CN106365451A - Antistatic and antibacterial ceramic glaze and preparation method thereof - Google Patents

Antistatic and antibacterial ceramic glaze and preparation method thereof Download PDF

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CN106365451A
CN106365451A CN201610748697.XA CN201610748697A CN106365451A CN 106365451 A CN106365451 A CN 106365451A CN 201610748697 A CN201610748697 A CN 201610748697A CN 106365451 A CN106365451 A CN 106365451A
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antibacterial
gqds
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aqueous solution
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CN106365451B (en
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麦浩
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Bright Cities And Towns Gaoming District Foshan City New Forms Of Energy New Material Industry Innovation Centers
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

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  • Geochemistry & Mineralogy (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses an antistatic and antibacterial ceramic glaze and a preparation method thereof. The preparation method includes the following steps of preparing antistatic and antibacterial glaze slip and then carrying out glazing and sintering to obtain the ceramic glaze, wherein the preparation method of the antistatic and antibacterial glaze slip includes the following steps that by mass, 25-35% of low-temperature frit, 30-40% of potassium feldspar, 10-20% of quartz, 3-6% of calcite, 3-6% of talc, 2-5% of calcium phosphate, 1-5% of kaolin and 5-10% of calcined clay are mixed to obtain mixed powder, an antibacterial/antistatic functional agent accounting for 0.5-5% of the mass of the mixed powder is added into the mixed powder and mixed evenly, fine grinding is carried out, water is added to obtain glaze slip, and the antistatic and antibacterial ceramic glaze slip is obtained. Compared with an existing ceramic glaze, the prepared ceramic glaze is scientific in blending, reasonable in preparation and stable in performance; besides, the ceramic glaze does not contain extremely toxic substances such as lead and cadmium and has a uniform and lasting spectral antibacterial property and an antistatic function, and the application range of the ceramic glaze is further widened.

Description

A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof
Technical field
The present invention relates to ceramic technology field, more particularly to a kind of Antistatic antimicrobial ceramic glaze and its preparation side Method.
Background technology
Antibacterial, mycete has very big harm as pathogen to the mankind and animals and plants, and the health of impact people even jeopardizes life Life, brings great economic loss.The research of therefore 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 it is used for commercial production or public place, after meeting outward appearance practicality, How to make it possess more functions of concerning health of people guarantee aspect, be also that industry researcher is kept up with the trend of the times and given birth to Live wind vane and the thinking made.
In the building and ornament materials such as existing wall brick, also it is rarely reported the antibacterial work(preferably stable with regard to uniformity at present The ceramic glaze of energy, if simply add antibacterial, 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 is not had with the product that anti-electrostatic ceramic material is usually simple function, i.e. a kind of product Standby multiple function, be this strongly limits its range of application and is arranged in pairs or groups using two kinds of functional agents although also having, but effect is still paid no attention to Think, need to improve further.
Content of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of Antistatic antimicrobial ceramic glaze and its preparation side Method.
The technical problem to be solved is achieved by the following technical programs:
A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, this preparation method comprises the following steps: first prepares anti-electrostatic antibiotic Glaze slip, then Antistatic antimicrobial ceramic glaze is obtained through glazing, sintering；Wherein, the preparation method of anti-electrostatic antibiotic glaze slip is as follows: by matter Amount percentages, by 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, add antibacterial/anti-quiet in mixed-powder Electricity Functional agent mix homogeneously, the addition of wherein said antibacterial/electrostatic-proof function agent is the 0.5 ~ 5% of mixed-powder quality, It is finely ground to 300 ~ 350 mesh, be subsequently adding water and obtain glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/cm3, obtain final product anti-electrostatic antibiotic pottery Form porcelain glaze slurry.
Wherein, the mass percent of described low temperature frit consists of: 6～10% potassium nitrate, 5～10% quartz, 12～15% potassium Anhydrite, 3～8% albites, 10～12% spodumenes, 30～35% boric acid, 3～5% brium carbonates, 5～8% fluorites, 1～3% Kaolin, 2～5% sodium fluoride and 3 ~ 8% antibacterials/electrostatic-proof function agent.
Wherein,
In the present invention, described antibacterial/electrostatic-proof function agent can be obtained 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 Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain Graphene quantum dot (gqds) suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, swashs Photoirradiation power is 0.5 ~ 2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus 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, adjust ph value to 11, then standing, from The heart, deionized water and ethanol replace washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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 to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8ml mass fraction is 50%, 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), adjust Ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Carry out being centrifuged and being cleaned with acetone and deionized water successively Obtain precipitation；This is deposited at 80 ~ 90 DEG C 2 ~ 4h is dried, 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 In fluoric acid, ultrasonic 10 ~ 15min is carried out with ultrasonic power 100 ~ 150w, remove surface local silicon dioxide, be centrifuged and be dried, obtain 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 than for 1:1 ~ 5；10~100w Ultrasonic 60 ~ 120min, standing, deionized water wash for several times, is centrifuged, is placed in confined space, carries out evacuation → heating pressurization 3 ~ 8 times (pumpdown time is 20 ~ 30min for circulation；It is pressurised into and is 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, that is, resist Mycopowder；
(6) antibacterial powder and conducting powder is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even stable dividing The weight of dispersion liquid, wherein antibacterial powder and conducting powder is than for 1 ~ 5:3 ~ 6；The 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, rolls around roller, make this homogeneous dispersion be scattered in this carbon and receive In mitron reticular membrane, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to carbon nanotube mesh film Multiple net holes；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and stays absorption to receive in carbon Antibacterial powder and conducting powder in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, carry out evacuation → heating 3 ~ 5 times (pumpdown time is 20 ~ 30min to pressurized circulation；It is pressurised into and is 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), then will be adsorbed with the carbon nano-tube network of antibacterial powder and conducting powder Shape film scrapes off this substrate, obtains antibacterial/electrostatic-proof function agent.
In the present invention, described antibacterial/electrostatic-proof function agent can also be obtained 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 Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain Graphene quantum dot (gqds) suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, swashs Photoirradiation power is 0.5 ~ 2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus 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, adjust ph value to 11, then standing, from The heart, deionized water and ethanol replace washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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, standing, 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 of o/zno is than for 1:1 ~ 5；Ultrasonic 60 ~ the 120min of 10 ~ 100w, standing, Deionized water wash for several times, is centrifuged, is placed in confined space, carries out evacuation → heating pressurized circulation 3 ~ 8 times (pumpdown time For 20 ~ 30min；It is pressurised into and is 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) antibacterial powder and conducting powder is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even stable dividing The weight of dispersion liquid, wherein antibacterial powder and conducting powder is than for 1 ~ 5:3 ~ 6；The 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, rolls around roller, make this homogeneous dispersion be scattered in this carbon and receive In mitron reticular membrane, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to carbon nanotube mesh film Multiple net holes；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and stays absorption to receive in carbon Antibacterial powder and conducting powder in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, carry out evacuation → heating 3 ~ 5 times (pumpdown time is 20 ~ 30min to pressurized circulation；It is pressurised into and is 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), then will be adsorbed with the carbon nano-tube network of antibacterial powder and conducting powder Shape film scrapes off this substrate, obtains antibacterial-deodorization functions 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 270ml water dilution, and with 5ml 30% h2o2 with many Remaining kmno4, the color of mixed solution is brown color, filtered while hot, and deionized water cyclic washing obtains to neutrality, ultrasonic disperse go；The graphene oxide solution that 200ml mass fraction is 5mg/ml is taken to pour diameter 25cm, the discoid reaction utensil of high 2cm into In, add ascorbic acid (vc) 0.5g stirring so that it is 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.
In the present invention, described conduction powder, preparation method thereof as follows: by 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphene, 2 ~ 6% aluminium powders, 5 ~ 10% white carbon blacks and 3 ~ 8% graphite are sufficiently mixed, wherein, described nano-graphene, aluminium powder, carbon Black and graphite weight sum accounts for the 15 ~ 25% of conducting powder gross weight, adds appropriate butyl acetate to put into dispersion solution in ball mill Glue, after discharge, detection, adjustment are configured to the slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then put In nitrogen filled protection atmosphere furnace, it is warmed up to 900 ~ 1000 DEG C, be incubated 1 ~ 2h；Film is scraped off this substrate, obtains conductive porous reticulated carbon Film, i.e. conducting powder.
The invention has the following beneficial effects: comparing with existing ceramic glaze, the ceramic glaze dispensing science that the present invention manufactures, system Standby reasonable, stable performance, and do not contain the extremely toxic substances such as lead cadmium, also there are the antibacterial characteristics of uniformly lasting spectrum simultaneously And electrostatic-proof function, widen the range of application of ceramic glaze further.This method loads and fixing anti-on three-dimensional grapheme Microbial inoculum, not only prevents its reunion, significantly improves the stability of the antibacterial such as metal nanoparticle so as to low temperature can be more preferably dispersed in In frit and glaze slip, and there is more efficient antibacterial activity and silver ion will not overflow oxidation stain；It is compounded with multiple simultaneously The anti-microbial property of antibacterial, has more preferable antibacterial effect compared to single silver nano antibacterial agent, and antibacterial is lasting, and uniformly Dispersibility is more preferable；By reasonably combined antibacterial powder and conducting powder, and adsorb on the netted CNT of multilamellar, can be further Improve dispersing uniformity in ceramic glaze for the functional agent and functional stabilization.
Specific embodiment
To further illustrate technical scheme below by specific preferred implementation.
Embodiment 1
A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, this preparation method comprises the steps:
Step a, prepares low temperature frit: by mass percentage, by 10% potassium nitrate, 7% quartz, 12% potassium feldspar, 5% albite, 10% spodumene, 30% boric acid, 5% brium carbonate, 8% fluorite, 3% Kaolin, 2% sodium fluoride and 8% antibacterial/electrostatic-proof function agent mixing Uniformly, through sieving, calcine at 1250～1300 DEG C after ground and mixed after quick quenching, obtained melt temperature 650～800 DEG C low temperature frit；
Step b, prepares anti-electrostatic antibiotic glaze slip: by mass percentage, by 30% low temperature frit, 30% potassium feldspar, 10% stone English, 5% calcite, 8% Talcum, 4% calcium phosphate, 5% Kaolin, 8% calcined earth are mixed to get mixed-powder, in mixed-powder Add antibacterial/electrostatic-proof function agent mix homogeneously, be finely ground to 300 ~ 350 mesh, be subsequently adding water and obtain glaze slip and modulate glaze slip ratio It is 1.6 ~ 1.7g/cm again3, obtain final product Antistatic antimicrobial ceramic glaze slurry；Wherein, the addition of antibacterial/electrostatic-proof function agent is mixing The 0.5% of powder quality；
Step c, product glazing: by the way of glaze spraying, Antistatic antimicrobial ceramic glaze is sprayed on adobe surface, adobe during glaze spraying At 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g to temperature control；
Step d, sintering: the adobe that step b is coated with Antistatic antimicrobial ceramic glaze is put in roller kilns and burnt till, firing temperature control It is made as 900 ± 5 DEG C, firing period is 65 ± 3min.
Wherein, described antibacterial/electrostatic-proof function agent is obtained by the following method:
(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 Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1ggqds/ag2O 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；Continue ultrasonic agitation, regulation mixed solution ph value to 7.0；Side is ultrasonic to be stirred Mix, side adds the hydrazine hydrate that 6ml mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45ml mass to divide The hydrazine hydrate for 50% for the number, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain 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), adjust ph value for 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will This is deposited in and 3h is dried at 90 DEG C, to obtain gqds/ag2o/ag-zn-ce/sio2；By gqds/ag2o/ag-zn-ce/sio2Put Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in Fluohydric acid. and surpassed with ultrasonic power 100w Sound 10min, removes surface local silicon dioxide, is centrifuged and is dried, obtains 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 than for 1:5；50w is ultrasonic 100min, standing, deionized water wash for several times, is centrifuged, is placed in confined space, carries out evacuation → heating pressurized circulation 3 times (pumpdown time is 25min；It is pressurised into and is 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 conducting powder: by 40% epoxy resin, 45% phenolic resin, 1% nano-graphene, 6% aluminium powder, 5% white carbon black and 3% stone Ink is sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for the 15% of conducting powder gross weight, Appropriate butyl acetate is added to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can apply； By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 1000 DEG C, be incubated 1.5h； Film is scraped off this 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 water, ultrasonic agitation 2h obtains all even stable dispersion liquid, The weight of wherein antibacterial powder and conducting powder is than for 1:6；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, will disperse Liquid adds in the substrate of concave shape, meanwhile, rolls around roller, makes this homogeneous dispersion be scattered in this carbon nanotube mesh film In, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and leaves absorption in carbon nanotube mesh Antibacterial powder and conducting powder in multiple net holes of film；Remove moisture, be placed in confined space, carry out evacuation → heating pressurized circulation 4 times (pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5mpa, pressurize 30min), then the carbon nanotube mesh film being adsorbed with antibacterial powder and conducting powder is scraped off this substrate, obtain anti- Bacterium/electrostatic-proof function agent.
Embodiment 2
A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, this preparation method comprises the steps:
Step a, prepares low temperature frit: by mass percentage, by 8% potassium nitrate, 8% quartz, 10% potassium feldspar, 6% albite, 11% spodumene, 35% boric acid, 4% brium carbonate, 7% fluorite, 2% Kaolin, 4% sodium fluoride and 5% antibacterial/electrostatic-proof function agent mixing Uniformly, through sieving, calcine at 1250～1300 DEG C after ground and mixed after quick quenching, obtained melt temperature 650～800 DEG C low temperature frit；
Step b, prepares anti-electrostatic antibiotic glaze slip: by mass percentage, by 25% low temperature frit, 35% potassium feldspar, 15% stone English, 3% calcite, 5% Talcum, 4% calcium phosphate, 3% Kaolin, 10% calcined earth are mixed to get mixed-powder, to mixed-powder Middle addition antibacterial/electrostatic-proof function agent mix homogeneously, are finely ground to 300 ~ 350 mesh, are subsequently adding water and obtain glaze slip and modulate glaze slip Proportion is 1.6 ~ 1.7g/cm3, obtain final product Antistatic antimicrobial ceramic glaze slurry；Wherein, the addition of antibacterial/electrostatic-proof function agent is mixed Close the 3% of powder quality；
Step c, product glazing: by the way of glaze spraying, Antistatic antimicrobial ceramic glaze is sprayed on adobe surface, adobe during glaze spraying At 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g to temperature control；
Step d, sintering: the adobe that step b is coated with Antistatic antimicrobial ceramic glaze is put in roller kilns and burnt till, firing temperature control It is made as 900 ± 5 DEG C, firing period is 65 ± 3min.
Wherein, described antibacterial/electrostatic-proof function agent is obtained by the following method:
(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 Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 2ggqds/ag2O 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；Continue ultrasonic agitation, regulation mixed solution ph value to 7.0；Side is ultrasonic to be stirred Mix, side adds the hydrazine hydrate that 6ml mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45ml mass to divide The hydrazine hydrate for 50% for the number, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain 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), adjust ph value for 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will This is deposited in and 3h is dried at 90 DEG C, to obtain gqds/ag2o/ag-zn-ce/sio2；By gqds/ag2o/ag-zn-ce/sio2Put Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in Fluohydric acid. and surpassed with ultrasonic power 100w Sound 12min, removes surface local silicon dioxide, is centrifuged and is dried, obtains 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 than for 1:3；50w is ultrasonic 100min, standing, deionized water wash for several times, is centrifuged, is placed in confined space, carries out evacuation → heating pressurized circulation 5 times (pumpdown time is 25min；It is pressurised into and is 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 conducting powder: by 35% epoxy resin, 43% phenolic resin, 3% nano-graphene, 5% aluminium powder, 8% white carbon black and 6% stone Ink is sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for the 22% of conducting powder gross weight, Appropriate butyl acetate is added to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can apply； By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 1000 DEG C, be incubated 1.5h； Film is scraped off this 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 water, ultrasonic agitation 2h obtains all even stable dispersion liquid, The weight of wherein antibacterial powder and conducting powder is than for 3:4；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, will disperse Liquid adds in the substrate of concave shape, meanwhile, rolls around roller, makes this homogeneous dispersion be scattered in this carbon nanotube mesh film In, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and leaves absorption in carbon nanotube mesh Antibacterial powder and conducting powder in multiple net holes of film；Remove moisture, be placed in confined space, carry out evacuation → heating pressurized circulation 4 times (pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5mpa, pressurize 30min), then the carbon nanotube mesh film being adsorbed with antibacterial powder and conducting powder is scraped off this substrate, obtain anti- Bacterium/electrostatic-proof function agent.
Embodiment 3
A kind of Antistatic antimicrobial ceramic glaze and preparation method thereof, this preparation method comprises the steps:
Step a, prepares low temperature frit: by mass percentage, by 6% potassium nitrate, 10% quartz, 15% potassium feldspar, 8% albite, 11% spodumene, 33% boric acid, 3% brium carbonate, 5% fluorite, 1% Kaolin, 5% sodium fluoride and 3% antibacterial/electrostatic-proof function agent mixing Uniformly, through sieving, calcine at 1250～1300 DEG C after ground and mixed after quick quenching, obtained melt temperature 650～800 DEG C low temperature frit；
Step b, prepares anti-electrostatic antibiotic glaze slip: by mass percentage, by 20% low temperature frit, 40% potassium feldspar, 20% stone English, 1% calcite, 3% Talcum, 5% calcium phosphate, 3% Kaolin, 8% calcined earth are mixed to get mixed-powder, in mixed-powder Add antibacterial/electrostatic-proof function agent mix homogeneously, be finely ground to 300 ~ 350 mesh, be subsequently adding water and obtain glaze slip and modulate glaze slip ratio It is 1.6 ~ 1.7g/cm again3, obtain final product Antistatic antimicrobial ceramic glaze slurry；Wherein, the addition of antibacterial/electrostatic-proof function agent is mixing The 5% of powder quality；
Step c, product glazing: by the way of glaze spraying, Antistatic antimicrobial ceramic glaze is sprayed on adobe surface, adobe during glaze spraying At 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g to temperature control；
Step d, sintering: the adobe that step b is coated with Antistatic antimicrobial ceramic glaze is put in roller kilns and burnt till, firing temperature control It is made as 900 ± 5 DEG C, firing period is 65 ± 3min.
Wherein, described antibacterial/electrostatic-proof function agent is obtained by the following method:
(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 Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 3ggqds/ag2O 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；Continue ultrasonic agitation, regulation mixed solution ph value to 7.0；Side is ultrasonic Stirring, side adds the hydrazine hydrate that 6ml mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45ml mass Fraction is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain gqds/ag2o/ag-zn-ce；
(4) by 0.1ggqds/ag2O/ag-zn-ce ultrasonic agitation is scattered in aqueous solution；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), adjust ph value for 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will This is deposited in and 3h is dried at 90 DEG C, to obtain gqds/ag2o/ag-zn-ce/sio2；By gqds/ag2o/ag-zn-ce/sio2Put Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in Fluohydric acid. and surpassed with ultrasonic power 100w Sound 15min, removes surface local silicon dioxide, is centrifuged and is dried, obtains 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 than for 1:1；50w is ultrasonic 100min, standing, deionized water wash for several times, is centrifuged, is placed in confined space, carries out evacuation → heating pressurized circulation 8 times (pumpdown time is 25min；It is pressurised into and is 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 conducting powder: by 30% epoxy resin, 45% phenolic resin, 5% nano-graphene, 2% aluminium powder, 10% white carbon black and 8% stone Ink is sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for the 25% of conducting powder gross weight, Appropriate butyl acetate is added to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can apply； By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 1000 DEG C, be incubated 1.5h； Film is scraped off this 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 water, ultrasonic agitation 2h obtains all even stable dispersion liquid, The weight of wherein antibacterial powder and conducting powder is than for 5:3；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, will disperse Liquid adds in the substrate of concave shape, meanwhile, rolls around roller, makes this homogeneous dispersion be scattered in this carbon nanotube mesh film In, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and leaves absorption in carbon nanotube mesh Antibacterial powder and conducting powder in multiple net holes of film；Remove moisture, be placed in confined space, carry out evacuation → heating pressurized circulation 4 times (pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5mpa, pressurize 30min), then the carbon nanotube mesh film being adsorbed with antibacterial powder and conducting powder is scraped off this substrate, obtain anti- Bacterium/electrostatic-proof function agent.
Embodiment 4
Based on the preparation method of embodiment 1, it the difference is that only: described antibacterial powder is obtained by the following method:
(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 Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1ggqds/ag2O 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, standing, 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 of o/zno is than for 1:5；The ultrasonic 100min of 50w, standing, deionization is washed Wash for several times, centrifugation, it is placed in confined space, (pumpdown time is 25min to carry out evacuation → heating pressurized circulation 3 times；Heating It is pressurised into and is 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
Based on the preparation method of embodiment 2, it the difference is that only: described antibacterial powder is obtained by the following method:
(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 Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 2ggqds/ag2O 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, standing, 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 of o/zno is than for 1:3；The ultrasonic 100min of 50w, standing, deionization is washed Wash for several times, centrifugation, it is placed in confined space, (pumpdown time is 25min to carry out evacuation → heating pressurized circulation 5 times；Heating It is pressurised into and is 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
Based on the preparation method of embodiment 3, it the difference is that only: described antibacterial powder is obtained by the following method:
(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 Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 3ggqds/ag2O 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, standing, 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 of o/zno is than for 1:1；The ultrasonic 100min of 50w, standing, deionization is washed Wash for several times, centrifugation, it is placed in confined space, (pumpdown time is 25min to carry out evacuation → heating pressurized circulation 8 times；Heating It is pressurised into and is 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
Based on the preparation method of embodiment 1, it the difference is that only: described antibacterial powder is metal antibacterial agent；Described conducting powder It is obtained by mixing by nano-graphene, aluminium powder, white carbon black and graphite.
Comparative example 2
Based on the preparation method of embodiment 4, it the difference is that only: described antibacterial powder is zinc oxide antibacterial；Without leading Electric powder.
The ceramic glaze that embodiment 1 ~ 6, comparative example 1 ~ 2 are obtained carries out anti-microbial property test, and test result is as follows:
Sterilization rate: take 105The escherichia coli 0.1ml of individual/ml, is spread evenly across on ceramic glaze, places 2h indoors, then will Bacterium solution sterilized water is eluted in culture medium, cultivates 24h, then detects bacterium number, calculate sterilization rate at 37 DEG C.
Wear testing: the abrasive material being 3～4 from Mohs' hardness, friction on ceramic glaze uses 2 imitating paving 1000 times Effect after year, tests its sterilization rate.
Heat stability testing: ceramic glaze is placed in electric furnace, is raised to 200 DEG C from room temperature, be incubated 20min, put into rapidly 25 In DEG C water, take out after 10min and dry, test its sterilization rate.
Sterilizing Evaluation for Uniformity: 100 regions are chosen on same ceramic material and carries out sterilizing test, to the data recording Carry out Uniformity Analysis, by the uniformity=100* (1- standard deviation/meansigma methodss).When the uniformity is more than 97%, then be labeled as ▲； When the uniformity is more than 90% and is less than 97%, then it is labeled as ☆；When the uniformity is less than 90%, then it is labeled as.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation Art scheme, all should fall within the scope and spirit of the invention.

Claims (9)

1. a kind of preparation method of Antistatic antimicrobial ceramic glaze, it comprises the following steps: first prepare anti-electrostatic antibiotic glaze slip, then warp Glazing, sintering are obtained Antistatic antimicrobial ceramic glaze；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, add antibacterial/electrostatic-proof function agent in mixed-powder And mix homogeneously, the addition of wherein said antibacterial/electrostatic-proof function agent is the 0.5 ~ 5% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, are subsequently adding water and obtain glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/cm3, obtain final product Antistatic antimicrobial ceramic glaze slurry；Institute State antibacterial/electrostatic-proof function agent and include gqds/ag2o/ag-zn-ce/sio2/ Graphene antibiosis powder and conducting powder.
2. the preparation method of Antistatic antimicrobial ceramic glaze according to claim 1 is it is characterised in that described low temperature frit Mass percent consists of: 6～10% potassium nitrate, 5～10% quartz, 12～15% potassium feldspars, 3～8% albites, 10～12% lithiums Pyroxene, 30～35% boric acid, 3～5% brium carbonates, 5～8% fluorites, 1～3% Kaolin, 2～5% sodium fluoride and 3 ~ 8% antibacterials/anti-quiet Electricity Functional agent.
3. the preparation method of Antistatic antimicrobial ceramic glaze according to claim 1 and 2 it is characterised in that described antibacterial/anti- The preparation method of electrostatic function agent 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 Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain Gqds suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, and laser irradiation power is 0.5~2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus 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, adjusts ph value to 11, then stands, is centrifuged, deionized water and ethanol replace washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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 to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8ml mass fraction is 50%, 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, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 30 ~ 60min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited at 80 ~ 90 DEG C 2 ~ 4h is dried, 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. carry out ultrasonic 10 with ultrasonic power 100 ~ 150w ~ 15min, removes surface local silicon dioxide, is centrifuged and is dried, obtains 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, standing, deionized water wash for several times, is centrifuged, 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) antibacterial powder and conducting powder is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even stable dividing The weight of dispersion liquid, wherein antibacterial powder and conducting powder is than for 1 ~ 5:3 ~ 6；The 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, rolls around roller, make this homogeneous dispersion be scattered in this carbon and receive In mitron reticular membrane, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to carbon nanotube mesh film Multiple net holes；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and stays absorption to receive in carbon Antibacterial powder and conducting powder in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, carry out evacuation → heating Then the carbon nanotube mesh film being adsorbed with antibacterial powder and conducting powder is scraped off this substrate by pressurized circulation 3 ~ 5 times, obtain antibacterial/ Electrostatic-proof function agent.
4. a kind of preparation method of Antistatic antimicrobial ceramic glaze, it comprises the following steps: first prepare anti-electrostatic antibiotic glaze slip, then warp Glazing, sintering are obtained Antistatic antimicrobial ceramic glaze；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, add antibacterial/electrostatic-proof function agent in mixed-powder And mix homogeneously, the addition of wherein said antibacterial/electrostatic-proof function agent is the 0.5 ~ 5% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, are subsequently adding water and obtain glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/cm3, obtain final product Antistatic antimicrobial ceramic glaze slurry；Institute State antibacterial/electrostatic-proof function agent and include conducting powder and gqds/ag2O/zno/ Graphene antibiosis powder.
5. the preparation method of Antistatic antimicrobial ceramic glaze according to claim 4 is it is characterised in that described low temperature frit Mass percent consists of: 6～10% potassium nitrate, 5～10% quartz, 12～15% potassium feldspars, 3～8% albites, 10～12% lithiums Pyroxene, 30～35% boric acid, 3～5% brium carbonates, 5～8% fluorites, 1～3% Kaolin, 2～5% sodium fluoride and 3 ~ 8% antibacterials/anti-quiet Electricity Functional agent.
6. the preparation method of the Antistatic antimicrobial ceramic glaze according to claim 4 or 5 it is characterised in that described antibacterial/anti- The preparation method of electrostatic function agent 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 Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain Gqds suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, and laser irradiation power is 0.5~2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus 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, adjusts ph value to 11, then stands, is centrifuged, deionized water and ethanol replace washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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, standing, 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/ag2In o/zno aqueous solution； Ultrasonic 60 ~ the 120min of 10 ~ 100w, standing, deionized water wash for several times, centrifugation, be placed in confined space, carry out evacuation → plus Hot pressurized circulation 3 ~ 8 times, obtains 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 water, ultrasonic agitation 2 ~ 3h obtains all even stable dividing The weight of dispersion liquid, wherein antibacterial powder and conducting powder is than for 1 ~ 5:3 ~ 6；The 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, rolls around roller, make this homogeneous dispersion be scattered in this carbon and receive In mitron reticular membrane, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to carbon nanotube mesh film Multiple net holes；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and stays absorption to receive in carbon Antibacterial powder and conducting powder in multiple net holes of mitron reticular membrane；Remove moisture, be placed in confined space, carry out evacuation → heating Then the carbon nanotube mesh film being adsorbed with antibacterial powder and conducting powder is scraped off this substrate by pressurized circulation 3 ~ 5 times, obtain antibacterial/ Electrostatic-proof function agent.
7. the preparation method of the Antistatic antimicrobial ceramic glaze according to claim 3 or 6 is it is characterised in that described three-dimensional is extra large Continuous shape graphene preparation method is as follows: by 3g graphite powder, 1g nano3 is mixed all with 250ml 98% concentrated sulphuric acid in ice-water bath Even, 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 reaction 20min；Add 270ml water dilution, and with 5ml 30% h2o2 with unnecessary kmno4, the color of mixed solution For brown color, filtered while hot, deionized water cyclic washing obtains go to neutrality, ultrasonic disperse；The 200ml mass fraction is taken to be The graphene oxide solution of 5mg/ml pours diameter 25cm into, in the discoid reaction utensil of high 2cm, adds ascorbic acid (vc) 0.5g Stirring makes it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, and the graphene oxide in reaction utensil is spontaneous Contraction is cross-linked into three-dimensional sponge structure, lyophilization, obtains the three-dimensional sponge shape Graphene of flexibility.
8. the preparation method of the Antistatic antimicrobial ceramic glaze according to claim 3 or 6 is it is characterised in that described conducting powder Preparation method is as follows: by 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphene, 2 ~ 6% aluminium powders, 5 ~ 10% charcoals Black and 3 ~ 8% graphite are sufficiently mixed, and wherein, it is total that the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for conducting powder The 15 ~ 25% of weight, add appropriate butyl acetate to put into dispersion dispergation in ball mill, after discharge, detect, adjustment is configured to can Slurry with coating；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, be warmed up to 900 ~ 1000 DEG C, it is incubated 1 ~ 2h；Film is scraped off this substrate, obtains conductive porous netted carbon film, i.e. conducting powder.
9. a kind of Antistatic antimicrobial ceramic glaze is it is characterised in that it presses described preparation method system as arbitrary in claim 1 to 8 ?.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111847879A (en) * 2020-08-08 2020-10-30 苏奕堂 Water-soluble black ceramic glaze and preparation method thereof
CN111892300A (en) * 2020-08-08 2020-11-06 苏奕堂 High-strength spray-painting crystalline ceramic glaze and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09263423A (en) * 1996-03-28 1997-10-07 Nippon Fueroo Kk Enamel graze having antifungal property
JP2001342087A (en) * 2000-05-31 2001-12-11 Toto Ltd Glaze for ceramic and glazed ceramic
CN105646006A (en) * 2016-01-07 2016-06-08 江苏锦宇环境工程有限公司 Preparation method of environment-friendly antimicrobial ceramic
CN105731801A (en) * 2015-12-30 2016-07-06 黄群好 Ceramic glaze with composite antibacterial function and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09263423A (en) * 1996-03-28 1997-10-07 Nippon Fueroo Kk Enamel graze having antifungal property
JP2001342087A (en) * 2000-05-31 2001-12-11 Toto Ltd Glaze for ceramic and glazed ceramic
CN105731801A (en) * 2015-12-30 2016-07-06 黄群好 Ceramic glaze with composite antibacterial function and preparation method thereof
CN105646006A (en) * 2016-01-07 2016-06-08 江苏锦宇环境工程有限公司 Preparation method of environment-friendly antimicrobial ceramic

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111847879A (en) * 2020-08-08 2020-10-30 苏奕堂 Water-soluble black ceramic glaze and preparation method thereof
CN111892300A (en) * 2020-08-08 2020-11-06 苏奕堂 High-strength spray-painting crystalline ceramic glaze and preparation method thereof

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