CN106348600A - Method for antibacterial luminous health ceramics and preparing method thereof - Google Patents
Method for antibacterial luminous health ceramics and preparing method thereof Download PDFInfo
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- CN106348600A CN106348600A CN201610748624.0A CN201610748624A CN106348600A CN 106348600 A CN106348600 A CN 106348600A CN 201610748624 A CN201610748624 A CN 201610748624A CN 106348600 A CN106348600 A CN 106348600A
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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
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/641—Chalcogenides
- C09K11/643—Chalcogenides with alkaline earth metals
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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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
Abstract
The invention discloses a method for antibacterial luminous health ceramics and a preparing method thereof. The method comprises the steps of:A, preparing glaze: by mass, mixing 10-15% of zinc oxide, 0.4-0.5% of barium carbonate, 0.3-0.4% of talc, 58-65% of borax, 10-12% of silicon oxide, 12-20% of boron oxide and 0.1-6% of functional agent, so that the finished powder is obtained, adding alumina milling ball and distilled water, ball milling; then adding tourmaline and cordierite, milling again, controlling the size of 300-350 mu(Chinese unit, the number of empty holes per square inch on screen mesh), so that the glaze is obtained, wherein the tourmaline and cordierite account for, by mass, 3-8% and 1-5% of mixed powder; B, soaking glaze, and burning the glaze again; C, spraying glaze, burning the glaze once more to obtain the health ceramics. Compared with prior ceramics, the method has the advantages that the ingredients of ceramics is scientific, preparing steps are reasonable, performance is stable, and no toxic substances such as lead and cadmium are in the glaze, meanwhile, the glaze has an antibaterical property with persistent spectra and an antifouling self-cleaning function, which broad further the application sphere for ceramics.
Description
Technical field
The present invention relates to ceramic technology field, more particularly to a kind of antibacterial noctilucence health-care ceramic 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 Tiles 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 ceramic material is usually the product of simple function, such as antibacterial, antistatic, noctilucence, photochromic etc.
Deng that is, a kind of product does not possess multiple function, this strongly limits its range of application and is carried out using two kinds of functional agents although having yet
Collocation, but effect is still undesirable, 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 antibacterial noctilucence health-care ceramic and its preparation side
Method.
The technical problem to be solved is achieved by the following technical programs:
A kind of antibacterial noctilucence health-care ceramic and preparation method thereof, this preparation method comprises the following steps:
Step a, prepares glaze slip: by mass percentage, by 10 ~ 15% zinc oxide, 0.4 ~ 0.5% brium carbonate, 0.3 ~ 0.4% Talcum
Powder, 58 ~ 65% Boraxs, 10 ~ 12% silicon oxides, 12 ~ 20% boron oxides and 0.1 ~ 6% functional agent mix to obtain mixed-powder, and addition contains
In the ball grinder of alumina balls abrading-ball and distilled water, ball grinder is fixed on vibration at high speed ball mill, and is rotated and ball
Mill；Add tourmaline and cordierite, be rotated further and ball milling, control slurry 300 ~ 350 mesh, prepared glaze slip；Wherein, described electricity
Gas stone and cordierite account for the 3 ~ 8% and 1 ~ 5% of mixed-powder quality respectively；
Step b, impregnates glaze slip: porous ceramicss are carried out impregnate glaze slip → evacuation → pressurized circulation process, at least circulate 1 time；
Then carry out 300 ~ 500 DEG C once sintered；
Step c, sprays glaze slip: by the way of glaze spraying, by glaze slip spraying porous ceramic surface after sintering；Then carry out
700 ~ 800 DEG C of double sintering, prepared health-care ceramic.
Wherein, described alumina balls abrading-ball and the mass ratio of distilled water are 1:2.
In the present invention, described functional 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 noctilucence complex is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even stable
Dispersion liquid, wherein the weight of antibacterial powder and noctilucence complex is than for 3 ~ 5:1 ~ 3；The substrate with carbon nanotube mesh film is put
When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, so that this homogeneous dispersion is scattered in
In this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to CNT
Multiple net holes of reticular membrane；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives most of moisture away and leave absorption
Antibacterial powder and noctilucence complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, taken out
(pumpdown time is 20 ~ 30min to vacuum → heating pressurized circulation 3 ~ 5 times；It is pressurised into and be passed through high temperature and high pressure gas, gas
Heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6mpa, pressurize 20 ~ 30min), then will be adsorbed with antibacterial powder and noctilucence will be combined
The carbon nanotube mesh film of thing scrapes off this substrate, obtains antibacterial-noctilucent function agent.
In the present invention, described functional 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 noctilucence complex is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even stable
Dispersion liquid, wherein the weight of antibacterial powder and noctilucence complex is than for 3 ~ 5:1 ~ 3；The substrate with carbon nanotube mesh film is put
When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, so that this homogeneous dispersion is scattered in
In this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to CNT
Multiple net holes of reticular membrane；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives most of moisture away and leave absorption
Antibacterial powder and noctilucence complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, taken out
(pumpdown time is 20 ~ 30min to vacuum → heating pressurized circulation 3 ~ 5 times；It is pressurised into and be passed through high temperature and high pressure gas, gas
Heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6mpa, pressurize 20 ~ 30min), then will be adsorbed with antibacterial powder and noctilucence will be combined
The carbon nanotube mesh film of thing scrapes off this substrate, obtains antibacterial-noctilucent function agent.
Wherein, described three-dimensional sponge shape graphene preparation method is as follows: by 3g graphite powder, 1g nano3 is in ice-water bath
Mix homogeneously with 250ml 98% concentrated sulphuric acid, be slowly added to 6g kmno4.Then heat at 35 DEG C, after stirring 40min, add
95ml deionized water, is warming up to 98 DEG C of reaction 20min；Add 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, the preparation method of described noctilucence complex is as follows: under nitrogen environment, by concentration be 0.05 ~
The protonic acid solution of 0.5mol/l and the DBSA that concentration is 0.05 ~ 0.5mol/l are mixed with volume ratio 3:1 ~ 3, with
When add luminescent powder, add aniline after magnetic agitation 60 ~ 120min, luminescent powder and aniline mass ratio are 1:5 ~ 10；Continuously stirred
After 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；
Acetone, deionized water wash are vacuum dried for several times afterwards, nano polyaniline/noctilucence flour complexes of milling to obtain；By 1 ~ 10g nanometer polyphenyl
Amine/noctilucence flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, after stirring
Add tetraethyl orthosilicate (mass ratio with nano polyaniline/noctilucence flour complexes is 5:1 ~ 3), adjusting ph value is 9 ~ 10, reaction
Temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is sunk
Shallow lake drying, to obtain nano polyaniline/noctilucence flour complexes/sio2；By nano polyaniline/noctilucence flour complexes/sio2It is placed in argon
Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under gas atmosphere, remove polyaniline, obtain luminescent powder/porous sio2.Described luminescent powder is flat
All particle diameter is less than the long afterglow sr of 10nm4al14o25Nano-phosphor.
The invention has the following beneficial effects: the ceramic batch science manufacturing with existing ceramic phase ratio, the present invention, preparation conjunction
Reason, stable performance, and do not contain the extremely toxic substances such as lead cadmium, also have simultaneously uniformly lasting spectrum antibacterial characteristics and
Noctilucent function, has widened the range of application of pottery further.
This method loads and fixing antibacterial on three-dimensional grapheme, not only prevents its reunion, significantly improves metal nano
The stability of the antibacterial such as particle is so as to can more preferably be dispersed in low temperature frit and glaze slip, and has more efficient antibacterial activity
And silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antibacterial, compared to single silver nanoparticle simultaneously
Antibacterial has more preferable antibacterial effect, and antibacterial is lasting, and uniformly dispersed more preferable；
The present invention is by reasonably combined antibacterial powder, noctilucence complex, and adsorbs respectively on the netted CNT of multilamellar, can
Improve dispersing uniformity in pottery for the functional agent and functional stabilization further.
Specific embodiment
To further illustrate technical scheme below by specific preferred implementation.
Embodiment 1
A kind of antibacterial noctilucence health-care ceramic and preparation method thereof, this preparation method comprises the steps:
Step a, prepares glaze slip: by mass percentage, by 13% zinc oxide, 0.4% brium carbonate, 0.4% Pulvis Talci, 58% Borax,
10% silicon oxide, 18% boron oxide and 0.2% functional agent mix to obtain mixed-powder, add containing alumina balls abrading-ball and distilled water
In ball grinder, ball grinder is fixed on gm-3b vibration at high speed ball mill, and carries out rotating and ball milling 30min；Add electrically
Stone and cordierite, are rotated further and ball milling 50min, control slurry 300 ~ 350 mesh, prepared glaze slip；Wherein, described tourmaline and violet
Cordierite accounts for the 3% and 5% of mixed-powder quality respectively；Described alumina balls abrading-ball is 1:2 with the mass ratio of distilled water；
Step b, impregnates glaze slip: porous ceramicss are carried out impregnate glaze slip → evacuation → pressurized circulation process (particularly as follows: being immersed in
10min in the glaze slip that step a is obtained, takes out, and carries out evacuation → pressurized treatments, evacuation vacuum to the porous ceramicss after dipping
Spend for -0.02mpa, pressurize 5min；It is forced into 0.3mpa, pressurize 10min), circulate 7 times；Then 300 ~ 500 DEG C are carried out once
Sintering；Described functional agent includes noctilucence complex and gqds/ag2o/ag-zn-ce/sio2/ Graphene antibiosis powder, i.e. antibacterial powder；
Step c, sprays glaze slip: by the way of glaze spraying, by glaze slip spraying porous ceramic surface after sintering, porous during glaze spraying
At 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g to ceramic surface temperature control；Then 700 are carried out
~ 800 DEG C of double sintering, prepared health-care ceramic.
Wherein, described functional 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 noctilucence complex: under nitrogen environment, the protonic acid solution for 0.3mol/l for the concentration and concentration are 0.3mol/l
DBSA with volume ratio 3:1 mix, be simultaneously introduced luminescent powder, after magnetic agitation 90min add aniline, luminescent powder
It is 1:10 with aniline mass ratio；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:
1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, nano polyaniline/luminescent powder of milling to obtain
Complex；1g nano polyaniline/noctilucence flour complexes ultrasonic agitation is scattered in aqueous solution；Add volume ratio 4:1 afterwards
Water and ammonia, are stirring evenly and then adding into tetraethyl orthosilicate (mass ratio with nano polyaniline/noctilucence flour complexes is 5:3), adjust
Section ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and is cleaned with acetone and deionized water successively and obtained
Must precipitate；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/noctilucence flour complexes/sio2；By nanometer polyphenyl
Amine/noctilucence flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h, remove polyaniline, obtain luminescent powder/many
Hole sio2, i.e. noctilucence complex.Described luminescent powder is less than the long afterglow sr of 10nm for mean diameter4al14o25Nano-phosphor；
(7) antibacterial powder and noctilucence complex is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even stable dispersion
Liquid, the wherein weight of antibacterial powder and noctilucence complex are than for 3:3；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C,
Dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this homogeneous dispersion be scattered in this CNT
In reticular membrane, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to the many of carbon nanotube mesh film
Individual net hole；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and leaves absorption in CNT
Antibacterial powder and noctilucence complex in multiple net holes of reticular membrane；Remove moisture, be placed in confined space, carry out evacuation → heating
4 times (pumpdown time is 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 0.5mpa, pressurize 30min), then the carbon nanotube mesh film being adsorbed with antibacterial powder and noctilucence complex is scraped off
This substrate, obtains antibacterial-noctilucent function agent.
Embodiment 2
A kind of antibacterial noctilucence health-care ceramic and preparation method thereof, this preparation method comprises the steps:
Step a, prepares glaze slip: by mass percentage, by 10% zinc oxide, 0.45% brium carbonate, 0.35% Pulvis Talci, 60% boron
Sand, 11% silicon oxide, 15% boron oxide and 3.2% functional agent mix to obtain mixed-powder, add and contain alumina balls abrading-ball and distilled water
Ball grinder in, ball grinder is fixed on gm-3b vibration at high speed ball mill, and carry out rotate and ball milling 30min；Add electricity
Gas stone and cordierite, are rotated further and ball milling 50min, control slurry 300 ~ 350 mesh, prepared glaze slip；Wherein, described tourmaline and
Cordierite accounts for the 5% and 3% of mixed-powder quality respectively；Described alumina balls abrading-ball is 1:2 with the mass ratio of distilled water；Described work(
Agent can include noctilucence complex and gqds/ag2o/ag-zn-ce/sio2/ Graphene antibiosis powder, i.e. antibacterial powder；
Step b, impregnates glaze slip: porous ceramicss are carried out impregnate glaze slip → evacuation → pressurized circulation process (particularly as follows: being immersed in
10min in the glaze slip that step a is obtained, takes out, and carries out evacuation → pressurized treatments, evacuation vacuum to the porous ceramicss after dipping
Spend for -0.02mpa, pressurize 5min；It is forced into 0.3mpa, pressurize 10min), circulate 5 times；Then 300 ~ 500 DEG C are carried out once
Sintering；
Step c, sprays glaze slip: by the way of glaze spraying, by glaze slip spraying porous ceramic surface after sintering, porous during glaze spraying
At 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g to ceramic surface temperature control；Then 700 are carried out
~ 800 DEG C of double sintering, prepared health-care ceramic.
Wherein, described functional 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 noctilucence complex: under nitrogen environment, the protonic acid solution for 0.3mol/l for the concentration and concentration are 0.3mol/l
DBSA with volume ratio 3:2 mix, be simultaneously introduced luminescent powder, after magnetic agitation 90min add aniline, luminescent powder
It is 1:8 with aniline mass ratio；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, mill nano polyaniline/luminescent powder is multiple
Compound；5g nano polyaniline/noctilucence flour complexes ultrasonic agitation is scattered in aqueous solution；Add the water of volume ratio 4:1 afterwards
And ammonia, it is stirring evenly and then adding into tetraethyl orthosilicate (mass ratio with nano polyaniline/noctilucence flour complexes is 5:2), adjust
Ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out being centrifuged and cleaning acquisition with acetone and deionized water successively
Precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/noctilucence flour complexes/sio2；By nano polyaniline/
Noctilucence flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h, remove polyaniline, obtain luminescent powder/porous
sio2, i.e. noctilucence complex.Described luminescent powder is less than the long afterglow sr of 10nm for mean diameter4al14o25Nano-phosphor；
(7) antibacterial powder and noctilucence complex is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even stable dispersion
Liquid, the wherein weight of antibacterial powder and noctilucence complex are than for 5:2；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C,
Dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this homogeneous dispersion be scattered in this CNT
In reticular membrane, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to the many of carbon nanotube mesh film
Individual net hole；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and leaves absorption in CNT
Antibacterial powder and noctilucence complex in multiple net holes of reticular membrane；Remove moisture, be placed in confined space, carry out evacuation → heating
4 times (pumpdown time is 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 0.5mpa, pressurize 30min), then the carbon nanotube mesh film being adsorbed with antibacterial powder and noctilucence complex is scraped off
This substrate, obtains antibacterial-noctilucent function agent.
Embodiment 3
A kind of antibacterial noctilucence health-care ceramic and preparation method thereof, this preparation method comprises the steps:
Step a, prepares glaze slip: by mass percentage, by 10% zinc oxide, 0.5% brium carbonate, 0.3% Pulvis Talci, 62% Borax,
10% silicon oxide, 12% boron oxide and 5.2% functional agent mix to obtain mixed-powder, add containing alumina balls abrading-ball and distilled water
In ball grinder, ball grinder is fixed on gm-3b vibration at high speed ball mill, and carries out rotating and ball milling 30min；Add electrically
Stone and cordierite, are rotated further and ball milling 50min, control slurry 300 ~ 350 mesh, prepared glaze slip；Wherein, described tourmaline and violet
Cordierite accounts for the 8% and 1% of mixed-powder quality respectively；Described alumina balls abrading-ball is 1:2 with the mass ratio of distilled water；
Step b, impregnates glaze slip: porous ceramicss are carried out impregnate glaze slip → evacuation → pressurized circulation process (particularly as follows: being immersed in
10min in the glaze slip that step a is obtained, takes out, and carries out evacuation → pressurized treatments, evacuation vacuum to the porous ceramicss after dipping
Spend for -0.02mpa, pressurize 5min；It is forced into 0.3mpa, pressurize 10min), circulate 1 time；Then 300 ~ 500 DEG C are carried out once
Sintering；Described functional agent includes noctilucence complex and antibacterial powder；
Step c, sprays glaze slip: by the way of glaze spraying, by glaze slip spraying porous ceramic surface after sintering, porous during glaze spraying
At 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays 160g to ceramic surface temperature control；Then 700 are carried out
~ 800 DEG C of double sintering, prepared health-care ceramic.
Wherein, described functional 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 noctilucence complex: under nitrogen environment, the protonic acid solution for 0.3mol/l for the concentration and concentration are 0.3mol/l
DBSA with volume ratio 1:1 mix, be simultaneously introduced luminescent powder, after magnetic agitation 90min add aniline, luminescent powder
It is 1:5 with aniline mass ratio；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, mill nano polyaniline/luminescent powder is multiple
Compound；10g nano polyaniline/noctilucence flour complexes ultrasonic agitation is scattered in aqueous solution；Add the water of volume ratio 4:1 afterwards
And ammonia, it is stirring evenly and then adding into tetraethyl orthosilicate (mass ratio with nano polyaniline/noctilucence flour complexes is 5:1), adjust
Ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out being centrifuged and cleaning acquisition with acetone and deionized water successively
Precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/noctilucence flour complexes/sio2；By nano polyaniline/
Noctilucence flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h, remove polyaniline, obtain luminescent powder/porous
sio2, i.e. noctilucence complex.Described luminescent powder is less than the long afterglow sr of 10nm for mean diameter4al14o25Nano-phosphor；
(7) antibacterial powder and noctilucence complex is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even stable dispersion
Liquid, the wherein weight of antibacterial powder and noctilucence complex are than for 4:1；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C,
Dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this homogeneous dispersion be scattered in this CNT
In reticular membrane, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to the many of carbon nanotube mesh film
Individual net hole；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and leaves absorption in CNT
Antibacterial powder and noctilucence complex in multiple net holes of reticular membrane；Remove moisture, be placed in confined space, carry out evacuation → heating
4 times (pumpdown time is 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 0.5mpa, pressurize 30min), then the carbon nanotube mesh film being adsorbed with antibacterial powder and noctilucence complex is scraped off
This substrate, obtains antibacterial-noctilucent 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 luminescent powder
Complex is less than the long afterglow sr of 10nm for mean diameter4al14o25Nano-phosphor.
Comparative example 2
Based on the preparation method of embodiment 4, it the difference is that only: described antibacterial powder is zinc oxide antibacterial.
The Ceramic Tiles that embodiment 1 ~ 6, comparative example 1 ~ 2 are obtained carry 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 in Ceramic Tiles, 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 in Ceramic Tiles uses 2 imitating paving 1000 times
Effect after year, tests its sterilization rate.
Heat stability testing: Ceramic Tiles are placed in electric furnace, are raised to 200 DEG C from room temperature, 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 (8)
1. a kind of preparation method of antibacterial noctilucence health-care ceramic, it comprises the following steps:
Step a, prepares glaze slip: by mass percentage, by 10 ~ 15% zinc oxide, 0.4 ~ 0.5% brium carbonate, 0.3 ~ 0.4% Talcum
Powder, 58 ~ 65% Boraxs, 10 ~ 12% silicon oxides, 12 ~ 20% boron oxides and 0.1 ~ 6% functional agent mix to obtain mixed-powder, and addition contains
In the ball grinder of alumina balls abrading-ball and distilled water, ball grinder is fixed on vibration at high speed ball mill, and is rotated and ball
Mill；Add tourmaline and cordierite, be rotated further and ball milling, control slurry 300 ~ 350 mesh, prepared glaze slip；Wherein, described electricity
Gas stone and cordierite account for the 3 ~ 8% and 1 ~ 5% of mixed-powder quality respectively；
Step b, impregnates glaze slip: porous ceramicss are carried out impregnate glaze slip → evacuation → pressurized circulation process, at least circulate 1 time；
Then carry out 300 ~ 500 DEG C once sintered；
Step c, sprays glaze slip: by the way of glaze spraying, by glaze slip spraying porous ceramic surface after sintering；Then carry out
700 ~ 800 DEG C of double sintering, prepared health-care ceramic；Wherein,
Described functional agent includes noctilucence complex and gqds/ag2o/ag-zn-ce/sio2/ Graphene antibiosis powder.
2. the preparation method of antibacterial noctilucence health-care ceramic according to claim 1, the preparation method of described functional 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 noctilucence complex is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even stable
Dispersion liquid, wherein the weight of antibacterial powder and noctilucence complex is than for 3 ~ 5:1 ~ 3；The substrate with carbon nanotube mesh film is put
When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, so that this homogeneous dispersion is scattered in
In this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to CNT
Multiple net holes of reticular membrane；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives most of moisture away and leave absorption
Antibacterial powder and noctilucence complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, taken out
Then the carbon nanotube mesh film being adsorbed with antibacterial powder and noctilucence complex is scraped off this by vacuum → heating pressurized circulation 3 ~ 5 times
Substrate, obtains antibacterial-noctilucent function agent.
3. the preparation method of antibacterial noctilucence health-care ceramic according to claim 2 is it is characterised in that described three-dimensional sponge shape
Graphene preparation method is as follows: by 3g graphite powder, 1g nano3 is mixed homogeneously with 250ml 98% concentrated sulphuric acid in ice-water bath, delays
Slow addition 6g kmno4；Then heat at 35 DEG C, after stirring 40min, add 95ml deionized water, be warming up to 98 DEG C of reactions
20min；Add the dilution of 270ml water, and with 5ml 30% h2o2 and unnecessary kmno4, the color of mixed solution is pale brown
Color, filtered while hot, deionized water cyclic washing obtains go to neutrality, ultrasonic disperse；200ml mass fraction is taken to be 5mg/ml
Graphene oxide solution pour diameter 25cm into, in the discoid reaction utensil of high 2cm, add ascorbic acid (vc) 0.5g stirring make
It is sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, and the graphene oxide Spontaneous Contraction in reaction utensil is handed over
It is unified into three-dimensional sponge structure, lyophilization, obtain the three-dimensional sponge shape Graphene of flexibility.
4. a kind of preparation method of antibacterial noctilucence health-care ceramic, it comprises the following steps:
Step a, prepares glaze slip: by mass percentage, by 10 ~ 15% zinc oxide, 0.4 ~ 0.5% brium carbonate, 0.3 ~ 0.4% Talcum
Powder, 58 ~ 65% Boraxs, 10 ~ 12% silicon oxides, 12 ~ 20% boron oxides and 0.1 ~ 6% functional agent mix to obtain mixed-powder, and addition contains
In the ball grinder of alumina balls abrading-ball and distilled water, ball grinder is fixed on vibration at high speed ball mill, and is rotated and ball
Mill；Add tourmaline and cordierite, be rotated further and ball milling, control slurry 300 ~ 350 mesh, prepared glaze slip；Wherein, described electricity
Gas stone and cordierite account for the 3 ~ 8% and 1 ~ 5% of mixed-powder quality respectively；
Step b, impregnates glaze slip: porous ceramicss are carried out impregnate glaze slip → evacuation → pressurized circulation process, at least circulate 1 time；
Then carry out 300 ~ 500 DEG C once sintered；
Step c, sprays glaze slip: by the way of glaze spraying, by glaze slip spraying porous ceramic surface after sintering；Then carry out
700 ~ 800 DEG C of double sintering, prepared health-care ceramic；Wherein,
Described functional agent includes noctilucence complex and gqds/ag2O/zno/ Graphene antibiosis powder.
5. the preparation method of antibacterial noctilucence health-care ceramic according to claim 4 is it is characterised in that the system of described functional agent
Preparation Method is as follows:
(1) weigh 0.3 ~ 1gc60 powder, measure the concentrated sulphuric acid that 80 ~ 100ml mass fraction is 98%, by c60 powder and concentrated sulphuric acid
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 noctilucence complex is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even stable
Dispersion liquid, wherein the weight of antibacterial powder and noctilucence complex is than for 3 ~ 5:1 ~ 3；The substrate with carbon nanotube mesh film is put
When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, so that this homogeneous dispersion is scattered in
In this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophilic, this dispersion liquid is attracted to CNT
Multiple net holes of reticular membrane；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives most of moisture away and leave absorption
Antibacterial powder and noctilucence complex in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, taken out
Then the carbon nanotube mesh film being adsorbed with antibacterial powder and noctilucence complex is scraped off this by vacuum → heating pressurized circulation 3 ~ 5 times
Substrate, obtains antibacterial-noctilucent function agent.
6. the preparation method of antibacterial noctilucence health-care ceramic according to claim 5 is it is characterised in that described three-dimensional sponge shape
Graphene preparation method is as follows: by 3g graphite powder, 1g nano3 is mixed homogeneously with 250ml 98% concentrated sulphuric acid in ice-water bath, delays
Slow addition 6g kmno4；Then heat at 35 DEG C, after stirring 40min, add 95ml deionized water, be warming up to 98 DEG C of reactions
20min；Add the dilution of 270ml water, and with 5ml 30% h2o2 and unnecessary kmno4, the color of mixed solution is pale brown
Color, filtered while hot, deionized water cyclic washing obtains go to neutrality, ultrasonic disperse；200ml mass fraction is taken to be 5mg/ml
Graphene oxide solution pour diameter 25cm into, in the discoid reaction utensil of high 2cm, add ascorbic acid (vc) 0.5g stirring make
It is sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, and the graphene oxide Spontaneous Contraction in reaction utensil is handed over
It is unified into three-dimensional sponge structure, lyophilization, obtain the three-dimensional sponge shape Graphene of flexibility.
7. the preparation method of the antibacterial noctilucence health-care ceramic according to claim 1 or 4 is it is characterised in that described noctilucence is multiple
The preparation method of compound is as follows: under nitrogen environment, concentration is the protonic acid solution of 0.05 ~ 0.5mol/l and concentration be 0.05 ~
The DBSA of 0.5mol/l is mixed with volume ratio 3:1 ~ 3, is simultaneously introduced luminescent powder, after magnetic agitation 60 ~ 120min
Add aniline, luminescent powder and aniline mass ratio are 1:5 ~ 10；After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline
It is 1:1 with Ammonium persulfate. mol ratio；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/noctilucence flour complexes；1 ~ 10g nano polyaniline/noctilucence flour complexes ultrasonic agitation is scattered in water
In solution；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, instead
Answer temperature to be 20 ~ 25 DEG C, react 60 ~ 90min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Should
Precipitation drying, to obtain nano polyaniline/noctilucence flour complexes/sio2；By nano polyaniline/noctilucence flour complexes/sio2It is placed in
Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under argon gas atmosphere, remove polyaniline, obtain luminescent powder/porous sio2.
8. a kind of antibacterial noctilucence health-care ceramic is it is characterised in that it presses described preparation method system as arbitrary in claim 1 to 7
?.
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