CN106318040A

CN106318040A - Anti-radiation low-temperature ceramic ink for ink jet and preparation method thereof

Info

Publication number: CN106318040A
Application number: CN201610749000.0A
Authority: CN
Inventors: 邱杰华; 于庆九
Original assignee: FOSHAN CITY GAOMING DISTRICT HAIDI CERAMIC MATERIALS Co Ltd
Current assignee: FOSHAN CITY GAOMING DISTRICT HAIDI CERAMIC MATERIALS Co Ltd
Priority date: 2016-08-29
Filing date: 2016-08-29
Publication date: 2017-01-11

Abstract

The invention discloses anti-radiation low-temperature ceramic ink for ink jet and a preparation method thereof. The preparation method includes the following steps that A, dried materials of pigment 25-38%, an antibacterial compound 0.5-5%, an anti-radiation compound 3-12% and low-temperature frit 15-20% are mixed and grinded; B, a dispersing agent 3-8%, a surface additive 2-5%, a flatting agent 0.1-0.3%, a defoaming agent 0.3-0.8%, a binding agent 0.5-1%, an anti-settling agent 0.08-0.1% and a solvent are weighed and added to a high-speed stirring machine for dispersion and grinding, and filtration is performed to obtain a finished ink product. Compared with existing low-temperature ceramic ink, the low-temperature ceramic ink prepared by adopting the preparation method is scientific in composition, and the low-temperature frit which does not contain lead, cadmium and other extremely toxic substances is adopted so that the color development performance of the ceramic ink can be also ensured during low-temperature firing. In addition, the anti-radiation compound and the antibacterial compound produce a synergistic effect through reasonable collocation, so that the ceramic ink further has lasting spectral antibacterial properties, antifouling and self-cleaning functions and anti-radiation characteristics, and the application range of the low-temperature ceramic ink is further widened.

Description

A kind of ink-jet radioprotective low-temp ceramics ink and preparation method thereof

Technical field

The present invention relates to ceramic technology field, particularly related to a kind of ink-jet radioprotective low-temp ceramics ink and Preparation method.

Background technology

Antibacterial, mycete has the biggest harm as pathogen to the mankind and animals and plants, and the health affecting people even jeopardizes life Life, brings great economic loss.Therefore the research of anti-biotic material and goods thereof causes the concern of people, antibacterial product day by day Demand will constitute huge market.

Progress and the high speed development of information industry, computer, mobile phone, facsimile machine, telephone set and net along with science and technology The equipment such as network or system be widely used to information generation, transmit, receive, the processing procedure such as storage.This kind equipment is in work Time be unable to do without the effect of electromagnetic wave.The extensively application of electromagnetic wave brings the most serious electromagnetic interference and pollution.Reduce electromagnetism One of effective ways of interference use microwave to inhale ripple (receipts) material exactly.When electromagnetic wave is by absorbing material, electromagnetism can be produced Ripple is lost, and makes electromagnetic wave energy be converted into the energy of other forms, namely is farthest absorbed in absorbing material medium. Ferrite is a kind of good absorbing material, occupies critical role in radio-radar absorber field always.

Wall brick, no matter household interior decoration, or for commercial production or public place, after meeting outward appearance practicality, How to make it possess more function concerned in terms of health of people guarantee, be also that industry researcher is kept up with the trend of the times and gives 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 containing substantial amounts of B, Li, Pb etc. fluxed from Son thus obtain 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, the chemistry of cadmium in a large number in order to reduce its temperature Material, although the effect of melt temperature can be reduced, but the chemical substance of lead, cadmium contains severe toxicity.Meanwhile, currently also rarely has report Road uses low temperature frit to prepare functional type low-temp ceramics ink, such as Mobyneb low-temp ceramics inks such as radioprotectives.

Summary of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of ink-jet radioprotective low-temp ceramics ink and Its preparation method.

The technical problem to be solved is achieved by the following technical programs:

A kind of ink-jet radioprotective low-temp ceramics ink and preparation method thereof, this preparation method comprises the following steps:

Step A, by 25 ~ 38% colorants, 0.5 ~ 5% antibiotic complex, 3 ~ 12% radioprotective complex, 15 ~ 20% low temperature frits dry Material mixing, is subsequently poured into mix homogeneously in quick mixer；Use sand mill sand milling 10h so that it is particle diameter distribution≤1 μm；

Step B, weigh 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.1 ~ 0.3% levelling agent, 0.3 ~ 0.8% defoamer, 0.5 ~ 1% Bonding agent, 0.08 ~ 0.1% anti-settling agent, solvent, carry out disperseing 30 ~ 60min in being subsequently adding the homogenizer of step A；To divide The mixed liquor dissipated loads in sand mill, and sand milling 8 ~ 12h obtains the ink semi-finished product of particle diameter distribution≤300nm；

Step C, ink semi-finished product step B obtained, in the constant temperature a mixing bowl of 80～100 DEG C, then carry out evacuation, height Speed vibration, strainer filtering, obtain ink.

In the present invention, the preparation method of described low temperature frit is as follows: by 10 ~ 18% quartz, 5 ~ 12% Anhydrites, 15 ~ 25% boron Sand, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 0 ~ 5% Kaolin mixing sand milling uniformly prepare mixed Close material；Compound is dispensed in loading fire resistant sagger, carry out 1250 ~ 1320 DEG C of high temperature meltings, obtain the slurry of molten state；Will slurry Material water quenching cooling, and it is broken into graininess, prepare low temperature frit.Wherein, described Anhydrite is by potassium feldspar and albite by weight 3 ~ 5:1 ~ 2 are obtained by mixing.Described carbonate is by least one group in potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate Become, it is preferable that described carbonate is mixed by weight 3:1:3:2:1 by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate Close and obtain.Described fluoride salt is obtained by mixing by weight 4:2:1 by sodium fluoride, calcium fluoride and lithium fluoride.

In the present invention, described radioprotective complex preparation method is as follows: take by weight by 30 ~ 40% epoxy resin, 30 ~ 45% phenolic resin, 1 ~ 5% tourmaline, 3 ~ 8% rare earths and 20 ~ 30% ferrites are sufficiently mixed, and add appropriate butyl acetate and put into Ball mill disperses dispergation, after discharge, detects, adjust the slurry being configured to apply；By this slurry coating on substrate, dry Dry film forming；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 substrate, obtains anti- Radiation holey carbon film.

Described rare earth is combined by weight 1:2:2:1 by Lanthanum (III) nitrate, neodymium nitrate, Erbium trinitrate and cerous nitrate.

Tourmaline is by referring to that iron tourmaline, elbaite and dravite are combined by 3:2:1.

Ferrite is the one in strontium oxygen iron, barium oxygen ferrum and cobalt oxygen iron.

In the present invention, described antibiotic complex can prepare 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 Mixing in beaker, beaker is placed in ice-water bath, stirs with the speed of 500 ~ 600rpm simultaneously, obtains mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, adds in above-mentioned mixed liquor slowly；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialyse 3 ~ 5 days with the bag filter that molecular cut off is 1000, Graphene quantum dot (GQDs) suspension；100 ~ 150rpm speed stirring GQDs suspension, simultaneously laser irradiation 30 ~ 60min, swash Photoirradiation 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 add 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, regulation pH value to 11, then stand, from The heart, with deionized water and ethanol alternately washing three times, vacuum drying, obtains GQDs/Ag₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O 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 is to 7.0；Limit ultrasonic agitation, it is the hydrazine hydrate of 50% that limit adds 4 ~ 8mL mass fraction, 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), regulation PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；It is centrifuged and cleans with acetone and deionized water successively Obtain precipitation；This is deposited at 80 ~ 90 DEG C and is dried 2 ~ 4h, 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 Fluoric acid carries out ultrasonic 10 ~ 15min with ultrasonic power 100 ~ 150W, removes local, surface silicon dioxide, be centrifuged and be dried, it is thus achieved that Antibacterial powder；

(5), under nitrogen environment, it is the ten of 0.05 ~ 0.5mol/L by protonic acid solution and the concentration that concentration is 0.05 ~ 0.5mol/L Dialkyl benzene sulfonic acids mixes with volume ratio 2 ~ 4:2, is simultaneously introduced the antibacterial powder that step (4) prepares, after magnetic agitation 60 ~ 120min Adding aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise drip 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 final vacuum for several times is dried, Mill to obtain nano polyaniline/antibacterial powder complex；

(6) prepare TiO 2 sol by sol-gel process, in colloidal sol, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% Amine/antibacterial powder complex, mix homogeneously；Still aging 3～5d 60 DEG C～120 DEG C of rearmounted baking oven drying；After milling by gained again Calcine 1 ~ 2h at compound 400～550 DEG C, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(7) taking 1 ~ 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains The most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, due to carbon nanometer Having hydrophilic when pipe is near 8 DEG C, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex absorption and receive at carbon In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial powder complex will be adsorbed with Film scrapes off this substrate, it is thus achieved that antibiotic complex.

It is preferred that increase by a step between step (4) and (5): take three-dimensional sponge shape Graphene ultrasonic agitation and 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 ratio be 1:1 ~ 5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, and 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 prepare by the following method:

(3) 1 ~ 3gGQDs/Ag is taken₂O 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, stand, filter, be washed with deionized for several times, Vacuum drying, obtains GQDs/Ag₂O/ZnO antibacterial powder；

(4), under nitrogen environment, it is the ten of 0.05 ~ 0.5mol/L by protonic acid solution and the concentration that concentration is 0.05 ~ 0.5mol/L Dialkyl benzene sulfonic acids mixes with volume ratio 2 ~ 4:2, is simultaneously introduced the antibacterial powder that step (4) prepares, after magnetic agitation 60 ~ 120min Adding aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise drip 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 final vacuum for several times is dried, Mill to obtain nano polyaniline/antibacterial powder complex；

(5) prepare TiO 2 sol by sol-gel process, in colloidal sol, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% Amine/antibacterial powder complex, mix homogeneously；Still aging 3～5d 60 DEG C～120 DEG C of rearmounted baking oven drying；After milling by gained again Calcine 1 ~ 2h at compound 400～550 DEG C, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(6) taking 1 ~ 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains The most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, due to carbon nanometer Having hydrophilic when pipe is near 8 DEG C, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex absorption and receive at carbon In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial powder complex will be adsorbed with Film scrapes off this substrate, it is thus achieved that antibiotic complex.

It is preferred that increase by a step between step (3) and (4): take three-dimensional sponge shape Graphene ultrasonic agitation and 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, stands, and deionized water wash for several times, is dried to obtain GQDs/Ag₂O/ZnO/ Graphene Antibacterial powder.

In the present invention, described colorant be praseodymium yellow, cobalt blue, reddish brown, orange, chrome tin pink, cobalt black at least one.

In the present invention, described dispersant is water solublity and oil-soluble high score subclass, polyacrylic acid and copolymer, benzoic acid And any one of derivant.The trade name that dispersant can list include BYK161, BYK163, BYK164, BYK168, EFKA4310, EFKA 4400, EFKA4401, Nuosperse FX9086, Solsperse 24000, Tego710, Tego671, But it is not limited to this.

In the present invention, described surface additive is amino or amido and salt thereof.Surface additive is NP-4, Span-80, At least one in AEO-3 and SRE-48000.

In the present invention, described solvent is in de-aromatic hydrocarbon solvent, environmental protection hydrocarbon solvent, alcohols, cycloalkane solvent At least one.Described bonding agent generally uses polymerizing resin, such as polyethylene, polypropylene, polrvinyl chloride and polystyrene tree One in fat, polymerizing resin plays combination and scattered dual function.

In the present invention, levelling agent is polyether modified siloxane, the trade name that levelling agent can list include BYK306, BYK333, Levaslip 8629, but it is not limited to this.Defoamer is the polymer-type defoamer without organosilicon, and defoamer is permissible The trade name listed includes BYK051, BYK052, but is not limited to this.Anti-settling agent be in polyamide wax, oxidic polyethylene extremely Few one, the trade name that anti-settling agent can list includes Disparlon NS-5501, Disparlon 6650, but is not limited to This.

There is advantages that this method loads on the carbon nanotubes and fixes antibacterial, not only prevent it Reunite, significantly improve the stability of the antibacterial such as metal nanoparticle so that it is more preferably can be dispersed in ceramic ink, 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, compares Have a more preferable antibacterial effect in single silver nano antibacterial agent, antibacterial persistently；In raw material forms, add rare earth component, and close Reason devises rare earth, tourmaline and ferritic component ratio, utilizes tourmaline to have spontaneous electrode sexual function, and rare earth has change Valency performance, activates Ferrite Material, collaborative ferritic magnetic ripple effect so that it is prepare structural absorbing mater ials and have higher Dielectric constant and pcrmeability, improve the absorbing property of material.Compare with existing low-temp ceramics ink, the low temperature that the present invention manufactures Ceramic ink dispensing science, preparation is reasonable, stable performance, and uses the low temperature frit not containing the extremely toxic substances such as lead cadmium, makes Obtain ceramic ink and also ensure that its chromophoric characteristic when easy fired, obtain bright-coloured, sharp keen hair color effect；Simultaneously through rationally Collocation radioprotective complex and antimicrobial composite material, both synergism, make ceramic ink also have the anti-of lasting spectrum Bacterium characteristic, antifouling self-cleaning function and radioprotective characteristic, widened the range of application of low-temp ceramics ink further.

Detailed description of the invention

Technical scheme is further illustrated below by concrete preferred implementation.For convenience of description, Following example all use cobalt blue as ceramic pigment, but those skilled in the art are readily apparent that, spendable colorant does not limits to In this.

Embodiment 1

Step A, the siccative of 24% cobalt blue, 5% antibiotic complex, 12% radioprotective complex, 20% low temperature frit is mixed, then fall Enter mix homogeneously in quick mixer；Use sand mill sand milling 10h so that it is particle diameter distribution≤1 μm；

Step B, weigh 4% Tego710,3.5% AEO-3,0.2% Levaslip 8629,0.4% BYK052,0.8% polyphenyl second Olefine resin, 0.1% Disparlon NS-5501,30% environmental protection hydrocarbon solvent, carried out in being subsequently adding the homogenizer of step A Dispersion 30 ~ 60min；Scattered mixed liquor is loaded in sand mill, sand milling 10h, obtain the ink half of particle diameter distribution≤300nm Finished product；

Step C, ink semi-finished product step B obtained, in the constant temperature a mixing bowl of 90 DEG C, then carry out evacuation, shake at a high speed Dynamic, strainer filtering, obtains ink.

The preparation method of described low temperature frit is as follows: by 12% quartz, 12% Anhydrite, 25% Borax, 6% carbonate, 35% boron Acid, 5% spodumene, 4% fluoride salt, 1% Kaolin mixing sand milling uniformly, prepare compound；Compound is dispensed loading fire resistant sagger In, carry out 1250 ~ 1320 DEG C of high temperature meltings, obtain the slurry of molten state；High temperature melting technique is: room temperature to 1000 DEG C, Insulation 10min；It is warming up to 1300 DEG C, is incubated 30min；It is cooled to 1250 DEG C, is incubated 15min；It is warming up to 1320 DEG C, insulation 30min；By slurry water quenching cooling, and it is broken into graininess and i.e. can get low temperature frit；Wherein said Anhydrite is by potassium feldspar and sodium Anhydrite is obtained by mixing by weight 4:1；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight It is obtained by mixing than 3:1:3:2:1；Described fluoride salt is obtained by mixing by weight 4:2:1 by sodium fluoride, calcium fluoride and lithium fluoride.

Wherein, described radioprotective complex preparation method is as follows: take by weight by 40% epoxy resin, 31% phenolic aldehyde tree Fat, 1% tourmaline, 8% rare earth and 20% ferrite are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, After discharge, detect, adjust the slurry being configured to apply；By this slurry coating on substrate, drying and forming-film；Then it is placed on and fills In nitrogen atmosphere stove, it is warmed up to 900 ~ 1000 DEG C, is incubated 1 ~ 2h；Film is scraped off this substrate, obtains radioprotective holey carbon film； Described rare earth refers to be combined by weight 1:2:2:1 by Lanthanum (III) nitrate, neodymium nitrate, Erbium trinitrate and cerous nitrate；Tourmaline Refer to that iron tourmaline, elbaite and dravite are combined by 3:2:1；Ferrite is strontium oxygen iron.

Wherein, described antibiotic complex prepares 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 Mixing in Bei, beaker is placed in ice-water bath, stirs with the speed of 600rpm simultaneously, obtains mixed liquor；Weigh 1g potassium permanganate powder, Add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, react 4h；Quickly add Enter 120ml pure water, filter, then dialyse 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (GQDs) and hang Supernatant liquid；100rpm speed stirring GQDs suspension, simultaneously laser irradiation 40min, 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；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 1gGQDs/Ag is taken₂O 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；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic to be stirred Mixing, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide Number is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, 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), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 10min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

(5) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:18 with aniline mass ratio, dropwise dripping 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 final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(6) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(7) taking 1g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains the most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 2

Step A, the siccative of 32% cobalt blue, 2% antibiotic complex, 8% radioprotective complex, 18% low temperature frit is mixed, then fall Enter mix homogeneously in quick mixer；Use sand mill sand milling 10h so that it is particle diameter distribution≤1 μm；

Step B, weigh 5% Tego710,3.5% AEO-3,0.2% Levaslip 8629,0.4% BYK052,0.8% polyphenyl second Olefine resin, 0.1% Disparlon NS-5501,30% environmental protection hydrocarbon solvent, carried out in being subsequently adding the homogenizer of step A Dispersion 30 ~ 60min；Scattered mixed liquor is loaded in sand mill, sand milling 10h, obtain the ink half of particle diameter distribution≤300nm Finished product；

The preparation method of described low temperature frit is as follows: by 15% quartz, 10% Anhydrite, 24% Borax, 10% carbonate, 28% boron Acid, 7% spodumene, 3% fluoride salt, 3% Kaolin mixing sand milling uniformly, prepare compound；Compound is dispensed loading fire resistant sagger In, carry out 1250 ~ 1320 DEG C of high temperature meltings, obtain the slurry of molten state；High temperature melting technique is: room temperature to 1000 DEG C, Insulation 10min；It is warming up to 1300 DEG C, is incubated 30min；It is cooled to 1250 DEG C, is incubated 15min；It is warming up to 1320 DEG C, insulation 30min；By slurry water quenching cooling, and it is broken into graininess and i.e. can get low temperature frit；Wherein said Anhydrite is by potassium feldspar and sodium Anhydrite is obtained by mixing by weight 4:1；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight It is obtained by mixing than 3:1:3:2:1；Described fluoride salt is obtained by mixing by weight 4:2:1 by sodium fluoride, calcium fluoride and lithium fluoride.

Wherein, the preparation method of described radioprotective complex is as follows: take by weight by 32% epoxy resin, 36% phenolic aldehyde tree Fat, 3% tourmaline, 5% rare earth and 24% ferrite are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, After discharge, detect, adjust the slurry being configured to apply；By this slurry coating on substrate, drying and forming-film；Then it is placed on and fills In nitrogen atmosphere stove, it is warmed up to 900 ~ 1000 DEG C, is incubated 1 ~ 2h；Film is scraped off this substrate, obtains radioprotective holey carbon film； Described rare earth refers to be combined by weight 1:2:2:1 by Lanthanum (III) nitrate, neodymium nitrate, Erbium trinitrate and cerous nitrate；Tourmaline Refer to that iron tourmaline, elbaite and dravite are combined by 3:2:1；Ferrite is strontium oxygen iron.

Wherein, described antibiotic complex prepares by the following method:

(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；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 2gGQDs/Ag is taken₂O 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；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic to be stirred Mixing, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide Number is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, 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), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 12min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

(5) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:15 with aniline mass ratio, dropwise dripping 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 final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(6) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(7) taking 2g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains the most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 3

Step A, the siccative of 38% cobalt blue, 0.5% antibiotic complex, 3% radioprotective complex, 15% low temperature frit is mixed, then Pour mix homogeneously in quick mixer into；Use sand mill sand milling 10h so that it is particle diameter distribution≤1 μm；

Step B, weigh 5% Tego710,3.5% AEO-3,0.2% Levaslip 8629,0.4% BYK052,0.8% polyphenyl second Olefine resin, 0.1% Disparlon NS-5501,34% environmental protection hydrocarbon solvent, carried out in being subsequently adding the homogenizer of step A Dispersion 30 ~ 60min；Scattered mixed liquor is loaded in sand mill, sand milling 10h, obtain the ink half of particle diameter distribution≤300nm Finished product；

The preparation method of described low temperature frit is as follows: by 18% quartz, 7% Anhydrite, 20% Borax, 12% carbonate, 28% boron Acid, 8% spodumene, 2% fluoride salt, 5% Kaolin mixing sand milling uniformly, prepare compound；Compound is dispensed loading fire resistant sagger In, carry out 1250 ~ 1320 DEG C of high temperature meltings, obtain the slurry of molten state；High temperature melting technique is: room temperature to 1000 DEG C, Insulation 10min；It is warming up to 1300 DEG C, is incubated 30min；It is cooled to 1250 DEG C, is incubated 15min；It is warming up to 1320 DEG C, insulation 30min；By slurry water quenching cooling, and it is broken into graininess and i.e. can get low temperature frit；Wherein said Anhydrite is by potassium feldspar and sodium Anhydrite is obtained by mixing by weight 4:1；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight It is obtained by mixing than 3:1:3:2:1；Described fluoride salt is obtained by mixing by weight 4:2:1 by sodium fluoride, calcium fluoride and lithium fluoride.

Wherein, the preparation method of described radioprotective complex is as follows: take by weight by 30% epoxy resin, 32% phenolic aldehyde tree Fat, 5% tourmaline, 3% rare earth and 30% ferrite are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, After discharge, detect, adjust the slurry being configured to apply；By this slurry coating on substrate, drying and forming-film；Then it is placed on and fills In nitrogen atmosphere stove, it is warmed up to 900 ~ 1000 DEG C, is incubated 1 ~ 2h；Film is scraped off this substrate, obtains radioprotective holey carbon film； Described rare earth refers to be combined by weight 1:2:2:1 by Lanthanum (III) nitrate, neodymium nitrate, Erbium trinitrate and cerous nitrate；Tourmaline Refer to that iron tourmaline, elbaite and dravite are combined by 3:2:1；Ferrite is strontium oxygen iron.

Wherein, antibiotic complex prepares by the following method:

(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；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 3gGQDs/Ag is taken₂O 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；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic Stirring, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass is added Mark is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, 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), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 15min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

(5) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:12 with aniline mass ratio, dropwise dripping 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 final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(6) prepare TiO 2 sol by sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial powder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To forge at gained complex 500 DEG C after milling Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(7) taking 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains the most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 4

Preparation method based on embodiment 2, difference is: increase 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 ratio be 1:3；The ultrasonic 90min of 50W, stands, deionized water Washing for several times, is dried to obtain 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 and go Ionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with in 5ml 30% H2O2 with unnecessary KMnO4, The color of mixed solution is brown color, filtered while hot, and with deionized water cyclic washing to neutral, ultrasonic disperse obtains GO；Take 200ml mass fraction is in the discoid reaction utensil that the graphene oxide solution of 5mg/ml pours diameter 25cm, high 2cm into, 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

Preparation method based on embodiment 1, difference is: described antibiotic complex prepares by the following method:

(3) 1gGQDs/Ag is taken₂O 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, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

(4) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:18 with aniline mass ratio, dropwise dripping 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 final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(5) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(6) taking 1g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains the most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 6

Preparation method based on embodiment 2, difference is: described antibiotic complex prepares by the following method:

(3) 2gGQDs/Ag is taken₂O 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, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

(4) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:15 with aniline mass ratio, dropwise dripping 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 final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(5) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(6) taking 2g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains the most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 7

Preparation method based on embodiment 3, difference is: described antibiotic complex prepares by the following method:

(3) 3gGQDs/Ag is taken₂O 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, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

(4) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:12 with aniline mass ratio, dropwise dripping 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 final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(5) prepare TiO 2 sol by sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial powder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To forge at gained complex 500 DEG C after milling Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(6) taking 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains the most 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, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, 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 being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 8

Preparation method based on embodiment 6, difference is: increase 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 Ink alkene and GQDs/Ag₂The weight ratio of O/ZnO is 1:3；The ultrasonic 90min of 50W, stands, and deionized water wash for several times, is dried GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

Comparative example 1

Preparation method based on embodiment 1, difference is: described antibiotic complex is the titanium dioxide carrying metal antibacterial agent Titanium.

Comparative example 2

Preparation method based on embodiment 5, difference is: described antibiotic complex is the mixing of zinc oxide and titanium dioxide Thing；Described radioprotective complex is strontium oxygen iron.

The low temperature frit that each embodiment and comparative example are used, the most leaded, cadmium toxic element, the experiment proved that low It is melting at 800 DEG C, can be used for preparing the flux material of various low-temperature environment-friendly pottery.

Embodiment 1 ~ 8 and comparative example 1,2 are carried out performance test, test result such as following table:

Sterilization rate: use inhibition zone method check qualitatively the antibacterial effect of ink, the strain of employing be staphylococcus aureus or Escherichia coli.

Wear testing: the abrasive material selecting Mohs' hardness to be 3～4, rubs 1000 times in the printed layer formed by this ink Imitate the effect after paving uses 2 years.

Heat stability testing: place 10h under the conditions of ceramic ink is placed in 60 DEG C.

Antifouling test: selection chrome green is pollutant.

Sterilizing Evaluation for Uniformity: by same emitting ink in whole piece pottery test piece and after easy fired, choose 100 Region carries out sterilizing test, and the data recorded are carried out Uniformity Analysis, by the uniformity=100* (1-standard deviation/average Value).When the uniformity is more than 97%, then be labeled as ▲；When the uniformity is more than 90% and less than 97%, then it is labeled as ☆；When the uniformity is low In 90%, then it is labeled as.

Utilize the wave-absorbing effect of electromagnetic radiation tester QX-5 test each sample.The electromagnetic wave radiant intensity of certain mobile phone is 800 ~ 900 μ W/cm2, employ spraying be printed with the potsherd that this ink is made after, test its radiant intensity.

Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained Art scheme, all should fall within the scope and spirit of the invention.

Claims

1. an ink-jet preparation method for radioprotective low-temp ceramics ink, it comprises the following steps:

The preparation method of ink-jet radioprotective low-temp ceramics ink the most according to claim 1, it is characterised in that described anti- The preparation method of bacterium 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 Mixing in beaker, beaker is placed in ice-water bath, stirs with the speed of 500 ~ 600rpm simultaneously, obtains mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, adds in above-mentioned mixed liquor slowly；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialyse 3 ~ 5 days with the bag filter that molecular cut off is 1000, GQDs suspension；100 ~ 150rpm speed stirring GQDs suspension, simultaneously laser irradiation 30 ~ 60min, 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 add 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, regulation pH value, to 11, then stands, is centrifuged, and with deionized water and ethanol alternately washing three times, is vacuum dried, GQDs/Ag₂O；

(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, regulation pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, react 30 ~ 60min；Carry out It is centrifuged and cleans with acetone and deionized water successively and obtain precipitation；This is deposited at 80 ~ 90 DEG C and is dried 2 ~ 4h, 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 Process 1 ~ 2h, after being cooled to room temperature, be immersed in Fluohydric acid. and carry out ultrasonic 10 ~ 15min with ultrasonic power 100 ~ 150W, remove table Local, face silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

The preparation method of ink-jet radioprotective low-temp ceramics ink the most according to claim 2, it is characterised in that step (4) and increase by a step between (5): take three-dimensional sponge shape Graphene ultrasonic agitation and be scattered in aqueous solution, be added dropwise over GQDs/ Ag₂O/Ag-Zn-Ce/SiO₂In aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1~5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, and deionized water wash for several times, is dried to obtain GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂/ Graphene antibiosis powder.

4. an ink-jet preparation method for radioprotective low-temp ceramics ink, it comprises the following steps:

Step C, ink semi-finished product step B obtained, in the constant temperature a mixing bowl of 80～100 DEG C, then carry out evacuation, height Speed vibration, strainer filtering, obtain ink；

Wherein, the preparation method of described antibiotic complex is as follows:

The preparation method of ink-jet radioprotective low-temp ceramics ink the most according to claim 4, it is characterised in that step (3) and increase by a step between (4): take three-dimensional sponge shape Graphene ultrasonic agitation and be scattered in aqueous solution, be added dropwise over GQDs/ Ag₂In O/ZnO aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:1 ~ 5；10 ~ 100W is ultrasonic 60 ~ 120min, stands, and deionized water wash for several times, is dried to obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

6. according to the preparation method of radioprotective low-temp ceramics ink of the ink-jet described in claim 2 or 4, it is characterised in that institute The preparation method stating low temperature frit is as follows: by 10 ~ 18% quartz, 5 ~ 12% Anhydrites, 15 ~ 25% Boraxs, 3 ~ 12% carbonate, 20 ~ 35% Boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 0 ~ 5% Kaolin mixing sand milling uniformly prepare compound；Compound is dispensed loading In fire resistant sagger, carry out 1250 ~ 1320 DEG C of high temperature meltings, obtain the slurry of molten state；By slurry water quenching cooling, and it is broken into Granular, prepare low temperature frit.

The preparation method of ink-jet radioprotective low-temp ceramics ink the most according to claim 6, it is characterised in that described anti- Radiation recombination thing preparation method is as follows: take by weight by 30 ~ 40% epoxy resin, 30 ~ 45% phenolic resin, 1 ~ 5% tourmaline, 3 ~ 8% rare earth and 20 ~ 30% ferrites are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, Detection, adjustment are configured to the slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then nitrogen filled protection it is placed on In atmosphere furnace, it is warmed up to 900 ~ 1000 DEG C, is incubated 1 ~ 2h；Film is scraped off this substrate, obtains radioprotective holey carbon film.

The preparation method of ink-jet radioprotective low-temp ceramics ink the most according to claim 7, it is characterised in that described length Stone is obtained by mixing by weight 3 ~ 5:1 ~ 2 by potassium feldspar and albite；Described fluoride salt is pressed by sodium fluoride, calcium fluoride and lithium fluoride Weight ratio 4:2:1 is obtained by mixing.

The preparation method of ink-jet radioprotective low-temp ceramics ink the most according to claim 7, it is characterised in that described carbon Hydrochlorate is made up of at least one in potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate.

10. an ink-jet radioprotective low-temp ceramics ink, it contains the component of following percentage by weight: 25 ~ 38% colorants, 0.5 ~ 5% antibiotic complex, 3 ~ 12% radioprotective complex, 15 ~ 20% low temperature frits, 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.1 ~ 0.3% levelling agent, 0.3 ~ 0.8% defoamer, 0.5 ~ 1% bonding agent, 0.08 ~ 0.1% anti-settling agent, surplus is solvent.