly through the electrostatic attraction between charges, and the charges mainly come from lattice defects, surface broken bonds, substitutions and the like. In the preparation process of the tourmaline powder, the surface composition and structure change to generate electric charge, which has adsorption effect on gas molecules. Due to the unique crystal structure of the tourmaline, the tourmaline has excellent pyroelectric property, piezoelectric property, spontaneous polarization effect, far infrared radiation, anion releasing property, surface activity, adsorption effect and the like.

The application of pure tourmaline powder in the ceramic field is limited, and the following reasons mainly exist: firstly, the anion material for ceramic glaze sold in the market at present is obtained by crushing and ball-milling tourmaline powder by a physical method, and has darker color, thereby influencing the color and appearance of the ceramic product; secondly, the anion release performance of unmodified tourmaline powder is very limited and needs to be further improved so as to meet the use requirement of the unmodified tourmaline powder in the field of ceramic glaze; thirdly, the currently used tourmaline powder has poor temperature resistance, and the negative ion function of the tourmaline powder is rapidly reduced after the tourmaline powder is calcined at the temperature higher than 1000 ℃; fourthly, the unmodified tourmaline powder is easy to agglomerate when the ceramic glaze slurry is prepared. Therefore, the reasonably modified tourmaline powder can effectively solve the problems, effectively improve the structural stability and increase the release amount of negative ions.

The zirconium dioxide is white powder, the Zr-O bond strength is about 94% of the Si-0 bond strength, but the Si0 ₂ In which one Si is coordinated to 4O, and Zr0 ₂ Zr in the zirconium oxide is coordinated with more than 7O, so that the zirconium oxide has good chemical stability and mechanical property. The added zirconium dioxide powder can improve the negative ion release amount of the tourmaline powder, and meanwhile, the auxiliary surface glaze layer improves the toughness, oxidation resistance and wear resistance of the ceramic tile from the inside.

Diatomaceous earth is a siliceous rock that is essentially amorphous silica containing water. The diatomite is a nonmetallic mineral which is formed by remains of unicellular aquatic plant diatoms and has large porosity, strong adsorbability, large specific surface area and stable chemical property after about twenty thousand years of accumulation period. The diatomite has the characteristics of light weight, multiple pores, heat preservation, heat insulation, flame retardance, humidity regulation and the like.

After the diatomite and the modified tourmaline react, besides a stable and firm structure, because the activity of Li, na, mg, fe and other ions in complex ore in the tourmaline is very strong, the high-activity ions exposed on the surface of a blank body or the inner wall of a pore in the blank body lose part of outermost electrons rotating around atomic nuclei through the radiation and discharge action of microelements when contacting with air, so that the air is ionized to generate free ions, and the free ions are combined with other neutral gas molecules to form air negative ions with negative charges.

The negative ion glaze layer takes the diatomite as a support, and a proper amount of modified tourmaline powder is introduced into the negative ion glaze layer, so that the functions of the diatomite are enriched, a carrier for exerting the negative ion effect is provided for the modified tourmaline powder, and the diatomite and the modified tourmaline powder complement each other. The agglomeration phenomenon of the modified tourmaline powder is obviously reduced, and the modified tourmaline powder shows better dispersibility.

The negative ion glaze layer plays the first important role of ionizing air to generate free ions The function of titanium dioxide for providing luminous energy to form negative ions in the air is the second superposition of the negative ion function. That is, the invention greatly improves the ceramic tile by utilizing the two different functions of forming the negative ion field in the air The quantity of negative ions generated in the ambient air further enhances the benefit of the negative ions to the human body。

Zeolite molecular sieves are inorganic crystalline materials having a particular framework structure and have a selective adsorption capacity primarily dominated by the regular structure. The zeolite molecular sieve has regular pore size arrangement and uniform distribution, and the selective adsorption is mainly because the pore sizes of different zeolites are different, and in general, only molecules with the molecular dynamics diameter smaller than the pore size of the molecular sieve can be adsorbed by the molecular sieve. There are also large differences in the framework structures and pore sizes of different types of molecular sieves, and the framework structures of molecular sieves have a degree of variability, so that some molecules with a molecular kinetic diameter slightly larger than the pore size can also be adsorbed by them, but the adsorption rate and adsorption capacity are reduced. Since the structure has cations and the framework structure is negatively charged, the molecular sieve itself has polarity. The positive ions of the zeolite molecular sieve can generate a strong positive electric field so as to attract the negative center of polar molecules, or polarizable molecules are polarized after electrostatic induction of the zeolite molecular sieve. Thus, zeolite molecular sieves are capable of adsorbing molecules that are more polar or more easily polarized, but have kinetic diameters slightly larger than the size of their channels. The molecular sieve has special pore channel structure, so that the molecular sieve has special performance and can exert the adsorption capacity under the conditions of high temperature and low pressure.

The presence of a large number of five-membered rings in the crystal structure of Mordenite (MOR) confers stability. The five-membered ring and the four-membered ring are connected with each other to form a twelve-membered ring and an eight-membered ring of the main channel. The two larger straight channels of mordenite are parallel to each other, but the pore diameter is reduced due to the dislocation between the channels, the size of the main channel of the twelve-membered ring is from 6.6 angstroms to 4 angstroms, and the adsorption action generally occurs in the channel. The molecular size of formaldehyde and the molecular size of toluene are both in the range, and the formaldehyde and the toluene are suitable for absorption.

The mordenite molecular sieve is a silicon-aluminum molecular sieve or a molecular sieve containing heteroatoms including boron, phosphorus and iron, and SiO is used as the mordenite molecular sieve ₂ /Al ₂ O ₃ The molar ratio is 9-20. The pore structure of the mordenite is a one-dimensional pore structure, although the pore diameter is smaller, molecules with small kinetic diameter can be adsorbed in the pore, and molecules with large kinetic diameter are excluded, so that the sieving effect is achieved. Mordenite has a greater affinity for polar molecules, particularly for adsorbates having a molecular dynamics diameter comparable to the pore size of mordenite, the more polar the adsorbate is, the more readily it is adsorbed by the mordenite. The adsorption performance of the common adsorbent is easily influenced by the environment, and the mordenite still has stronger adsorption capacity under the conditions of lower adsorbate-containing concentration or high adsorption condition temperature due to the stability and high temperature resistance of the mordenite.

The Y-type molecular sieve raw powder has an faujasite structure, and the main components forming the NaY molecular sieve framework are hexagonal column beta cages which are connected through cubic columns to form a super cage structure containing 4 twelve-element ring holes. The size of the pore channels is very close to that of toluene molecules, so that organic molecules with similar sizes, such as toluene molecules, can diffuse in the pore channels. The specific surface area of the raw powder of the Y-type molecular sieve is usually 400-500m ² The grain diameter is about 3-5nm, the aperture is about 0.74nm, and the rich three-dimensional pore channel structure and the larger specific surface area ensure that gas can generate stronger mutual dispersion action in the pore channel even under low pressure.

The silicon carbide has a hexagonal crystal structure, has high strength, high modulus, high hardness, corrosion resistance and wear resistance, improves high-temperature oxidation resistance, ablation resistance and high-temperature thermal stability, and has high thermal expansion coefficient and high thermal conductivity. The silicon carbide micro powder is used for modifying the performance of the integral overglaze, so that the stability, hardness, wear resistance and heat conductivity of the overglaze of the ceramic tile can be effectively improved, the problem that the ceramic tile is combined to form aggregates due to the formula can be reduced, the introduction of different functional molecular sieves can be tightly combined with the silicon carbide micro powder in the formula, the uniform distribution of pore channels is realized, and the wear resistance of the ceramic tile is improved together. High compactness, difficult dirt seepage, strong antifouling capacity and easy cleaning and cleaning

The invention combines two molecular sieves with completely different pore channel structuresThe smoothness of one-dimensional parallel pore channels of the mordenite for adsorbing formaldehyde and toluene, the covering property of three-dimensional pore channels of the Y-shaped molecular sieve for adsorbing formaldehyde and toluene and the dispersivity of internal adsorption are utilized, the property of the two that the specific surface area is increased is utilized to realize the multiple increase of the specific surface area together, the adsorption performance is greatly improved, and the adsorption performance of the ceramic tile to different organic pollutant molecules, formaldehyde and toluene molecules with different sizes, different types and different concentrations is also enriched. The introduction of the silicon carbide can effectively improve the stability, hardness, wear resistance and heat conductivity of the ceramic tile overglaze, and can also reduce the formation of aggregates formed by the combination of ceramic tile formulas, and the introduction of molecular sieves with different functions and quartz can also be matched with silicon carbide micro powderCan be tightly combined in the formula, realize the uniform distribution of pore canals and improve the wear resistance of the ceramic tile together. Meanwhile, the high heat-conducting property of the overglaze plays a role in complementing the conductivity of the flame-retardant property of the ceramic tile.

Kaolin is an aluminosilicate aggregate mainly composed of kaolinite and associated with minerals such as quartz, feldspar, illite and the like, and is a 1. Silicon-oxygen tetrahedrons are connected in a common vertex angle mode to form a grid layer in a hexagonal arrangement, aluminum-oxygen octahedrons are connected in a common edge mode to form a layer, the silicon-oxygen tetrahedrons and the aluminum-oxygen octahedrons are connected through the pinnacle oxygen of a silicon-oxygen tetrahedron layer, structural light radicals are distributed in the aluminum-oxygen octahedron layer, and structural units are combined through hydrogen bonds.

During the heating process of the kaolin, the kaolin loses crystal water at 450-750 ℃, dehydroxylation reaction occurs, the original ordered kaolin crystal lamellar structure is distorted and destroyed and is changed into an amorphous metakaolin structure, so that part of radicals in the crystal inner layer are exposed, surface active sites are increased, and the reactivity is increased. The essence is that the A1 atom in the octahedral structure changes from hexacoordinate to pentacoordinate and tetracoordinate. The metakaolin is transformed in crystal form at 925-1100 deg.C to obtain spinel and poor-crystalline mullite. The zinc oxide is introduced into the system, and the addition of the zinc oxide promotes the reduction of the mullite synthesis temperature and improves the mullite phase content; meanwhile, the addition of quartz is beneficial to improving the volume density of mullite. The temperature required by calcination is reduced integrally, the energy consumption is reduced, and meanwhile, the generated product is harder and keeps high adsorption performance.

Citric acid (2-hydroxypropane-1, 2, 3-tricarboxylic acid) is one of low molecular organic acids, and has a molecular formula of C ₆ H ₈ 0 ₇ It is easily soluble in water, ethanol, and diethyl ether, slightly soluble in chloroform, insoluble in benzene, and usually white granule or white crystalline powder at room temperature, and can be decomposed to generate carbon dioxide and water when heated to 175 deg.C. Depending on the temperature at which the solution is extracted, citric acid may form either as citric acid monohydrate or as anhydrous citric acid. From the structureThe citric acid is a stronger ternary organic acid, and the hydrogen in three carboxyl groups can be ionized. The molecule has one hydroxyl group and three carboxyl groups and is a polydentate ligand, the double bonds in the hydroxyl group and the carboxyl groups are easy to form strong hydrogen bonds, in addition, citric acid is also a good ligand, has strong complexation in solution, and can be combined with Mg through the hydroxyl group and the carboxyl groups ²⁺ 、Fe ³⁺ 、Al ³⁺ The plasma metal ions complex to form stable metal-citrate chelates that are linked together in a three-dimensional network with evenly distributed cations.

Citric acid is commonly used for preparing complex oxides with complex components at low temperature by a citrate sol-gel method, and the principle is that a metal-citric acid sol system is formed by utilizing the strong complexing ability of a plurality of carboxyl groups of the citric acid and metal ions, in the process of converting sol into gel, as part of groups are discharged in the form of water molecules, colloid particles collide, gather and are mutually connected to form three-dimensional reticular citrate gel, and then the three-dimensional citrate gel is subjected to heat treatment and self-combustion to obtain oxide powder with uniform particle size.

The firing temperature of the ceramic is too high, the liquid phase at high temperature is too much, the viscosity is too low, the product, especially the product is easy to deform, soften and collapse, and the overburning is generated, so that the firing temperature is reduced, the early formation of mullite phase is promoted, the rigidity of the framework is favorably enhanced, and the influence of internal deformation on the performance is prevented. Under the same conditions, therefore, the synergy between the components enables the temperature of the firing to be lowered, and is extremely important for the quality assurance.

The citric acid acidified kaolin is mainly subjected to layer stripping firstly, and the destruction degree is large, so that the specific surface area is obviously increased, and then aluminum octahedrons and silicon-oxygen tetrahedrons are destroyed, so that the structure is deformed or disintegrated, the breaking of bonds such as Si-O, al-O and the like is promoted, the orderliness is reduced, the surface area can be increased by about four times, the reaction activity of the kaolin is greatly increased, and the early generation of mullite is promoted.

According to the ground glaze component, the citric acid acidified kaolin can promote the crystalline phase of mullite to be formed in advance at a relatively low temperature, and under the condition, the components of zinc oxide and quartz are added, so that the zinc oxide introduced into the system further promotes the reduction of the mullite synthesis temperature and improves the content of the mullite phase; meanwhile, the addition of quartz is beneficial to improving the volume density of mullite. The temperature required by calcination is reduced integrally, the energy consumption is reduced, and meanwhile, the generated product has stronger skeleton rigidity and keeps efficient adsorption structure performance.

The invention has the following beneficial effects:

1. the ceramic tile has strong bacteriostatic function: the properties of nano silver and nano titanium dioxide are highly combined through the selection of the composite functional fiber cloth, and the porous carbon material activated carbon fiber of the carbon nano tube is added, so that the combined action of the nano silver and the nano titanium dioxide can be further fused by adding the carbon fiber material, the advantages of the nano silver and the nano titanium dioxide are complemented, the adsorption and the photocatalysis generate a synergistic effect, and the perfect combination of bacteriostasis, adsorption and photocatalysis is realized. More importantly, the nano bismuth oxysulfide component is added into the components of the ground coat and the overglaze to assist in antibiosis, so that the whole structure of the ceramic tile from the blank body to the ground coat, then to the negative ion glaze layer and finally to the overglaze has antibacterial and antibacterial performances, and the upper-lower penetrating type whole antibacterial effect is achieved. The highest antibacterial rate can reach 89%. Around the tile may be produced 10 ⁴ -10 ⁷ The strong electric field of V/m can effectively kill bacteria or inhibit division and proliferation under the action of the electric field and micro-current formed by the electric field.

2. The negative ion glaze layer plays a first important role in ionizing air to generate free ions, and the nanometer titanium dioxide provides luminous power to form negative ions in the air, so that the negative ions are superposed secondarily. That is to say, the invention utilizes two different functions of forming the negative ion field in the air, which greatly improves the quantity of the negative ions generated in the air around the ceramic tile, and further enhances the benefit of the negative ions to the human body.

3. The surface glaze layer of the invention is fused with two molecular sieves with completely different pore channel structures, thereby not only utilizing the smoothness of one-dimensional parallel pore channels of mordenite for absorbing formaldehyde and methylbenzene, but also utilizing the covering property and the internal absorption dispersivity of three-dimensional stereo pore channels of Y-shaped molecular sieves for absorbing formaldehyde and methylbenzene, and simultaneously utilizing the property of the two molecular sieves for increasing the specific surface area to jointly realize the multiple increase of the specific surface area, thereby greatly improving the absorption performance, and simultaneously enriching the absorption performance of the ceramic tiles for different organic pollutant molecules, formaldehyde and methylbenzene molecules with different sizes, different types and different concentrations. The introduction of the silicon carbide can effectively improve the stability, hardness, wear resistance and heat conductivity of the ceramic tile overglaze, and can also reduce the formation of aggregates formed by the combination of the ceramic tile formula, and the introduction of different functional molecular sieves and quartz can be closely combined with silicon carbide micro powder in the formula, so that the uniform distribution of pore channels is realized, and the wear resistance of the ceramic tile is improved together. Meanwhile, the high heat-conducting property of the overglaze also plays a role in complementing conductivity for the flame-retardant property of the ceramic tile.

4. The embryo body component selected by the invention ensures that the embryo body layer has excellent antibacterial performance, adsorption performance and mechanical property: the hydroxyapatite HAP material has a micro-nano structure, excellent properties of micron-sized h-BN powder retained by BNNSs, reduced lamella and high specific surface area. The use of two components of hexagonal structure has a synergistic effect. The two components respectively have a Ca-O polyhedron in a trigonal column structure and a high-hardness lamellar structure, and have introduced submicron and micron-level pore channels of the diatomite to absorb peculiar smell, and the porous texture of the diatomite can also absorb moisture and adjust humidity. The selection of the composite components enables the layer to have rich pore channel types, integrates physical and chemical adsorption, has firm and wear-resistant properties, has a more stable structure by taking the aluminum hydroxide as a sintering aid, can further absorb and convert residual pollutant gas, peculiar smell, particles and the like entering the lower blank body and absorbed and entered through the upper cover glaze layer and the negative ion glaze layer, and has a better effect.

5. The tile of the invention also has excellent flame retardant properties: BNNSs is the dual fire behaviour who has nitrogen system fire retardant and boron system fire retardant itself concurrently, BNNSs's lamellar structure has good thermal-insulated effect, and the hexagonal grid layer structure who arranges of combination kaolin itself again can delay the combustion process in fire-retardant process, uses with aluminium hydroxide ATH complex, can delay the conduction of combustion heat on the one hand, BNNSs's lamellar structure has increased the degree of difficulty of inside gas release on the one hand, make the vapor that ATH was heated and is produced absorb more heats, delay and absorb two aspects combined action and reach fire-retardant purposes. Meanwhile, the nano hydroxyapatite is added in the system components, and the porous structure of the HAP can adsorb a large amount of smoke generated during combustion, so that the smoke can be further suppressed while the flame is retarded, and the flame retardant property of the whole ceramic tile is improved. Further, the diatomite in the anion layer in the invention can also provide an auxiliary effect from the upper layer for the flame retardant performance of the ceramic tile. The silicon carbide component added into the overglaze can improve the high thermal conductivity of the whole ceramic tile and provide assistance for the flame retardant property of the ceramic tile.

6. According to the ground coat component, the citric acid acidified kaolin can promote the crystal phase of mullite to be formed in advance at a relatively low temperature, and under the condition, the components of zinc oxide and quartz are added, so that the zinc oxide introduced into the system further promotes the reduction of the mullite synthesis temperature, and the content of the mullite phase is improved; meanwhile, the addition of quartz is beneficial to improving the volume density of mullite. The temperature required by calcination is reduced integrally, the energy consumption is reduced, and meanwhile, the generated product has stronger skeleton rigidity and keeps efficient adsorption structure performance.

7. The design of the tile structure can play a role in continuously helping the internal infiltration absorption and the uniform distribution absorption, is more beneficial to playing the combined action of the four-layer structure of the tile, and achieves a more excellent air purification effect. The structural design of the ceramic tile strengthens the diffusion effect of polluted gas and particles, the absorption of the ceramic tile to the outside is not influenced by concentration and internal adsorption sites, and the increase of the whole adsorption inner surface is equivalent. The ceramic tile disclosed by the invention not only selects the optimal combination of formaldehyde and toluene adsorption performance and antibacterial performance from the components, but also is matched from the external structure, so that the external absorption of the ceramic tile is not influenced by the concentration and the internal adsorption sites, and the purpose of continuously adsorbing and purifying air for 24 hours in a home can be realized.

8. The scientific matching of the four layers of components and the assistance of the structure can realize that the removal rate of formaldehyde is higher than 85% in 24h, the removal rate of ammonia is higher than 80%, the removal rate of toluene is higher than 90%, and the removal rate of particulate matters such as PM2.5 is close to 50%. The decay rate of the tile formaldehyde removal in 7 days is less than 20%, which shows that the long-term effect is stable.

Drawings

1-the embryoid body layer; 2-a ground coat; 3-negative ion glaze layer; 4-cover glaze layer; 5, air vent.

FIG. 1: the invention discloses a structural schematic diagram of a bacteriostatic ceramic tile for removing formaldehyde and toluene;

FIG. 2: the invention discloses a structural schematic diagram of the bottom surface of a blank of an antibacterial ceramic tile for removing formaldehyde and toluene.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.

Example 1

The bacteriostatic ceramic tile for removing formaldehyde and toluene comprises an embryo body layer, a ground glaze layer, a negative ion glaze layer and a surface glaze layer;

the embryo layer comprises the following components in percentage by weight: 20kg of clay, 20kg of kaolin, 5kg of nano hydroxyapatite, 2kg of aluminum hydroxide, 5kg of boron nitride nanosheet, 0.5kg of diatomite and 3kg of functional fiber cloth; the functional fiber cloth is nano silver fiber cloth, nano titanium dioxide fiber cloth and carbon nanotube fiber cloth, and the weight ratio of the nano silver fiber cloth to the nano titanium dioxide fiber cloth to the carbon nanotube fiber cloth is 1.

The ground coat comprises the following components in percentage by weight: 16kg of clay, 20kg of citric acid activated kaolin, 22kg of quartz, 5kg of zinc oxide, 0.1kg of nano silver and 0.1kg of nano bismuth oxysulfide;

the negative ion glaze layer comprises the following components in percentage by weight: 5kg of modified tourmaline powder and 25kg of diatomite;

the overglaze layer comprises the following components in percentage by weight: 12kg of clay, 20kg of quartz, 10kg of mordenite, 8kg of Y-type molecular sieve, 3kg of silicon carbide, 0.1kg of nano-silver and 0.05kg of nano bismuth oxysulfide.

The preparation method of the bacteriostatic ceramic tile for removing formaldehyde and toluene comprises the following steps:

B. taking embryo components: the preparation method comprises the steps of crushing clay, kaolin, nano-hydroxyapatite, aluminum hydroxide, boron nitride nanosheets and diatom opal, adding a proper amount of water, stirring, adding into a mold while uniformly scattering functional fiber cloth, molding and sintering to obtain a blank.

C. Taking a ground coat component: the preparation method comprises the steps of crushing clay, citric acid activated kaolin, quartz and zinc oxide, adding a proper amount of water, stirring, adding nano silver and nano bismuth oxysulfide while stirring to obtain a glaze, spraying glaze on a blank, sintering, and preparing a ground glaze.

D. Taking negative ion glaze layer components: weighing diatomite and modified tourmaline powder, adding a proper amount of water, mixing, grinding in a quick grinding machine for 20-40 min, and performing vacuum drying treatment on the ground negative ion glaze slurry to obtain a negative ion glaze fabric; c, glaze spraying is carried out on the blank obtained in the step C, sintering is carried out, and the preparation of the negative ion glaze layer is finished; wherein the weight ratio of the negative ion glaze layer is as follows.

E. Taking a glaze component: and D, clay, quartz, mordenite, a Y-type molecular sieve and silicon carbide are crushed, a proper amount of water is added and stirred, nano silver and nano bismuth oxysulfide are added while stirring to obtain glaze, the blank subjected to the step D is sprayed with glaze, sintered and overglaze is prepared.

The sintering temperature of the above-mentioned ground coat is between 1000 ℃ and 1100 ℃, and the sintering temperature of other steps is 1200 ℃.

The sintering of the common ceramic tile basically needs the temperature of 1200 ℃ or higher to complete the stability of the crystal form and the composite requirement of various properties. In the ground coat component, the citric acid acidified kaolin can promote the crystal phase of mullite to be formed in advance at a relatively low temperature, and under the condition, the components of zinc oxide and quartz are added, so that the zinc oxide introduced into the system further promotes the reduction of the mullite synthesis temperature and improves the content of the mullite phase; meanwhile, the addition of quartz is beneficial to improving the volume density of mullite. The temperature required by calcination is reduced integrally, the energy consumption is reduced, and meanwhile, the generated product has stronger skeleton rigidity and keeps efficient adsorption structure performance.

The modified tourmaline powder in the negative ion glaze layer in the embodiment is prepared by the following method:

(1) crushing tourmaline, adding water, ball-milling until the tourmaline passes through a 100-mesh sieve, drying, and performing jet milling to obtain tourmaline powder, wherein the mass of the water added during ball milling is 1/8 of that of the tourmaline powder;

(2) adding 10 parts by weight of the tourmaline powder and 15 parts by weight of tetradecene succinic anhydride into 80 parts by weight of N, N-dimethylformamide, ultrasonically vibrating for 35min to obtain an ultrasonic mixed solution, heating the ultrasonic mixed solution to 60 ℃, stirring for 3h, and then distilling under reduced pressure to remove the solvent to obtain tourmaline powder A;

(3) adding 10 parts of tourmaline powder A into 100 parts of deionized water according to parts by weight, stirring and heating to 55 ℃, stirring for 50min, adding 1 part of nano zirconia, heating to 75 ℃, stirring at constant temperature for 2h, heating to reflux, carrying out reflux reaction for 3h, stopping the reaction, carrying out suction filtration, taking filter residues, and drying to obtain the modified tourmaline powder.

In this example, the citric acid-activated kaolin clay in the glaze composition was obtained as follows:

drying and grinding kaolin raw ore, sieving the kaolin raw ore with a 100-mesh sieve, adding kaolin into citric acid with a certain concentration according to the solid-liquid weight ratio of 1. The concentration of citric acid is 1.5mol/L, and the reaction time is 6h.

The method for preparing the nano silver fiber cloth comprises the following specific steps:

(1) taking 50g of sodium dodecyl benzene sulfonate, 200g of polyoxyethylene sorbitan monooleate, 50g of sodium silicate and 600g of nano-silver with the particle size of 30nm, mixing, placing in 10KG purified water, ultrasonically stirring at high speed for dispersing for 3h, adding 800g of high-temperature glue, and mixing to obtain a mixed material;

(2) adding chopped fiber cloth into the mixed material, wherein the area size of the chopped fiber cloth is 1 x 5mm-1 x 8mm;

(3) filtering, and oven drying the fiber cloth.

The preparation method of the nano titanium dioxide fiber cloth comprises the following specific steps:

(1) placing 2Kg of nano titanium dioxide with the particle size of 30nm in 10Kg of purified water with the pH value of 8.0, stirring for 15 minutes, ultrasonically stirring and dispersing at a high speed for 2 hours, adding 150g of sodium dodecyl benzene sulfonate, and ultrasonically treating for 60 minutes; adding 800g of high-temperature glue, and mixing to obtain a mixed material;

(3) filtering, and oven drying the fiber cloth.

The appropriate amount of water mentioned above can be set according to the purpose of the prior art formulation, and is well known to those skilled in the art and will not be described herein in any unnecessary detail.

Example 2

This example 2 is essentially the same as example 1, except for the differences in weight of the components:

the embryo layer comprises the following components in percentage by weight: 23kg of clay, 25kg of kaolin, 6kg of nano hydroxyapatite, 2kg of aluminum hydroxide, 3kg of boron nitride nanosheets, 1kg of diatomite and 2kg of functional fiber cloth; the functional fiber cloth is nano silver fiber cloth, nano titanium dioxide fiber cloth and carbon nanotube fiber cloth, and the weight ratio of the nano silver fiber cloth to the nano titanium dioxide fiber cloth to the carbon nanotube fiber cloth is 1.

The ground coat layer comprises the following components in percentage by weight: 18kg of clay, 15kg of citric acid activated kaolin, 15kg of quartz, 5kg of zinc oxide, 0.1kg of nano silver and 0.15kg of nano bismuth oxysulfide;

the negative ion glaze layer comprises the following components in percentage by weight: 2kg of modified tourmaline powder and 20kg of diatomite;

the overglaze layer comprises the following components in percentage by weight: 11kg of clay, 22kg of quartz, 11kg of mordenite, 5kg of Y-type molecular sieve, 1kg of silicon carbide, 0.05kg of nano silver and 0.05kg of nano bismuth oxysulfide.

The modified tourmaline powder of example 2 differs from that of example 1 in the step (3):

(3) according to the weight parts, 10 parts of tourmaline powder A is added into 100 parts of deionized water, the mixture is stirred and heated to 55 ℃, stirred for 50min, 0.5 part of nano zirconia is added, the mixture is heated to 75 ℃, stirred for 2h at constant temperature, heated to reflux, refluxed and reacted for 3h, the reaction is stopped, filtered, filter residue is taken out, and dried, and the modified tourmaline powder is obtained.

drying and grinding kaolin raw ore, sieving the kaolin raw ore with a 100-mesh sieve, adding kaolin into citric acid with a certain concentration according to the solid-liquid weight ratio of 1. The concentration of the citric acid is 1.5mol/L, and the reaction time is 7h.

Example 3

This example 3 is essentially the same as example 1, except for the differences in weight of the components:

the embryo layer comprises the following components in percentage by weight: 18kg of clay, 22kg of kaolin, 6kg of nano hydroxyapatite, 3kg of aluminum hydroxide, 6kg of boron nitride nanosheet, 1kg of diatomite and 3kg of functional fiber cloth; the functional fiber cloth is nano silver fiber cloth, nano titanium dioxide fiber cloth and carbon nanotube fiber cloth, and the weight ratio of the nano silver fiber cloth to the nano titanium dioxide fiber cloth to the carbon nanotube fiber cloth is 1.

The ground coat comprises the following components in percentage by weight: 13kg of clay, 20kg of citric acid activated kaolin, 22kg of quartz, 6kg of zinc oxide, 0.1kg of nano silver and 0.15kg of nano bismuth oxysulfide;

the negative ion glaze layer comprises the following components in percentage by weight: 5kg of modified tourmaline powder and 20kg of diatomite;

the overglaze layer comprises the following components in percentage by weight: 10kg of clay, 17kg of quartz, 12kg of mordenite, 7kg of Y-type molecular sieve, 2kg of silicon carbide, 0.1kg of nano silver and 0.15kg of nano bismuth oxysulfide.

drying and grinding kaolin raw ore, sieving the kaolin raw ore with a 100-mesh sieve, adding the kaolin into citric acid with a certain concentration according to the solid-liquid weight ratio of 1 to 13, carrying out ball milling in a planetary mill for a certain time, wherein the ball-material ratio is 5, the ball milling speed is 300r/min, and drying to obtain the citric acid activated kaolin. The concentration of citric acid is 1.5mol/L, and the reaction time is 5h.

In examples 1 and 3, the amount of the functional fiber cloth is the same, the proportion of the functional fiber cloth to other components is similar, and the adding amount of the silicon carbide is mainly changed.

The toughness of the ceramic tile is judged through the impact strength: the toughness of example 1 is the strongest, and the toughness of example 3 is centered; in example 2, the amount of the functional fiber cloth added is reduced as a whole, the amount of the silicon carbide is also reduced, the toughness is the lowest, and the functions of the functional fiber cloth and the silicon carbide are also highlighted in terms of the ratio of the toughness.

Using a zone of inhibition experiment, the tiles of examples 1-3 were cut into small pieces, 2 tiles of the same weight were selected for each example, and were placed in 6 zones of inhibition cultured simultaneously, and the conditions of inhibition were observed, and the bacteriostatic, sterilizing and purifying abilities of examples 1-3 were all very strong after standing for 10 days.

The negative ion induction amount of the ceramic tile prepared in the embodiment 1-3 can reach 2200-2680/cm ³ The health grade is grade I. According to the standard of the health organization of the United nations, when the concentration of negative ions in the air reaches 1500/cm ³ The ceramic tile of the invention can reach the concentration within the range of 1-2m when the air is fresh, has better anion induction amount compared with the ceramic product of the anion in the prior art, and proves that good purification effect can be achieved for the indoor air.

As shown in fig. 1 and 2, the ceramic tile of the present invention comprises four layers from bottom to top, which are a blank layer 1, a ground glaze layer 2, a negative ion glaze layer 3 and a surface glaze layer 4; vent hole 5 structures extending towards the inside of the ceramic tile are arranged at intervals at the bottom of the blank layer and close to the peripheral edge; the distance between the vent hole 5 and the edge of the ceramic tile is 0.5-1.5cm, and the aperture of the vent hole is 10-100 mu m.

The design of the vent hole structure is suitable for the entrance of organic pollutants such as formaldehyde, toluene and the like, and simultaneously, particles such as PM2.5 and other peculiar smell agglomerated molecules can enter. More importantly, the design of the structure can help the inner part to permeate and absorb and distribute uniformly, so that the combined action of the four-layer structure of the ceramic tile can be more favorably exerted, and the more excellent air purifying effect can be achieved. The structural design of the ceramic tile strengthens the diffusion effect of polluted gas and particles, the absorption of the ceramic tile to the outside is not influenced by concentration and internal adsorption sites, and the increase of the whole adsorption inner surface is equivalent. The ceramic tile disclosed by the invention not only selects the optimal combination of formaldehyde and toluene adsorption performance and antibacterial performance from the components, but also is matched from the external structure, so that the external absorption of the ceramic tile is not influenced by the concentration and the internal adsorption sites, and the purpose of continuously adsorbing and purifying air for 24 hours in a home can be realized.

The ceramic tile blank body and the glaze layer are tightly combined, the bottom blank is compact, the density is high, the dirt is not easy to seep, the antifouling capacity is strong, and the cleaning are easy.

The ceramic tile provided by the invention has a good effect on improving sleep. The released negative ions can cause the obvious physiological changes of endocrine and nervous systems, and have good regulating effect on autonomic nerve higher centers and vegetative nervous systems. Thereby improving the function of cerebral cortex, revivifying, eliminating fatigue and improving sleep. Effectively adsorb and convert harmful gases such as formaldehyde, methylbenzene and the like, remove harmful particles, get rid of the harm of first-grade gas killer formaldehyde in decoration, and build environment-friendly green healthy new life.

In external design, the invention also adopts a universal unbounded grain-connecting design, bricks are spliced randomly and have unlimited grain connection, the grains of the large-amplitude natural marble are natural, coherent and harmonious, and the natural aesthetics of the real stone is explained. The color-changeable decorative board has 4 specifications of 800X800mm, 600X1200mm, 750X1500mm and 900X1800mm, the color relates to various mainstream modern color gamut, meanwhile, the texture relates to rock, marble, cement and the like, the optimal matching can be realized according to different application areas of different use scenes, and the aesthetic feeling of different vision is created.

The present invention has been described in detail with reference to the embodiments, and it is obvious that the present invention is not limited by the above-mentioned manner, and it is within the scope of the present invention to adopt various modifications of the method concept and technical solution of the present invention, or to directly apply the concept and technical solution of the present invention to other occasions without modification.

Claims

1. The utility model provides a remove antibacterial ceramic tile of formaldehyde toluene which characterized in that: comprises an embryo body layer, a ground glaze layer, a negative ion glaze layer and a surface glaze layer;

the embryo body layer comprises the following components in percentage by weight: 18-23 parts of clay, 20-25 parts of kaolin, 5-6 parts of nano hydroxyapatite, 2-3 parts of aluminum hydroxide, 3-6 parts of boron nitride nanosheet, 0.5-1 part of diatomite and 2-3 parts of functional fiber cloth;

the ground coat layer comprises the following components in percentage by weight: 12-18 parts of clay, 15-20 parts of citric acid activated kaolin, 15-22 parts of quartz, 5-6 parts of zinc oxide, 0.05-0.1 part of nano silver and 0.05-0.15 part of nano bismuth oxysulfide;

the overglaze layer comprises the following components in percentage by weight: 10-12 parts of clay, 15-22 parts of quartz, 10-12 parts of mordenite, 5-8 parts of Y-type molecular sieve, 1-3 parts of silicon carbide, 0.05-0.1 part of nano silver and 0.05-0.15 part of nano bismuth oxysulfide;

the functional fiber cloth of the embryo body layer is nano silver fiber cloth, nano titanium dioxide fiber cloth and carbon nanotube fiber cloth, and the weight ratio of the nano silver fiber cloth to the nano titanium dioxide fiber cloth to the carbon nanotube fiber cloth is 1;

the modified tourmaline powder in the negative ion glaze layer is prepared by treating calcium carbide gas powder with tetradecene succinic anhydride and then doping nano-zirconia in the calcium carbide gas powder for modification.

2. The bacteriostatic ceramic tile for removing formaldehyde and toluene according to claim 1, which is characterized in that: the ceramic tile comprises four layers of structures from bottom to top, namely a body layer, a bottom glaze layer, a negative ion glaze layer and a surface glaze layer; vent structures extending towards the inside of the ceramic tile are arranged at intervals at the positions, close to the peripheral edge, of the bottom of the blank layer; the distance between the vent hole and the edge of the ceramic tile is 0.5-1.5cm, and the aperture of the vent hole is 10-100 mu m.

3. The preparation method of the bacteriostatic ceramic tile for removing formaldehyde and toluene as claimed in claim 1, which is characterized by comprising the following steps:

B. taking embryo components: crushing clay, kaolin, nano hydroxyapatite, aluminum hydroxide, boron nitride nanosheets and diatom opals, adding a proper amount of water, stirring, adding into a mold while uniformly scattering functional fiber cloth, molding and sintering to obtain a blank; wherein the weight ratio of the components of the embryo body is as follows: 18-23 parts of clay, 20-25 parts of kaolin, 5-6 parts of nano hydroxyapatite, 2-3 parts of aluminum hydroxide, 3-6 parts of boron nitride nanosheet, 0.5-1 part of diatom opal and 2-3 parts of functional fiber cloth;

D. taking negative ion glaze layer components: weighing diatomite and modified tourmaline powder, adding a proper amount of water, mixing, grinding in a quick grinding machine for 20-40 min, and performing vacuum drying treatment on ground negative ion glaze slurry to obtain a negative ion glaze fabric; c, glaze spraying and sintering the blank obtained in the step C, and finishing the preparation of the negative ion glaze layer; wherein, the weight ratio of the negative ion glaze layer is: 2-5 parts of modified tourmaline powder and 20-25 parts of diatomite;

4. The preparation method of the bacteriostatic ceramic tile for removing formaldehyde and toluene according to claim 3, wherein the modified tourmaline powder in the negative ion glaze layer is prepared by the following steps:

(3) adding 10 parts of tourmaline powder A into 100 parts of deionized water according to parts by weight, stirring and heating to 55 ℃, stirring for 50min, adding 0.5-1 part of nano zirconia, heating to 75 ℃, stirring at constant temperature for 2h, heating to reflux, carrying out reflux reaction for 3h, stopping reaction, carrying out suction filtration, taking filter residue, and drying to obtain the modified tourmaline powder.

5. The preparation method of the bacteriostatic ceramic tile for removing formaldehyde and toluene according to claim 3, characterized in that the citric acid activated kaolin in the ground glaze component is obtained by the following method:

drying and grinding kaolin raw ore, sieving the kaolin raw ore with a 100-mesh sieve, adding the kaolin into citric acid with a certain concentration according to the solid-liquid weight ratio of 1 to 13, carrying out ball milling in a planetary mill for a certain time, wherein the ball-material ratio is 5, the ball milling speed is 300r/min, and drying to obtain the citric acid activated kaolin.

6. The preparation method of the bacteriostatic ceramic tile for removing formaldehyde and toluene according to claim 5, characterized in that the concentration of the citric acid is 1.5mol/L, and the reaction time is 5-7h.

7. The preparation method of the bacteriostatic ceramic tile for removing formaldehyde and toluene according to claim 3, wherein the specific steps for preparing the nano-silver fiber cloth are as follows:

(1) mixing sodium dodecyl benzene sulfonate, polyoxyethylene sorbitan monooleate, sodium silicate and nano silver with the particle size of 20-60nm, placing in purified water, ultrasonically stirring at high speed for dispersing for 1-3h, adding inorganic high-temperature glue, and mixing to obtain a mixed material; wherein, the weight ratio of the sodium dodecyl benzene sulfonate, the polyoxyethylene sorbitan monooleate, the sodium silicate, the purified water and the nano silver is as follows: 0.2-0.8:1.5-3:0.3-0.6:100:6;

(3) filtering, and oven drying the fiber cloth.

8. The preparation method of the bacteriostatic ceramic tile for removing formaldehyde and toluene according to claim 3, wherein the specific steps for preparing the nano titanium dioxide fiber cloth are as follows:

(3) filtering, and oven drying the fiber cloth.