CN106746652A - A kind of antibacterial ceramic glaze and preparation method thereof - Google Patents
A kind of antibacterial ceramic glaze and preparation method thereof Download PDFInfo
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- CN106746652A CN106746652A CN201611198802.3A CN201611198802A CN106746652A CN 106746652 A CN106746652 A CN 106746652A CN 201611198802 A CN201611198802 A CN 201611198802A CN 106746652 A CN106746652 A CN 106746652A
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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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
Abstract
The invention discloses a kind of antibacterial ceramic glaze and preparation method thereof, the preparation method is comprised the following steps：Antibacterial glaze slip is first prepared, then antibacterial ceramic glaze is obtained through glazing, sintering；Wherein, the preparation method of antibacterial 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 powder and it is well mixed to being added in mixed-powder, the addition of wherein described antibacterial powder is the 0.1 ~ 1% of mixed-powder quality, 300 ~ 350 mesh are finely ground to, water are subsequently adding and are obtained glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/cm3, obtain final product anti-bacteria ceramic glaze slip.Compared with existing ceramic glaze, ceramic glaze dispensing science produced by the present invention, it is reasonable to prepare, stable performance, and does not contain the extremely toxic substances such as lead cadmium, while also having the antibacterial characteristics of uniform lasting spectrum, further widened the range of application of ceramic glaze.
Description
Technical field
The present invention relates to ceramic technology field, a kind of more particularly to antibacterial ceramic glaze and preparation method thereof.
Background technology
Bacterium, mould even jeopardizes life as the health that pathogen has very big harm, influence people to the mankind and animals and plants
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 for industrial production or public place, after outward appearance practicality is met,
It is possessed more functions of concerning in terms of health of people guarantee, be also that industry researcher is kept up with the trend of the times and given birth to
Wind vane living and the thinking made.
In the building and ornament materials such as existing wall brick, also it is rarely reported at present on the preferably stable antibacterial work(of uniformity
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.
The content of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of antibacterial ceramic glaze and preparation method thereof.
The technical problems to be solved by the invention are achieved by the following technical programs：
A kind of antibacterial ceramic glaze and preparation method thereof, the preparation method is comprised the following steps：Antibacterial glaze slip is first prepared, then through applying
Glaze, sintering are obtained antibacterial ceramic glaze；Wherein, the preparation method of antibacterial glaze slip is as follows：By mass percentage, it is low by 25 ~ 35%
Warm frit, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% calcium phosphate, 1 ~ 5% kaolinite
Soil, 5 ~ 10% calcined earths are mixed to get mixed-powder, to adding antibacterial powder in mixed-powder and being well mixed, wherein the antibacterial
The addition of powder is the 0.1 ~ 1% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, is subsequently adding water and obtains glaze slip and modulate glaze slip
Proportion is 1.6 ~ 1.7g/cm3, obtain final product anti-bacteria ceramic glaze slip.
Wherein, the mass percent 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 1 ~ 5% antibacterial powder.
In the present invention, the antibacterial powder can be obtained by the following method：
（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
Mix in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 500 ~ 600rpm, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, in slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead
Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtained
Graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, swashs
Light irradiation power is 0.5 ~ 2W；It is standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus
Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 ~ 3 with silver nitrate aqueous solution volume ratio:
1）, 10 ~ 20min of ultrasonic agitation；Be added dropwise over 0.5 ~ 1mol/L sodium hydroxide solutions, regulation pH value to 11, then stand, from
The heart, with alternately washing three times of deionized water and ethanol, vacuum drying obtains GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration for 0.005 ~
The 0.05mol/L cerous nitrate aqueous solution, is added dropwise over concentration for 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions after 30 ~ 60min,
GQDs/Ag2The O aqueous solution, the cerous nitrate aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1~0.2:0.2~0.4；Continue ultrasound
Stirring, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fractions are 50%, 30 ~
0.5 ~ 1h of reduction reaction at 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fractions are 50%, the reduction reaction at 85 DEG C are 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 the aqueous solution；Volume ratio 3 ~ 5 is added afterwards:1
Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:1~3）, regulation
PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Be centrifuged and cleaned with acetone and deionized water successively
Precipitated；2 ~ 4h is dried at this is deposited in into 80 ~ 90 DEG C, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/
Ag2O/Ag-Zn-Ce/SiO2Being placed under argon gas atmosphere carries out 500 ~ 800 DEG C of 1 ~ 2h of heat treatment, after being cooled to room temperature, is immersed in hydrogen
10 ~ 15min of ultrasound is carried out with 100 ~ 150W of ultrasonic power in fluoric acid, removal surface part silica is centrifuged and dries, obtains
GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/
SiO2In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag2O/Ag-Zn-Ce/SiO2Weight ratio be 1:1~5；10~100W
60 ~ 120min of ultrasound, is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heating pressurization
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-up 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, resist
Bacterium powder.
In the present invention, the antibacterial powder can also be obtained by the following method：
（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
Mix in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 500 ~ 600rpm, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, in slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead
Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtained
Graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, swashs
Light irradiation power is 0.5 ~ 2W；It is standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus
Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 ~ 3 with silver nitrate aqueous solution volume ratio:
1）, 10 ~ 20min of ultrasonic agitation；Be added dropwise over 0.5 ~ 1mol/L sodium hydroxide solutions, regulation pH value to 11, then stand, from
The heart, with alternately washing three times of deionized water and ethanol, vacuum drying obtains GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.05 ~ 0.5g/100mlZnO
The quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, stand, filtering is 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 the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution
In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight ratio of O/ZnO is 1:1~5；10 ~ 100W, 60 ~ 120min of ultrasound, stand,
Deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 3 ~ 8 times（Pumpdown time
It is 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,
20 ~ 30min of pressurize）, obtain GQDs/Ag2O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.
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 well mixed with the concentrated sulfuric acids of 250ml 98%, is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add
95ml deionized waters, are warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with the H2O2 of 5ml 30% with it is many
Remaining KMnO4, the color of mixed solution is brown color, is filtered while hot, and with deionized water cyclic washing to neutrality, ultrasonic disperse is obtained
GO；Take the discoid reaction utensil that the graphene oxide solution that 200ml mass fractions are 5mg/ml pours into diameter 25cm, 2cm high
In, add ascorbic acid (VC) 0.5g stirrings to be sufficiently mixed it；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 the three-dimensional sponge shape of flexibility
Graphene.
The present invention has the advantages that：This method is loaded and fixed antiseptic on three-dimensional grapheme, is not only prevented
It is reunited, and significantly improves the stability of the antiseptics such as metal nanoparticle, can more preferably be dispersed in low temperature frit and glaze slip,
And will not overflow oxidation stain with more efficient antibacterial activity and silver ion；The antibiotic property of various antiseptics is compounded with simultaneously
Can, there is more preferable antibacterial effect compared to single silver nano antibacterial agent, antibacterial is lasting, and uniformly dispersed more preferable；With
Existing ceramic glaze is compared, ceramic glaze dispensing science produced by the present invention, and it is reasonable to prepare, stable performance, and does not contain lead cadmium etc.
Extremely toxic substance, while also having the antibacterial characteristics of uniform lasting spectrum, has further widened the range of application of ceramic glaze.
Specific embodiment
Technical scheme is further illustrated below by specific preferred embodiment.
Embodiment 1
A kind of antibacterial ceramic glaze and preparation method thereof, the preparation method comprises the following steps：
Step A, prepares low temperature frit：By mass percentage, by 10% potassium nitrate, 9% quartz, 15% potassium feldspar, 5% albite,
12% spodumene, 30% boric acid, 5% barium carbonate, 8% fluorite, 3% kaolin, 2% sodium fluoride and 1% antibacterial powder are well mixed, and pass through
Quick quenching after being calcined at 1250~1300 DEG C after sieve, ground and mixed, the low temperature for having obtained 650~800 DEG C of melt temperature melts
Block；
Step B, prepares antibacterial 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, anti-to being added in mixed-powder
Bacterium powder is simultaneously well mixed, and is finely ground to 300 ~ 350 mesh, is subsequently adding water and obtains glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/cm3,
Obtain final product anti-bacteria ceramic glaze slip；Wherein, the addition of antibacterial powder is the 0.1% of mixed-powder quality；
Step C, product glazing：By the way of glaze spraying, antibacterial ceramic glaze is sprayed on adobe surface, adobe temperature control during glaze spraying
System is in 75 ± 2 DEG C, the adobe spraying 160g of the every 600mm × 600mm of weight of glazing；
Step D, sintering：The adobe that step B is coated with antibacterial ceramic glaze is put into roller kilns and is burnt till, firing temperature is controlled to
900 ± 5 DEG C, firing period is 65 ± 3min.
Wherein, the antibacterial powder is obtained by the following method：
（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, C60 powder and the concentrated sulfuric acid are being burnt
Mix in cup, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, obtain mixed liquor；1g potassium permanganate powders are weighed,
In slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It is quick to 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）It is outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, while laser irradiation 40min, laser irradiation power is 1W；It is standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solutions；Being added dropwise over concentration 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 over, regulation pH value to 11 then stands, is centrifuged, with deionized water and ethanol
Alternately washing three times, vacuum drying obtains GQDs/Ag2O；
（3）Take 1gGQDs/Ag2O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise over for 0.05mol/L cerous nitrates
The aqueous solution, is added dropwise over concentration for 0.005mol/L zinc nitrate aqueous solutions, GQDs/Ag after 30min2The O aqueous solution, cerous nitrate are water-soluble
Liquid is 1 with zinc nitrate aqueous solution volume ratio:0.1:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side ultrasound is stirred
Mix, side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass point is added
Number is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filtering, is washed with deionized for several times, and vacuum drying is obtained
GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.5gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and
Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:2）, regulation pH value be 9 ~
10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Be centrifuged and cleaned with acetone and deionized water successively being precipitated；Will
This dries 3h at being deposited in 90 DEG C, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Put
In 600 DEG C of heat treatment 1h are carried out under argon gas atmosphere, after being cooled to room temperature, it is immersed in hydrofluoric acid and is surpassed with ultrasonic power 100W
Sound 10min, removal surface part silica, is centrifuged and dries, and obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/
SiO2In the 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-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.
Embodiment 2
A kind of antibacterial ceramic glaze and preparation method thereof, the preparation method comprises the following steps：
Step A, prepares low temperature frit：By mass percentage, by 8% potassium nitrate, 8% quartz, 12% potassium feldspar, 6% albite,
11% spodumene, 35% boric acid, 4% barium carbonate, 7% fluorite, 2% kaolin, 4% sodium fluoride and 3% antibacterial powder are well mixed, and pass through
Quick quenching after being calcined at 1250~1300 DEG C after sieve, ground and mixed, the low temperature for having obtained 650~800 DEG C of melt temperature melts
Block；
Step B, prepares antibacterial 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, are added in mixed-powder
Antibacterial powder is simultaneously well mixed, and is finely ground to 300 ~ 350 mesh, is subsequently adding water and obtains glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/
cm3, obtain final product anti-bacteria ceramic glaze slip；Wherein, the addition of antibacterial powder is the 0.5% of mixed-powder quality；
Step C, product glazing：By the way of glaze spraying, antibacterial ceramic glaze is sprayed on adobe surface, adobe temperature control during glaze spraying
System is in 75 ± 2 DEG C, the adobe spraying 160g of the every 600mm × 600mm of weight of glazing；
Step D, sintering：The adobe that step B is coated with antibacterial ceramic glaze is put into roller kilns and is burnt till, firing temperature is controlled to
900 ± 5 DEG C, firing period is 65 ± 3min.
Wherein, the antibacterial powder is obtained by the following method：
（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, C60 powder and the concentrated sulfuric acid are being burnt
Mix in cup, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, obtain mixed liquor；1g potassium permanganate powders are weighed,
In slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It is quick to 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）It is outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, while laser irradiation 40min, laser irradiation power is 1W；It is standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solutions；Being added dropwise over concentration 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 over, regulation pH value to 11 then stands, is centrifuged, with deionized water and ethanol
Alternately washing three times, vacuum drying obtains GQDs/Ag2O；
（3）Take 2gGQDs/Ag2O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise over for 0.03mol/L cerous nitrates
The aqueous solution, is added dropwise over concentration for 0.03mol/L zinc nitrate aqueous solutions, GQDs/Ag after 30min2The O aqueous solution, cerous nitrate are water-soluble
Liquid is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.3；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side ultrasound is stirred
Mix, side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass point is added
Number is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filtering, is washed with deionized for several times, and vacuum drying is obtained
GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.3gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and
Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:2）, regulation pH value be 9 ~
10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Be centrifuged and cleaned with acetone and deionized water successively being precipitated；Will
This dries 3h at being deposited in 90 DEG C, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Put
In 600 DEG C of heat treatment 1h are carried out under argon gas atmosphere, after being cooled to room temperature, it is immersed in hydrofluoric acid and is surpassed with ultrasonic power 100W
Sound 12min, removal surface part silica, is centrifuged and dries, and obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/
SiO2In the 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-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.
Embodiment 3
A kind of antibacterial ceramic glaze and preparation method thereof, the preparation method comprises the following steps：
Step A, prepares low temperature frit：By mass percentage, by 6% potassium nitrate, 10% quartz, 14% potassium feldspar, 8% albite,
10% spodumene, 33% boric acid, 3% barium carbonate, 5% fluorite, 1% kaolin, 5% sodium fluoride and 5% antibacterial powder are well mixed, and pass through
Quick quenching after being calcined at 1250~1300 DEG C after sieve, ground and mixed, the low temperature for having obtained 650~800 DEG C of melt temperature melts
Block；
Step B, prepares antibacterial 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, anti-to being added in mixed-powder
Bacterium powder is simultaneously well mixed, and is finely ground to 300 ~ 350 mesh, is subsequently adding water and obtains glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/cm3,
Obtain final product anti-bacteria ceramic glaze slip；Wherein, the addition of antibacterial powder is the 1% of mixed-powder quality；
Step C, product glazing：By the way of glaze spraying, antibacterial ceramic glaze is sprayed on adobe surface, adobe temperature control during glaze spraying
System is in 75 ± 2 DEG C, the adobe spraying 160g of the every 600mm × 600mm of weight of glazing；
Step D, sintering：The adobe that step B is coated with antibacterial ceramic glaze is put into roller kilns and is burnt till, firing temperature is controlled to
900 ± 5 DEG C, firing period is 65 ± 3min.
Wherein, the antibacterial powder is obtained by the following method：
（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, C60 powder and the concentrated sulfuric acid are being burnt
Mix in cup, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, obtain mixed liquor；1g potassium permanganate powders are weighed,
In slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It is quick to 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）It is outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, while laser irradiation 40min, laser irradiation power is 1W；It is standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solutions；Being added dropwise over concentration 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 over, regulation pH value to 11 then stands, is centrifuged, with deionized water and ethanol
Alternately washing three times, vacuum drying obtains GQDs/Ag2O；
（3）Take 3gGQDs/Ag2O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise over for 0.005mol/L nitric acid
The cerium aqueous solution, is added dropwise over concentration for 0.05mol/L zinc nitrate aqueous solutions, GQDs/Ag after 30min2The O aqueous solution, cerous nitrate water
Solution is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side ultrasound
Stirring, side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass is added
Fraction is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filtering, is washed with deionized for several times, and vacuum drying is obtained
GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.1gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and
Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:2）, regulation pH value be 9 ~
10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and cleaned with acetone and deionized water successively being precipitated；Will
This dries 3h at being deposited in 90 DEG C, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Put
In 600 DEG C of heat treatment 1h are carried out under argon gas atmosphere, after being cooled to room temperature, it is immersed in hydrofluoric acid and is surpassed with ultrasonic power 100W
Sound 15min, removal surface part silica, is centrifuged and dries, and obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/
SiO2In the 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-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.
Embodiment 4
Based on the preparation method of embodiment 1, it the difference is that only：The antibacterial powder is obtained by the following method：
（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, C60 powder and the concentrated sulfuric acid are being burnt
Mix in cup, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, obtain mixed liquor；1g potassium permanganate powders are weighed,
In slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It is quick to 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）It is outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, while laser irradiation 40min, laser irradiation power is 1W；It is standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solutions；Being added dropwise over concentration 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 over, regulation pH value to 11 then stands, is centrifuged, with deionized water and ethanol
Alternately washing three times, vacuum drying obtains GQDs/Ag2O；
（3）Take 1gGQDs/Ag2O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.5g/100mlZnO quantum dots
The aqueous solution, ultrasonic power mixing speed respectively halves；After 60min, stand, filtering is 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 the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution
In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight ratio of O/ZnO is 1:5；50W ultrasound 100min, stand, deionization washing
Wash for several times, centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 3 times（Pumpdown time is 25min；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：The antibacterial powder is obtained by the following method：
（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, C60 powder and the concentrated sulfuric acid are being burnt
Mix in cup, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, obtain mixed liquor；1g potassium permanganate powders are weighed,
In slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It is quick to 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）It is outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, while laser irradiation 40min, laser irradiation power is 1W；It is standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solutions；Being added dropwise over concentration 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 over, regulation pH value to 11 then stands, is centrifuged, with deionized water and ethanol
Alternately washing three times, vacuum drying obtains GQDs/Ag2O；
（3）Take 2gGQDs/Ag2O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.2g/100mlZnO quantum dots
The aqueous solution, ultrasonic power mixing speed respectively halves；After 80min, stand, filtering is 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 the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution
In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight ratio of O/ZnO is 1:3；50W ultrasound 100min, stand, deionization washing
Wash for several times, centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 5 times（Pumpdown time is 25min；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：The antibacterial powder is obtained by the following method：
（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, C60 powder and the concentrated sulfuric acid are being burnt
Mix in cup, beaker is placed in ice-water bath, while being stirred with the speed of 600rpm, obtain mixed liquor；1g potassium permanganate powders are weighed,
In slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It is quick to 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）It is outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, while laser irradiation 40min, laser irradiation power is 1W；It is standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solutions；Being added dropwise over concentration 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 over, regulation pH value to 11 then stands, is centrifuged, with deionized water and ethanol
Alternately washing three times, vacuum drying obtains GQDs/Ag2O；
（3）Take 3gGQDs/Ag2O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.05g/100mlZnO quantum dots
The aqueous solution, ultrasonic power mixing speed respectively halves；After 90min, stand, filtering is 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 the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution
In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight ratio of O/ZnO is 1:1；50W ultrasound 100min, stand, deionization washing
Wash for several times, centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 8 times（Pumpdown time is 25min；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：The antibacterial powder is metal antibacterial agent.
Comparative example 2
Based on the preparation method of embodiment 4, it the difference is that only：The antibacterial powder is zinc oxide antiseptic.
Anti-microbial property test is carried out to the ceramic glaze that embodiment 1 ~ 6, comparative example 1 ~ 2 are obtained, test result is as follows：
Sterilization rate：Take 105The Escherichia coli 0.1ml of individual/ml, is spread evenly across on ceramic glaze, and 2h is placed indoors, then will
Bacterium solution sterilized water is eluted in culture medium, and 24h is cultivated at 37 DEG C, then detects bacterium number, calculates sterilization rate.
Wear testing：From the abrasive material that Mohs' hardness is 3~4, rubbed on ceramic glaze 1000 times and use 2 imitating paving
Effect after year, tests its sterilization rate.
Heat stability testing：Ceramic glaze is placed in electric furnace, 200 DEG C are raised to from room temperature, be incubated 20min, 25 are put into rapidly
Taken out in DEG C water, after 10min and dried, test its sterilization rate.
Sterilizing Evaluation for Uniformity：100 regions are chosen on same ceramic material carries out sterilizing test, to the data for measuring
Uniformity Analysis are carried out, by the uniformity=100* (1- standard deviations/average value).When the uniformity be more than 97%, then labeled as ▲；
When the uniformity is more than 90% and less than 97%, then labeled as ☆；When the uniformity is less than 90%, then Biao Ji Wei ╳.
Embodiment described above only expresses embodiments of the present invention, and its description is more specific and detailed, but can not
Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill 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 antibacterial ceramic glaze, it is comprised the following steps：Antibacterial glaze slip is first prepared, then through glazing, sintering system
Obtain antibacterial ceramic glaze；Wherein, the preparation method of antibacterial glaze slip is as follows：By mass percentage, by 25 ~ 35% low temperature frits, 30 ~
40% potassium feldspar, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% calcium phosphate, 1 ~ 5% kaolin, 5 ~ 10% calcinings
Soil is mixed to get mixed-powder, to adding antibacterial powder in mixed-powder and being well mixed, wherein the addition of the antibacterial powder is
The 0.1 ~ 1% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, be subsequently adding water obtain glaze slip and modulate glaze slip proportion for 1.6 ~
1.7g/cm3, obtain final product anti-bacteria ceramic glaze slip；The antibacterial powder is GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder.
2. the preparation method of antibacterial ceramic glaze according to claim 1, it is characterised in that the quality hundred of the low temperature frit
Divide and be than composition：6~10% potassium nitrate, 5~10% quartz, 12~15% potassium feldspars, 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 1 ~ 5% antibacterial powder.
3. the preparation method of antibacterial ceramic glaze according to claim 1 and 2, it is characterised in that the preparation of the antibacterial powder
Method 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
Mix in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 500 ~ 600rpm, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, in slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead
Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtained
GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, laser irradiation power is
0.5~2W；It is standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus
Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min of ultrasonic agitation；It is added dropwise over 0.5 ~ 1mol/L hydroxides
Sodium solution, regulation pH value to 11 is then stood, is centrifuged, and with alternately washing three times of deionized water and ethanol, vacuum drying is obtained
GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration for 0.005 ~
The 0.05mol/L cerous nitrate aqueous solution, is added dropwise over concentration for 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions after 30 ~ 60min；After
Continuous ultrasonic agitation, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fractions are 50%,
0.5 ~ 1h of reduction reaction at 30 ~ 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fractions are 50% is added, at 85 DEG C also
After 30 ~ 48h of original reaction；Filtering, is washed with deionized for several times, and vacuum drying obtains GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.1 ~ 0.5gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 3 ~ 5 is added afterwards:1
Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 30 ~
60min；Be centrifuged and cleaned with acetone and deionized water successively being precipitated；2 ~ 4h is dried at this is deposited in into 80 ~ 90 DEG C,
To obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Be placed under argon gas atmosphere and carry out 500 ~
800 DEG C heat treatment 1 ~ 2h, after being cooled to room temperature, be immersed in hydrofluoric acid with 100 ~ 150W of ultrasonic power carry out ultrasound 10 ~
15min, removal surface part silica, is centrifuged and dries, and obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/
SiO2In the 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,
Carry out vacuumizing → heat pressurized circulation 3 ~ 8 times, obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder, i.e. antibacterial powder.
4. the preparation method of antibacterial ceramic glaze according to claim 3, it is characterised in that the three-dimensional sponge shape Graphene
Preparation method is as follows：By 3g graphite powders, 1g NaNO3 are well mixed in ice-water bath with the concentrated sulfuric acids of 250ml 98%, are slowly added to
6g KMnO4；Then heat at 35 DEG C, after stirring 40min, add 95ml deionized waters, be warming up to 98 DEG C of reaction 20min；
The dilution of 270ml water is added, and with the H2O2 of 5ml 30% and unnecessary KMnO4, the color of mixed solution is brown color, while hot
Filtering, with deionized water cyclic washing to neutrality, ultrasonic disperse obtains GO；Take the oxidation stone that 200ml mass fractions are 5mg/ml
Black alkene solution is poured into the discoid reaction utensil of diameter 25cm, 2cm high, adds ascorbic acid (VC) 0.5g stirrings it is fully mixed
Close；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 the three-dimensional sponge shape Graphene of flexibility.
5. a kind of preparation method of antibacterial ceramic glaze, it is comprised the following steps：Antibacterial glaze slip is first prepared, then through glazing, sintering system
Obtain antibacterial ceramic glaze；Wherein, the preparation method of antibacterial glaze slip is as follows：By mass percentage, by 25 ~ 35% low temperature frits, 30 ~
40% potassium feldspar, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% calcium phosphate, 1 ~ 5% kaolin, 5 ~ 10% calcinings
Soil is mixed to get mixed-powder, to adding antibacterial powder in mixed-powder and being well mixed, wherein the addition of the antibacterial powder is
The 0.1 ~ 1% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, be subsequently adding water obtain glaze slip and modulate glaze slip proportion for 1.6 ~
1.7g/cm3, obtain final product anti-bacteria ceramic glaze slip；The antibacterial powder is GQDs/Ag2O/ZnO/ Graphene antibiosis powder.
6. the preparation method of antibacterial ceramic glaze according to claim 5, it is characterised in that the quality hundred of the low temperature frit
Divide and be than composition：6~10% potassium nitrate, 5~10% quartz, 12~15% potassium feldspars, 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 1 ~ 5% antibacterial powder.
7. the preparation method of the antibacterial ceramic glaze according to claim 5 or 6, it is characterised in that the preparation of the antibacterial powder
Method 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
Mix in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 500 ~ 600rpm, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, in slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead
Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtained
GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, laser irradiation power is
0.5~2W；It is standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus
Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min of ultrasonic agitation；It is added dropwise over 0.5 ~ 1mol/L hydroxides
Sodium solution, regulation pH value to 11 is then stood, is centrifuged, and with alternately washing three times of deionized water and ethanol, vacuum drying is obtained
GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.05 ~ 0.5g/100mlZnO
The quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, stand, filtering is 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 the aqueous solution, be added dropwise over GQDs/Ag2In the O/ZnO 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, vacuumize → add
Hot pressurized circulation 3 ~ 8 times, obtains GQDs/Ag2O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.
8. the preparation method of antibacterial ceramic glaze according to claim 7, it is characterised in that the three-dimensional sponge shape Graphene
Preparation method is as follows：By 3g graphite powders, 1g NaNO3 are well mixed in ice-water bath with the concentrated sulfuric acids of 250ml 98%, are slowly added to
6g KMnO4；Then heat at 35 DEG C, after stirring 40min, add 95ml deionized waters, be warming up to 98 DEG C of reaction 20min；
The dilution of 270ml water is added, and with the H2O2 of 5ml 30% and unnecessary KMnO4, the color of mixed solution is brown color, while hot
Filtering, with deionized water cyclic washing to neutrality, ultrasonic disperse obtains GO；Take the oxidation stone that 200ml mass fractions are 5mg/ml
Black alkene solution is poured into the discoid reaction utensil of diameter 25cm, 2cm high, adds ascorbic acid (VC) 0.5g stirrings it is fully mixed
Close；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 the three-dimensional sponge shape Graphene of flexibility.
9. a kind of antibacterial ceramic glaze, it is characterised in that its preparation method as described in as any such as claim 1 to 8 is obtained.
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| CN108383127A (en) * | 2018-04-28 | 2018-08-10 | 四川南联环资科技股份有限公司 | A kind of preparation method producing finished product ceramic glaze using quartz sand tailings |
| CN110122995A (en) * | 2019-05-29 | 2019-08-16 | 深圳市甘露珠宝首饰有限公司 | Compound enamel precious metal jewelry and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107311619A (en) * | 2017-07-06 | 2017-11-03 | 董孟富 | The production method of novel antibacterial ceramics |
| CN108383127A (en) * | 2018-04-28 | 2018-08-10 | 四川南联环资科技股份有限公司 | A kind of preparation method producing finished product ceramic glaze using quartz sand tailings |
| CN110122995A (en) * | 2019-05-29 | 2019-08-16 | 深圳市甘露珠宝首饰有限公司 | Compound enamel precious metal jewelry and preparation method thereof |
| CN114158569A (en) * | 2021-11-17 | 2022-03-11 | 中国地质大学（武汉） | Black talc-based antibacterial agent and preparation method and application thereof |
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