CN106348595A - Noctilucent antibacterial lead and cadmium-free low-temperature frit and preparing method thereof - Google Patents

Abstract

The invention discloses an noctilucent antibacterial lead and cadmium-free low-temperature frit and a preparing method thereof. The method comprises the steps of: A mixing: mixing and grinding evenly 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 fluorinated salt and 0 - 5% of kaolin, adding 0.1-5% of antibacterial composite and 1 to 5% of noctilucent powder composite, grinding evenly to prepare a mixture; b melting, and c cooling for molding. Compared with the conventional low-temperature frit, the low-temperature frit prepared by the method has the advantages of scientific ingredients, reasonable preparation, stable performance and no toxic substances, such as lead and cadmium, meanwhile, the frit has the persistent antibaterical property of spectra, the antifouling self-cleaning function and the noctilucent function, does not have agglomeration and is high in uniformity and stability of luminance and antibacterial stability, which further broads the application range of the low-temperature frit. The frit can be used as raw materials to manufacture rich building materials,such as noctilucent antibacterial mosaic, noctilucent antibacterial microcrystalline ceramic composite panels and noctilucent antibacterial low-temperature ceramic ink.

Description

A kind of noctilucence antibacterial lead and cadmium free low temperature frit and preparation method thereof

Technical field

The present invention relates to ceramic technology field, more particularly to a kind of noctilucence antibacterial lead and cadmium free low temperature frit and its system Preparation 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.

Long after glow luminous material is commonly called as luminescent powder, has unsaturated energy level in its electronic structure, under illumination condition, absorbing light Sub- energy, makes electronics that energy level transition to occur, and in dark environment, the energy of Electron absorption can discharge, and produces fluorescence Effect.At present, long after glow luminous material mostly is in the application of ceramic and adds in glaze, makes luminous glaze, luminous glaze is permissible As referential index effect, the such as indicating bit of staircase, indicating bit of room switch etc., and it is abundant that product can be allowed to present Effect.

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, 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 and noctilucent function；And, low temperature frit is not suitable for directly adding antibacterial and/or long afterglow is sent out Luminescent material, due to hot environment and be susceptible to reunite and cause luminous and antibacterial and other effects not good problem.

Content of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of noctilucence antibacterial 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 noctilucence antibacterial 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% Anhydrites, 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 1 ~ 5% luminescent powder are combined Thing, grinds and 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 molding cools down: step b is obtained slurry water quenching cooling, and being broken into graininess, to can get noctilucence antibacterial lead and cadmium free low Warm frit.

In the present invention, described Anhydrite is obtained by mixing by weight 3 ~ 5:1 ~ 2 by potassium feldspar and albite.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 are obtained by mixing by weight 3:1:3:2:1.Described fluoride salt by sodium fluoride, Calcium fluoride and lithium fluoride are obtained by mixing by weight 4:2:1.

In the present invention, described noctilucence flour complexes preparation method is as follows:

Weigh porous graphene and be configured to graphene aqueous solution, water bath sonicator 1 ~ 2h obtains all even stable dispersion liquid；To receive Rice long lad phosphor adds in deionized water, in 500 ~ 1000kw ultrasonic vibration and the stirring of 500 ~ 1000r/min centrifugal speed Long lad phosphor dispersion liquid is obtained after lower dispersion 300 ~ 600min；100 ~ 200w ultrasonic lower toward graphene dispersing solution in slow Deca long lad phosphor dispersion liquid, the weight of porous graphene and fluorescent material is than for 1:1 ~ 5, ultrasonic 60 ~ 90min, Ran Houjing Put, sucking filtration, drying, carry out 800 ~ 900 DEG C of heat treatment 30 ~ 60min, prepared luminescent powder/porous graphene under vacuum environment.Institute Stating long lad phosphor for mean diameter is long afterglow sr less than 10nm₄al₁₄o₂₅Nano-phosphor.

The preparation of porous graphene: 1g graphite powder adds in 25ml concentrated sulphuric acid, and ice salt bath is cooled to 0 DEG C, is slowly added to 3g Kmno4, then heat to 30 DEG C, 60rpm stirs 2h, add 200ml water, add 4ml hydrogen peroxide, 600rpm centrifugation removes After impurity, ultrasonic (400w, 50hz) processes 1h, and microwave (800w, 2450hz) processes 1h then, obtains graphene oxide, then Add the naoh of 4g, nitrogen protects 760 DEG C of heating 1h in tube furnace, obtains porous graphene.

In the present invention, described antibiotic complex 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 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 mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline It is 1:1 with Ammonium persulfate. mol ratio；15 ~ 30h 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/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, mix homogeneously；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 hydrophilic, 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 increasing by a step between step (4) and (5): take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in In aqueous solution, it is 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；Ultrasonic 60 ~ the 120min of 10 ~ 100w, standing, deionized water wash 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 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 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 mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline It is 1:1 with Ammonium persulfate. mol ratio；15 ~ 30h 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/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, mix homogeneously；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 hydrophilic, 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 increasing by a step between step (3) and (4): take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in In aqueous solution, it is added dropwise over gqds/ag₂In 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 wash for several times, dry gqds/ag₂O/zno/ Graphene Antibacterial powder.

The invention has the following beneficial effects: this method loads and fixing antibacterial on the carbon nanotubes, not only prevent it Reunite, significantly improve the stability of the antibacterial 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 antibacterial simultaneously, compare There is more preferable antibacterial effect in single silver nano antibacterial agent, antibacterial is lasting；Compare with existing low temperature frit, manufacture of the present invention Low temperature frit dispensing science, preparation rationally, stable performance, and do not contain the extremely toxic substances such as lead cadmium, also have persistently simultaneously The antibacterial characteristics of spectrum, antifouling self-cleaning function and noctilucence performance, there is not agglomeration, uniformity of luminance stability is relatively Good, antibacterial stability preferably, has widened the range of application of low temperature frit further, the building that can enrich as raw material manufacture Material, such as noctilucence antibacterial mosaic, noctilucence antibacterial micro-crystalline ceramic composite plate, noctilucence antibacterial low-temp ceramics ink etc..

Specific embodiment

To further illustrate technical scheme below by specific preferred implementation.

Embodiment 1

A kind of noctilucence antibacterial 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% Anhydrite, 15% Borax, 8% carbonate, 35% boric acid, 8% spodumene, 4% fluoride salt, 0.9% height Ridge soil mixed grinding uniformly, adds 0.1% antibiotic complex and 5% noctilucence flour complexes, grinds and compound is uniformly obtained；Described Anhydrite is obtained by mixing by weight 4:1 by potassium feldspar and albite；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, carbonic acid Lithium and Calcium Carbonate are obtained by mixing by weight 3:1:3:2:1；Described fluoride salt is by sodium fluoride, calcium fluoride and lithium fluoride by weight 4:2:1 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 molding cools down: step b is obtained slurry water quenching cooling, and being broken into graininess, to can get noctilucence antibacterial lead and cadmium free low Warm frit.

Wherein, described noctilucence flour complexes preparation method is as follows: weighs porous graphene and is configured to graphene aqueous solution, water Bathe ultrasonic 2h and obtain all even stable dispersion liquid；Nanometer long lad phosphor is added in deionized water, ultrasonic in 1000kw Long lad phosphor dispersion liquid is obtained after vibrations and 1000r/min centrifugal speed stirring lower dispersion 300min；Under 120w is ultrasonic It is slowly added dropwise long lad phosphor dispersion liquid toward in graphene dispersing solution, the weight of porous graphene and fluorescent material ratio for 1:1, surpasses Sound 90min, then stands, sucking filtration, drying, carries out 850 DEG C of heat treatment 30min, prepared luminescent powder/porous stone under vacuum environment Black alkene.

Described antibiotic complex 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 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, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:18 with aniline mass ratio, 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/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- Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex 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 hydrophilic, 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 noctilucence antibacterial lead and cadmium free low temperature frit and preparation method thereof, this preparation method comprises the following steps:

A batch mixing: by 15% quartz, 6% Anhydrite, 23% Borax, 10% carbonate, 28% boric acid, 6% spodumene, 3% fluoride salt, 3% kaolinite Native mixed grinding uniformly, adds 3% antibiotic complex and 3% noctilucence flour complexes, grinds and compound is uniformly obtained；Described Anhydrite It is obtained by mixing by weight 4:1 by potassium feldspar and albite；Described carbonate by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and Calcium Carbonate is obtained by mixing by weight 3:1:3:2:1；Described fluoride salt is by sodium fluoride, calcium fluoride and lithium fluoride by weight 4:2: 1 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 molding cools down: step b is obtained slurry water quenching cooling, and being broken into graininess, to can get noctilucence antibacterial lead and cadmium free low Warm frit.

Wherein, the preparation method of described noctilucence flour complexes is as follows: weigh porous graphene and be configured to graphene aqueous solution, Water bath sonicator 2h obtains all even stable dispersion liquid；Nanometer long lad phosphor is added in deionized water, surpasses in 1000kw Long lad phosphor dispersion liquid is obtained after acoustic vibration and 1000r/min centrifugal speed stirring lower dispersion 300min；Ultrasonic in 120w Lower be slowly added dropwise long lad phosphor dispersion liquid toward in graphene dispersing solution, the weight of porous graphene and fluorescent material ratio for 1:3, Ultrasonic 90min, then stands, sucking filtration, drying, carries out 850 DEG C of heat treatment 30min, prepared luminescent powder/porous under vacuum environment Graphene.

Described antibiotic complex 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 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, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:15 with aniline mass ratio, 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/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- Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex 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 hydrophilic, 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 noctilucence antibacterial 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% Anhydrite, 25% Borax, 12% carbonate, 24% boric acid, 4% spodumene, 1% fluoride salt, 5% kaolinite Native mixed grinding uniformly, adds 5% antibiotic complex and 1% noctilucence flour complexes, grinds and compound is uniformly obtained；Described Anhydrite It is obtained by mixing by weight 4:1 by potassium feldspar and albite；Described carbonate by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and Calcium Carbonate is obtained by mixing by weight 3:1:3:2:1；Described fluoride salt is by sodium fluoride, calcium fluoride and lithium fluoride by weight 4:2: 1 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 molding cools down: step b is obtained slurry water quenching cooling, and being broken into graininess, to can get noctilucence antibacterial lead and cadmium free low Warm frit.

Wherein, the preparation method of described noctilucence flour complexes is as follows: weigh porous graphene and be configured to graphene aqueous solution, Water bath sonicator 2h obtains all even stable dispersion liquid；Nanometer long lad phosphor is added in deionized water, surpasses in 1000kw Long lad phosphor dispersion liquid is obtained after acoustic vibration and 1000r/min centrifugal speed stirring lower dispersion 300min；Ultrasonic in 120w Lower be slowly added dropwise long lad phosphor dispersion liquid toward in graphene dispersing solution, the weight of porous graphene and fluorescent material ratio for 1:5, Ultrasonic 90min, then stands, sucking filtration, drying, carries out 850 DEG C of heat treatment 30min, prepared luminescent powder/porous under vacuum environment Graphene.

Antibiotic complex 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 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, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:12 with aniline mass ratio, 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/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 homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained complex 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 hydrophilic, 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: increases following steps between step (4) and (5): take three-dimensional sea Continuous shape Graphene ultrasonic agitation is scattered in aqueous solution, is added dropwise over gqds/ag₂o/ag-zn-ce/sio₂In 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 sulphuric acid mix homogeneously, 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, filtered 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, lyophilization, 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 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 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, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:18 with aniline mass ratio, 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/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- Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex 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 hydrophilic, 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 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 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, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:15 with aniline mass ratio, 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/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- Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex 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 hydrophilic, 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 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 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, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:12 with aniline mass ratio, 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/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 homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained complex 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 hydrophilic, 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: increases such as next step between step (3) and (4): take three-dimensional Spongy graphene ultrasonic agitation is scattered in aqueous solution, is added dropwise over gqds/ag₂In 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 wash is 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 sulphuric acid mix homogeneously, 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, filtered 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, lyophilization, 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；Described noctilucence flour complexes are long afterglow sr that mean diameter is less than 10nm₄al₁₄o₂₅Nano-phosphor.

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 noctilucence flour complexes are long afterglow sr that mean diameter is less than 10nm₄al₁₄o₂₅Nano-phosphor.

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 room temperature When binding agent, add Radix Acaciae senegalis 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 photism 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: be 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/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 (10)

1. a kind of preparation method of noctilucence antibacterial lead and cadmium free low temperature frit, it comprises the following steps:

A batch mixing: by 10 ~ 18% quartz, 5 ~ 12% Anhydrites, 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 1 ~ 5% luminescent powder are combined Thing, grinds and 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 molding cools down: step b is obtained slurry water quenching cooling, and being broken into graininess, to can get noctilucence antibacterial lead and cadmium free low Warm frit.

2. the preparation method of noctilucence antibacterial lead and cadmium free low temperature frit according to claim 1 is it is characterised in that described noctilucence Flour complexes preparation method is as follows: weighs porous graphene and is configured to graphene aqueous solution, water bath sonicator 1 ~ 2h obtains all even Stable dispersion liquid；Nanometer long lad phosphor is added in deionized water, 500 ~ 1000kw ultrasonic vibration and 500 ~ Long lad phosphor dispersion liquid is obtained after the lower dispersion 300 ~ 600min of 1000r/min centrifugal speed stirring；Ultrasonic in 100 ~ 200w Lower be slowly added dropwise long lad phosphor dispersion liquid toward in graphene dispersing solution, the weight of porous graphene and fluorescent material than for 1:1 ~ 5, ultrasonic 60 ~ 90min, then stand, sucking filtration, drying, carry out 800 ~ 900 DEG C of heat treatment 30 ~ 60min under vacuum environment, system Obtain luminescent powder/porous graphene.

3. the preparation method of noctilucence antibacterial lead and cadmium free low temperature frit according to claim 2 is it is characterised in that described porous Preparing of Graphene is as follows: 1g graphite powder adds in 25ml concentrated sulphuric acid, and ice salt bath is cooled to 0 DEG C, is slowly added to the kmno4 of 3g, Then heat to 30 DEG C, 60rpm stirs 2h, add 200ml water, add 4ml hydrogen peroxide, after the removal of impurity is gone in 600rpm centrifugation, Supersound process 1h, microwave treatment 1h then, obtain graphene oxide, be subsequently adding the naoh of 4g, nitrogen protection in tube furnace 760 DEG C of heating 1h, obtain porous graphene.

4. the preparation method of noctilucence antibacterial lead and cadmium free low temperature frit according to claim 2 is it is characterised in that described Long lad phosphor is long afterglow sr that mean diameter is less than 10nm₄al₁₄o₂₅Nano-phosphor.

5. the preparation method according to the arbitrary described noctilucence antibacterial lead and cadmium free low temperature frit of Claims 1-4 it is characterised in that The preparation method of described antibiotic complex 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, 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, 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 Fluohydric acid. and ultrasonic 10 ~ 15min is carried out with ultrasonic power 100 ~ 150w, remove table Face local silicon dioxide, 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 mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline It is 1:1 with Ammonium persulfate. mol ratio；15 ~ 30h 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/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, mix homogeneously；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 hydrophilic, 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.

6. a kind of preparation method of noctilucence antibacterial lead and cadmium free low temperature frit, it comprises the following steps:

A batch mixing: by 10 ~ 18% quartz, 5 ~ 12% Anhydrites, 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 1 ~ 5% luminescent powder are combined Thing, grinds and 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 molding cools down: step b is obtained slurry water quenching cooling, and being broken into graininess, to can get noctilucence antibacterial 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 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 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 mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline It is 1:1 with Ammonium persulfate. mol ratio；15 ~ 30h 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/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, mix homogeneously；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 hydrophilic, 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.

7. the preparation method of noctilucence antibacterial lead and cadmium free low temperature frit according to claim 6 is it is characterised in that described noctilucence Flour complexes preparation method is as follows: weighs porous graphene and is configured to graphene aqueous solution, water bath sonicator 1 ~ 2h obtains all even Stable dispersion liquid；Nanometer long lad phosphor is added in deionized water, 500 ~ 1000kw ultrasonic vibration and 500 ~ Long lad phosphor dispersion liquid is obtained after the lower dispersion 300 ~ 600min of 1000r/min centrifugal speed stirring；Ultrasonic in 100 ~ 200w Lower be slowly added dropwise long lad phosphor dispersion liquid toward in graphene dispersing solution, the weight of porous graphene and fluorescent material than for 1:1 ~ 5, ultrasonic 60 ~ 90min, then stand, sucking filtration, drying, carry out 800 ~ 900 DEG C of heat treatment 30 ~ 60min under vacuum environment, system Obtain luminescent powder/porous graphene.

8. the preparation method of noctilucence antibacterial lead and cadmium free low temperature frit according to claim 6 is it is characterised in that described porous Preparing of Graphene is as follows: 1g graphite powder adds in 25ml concentrated sulphuric acid, and ice salt bath is cooled to 0 DEG C, is slowly added to the kmno4 of 3g, Then heat to 30 DEG C, 60rpm stirs 2h, add 200ml water, add 4ml hydrogen peroxide, after the removal of impurity is gone in 600rpm centrifugation, Supersound process 1h, microwave treatment 1h then, obtain graphene oxide, be subsequently adding the naoh of 4g, nitrogen protection in tube furnace 760 DEG C of heating 1h, obtain porous graphene.

9. the preparation method of noctilucence antibacterial lead and cadmium free low temperature frit according to claim 6 is it is characterised in that described Long lad phosphor is long afterglow sr that mean diameter is less than 10nm₄al₁₄o₂₅Nano-phosphor.

10. a kind of noctilucence antibacterial lead and cadmium free low temperature frit is it is characterised in that by the preparation method system as described in claim 2 or 6 ?.