CN106315666A - ATO nanocrystal, ATO nanometer slurry, ATO/macromolecular polymer compound and preparation methods - Google Patents
ATO nanocrystal, ATO nanometer slurry, ATO/macromolecular polymer compound and preparation methods Download PDFInfo
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Abstract
The invention provides a preparation method of an ATO nanocrystal. The method comprises the following steps that antimonic salt and tin salt are added into an alcohol solvent according to the molar ratio of (1-15):100, a mixed solution is obtained after uniform stirring and mixing, the mixed solution is added into a self-pressure reaction still, a reaction is maintained at the temperature of 150-200 DEG C for 18-48 hours, the product is naturally cooled to room temperature after the reaction is over, and the obtained product is subjected to centrifugal separation, washing and drying to obtain the ATO nanocrystal. The preparation method is simple in process and easy to control, and the monodisperse ATO nanocrystal with uniform and controllable size can be obtained. The invention further provides the ATO nanocrystal obtained through the preparation method, ATO nanometer slurry and an ATO/macromolecular polymer compound which contain the ATO nanocrystal and preparation methods of the ATO nanometer slurry and the ATO/macromolecular polymer compound.
Description
Technical field
The present invention relates to nanocomposite optical field of material preparation, particularly relate to a kind of ATO nanocrystalline and preparation method thereof, one
Kind ATO nanometer slurry, and a kind of ATO/ high molecular polymer complex and preparation method thereof.
Background technology
Increasing along with portable electric appts, display, flexible electronic, multifunctional window, solaode and transistor etc.
Adding, transparent conductive oxide causes the interest in various field thus material and the method emerged in large numbers have multiformity in recent years.Transparent
Most of material of conductive oxide (TCO) is concentrated mainly on the doping to zinc oxide, Indium sesquioxide. and tin ash and improves；Basis
The development studying this field with applied science has great facilitation.These transparent conductive oxide film include Fluorin doped
Stannum oxide (FTO), the zinc oxide (AZO) of aluminum doping and tin indium oxide (ITO) etc..Wherein, it is widely used as in system at ito thin film
Standby low resistance and the transparent electrode material of high transparent.
Along with the tremendous growth in optical electronic device market, the demand of ITO dramatically increases, but owing to indium amount of storage is rare,
Its price ramps the most in recent years.The stannum oxide (ATO) of Sb doped is considered as the most potential material substituting indium ITO
One of material, its shortage that can avoid indium source and toxicity.SnO2In band gap be 3.8eV, after tin dope, the form of this material is
N-type semiconductor, presents a kind of special photoelectricity and gas sensitivity characteristic, high conductivity, high transparent, high IR line rejection rate
Deng.Therefore, it can many fields such as light-emitting diode display, LCD touch screen, antistatic coating, transparency electrode, thin film transistor (TFT),
Solar-energy photo-voltaic cell and gas sensor etc. use.Nano material can show special chemical and physical properties, therefore
Design an easy synthetic route prepare high-purity, size Control and dispersible nano ATO and become the focus of research.
The synthetic method of ATO can be divided into: solid-state, liquid and gaseous state.Due to costly and complex operating parameter, gaseous state
Method of formation is generally not used.It is well known that solid-state reaction needs high calcining heat, what it caused grain growth can not
Control, the volatilization at high temperature of dopant oxygen compound may result in reactant stoichiometric deviation, therefore, this method is mainly applied
At the product of the requirement of low value, such as pottery and dyestuff.Liquid phase process is widely used in industry, co-precipitation, sol-gel, water
Heat and spray pyrolysis.Coprecipitation method improves the reactivity of each component, but the dissolving between various chemical species and network
Right difference will cause incomplete precipitation so that the stoichiometry of material changes.Metal alkoxide has been used for synthesis
ATO thin film is it can also be used to sol-gel process synthesizes nano-particle, but metal alkoxide is special wet sensitive sense and need to be dried
Process with under inert atmosphere.Consider the specific properties of the stannum species of matrix material, tin ion (Sn4+) be particularly easy in water
Hydrolysis, stannic hydroxide Sn (OH)4β type SnO of relative inertness can be converted into2, this is detrimental to crystal growth, the most how to slow down
Sn4+Hydrolysis is reunited and is reacted the key issue being to synthesize ATO.In our work, single dispersing ATO its size nanocrystalline can be passed through
Change solvent thermal reaction parameter to control.Control by crucial factor, it is ensured that being uniformly distributed of nano-particle.Sell on the market
The ATO powder body sold is usually what roasting after coprecipitation prepared, the uneven more difficult nanometer slurry making stable performance of granular size.
Therefore this patent proposes to use.
Summary of the invention
In consideration of it, first aspect present invention provides the preparation method that a kind of ATO is nanocrystalline, the method technique is simple, can
Prepare grain diameter little, and the controlled ATO of size uniform is nanocrystalline, meanwhile, by nanocrystalline for gained ATO by dispersant
Modify and ball milling disperses, oiliness or water nano slip can be prepared, and solids in pulp amount is higher, can be used for preparing electrically conducting transparent thin
Film and optical nano complex.
Specifically, first aspect, the invention provides the nanocrystalline preparation method of a kind of ATO, comprise the following steps:
Antimonic salt and pink salt 1～15:100 are joined in alcoholic solvent in molar ratio, obtains mixing molten after being uniformly mixed
Liquid, joins described mixed solution in pressure reactor, maintains reaction 18～48 hours at 150～200 DEG C, and reaction terminates
After, naturally cool to room temperature, be then centrifuged products therefrom separating, washing, after drying, obtain ATO nanocrystalline.
In the present invention, can be obtained by the doping controlling different antimony that to have the ATO of different electrical conductivity nanocrystalline.Optional
Ground, 5～10:100 joins in alcoholic solvent in molar ratio by antimonic salt and pink salt.
In the present invention, described pink salt is 1:5～50 with the mol ratio of described alcoholic solvent；Further, described pink salt and alcohol
The mol ratio of solvent can be 1:15～50.
In the present invention, described alcoholic solvent is selected from ethanol, propanol, isopropanol, butanol, amylalcohol, ethylene glycol, 2,2'-ethylenedioxybis(ethanol)., four sweet
At least one in alcohol and glycerol.
In the present invention, the reaction in above-mentioned preparation method is high temperature pressure alcoholysis reaction process certainly, and alcoholic solvent is as alcoholysis
It is also can serve as class surfactant while reaction media, in the course of reaction of pink salt alcoholysis, contributes to obtaining distribution of sizes
Uniform ATO is nanocrystalline, also can effectively slow down Sn4+Hydrolysis reunite reaction, the inventive method by select different boiling alcohol
Solvent or alcoholic solvent addition, the ATO that can prepare different-grain diameter size is nanocrystalline, thus realizes particle diameter nanocrystalline to ATO
The Effective Regulation of size.Usually, under conditions of same materials mol ratio, alcoholic solvent boiling point is the highest, the nanocrystalline particle diameter of gained ATO
The least.It is nanocrystalline that the inventive method can obtain the ATO that particle size range is 5-100nm, further particle size range 50-80nm,
20-40nm or 10-30nm.
In the present invention, at least one in stannic chloride, nitric acid stannum, STANNOUS SULPHATE CRYSTALLINE and tin acetate of described pink salt；Described antimony
At least one in antimony chloride, nitric acid antimony, Antimonous sulfate and antimony acetate of salt.
In the present invention, alternatively, above-mentioned reaction temperature is 150～180 DEG C；Response time is 24～36 hours.
In the present invention, the rotating speed of described centrifugal separation processes is 6000～10000rpm, and the time is 5～15min；Described wash
Wash and operate particularly as follows: be first washed with deionized 2-3 time, then use absolute ethanol washing 1-2 time；The temperature of described drying is
50-80℃。
The preparation method nanocrystalline for ATO that first aspect present invention provides, technique is simple, can prepare grain diameter
Little, and the controlled ATO of size uniform is nanocrystalline.
Correspondingly, second aspect present invention provide a kind of by above-mentioned first aspect preparation method prepare ATO nanocrystalline.
The nanocrystalline even size distribution of this ATO, particle size range is 5-100nm, further particle size range at 50-80nm, 20-40nm or
10-30nm。
The third aspect, the invention provides a kind of ATO nanometer slurry, and it uses the ATO described in second aspect present invention to receive
The brilliant preparation of rice.This ATO nanometer slurry can be oiliness or water nano slip, and solid content is higher, and ATO good dispersion can be used for
Prepare transparent conductive film and optical nano complex.
Fourth aspect, the invention provides a kind of ATO/ high molecular polymer complex, described in second aspect present invention
ATO nanocrystalline be composited with high molecular polymer, described high molecular polymer is transparent polymer material, it may include PVB,
At least one in PMMA, PC, PP and PE.This ATO/ high molecular polymer complex has the well ultrared merit of obstruct
Can, it is seen that light light transmission is good.
5th aspect, the invention provides the preparation method of a kind of ATO/ high molecular polymer complex, including following step
Rapid:
Take a certain amount of high molecular polymer solvent to dissolve, obtain macromolecule polymer solution；
Taking the ATO described in a certain amount of second aspect nanocrystalline, adding the nanocrystalline mass fraction of relative ATO is 1-10%'s
Dispersant, obtains mixed dispersion liquid, is ground 3-12 hour by described mixed dispersion liquid planetary ball mill, then uses 2000-4000
Rev/min centrifuge washing removes impurity, is subsequently dispersed in above-mentioned solvent, obtains the ATO nanometer slurry of stable dispersion；
Being mixed with described ATO nanometer slurry by described macromolecule polymer solution, and add additive, ultrasonic agitation is also mixed
Close and form uniform mixed solution, described mixed solution is poured into evaporation solvent in mould, obtains ATO/ high molecular polymer multiple
Compound；
Or take a certain amount of high molecular polymer powder, by described high molecular polymer powder and above-mentioned ATO nanometer slurry with
And the mixing of above-mentioned additive, obtain mixed material, gained mixed material is joined in two-roll mill by the temperature set and
Program mixes, and then extrusion molding obtains ATO/ high molecular polymer complex diaphragm.
In the present invention, ATO nanometer slurry can be oiliness or water nano slip；Can make according to different slip Attributions selection
With different dispersants and solvent.Such as, when described ATO nanometer slurry is aqueous slip, described solvent can be water, ethanol or
Isopropanol, described dispersant can be silane coupler, sodium salt or titanate coupling agent；And when described ATO nanometer slurry is oil
Property slip time, described solvent can be toluene, dichlorotoleune, ketone or chloroform, described dispersant can be long-chain fatty acid superficiality live
Agent, such as, can be stearic acid, oleic acid, lauric acid, Palmic acid etc..
Alternatively, the mass fraction that dispersant is nanocrystalline relative to ATO is 5-8%；The rotating speed of planetary ball mill is 250-350
Rev/min, milling time is 6-9 hour.
In the present invention, first by nanocrystalline for ATO roasting 30-60 minute at 500-700 DEG C, then can be ground.Roasting it
After can strengthen antimony embedding in tin ash lattice, improve conductive capability, improve it simultaneously and intercept ultrared efficiency.
In the present invention, described macromolecule polymer solution or described high molecular polymer powder press ATO and high molecular polymerization
The mass ratio of thing is 0.5～5:100 to mix with described ATO nanometer slurry.
In the present invention, described additive includes plasticizer, antioxidant, ultraviolet absorber etc..
In described ATO nanometer slurry, the concentration of ATO is 0.5-5%, preferably 1-2%.The material of mould is preferably glass
Glass.
In the present invention, if compound high molecular polymer is PVB, with ethanol as miscible agent, then prepare ATO nanometer slurry
Time, dispersant may select silane coupler KH540, KH550 or KH792 etc.；And with chloroform as miscible agent, then dispersant may select
The long-chain fatty acid Surfactants such as stearic acid, oleic acid, lauric acid, Palmic acid.
If compound high molecular polymer is PC, then, when preparing ATO nanometer slurry, dispersant may be selected to be silane coupler
KH540, KH550, KH792 or KH791；If compound high molecular polymer is PP, then dispersant may select the normal of band pi-allyl
See silane coupler KH570.
To sum up, the preparation method nanocrystalline for ATO that the present invention provides, technique is simple, can prepare grain diameter little, and
The controlled ATO of size uniform is nanocrystalline, meanwhile, nanocrystalline for the gained ATO modification by dispersant and ball milling is disperseed, can prepare
Oiliness or water nano slip, gained solids in pulp amount is higher, and gained slip can be used for preparing transparent conductive film and optics is received
Rice complex, ATO/ high molecular polymer complex of the present invention has the well ultrared function of obstruct, it is seen that light light transmission
Good, can be used for preparing safe doubling glass.
Advantages of the present invention will partly illustrate, and a part is apparent according to description
, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope picture (TEM) nanocrystalline for ATO in the embodiment of the present invention 1；
Fig. 2 is the X ray diffracting spectrum nanocrystalline for ATO (XRD) of the embodiment of the present invention 1 preparation；
Fig. 3 is scanning electron microscope nanocrystalline for ATO (SEM) and the high-resolution-ration transmission electric-lens of the embodiment of the present invention 1 preparation
(HRTEM) figure；
Fig. 4, Fig. 5, Fig. 6, Fig. 7 are respectively the transmission electron microscope picture nanocrystalline for ATO of the embodiment of the present invention 2,5,6,7 preparation
(TEM)；
Fig. 8 is transmission electron microscope picture (TEM) nanocrystalline for ATO in embodiment of the present invention 13-15；
Fig. 9 is the transmission electron microscope collection of illustrative plates (TEM) of ATO slip in the embodiment of the present invention 17；
Figure 10 is the transmission electron microscope collection of illustrative plates (TEM) of 2wt%ATO/PVB transparent nano complex in the embodiment of the present invention 18；
Figure 11 is the spectrum of the UV-Vis-NIR of the doubling glass of different ATO additions in the embodiment of the present invention 18.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some improvements and modifications, these improve
With the protection domain that retouching is also considered as the embodiment of the present invention.
Embodiment 1
The preparation method that a kind of ATO is nanocrystalline, comprises the following steps:
Weigh 6.28g five water stannic chloride, 0.47g antimony chloride (corresponding Sb doped amount is 10%), join containing
In the 100mL hydrothermal reaction kettle of 31.4mL ethanol, it is stirred at room temperature 30min and is completely dissolved to slaine, and the perseverance of 150 DEG C
Keeping reaction 24 hours in incubator, reaction is cooled to room temperature after terminating, with deionized water supersound washing three times, 10000 rotating speeds from
The heart 15 minutes, then with washing with alcohol once after, put into 80 DEG C of oven dried overnight, obtain ATO nanocrystalline.Will a small amount of this be nanocrystalline
Again disperse in ethanol, drop in cover and on carbon film copper mesh, carry out transmission electron microscope sign.Fig. 1 is nanocrystalline saturating of the present embodiment ATO
Radio mirror figure (TEM), it can be seen that ATO nano-crystalline granule size uniform, about 80-90nm.Fig. 2 is prepared by the present embodiment
The X ray diffracting spectrum of ATO, diffracting spectrum shows only SnO2Characteristic peak and there is no any miscellaneous peak of antimony, this shows antimony
Atom has been embedded in tin ash SnO2Lattice in, Fig. 3 (a) and Fig. 3 (b) are respectively nanocrystalline the sweeping of the present embodiment ATO
Retouch Electronic Speculum (SEM) and high-resolution-ration transmission electric-lens (HRTEM) figure.Additionally, the result display Sn:Sb=of XRF, ICP and TEM-EDS
9:1 (mol ratio) is identical with the mol ratio putting into raw material.
Embodiment 2
The present embodiment differs only in embodiment 1, and alcoholic solvent used is 21.8mL methanol.
Embodiment 3
The present embodiment differs only in embodiment 1, and alcoholic solvent used is 41.3mL isopropanol.
Embodiment 4
The present embodiment differs only in embodiment 1, and alcoholic solvent used is 49.4mL butanol.
Embodiment 5
The present embodiment differs only in embodiment 1, and alcoholic solvent used is 30.1mL ethylene glycol.
Embodiment 6
The present embodiment differs only in embodiment 1, and alcoholic solvent used is 72.2mL 2,2'-ethylenedioxybis(ethanol)..
Embodiment 7
The present embodiment differs only in embodiment 1, and alcoholic solvent used is 39.3mL glycerol.
Fig. 4, Fig. 5, Fig. 6, Fig. 7 are respectively the transmission electron microscope picture nanocrystalline for ATO (TEM) of embodiment 2,5,6,7 preparation, thoroughly
The ATO that radio mirror figure illustrates different-grain diameter is nanocrystalline, and integrated embodiment 1 understands, and the nanocrystalline size of ATO is controlled 5～90nm.
As can be seen here, the present invention is by selecting different types of alcoholic solvent, and the ATO that can prepare different-grain diameter size is nanocrystalline, from
And realize the Effective Regulation of particle diameter nanocrystalline to ATO.
Embodiment 8
The preparation method that a kind of ATO is nanocrystalline, comprises the following steps:
Weigh 6.28g five water stannic chloride, 0.042g antimony chloride (corresponding Sb doped amount is 1%) be separately added into containing
In the hydrothermal reaction kettle of 31.4mL ethanol, it is stirred at room temperature 30min and is completely dissolved to slaine, and at the calorstat of 150 DEG C
Middle holding, reacts 24 hours, and reaction is cooled to room temperature after terminating, and with deionized water supersound washing three times, 10000 rotating speeds are centrifuged 15
Minute, then with washing with alcohol once after, put into 80 DEG C of oven dried overnight, the ATO obtaining different Sb doped amount is nanocrystalline.Obtain
X-ray diffractogram nanocrystalline for ATO all only have SnO2Characteristic peak and there is no any miscellaneous peak of antimony, this shows that antimony atoms is
It is embedded into tin ash SnO2Lattice in, and the doping of antimony may be up to 20%.
Embodiment 9
The present embodiment differs only in embodiment 8, and the addition of antimony chloride is that (corresponding Sb doped amount is 0.171g
4%).
Embodiment 10
The present embodiment differs only in embodiment 8, and the addition of antimony chloride is that (corresponding Sb doped amount is 0.309g
7%).
Embodiment 11
The present embodiment differs only in embodiment 8, and the addition of antimony chloride is that (corresponding Sb doped amount is 0.725g
15%).
Embodiment 12
The present embodiment differs only in embodiment 8, and the addition of antimony chloride is that (corresponding Sb doped amount is 1.03g
20%).
Embodiment 13
The preparation method that a kind of ATO is nanocrystalline, comprises the following steps:
Weighing 6.28g five water stannic chloride, 0.47g antimony chloride is separately added in the hydrothermal reaction kettle containing 10mL ethylene glycol
(corresponding pink salt is 1:10 with the mol ratio of alcoholic solvent, 1:30,1:50), is stirred at room temperature 30min the most molten to slaine
Solving, and keep reaction 24 hours in the calorstat of 150 DEG C, reaction is cooled to room temperature after terminating, uses deionized water supersound washing
Three times, 10000 rotating speeds are centrifuged 15 minutes, then with washing with alcohol once after, put into 80 DEG C of oven dried overnight, available size is equal
Even ATO is nanocrystalline.
Embodiment 14
The present embodiment differs only in embodiment 13, and the addition of ethylene glycol is that (corresponding pink salt is molten with alcohol for 30mL
The mol ratio of agent is 1:30).
Embodiment 15
The present embodiment differs only in embodiment 13, and the addition of ethylene glycol is that (corresponding pink salt is molten with alcohol for 50mL
The mol ratio of agent is 1:50).
Fig. 8 (a), 8 (b), 8 (c) are respectively transmission electron microscope picture nanocrystalline for ATO in the embodiment of the present invention 13,14,15
(TEM) figure, as it can be seen, embodiment 13,14,15 has obtained size, to respectively may be about the ATO of 50nm, 35nm, 8nm nanocrystalline.
Embodiment 16
The preparation method that a kind of ATO is nanocrystalline, comprises the following steps:
Weighing 6.28g five water stannic chloride, 0.47g antimony chloride adds containing 5.2mL ethanol and 10mL ethylene glycol mixed solvent
Hydrothermal reaction kettle in, be stirred at room temperature 30min and be completely dissolved to slaine, and in the calorstat of 150 DEG C keep reaction
24 hours, reaction was cooled to room temperature after terminating, and with deionized water supersound washing three times, 10000 rotating speeds are centrifuged 15 minutes, then use second
Alcohol washing by soaking once after, put into 80 DEG C of oven dried overnight, the ATO that available size is about 60nm is nanocrystalline.
Embodiment 17
The preparation method of a kind of ATO nanometer slurry, comprises the following steps:
Weigh that ATO prepared by 1g methanol is nanocrystalline after roasting 30 minutes, to be added the stearic acid of 0.08g, use at 600 DEG C
Retsch PM100 ball mill grinding 5 hours, then remove impurity with 4000 revs/min of centrifuge washings, by nanocrystalline for gained ATO dispersion
The ATO nanometer slurry TEM figure spectrogram of ATO nanometer slurry (Fig. 9 be) of stable dispersion is obtained in chloroform.
Embodiment 18
The preparation method of a kind of ATO/PVB complex, comprises the following steps:
Taking a certain amount of high molecular polymer PVB chloroform to dissolve, the ATO slip and the additive that add same solvent (increase
Mould agent 3GO, be 30:100 with the ratio of PVB；A small amount of antioxidant and ultraviolet absorber), ATO and the quality of high molecular polymer
Ratio is 0.5～2:100, and ultrasonic agitation is also mixed to form uniform solution (Figure 10 is that in embodiment 18,2wt%ATO/PVB is transparent
The transmission electron microscope collection of illustrative plates (TEM) of nano-complex), solution is poured into evaporation solvent in glass mold, obtains that there is obstruct infrared
The transparent ATO/PVB nano-complex diaphragm of line function.
Embodiment 19
The preparation method of a kind of ATO/PVB complex, comprises the following steps:
By the ATO nanometer slurry that obtains in embodiment 17 and high molecular polymer PVB powder end, additive (plasticizer 3GO,
Antioxidant Irganox1010, ultraviolet absorber UV-326) it is sufficiently mixed, it is subsequently poured in two-roll mill mixing, film is set
Thickness is 0.38mm, preparation pull-out ATO/PVB complex diaphragm at 120 DEG C.
Embodiment 20
Respectively by simple pvb film and by the embodiment of the present invention 18 method prepare different ATO additions
The glass that the ATO/PVB diaphragm of (0.2wt%, 0.5wt%, 1.0wt%, 2.0wt%) is thick with business 3mm is carried out at 135 DEG C
Doubling, then intercepts ultrared performance with UV-VIS-NIR spectrum test to doubling glass and is evaluated.Figure 11 presents not
With the spectrum of UV-Vis-NIR of the doubling glass of ATO addition, in figure, curve 1,2,3,4,5 is respectively pure PVB, ATO and adds
Amount is the spectrum of the UV-Vis-NIR of the doubling glass of 0.2wt%, 0.5wt%, 1.0wt%, 2.0wt%.Figure showing, ATO contains
Amount can intercept the near infrared ray after 1600nm completely for the doubling glass (thickness of film is about 0.2mm) of 2wt%, and visible
Light light transmittance is more than 80%.If by the 0.38mm THICKNESS CALCULATION of industrial doubling glass, the nanometer of the ATO of 1wt% content is multiple
Compound just has the near infrared function of obstruct very well.
Claims (10)
1. a preparation method nanocrystalline for ATO, it is characterised in that comprise the following steps:
Antimonic salt and pink salt 1～15:100 are joined in alcoholic solvent in molar ratio, after being uniformly mixed, obtains mixed solution, will
Described mixed solution joins in pressure reactor, maintains reaction 18～48 hours at 150～200 DEG C, after reaction terminates, from
So it is cooled to room temperature, is then centrifuged products therefrom separating, washing, after drying, obtains ATO nanocrystalline.
2. preparation method as claimed in claim 1, it is characterised in that described pink salt is 1:5 with the mol ratio of described alcoholic solvent
～50；Described alcoholic solvent is in ethanol, propanol, isopropanol, butanol, amylalcohol, ethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG) and glycerol
At least one.
3. preparation method as claimed in claim 1, it is characterised in that described pink salt selected from stannic chloride, nitric acid stannum, STANNOUS SULPHATE CRYSTALLINE and
At least one in tin acetate；At least one in antimony chloride, nitric acid antimony, Antimonous sulfate and antimony acetate of described antimonic salt.
4. preparation method as claimed in claim 1, it is characterised in that the rotating speed of described centrifugal separation processes be 6000～
10000rpm, the time is 5～15 minutes；Described washing operation is particularly as follows: be first washed with deionized 2-3 time, then with anhydrous
Washing with alcohol 1-2 time；The temperature of described drying is 50-80 DEG C.
5. the ATO that the preparation method as described in any one of claim 1-4 prepares is nanocrystalline, the grain that described ATO is nanocrystalline
Footpath is 5-100nm.
6. an ATO nanometer slurry, it is characterised in that use the nanocrystalline preparation of ATO as claimed in claim 5.
7. an ATO/ high molecular polymer complex, it is characterised in that nanocrystalline and high by ATO as claimed in claim 5
Molecularly Imprinted Polymer is composited, and described high molecular polymer is transparent polymer material, including in PVB, PMMA, PC, PP and PE
At least one.
8. the preparation method of an ATO/ high molecular polymer complex, it is characterised in that comprise the following steps:
Take a certain amount of high molecular polymer solvent to dissolve, obtain macromolecule polymer solution；
Taking a certain amount of ATO as claimed in claim 5 nanocrystalline, adding the nanocrystalline mass fraction of relative ATO is 1-10%'s
Dispersant, obtains mixed dispersion liquid, is ground 3-12 hour by described mixed dispersion liquid planetary ball mill, then uses 2000-4000
Rev/min centrifuge washing removes impurity, is subsequently dispersed in above-mentioned solvent, obtains the ATO nanometer slurry of stable dispersion；
Being mixed with described ATO nanometer slurry by described macromolecule polymer solution, and add additive, ultrasonic agitation also mixes shape
Uniformly mixed solution, pours described mixed solution evaporation solvent in mould into, obtains ATO/ high molecular polymer complex；
Or take a certain amount of high molecular polymer powder, by described high molecular polymer powder and above-mentioned ATO nanometer slurry and on
State additive mixing, obtain mixed material, gained mixed material is joined in two-roll mill by the temperature set and program
Mixing, then extrusion molding obtains ATO/ high molecular polymer complex diaphragm.
9. preparation method as claimed in claim 8, it is characterised in that when described ATO nanometer slurry is aqueous slip, described
Solvent is water, ethanol or isopropanol, and described dispersant is silane coupler, sodium salt or titanate coupling agent；When described ATO receives
When rice slip is oiliness slip, described solvent is toluene, dichlorotoleune, ketone or chloroform, and described dispersant is long-chain fatty acid table
The agent alive of face property.
10. preparation method as claimed in claim 8, it is characterised in that described macromolecule polymer solution or described macromolecule
Polymer powder is 0.5～5:100 to mix with described ATO nanometer slurry by ATO and the mass ratio of high molecular polymer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111070606A (en) * | 2019-12-27 | 2020-04-28 | 苏州耐思特塑胶有限公司 | Processing technology of electronic instrument plastic cover plate |
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| JPH05279039A (en) * | 1992-03-27 | 1993-10-26 | Mitsubishi Materials Corp | Production of tin oxide fine powder |
| CN101428849A (en) * | 2008-12-03 | 2009-05-13 | 江苏柏鹤涂料有限公司 | Stibium doped tin dioxide nano-powder and method for producing the same |
| CN101896430A (en) * | 2007-10-09 | 2010-11-24 | 凯门知识产权有限公司 | Dispersion of nanoparticles in organic solvents |
| WO2013147029A1 (en) * | 2012-03-29 | 2013-10-03 | 三菱マテリアル株式会社 | Antimony-doped tin oxide powder and process for manufacturing same |
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2016
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|---|---|---|---|---|
| JPH05279039A (en) * | 1992-03-27 | 1993-10-26 | Mitsubishi Materials Corp | Production of tin oxide fine powder |
| CN101896430A (en) * | 2007-10-09 | 2010-11-24 | 凯门知识产权有限公司 | Dispersion of nanoparticles in organic solvents |
| CN101428849A (en) * | 2008-12-03 | 2009-05-13 | 江苏柏鹤涂料有限公司 | Stibium doped tin dioxide nano-powder and method for producing the same |
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| 朱冰洁: "ATO纳米粉体及其有机复合材料的合成与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| CN111070606A (en) * | 2019-12-27 | 2020-04-28 | 苏州耐思特塑胶有限公司 | Processing technology of electronic instrument plastic cover plate |
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