CN106242297A

CN106242297A - A kind of antibacterial and deodouring Ceramic Tiles and preparation method thereof

Info

Publication number: CN106242297A
Application number: CN201610748592.4A
Authority: CN
Inventors: 麦浩
Original assignee: Bright Cities And Towns Gaoming District Foshan City New Forms Of Energy New Material Industry Innovation Centers
Current assignee: Bright Cities And Towns Gaoming District Foshan City New Forms Of Energy New Material Industry Innovation Centers
Priority date: 2016-08-29
Filing date: 2016-08-29
Publication date: 2016-12-21

Abstract

The invention discloses a kind of antibacterial and deodouring Ceramic Tiles and preparation method thereof, this preparation method comprises the following steps: step A, prepares ground-coat enamel: by mass percentage, by frit, functional agent, lithium porcelain stone, Zirconium orthosilicate., Kaolin and quartz mix homogeneously, wet ball grinding, obtains pulpous state ground-coat enamel after sieving；Step B, prepares cover-coat enamel: by mass percentage, by frit, deodorizer, Kaolin, aluminium oxide, zinc oxide and Zirconium orthosilicate. mix homogeneously, wet ball grinding, obtains pulpous state cover-coat enamel after sieving；The successively glazing of step C, ground-coat enamel step A, B prepared and cover-coat enamel, in ceramic tile base soil, burns till to obtain Ceramic Tiles.Comparing with existing Ceramic Tiles, the Ceramic Tiles dispensing science that the present invention manufactures, preparation is reasonable, stable performance；And through reasonably arrange in pairs or groups photochromic complex, deodorizer and antibacterial powder so that Ceramic Tiles has excellent antibacterial and purifies air and photochromic properties, has widened the range of application of Ceramic Tiles further.

Description

A kind of antibacterial and deodouring Ceramic Tiles and preparation method thereof

Technical field

The present invention relates to quartz technical field, particularly relate to a kind of antibacterial and deodouring Ceramic Tiles and preparation side thereof Method.

Background technology

Antibacterial, mycete has the biggest harm as pathogen to the mankind and animals and plants, and the health affecting people even jeopardizes life Life, brings great economic loss.Therefore the research of anti-biotic material and goods thereof causes the concern of people, antibacterial product day by day Demand will constitute huge market.

Ceramic Tiles is by clay and other inorganic non-metallic raw materials, through tabular or the bulk of the production of the technique such as molding, sintering Ceramic, for decorating and protect building, the metope of structures and ground.

But, currently also rarely have the Ceramic Tiles reporting the antibacterial functions the most stable about uniformity.And existing pottery Ceramic tile is usually the product of simple function, and function is the most antibacterial, antistatic etc., and i.e. a kind of product does not possess multiple function, this pole Limit greatly its range of application, need to improve further.

Summary of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of antibacterial and deodouring Ceramic Tiles and preparation side thereof Method.

The technical problem to be solved is achieved by the following technical programs:

A kind of antibacterial and deodouring Ceramic Tiles and preparation method thereof, this preparation method comprises the following steps:

Step A, prepares ground-coat enamel: by mass percentage, by 30 ~ 35% frits, 3 ~ 9% functional agents, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium orthosilicate., 20 ~ 25% Kaolin and 10 ~ 12% quartz mix homogeneously, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；

Step B, prepares cover-coat enamel: by mass percentage, by 70 ~ 80% frits, 1 ~ 6% deodorizer, 10 ~ 20% Kaolin, 5 ~ 8% Aluminium oxide, 1 ~ 2% zinc oxide and 1 ~ 5% Zirconium orthosilicate. mix homogeneously, wet ball grinding, obtain pulpous state cover-coat enamel after crossing 300 ~ 350 mesh sieves；

Step C, ground-coat enamel step A, B prepared and cover-coat enamel use and drench the successively glazing of glaze mode in ceramic tile base soil；Then in kiln Burning till, firing temperature is 800 ~ 900 DEG C, and firing period is 40 ~ 50min, obtains Ceramic Tiles；

Wherein, described frit prepares by the following method: by weight percentage, by 10 ~ 18% quartz, 5 ~ 12% Anhydrites, 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 after high-temperature fusion, quick quenching prepares.

In the present invention, described Anhydrite is obtained by mixing by weight 3 ~ 5:1 ~ 2 by potassium feldspar and albite.Described carbonate It is made up of at least one in potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate, it is preferable that described carbonate is by carbonic acid Potassium, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate are obtained by mixing by weight 3:1:3:2:1.Described fluoride salt by sodium fluoride, Calcium fluoride and lithium fluoride are obtained by mixing by weight 4:2:1.

In the present invention, described deodoriser preparing process is as follows: mix the raw material of following percentage by weight: ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃ 10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂1 ~ 10%, put into the big flow circulation horizontal sand of PUHLER company exploitation Being ground in grinding machine, control particle diameter, between 10 ~ 300nm, obtains inorganic oxide；Kieselguhr is dispersed in 100 ~ 200ml's In aqueous solution, adding inorganic oxide, wherein said kieselguhr is 1:1 ~ 6 with the weight ratio of inorganic oxide, and 100 ~ 200W surpasses Sound 100 ~ 300rpm stirs 1 ~ 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans；It is placed in confined space In, (pumpdown time is 20 ~ 30min to carry out evacuation → heating pressurized circulation 3 ~ 8 times；It is pressurised into and is passed through High Temperature High Pressure Gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min), obtain deodorizer.

In the present invention, described functional agent can prepare by the following method:

(1) weigh 0.3 ~ 1gC60 powder, measure the concentrated sulphuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and concentrated sulphuric acid Mixing in beaker, beaker is placed in ice-water bath, stirs with the speed of 500 ~ 600rpm simultaneously, obtains mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, adds in above-mentioned mixed liquor slowly；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialyse 3 ~ 5 days with the bag filter that molecular cut off is 1000, Graphene quantum dot (GQDs) suspension；100 ~ 150rpm speed stirring GQDs suspension, simultaneously laser irradiation 30 ~ 60min, swash Photoirradiation power is 0.5 ~ 2W；Standby；

(2) ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise add Enter concentration be 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2 ~ 3: 1), ultrasonic agitation 10 ~ 20min；Be added dropwise over 0.5 ~ 1mol/L sodium hydroxide solution, regulation pH value to 11, then stand, from The heart, with deionized water and ethanol alternately washing three times, vacuum drying, obtains GQDs/Ag₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration be 0.005 ~ 0.05mol/L cerous nitrate aqueous solution, being added dropwise over concentration after 30 ~ 60min is 0.005 ~ 0.05mol/L zinc nitrate aqueous solution, 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 ultrasonic Stirring, regulation mixed solution pH value is to 7.0；Limit ultrasonic agitation, it is the hydrazine hydrate of 50% that limit adds 4 ~ 8mL mass fraction, 30 ~ Reduction reaction 0.5 ~ 1h at 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fraction is 50%, reduction reaction at 85 DEG C are added After 30 ~ 48h；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:1 ~ 3), regulation PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；It is centrifuged and cleans with acetone and deionized water successively Obtain precipitation；This is deposited at 80 ~ 90 DEG C and is dried 2 ~ 4h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/ Ag₂O/Ag-Zn-Ce/SiO₂It is placed under argon gas atmosphere and carries out 500 ~ 800 DEG C of heat treatment 1 ~ 2h, after being cooled to room temperature, be immersed in hydrogen Fluoric acid carries out ultrasonic 10 ~ 15min with ultrasonic power 100 ~ 150W, removes local, surface silicon dioxide, be centrifuged and be dried, it is thus achieved that GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/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 Ultrasonic 60 ~ 120min, stands, and deionized water wash is for several times, centrifugal, is placed in confined space, carries out evacuation → heating pressurization Circulate that (pumpdown time is 20 ~ 30min 3 ~ 8 times；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, the most anti- Mycopowder；

(6) taking antibacterial powder and photochromic complex is scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains the most even Stable dispersion liquid, wherein the weight ratio of antibacterial powder and photochromic complex is 5 ~ 10:1 ~ 6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this dispersion liquid Being dispersed in this carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is adsorbed Multiple net holes at carbon nanotube mesh film；Being warming up to about 25 DEG C, CNT has hydrophobicity and is caught up with by most of moisture Walk to stay absorption antibacterial powder and photochromic complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Closing in space, (pumpdown time is 20 ~ 30min to carry out evacuation → heating pressurized circulation 3 ~ 5 times；It is pressurised into and is passed through height Temperature gases at high pressure, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min), then will be adsorbed with The carbon nanotube mesh film of antibacterial powder and photochromic complex scrapes off this substrate, it is thus achieved that antibacterial-photochromic function agent.

In the present invention, described functional agent can also prepare by the following method:

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

(4) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:1 ~ 5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, Deionized water wash is for several times, centrifugal, is placed in confined space, carries out evacuation → heating pressurized circulation 3 ~ 8 times (pumpdown time It is 20 ~ 30min；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, Pressurize 20 ~ 30min), obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder；

(5) taking antibacterial powder and photochromic complex is scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains the most even Stable dispersion liquid, wherein the weight ratio of antibacterial powder and photochromic complex is 5 ~ 10:1 ~ 6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this dispersion liquid Being dispersed in this carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is adsorbed Multiple net holes at carbon nanotube mesh film；Being warming up to about 25 DEG C, CNT has hydrophobicity and is caught up with by most of moisture Walk to stay absorption antibacterial powder and photochromic complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Closing in space, (pumpdown time is 20 ~ 30min to carry out evacuation → heating pressurized circulation 3 ~ 5 times；It is pressurised into and is passed through height Temperature gases at high pressure, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min), then will be adsorbed with The carbon nanotube mesh film of antibacterial powder and photochromic complex scrapes off this substrate, it is thus achieved that antibacterial-photochromic function agent.

Wherein, described three-dimensional sponge shape graphene preparation method is as follows: by 3g graphite powder, 1g NaNO3 is in ice-water bath Mix homogeneously with 250ml 98% concentrated sulphuric acid, be slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml deionized water, is warming up to 98 DEG C of reaction 20min；Add the dilution of 270ml water, and with in 5ml 30% H2O2 and many Remaining KMnO4, the color of mixed solution is brown color, filtered while hot, and with deionized water cyclic washing to neutral, ultrasonic disperse obtains GO；Take the graphene oxide solution that 200ml mass fraction is 5mg/ml and pour the discoid reaction utensil of diameter 25cm, high 2cm into In, add ascorbic acid (VC) 0.5g stirring and make it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, Graphene oxide Spontaneous Contraction in reaction utensil is cross-linked into three-dimensional sponge structure, lyophilization, obtains the three-dimensional sponge shape of flexibility Graphene.

Wherein, described photochromic complex preparation method is as follows: under nitrogen environment, is 0.05 ~ 0.5mol/L by concentration Protonic acid solution and DBSA that concentration is 0.05 ~ 0.5mol/L mix with volume ratio 3:1 ~ 3, be simultaneously introduced light Mutagens toner, adds aniline after magnetic agitation 60 ~ 120min, photochromic powder and aniline mass ratio are 1:5 ~ 10；Continuously stirred After 60 ~ 90min, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C； Acetone, deionized water wash final vacuum for several times is dried, nano polyaniline/photochromic flour complexes of milling to obtain；By 1 ~ 10g nanometer Polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, stir Add tetraethyl orthosilicate (being 5:1 ~ 3 with the mass ratio of nano polyaniline/photochromic flour complexes) after mixing uniformly, regulate pH value Being 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged and cleans with acetone and deionized water successively obtaining Precipitation；This is deposited at 90 DEG C and is dried 3h, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nanometer polyphenyl Amine/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove polyaniline, light Mutagens toner/porous SiO₂, the most photochromic complex.

Described photochromic powder is rare earth oxide, and described rare earth oxide is Nd₂O₃、Er₂O₃、Pr₂O₃、CeO₂、Sm₂O₃、 La₂O₃、Y₂O₃、Yb₂O₃In at least one.

There is advantages that

Comparing with existing Ceramic Tiles, the Ceramic Tiles dispensing science that the present invention manufactures, preparation is reasonable, stable performance, mechanical strength height, It is unlikely to deform and is difficult to aging；And through reasonably arrange in pairs or groups photochromic complex, deodorizer and antibacterial powder, both are collaborative makees With so that Ceramic Tiles has excellent antibacterial and deodorization purifies air and photochromic properties, has widened Ceramic Tiles further Range of application；

This method loads on three-dimensional grapheme and fixes antibacterial, not only prevents it from reuniting, significantly improves metal nanoparticle Stability Deng antibacterial so that it is can more preferably be dispersed in Ceramic Tiles, and there is more efficient antibacterial activity and silver ion not Oxidation stain can be overflowed；It is compounded with the anti-microbial property of multiple antibacterial simultaneously, has more compared to single silver nano antibacterial agent Good antibacterial effect, antibacterial persistently；Inorganic oxide main component has the trace unit that magnesium, aluminum, ferrum etc. more than 10 kind are favourable to human body Element, owing to it is the special polarity crystalline solid of a kind of structure, self can produce electron ion for a long time, and forever release air bear from Son, reaches deodorization and purifies the effect of air；Photochromic complex has photochromic effect, makes product more abundant many Coloured silk, utilizing its Ceramic Tiles produced is that the Ceramic Tiles using conventional colorants to produce is incomparable, can be strong along with irradiation light Weak difference and the shades of colour that changes, be a splendid legacy, full of magnificent carriage, beautiful mystery, pure and fresh height so that ceramic product seems Refined, intersperse city night life, increase sentiment and artistic effect to building and interior decoration.

Detailed description of the invention

Technical scheme is further illustrated below by concrete preferred implementation.

Embodiment 1

Step A, prepares ground-coat enamel: by mass percentage, by 30% frit, 9% functional agent, 24% lithium porcelain stone, 5% Zirconium orthosilicate., 20% height Ridge soil and 12% quartz mix homogeneously, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；

Step B, prepares cover-coat enamel: by mass percentage, by 72% frit, 1% deodorizer, 20% Kaolin, 5% aluminium oxide, 1% oxygen Change zinc and 1% Zirconium orthosilicate. mix homogeneously, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state cover-coat enamel；

Step C, ground-coat enamel step A, B prepared and cover-coat enamel use and drench the successively glazing of glaze mode in ceramic tile base soil；Then in kiln Burning till, firing temperature is 800 ~ 900 DEG C, and firing period is 45min, obtains Ceramic Tiles；

Wherein, described frit prepares by the following method: by weight percentage, by 15% quartz, 9% Anhydrite, 24% Borax, 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 it is broken into graininess, to obtain final product；Wherein, described Anhydrite is mixed by weight 4:1 by potassium feldspar and albite Close and obtain；Described carbonate is by the mixing of 3:2:1:2:3 by weight of potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate ?；Described fluoride salt is obtained by mixing by weight 4:2:3 by sodium fluoride, calcium fluoride and lithium fluoride；

Described ceramic tile base soil prepares by the following method: general glaze for glazed tile base substrate enters klining, firing period 30min, Firing temperature 1170 DEG C, makes biscuit, standby.

Wherein, the preparation method of described deodorizer is as follows: mix the raw material of following percentage by weight: ZrO₂2%, TiO₂ 15%, SiO₂20%, V₂O₅5%, K₂O 1%, SnO₂5%, Cr₂O₃2%, Al₂O₃12%, Fe₂O₃15%, MgO 12%, Na₂O10%, MnO₂1%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and be ground, control particle diameter 10 ~ Between 300nm, obtain inorganic oxide；Kieselguhr is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein Described kieselguhr is that the ultrasonic 150rpm of 1:1,150W stirs 2h with the weight ratio of inorganic oxide, allows nano material well into silicon In diatomaceous earth hole, repeatedly sucking filtration cleans；It is placed in confined space, carries out evacuation → heating pressurized circulation 5 times (pumpdown time For 30min；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), deodorizer is obtained.

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

(1) weigh 0.6gC60 powder, measure the concentrated sulphuric acid that 100ml mass fraction is 98%, C60 powder and concentrated sulphuric acid are being burnt Mixing in Bei, beaker is placed in ice-water bath, stirs with the speed of 600rpm simultaneously, obtains mixed liquor；Weigh 1g potassium permanganate powder, Add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, react 4h；Quickly add Enter 120ml pure water, filter, then dialyse 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (GQDs) and hang Supernatant liquid；100rpm speed stirring GQDs suspension, simultaneously laser irradiation 40min, laser irradiation power is 1W；Standby；

(2) ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.001mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.1mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 1gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；Being added dropwise over concentration is 0.05mol/L cerous nitrate Aqueous solution, being added dropwise over concentration after 30min is 0.005mol/L zinc nitrate aqueous solution, GQDs/Ag₂O aqueous solution, cerous nitrate are water-soluble Liquid and zinc nitrate aqueous solution volume ratio are 1:0.1:0.4；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic to be stirred Mixing, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide Number is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Afterwards add volume ratio 4:1 water and Ammonia, is stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 10min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂In aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:5；50W is ultrasonic 100min, stands, and deionized water wash is for several times, centrifugal, is placed in confined space, carries out evacuation → heating pressurized circulation 3 times (pumpdown time is 25min；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(6) (6) prepare photochromic complex: under nitrogen environment, by protonic acid solution and the concentration that concentration is 0.4mol/L are The DBSA of 0.3mol/L mixes with volume ratio 3:2, is simultaneously introduced photochromic powder (Nd₂O₃、Pr₂O₃、La₂O₃With Yb₂O₃It is obtained by mixing by weight 1:2:2:1), add aniline after magnetic agitation 90min, photochromic powder with aniline mass ratio is 1:8；After continuously stirred 90min, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；At 20 DEG C～30 DEG C instead Answer 20h；Acetone, deionized water wash final vacuum for several times is dried, nano polyaniline/photochromic flour complexes of milling to obtain；By 6g Nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards Water, is stirring evenly and then adding into tetraethyl orthosilicate (being 5:2 with the mass ratio of nano polyaniline/photochromic flour complexes), regulation PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining Precipitation；This is deposited at 90 DEG C and is dried 3h, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nanometer polyphenyl Amine/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, obtain photochromic Powder/porous SiO₂, the most photochromic complex；

(7) taking antibacterial powder and photochromic complex is scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains the most even stable Dispersion liquid, wherein the weight ratio of antibacterial powder and photochromic complex is 5:6；The substrate with carbon nanotube mesh film is placed in When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this In carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to carbon nano-tube network Multiple net holes of shape film；Being warming up to about 25 DEG C, CNT has hydrophobicity being driven away by most of moisture and stays absorption to exist Antibacterial powder and photochromic complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, carry out (pumpdown time is 30min to evacuation → heating pressurized circulation 4 times；Being pressurised into and be passed through high temperature and high pressure gas, gas heats Temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), then will be adsorbed with antibacterial powder and the carbon of photochromic complex Nanotube reticular membrane scrapes off this substrate, it is thus achieved that antibacterial-photochromic function agent.

Embodiment 2

Step A, prepares ground-coat enamel: by mass percentage, by 32% frit, 6% functional agent, 24% lithium porcelain stone, 5% Zirconium orthosilicate., 22% height Ridge soil and 11% quartz mix homogeneously, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；

Step B, prepares cover-coat enamel: by mass percentage, by 70% frit, 4% deodorizer, 14% Kaolin, 7% aluminium oxide, 1% oxygen Change zinc and 3% Zirconium orthosilicate. mix homogeneously, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state cover-coat enamel；

Wherein, the preparation method of described deodorizer is as follows: mix the raw material of following percentage by weight: ZrO₂6%, TiO₂ 8%, SiO₂15%, V₂O₅3%, K₂O 2%, SnO₂3%, Cr₂O₃4%, Al₂O₃15%, Fe₂O₃10%, MgO 20%, Na₂O 6%, MnO₂8%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and be ground, control particle diameter 10 ~ Between 300nm, obtain inorganic oxide；Kieselguhr is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein Described kieselguhr is that the ultrasonic 150rpm of 1:3,150W stirs 2h with the weight ratio of inorganic oxide, allows nano material well into silicon In diatomaceous earth hole, repeatedly sucking filtration cleans；It is placed in confined space, carries out evacuation → heating pressurized circulation 5 times (pumpdown time For 30min；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), deodorizer is obtained.

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

(2) ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.005mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.2mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 2gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；Being added dropwise over concentration is 0.03mol/L cerous nitrate Aqueous solution, being added dropwise over concentration after 30min is 0.03mol/L zinc nitrate aqueous solution, GQDs/Ag₂O aqueous solution, cerous nitrate are water-soluble Liquid and zinc nitrate aqueous solution volume ratio are 1:0.2:0.3；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic to be stirred Mixing, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide Number is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.3gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Afterwards add volume ratio 4:1 water and Ammonia, is stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 12min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂In aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:3；50W is ultrasonic 100min, stands, and deionized water wash is for several times, centrifugal, is placed in confined space, carries out evacuation → heating pressurized circulation 5 times (pumpdown time is 25min；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(6) prepare photochromic complex: under nitrogen environment, by protonic acid solution and the concentration that concentration is 0.4mol/L be The DBSA of 0.3mol/L mixes with volume ratio 3:2, is simultaneously introduced photochromic powder (Nd₂O₃、Pr₂O₃、La₂O₃With Yb₂O₃It is obtained by mixing by weight 1:2:2:1), add aniline after magnetic agitation 90min, photochromic powder with aniline mass ratio is 1:8；After continuously stirred 90min, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；At 20 DEG C～30 DEG C instead Answer 20h；Acetone, deionized water wash final vacuum for several times is dried, nano polyaniline/photochromic flour complexes of milling to obtain；By 6g Nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards Water, is stirring evenly and then adding into tetraethyl orthosilicate (being 5:2 with the mass ratio of nano polyaniline/photochromic flour complexes), regulation PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining Precipitation；This is deposited at 90 DEG C and is dried 3h, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nanometer polyphenyl Amine/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, obtain photochromic Powder/porous SiO₂, the most photochromic complex；

(7) taking antibacterial powder and photochromic complex is scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains the most even stable Dispersion liquid, wherein the weight ratio of antibacterial powder and photochromic complex is 10:3；The substrate with carbon nanotube mesh film is put In about 8 DEG C time, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this homogeneous dispersion be scattered in In this carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to CNT Multiple net holes of reticular membrane；Being warming up to about 25 DEG C, CNT has hydrophobicity and is driven away by most of moisture and leave absorption Antibacterial powder and photochromic complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, enter (pumpdown time is 30min to row evacuation → heating pressurized circulation 4 times；Being pressurised into and be passed through high temperature and high pressure gas, gas adds Hot temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), then will be adsorbed with antibacterial powder and photochromic complex Carbon nanotube mesh film scrapes off this substrate, it is thus achieved that antibacterial-photochromic function agent.

Embodiment 3

Step A, prepares ground-coat enamel: by mass percentage, by 37% frit, 3% functional agent, 15% lithium porcelain stone, 10% Zirconium orthosilicate., 25% Kaolin and 10% quartz mix homogeneously, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；

Step B, prepares cover-coat enamel: by mass percentage, by 62% frit, 6% deodorizer, 20% Kaolin, 8% aluminium oxide, 1% oxygen Change zinc and 3% Zirconium orthosilicate. mix homogeneously, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state cover-coat enamel；

Wherein, the preparation method of described deodorizer is as follows: mix the raw material of following percentage by weight: ZrO₂8%, TiO₂ 10%, SiO₂18%, V₂O₅2%, K₂O 5%, SnO₂1%, Cr₂O₃5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂10%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and be ground, control particle diameter 10 ~ Between 300nm, obtain inorganic oxide；Kieselguhr is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein Described kieselguhr is that the ultrasonic 150rpm of 1:6,150W stirs 2h with the weight ratio of inorganic oxide, allows nano material well into silicon In diatomaceous earth hole, repeatedly sucking filtration cleans；It is placed in confined space, carries out evacuation → heating pressurized circulation 5 times (pumpdown time For 30min；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), deodorizer is obtained.

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

(2) ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.01mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；Being added dropwise over concentration is 0.005mol/L nitric acid Cerium aqueous solution, being added dropwise over concentration after 30min is 0.05mol/L zinc nitrate aqueous solution, GQDs/Ag₂O aqueous solution, cerous nitrate water Solution and zinc nitrate aqueous solution volume ratio are 1:0.2:0.4；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic Stirring, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass is added Mark is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Afterwards add volume ratio 4:1 water and Ammonia, is stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 15min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂In aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1；50W is ultrasonic 100min, stands, and deionized water wash is for several times, centrifugal, is placed in confined space, carries out evacuation → heating pressurized circulation 8 times (pumpdown time is 25min；Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(7) taking antibacterial powder and photochromic complex is scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains the most even stable Dispersion liquid, wherein the weight ratio of antibacterial powder and photochromic complex is 8:1；The substrate with carbon nanotube mesh film is placed in When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this In carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to carbon nano-tube network Multiple net holes of shape film；Being warming up to about 25 DEG C, CNT has hydrophobicity being driven away by most of moisture and stays absorption to exist Antibacterial powder and photochromic complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, carry out (pumpdown time is 30min to evacuation → heating pressurized circulation 4 times；Being pressurised into and be passed through high temperature and high pressure gas, gas heats Temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), then will be adsorbed with antibacterial powder and the carbon of photochromic complex Nanotube reticular membrane scrapes off this substrate, it is thus achieved that antibacterial-photochromic function agent.

Embodiment 4

Preparation method based on embodiment 1, it the difference is that only: described antibacterial powder prepares by the following method:

(3) 1gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；Being added dropwise over concentration is 0.5g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 60min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO；

(4) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:5；The ultrasonic 100min of 50W, stands, and deionization is washed Wash for several times, centrifugal, it is placed in confined space, (pumpdown time is 25min to carry out evacuation → heating pressurized circulation 3 times；Heating Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), obtain GQDs/ Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 5

Preparation method based on embodiment 2, it the difference is that only: described antibacterial powder prepares by the following method:

(3) 2gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；Being added dropwise over concentration is 0.2g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 80min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO；

(4) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:3；The ultrasonic 100min of 50W, stands, and deionization is washed Wash for several times, centrifugal, it is placed in confined space, (pumpdown time is 25min to carry out evacuation → heating pressurized circulation 5 times；Heating Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), obtain GQDs/ Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 6

Preparation method based on embodiment 3, it the difference is that only: described antibacterial powder prepares by the following method:

(3) 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；Being added dropwise over concentration is 0.05g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 90min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO；

(4) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:1；The ultrasonic 100min of 50W, stands, and deionization is washed Wash for several times, centrifugal, it is placed in confined space, (pumpdown time is 25min to carry out evacuation → heating pressurized circulation 8 times；Heating Being pressurised into and be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min), obtain GQDs/ Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Comparative example 1

Preparation method based on embodiment 1, difference is: described antibacterial powder is metal antibacterial agent；Described photochromic multiple Compound is by Nd₂O₃、Pr₂O₃、La₂O₃And Yb₂O₃It is obtained by mixing by weight 1:2:2:1；Without deodorizer.

Comparative example 2

Preparation method based on embodiment 4, difference is: described antibacterial powder is zinc oxide antibacterial；Described deodorizer is pressed The raw material composition of following percentage by weight: ZrO₂8%, TiO₂10%, SiO₂18%, V₂O₅2%, K₂O 5%, SnO₂1%, Cr₂O₃ 5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂10%。

Embodiment 1 ~ 6, comparative example 1 ~ 2 are carried out performance test, and test result is as follows:

Wear testing: the abrasive material selecting Mohs' hardness to be 3～4, after in Ceramic Tiles, friction imitates paving use for 1000 times 2 years Effect, test its sterilization rate.

Heat stability testing: Ceramic Tiles be placed in electric furnace, is raised to 200 DEG C from room temperature, is incubated 20min, puts into rapidly 25 In DEG C water, take out after 10min and dry, test its sterilization rate.

Sterilizing Evaluation for Uniformity: choose 100 regions in same Ceramic Tiles and carry out sterilizing test, the data recorded are entered Row Uniformity Analysis, by the uniformity=100* (1-standard deviation/meansigma methods).When the uniformity is more than 97%, then be labeled as ▲；When The uniformity more than 90% and less than 97%, is then labeled as ☆；When the uniformity is less than 90%, then it is labeled as.

Deodorizing test: prepare two 51PVF resin airbags, put into one piece of sample print in an air bag, another tree Fat air bag not setting-out sheet.Then being blown into 500ppmNH3-air gas mixture in two air bags respectively and seal, 120min makes Measure the concentration of NH3 in air bag with gas detecting tube, calculate deodorization rate.

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

Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained Art scheme, all should fall within the scope and spirit of the invention.

Claims

1. a preparation method for antibacterial and deodouring Ceramic Tiles, it comprises the following steps:

Step A, prepares ground-coat enamel: by mass percentage, by 30 ~ 35% frits, 3 ~ 9% functional agents, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium orthosilicate., 20 ~ 25% Kaolin and 10 ~ 12% quartz mix homogeneously, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；Institute Stating functional agent is photochromic complex and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder；

Step B, prepares cover-coat enamel: by mass percentage, by 70 ~ 80% frits, 1 ~ 6% deodorizer, 10 ~ 20% Kaolin, 5 ~ 8% oxygen Change aluminum, 1 ~ 2% zinc oxide and 1 ~ 5% Zirconium orthosilicate. mix homogeneously, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state cover-coat enamel；

The preparation method of antibacterial and deodouring Ceramic Tiles the most according to claim 1, it is characterised in that described deodorizer preparation side Method is as follows: mix the raw material of following percentage by weight: ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂1 ~ 10%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and be ground, control particle diameter at 10 ~ 300nm Between, obtain inorganic oxide；Kieselguhr is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein said silicon Diatomaceous earth is 1:1 ~ 6 with the weight ratio of inorganic oxide, and the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 1 ~ 2h, makes nano material abundant Entering in kieselguhr hole, repeatedly sucking filtration cleans；It is placed in confined space, carries out evacuation → heating pressurized circulation 3 ~ 8 times, Deodorizer.

The preparation method of antibacterial and deodouring Ceramic Tiles the most according to claim 1 and 2, it is characterised in that described functional agent Preparation method is as follows:

(1) weigh 0.3 ~ 1gC60 powder, measure the concentrated sulphuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and concentrated sulphuric acid Mixing in beaker, beaker is placed in ice-water bath, stirs with the speed of 500 ~ 600rpm simultaneously, obtains mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, adds in above-mentioned mixed liquor slowly；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialyse 3 ~ 5 days with the bag filter that molecular cut off is 1000, GQDs suspension；100 ~ 150rpm speed stirring GQDs suspension, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 0.5~2W；Standby；

(2) ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise add Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate, ultrasonic agitation 10 ~ 20min；It is added dropwise over 0.5 ~ 1mol/L hydroxide Sodium solution, regulation pH value, to 11, then stands, is centrifuged, and with deionized water and ethanol alternately washing three times, is vacuum dried, GQDs/Ag₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration be 0.005 ~ 0.05mol/L cerous nitrate aqueous solution, being added dropwise over concentration after 30 ~ 60min is 0.005 ~ 0.05mol/L zinc nitrate aqueous solution；Continue Continuous ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit ultrasonic agitation, it is the hydrazine hydrate of 50% that limit adds 4 ~ 8mL mass fraction, Reduction reaction 0.5 ~ 1h at 30 ~ 40 DEG C；Afterwards, add the hydrazine hydrate that 40 ~ 50mL mass fraction is 50%, at 85 DEG C also After former reaction 30 ~ 48h；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 30 ~ 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited at 80 ~ 90 DEG C and is dried 2 ~ 4h, To obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Be placed under argon gas atmosphere carry out 500 ~ 800 DEG C of heat treatment 1 ~ 2h, after being cooled to room temperature, be immersed in Fluohydric acid. with ultrasonic power 100 ~ 150W carry out ultrasonic 10 ~ 15min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

(5) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂In aqueous solution；Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, and deionized water wash is for several times, centrifugal, is placed in confined space, Carry out evacuation → heating pressurized circulation 3 ~ 8 times, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

(6) taking antibacterial powder and photochromic complex is scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains the most even Stable dispersion liquid, wherein the weight ratio of antibacterial powder and photochromic complex is 5 ~ 10:1 ~ 6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this dispersion liquid Being dispersed in this carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is adsorbed Multiple net holes at carbon nanotube mesh film；Being warming up to about 25 DEG C, CNT has hydrophobicity and is caught up with by most of moisture Walk to stay absorption antibacterial powder and photochromic complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out evacuation → heating pressurized circulation 3 ~ 5 times, then will be adsorbed with antibacterial powder and the carbon of photochromic complex Nanotube reticular membrane scrapes off this substrate, it is thus achieved that antibacterial-photochromic function agent.

4. a preparation method for antibacterial and deodouring Ceramic Tiles, it comprises the following steps:

Step A, prepares ground-coat enamel: by mass percentage, by 30 ~ 35% frits, 3 ~ 9% functional agents, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium orthosilicate., 20 ~ 25% Kaolin and 10 ~ 12% quartz mix homogeneously, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；Institute Stating functional agent is photochromic complex and GQDs/Ag₂O/ZnO/ Graphene antibiosis powder；

The preparation method of antibacterial and deodouring Ceramic Tiles the most according to claim 4, it is characterised in that described deodorizer preparation side Method is as follows: mix the raw material of following percentage by weight: ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂1 ~ 10%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and be ground, control particle diameter at 10 ~ 300nm Between, obtain inorganic oxide；Kieselguhr is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein said silicon Diatomaceous earth is 1:1 ~ 6 with the weight ratio of inorganic oxide, and the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 1 ~ 2h, makes nano material abundant Entering in kieselguhr hole, repeatedly sucking filtration cleans；It is placed in confined space, carries out evacuation → heating pressurized circulation 3 ~ 8 times, Deodorizer.

6. according to the preparation method of the antibacterial and deodouring Ceramic Tiles described in claim 4 or 5, it is characterised in that described functional agent Preparation method is as follows:

(4) take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over GQDs/Ag₂In O/ZnO aqueous solution； Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, and deionized water wash is for several times, centrifugal, is placed in confined space, carries out evacuation → add Hot pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder；

(5) taking antibacterial powder and photochromic complex is scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains the most even Stable dispersion liquid, wherein the weight ratio of antibacterial powder and photochromic complex is 5 ~ 10:1 ~ 6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this dispersion liquid Being dispersed in this carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is adsorbed Multiple net holes at carbon nanotube mesh film；Being warming up to about 25 DEG C, CNT has hydrophobicity and is caught up with by most of moisture Walk to stay absorption antibacterial powder and photochromic complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out evacuation → heating pressurized circulation 3 ~ 5 times, then will be adsorbed with antibacterial powder and the carbon of photochromic complex Nanotube reticular membrane scrapes off this substrate, it is thus achieved that antibacterial-photochromic function agent.

7. according to the preparation method of the antibacterial and deodouring Ceramic Tiles described in claim 3 or 6, it is characterised in that described three-dimensional sponge Shape graphene preparation method is as follows: by 3g graphite powder, and 1g NaNO3 is mixed homogeneously with 250ml 98% concentrated sulphuric acid in ice-water bath, It is slowly added to 6g KMnO4；Then heat at 35 DEG C, after stirring 40min, add 95ml deionized water, be warming up to 98 DEG C instead Answer 20min；Add the dilution of 270ml water, and with in 5ml 30% H2O2 and unnecessary KMnO4, the color of mixed solution is brown Yellow, filtered while hot, with deionized water cyclic washing to neutral, ultrasonic disperse obtains GO；Taking 200ml mass fraction is 5mg/ The graphene oxide solution of ml is poured in the discoid reaction utensil of diameter 25cm, high 2cm, adds ascorbic acid (VC) 0.5g stirring Make it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, the graphene oxide Spontaneous Contraction in reaction utensil It is cross-linked into three-dimensional sponge structure, lyophilization, obtains the three-dimensional sponge shape Graphene of flexibility.

8. according to the preparation method of the antibacterial and deodouring Ceramic Tiles described in claim 3 or 6, it is characterised in that described photochromic Complex preparation method is as follows: under nitrogen environment, by protonic acid solution that concentration is 0.05 ~ 0.5mol/L and concentration be 0.05 ~ The DBSA of 0.5mol/L mixes with volume ratio 3:1 ~ 3, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~ Adding aniline after 120min, photochromic powder and aniline mass ratio are 1:5 ~ 10；After continuously stirred 60 ~ 90min, dropwise dripped Ammonium sulfate, aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are for several times Final vacuum is dried, nano polyaniline/photochromic flour complexes of milling to obtain；1 ~ 10g nano polyaniline/photochromic powder is combined Thing ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into positive silicic acid second Ester, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged and successively with acetone and deionization Water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, to obtain nano polyaniline/photochromic flour complexes/SiO₂； By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove Polyaniline, photochromic powder/porous SiO₂, the most photochromic complex.

9. an antibacterial and deodouring Ceramic Tiles, it is characterised in that prepared by the preparation method as described in claim 1 or 4.