CN106084922A - A kind of preparation method of aqueous radioprotective inorganic coating - Google Patents
A kind of preparation method of aqueous radioprotective inorganic coating Download PDFInfo
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- CN106084922A CN106084922A CN201610748741.7A CN201610748741A CN106084922A CN 106084922 A CN106084922 A CN 106084922A CN 201610748741 A CN201610748741 A CN 201610748741A CN 106084922 A CN106084922 A CN 106084922A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Abstract
The invention discloses the preparation method of a kind of aqueous radioprotective inorganic coating, it comprises the following steps: kieselguhr is scattered in aqueous solution by (1), drips antibiotic complex aqueous dispersions；Standing, sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；(2) by water, defoamer mix and blend, add pigment and filler, kieselguhr/bamboo charcoal nano, stir to obtain solution A；(3) Ludox and polymer solution are mixed, be sufficiently stirred for；Add kieselguhr/antibiotic complex, stir to obtain solution B；(4) in gained solution B, add coalescents, thickening agent and photochromic complex, be sufficiently stirred for obtaining solution C；(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for filtering.Inorganic coating of the present invention has excellent antibacterial and radioprotective characteristic, has photochromic characteristic simultaneously, meets multi-functional demand, widens the application of inorganic coating further.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to the preparation side of a kind of aqueous radioprotective inorganic coating
Method.
Background technology
Inorganic coating is primarily referred to as, using silicate and phosphate compound as binding agent, adding various face, filler, helping
The coating that agent, firming agent are formulated, wherein silicate macromolecular compound can be divided into again alkali silicate and Ludox.This
Coating kind using inorganic binder as film forming matter has that film-forming temperature is low, its film has excellent weatherability, in ultraviolet
Thermostability highly stable, good under light action, meet fire and do not fire, preferable stain resistance, be difficult to inhale ash, lucid and lively dress can be kept
Decorations effect, make with use during non-volatility Organic substance produces, does not pollutes the environment, raw material resources enriches, cost
The series of advantages such as cheap, thus be widely used.But existing aqueous inorganic paint function is more single, it is more difficult to full
The multi-functional feature of foot.
Summary of the invention
The technical problem to be solved there is provided the preparation method of a kind of aqueous radioprotective inorganic coating.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of aqueous radioprotective inorganic coating, it comprises the following steps:
(1) being scattered in aqueous solution by 2 ~ 5 parts of kieselguhr, (100 ~ 300W ultrasonic power, 100 ~ 300rpm stirs limit ultrasonic agitation
Speed) limit dropping 3 ~ 8mL concentration is the antibiotic complex aqueous dispersions of 0.01 ~ 0.1mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex.
(2) at room temperature, first by 25 ~ 35 parts of water, 0.5 ~ 1 part of defoamer mix and blend, add 5 ~ 10 parts of pigment and 20 ~
30 parts of filleies, after being sufficiently stirred for, add 1 ~ 3 part of kieselguhr/bamboo charcoal nano, stir 30 ~ 60min；It is filtrated to get homogeneous solution
A；
(3) by described 20 ~ 30 parts of Ludox and 5 ~ 12 parts of polymer solution mixing, it is sufficiently stirred for；Add 1 ~ 5 part of kieselguhr/anti-
Bacterium complex, stirs 30 ~ 60min, obtains homogeneous solution B；
(4) in the solution B of step (3) gained, 1 ~ 3 part of coalescents, 0.05 ~ 0.3 part of thickening agent and 1 ~ 3 part of light-induced variable are added
Color complex, is sufficiently stirred for, and is filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Preferably, described Ludox is the nano level silica dioxide granule (particle diameter about 10nm) dispersion liquid in water.
The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol.Described pigment is titanium dioxide or white carbon black.
Described filler is selected from Pulvis Talci, calcium carbonate, the combination of one or more in silicon calcium powder.
Described defoamer is selected from isooctanol, the combination of one or more in isopropanol.
Described coalescents one in ethylene glycol, 2-Butoxyethyl acetate, acetic acid, ethanol, the ethyl acetate or
Multiple combination.
Described thickening agent is PUR40 polyurethane thickener.
In the present invention, described kieselguhr/bamboo charcoal nano preparation method is as follows: kieselguhr is dispersed in the water-soluble of 120ml
In liquid, adding bamboo charcoal nano (particle diameter is between 100 ~ 500nm), the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 2h, allows nano material
Well in kieselguhr hole, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/bamboo charcoal nano；Wherein said kieselguhr and nanometer
The weight ratio of bamboo charcoal is 1 ~ 2:5 ~ 8.
In the present invention, described photochromic complex preparation method is as follows: under nitrogen environment, by concentration be 0.05 ~
The protonic acid solution of 0.5mol/L and the DBSA that concentration is 0.05 ~ 0.5mol/L mix with volume ratio 3:1 ~ 3, with
Time add photochromic powder, add aniline after magnetic agitation 60 ~ 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10；
After continuously stirred 60 ~ 90min, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；At 20 DEG C～30 DEG C instead
Answer 12 ~ 36h；Acetone, deionized water wash final vacuum for several times is dried, nano polyaniline/photochromic flour complexes of milling to obtain；Will
1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add the water of volume ratio 4:1 afterwards
And ammonia, it being stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 60 ~
90min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited at 90 DEG C and is dried 3h, with
To nano polyaniline/photochromic flour complexes/SiO2；By nano polyaniline/photochromic flour complexes/SiO2It is placed in argon
Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under atmosphere, remove polyaniline, photochromic powder/porous SiO2, the most photochromic compound
Thing.Described photochromic powder is rare earth oxide, and described rare earth oxide is Nd2O3、Er2O3、Pr2O3、CeO2、Sm2O3、La2O3、
Y2O3、Yb2O3In at least one.
In the present invention, the preparation method of a kind of antimicrobial composite material comprises the following steps:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is
Water；Ultrasonic agitation (500 ~ 1000W ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, dropping step
Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature
Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 M sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis-
Titanium oxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(8) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.2
The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (the ultrasonic merit of 500 ~ 1000W
Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that ink alkene quantum dot and step (7) prepare
10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
There is advantages that
The present invention the most first prepares graphene quantum dot and the graphene quantum dot of load silver/titanium dioxide of load zinc oxide,
Then surface processes, and is finally attached on porous graphene, can preferably load and fix Nano silver grain and zinc oxide, anti-
Only it is reunited, and significantly improves the stability of Nano silver grain and zinc oxide, makes Nano silver grain and zinc oxide have more efficient
Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously
Agent has a more preferable antibacterial effect, antibacterial persistently；
The bamboo charcoal nano that the present invention uses contains the multiple beneficial elements such as charcoal, hydrogen, oxygen, fine and closely woven porous, can block and absorb each
The erosion of the harm ray that kind of electrical equipment produces, makes human body thoroughly exempt the harm of harm ray, bamboo charcoal nano also can produce bear from
Son, adsorbs and decomposes various free harmful substance, be automatically adjusted humidity, also can produce the far infrared being best suitable for human body；
The photochromic complex that the present invention uses has photochromic effect, makes product more rich and varied, can be along with photograph
The shades of colour penetrating the difference of light intensity and change, is a splendid legacy, full of magnificent carriage, increases sentiment and artistic effect；
The present invention is through reasonably arranging in pairs or groups kieselguhr/bamboo charcoal nano and kieselguhr/antimicrobial composite material and photochromic compound
Thing, the synergism between functional additive so that inorganic coating has excellent antibacterial and radioprotective characteristic, has photic simultaneously
Color shifting properties, meets multi-functional demand, widens the application of inorganic coating further.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 50ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash
Photoirradiation power is 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml zinc oxide fluid dispersion, dropping step (1) prepare one
Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene of zinc oxide
Quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005g graphite oxide joins the dispersion of 8mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.2g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.1g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.3mol/L titanium source (titanium source is potassium fluotitanate) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.3g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries
The load silver/titanium dioxide graphene quantum dot that surface processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the graphene quantum dot of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min prepared with step (7), then moves
To the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.7g C60 powder, measure the dense sulfur that 80ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash
Photoirradiation power is 1.5W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, dropping step (1) prepares
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 5h；Rapidly join 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 60min, swash
Photoirradiation power is 1W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 1mg/ml, solvent is water；
Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, the half that dropping step (1) prepares
Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene amount of zinc oxide
Sub-point.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.3g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.01mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.1mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined
In 1 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
110 DEG C, after reaction 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide
Graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.1g load silver/titanium dioxide Graphene
Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The load silver/titanium dioxide graphene quantum dot processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min that step (7) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 1
The preparation method of a kind of antimicrobial composite material, comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.01mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the SiO that step (3) prepares2Cladding carries silver graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean,
Dry to obtain antimicrobial composite material.
Comparative example 2
The preparation method of a kind of antimicrobial composite material, comprises the following steps: weigh porous graphene (2 ~ 5 layers, hole size about 3 ~
6nm, layer size 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan
Base sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, dropping concentration is
0.003mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and dropping concentration is 0.04mol/L bis-citric acid monohydrate trisodium,
Continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene antibiosis material of silver.
Detailed process and step that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated are as follows:
The antibacterial of test is respectively staphylococcus aureus and escherichia coli；With reference to minimal inhibitory concentration (minimal
Inhibitory concentration, MIC) method of testing (Xiang Cai, Shaozao Tan, Aili Yu,
Jinglin Zhang, Jiahao Liu, Wenjie Mai, Zhenyou Jiang. Sodium1-
naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver
nanoparticles with lower cytotoxicity and long-term antibacterial
Activity.Chemistry-An Asian Journal. 2012,7 (7): 1664-1670.), first weigh with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material MH meat soup to the most serial dilute
Release variable concentrations, be added separately in the MH culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/mL,
Then shaken cultivation 24h at 37 DEG C, observes its result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, nothing
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of the longest tube.
Table 1: embodiment 1 ~ 3 and the anti-microbial property of comparative example 1,2 antimicrobial composite material
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, adds prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200mL saline (0.9mass%), and in water, soak 6 respectively, 24, sample after 72h, measure it
Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite material
Embodiment 4
A kind of preparation method of waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 1 part of kieselguhr, (200W ultrasonic power, 100rpm stirs speed to limit ultrasonic agitation
Degree) limit dropping 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.08mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex；
(2) at room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of calcium carbonate, fully stir
After mixing, add 1 part of kieselguhr/bamboo charcoal nano, stir 60min；It is filtrated to get homogeneous solution A；Described kieselguhr/bamboo charcoal nano system
Preparation Method is as follows: be dispersed in the aqueous solution of 120ml by kieselguhr, adds bamboo charcoal nano (particle diameter is between 100 ~ 500nm), 200W
Ultrasonic 300rpm stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/receive
Rice bamboo charcoal；Wherein said kieselguhr is 2:7 with the weight ratio of bamboo charcoal nano；
(3) by described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；Add 3 parts of kieselguhr/antibacterial compound
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is that nano level silica dioxide granule (particle diameter about 10nm) is in water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
(4) in the solution B of step (3) gained, 2 parts of coalescents, 0.1 part of PUR40 polyurethane thickener and 3 parts of light are added
Mutagens color complex, is sufficiently stirred for, and is filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Wherein, described photochromic complex prepares by the following method: under nitrogen environment, is 0.4mol/L's by concentration
Protonic acid solution and the DBSA that concentration is 0.3mol/L mix with volume ratio 3:2, are simultaneously introduced photochromic powder
(Nd2O3、Pr2O3、La2O3And Yb2O3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min
Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise dripping Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is
1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain
Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and
Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain nano polyaniline/photochromic powder
Thing/SiO2；By nano polyaniline/photochromic flour complexes/SiO2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove
Polyaniline, obtains photochromic powder/porous SiO2, the most photochromic complex.
Embodiment 5
A kind of preparation method of waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 3 parts of kieselguhr, (200W ultrasonic power, 100rpm stirs speed to limit ultrasonic agitation
Degree) limit dropping 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.05mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex；
(2) at room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of calcium carbonate, fully stir
After mixing, add 2 parts of kieselguhr/bamboo charcoal nanos, stir 60min；It is filtrated to get homogeneous solution A；Described kieselguhr/bamboo charcoal nano system
Preparation Method is as follows: be dispersed in the aqueous solution of 120ml by kieselguhr, adds bamboo charcoal nano (particle diameter is between 100 ~ 500nm), 200W
Ultrasonic 300rpm stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/receive
Rice bamboo charcoal；Wherein said kieselguhr is 2:7 with the weight ratio of bamboo charcoal nano；
(3) by described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；Add 3 parts of kieselguhr/antibacterial compound
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is that nano level silica dioxide granule (particle diameter about 10nm) is in water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
(4) in the solution B of step (3) gained, 2 parts of coalescents, 0.1 part of PUR40 polyurethane thickener and 2 parts of light are added
Mutagens color complex, is sufficiently stirred for, and is filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Wherein, described photochromic complex prepares by the following method: under nitrogen environment, is 0.4mol/L's by concentration
Protonic acid solution and the DBSA that concentration is 0.3mol/L mix with volume ratio 3:2, are simultaneously introduced photochromic powder
(Nd2O3、Pr2O3、La2O3And Yb2O3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min
Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise dripping Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is
1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain
Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and
Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain nano polyaniline/photochromic powder
Thing/SiO2；By nano polyaniline/photochromic flour complexes/SiO2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove
Polyaniline, obtains photochromic powder/porous SiO2, the most photochromic complex.
Embodiment 6
A kind of preparation method of waterborne antibacterial inorganic coating, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 5 parts of kieselguhr, (200W ultrasonic power, 100rpm stirs speed to limit ultrasonic agitation
Degree) limit dropping 5mL concentration is the embodiment 2 antibiotic complex aqueous dispersions of 0.01mol/L；Standing 90min, repeatedly sucking filtration is clear
Wash, be dried to obtain kieselguhr/antibiotic complex；
(2) at room temperature, first by 30 parts of water, 1 part of isopropanol mix and blend, add 8 parts of pigment and 25 parts of calcium carbonate, fully stir
After mixing, add 3 parts of kieselguhr/bamboo charcoal nanos, stir 60min；It is filtrated to get homogeneous solution A；Described kieselguhr/bamboo charcoal nano system
Preparation Method is as follows: be dispersed in the aqueous solution of 120ml by kieselguhr, adds bamboo charcoal nano (particle diameter is between 100 ~ 500nm), 200W
Ultrasonic 300rpm stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/receive
Rice bamboo charcoal；Wherein said kieselguhr is 2:7 with the weight ratio of bamboo charcoal nano；
(3) by described 25 parts of Ludox and 10 parts of polymer solution mixing, it is sufficiently stirred for；Add 3 parts of kieselguhr/antibacterial compound
Thing, stirs 60min, obtains homogeneous solution B；Described Ludox is that nano level silica dioxide granule (particle diameter about 10nm) is in water
Dispersion liquid；The solvent of described polymer solution is water, and solute is selected from the polyethylene that mean molecule quantity is 30,000～70,000
Alcohol；
(4) in the solution B of step (3) gained, 2 parts of coalescents, 0.1 part of PUR40 polyurethane thickener and 1 part of light are added
Mutagens color complex, is sufficiently stirred for, and is filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
Wherein, described photochromic complex prepares by the following method: under nitrogen environment, is 0.4mol/L's by concentration
Protonic acid solution and the DBSA that concentration is 0.3mol/L mix with volume ratio 3:2, are simultaneously introduced photochromic powder
(Nd2O3、Pr2O3、La2O3And Yb2O3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min
Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise dripping Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is
1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain
Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and
Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain nano polyaniline/photochromic powder
Thing/SiO2；By nano polyaniline/photochromic flour complexes/SiO2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove
Polyaniline, obtains photochromic powder/porous SiO2, the most photochromic complex.
Comparative example 3
Preparation method based on embodiment 6, difference is: remove step (1), and kieselguhr/antibiotic complex changes into antibacterial
Complex；Described kieselguhr/bamboo charcoal nano is only bamboo charcoal nano.
Comparative example 4
Preparation method based on embodiment 6, difference is: remove antibiotic complex；Described photochromic complex is
Nd2O3、Pr2O3、La2O3And Yb2O3It is obtained by mixing by weight 1:2:1:3.
Comparative example 5
Preparation method based on embodiment 6, difference is: remove kieselguhr/bamboo charcoal nano.
Antibacterial Evaluation for Uniformity: be coated uniformly on by coating on glass or ceramic wafer, chooses 100 regions and carries out sterilizing survey
The data recorded are carried out Uniformity Analysis, by the uniformity=100* (1-standard deviation/meansigma methods) by examination.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 less than 90%, then it is labeled as
╳。
Air purification effect test is as follows: indoor concentration of formaldehyde and electromagnetic radiation etc. before and after contrast use, to characterize it
Absorbability.Between one in the vacant room of 10 square metres, place following article: 1. make 10, the clamping plate of furniture, surface without
Packaging；2. paint 5 barrels, bung is opened；3. television set 1, opening；4. electric fan 1, opening.
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 (7)
1. a preparation method for aqueous radioprotective inorganic coating, it comprises the following steps:
(1) being scattered in aqueous solution by 2 ~ 5 parts of kieselguhr, ultrasonic agitation limit, limit dropping 3 ~ 8mL concentration is 0.01 ~ 0.1mol/L's
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；
(2) at room temperature, first by 25 ~ 35 parts of water, 0.5 ~ 1 part of defoamer mix and blend, 5 ~ 10 parts of pigment and 20 ~ 30 parts are added
Filler, after being sufficiently stirred for, adds 1 ~ 3 part of kieselguhr/bamboo charcoal nano, stirs 30 ~ 60min, be filtrated to get homogeneous solution A；
(3) by described 20 ~ 30 parts of Ludox and 5 ~ 12 parts of polymer solution mixing, it is sufficiently stirred for；Add 1 ~ 5 part of kieselguhr/anti-
Bacterium complex, stirs 30 ~ 60min, obtains homogeneous solution B；
(4) in the solution B of step (3) gained, 1 ~ 3 part of coalescents, 0.05 ~ 0.3 part of thickening agent and 1 ~ 3 part of light-induced variable are added
Color complex, is sufficiently stirred for, and is filtrated to get homogeneous solution C；
(5) by solution C, it is added dropwise in solution A, is sufficiently stirred for, filter, the described High-performance waterborne inorganic paint i.e. made.
The preparation method of aqueous radioprotective inorganic coating the most according to claim 1, it is characterised in that described antibacterial compound
Thing prepares by the following method:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30
~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that dropping step (1) prepares, continue ultrasonic agitation 30 ~
60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry to load the graphene quantum dot of silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2
Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~
100ml graphene dispersion solution, the graphene quantum dot of the load zinc oxide that addition step (3) prepares and step (7) prepare
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of aqueous radioprotective inorganic coating the most according to claim 2, it is characterised in that described Graphene amount
Son point suspension preparation method as follows: weigh 0.5 ~ 0.8g C60 powder, measure 50 ~ 100ml mass fraction be 98% dense
Sulphuric acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 300 ~ 500rpm simultaneously
Mix, obtain mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water into
Bath, keeps bath temperature 30 ~ 40 DEG C, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with molecular cut off be
The bag filter of 1000 is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, with
Shi Jiguang irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
The preparation method of aqueous radioprotective inorganic coating the most according to claim 2, it is characterised in that ink alkene is 2 ~ 5 layers,
Hole size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
The preparation method of aqueous radioprotective inorganic coating the most according to claim 2, it is characterised in that described load silver/bis-
The surface of titanium oxide graphene quantum dot processes particularly as follows: 0.005 ~ 0.01g graphite oxide joins the dispersant of 5 ~ 10mL
In, ultrasonic agitation also adds 0.1 ~ 0.3g load silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to
Liner is in the microwave hydrothermal reaction kettle of politef, seals and is placed in microwave assisted hydrothermal synthesis apparatus, and microwave power is
200 ~ 400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphite
Alkene quantum dot.
The preparation method of aqueous radioprotective inorganic coating the most according to claim 2, it is characterised in that described load aoxidizes
The surface of the graphene quantum dot of zinc processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL,
Ultrasonic agitation and add 0.1 ~ 0.3g load zinc oxide graphene quantum dot, continue ultrasonic agitation 10 ~ 30min, move to liner
For in the microwave hydrothermal reaction kettle of politef, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~
400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load zinc oxide Graphene quantum
Point.
The preparation method of aqueous radioprotective inorganic coating the most according to claim 2, it is characterised in that described photochromic
Complex preparation method is as follows: under nitrogen environment, by protonic acid solution that concentration is 0.05 ~ 0.5mol/L and concentration be 0.05 ~
The DBSA of 0.5mol/L mixes with volume ratio 3:1 ~ 3, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~
Adding aniline after 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10；After continuously stirred 60 ~ 90min, dropwise dripped
Ammonium sulfate, aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are for several times
Final vacuum is dried, nano polyaniline/photochromic flour complexes of milling to obtain；1 ~ 10g nano polyaniline/photochromic powder is combined
Thing ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into positive silicic acid second
Ester, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged and successively with acetone and deionization
Water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, to obtain nano polyaniline/photochromic flour complexes/SiO2；
By nano polyaniline/photochromic flour complexes/SiO2It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove
Polyaniline, photochromic powder/porous SiO2, the most photochromic complex.
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