CN106336249B - A kind of antibiotic antistatic Ceramic Tiles and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of antibiotic antistatic Ceramic Tiles and preparation method thereof, the preparation method is the following steps are included: step A, prepare ground coat enamel: by mass percentage, 30 ~ 35% frits, 2 ~ 8% functional agents, 20 ~ 28% lithium porcelain stones, 5 ~ 10% zirconium silicates, 20 ~ 25% kaolin and 10 ~ 12% quartz are uniformly mixed, wet ball grinding obtains pulpous state ground coat enamel after sieving；Step B, prepares overglaze: by mass percentage, 70 ~ 80% frits, 1 ~ 5% conducting powder, 10 ~ 20% kaolin, 5 ~ 8% aluminium oxide, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate being uniformly mixed, wet ball grinding, pulpous state overglaze is obtained after sieving；Step C is burnt into obtain Ceramic Tiles by the ground coat enamel of step A, B preparation and the successive glazing of overglaze in ceramic tile base soil.It is compared with existing Ceramic Tiles, Ceramic Tiles ingredient science produced by the present invention, rationally, performance is stablized for preparation；And the application range of Ceramic Tiles has further been widened so that Ceramic Tiles have excellent antibacterial and antistatic and purification air performance by reasonable collocation conducting powder, deodorant and antibacterial powder.

Description

A kind of antibiotic antistatic Ceramic Tiles and preparation method thereof

Technical field

The present invention relates to quartz technical fields, more particularly to a kind of antibiotic antistatic Ceramic Tiles and its preparation side Method.

Background technique

Bacterium, mould have very big harm to the mankind and animals and plants as pathogen, influence people's health and even jeopardize life Life brings weight huge economic loss.Therefore the research of anti-biotic material and its product increasingly causes the concern of people, antibacterial product Demand will constitute huge market.

Ceramic Tiles are the plate or bulk of techniques production such as to be formed, be sintered by clay and other inorganic non-metallic raw materials Ceramic, for decorating and protecting metope and the ground of building, structures.

But it is also rarely reported the Ceramic Tiles about stable antibacterial functions with good uniformity at present.And existing pottery Ceramic tile is usually the product of simple function, function such as antibacterial, antistatic etc., i.e., a kind of product does not have multiple function, this pole It limits its scope of application greatly, it still needs further improvement.

Summary of the invention

In order to solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of antibiotic antistatic Ceramic Tiles and its preparation sides Method.

The technical problems to be solved by the invention are achieved by the following technical programs:

A kind of antibiotic antistatic Ceramic Tiles and preparation method thereof, the preparation method the following steps are included:

Step A, prepares ground coat enamel: by mass percentage, by 30 ~ 35% frits, 2 ~ 8% functional agents, 20 ~ 28% lithium porcelain stones, 5 ~ 10% zirconium silicate, 20 ~ 25% kaolin and 10 ~ 12% quartz are uniformly mixed, and wet ball grinding obtains pulpous state bottom after crossing 300 ~ 350 meshes Glaze；

Step B, prepares overglaze: by mass percentage, by 70 ~ 80% frits, 1 ~ 5% conducting powder, 10 ~ 20% kaolin, 5 ~ 8% aluminium oxide, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate are uniformly mixed, wet ball grinding, obtain pulpous state overglaze after crossing 300 ~ 350 meshes；

Step C, by the ground coat enamel of step A, B preparation and overglaze using the leaching successive glazing of glaze mode in ceramic tile base soil；Then exist Firing in kiln, firing temperature are 800 ~ 900 DEG C, and firing period is 40 ~ 50min, obtains Ceramic Tiles；

Wherein, the frit is made by the following method: by weight percentage, by 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% boraxs, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 1 ~ 5% kaolin mixed grinding are equal Even, then quick quenching is made after high-temperature fusion.

In the present invention, the feldspar is obtained by mixing by potassium feldspar and albite by weight 3 ~ 5:1 ~ 2.The carbonate It is made of at least one of potassium carbonate, sodium carbonate, barium carbonate, lithium carbonate and calcium carbonate, it is preferable that the carbonate is by carbonic acid Potassium, sodium carbonate, barium carbonate, lithium carbonate and calcium carbonate are obtained by mixing by weight 3:1:3:2:1.The fluoride salt by sodium fluoride, Calcirm-fluoride and lithium fluoride are obtained by mixing by weight 4:2:1.

In the present invention, the conducting powder the preparation method is as follows: by 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphene, 2 ~ 6% aluminium powders, 5 ~ 10% carbon blacks and 3 ~ 8% graphite are sufficiently mixed, wherein the nano-graphene, aluminium powder, carbon The sum of black and graphite weight accounts for the 15 ~ 25% of conducting powder total weight, and suitable butyl acetate is added and is put into ball mill and disperses solution Glue, after discharge, detection, adjustment are configured to the slurry that can be applied；By this slurry coating on substrate, drying and forming-film；Then it puts In nitrogen filled protection atmosphere furnace, 900 ~ 1000 DEG C are warming up to, keeps the temperature 1 ~ 2h；Film is scraped off into the substrate, obtains conductive porous reticulated carbon Film, i.e. conducting powder.

In the present invention, the functional agent can be made by the following method:

(1) it weighs 0.3 ~ 1gC60 powder, measures the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and dense Sulfuric acid mixes in beaker, and beaker is placed in ice-water bath, while with the stirring of the speed of 500 ~ 600rpm, obtaining mixed liquor；Weigh 1 ~ 3g potassium permanganate powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, keeps bath temperature 30 ~ 40 DEG C, react 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, the bag filter dialysis 3 ~ 5 for being then 1000 with molecular cut off It, obtains graphene quantum dot (GQDs) suspension；100 ~ 150rpm speed stirring GQDs suspension, while laser irradiation 30 ~ 60min, laser irradiation power are 0.5 ~ 2W；It is spare；

(2) 50 ~ 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；By Be added dropwise to concentration be 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio be 2 ~ 3:1), 10 ~ 20min is stirred by ultrasonic；Be added dropwise 0.5 ~ 1mol/L sodium hydroxide solution, adjust pH value to 11, then stand, from The heart, with deionized water and ethyl alcohol, alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 80 ~ 120ml aqueous solution；Be added dropwise concentration be 0.005 ~ 0.05mol/L cerous nitrate aqueous solution, it is 0.005 ~ 0.05mol/L zinc nitrate aqueous solution that concentration is added dropwise after 30 ~ 60min, GQDs/Ag₂O aqueous solution, cerous nitrate aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1 ~ 0.2:0.2 ~ 0.4；Continue ultrasound Stirring adjusts mixed solution pH value to 7.0；The hydrazine hydrate that 4 ~ 8mL mass fraction is 50% is added in side ultrasonic agitation, side, 30 ~ 0.5 ~ 1h of reduction reaction at 40 DEG C；And then the hydrazine hydrate that 40 ~ 50mL mass fraction is 50%, the reduction reaction at 85 DEG C is added After 30 ~ 48h；Filtering is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Volume ratio 3 is added later The water and ammonium hydroxide of ~ 5:1 is stirring evenly and then adding into ethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:1 ~ 3), Adjusting pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Be centrifuged and successively with acetone and deionized water Cleaning is precipitated；This is deposited at 80 ~ 90 DEG C dry 2 ~ 4h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/ Ag₂O/Ag-Zn-Ce/SiO₂500 ~ 800 DEG C of 1 ~ 2h of heat treatment of progress under argon atmosphere are placed in, after being cooled to room temperature, are immersed in hydrogen 10 ~ 15min of ultrasound is carried out with 100 ~ 150W of ultrasonic power in fluoric acid, removes surface part silica, is centrifuged and dry, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1 ~ 5；10~ 100W 60 ~ 120min of ultrasound is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, vacuumize → heat (pumpdown time is 20 ~ 30min for pressurized circulation 3 ~ 8 times；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressure maintaining), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, That is antibacterial powder；

(6) antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultrapure water, 2 ~ 3h of ultrasonic agitation obtains uniform stabilization Dispersion liquid, wherein antibacterial powder and the weight ratio of deodorant are 3 ~ 5:2 ~ 4；Substrate with carbon nanotube mesh film is placed in about At 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, idler wheel is rolled around, the homogeneous dispersion is made to be scattered in the carbon In nanotube reticular membrane, due to having hydrophily when carbon nanotube is near 8 DEG C, which is attracted to carbon nanotube mesh Multiple net holes of film；About 25 DEG C are warming up to, carbon nanotube, which has hydrophobicity and drives away to leave by most of moisture, is adsorbed on carbon Antibacterial powder and deodorant in multiple net holes of nanotube reticular membrane；Remove moisture, be placed in confined space, vacuumize → add (pumpdown time is 20 ~ 30min for hot pressurized circulation 3 ~ 5 times；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature It is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressure maintaining), it then will be adsorbed with the carbon nanotube of antibacterial powder and deodorant Reticular membrane scrapes off the substrate, obtains antibacterial-deodorization functions agent.

In the present invention, the functional agent can also be made by the following method:

(1) it weighs 0.3 ~ 1gC60 powder, measures the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and dense Sulfuric acid mixes in beaker, and beaker is placed in ice-water bath, while with the stirring of the speed of 500 ~ 600rpm, obtaining mixed liquor；Weigh 1 ~ 3g potassium permanganate powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, keeps bath temperature 30 ~ 40 DEG C, react 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, the bag filter dialysis 3 ~ 5 for being then 1000 with molecular cut off It, obtains graphene quantum dot (GQDs) suspension；100 ~ 150rpm speed stirring GQDs suspension, while laser irradiation 30 ~ 60min, laser irradiation power are 0.5 ~ 2W；It is spare；

(2) 50 ~ 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；By Be added dropwise to concentration be 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio be 2 ~ 3:1), 10 ~ 20min is stirred by ultrasonic；Be added dropwise 0.5 ~ 1mol/L sodium hydroxide solution, adjust pH value to 11, then stand, from The heart, with deionized water and ethyl alcohol, alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；It is 0.05 ~ 0.5g/ that concentration, which is added dropwise, 100mlZnO quantum dot aqueous solution, ultrasonic power mixing speed respectively halve；It after 60 ~ 90min, stands, filtering is washed with deionized water It washs for several times, vacuum drying obtains GQDs/Ag₂O/ZnO；

(4) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:1 ~ 5；10 ~ 100W ultrasound 60 ~ 120min, it is quiet It sets, deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 3 ~ 8 times (vacuumizing Time is 20 ~ 30min；It being pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressure maintaining), obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder；

(5) antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultrapure water, 2 ~ 3h of ultrasonic agitation obtains uniform stabilization Dispersion liquid, wherein antibacterial powder and the weight ratio of deodorant are 3 ~ 5:2 ~ 4；Substrate with carbon nanotube mesh film is placed in about At 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, idler wheel is rolled around, the homogeneous dispersion is made to be scattered in the carbon In nanotube reticular membrane, due to having hydrophily when carbon nanotube is near 8 DEG C, which is attracted to carbon nanotube mesh Multiple net holes of film；About 25 DEG C are warming up to, carbon nanotube, which has hydrophobicity and drives away to leave by most of moisture, is adsorbed on carbon Antibacterial powder and deodorant in multiple net holes of nanotube reticular membrane；Remove moisture, be placed in confined space, vacuumize → add (pumpdown time is 20 ~ 30min for hot pressurized circulation 3 ~ 5 times；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature It is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressure maintaining), it then will be adsorbed with the carbon nanotube of antibacterial powder and deodorant Reticular membrane scrapes off the substrate, obtains antibacterial-deodorization functions agent.

Wherein, the three-dimensional sponge shape graphene preparation method is as follows: by 3g graphite powder, 1g NaNO3 is in ice-water bath It is uniformly mixed with 98% concentrated sulfuric acid of 250ml, is slowly added to 6g KMnO4.It then heats at 35 DEG C, after stirring 40min, is added 95ml deionized water is warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, and more with 30% H2O2 of 5ml neutralization The color of remaining KMnO4, mixed solution are brown color, filter, are washed repeatedly with deionized water to neutrality, ultrasonic disperse obtains while hot GO；Taking 200ml mass fraction is that the graphene oxide solution of 5mg/ml pours into diameter 25cm, the discoid reaction utensil of high 2cm In, ascorbic acid (VC) 0.5g stirring is added and mixes them thoroughly；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, Graphene oxide Spontaneous Contraction in reaction utensil is cross-linked into three-dimensional sponge structure, and freeze-drying obtains three-dimensional sponge shape flexible Graphene.

Wherein, the deodoriser preparing process is as follows: mixing the raw material of following weight percent: ZrO₂2 ~ 8%, TiO₂ 5~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃ 10~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂ 1 ~ 10%, the big flow circulation horizontal for putting into the exploitation of PUHLER company is sanded It is ground in machine, controls partial size between 10 ~ 300nm, obtain inorganic oxide；Diatomite is dispersed in the water of 100 ~ 200ml In solution, inorganic oxide is added, wherein the weight ratio of the diatomite and inorganic oxide is 1:1 ~ 6,100 ~ 200W ultrasound 100 ~ 300rpm stirs 1 ~ 2h, allows nano material well into diatom soil pores, repeatedly filters cleaning；It is placed in confined space It is interior, carry out vacuumizing → heat pressurized circulation 3 ~ 8 times that (pumpdown time is 20 ~ 30min；It is pressurised into and is passed through high temperature and pressure Gas, gas heating temperature are 80 ~ 90 DEG C, are forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressure maintaining), obtain deodorant.

The invention has the following beneficial effects:

It is compared with existing Ceramic Tiles, Ceramic Tiles ingredient science produced by the present invention, rationally, performance is stablized for preparation, mechanical strong Degree is high, is unlikely to deform and non-aging；And act synergistically by reasonable collocation conducting powder, deodorant and antibacterial powder, the two, So that Ceramic Tiles have excellent antibacterial and antistatic and purification air performance, the application range of Ceramic Tiles has further been widened；

This method loads on three-dimensional grapheme and fixed antibacterial agent, not only prevents its reunion, significantly improves metal nano The stability of the antibacterial agents such as particle can be more preferably dispersed in Ceramic Tiles, and with more efficient antibacterial activity and silver from Son does not overflow oxidation stain；It is compounded with the anti-microbial property of a variety of antibacterial agents simultaneously, has compared to single silver nano antibacterial agent Better antibacterial effect, antibacterial it is lasting；Inorganic oxide main component have more than 10 kinds of magnesium, aluminium, iron etc. it is advantageous to human body micro- Secondary element, since it is a kind of polarity crystalline solid that structure is special, itself can generate electron ion for a long time, and permanently release air is negative Ion achievees the effect that deodorization purifies air.

Specific embodiment

Below by specific preferred embodiment to further illustrate the technical scheme of the present invention.

Embodiment 1

A kind of antibiotic antistatic Ceramic Tiles and preparation method thereof, the preparation method the following steps are included:

Step A, prepares ground coat enamel: by mass percentage, by 30% frit, 8% functional agent, 25% lithium porcelain stone, 5% zirconium silicate, 20% kaolin and 12% quartz are uniformly mixed, and wet ball grinding obtains pulpous state ground coat enamel after crossing 300 ~ 350 meshes；

Step B, prepares overglaze: by mass percentage, by 72% frit, 1% conducting powder, 20% kaolin, 5% aluminium oxide, 1% zinc oxide and 1% zirconium silicate are uniformly mixed, wet ball grinding, obtain pulpous state overglaze after crossing 300 ~ 350 meshes；

Step C, by the ground coat enamel of step A, B preparation and overglaze using the leaching successive glazing of glaze mode in ceramic tile base soil；Then exist Firing in kiln, firing temperature are 800 ~ 900 DEG C, and firing period 45min obtains Ceramic Tiles；

Wherein, the frit is made by the following method: by weight percentage, by 15% quartz, 9% feldspar, 24% boron Sand, 10% carbonate, 30% boric acid, 5% spodumene, 3% fluoride salt, 4% kaolin mixed grinding are uniform, then high-temperature fusion (1250 ~ 1320 DEG C) quick quenching afterwards, and be broken into graininess to get；Wherein, the feldspar by potassium feldspar and albite by weight 4:1 is obtained by mixing；The carbonate is by potassium carbonate, sodium carbonate, barium carbonate, lithium carbonate and calcium carbonate by weight 3:2:1:2:3 It is obtained by mixing；The fluoride salt is obtained by mixing by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:3；

The ceramic tile base soil is made by the following method: general glaze for glazed tile green body is entered kiln firing, firing period 1170 DEG C of firing temperature, biscuit is made in 30min, spare.

Wherein, the conducting powder is the preparation method is as follows: by 40% epoxy resin, 45% phenolic resin, 1% nano-graphene, 6% Aluminium powder, 5% carbon black and 3% graphite are sufficiently mixed, wherein the sum of the nano-graphene, aluminium powder, carbon black and weight of graphite, which account for, to be led The 15% of electric powder total weight is added suitable butyl acetate and is put into ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to The slurry that can be applied；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warming up to 1000 DEG C, keep the temperature 1.5h；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

Wherein, the functional agent the preparation method is as follows:

(1) 0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 600rpm, obtaining mixed liquor；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, reacts 4h；Fastly 120ml pure water is added in speed, then filtering is dialysed 4 days with the bag filter that molecular cut off is 1000, obtains graphene quantum dot (GQDs) suspension；100rpm speed stirs GQDs suspension, while laser irradiation 40min, and laser irradiation power is 1W；It is standby With；

(2) 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solution；It is added dropwise dense Degree is 0.1mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；1mol/L sodium hydroxide solution is added dropwise, adjusts pH value to 11, then stands, is centrifuged, with deionized water and ethyl alcohol Alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 1gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；It is 0.05mol/L nitre that concentration, which is added dropwise, Sour cerium aqueous solution, it is 0.005mol/L zinc nitrate aqueous solution, GQDs/Ag that concentration is added dropwise after 30min₂O aqueous solution, cerous nitrate Aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1:0.4；Continue to be stirred by ultrasonic, adjusts mixed solution pH value to 7.0；Bian Chao The hydrazine hydrate that 6mL mass fraction is 50%, the reduction reaction 0.5h at 30 DEG C is added in sound stirring, side；And then 45mL matter is added The hydrazine hydrate that score is 50% is measured, at 85 DEG C after reduction reaction 36h；Filtering is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；It is added volume ratio 4:1's later Water and ammonium hydroxide are stirring evenly and then adding into ethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), adjust pH value It is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Be centrifuged and successively cleaned with acetone and deionized water being sunk It forms sediment；This is deposited at 90 DEG C dry 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂600 DEG C of heat treatment 1h of progress under argon atmosphere are placed in, after being cooled to room temperature, are immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 10min is carried out, surface part silica is removed, is centrifuged and dry, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:5；50W ultrasound 100min is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, vacuumize → heat pressurized circulation 3 times (pumpdown time 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(6) (6) prepare deodorant: mixing the raw material of following weight percent: ZrO₂2%, TiO₂15%, SiO₂20%, V₂O₅5%, K₂O 1%, SnO₂5%, Cr₂O₃2%, Al₂O₃12%, Fe₂O₃15%, MgO 12%, Na₂O10%, MnO₂ 1%, investment It is ground in the big flow circulation horizontal sand mill developed to PUHLER company, controls partial size between 10 ~ 300nm, obtain nothing Machine oxide；Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, inorganic oxide is added, wherein the diatomite and nothing The weight ratio of machine oxide is 1:1, and 150W ultrasound 150rpm stirs 2h, allows nano material well into diatom soil pores, more Secondary suction filtration cleaning；It is placed in confined space, carries out vacuumizing → heating 5 (pumpdown time 30min of pressurized circulation；Heating It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), obtain deodorization Agent；

(7) antibacterial powder and deodorant is taken to be scattered in 150ml ultrapure water, ultrasonic agitation 2h obtains uniform stable dispersion Liquid, wherein antibacterial powder and the weight ratio of deodorant are 3:4；When substrate with carbon nanotube mesh film is placed in about 8 DEG C, it will divide Dispersion liquid is added in the substrate of concave shape, meanwhile, idler wheel is rolled around, the homogeneous dispersion is made to be scattered in the carbon nanotube mesh In film, due to having hydrophily when carbon nanotube is near 8 DEG C, which is attracted to multiple nets of carbon nanotube mesh film Hole；About 25 DEG C are warming up to, carbon nanotube, which has hydrophobicity and drives away to leave by most of moisture, is adsorbed on carbon nanotube mesh Antibacterial powder and deodorant in multiple net holes of film；Remove moisture, is placed in confined space, vacuumize → heat pressurized circulation 4 (pumpdown time 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, is resisted Bacterium-deodorization functions agent.

Embodiment 2

A kind of antibiotic antistatic Ceramic Tiles and preparation method thereof, the preparation method the following steps are included:

Step A, prepares ground coat enamel: by mass percentage, by 32% frit, 5% functional agent, 24% lithium porcelain stone, 6% zirconium silicate, 22% kaolin and 11% quartz are uniformly mixed, and wet ball grinding obtains pulpous state ground coat enamel after crossing 300 ~ 350 meshes；

Step B, prepares overglaze: by mass percentage, by 70% frit, 3% conducting powder, 15% kaolin, 7% aluminium oxide, 1% zinc oxide and 3% zirconium silicate are uniformly mixed, wet ball grinding, obtain pulpous state overglaze after crossing 300 ~ 350 meshes；

Step C, by the ground coat enamel of step A, B preparation and overglaze using the leaching successive glazing of glaze mode in ceramic tile base soil；Then exist Firing in kiln, firing temperature are 800 ~ 900 DEG C, and firing period 45min obtains Ceramic Tiles；

Wherein, the frit is made by the following method: by weight percentage, by 15% quartz, 9% feldspar, 24% boron Sand, 10% carbonate, 30% boric acid, 5% spodumene, 3% fluoride salt, 4% kaolin mixed grinding are uniform, then high-temperature fusion (1250 ~ 1320 DEG C) quick quenching afterwards, and be broken into graininess to get；Wherein, the feldspar by potassium feldspar and albite by weight 4:1 is obtained by mixing；The carbonate is by potassium carbonate, sodium carbonate, barium carbonate, lithium carbonate and calcium carbonate by weight 3:2:1:2:3 It is obtained by mixing；The fluoride salt is obtained by mixing by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:3；

The ceramic tile base soil is made by the following method: general glaze for glazed tile green body is entered kiln firing, firing period 1170 DEG C of firing temperature, biscuit is made in 30min, spare.

Wherein, the conducting powder is the preparation method is as follows: by 35% epoxy resin, 43% phenolic resin, 3% nano-graphene, 5% Aluminium powder, 8% carbon black and 6% graphite are sufficiently mixed, wherein the sum of the nano-graphene, aluminium powder, carbon black and weight of graphite, which account for, to be led The 22% of electric powder total weight is added suitable butyl acetate and is put into ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to The slurry that can be applied；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warming up to 1000 DEG C, keep the temperature 1.5h；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

Wherein, the functional agent the preparation method is as follows:

(1) 0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 600rpm, obtaining mixed liquor；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, reacts 4h；Fastly 120ml pure water is added in speed, then filtering is dialysed 4 days with the bag filter that molecular cut off is 1000, obtains graphene quantum dot (GQDs) suspension；100rpm speed stirs GQDs suspension, while laser irradiation 40min, and laser irradiation power is 1W；It is standby With；

(2) 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solution；It is added dropwise dense Degree is 0.2mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；1mol/L sodium hydroxide solution is added dropwise, adjusts pH value to 11, then stands, is centrifuged, with deionized water and ethyl alcohol Alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 2gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；It is 0.03mol/L nitre that concentration, which is added dropwise, Sour cerium aqueous solution, it is 0.03mol/L zinc nitrate aqueous solution, GQDs/Ag that concentration is added dropwise after 30min₂O aqueous solution, cerous nitrate Aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.2:0.3；Continue to be stirred by ultrasonic, adjusts mixed solution pH value to 7.0；Bian Chao The hydrazine hydrate that 6mL mass fraction is 50%, the reduction reaction 0.5h at 30 DEG C is added in sound stirring, side；And then 45mL matter is added The hydrazine hydrate that score is 50% is measured, at 85 DEG C after reduction reaction 36h；Filtering is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.3gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；It is added volume ratio 4:1's later Water and ammonium hydroxide are stirring evenly and then adding into ethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), adjust pH value It is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Be centrifuged and successively cleaned with acetone and deionized water being sunk It forms sediment；This is deposited at 90 DEG C dry 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂600 DEG C of heat treatment 1h of progress under argon atmosphere are placed in, after being cooled to room temperature, are immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 12min is carried out, surface part silica is removed, is centrifuged and dry, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:3；50W ultrasound 100min is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, vacuumize → heat pressurized circulation 5 times (pumpdown time 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(6) it prepares deodorant: mixing the raw material of following weight percent: ZrO₂6%, TiO₂8%, SiO₂15%, V₂O₅ 3%, K₂O 2%, SnO₂3%, Cr₂O₃4%, Al₂O₃15%, Fe₂O₃10%, MgO 20%, Na₂O 6%, MnO₂ 8%, it puts into It is ground in the big flow circulation horizontal sand mill of PUHLER company exploitation, controls partial size between 10 ~ 300nm, obtain inorganic Oxide；Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, be added inorganic oxide, wherein the diatomite with it is inorganic The weight ratio of oxide is 1:3, and 150W ultrasound 150rpm stirs 2h, allows nano material well into diatom soil pores, repeatedly Filter cleaning；It is placed in confined space, carries out vacuumizing → heating 5 (pumpdown time 30min of pressurized circulation；Heating adds For pressure to be passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), obtain deodorant；

(7) antibacterial powder and deodorant is taken to be scattered in 150ml ultrapure water, ultrasonic agitation 2h obtains uniform stable dispersion Liquid, wherein antibacterial powder and the weight ratio of deodorant are 4:3；When substrate with carbon nanotube mesh film is placed in about 8 DEG C, it will divide Dispersion liquid is added in the substrate of concave shape, meanwhile, idler wheel is rolled around, the homogeneous dispersion is made to be scattered in the carbon nanotube mesh In film, due to having hydrophily when carbon nanotube is near 8 DEG C, which is attracted to multiple nets of carbon nanotube mesh film Hole；About 25 DEG C are warming up to, carbon nanotube, which has hydrophobicity and drives away to leave by most of moisture, is adsorbed on carbon nanotube mesh Antibacterial powder and deodorant in multiple net holes of film；Remove moisture, is placed in confined space, vacuumize → heat pressurized circulation 4 (pumpdown time 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, is resisted Bacterium-deodorization functions agent.

Embodiment 3

A kind of antibiotic antistatic Ceramic Tiles and preparation method thereof, the preparation method the following steps are included:

Step A, prepares ground coat enamel: by mass percentage, by 35% frit, 2% functional agent, 20% lithium porcelain stone, 10% zirconium silicate, 25% kaolin and 8% quartz are uniformly mixed, and wet ball grinding obtains pulpous state ground coat enamel after crossing 300 ~ 350 meshes；

Step B, prepares overglaze: by mass percentage, by 63% frit, 5% conducting powder, 20% kaolin, 8% aluminium oxide, 1% zinc oxide and 3% zirconium silicate are uniformly mixed, wet ball grinding, obtain pulpous state overglaze after crossing 300 ~ 350 meshes；

Step C, by the ground coat enamel of step A, B preparation and overglaze using the leaching successive glazing of glaze mode in ceramic tile base soil；Then exist Firing in kiln, firing temperature are 800 ~ 900 DEG C, and firing period 45min obtains Ceramic Tiles；

Wherein, the frit is made by the following method: by weight percentage, by 15% quartz, 9% feldspar, 24% boron Sand, 10% carbonate, 30% boric acid, 5% spodumene, 3% fluoride salt, 4% kaolin mixed grinding are uniform, then high-temperature fusion (1250 ~ 1320 DEG C) quick quenching afterwards, and be broken into graininess to get；Wherein, the feldspar by potassium feldspar and albite by weight 4:1 is obtained by mixing；The carbonate is by potassium carbonate, sodium carbonate, barium carbonate, lithium carbonate and calcium carbonate by weight 3:2:1:2:3 It is obtained by mixing；The fluoride salt is obtained by mixing by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:3；

The ceramic tile base soil is made by the following method: general glaze for glazed tile green body is entered kiln firing, firing period 1170 DEG C of firing temperature, biscuit is made in 30min, spare.

Wherein, the conducting powder is the preparation method is as follows: by 30% epoxy resin, 45% phenolic resin, 5% nano-graphene, 2% Aluminium powder, 10% carbon black and 8% graphite are sufficiently mixed, wherein the sum of the nano-graphene, aluminium powder, carbon black and weight of graphite account for The 25% of conducting powder total weight is added suitable butyl acetate and is put into ball mill and disperses dispergation, and after discharge, detection, adjustment are prepared At the slurry that can be applied；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, heats up To 1000 DEG C, 1.5h is kept the temperature；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

Wherein, the functional agent the preparation method is as follows:

(1) 0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 600rpm, obtaining mixed liquor；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, reacts 4h；Fastly 120ml pure water is added in speed, then filtering is dialysed 4 days with the bag filter that molecular cut off is 1000, obtains graphene quantum dot (GQDs) suspension；100rpm speed stirs GQDs suspension, while laser irradiation 40min, and laser irradiation power is 1W；It is standby With；

(2) 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solution；It is added dropwise dense Degree is 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；1mol/L sodium hydroxide solution is added dropwise, adjusts pH value to 11, then stands, is centrifuged, with deionized water and ethyl alcohol Alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；It is 0.005mol/L that concentration, which is added dropwise, Cerous nitrate aqueous solution, it is 0.05mol/L zinc nitrate aqueous solution, GQDs/Ag that concentration is added dropwise after 30min₂O aqueous solution, nitric acid Cerium aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.2:0.4；Continue to be stirred by ultrasonic, adjusts mixed solution pH value to 7.0；Side The hydrazine hydrate that 6mL mass fraction is 50%, the reduction reaction 0.5h at 30 DEG C is added in ultrasonic agitation, side；And then 45mL is added The hydrazine hydrate that mass fraction is 50%, at 85 DEG C after reduction reaction 36h；Filtering is washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；It is added volume ratio 4:1's later Water and ammonium hydroxide are stirring evenly and then adding into ethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), adjust pH value It is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively cleaned with acetone and deionized water being sunk It forms sediment；This is deposited at 90 DEG C dry 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂600 DEG C of heat treatment 1h of progress under argon atmosphere are placed in, after being cooled to room temperature, are immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 15min is carried out, surface part silica is removed, is centrifuged and dry, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1；50W ultrasound 100min is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, vacuumize → heat pressurized circulation 8 times (pumpdown time 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(6) it prepares deodorant: mixing the raw material of following weight percent: ZrO₂8%, TiO₂10%, SiO₂18%, V₂O₅ 2%, K₂O 5%, SnO₂1%, Cr₂O₃5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂ 10%, it puts into It is ground in the big flow circulation horizontal sand mill of PUHLER company exploitation, controls partial size between 10 ~ 300nm, obtain inorganic Oxide；Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, be added inorganic oxide, wherein the diatomite with it is inorganic The weight ratio of oxide is 1:6, and 150W ultrasound 150rpm stirs 2h, allows nano material well into diatom soil pores, repeatedly Filter cleaning；It is placed in confined space, carries out vacuumizing → heating 5 (pumpdown time 30min of pressurized circulation；Heating adds For pressure to be passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), obtain deodorant；

(7) antibacterial powder and deodorant is taken to be scattered in 150ml ultrapure water, ultrasonic agitation 2h obtains uniform stable dispersion Liquid, wherein antibacterial powder and the weight ratio of deodorant are 5:2；When substrate with carbon nanotube mesh film is placed in about 8 DEG C, it will divide Dispersion liquid is added in the substrate of concave shape, meanwhile, idler wheel is rolled around, the homogeneous dispersion is made to be scattered in the carbon nanotube mesh In film, due to having hydrophily when carbon nanotube is near 8 DEG C, which is attracted to multiple nets of carbon nanotube mesh film Hole；About 25 DEG C are warming up to, carbon nanotube, which has hydrophobicity and drives away to leave by most of moisture, is adsorbed on carbon nanotube mesh Antibacterial powder and deodorant in multiple net holes of film；Remove moisture, is placed in confined space, vacuumize → heat pressurized circulation 4 (pumpdown time 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, is resisted Bacterium-deodorization functions agent.

Embodiment 4

Based on the preparation method of embodiment 1, the difference is that only: the antibacterial powder is made by the following method:

(1) 0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 600rpm, obtaining mixed liquor；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, reacts 4h；Fastly 120ml pure water is added in speed, then filtering is dialysed 4 days with the bag filter that molecular cut off is 1000, obtains graphene quantum dot (GQDs) suspension；100rpm speed stirs GQDs suspension, while laser irradiation 40min, and laser irradiation power is 1W；It is standby With；

(2) 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solution；It is added dropwise dense Degree is 0.1mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；1mol/L sodium hydroxide solution is added dropwise, adjusts pH value to 11, then stands, is centrifuged, with deionized water and ethyl alcohol Alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 1gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；It is 0.5g/100mlZnO amount that concentration, which is added dropwise, Son point aqueous solution, ultrasonic power mixing speed respectively halve；It after 60min, stands, filtering is washed with deionized for several times, and vacuum is dry It is dry, obtain GQDs/Ag₂O/ZnO；

(4) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:5；50W ultrasound 100min is stood, deionized water For several times, centrifugation is placed in confined space, carries out vacuumizing → heating 3 (pumpdown time 25min of pressurized circulation for washing；Add Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), it obtains GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 5

Based on the preparation method of embodiment 2, the difference is that only: the antibacterial powder is made by the following method:

(1) 0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 600rpm, obtaining mixed liquor；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, reacts 4h；Fastly 120ml pure water is added in speed, then filtering is dialysed 4 days with the bag filter that molecular cut off is 1000, obtains graphene quantum dot (GQDs) suspension；100rpm speed stirs GQDs suspension, while laser irradiation 40min, and laser irradiation power is 1W；It is standby With；

(2) 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solution；It is added dropwise dense Degree is 0.2mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；1mol/L sodium hydroxide solution is added dropwise, adjusts pH value to 11, then stands, is centrifuged, with deionized water and ethyl alcohol Alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 2gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；It is 0.2g/100mlZnO amount that concentration, which is added dropwise, Son point aqueous solution, ultrasonic power mixing speed respectively halve；It after 80min, stands, filtering is washed with deionized for several times, and vacuum is dry It is dry, obtain GQDs/Ag₂O/ZnO；

(4) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:3；50W ultrasound 100min is stood, deionized water For several times, centrifugation is placed in confined space, carries out vacuumizing → heating 5 (pumpdown time 25min of pressurized circulation for washing；Add Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), it obtains GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 6

Based on the preparation method of embodiment 3, the difference is that only: the antibacterial powder is made by the following method:

(1) 0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 600rpm, obtaining mixed liquor；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, reacts 4h；Fastly 120ml pure water is added in speed, then filtering is dialysed 4 days with the bag filter that molecular cut off is 1000, obtains graphene quantum dot (GQDs) suspension；100rpm speed stirs GQDs suspension, while laser irradiation 40min, and laser irradiation power is 1W；It is standby With；

(2) 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solution；It is added dropwise dense Degree is 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；1mol/L sodium hydroxide solution is added dropwise, adjusts pH value to 11, then stands, is centrifuged, with deionized water and ethyl alcohol Alternately three times, vacuum drying obtains GQDs/Ag for washing₂O；

(3) 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；It is 0.05g/100mlZnO amount that concentration, which is added dropwise, Son point aqueous solution, ultrasonic power mixing speed respectively halve；It after 90min, stands, filtering is washed with deionized for several times, and vacuum is dry It is dry, obtain GQDs/Ag₂O/ZnO；

(4) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:1；50W ultrasound 100min is stood, deionized water For several times, centrifugation is placed in confined space, carries out vacuumizing → heating 8 (pumpdown time 25min of pressurized circulation for washing；Add Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressure maintaining 30min), it obtains GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Comparative example 1

Based on the preparation method of embodiment 1, the difference is that: the antibacterial powder is metal antibacterial agent；The deodorant By ZrO₂8%, TiO₂10%, SiO₂18%, V₂O₅2%, K₂O 5%, SnO₂1%, Cr₂O₃5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂ 10%(weight percent) it mixes；Do not add conducting powder.

Comparative example 2

Based on the preparation method of embodiment 4, the difference is that: the antibacterial powder is zinc oxide antibacterial agent；It does not add and removes Smelly dose.

Embodiment 1 ~ 6, comparative example 1 ~ 2 are tested for the property, test result is as follows:

Wear testing: selecting Mohs' hardness is 3~4 abrasive material, rubs 1000 times in Ceramic Tiles and uses 2 to imitate paving Effect after year, tests its sterilization rate.

Heat stability testing: Ceramic Tiles are placed in electric furnace, are raised to 200 DEG C from room temperature, are kept the temperature 20min, put into 25 rapidly In DEG C water, takes out and dry after 10min, test its sterilization rate.

Sterilizing Evaluation for Uniformity: in same Ceramic Tiles choose 100 regions carry out sterilizing test, to the data measured into Row Uniformity Analysis passes through the uniformity=100* (1- standard deviation/average value).When the uniformity be greater than 97%, then labeled as ▲；When The uniformity is greater than 90% and less than 97%, then is labeled as ☆；When the uniformity is lower than 90%, then Biao Ji Wei ╳.

Deodorizing test: preparing two 51PVF resin airbags, one piece of sample print be put into an air bag, another tree Rouge air bag not setting-out piece.Then it is blown into 500ppmNH3- air gas mixture respectively in two air bags and seals, 120min makes With the concentration of NH3 in gas detecting tube measurement air bag, deodorizing rate is calculated.

Radiate performance: detection indicate that, quartz prepared by the present invention meets GB6566-2001 " construction material radiation Property radionuclides limitation " in A class finishing material requirement.

Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations Art scheme should all be fallen within the scope and spirit of the invention.

Claims (3)

1. a kind of preparation method of antibiotic antistatic Ceramic Tiles comprising following steps:

Step A, prepares ground coat enamel: by mass percentage, by 30 ~ 35% frits, 2 ~ 8% functional agents, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium silicate, 20 ~ 25% kaolin and 10 ~ 12% quartz are uniformly mixed, and wet ball grinding obtains pulpous state ground coat enamel after crossing 300 ~ 350 meshes；Institute Stating functional agent is deodorant and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder；

Step B, prepares overglaze: by mass percentage, by 70 ~ 80% frits, 1 ~ 5% conducting powder, 10 ~ 20% kaolin, 5 ~ 8% Aluminium oxide, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate are uniformly mixed, wet ball grinding, obtain pulpous state overglaze after crossing 300 ~ 350 meshes；

Step C, by the ground coat enamel of step A, B preparation and overglaze using the leaching successive glazing of glaze mode in ceramic tile base soil；Then in kiln Firing, firing temperature are 800 ~ 900 DEG C, and firing period is 40 ~ 50min, obtains Ceramic Tiles；

Wherein, the frit is made by the following method: by weight percentage, by 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% borax, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 1 ~ 5% kaolin mixed grinding are uniform, Then quick quenching is made after high-temperature fusion；

Wherein, the conducting powder is the preparation method is as follows: by 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphite Alkene, 2 ~ 6% aluminium powders, 5 ~ 10% carbon blacks and 3 ~ 8% graphite are sufficiently mixed, wherein the nano-graphene, aluminium powder, carbon black and graphite The sum of weight accounts for the 15 ~ 25% of conducting powder total weight, and suitable butyl acetate is added and is put into ball mill and disperses dispergation, after discharge, Detection, adjustment are configured to the slurry that can be applied；By this slurry coating on substrate, drying and forming-film；Then it is placed on nitrogen filled protection In atmosphere furnace, 900 ~ 1000 DEG C are warming up to, keeps the temperature 1 ~ 2h；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e., it is conductive Powder；

The functional agent the preparation method is as follows:

(1) 0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 500 ~ 600rpm, obtaining mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, is then dialysed 3 ~ 5 days, is obtained with the bag filter that molecular cut off is 1000 GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while 30 ~ 60min of laser irradiation, laser irradiation power are 0.5~2W；It is spare；

(2) 50 ~ 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate, and 10 ~ 20min is stirred by ultrasonic；0.5 ~ 1mol/L hydroxide is added dropwise Sodium solution adjusts pH value to 11, then stands, is centrifuged, alternately three times, vacuum drying obtains for washing with deionized water and ethyl alcohol GQDs/Ag₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 80 ~ 120ml aqueous solution；Be added dropwise concentration be 0.005 ~ 0.05mol/L cerous nitrate aqueous solution, it is 0.005 ~ 0.05mol/L zinc nitrate aqueous solution that concentration is added dropwise after 30 ~ 60min；After Continuous ultrasonic agitation adjusts mixed solution pH value to 7.0；The hydrazine hydrate that 4 ~ 8mL mass fraction is 50% is added in side ultrasonic agitation, side, 0.5 ~ 1h of reduction reaction at 30 ~ 40 DEG C；And then the hydrazine hydrate that 40 ~ 50mL mass fraction is 50% is added, at 85 DEG C also After 30 ~ 48h of original reaction；Filtering is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；3 ~ 5:1 of volume ratio is added later Water and ammonium hydroxide, be stirring evenly and then adding into ethyl orthosilicate, adjusting pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 30 ~ 60min；Be centrifuged and successively cleaned with acetone and deionized water being precipitated；This is deposited at 80 ~ 90 DEG C dry 2 ~ 4h, To obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Be placed under argon atmosphere carry out 500 ~ 800 DEG C of 1 ~ 2h of heat treatment, after being cooled to room temperature, be immersed in hydrofluoric acid with 100 ~ 150W of ultrasonic power carry out ultrasound 10 ~ 15min removes surface part silica, is centrifuged and dry, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn-Ce/ SiO₂In aqueous solution；10 ~ 100W, 60 ~ 120min of ultrasound is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, Vacuumize → heat pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(6) antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultrapure water, 2 ~ 3h of ultrasonic agitation obtains uniform stable point Dispersion liquid, wherein antibacterial powder and the weight ratio of deodorant are 3 ~ 5:2 ~ 4；Substrate with carbon nanotube mesh film is placed in about 8 DEG C When, dispersion liquid is added in the substrate of concave shape, meanwhile, idler wheel is rolled around, so that the homogeneous dispersion is scattered in the carbon and receives In mitron reticular membrane, due to having hydrophily when carbon nanotube is near 8 DEG C, which is attracted to carbon nanotube mesh film Multiple net holes；It is warming up to about 25 DEG C, carbon nanotube there is hydrophobicity and drive most of moisture away to leave be adsorbed on carbon and receive Antibacterial powder and deodorant in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, vacuumize → heat Pressurized circulation 3 ~ 5 times, the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, obtains antibacterial- Deodorization functions agent；

The three-dimensional sponge shape graphene preparation method is as follows: by 3g graphite powder, 1g NaNO3 in ice-water bath with 250ml 98% concentrated sulfuric acid is uniformly mixed, and is slowly added to 6g KMnO4；It then heats at 35 DEG C, after stirring 40min, 95ml is added and goes Ionized water is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and in 30% H2O2 of 5ml with extra KMnO4, The color of mixed solution is brown color, filters, is washed repeatedly with deionized water to neutrality, ultrasonic disperse obtains GO while hot；It takes 200ml mass fraction is that the graphene oxide solution of 5mg/ml pours into diameter 25cm, in the discoid reaction utensil of high 2cm, is added Ascorbic acid (VC) 0.5g stirring mixes them thoroughly；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, in reaction utensil Graphene oxide Spontaneous Contraction be cross-linked into three-dimensional sponge structure, be freeze-dried, obtain three-dimensional sponge shape graphene flexible；

The deodoriser preparing process is as follows: mixing the raw material of following weight percent: ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂ 10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂ 1 ~ 10%, it puts into the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground Mill controls partial size between 10 ~ 300nm, obtains inorganic oxide；Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, is added Inorganic oxide, wherein the weight ratio of the diatomite and inorganic oxide is 1:1 ~ 6,100 ~ 200W ultrasound, 100 ~ 300rpm is stirred 1 ~ 2h is mixed, allows nano material well into diatom soil pores, repeatedly filters cleaning；It is placed in confined space, is vacuumized → heating pressurized circulation 3 ~ 8 times, obtains deodorant.

2. a kind of preparation method of antibiotic antistatic Ceramic Tiles comprising following steps:

Step A, prepares ground coat enamel: by mass percentage, by 30 ~ 35% frits, 2 ~ 8% functional agents, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium silicate, 20 ~ 25% kaolin and 10 ~ 12% quartz are uniformly mixed, and wet ball grinding obtains pulpous state ground coat enamel after crossing 300 ~ 350 meshes；Institute Stating functional agent is deodorant and GQDs/Ag₂O/ZnO/ Graphene antibiosis powder；

Step B, prepares overglaze: by mass percentage, by 70 ~ 80% frits, 1 ~ 5% conducting powder, 10 ~ 20% kaolin, 5 ~ 8% Aluminium oxide, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate are uniformly mixed, wet ball grinding, obtain pulpous state overglaze after crossing 300 ~ 350 meshes；

Step C, by the ground coat enamel of step A, B preparation and overglaze using the leaching successive glazing of glaze mode in ceramic tile base soil；Then in kiln Firing, firing temperature are 800 ~ 900 DEG C, and firing period is 40 ~ 50min, obtains Ceramic Tiles；

Wherein, the frit is made by the following method: by weight percentage, by 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% borax, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 1 ~ 5% kaolin mixed grinding are uniform, Then quick quenching is made after high-temperature fusion；Wherein,

The conducting powder the preparation method is as follows: by 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphene, 2 ~ 6% aluminium powder, 5 ~ 10% carbon blacks and 3 ~ 8% graphite are sufficiently mixed, wherein the weight of the nano-graphene, aluminium powder, carbon black and graphite The sum of account for the 15 ~ 25% of conducting powder total weight, suitable butyl acetate is added and is put into ball mill and disperses dispergation, after discharge, inspection It surveys, adjustment is configured to the slurry that can be applied；By this slurry coating on substrate, drying and forming-film；Then it is placed on nitrogen filled protection gas In atmosphere furnace, 900 ~ 1000 DEG C are warming up to, keeps the temperature 1 ~ 2h；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e. conducting powder；

The functional agent the preparation method is as follows:

(1) 0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while with the stirring of the speed of 500 ~ 600rpm, obtaining mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept for 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, is then dialysed 3 ~ 5 days, is obtained with the bag filter that molecular cut off is 1000 GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while 30 ~ 60min of laser irradiation, laser irradiation power are 0.5~2W；It is spare；

(2) 50 ~ 60mlGQDs suspension is stirred by ultrasonic, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate, and 10 ~ 20min is stirred by ultrasonic；0.5 ~ 1mol/L hydroxide is added dropwise Sodium solution adjusts pH value to 11, then stands, is centrifuged, alternately three times, vacuum drying obtains for washing with deionized water and ethyl alcohol GQDs/Ag₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；It is 0.05 ~ 0.5g/100mlZnO that concentration, which is added dropwise, Quantum dot aqueous solution, ultrasonic power mixing speed respectively halve；After 60 ~ 90min, standing, filtering is washed with deionized for several times, Vacuum drying, obtains GQDs/Ag₂O/ZnO；

(4) it takes three-dimensional sponge shape graphene ultrasonic agitation to be scattered in aqueous solution, GQDs/Ag is added dropwise₂In O/ZnO aqueous solution； 10 ~ 100W, 60 ~ 120min of ultrasound is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, vacuumize → add Hot pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder；

(5) antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultrapure water, 2 ~ 3h of ultrasonic agitation obtains uniform stable point Dispersion liquid, wherein antibacterial powder and the weight ratio of deodorant are 3 ~ 5:2 ~ 4；Substrate with carbon nanotube mesh film is placed in about 8 DEG C When, dispersion liquid is added in the substrate of concave shape, meanwhile, idler wheel is rolled around, so that the homogeneous dispersion is scattered in the carbon and receives In mitron reticular membrane, due to having hydrophily when carbon nanotube is near 8 DEG C, which is attracted to carbon nanotube mesh film Multiple net holes；It is warming up to about 25 DEG C, carbon nanotube there is hydrophobicity and drive most of moisture away to leave be adsorbed on carbon and receive Antibacterial powder and deodorant in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, vacuumize → heat Pressurized circulation 3 ~ 5 times, the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, obtains antibacterial- Deodorization functions agent；

The three-dimensional sponge shape graphene preparation method is as follows: by 3g graphite powder, 1g NaNO3 in ice-water bath with 250ml 98% concentrated sulfuric acid is uniformly mixed, and is slowly added to 6g KMnO4；It then heats at 35 DEG C, after stirring 40min, 95ml is added and goes Ionized water is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and in 30% H2O2 of 5ml with extra KMnO4, The color of mixed solution is brown color, filters, is washed repeatedly with deionized water to neutrality, ultrasonic disperse obtains GO while hot；It takes 200ml mass fraction is that the graphene oxide solution of 5mg/ml pours into diameter 25cm, in the discoid reaction utensil of high 2cm, is added Ascorbic acid (VC) 0.5g stirring mixes them thoroughly；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, in reaction utensil Graphene oxide Spontaneous Contraction be cross-linked into three-dimensional sponge structure, be freeze-dried, obtain three-dimensional sponge shape graphene flexible；

The deodoriser preparing process is as follows: mixing the raw material of following weight percent: ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂ 10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂ 1 ~ 10%, it puts into the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground Mill controls partial size between 10 ~ 300nm, obtains inorganic oxide；Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, is added Inorganic oxide, wherein the weight ratio of the diatomite and inorganic oxide is 1:1 ~ 6,100 ~ 200W ultrasound, 100 ~ 300rpm is stirred 1 ~ 2h is mixed, allows nano material well into diatom soil pores, repeatedly filters cleaning；It is placed in confined space, is vacuumized → heating pressurized circulation 3 ~ 8 times, obtains deodorant.

3. a kind of antibiotic antistatic Ceramic Tiles, which is characterized in that be made by preparation method as claimed in claim 1 or 2.