CN106365451B - A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, which includes the following steps：Anti-electrostatic antibiotic glaze slip is first prepared, then ceramic glaze is made through glazing, sintering；Wherein, the preparation method of anti-electrostatic antibiotic glaze slip is as follows：By mass percentage, 25 ~ 35% low temperature frits, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% calcium phosphate, 1 ~ 5% kaolin, 5 ~ 10% calcined earths are mixed to get mixed-powder, antibacterial/anti-static function agent is added into mixed-powder and is uniformly mixed, wherein the addition of antibacterial/anti-static function agent is the 0.5 ~ 5% of mixed-powder quality, fine grinding, water is added and obtains glaze slip to get Antistatic antimicrobial ceramic glaze slurry.It is compared with existing ceramic glaze, ceramic glaze dispensing science produced by the present invention, it is reasonable to prepare, performance is stablized, and without containing extremely toxic substances such as lead cadmiums, while also there are the antibacterial characteristics and anti-static function of uniform lasting spectrum, has further widened the application range of ceramic glaze.

Description

A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof

Technical field

The present invention relates to ceramic technology fields, more particularly to a kind of Antistatic antimicrobial ceramic glaze and its preparation side Method.

Background technology

Bacterium, mould have very big harm as pathogen to the mankind and animals and plants, influence people's health and even jeopardize life Life, brings great 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.

Wall brick, no matter household interior decoration, or be used for industrial production or public place, after meeting appearance practicality, How to make it have more concerning health of people guarantee in terms of function and industry researcher keep up with the trend of the times and give birth to Wind vane living and the thinking made.

In the building and ornament materials such as existing wall brick, it is also rarely reported the antibacterial work(preferably stable about uniformity at present The ceramic glaze of energy, if simply adding antiseptic, due to high temperature melting technique so that antibacterial stability weakens, in some instances it may even be possible to lose Remove antibacterial effect.Existing anti-bacteria ceramic does not have with the product that anti-electrostatic ceramic material is usually simple function, i.e., a kind of product Standby multiple function, this strongly limits its application ranges, are arranged in pairs or groups using two kinds of functional agents although also having, effect is still paid no attention to Think, it still needs further improvement.

Invention content

In order to solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of Antistatic antimicrobial ceramic glaze and its preparation sides Method.

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

A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, which includes the following steps：First prepare antistatic Antibacterial glaze slip, then Antistatic antimicrobial ceramic glaze is made through glazing, sintering；Wherein, the preparation method of anti-electrostatic antibiotic glaze slip is as follows： By mass percentage, by 25 ~ 35% low temperature frits, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% Talcum, 2 ~ 5% calcium phosphate, 1 ~ 5% kaolin, 5 ~ 10% calcined earths are mixed to get mixed-powder, into mixed-powder be added antibacterial/ Anti-static function agent is simultaneously uniformly mixed, wherein the addition of the antibacterial/anti-static function agent be mixed-powder quality 0.5 ~ 5%, 300 ~ 350 mesh are finely ground to, it is 1.6 ~ 1.7g/cm that water, which is then added, and obtains glaze slip and modulates glaze slip proportion³It is anti-to get antistatic Bacterium Glaze Slip.

Wherein, the mass percentage composition of the low temperature frit is：6~10% potassium nitrate, 5~10% quartz, 12~15% potassium Feldspar, 3~8% albites, 10~12% spodumenes, 30~35% boric acid, 3~5% barium carbonates, 5~8% fluorites, 1~3% kaolin, 2~5% sodium fluorides and 3 ~ 8% antibacterials/anti-static function agent.

Wherein,

In the present invention, the antibacterial/anti-static function agent can be made by the following method：

（1）It weighs 0.3 ~ 1gC60 powder, measures the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98%, by C60 powder and dense Sulfuric acid mixes in beaker, and beaker is placed in ice-water bath, while being stirred with the speed of 500 ~ 600rpm, obtains mixed liquor；Weigh 1 ~ 3g potassium permanganate powders are 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 that molecular cut off is 1000 is then used 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, a concentration of 0.001 ~ 0.01mol/L silver nitrate aqueous solutions are added dropwise；By It is added dropwise to a concentration of 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（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 solutions, 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）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solutions；It is added dropwise a concentration of 0.005 ~ A concentration of 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions are added dropwise after 30 ~ 60min in 0.05mol/L cerous nitrate aqueous solutions, GQDs/Ag₂O aqueous solutions, 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；Side is stirred by ultrasonic, and the hydrazine hydrate that 4 ~ 8mL mass fractions are 50% is added in side, 30 ~ 0.5 ~ 1h of reduction reaction at 40 DEG C；And then the hydrazine hydrate that 40 ~ 50mL mass fractions are 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 agitations are scattered in aqueous solution；Volume ratio 3 is added later ~5:1 water and ammonium hydroxide, is stirring evenly and then adding into ethyl orthosilicate（With GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:1~3）, It is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Centrifuge and uses acetone and deionized water successively 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/SiO₂It is placed under argon gas atmosphere and carries out 500 ~ 800 DEG C of 1 ~ 2h of heat treatment, after being cooled to room temperature, be immersed in hydrogen 10 ~ 15min of ultrasound is carried out with 100 ~ 150W of ultrasonic power in fluoric acid, removes surface part silica, centrifuges 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 are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, vacuumize → heat Pressurized circulation 3 ~ 8 times（Pumpdown time is 20 ~ 30min；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 pressurize）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, That is antibacterial powder；

（6）Antibacterial powder and conducting powder is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains uniform stabilization Dispersion liquid, wherein the weight ratio of antibacterial powder and conducting powder be 1 ~ 5:3~6；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 when carbon nanotube is near 8 DEG C there is hydrophily, the dispersion liquid to be 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 conducting powder in multiple net holes of nanotube reticular membrane；Remove moisture, be placed in confined space, vacuumize → add Hot pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；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 pressurize）, then will be adsorbed with the carbon nanotube of antibacterial powder and conducting powder Reticular membrane scrapes off the substrate, obtains antibacterial/anti-static function agent.

In the present invention, the antibacterial/anti-static function 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 fractions are 98%, by C60 powder and dense Sulfuric acid mixes in beaker, and beaker is placed in ice-water bath, while being stirred with the speed of 500 ~ 600rpm, obtains mixed liquor；Weigh 1 ~ 3g potassium permanganate powders are 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 that molecular cut off is 1000 is then used 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, a concentration of 0.001 ~ 0.01mol/L silver nitrate aqueous solutions are added dropwise；By It is added dropwise to a concentration of 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（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 solutions, 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）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in aqueous solution；A concentration of 0.05 ~ 0.5g/ is added dropwise 100mlZnO quantum dot aqueous solutions, 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 ultrasounds 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（It vacuumizes 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 pressurize）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder；

（5）Antibacterial powder and conducting powder is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains uniform stabilization Dispersion liquid, wherein the weight ratio of antibacterial powder and conducting powder be 1 ~ 5:3~6；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 when carbon nanotube is near 8 DEG C there is hydrophily, the dispersion liquid to be 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 conducting powder in multiple net holes of nanotube reticular membrane；Remove moisture, be placed in confined space, vacuumize → add Hot pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；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 pressurize）, then will be adsorbed with the carbon nanotube of antibacterial powder and conducting powder 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 powders, 1g NaNO3 are in ice-water bath It is uniformly mixed with 98% concentrated sulfuric acids of 250ml, is slowly added to 6g KMnO4.It then heats at 35 DEG C, after stirring 40min, is added 95ml deionized waters are warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, is used in combination 30% H2O2 of 5ml to neutralize more 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；It is the discoid reaction utensil that the graphene oxide solution of 5mg/ml pours into diameter 25cm, high 2cm to take 200ml mass fractions In, ascorbic acid (VC) 0.5g stirrings, which are added, makes it be sufficiently mixed；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.

In the present invention, the conductive powder, preparation method thereof 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.

The present invention has the advantages that：It compares, ceramic glaze dispensing science produced by the present invention, makes with existing ceramic glaze Standby rationally performance is stablized, and without containing extremely toxic substances such as lead cadmiums, while also having the antibacterial characteristics of uniform lasting spectrum And anti-static function, further widen the application range of ceramic glaze.This method is loaded on three-dimensional grapheme and is fixed anti- Microbial inoculum not only prevents its reunion, significantly improves the stability of the antiseptics such as metal nanoparticle, can more preferably be dispersed in low temperature In frit and glaze slip, and oxidation stain is not overflowed with more efficient antibacterial activity and silver ion；It is compounded with simultaneously a variety of The anti-microbial property of antiseptic has better antibacterial effect compared to single silver nano antibacterial agent, and antibacterial is lasting, and uniformly It is dispersed more preferable；By reasonably combined antibacterial powder and conducting powder, and it is adsorbed in the netted carbon nanotube of multilayer, it can be further Improve dispersing uniformity and functional stabilization of the functional agent in ceramic glaze.

Specific implementation mode

The technical solution further illustrated the present invention below by specific preferred embodiment.

Embodiment 1

A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, which includes the following steps：

Step A, prepares low temperature frit：By mass percentage, 10% potassium nitrate, 7% quartz, 12% potassium feldspar, 5% sodium is long Stone, 10% spodumene, 30% boric acid, 5% barium carbonate, 8% fluorite, 3% kaolin, 2% sodium fluoride and 8% antibacterial/anti-static function agent are mixed Close uniform, quick quenching after being calcined at 1250~1300 DEG C after sieving, ground and mixed, obtained melting temperature 650~ 800 DEG C of low temperature frit；

Step B prepares anti-electrostatic antibiotic glaze slip：By mass percentage, by 30% low temperature frit, 30% potassium feldspar, 10% quartz, 5% calcite, 8% talcum, 4% calcium phosphate, 5% kaolin, 8% calcined earth are mixed to get mixed-powder, to mixing Antibacterial/anti-static function agent is added in powder and is uniformly mixed, is finely ground to 300 ~ 350 mesh, water is then added and obtains glaze slip and modulates Glaze slip proportion is 1.6 ~ 1.7g/cm³It is starched to get Antistatic antimicrobial ceramic glaze；Wherein, the addition of antibacterial/anti-static function agent It is the 0.5% of mixed-powder quality；

Step C, product glazing：By the way of glaze spraying, Antistatic antimicrobial ceramic glaze is sprayed on adobe surface, when glaze spraying For the control of adobe temperature at 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g；

Step D, sintering：The adobe that step B is coated with to Antistatic antimicrobial ceramic glaze is put into roller kilns and is burnt into, firing temperature Degree control is 900 ± 5 DEG C, and firing period is 65 ± 3min.

Wherein, the antibacterial/anti-static function agent is made by the following method：

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

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

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in 100ml aqueous solutions；A concentration of 0.05mol/L nitre is added dropwise A concentration of 0.005mol/L zinc nitrate aqueous solutions, GQDs/Ag is added dropwise after 30min in sour cerium aqueous solution₂O aqueous solutions, cerous nitrate Aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.1:0.4；Continue to be stirred by ultrasonic, adjusts mixed solution pH value to 7.0；Bian Chao Sound stirs, and the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C is added in 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 agitations are scattered in aqueous solution；Volume ratio 4 is added later:1 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；Centrifuge and cleaned with acetone and deionized water successively 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/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 10min is carried out, surface part silica is removed, centrifuges 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 ultrasounds 100min is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 3 times （Pumpdown time is 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, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

（6）Prepare conducting powder：By 40% epoxy resin, 45% phenolic resin, 1% nano-graphene, 6% aluminium powder, 5% carbon black and 3% graphite is sufficiently mixed, wherein the nano-graphene, aluminium powder, carbon black and graphite the sum of weight account for conducting powder total weight 15%, 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 Material；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, heat preservation 1.5h；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e. conducting powder；

（7）Antibacterial powder and conducting powder is taken to be scattered in 150ml ultra-pure waters, ultrasonic agitation 2h obtains the dispersion of uniform stabilization The weight ratio of liquid, wherein antibacterial powder and conducting powder is 1:6；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 when carbon nanotube is near 8 DEG C there is hydrophily, the dispersion liquid to be 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 conducting powder in multiple net holes of film；Remove moisture, is placed in confined space, vacuumize → heat pressurized circulation 4 times（Pumpdown time is 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, pressurize 30min）, the carbon nanotube mesh film for being adsorbed with antibacterial powder and conducting powder is then scraped off into the substrate, is resisted Bacterium/anti-static function agent.

Embodiment 2

A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, which includes the following steps：

Step A, prepares low temperature frit：By mass percentage, 8% potassium nitrate, 8% quartz, 10% potassium feldspar, 6% sodium is long Stone, 11% spodumene, 35% boric acid, 4% barium carbonate, 7% fluorite, 2% kaolin, 4% sodium fluoride and 5% antibacterial/anti-static function agent are mixed Close uniform, quick quenching after being calcined at 1250~1300 DEG C after sieving, ground and mixed, obtained melting temperature 650~ 800 DEG C of low temperature frit；

Step B prepares anti-electrostatic antibiotic glaze slip：By mass percentage, by 25% low temperature frit, 35% potassium feldspar, 15% quartz, 3% calcite, 5% talcum, 4% calcium phosphate, 3% kaolin, 10% calcined earth are mixed to get mixed-powder, to mixed It closes and antibacterial/anti-static function agent is added in powder and is uniformly mixed, be finely ground to 300 ~ 350 mesh, water is then added and obtains glaze slip and adjusts It is 1.6 ~ 1.7g/cm that proportion is starched in enamel frit makeing³It is starched to get Antistatic antimicrobial ceramic glaze；Wherein, the addition of antibacterial/anti-static function agent Amount is the 3% of mixed-powder quality；

Step C, product glazing：By the way of glaze spraying, Antistatic antimicrobial ceramic glaze is sprayed on adobe surface, when glaze spraying For the control of adobe temperature at 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g；

Step D, sintering：The adobe that step B is coated with to Antistatic antimicrobial ceramic glaze is put into roller kilns and is burnt into, firing temperature Degree control is 900 ± 5 DEG C, and firing period is 65 ± 3min.

Wherein, the antibacterial/anti-static function agent is made by the following method：

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

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

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in 100ml aqueous solutions；A concentration of 0.03mol/L nitre is added dropwise A concentration of 0.03mol/L zinc nitrate aqueous solutions, GQDs/Ag is added dropwise after 30min in sour cerium aqueous solution₂O aqueous solutions, cerous nitrate Aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.3；Continue to be stirred by ultrasonic, adjusts mixed solution pH value to 7.0；Bian Chao Sound stirs, and the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C is added in 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 agitations are scattered in aqueous solution；Volume ratio 4 is added later:1 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；Centrifuge and cleaned with acetone and deionized water successively 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/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 12min is carried out, surface part silica is removed, centrifuges 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 ultrasounds 100min is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 5 times （Pumpdown time is 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, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

（6）Prepare conducting powder：By 35% epoxy resin, 43% phenolic resin, 3% nano-graphene, 5% aluminium powder, 8% carbon black and 6% graphite is sufficiently mixed, wherein the nano-graphene, aluminium powder, carbon black and graphite the sum of weight account for conducting powder total weight 22%, 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 Material；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, heat preservation 1.5h；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e. conducting powder；

（7）Antibacterial powder and conducting powder is taken to be scattered in 150ml ultra-pure waters, ultrasonic agitation 2h obtains the dispersion of uniform stabilization The weight ratio of liquid, wherein antibacterial powder and conducting powder is 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 when carbon nanotube is near 8 DEG C there is hydrophily, the dispersion liquid to be 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 conducting powder in multiple net holes of film；Remove moisture, is placed in confined space, vacuumize → heat pressurized circulation 4 times（Pumpdown time is 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, pressurize 30min）, the carbon nanotube mesh film for being adsorbed with antibacterial powder and conducting powder is then scraped off into the substrate, is resisted Bacterium/anti-static function agent.

Embodiment 3

A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, which includes the following steps：

Step A, prepares low temperature frit：By mass percentage, 6% potassium nitrate, 10% quartz, 15% potassium feldspar, 8% sodium is long Stone, 11% spodumene, 33% boric acid, 3% barium carbonate, 5% fluorite, 1% kaolin, 5% sodium fluoride and 3% antibacterial/anti-static function agent are mixed Close uniform, quick quenching after being calcined at 1250~1300 DEG C after sieving, ground and mixed, obtained melting temperature 650~ 800 DEG C of low temperature frit；

Step B prepares anti-electrostatic antibiotic glaze slip：By mass percentage, by 20% low temperature frit, 40% potassium feldspar, 20% quartz, 1% calcite, 3% talcum, 5% calcium phosphate, 3% kaolin, 8% calcined earth are mixed to get mixed-powder, to mixing Antibacterial/anti-static function agent is added in powder and is uniformly mixed, is finely ground to 300 ~ 350 mesh, water is then added and obtains glaze slip and modulates Glaze slip proportion is 1.6 ~ 1.7g/cm³It is starched to get Antistatic antimicrobial ceramic glaze；Wherein, the addition of antibacterial/anti-static function agent It is the 5% of mixed-powder quality；

Step C, product glazing：By the way of glaze spraying, Antistatic antimicrobial ceramic glaze is sprayed on adobe surface, when glaze spraying For the control of adobe temperature at 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g；

Step D, sintering：The adobe that step B is coated with to Antistatic antimicrobial ceramic glaze is put into roller kilns and is burnt into, firing temperature Degree control is 900 ± 5 DEG C, and firing period is 65 ± 3min.

Wherein, the antibacterial/anti-static function agent is made by the following method：

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

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

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in 100ml aqueous solutions；A concentration of 0.005mol/L is added dropwise A concentration of 0.05mol/L zinc nitrate aqueous solutions, GQDs/Ag is added dropwise after 30min in cerous nitrate aqueous solution₂O aqueous solutions, nitric acid Cerium aqueous solution is 1 with zinc nitrate aqueous solution volume ratio: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 fractions are 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 agitations are scattered in aqueous solution；Volume ratio 4 is added later:1 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；Centrifuge and cleaned with acetone and deionized water successively 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/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 15min is carried out, surface part silica is removed, centrifuges 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 ultrasounds 100min is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 8 times （Pumpdown time is 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, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

（6）Prepare conducting powder：By 30% epoxy resin, 45% phenolic resin, 5% nano-graphene, 2% aluminium powder, 10% carbon black and 8% graphite is sufficiently mixed, wherein the nano-graphene, aluminium powder, carbon black and graphite the sum of weight account for conducting powder total weight 25%, 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 Material；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, heat preservation 1.5h；Film is scraped off into the substrate, obtains conductive porous netted carbon film, i.e. conducting powder；

（7）Antibacterial powder and conducting powder is taken to be scattered in 150ml ultra-pure waters, ultrasonic agitation 2h obtains the dispersion of uniform stabilization The weight ratio of liquid, wherein antibacterial powder and conducting powder is 5:3；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 when carbon nanotube is near 8 DEG C there is hydrophily, the dispersion liquid to be 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 conducting powder in multiple net holes of film；Remove moisture, is placed in confined space, vacuumize → heat pressurized circulation 4 times（Pumpdown time is 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, pressurize 30min）, the carbon nanotube mesh film for being adsorbed with antibacterial powder and conducting powder is then scraped off into the substrate, is resisted Bacterium/anti-static function 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 fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, and mixed liquor is obtained；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, keeps 30 ~ 40 DEG C of bath temperature, reacts 4h；Soon 120ml pure water is added in speed, then filtering uses the bag filter that molecular cut off is 1000 to dialyse 4 days, obtains graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, and laser irradiation power is 1W；It is standby With；

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

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in aqueous solution；A concentration of 0.5g/100mlZnO amounts are 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 are stood, deionized water For several times, centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 3 times for washing（Pumpdown time is 25min；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, pressurize 30min）, obtain 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 fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, and mixed liquor is obtained；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, keeps 30 ~ 40 DEG C of bath temperature, reacts 4h；Soon 120ml pure water is added in speed, then filtering uses the bag filter that molecular cut off is 1000 to dialyse 4 days, obtains graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, and laser irradiation power is 1W；It is standby With；

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

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in aqueous solution；A concentration of 0.2g/100mlZnO amounts are 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 are stood, deionized water For several times, centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 5 times for washing（Pumpdown time is 25min；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, pressurize 30min）, obtain 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 fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid It is mixed in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, and mixed liquor is obtained；Weigh 1g potassium permanganate Powder is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, keeps 30 ~ 40 DEG C of bath temperature, reacts 4h；Soon 120ml pure water is added in speed, then filtering uses the bag filter that molecular cut off is 1000 to dialyse 4 days, obtains graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, and laser irradiation power is 1W；It is standby With；

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

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in aqueous solution；A concentration of 0.05g/100mlZnO amounts are 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 are stood, deionized water For several times, centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 8 times for washing（Pumpdown time is 25min；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, pressurize 30min）, obtain 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 only：The antibacterial powder is metal antibacterial agent；It is described to lead Electric powder is obtained by mixing by nano-graphene, aluminium powder, carbon black and graphite.

Comparative example 2

Based on the preparation method of embodiment 4, the difference is that only：The antibacterial powder is zinc oxide antiseptic；Do not add Add conducting powder.

Anti-microbial property test is carried out to the ceramic glaze that embodiment 1 ~ 6, comparative example 1 ~ 2 obtain, test result is as follows：

Sterilization rate：Take 10⁵The Escherichia coli 0.1ml of a/ml, is spread evenly across on ceramic glaze, places 2h indoors, so Bacterium solution is eluted to sterile water in culture medium afterwards, is cultivated at 37 DEG C for 24 hours, bacterium number is then detected, calculates sterilization rate.

Wear testing：It is 3~4 abrasive material to select Mohs' hardness, rubs on ceramic glaze 1000 times and uses 2 to imitate paving Effect after year, tests its sterilization rate.

Heat stability testing：Ceramic glaze is placed in electric furnace, 200 DEG C is raised to from room temperature, keeps the temperature 20min, put into 25 rapidly It takes out and dries in DEG C water, after 10min, test its sterilization rate.

Sterilize Evaluation for Uniformity：100 regions are chosen on same ceramic material and carry out sterilizing test, to the data measured Uniformity Analysis is carried out, is passed through the uniformity=100* (1- standard deviations/average value).When the uniformity be more than 97%, then be labeled as ▲； When the uniformity is more than 90% and less than 97%, is then labeled as ☆；When the uniformity is less than 90%, then Biao Ji Wei ╳.

Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not Therefore it is interpreted as the limitation to the scope of the claims of the present invention, 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 Antistatic antimicrobial ceramic glaze comprising following steps：Anti-electrostatic antibiotic glaze slip is first prepared, then is passed through Antistatic antimicrobial ceramic glaze is made in glazing, sintering；Wherein, the preparation method of anti-electrostatic antibiotic glaze slip is as follows：By mass percentage Meter, by 25 ~ 35% low temperature frits, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% phosphorus Sour calcium, 1 ~ 5% kaolin, 5 ~ 10% calcined earths are mixed to get mixed-powder, and antibacterial/anti-static function agent is added into mixed-powder And be uniformly mixed, wherein the addition of the antibacterial/anti-static function agent is the 0.5 ~ 5% of mixed-powder quality, it is finely ground to 300 ~ 350 mesh, it is 1.6 ~ 1.7g/cm that water, which is then added, and obtains glaze slip and modulates glaze slip proportion³It is starched to get Antistatic antimicrobial ceramic glaze；Institute It includes GQDs/Ag to state antibacterial/anti-static function agent₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder and conducting powder；

The mass percentage composition of the low temperature frit is：6~10% potassium nitrate, 5~10% quartz, 12~15% potassium feldspars, 3~ 8% albite, 10~12% spodumenes, 30~35% boric acid, 3~5% barium carbonates, 5~8% fluorites, 1~3% kaolin, 2~5% fluorine Change sodium and 3 ~ 8% antibacterials/anti-static function agent；

The preparation method of antibacterial/anti-static function agent in the component of the anti-electrostatic antibiotic glaze slip and low temperature frit is as follows：

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

（2）50 ~ 60mlGQDs suspension is stirred by ultrasonic, a concentration of 0.001 ~ 0.01mol/L silver nitrate aqueous solutions are added dropwise；Dropwise plus Enter a concentration of 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min is stirred by ultrasonic；0.5 ~ 1mol/L hydroxides are added dropwise Sodium solution adjusts p H values to 11, then stands, centrifuges, and with deionized water and ethyl alcohol, alternately three times, vacuum drying obtains for washing GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solutions；It is added dropwise a concentration of 0.005 ~ A concentration of 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions are added dropwise after 30 ~ 60min in 0.05mol/L cerous nitrate aqueous solutions；After Continuous ultrasonic agitation adjusts mixed solution p H values to 7.0；Side is stirred by ultrasonic, and the hydration that 4 ~ 8mL mass fractions are 50% is added in side Hydrazine, 0.5 ~ 1h of reduction reaction at 30 ~ 40 DEG C；And then the hydrazine hydrate that 40 ~ 50mL mass fractions are 50% is added, at 85 DEG C After 30 ~ 48h of reduction 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 agitations are scattered in aqueous solution；Volume ratio 3 ~ 5 is added later:1 Water and ammonium hydroxide, be stirring evenly and then adding into ethyl orthosilicate, it is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, reaction 30 ~ 60min；Centrifuge and cleaned with acetone and deionized water successively 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 gas 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 ultrasonic power 100 ~ 150W carry out ultrasound 10 ~ 15min removes surface part silica, centrifuges 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 are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, It carries out vacuumizing → heat pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder； The three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powders, 1g NaNO₃It is dense with 250ml 98% in ice-water bath Sulfuric acid is uniformly mixed, and is slowly added to 6g KMnO₄；It then heats at 35 DEG C, after stirring 40min, 95ml deionizations is added Water is warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, 30% H of 5ml are used in combination₂O₂Neutralize extra KMnO₄, mixing The color of solution is brown color, filters, is washed repeatedly with deionized water to neutrality, ultrasonic disperse obtains GO while hot；Take 200ml Mass fraction is that the graphene oxide solution of 5mg/ml is poured into the discoid reaction utensil of diameter 25cm, high 2cm, and Vitamin C is added Acid (VC) 0.5g stirrings make it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, the oxidation in reaction utensil Graphene Spontaneous Contraction is cross-linked into three-dimensional sponge structure, and freeze-drying obtains three-dimensional sponge shape graphene flexible；

（6）Antibacterial powder and conducting powder is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains point of uniform stabilization The weight ratio of dispersion liquid, wherein antibacterial powder and conducting powder is 1 ~ 5:3~6；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 when carbon nanotube is near 8 DEG C there is hydrophily, the dispersion liquid to be 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 conducting powder in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, vacuumize → heat Then the carbon nanotube mesh film for being adsorbed with antibacterial powder and conducting powder is scraped off the substrate by pressurized circulation 3 ~ 5 times, obtain antibacterial/ Anti-static function agent；

The conduction powder, preparation method thereof 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 nano-graphene, aluminium powder, carbon black and graphite weight 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 stove, 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.

2. a kind of preparation method of Antistatic antimicrobial ceramic glaze comprising following steps：Anti-electrostatic antibiotic glaze slip is first prepared, then is passed through Antistatic antimicrobial ceramic glaze is made in glazing, sintering；Wherein, the preparation method of anti-electrostatic antibiotic glaze slip is as follows：By mass percentage Meter, by 25 ~ 35% low temperature frits, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% phosphorus Sour calcium, 1 ~ 5% kaolin, 5 ~ 10% calcined earths are mixed to get mixed-powder, and antibacterial/anti-static function agent is added into mixed-powder And be uniformly mixed, wherein the addition of the antibacterial/anti-static function agent is the 0.5 ~ 5% of mixed-powder quality, it is finely ground to 300 ~ 350 mesh, it is 1.6 ~ 1.7g/cm that water, which is then added, and obtains glaze slip and modulates glaze slip proportion³It is starched to get Antistatic antimicrobial ceramic glaze；Institute It includes conducting powder and GQDs/Ag to state antibacterial/anti-static function agent₂O/ZnO/ Graphene antibiosis powder；

The mass percentage composition of the low temperature frit is：6~10% potassium nitrate, 5~10% quartz, 12~15% potassium feldspars, 3~ 8% albite, 10~12% spodumenes, 30~35% boric acid, 3~5% barium carbonates, 5~8% fluorites, 1~3% kaolin, 2~5% fluorine Change sodium and 3 ~ 8% antibacterials/anti-static function agent；

The preparation method of antibacterial/anti-static function agent in the component of the anti-electrostatic antibiotic glaze slip and low temperature frit is as follows：

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

（2）50 ~ 60mlGQDs suspension is stirred by ultrasonic, a concentration of 0.001 ~ 0.01mol/L silver nitrate aqueous solutions are added dropwise；Dropwise plus Enter a concentration of 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min is stirred by ultrasonic；0.5 ~ 1mol/L hydroxides are added dropwise Sodium solution adjusts p H values to 11, then stands, centrifuges, and with deionized water and ethyl alcohol, alternately three times, vacuum drying obtains for washing GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in aqueous solution；A concentration of 0.05 ~ 0.5g/100mlZnO 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 solutions； 10 ~ 100W, 60 ~ 120min of ultrasound are 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；The three-dimensional sponge shape graphene system Preparation Method is as follows：By 3g graphite powders, 1g NaNO₃It is uniformly mixed with 98% concentrated sulfuric acids of 250ml in ice-water bath, is slowly added to 6g KMnO₄；It then heats at 35 DEG C, after stirring 40min, 95ml deionized waters is added, be warming up to 98 DEG C of reaction 20min；Again The dilution of 270ml water is added, 30% H of 5ml are used in combination₂O₂Neutralize extra KMnO₄, the color of mixed solution is brown color, while hot mistake Filter, is washed with deionized water to neutrality, ultrasonic disperse obtains GO repeatedly；It is the graphite oxide of 5mg/ml to take 200ml mass fractions Alkene solution pours into the discoid reaction utensil of diameter 25cm, high 2cm, and ascorbic acid (VC) 0.5g stirrings, which are added, keeps it fully mixed It closes；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, and the graphene oxide Spontaneous Contraction in reaction utensil is cross-linked into three-dimensional Sponge structure, freeze-drying, obtains three-dimensional sponge shape graphene flexible；

（5）Antibacterial powder and conducting powder is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains point of uniform stabilization The weight ratio of dispersion liquid, wherein antibacterial powder and conducting powder is 1 ~ 5:3~6；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 when carbon nanotube is near 8 DEG C there is hydrophily, the dispersion liquid to be 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 conducting powder in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, vacuumize → heat Then the carbon nanotube mesh film for being adsorbed with antibacterial powder and conducting powder is scraped off the substrate by pressurized circulation 3 ~ 5 times, obtain antibacterial/ Anti-static function agent；

The conduction powder, preparation method thereof 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 nano-graphene, aluminium powder, carbon black and graphite weight 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 stove, 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.

3. a kind of Antistatic antimicrobial ceramic glaze, which is characterized in that it is made by preparation method as claimed in claim 1 or 2.