CN106396392A - Antibacterial and deodorant lead and cadmium free low temperature frit and preparation method thereof - Google Patents
Antibacterial and deodorant lead and cadmium free low temperature frit and preparation method thereof Download PDFInfo
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- CN106396392A CN106396392A CN201610748960.5A CN201610748960A CN106396392A CN 106396392 A CN106396392 A CN 106396392A CN 201610748960 A CN201610748960 A CN 201610748960A CN 106396392 A CN106396392 A CN 106396392A
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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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Abstract
The invention discloses an antibacterial and deodorant lead and cadmium free low temperature frit and a preparation method thereof. The preparation method comprises the steps of: A material mixing: mixing and grinding 10-18% of quartz, 5-12% of feldspar, 15-25% of borax, 3-12% of carbonate, 20-35% of boric acid, 3-8% of spodumene, 1-4% of a fluoride salt, and 0-5% of kaolin, then adding 0.1-5% of an antibacterial compound and 3-8% of a deodorant, and grinding the substances uniformly to obtain a mixture; B melting; and C molding and cooling. Compared with existing low temperature frits, the low temperature frit prepared by the method provided by the invention has the advantages of scientific compounding, reasonable preparation, stable performance, and no lead, cadmium or other extremely toxic substances. Also through reasonable collocation with the deodorant and an antibacterial composite material, the two play a synergistic role, and endow the obtained frit with excellent antibacterial and deodorant performance, thus further broadening the application scope of the low temperature frit. The firt can be used as the raw material to manufacture abundant building materials, like antibacterial and deodorant mosaics, antibacterial and deodorant microcrystalline ceramic composite plates, and antibacterial and deodorant low-temperature ceramic ink, etc.
Description
Technical field
The present invention relates to ceramic technology field, more particularly to a kind of antibacterial and deodouring lead and cadmium free low temperature frit and its system
Preparation Method.
Background technology
Bacterium, mould 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 industrial 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, due in low temperature frit contain substantial amounts of B, Li, Pb etc. fluxed from
Thus obtaining the characteristic of watery fusion, this kind of raw material has been widely applied in the glaze of conventional ceramic to reduce glaze
Melt temperature, raising glaze quality.But, traditional low temperature frit uses leaded, cadmium chemistry in a large number in order to reduce its temperature
Material is although the effect of melt temperature can be reduced, but the chemical substance of lead, cadmium contains severe toxicity.Meanwhile, also rarely has report at present
Road is with regard to the low temperature frit of antibacterial functions, particularly multi-functional low temperature frit.
Content of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of antibacterial and deodouring lead and cadmium free low temperature frit and its
Preparation method
The technical problem to be solved is achieved by the following technical programs：
A kind of antibacterial and deodouring lead and cadmium free low temperature frit and preparation method thereof, this preparation method comprises the following steps：
A batch mixing：By 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% boraxs, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% lithium brightness
Stone, 1 ~ 4% fluoride salt, 0 ~ 5% kaolin mixed grinding uniformly, add 0.1 ~ 5% antibiotic complex and 3 ~ 8% deodorant, grind
Compound is uniformly obtained；
B founds：The compound that step A is obtained dispenses in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, obtains
The slurry of molten state；
C shaping cooling：Step B is obtained slurry water quenching cooling, and being broken into graininess, to can get antibacterial and deodouring lead and cadmium free low
Warm frit.
In the present invention, described feldspar is by potassium feldspar and albite by weight 3 ~ 5:1 ~ 2 is obtained by mixing.Described carbonate
It is made up of at least one in potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate it is preferable that described carbonate is by carbonic acid
Potassium, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight 3:1:3:2:1 is obtained by mixing.Described fluoride salt by sodium fluoride,
Calcirm-fluoride and lithium fluoride by weight 4:2:1 is obtained by mixing.
In the present invention, described deodoriser preparing process is as follows：Mix the raw material of following percentage by weight：ZrO21~
10%, TiO25 ~ 15%, SiO210 ~ 20%, V2O51 ~ 5%, K2O 1 ~ 5%, SnO21 ~ 5%, Cr2O31 ~ 3%, Al2O310 ~ 15%,
Fe2O310 ~ 15%, MgO 10 ~ 20%, Na2O 5 ~ 10%, MnO25 ~ 10%, put in grinder and be ground, control particle diameter
Between 10 ~ 500nm, prepared inorganic oxide；By 30 ~ 40% epoxy resin, 30 ~ 50% phenolic resin and 20 ~ 30% inorganic oxides
Thing is sufficiently mixed, and adds appropriate butyl acetate to put into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to permissible
The slurry of coating；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, it is warmed up to 900 ~
1000 DEG C, it is incubated 1 ~ 2h；Film is scraped off this substrate, obtains deodorant.
In the present invention, described antibiotic complex can be obtained by the following method：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric 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
Light irradiation power is 0.5 ~ 2W；Standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus
Entering concentration is 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 ~
The 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/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 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 the aqueous solution；Add volume ratio 3 ~ 5 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）, 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 silica, be centrifuged and be dried, obtain
Antibacterial powder；
（5）Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is the ten of 0.05 ~ 0.5mol/L
Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12~18；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline
It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
（6）Prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mixes；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
（7）1 ~ 3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains
All even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added concave shape
Substrate in, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, due to carbon nanometer
When pipe is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25
DEG C, CNT has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes absorption to be received in carbon
In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial flour complexes will be adsorbed with
Film scrapes off this substrate, obtains antibiotic complex.
It is preferred that in step（4）With（5）Between increase by a step：Three-dimensional sponge shape Graphene ultrasonic agitation is taken to be scattered in
In the aqueous solution, it is added dropwise over GQDs/Ag2O/Ag-Zn-Ce/SiO2In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag2O/
Ag-Zn-Ce/SiO2Weight than for 1:1~5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, standing, deionized water is washed for several times, is dried
Obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder.
In the present invention, described antibiotic complex can also be obtained by the following method：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric 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
Light irradiation power is 0.5 ~ 2W；Standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus
Entering concentration is 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 the aqueous solution；Being added dropwise over concentration is 0.05 ~ 0.5g/100mlZnO
The 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 antibacterial powder；
（4）Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is the ten of 0.05 ~ 0.5mol/L
Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12~18；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline
It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
（5）Prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mixes；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
（6）1 ~ 3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains
All even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added concave shape
Substrate in, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, due to carbon nanometer
When pipe is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25
DEG C, CNT has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes absorption to be received in carbon
In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial flour complexes will be adsorbed with
Film scrapes off this substrate, obtains antibiotic complex.
It is preferred that in step（3）With（4）Between increase by a step：Three-dimensional sponge shape Graphene ultrasonic agitation is taken to be scattered in
In the aqueous solution, it is added dropwise over GQDs/Ag2In the O/ZnO aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag2The weight ratio of O/ZnO
For 1:1~5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, standing, deionized water is washed for several times, dry GQDs/Ag2O/ZnO/ Graphene
Antibacterial powder.
The present invention has the advantages that：This method loads and fixing antiseptic on the carbon nanotubes, not only prevents it
Reunite, significantly improve the stability of the antiseptics such as metal nanoparticle so as to can more preferably be dispersed in low temperature frit, and have more
Long-acting antibacterial activity and silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antiseptics simultaneously, compare
There is more preferable antibacterial effect in single silver nano antibacterial agent, antibacterial is lasting；Inorganic oxide main component has magnesium, aluminium, iron
Deng more than the 10 kinds of trace elements favourable to human body, because it is a kind of special polarity crystalline solid of structure, itself can produce for a long time
Electron ion, and forever discharge negative aeroion, reach the effect of deodorant purify air.Compare with existing low temperature frit, the present invention
The low temperature frit dispensing science manufacturing, preparation is reasonable, stable performance, and does not contain the extremely toxic substances such as lead cadmium, through rational
Collocation deodorant and antimicrobial composite material, both synergies, so that frit has excellent antibacterial and deodoriging properties, are opened up further
The wide range of application of low temperature frit, the construction material that can enrich as raw material manufacture, such as antibacterial and deodouring mosaic, anti-
Bacterium deodorant micro-crystalline ceramic composite plate, antibacterial and deodouring low-temp ceramics ink etc..
Specific embodiment
To further illustrate technical scheme below by specific preferred embodiment.
Embodiment 1
A kind of antibacterial and deodouring lead and cadmium free low temperature frit and preparation method thereof, this preparation method comprises the following steps：
A batch mixing：By 12% quartz, 12% feldspar, 15% borax, 6% carbonate, 35% boric acid, 5% spodumene, 4% fluoride salt, 2.9% height
Ridge soil mixed grinding uniformly, adds 0.1% antibiotic complex and 8% deodorant, grinds and compound is uniformly obtained；Described feldspar by
Potassium feldspar and albite by weight 4:1 is obtained by mixing；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and carbon
Sour calcium by weight 3:1:3:2:1 is obtained by mixing；Described fluoride salt is by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:1
It is obtained by mixing；
B founds：The compound that step A is obtained dispenses in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, obtains
The slurry of molten state；High temperature melting technique is：Room temperature, to 1000 DEG C, is incubated 10min；It is warming up to 1300 DEG C, insulation
30min；It is cooled to 1250 DEG C, be incubated 15min；It is warming up to 1320 DEG C, be incubated 30min；
C shaping cooling：Step B is obtained slurry water quenching cooling, and being broken into graininess, to can get antibacterial and deodouring lead and cadmium free low
Warm frit.
Wherein, described deodoriser preparing process is as follows：Mix the raw material of following percentage by weight：ZrO25%, TiO210%,
SiO216%, V2O54%, K2O 3%, SnO22%, Cr2O32%, Al2O313%, Fe2O312%, MgO 18%, Na2O 8%, MnO2
7%, put into PUHLER company exploitation big flow circulation horizontal sand mill in be ground, control particle diameter 10 ~ 500nm it
Between, prepared inorganic oxide；30% epoxy resin, 50% phenolic resin and 20% inorganic oxide are sufficiently mixed, add appropriate
Butyl acetate puts into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to the slurry that can apply；This slurry is applied
Spread on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1h；Film is scraped off this base
Plate, obtains inorganic oxide/holey carbon film.
Described antibiotic complex is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric 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）Outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.001mol/L silver nitrate aqueous solution；Being added dropwise over concentration is
0.1mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation
20min；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 the 100ml aqueous solution；Being added dropwise over concentration is 0.05mol/L cerous nitrate
The aqueous solution, being added dropwise over concentration after 30min is 0.005mol/L zinc nitrate aqueous solution, GQDs/Ag2The O 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 the aqueous solution；Add volume ratio 4 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）, adjust pH value be 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 hydrofluoric acid and surpassed with ultrasonic power 100W
Sound 10min, removes surface local silica, is centrifuged and is dried, obtains antibacterial powder；
（5）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration
Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min
It is 2 with aniline mass ratio:After 18 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple
Compound；
（6）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti-
Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
（7）1g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even
Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape
In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C
When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer
Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film
Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base
Plate, obtains antibiotic complex.
Embodiment 2
A kind of antibacterial and deodouring lead and cadmium free low temperature frit and preparation method thereof, this preparation method comprises the following steps：
A batch mixing：By 15% quartz, 7% feldspar, 22% borax, 9% carbonate, 25% boric acid, 8% spodumene, 3% fluoride salt, 3% kaolinite
Native mixed grinding uniformly, adds 3% antibiotic complex and 5% deodorant, grinds and compound is uniformly obtained；Described feldspar is long by potassium
Stone and albite by weight 4:1 is obtained by mixing；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate
By weight 3:1:3:2:1 is obtained by mixing；Described fluoride salt is by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:1 mixing
And obtain；
B founds：The compound that step A is obtained dispenses in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, obtains
The slurry of molten state；High temperature melting technique is：Room temperature, to 1000 DEG C, is incubated 10min；It is warming up to 1300 DEG C, insulation
30min；It is cooled to 1250 DEG C, be incubated 15min；It is warming up to 1320 DEG C, be incubated 30min；
C shaping cooling：Step B is obtained slurry water quenching cooling, and being broken into graininess, to can get antibacterial and deodouring lead and cadmium free low
Warm frit.
Wherein, the preparation method of described deodorant is as follows：Mix the raw material of following percentage by weight：ZrO25%, TiO2
10%, SiO216%, V2O54%, K2O 3%, SnO22%, Cr2O32%, Al2O313%, Fe2O312%, MgO 18%, Na2O 8%,
MnO27%, be ground in the big flow circulation horizontal sand mill putting into the exploitation of PUHLER company, control particle diameter 10 ~
Between 500nm, prepared inorganic oxide；36% epoxy resin, 40% phenolic resin and 24% inorganic oxide are sufficiently mixed, plus
Enter appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can apply；Will
This slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 1000 DEG C, be incubated 2h；By film
Scrape off this substrate, obtain inorganic oxide/holey carbon film.
Described antibiotic complex is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric 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）Outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.005mol/L silver nitrate aqueous solution；Being added dropwise over concentration is
0.2mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation
20min；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 the 100ml aqueous solution；Being added dropwise over concentration is 0.03mol/L cerous nitrate
The aqueous solution, being added dropwise over concentration after 30min is 0.03mol/L zinc nitrate aqueous solution, GQDs/Ag2The O 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 the aqueous solution；Add volume ratio 4 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）, adjust pH value be 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 hydrofluoric acid and surpassed with ultrasonic power 100W
Sound 12min, removes surface local silica, is centrifuged and is dried, obtains antibacterial powder；
（5）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration
Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min
It is 2 with aniline mass ratio:After 15 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple
Compound；
（6）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti-
Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
（7）2g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even
Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape
In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C
When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer
Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film
Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base
Plate, obtains antibiotic complex.
Embodiment 3
A kind of antibacterial and deodouring lead and cadmium free low temperature frit and preparation method thereof, this preparation method comprises the following steps：
A batch mixing：By 18% quartz, 5% feldspar, 25% borax, 12% carbonate, 20% boric acid, 6% spodumene, 1% fluoride salt, 5% kaolinite
Native mixed grinding uniformly, adds 5% antibiotic complex and 3% deodorant, grinds and compound is uniformly obtained；Described feldspar is long by potassium
Stone and albite by weight 4:1 is obtained by mixing；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate
By weight 3:1:3:2:1 is obtained by mixing；Described fluoride salt is by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:1 mixing
And obtain；
B founds：The compound that step A is obtained dispenses in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, obtains
The slurry of molten state；High temperature melting technique is：Room temperature, to 1000 DEG C, is incubated 10min；It is warming up to 1300 DEG C, insulation
30min；It is cooled to 1250 DEG C, be incubated 15min；It is warming up to 1320 DEG C, be incubated 30min；
C shaping cooling：Step B is obtained slurry water quenching cooling, and being broken into graininess, to can get antibacterial and deodouring lead and cadmium free low
Warm frit.
Wherein, the preparation method of described deodorant is as follows：Mix the raw material of following percentage by weight：ZrO25%, TiO2
10%, SiO216%, V2O54%, K2O 3%, SnO22%, Cr2O32%, Al2O313%, Fe2O312%, MgO 18%, Na2O 8%,
MnO27%, be ground in the big flow circulation horizontal sand mill putting into the exploitation of PUHLER company, control particle diameter 10 ~
Between 500nm, prepared inorganic oxide；40% epoxy resin, 30% phenolic resin and 30% inorganic oxide are sufficiently mixed, plus
Enter appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can apply；Will
This slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 1000 DEG C, be incubated 1h；By film
Scrape off this substrate, obtain inorganic oxide/holey carbon film.
Antibiotic complex is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric 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）Outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.01mol/L silver nitrate aqueous solution；Being added dropwise over concentration is
0.5mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation
20min；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 the 100ml aqueous solution；Being added dropwise over concentration is 0.005mol/L nitric acid
The cerium aqueous solution, being added dropwise over concentration after 30min is 0.05mol/L zinc nitrate aqueous solution, GQDs/Ag2The O 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 the aqueous solution；Add volume ratio 4 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）, adjust pH value be 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 hydrofluoric acid and surpassed with ultrasonic power 100W
Sound 15min, removes surface local silica, is centrifuged and is dried, obtains antibacterial powder；
（5）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration
Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min
It is 2 with aniline mass ratio:After 12 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple
Compound；
（6）Prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/
Antibacterial flour complexes, mix；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained compound after milling
Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
（7）3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even
Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape
In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C
When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer
Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film
Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base
Plate, obtains antibiotic complex.
Embodiment 4
Based on the preparation method of embodiment 2, difference is：Step（4）With（5）Between increase following steps：Take three-dimensional sea
Continuous shape Graphene ultrasonic agitation is scattered in the aqueous solution, is added dropwise over GQDs/Ag2O/Ag-Zn-Ce/SiO2In the aqueous solution, three-dimensional
Spongy graphene and GQDs/Ag2O/Ag-Zn-Ce/SiO2Weight than for 1:3；The ultrasonic 90min of 50W, standing, deionized water
Washing for several times, dry GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder.
Three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powder, 1g NaNO3 in ice-water bath with 250ml
98% concentrated sulfuric acid mixes, and is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml to go
Ionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with 5ml 30% H2O2 with unnecessary KMnO4,
The color of mixed solution is brown color, filters while hot, and deionized water cyclic washing obtains GO to neutrality, ultrasonic disperse；Take
200ml mass fraction is that the graphene oxide solution of 5mg/ml pours diameter 25cm into, in the discoid reaction utensil of high 2cm, adds
Ascorbic acid (VC) 0.5g stirring makes it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, in reaction utensil
Graphene oxide Spontaneous Contraction be cross-linked into three-dimensional sponge structure, freeze-drying, obtain flexibility three-dimensional sponge shape Graphene.
Embodiment 5
Based on the preparation method of embodiment 1, difference is：Described antibiotic complex is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric 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）Outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.001mol/L silver nitrate aqueous solution；Being added dropwise over concentration is
0.1mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation
20min；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 the aqueous solution；Being added dropwise over concentration is 0.5g/100mlZnO quantum dot
The 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 antibacterial powder；
（4）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration
Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min
It is 2 with aniline mass ratio:After 18 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple
Compound；
（5）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti-
Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
（6）1g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even
Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape
In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C
When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer
Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film
Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base
Plate, obtains antibiotic complex.
Embodiment 6
Based on the preparation method of embodiment 2, difference is：Described antibiotic complex is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric 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）Outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.005mol/L silver nitrate aqueous solution；Being added dropwise over concentration is
0.2mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation
20min；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 the aqueous solution；Being added dropwise over concentration is 0.2g/100mlZnO quantum dot
The 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 antibacterial powder；
（4）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration
Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min
It is 2 with aniline mass ratio:After 15 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple
Compound；
（5）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti-
Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
（6）2g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even
Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape
In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C
When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer
Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film
Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base
Plate, obtains antibiotic complex.
Embodiment 7
Based on the preparation method of embodiment 3, difference is：Described antibiotic complex is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric 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）Outstanding
Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.01mol/L silver nitrate aqueous solution；Being added dropwise over concentration is
0.5mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation
20min；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 the aqueous solution；Being added dropwise over concentration is 0.05g/100mlZnO quantum dot
The 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 antibacterial powder；
（4）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration
Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min
It is 2 with aniline mass ratio:After 12 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；
20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple
Compound；
（5）Prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/
Antibacterial flour complexes, mix；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained compound after milling
Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
（6）3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even
Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape
In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C
When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer
Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film
Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base
Plate, obtains antibiotic complex.
Embodiment 8
Based on the preparation method of embodiment 6, difference is：Step（3）With（4）Between increase as next step：Take three-dimensional
Spongy graphene ultrasonic agitation is scattered in the aqueous solution, is added dropwise over GQDs/Ag2In the O/ZnO aqueous solution, three-dimensional sponge shape stone
Black alkene and GQDs/Ag2The weight of O/ZnO is than for 1:3；The ultrasonic 90min of 50W, standing, deionized water is washed for several times, dry
GQDs/Ag2O/ZnO/ Graphene antibiosis powder.
Three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powder, 1g NaNO3 in ice-water bath with 250ml
98% concentrated sulfuric acid mixes, and is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml to go
Ionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with 5ml 30% H2O2 with unnecessary KMnO4,
The color of mixed solution is brown color, filters while hot, and deionized water cyclic washing obtains GO to neutrality, ultrasonic disperse；Take
200ml mass fraction is that the graphene oxide solution of 5mg/ml pours diameter 25cm into, in the discoid reaction utensil of high 2cm, adds
Ascorbic acid (VC) 0.5g stirring makes it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, in reaction utensil
Graphene oxide Spontaneous Contraction be cross-linked into three-dimensional sponge structure, freeze-drying, obtain flexibility three-dimensional sponge shape Graphene.
Comparative example 1
Based on the preparation method of embodiment 1, difference is：Described antibiotic complex is the titanium dioxide carrying metal antibacterial agent
Titanium；Without deodorant.
Comparative example 2
Based on the preparation method of embodiment 5, difference is：Described antibiotic complex is the mixing of zinc oxide and titanium dioxide
Thing；Described deodorant is inorganic oxide, is obtained by the following method：Mix the raw material of following percentage by weight：ZrO25%,
TiO210%, SiO216%, V2O54%, K2O 3%, SnO22%, Cr2O32%, Al2O313%, Fe2O312%, MgO 18%,
Na2O 8%, MnO27%, it is ground in the big flow circulation horizontal sand mill putting into the exploitation of PUHLER company, control particle diameter
Between 10 ~ 500nm, prepared inorganic oxide.
Each embodiment and the low temperature frit of comparative example offer, wherein not leaded, cadmium toxic element, the experiment proved that and be less than
It is melting at 800 DEG C, can be used for preparing the flux material of various low-temperature environment-friendly potteries.
The frit that embodiment 1 ~ 8, comparative example 1 ~ 2 are obtained is through sieving, after ground and mixed, faced by the use of PVA as normal temperature
When binding agent, add gum arabic suspending agent, by mixed powder addition water make the slip possessing certain suspendability.By 16
After the cordierite-quality honeycombed ceramics of hole/cm2 cut into 1cm × 1cm fritter, it is immersed in this slip, take out after several minutes, do
Dry, after 700 DEG C of calcinings, obtain cordierite ceramica material；And it is carried out with antibacterial antifouling property test and deodorization
Can test, test result is as follows：
Sterilization rate：Take 105The large intestine stalk bacterium 0.1ml of individual/ml, is spread evenly across on ceramic material, places 2h indoors, then
Bacterium solution sterilized water is eluted in culture medium, cultivates 24h at 37 DEG C, then detect bacterium number, calculate sterilization rate.
Wear testing：The abrasive material being 3～4 from Mohs' hardness, friction on the ceramic material makes imitating paving for 1000 times
With the effect after 2 years, test its sterilization rate.
Heat stability testing：Ceramic material is placed in electric furnace, is raised to 200 DEG C from room temperature, be incubated 20min, rapid input
In 25 DEG C of water, take out after 10min and dry, test its sterilization rate.
Antifouling test：It is pollutant from chrome green.
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/mean value).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.
Deodorizing test：Prepare two 51PVF resin airbags, an air bag is put into one piece of sample print, another tree
Fat air bag not setting-out piece.Then it is blown into 500ppmNH3- air gas mixture in two air bags respectively and seal.At interval of
30min uses gas detecting tube to measure the concentration of NH3 in air bag, until terminating after 2 hours of on-test.
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 (6)
1. a kind of preparation method of antibacterial and deodouring lead and cadmium free low temperature frit, it comprises the following steps：
A batch mixing：By 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% boraxs, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% lithium brightness
Stone, 1 ~ 4% fluoride salt, 0 ~ 5% kaolin mixed grinding uniformly, add 0.1 ~ 5% antibiotic complex and 3 ~ 8% deodorant, grind
Compound is uniformly obtained；
B founds：The compound that step A is obtained dispenses in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, obtains
The slurry of molten state；
C shaping cooling：Step B is obtained slurry water quenching cooling, and being broken into graininess, to can get antibacterial and deodouring lead and cadmium free low
Warm frit.
2. the preparation method of antibacterial and deodouring lead and cadmium free low temperature frit according to claim 1 is it is characterised in that described deodorant
Agent preparation method is as follows：Mix the raw material of following percentage by weight：ZrO21 ~ 10%, TiO25 ~ 15%, SiO210 ~ 20%, V2O5
1 ~ 5%, K2O 1 ~ 5%, SnO21 ~ 5%, Cr2O31 ~ 3%, Al2O310 ~ 15%, Fe2O310 ~ 15%, MgO 10 ~ 20%, Na2O 5~
10%, MnO25 ~ 10%, put in grinder and be ground, control particle diameter between 10 ~ 500nm, prepared inorganic oxide；
30 ~ 40% epoxy resin, 30 ~ 50% phenolic resin and 20 ~ 30% inorganic oxides are sufficiently mixed, add appropriate butyl acetate
Put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can apply；By this slurry coating in substrate
On, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 ~ 1000 DEG C, be incubated 1 ~ 2h；Film is scraped off this base
Plate, obtains deodorant.
3. the preparation method according to the arbitrary described antibacterial and deodouring lead and cadmium free low temperature frit of claim 1 or 2 it is characterised in that
The preparation method of described antibiotic complex is as follows：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric 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, dropping 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 ~
The 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/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 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 the aqueous solution；Add volume ratio 3 ~ 5 afterwards:1
Water and ammoniacal liquor, be stirring evenly and then adding into, adjust pH value be 9 ~ 10, reaction temperature be 20 ~ 25 DEG C, react 30 ~ 60min；Carry out
Centrifugation simultaneously cleans 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/SiO2It is placed under argon gas atmosphere and carry out 500 ~ 800 DEG C of heat
Process 1 ~ 2h, after being cooled to room temperature, be immersed in hydrofluoric acid and ultrasonic 10 ~ 15min is carried out with ultrasonic power 100 ~ 150W, remove table
Face local silica, is centrifuged and is dried, obtain antibacterial powder；
（5）Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is the ten of 0.05 ~ 0.5mol/L
Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12~18；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline
It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
（6）Prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mixes；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
（7）1 ~ 3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains
All even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added concave shape
Substrate in, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, due to carbon nanometer
When pipe is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25
DEG C, CNT has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes absorption to be received in carbon
In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial flour complexes will be adsorbed with
Film scrapes off this substrate, obtains antibiotic complex.
4. a kind of preparation method of antibacterial and deodouring lead and cadmium free low temperature frit, it comprises the following steps：
A batch mixing：By 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% boraxs, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% lithium brightness
Stone, 1 ~ 4% fluoride salt, 0 ~ 5% kaolin mixed grinding uniformly, add 0.1 ~ 5% antibiotic complex and 3 ~ 8% deodorant, grind
Compound is uniformly obtained；
B founds：The compound that step A is obtained dispenses in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, obtains
The slurry of molten state；
C shaping cooling：Step B is obtained slurry water quenching cooling, and being broken into graininess, to can get antibacterial and deodouring lead and cadmium free low
Warm frit；
Wherein, the preparation method of described antibiotic complex is as follows：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric 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, dropping 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 the aqueous solution；Being added dropwise over concentration is 0.05 ~ 0.5g/100mlZnO
The 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 antibacterial powder；
（4）Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is the ten of 0.05 ~ 0.5mol/L
Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12~18；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline
It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
（5）Prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mixes；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
（6）1 ~ 3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains
All even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added concave shape
Substrate in, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, due to carbon nanometer
When pipe is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25
DEG C, CNT has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes absorption to be received in carbon
In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial flour complexes will be adsorbed with
Film scrapes off this substrate, obtains antibiotic complex.
5. the preparation method of antibacterial and deodouring lead and cadmium free low temperature frit according to claim 4 is it is characterised in that described deodorant
Agent preparation method is as follows：Mix the raw material of following percentage by weight：ZrO21 ~ 10%, TiO25 ~ 15%, SiO210 ~ 20%, V2O5
1 ~ 5%, K2O 1 ~ 5%, SnO21 ~ 5%, Cr2O31 ~ 3%, Al2O310 ~ 15%, Fe2O310 ~ 15%, MgO 10 ~ 20%, Na2O 5~
10%, MnO25 ~ 10%, put in grinder and be ground, control particle diameter between 10 ~ 500nm, prepared inorganic oxide；
30 ~ 40% epoxy resin, 30 ~ 50% phenolic resin and 20 ~ 30% inorganic oxides are sufficiently mixed, add appropriate butyl acetate
Put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can apply；By this slurry coating in substrate
On, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 ~ 1000 DEG C, be incubated 1 ~ 2h；Film is scraped off this base
Plate, obtains deodorant.
6. a kind of antibacterial and deodouring lead and cadmium free low temperature frit is it is characterised in that by the preparation method system as described in claim 2 or 4
?.
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