CN101148550B - Multi-substance straggling effect nano structure liquid membrane and its preparation method and application - Google Patents
Multi-substance straggling effect nano structure liquid membrane and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to nanometer structure film paint, and is especially one kind of nanometer structure film paint with excellent expelling effect and its preparation process and application. The nanometer structure film paint has nanometer composite powder accounting 0.1-2 wt% of the paint dispersed homogeneously in active film forming material. The nanometer composite powder is prepared with over two kinds of powdered material in the grain size smaller than 100 nm and through modification with fluorocarbon surfactant; and the active film forming material includes film forming material and dispersing medium. The multifunctional nanometer composite powder material makes the film possess effects of expelling and dispersing oil, water, organic impurity, inorganic dust, bacteria, etc.
Description
Technical field
The present invention relates to a kind of nano structure membrane coating, relate in particular to a kind of multi-substance straggling effect nano structure liquid membrane coating and its production and application.
Background technology
At present, the preparation method and the kind of the nano film material in the background technology are a lot, have as the preparation method: colloidal suspension chemical precipitation method, self-assembly method, surface-modification method, electrochemical deposition method etc.; The functional film of the nanostructure of its preparation also has numerous species, as Nano semiconductor film, nano-porous film, nanocomposite optical film, nanometer magnetics film, Nanotribology film etc.The preparation of the film of nanostructure in the prior art is generally realized by particle and substrate.On the kind of above-described nano structure membrane function, there is not to propose nano structure membrane about " many matter loose effect " and preparation method thereof.Its characteristics of this film are utilized the straggling effect principle exactly, and the many kinds of materials that will promptly will be attached on the base-material (substrate) speed away, and perhaps decompose to leave, and so as to not make that base material contacts, thereby reach the effect of straggling effect.
Although do not propose many matter straggling effect theory in the background technology, the material of many decomposition, oleophobic, hydrophobic aspect is arranged, promptly single thin, two thin notions.Its product essence is to water or the estranged effect of smeary, can reach purpose grease proofing, waterproof; In the prior art only having crying of single estranged effect single thin to water or oil; To water, that oil has crying of estranged effect simultaneously is two thin.We are defined as the straggling effect material this material.
The material of the straggling effect in the background technology generally is made up of the number of chemical material, its mechanism is that chemical reaction or bonding scheme combine with base material, change the physical and chemical performance of base material, as representative products holder fluorine dragon, N (ternary-butyl) acrylamide, second-tetradecyl CALCIUM ACRYLATE, ethene laurostearic acid fat and halogen class monomer, N-fluorobenzene ethene etc.; Solving waterproof, grease proofing method on the other hand adds in base-material and has hydrophobic or oleophobic group (functional group) coating material, these materials are generally superfine powder or liquid, reported permanent treatment technology as external, the technology culvert is general many chemical basic principles and various nano material, its product performance and use are similar substantially to other products, in view of to the background technology analysis, the inventor analyzes the kind and the function of nano structure membrane of the prior art, thinks that there are following deficiency in nano structure membrane kind and function in the background technology:
One, existing nano structure membrane does not have the function of many matter straggling effect, and the kind great majority are optical thin film, magnetics, semi-conductor or conducting film and friction film.The invention provides new kind replenishes.
Two, " straggling effect " material in the prior art is functions such as single waterproof, grease proofing, antibiotic, anti-electromagnetism, does not generally have the decomposition discrete functionality to multiple material, the invention provides replenishing of new function.
Three, the chemical composition in the prior art is substantially based on organism or coating material, and product performance are stable inadequately, and poor durability, even some pollutant component do not reach environmental requirement.
Four, the list that uses in the prior art is dredged material also the part powder body material, but since pellet more generally more than 1000nm, this material is difficult for disperseing in liquid phase or colloid, makes them be added in the dielectric material DeGrain.And influence the gloss of goods, and mostly the group on the function powder is to be adsorbed on powder surface with physics mode simultaneously, and group combines insecure with powder, and these groups are damaged along with the raising of time lengthening and temperature, thereby influence the function of material and goods.
Five, analogous material of the prior art mostly adopts nano material, titanium dioxide, zinc oxide, silicon oxide, aluminium sesquioxide, lime carbonate etc., though these materials are widely used, but the preparation method is many, processing parameter control is changeable, cause the character of material stable inadequately, be difficult to guarantee the performance index of prepared thin-film material aborning.
Summary of the invention
According to the deficiency that exists in the aforementioned background art, the purpose of this invention is to provide a kind of multi-substance straggling effect nano structure liquid membrane coating that keeps base material and goods stability thereof and can reach hydrophobic, oleophobic, dustproof, antibiotic, anti-aging function.
Another object of the present invention provides the preparation method of above-mentioned multi-substance straggling effect nano structure liquid membrane coating and the application of this coating.
" many matter straggling effect " theory among the present invention is meant that this nano thin-film can comprise that multiple materials such as water, oil, organic impurity, inorganic dust, bacterium and light, electricity, magnetic carry out catalysis, decomposition, divorce, dispersive effect to material more than three kinds on function, define angle from the present invention, the list in the background technology is dredged, two thin materials all belong to " simple substance discrete type material ".
In order to realize above-mentioned purpose, the present invention has adopted following technical scheme.
Multi-substance straggling effect nano structure liquid membrane coating, be evenly distributed on in the film activity dispersed substance by composite nano-powder and constitute: composite nano-powder accounts for the 0.1-2% of coating gross weight, composite nano-powder is all mixed after fluorocarbon surfactant modified less than the 100nm nano-powder material by granularity, and nano-powder material comprises following 2 kinds of powder body materials at least: nano anti-biotic material, nano catalytic material, nanometer decomposing material, nano-interface material and Nanosurface power consumption material; Become the film activity dispersed substance to comprise filmogen and water dispersion medium, filmogen accounts for the 2-10% of coating gross weight; Surplus is a water dispersion medium.
As preferably, above-mentioned one-tenth film activity dispersed substance also comprises functional agent, and functional agent accounts for the 0.05-0.1% of coating gross weight.As preferred again, functional agent is a fatty alcohol-polyoxyethylene ether.Fatty alcohol-polyoxyethylene ether can be used for system balance and stable performance.
As preferably, nano-powder material comprises: nano anti-biotic material, nano catalytic material, nanometer decomposing material, nano-interface material and Nanosurface power consumption material, and each compositions in weight percentage is as follows:
Nano anti-biotic material 20-30%;
Nano catalytic material 15-25%;
Nanometer decomposing material 20-30%;
Nano-interface material 15-25%;
Nanosurface power consumption material 15-20%.
As preferably, above-mentioned fluorocarbon surfactant adopts respectively at powder body material: nano anti-biotic material is selected the different phthalonitrile tensio-active agent of tetrafluoro for use; Nano catalytic material is selected fluorine carbon silane surface active agent for use; The nanometer decomposing material is selected perfluor base fluorine polymeric silicon tensio-active agent for use; The fluoroalkylation compound tensio-active agent of nano-interface material and Nanosurface power consumption material selection 5%.
As preferably, above-mentioned nano anti-biotic material is selected silicon-base oxide (SiO for use
2-x) be the metal ion anti-biotic material of carrier; Nano catalytic material is selected titanium dioxide (TiO for use
2) or yttrium oxide (Y
2O
3); The nanometer decomposing material is selected zinc oxide (ZnO) or zinc dichloride (ZnCl for use
2); Nano-interface material selection aluminium sesquioxide (Al
2O
3) or samarium sesquioxide (Sm
2O
3); Nanosurface power consumption material selection titanium dioxide (TiO
2) or neodymium sesquioxide (Nd
2O
3).
As a preferred version, above-mentioned nano anti-biotic material selects for use the silicon-dioxide of particle diameter 30nm to carry ag material, 23%; Nano catalytic material is selected the titanium dioxide of particle diameter 20nm, 20% for use; The nanometer decomposing material is selected the zinc oxide of particle diameter 60nm, 22% for use; The aluminium sesquioxide of nano-interface material selection particle diameter 50nm, 20%; Nanosurface power consumption material selection is the titanium dioxide of particle diameter 10nm, 15%.
As a preferred version, above-mentioned nano anti-biotic material selects for use the silicon-dioxide of particle diameter 30nm to carry ag material, 23%; Nano catalytic material is selected the yttrium oxide of particle diameter 20nm, 20% for use; The nanometer decomposing material is selected the zinc dichloride of particle diameter 60nm, 22% for use; The samarium sesquioxide of nano-interface material selection particle diameter 50nm, 20%; Nanosurface power consumption material selection is the neodymium sesquioxide of particle diameter 10nm, 15%.
As preferably, filmogen is selected from: urethane resin, silicone resin, acrylic resin or fluorocarbon resin.As preferred again, filmogen is a perfluoro alkyl sulfonic acid acyl alkyl acrylic acid fat.Perfluoro alkyl sulfonic acid acyl alkyl acrylic fat is used for load nano particle, and makes it to combine firmly with matrix.
As a preferred version, by weight percentage, composite nano-powder is 2%, and perfluoro alkyl sulfonic acid acyl alkyl acrylic fat is 4%, and fatty alcohol-polyoxyethylene ether is 0.1%, and deionized water is 93.9%.
In order to realize second purpose, the invention provides the preparation method of above-mentioned multi-substance straggling effect nano structure liquid membrane coating, it comprises the steps:
1) above-mentioned nano-powder material is disperseed in dispersion medium respectively, be that 1: 0.005～1: 0.01 ratio is added in the dispersion medium in the ratio of the amount between nano-powder material and the fluorocarbon surfactant respectively then, nano-material surface hydroxyl and fluorocarbon surfactant are fully reacted, remove dispersion medium, obtain various nano modified material powders through super-dry;
2) the above-mentioned nano modified material powder mixing and stirring that makes is respectively made composite nano-powder;
3) under 50～70 ℃, the above-mentioned functions auxiliary agent is joined in the water dispersion medium, stirring makes functional agent be dissolved in the water dispersion medium uniformly, then the above-mentioned composite nano-powder that makes is joined in the above-mentioned solution, stir, emulsification makes nano material be dispersed in the liquid phase uniformly;
4) with filmogen joining in the scattered nanometer liquid phase slowly, stirring makes described coating.
As preferably, the dispersion medium in the above-mentioned step 1) can adopt toluene or dimethylbenzene.
Above-mentioned multi-substance straggling effect nano structure liquid membrane coating can be applied in handling cloth, fabric, glasswork, car body, tables and metope.The film-forming process of its nano structure membrane is as follows:
To promptly want the film forming cloth of original position, fabric, glasswork, car body, tables or metope base material to clean up, with the method that sprays, pads, the film forming slurry is arranged on the base material top, the base material that is provided with the film forming slurry was got final product at 120～180 ℃ of following heating, dryings in 0.5～1 minute.Produce adjusting and become film pressure by adjusting slurry concentration or control, can realize the gauge control of nano structure membrane, nano structure membrane is solidified as a whole with the form and the base material of absorption, bonding, infiltration, the nano structure membrane thickness that forms is less than 500nm, and having has the divorce divergent function to materials such as water, oil, dust, thermoelectricity, magnetic, light.
Owing to adopt technique scheme, function mechanism, film, materials used, the nano thin-film microtexture of the film of feasible preparation are different, and its advantage is:
1, the nano structure membrane among the present invention is to be composited with the base material original position to have and the base material inseparability.
2, the nano material in the nano structure membrane among the present invention is a multifunctional composite, after surface modification, make film have divorce and dissemination, remedied deficiency singly thin in the background technology, two thin materials oil, water, organic impurity, inorganic dust, bacterium and light, electricity, magnetic.
3, the nano-material modified auxiliary agent that adopts among the present invention is based on fluorocarbon surfactant, and addition seldom descends the surface tension of liquid, as water 73MN/M, is reduced to 18MN/M, and effect is remarkable.
4, because making, factors such as the geometrical dimension of fluorine atom uniqueness and electronegativity nano material after the modification have very high thermostability, very high anti-strong acid, high concentration alkali and strong oxidizing property.
5, the filmogen among the present invention adopts fluorine carbon film forming material, makes thickness obviously descend, and keeps the physical chemical characteristics and the color of former base material, and still has high transparency and ventilation property.
6, good catalytic and the carrier of nano rare earth material use nano rare earth material among the present invention, improve activity of such catalysts by improving active ingredient dispersity from the teeth outwards, and make it stable, and can also reach the adjusting surface acid by the ratio that changes rare earth oxide--the purpose of alkalescence.Thereby better realize the discrete effect of many matter such as water, oil, dust, thermoelectricity, magneto-optic.
Embodiment
Embodiment one
One, nano-powder material modification:
1, starting material are selected:
A. nano anti-biotic material: the silicon-dioxide of particle diameter 30nm carries ag material;
B. nano catalytic material: the titanium dioxide of particle diameter 20nm;
C. nanometer decomposing material: the zinc oxide of particle diameter 60nm;
D. nano-interface material: the aluminium sesquioxide of particle diameter 50nm.
E. Nanosurface power consumption material: particle diameter is the titanium dioxide of 10nm.
Getting the 30g fluorocarbon surfactant trade mark is PN-80, be added in the 200ml toluene solvant, after treating to dissolve fully, the 200g nano silicon oxide carried in the above-mentioned solvent that contains tensio-active agent of ag material powder joining slowly stir, make its complete reaction, slough toluene again, dry in loft drier, drying temperature is 120 ℃, after micronizer mill disperses, obtains the white powder nano modified material.
The 100g nano-titanium oxide is joined in the 800mL dimethylbenzene, stir at ambient temperature then, make its uniform mixing, slowly the 8g fluorocarbon surfactant is added in the mixed solution then, the limit adds drips the limit ultrasonic dispersing, after dropwising, continued ultrasonic stirring 10 minutes, make complete reaction, therefrom slough dimethylbenzene again, obtain the reactant of titanium dioxide and fluorocarbon surfactant, dry in baking oven, drying temperature be 150 ℃ after micronizer mill disperses, obtain the modified nano-titanium dioxide powder.
Other modified powder can obtain nano materials such as modified nano zinc oxide, nano-aluminium oxide as stated above.
Two, the preparation of composite nano-powder
1, with the nano modification powder of step 1 preparation, presses following formula rate
a∶b∶c∶d∶e＝23％∶20％∶22％∶20％∶15％
2, technological process:
The nano material of above-mentioned modification is joined in the stir mixing machine with ratio in order, stirred 30 minutes with 150 rev/mins rotating speeds, the back of waiting to stir is taken out standby.
Three, the preparation of nanometer film forming slurry
1, raw material is selected for use:
A. composite nano-powder 0.5%;
B. fluorine carbon filmogen total oxygen alkylsulphonic acid acyl alkyl acrylic fat 5%;
C. functional agent: select fatty alcohol-polyoxyethylene ether 0.1% for use;
D. dispersion medium is that deionized water, specific conductivity are less than 0.1.
2, configuration proportion:
a∶b∶c∶d＝0.5％∶5％∶0.1％∶94.4％
3, the preparation technology of film forming slurry:
Be ready to starting material according to the above ratio, functional agent is joined in the dispersion medium deionized water, quicken to stir, make functional agent be dissolved in the dispersion medium uniformly, with the composite nano-powder after the modification, slowly join in the above-mentioned solution, with the rotating speed of stirrer with 160 rev/mins, stir after 30 minutes, disperseed 10 minutes with mulser, nano material is dispersed in the liquid phase uniformly, again fluorine carbon filmogen is disperseed uniformly, joining in the scattered nanometer liquid phase slowly, it is evenly standby that slowly stirring makes the filmogen dissolving.
Embodiment two
One, nano-powder material modification:
1, starting material are selected:
A. nano anti-biotic material: the silicon-dioxide of particle diameter 30nm carries ag material;
B. nano catalytic material: the yttrium oxide of particle diameter 20nm;
C. nanometer decomposing material: the zinc dichloride of particle diameter 60nm;
D. nano-interface material: the samarium sesquioxide of particle diameter 50nm.
E. Nanosurface power consumption material: particle diameter is the neodymium sesquioxide of 10nm.
Silicon-dioxide is carried the method modification by modification among the embodiment one of ag material, yttrium oxide, zinc dichloride, samarium sesquioxide and neodymium sesquioxide.
Two, the preparation of composite nano-powder
1, with the nano modification powder of step 1 preparation, presses following formula rate
a∶b∶c∶d∶e＝23％∶20％∶22％∶20％∶15％
2, technological process:
The nano material of above-mentioned modification is joined in the stir mixing machine with ratio in order, stirred 30 minutes with 150 rev/mins rotating speeds, the back of waiting to stir is taken out standby.
Three, the preparation of nanometer film forming slurry
1, raw material is selected for use:
A. composite nano-powder 0.5%;
B. fluorine carbon filmogen total oxygen alkylsulphonic acid acyl alkyl acrylic fat 5%;
C. functional agent: select fatty alcohol-polyoxyethylene ether 0.1% for use;
D. dispersion medium is that deionized water, specific conductivity are less than 0.1.
2, configuration proportion:
a∶b∶c∶d＝0.5％∶5％∶0.1％∶94.4％
3, the preparation technology of film forming slurry:
Be ready to starting material according to the above ratio, functional agent is joined in the dispersion medium deionized water, quicken to stir, make functional agent be dissolved in the dispersion medium uniformly, with the composite nano-powder after the modification, slowly join in the above-mentioned solution, with the rotating speed of stirrer with 160 rev/mins, stir after 30 minutes, disperseed 10 minutes with mulser, nano material is dispersed in the liquid phase uniformly, again fluorine carbon filmogen is disperseed uniformly, joining in the scattered nanometer liquid phase slowly, it is evenly standby that slowly stirring makes the filmogen dissolving.
Embodiment three
The preparation of fabric nano structure membrane:
To promptly want the film forming fabric of original position to clean, method with spraying uniformly sprays surface at fabric with above-mentioned slurry, two times repeatedly, the fabric that has sprayed slurry is put in 150 ℃ the drying plant, dry 1 minute, promptly obtain having the nano structure membrane fabric.
Embodiment four
The preparation of glass article surface nano structure membrane:
Glass article surface is cleaned up, with the method for sticking bubble with nanometer film forming slurry attached to glass article surface, take out glasswork, the loft drier of putting into 120 ℃ was dried 5 minutes, took out cooling.
Embodiment five
The preparation of car body surface nano structure membrane:
Car body surface is cleaned up, evenly be sprayed on car body surface, car body is inserted in the drying shed, under 80 ℃ condition, heated 10 minutes with nanometer film forming slurry.
Embodiment six
The preparation of masonry wooden structures surface of wall nano thin-film:
The surface of wall of brick, stone wooden structures is cleaned out, with the method that sprays above-mentioned slurry is uniformly sprayed at surface of wall, contact with surface of wall with infrared source, its contact temperature is the 100 ℃ of following surface of wall that can realize nano thin-film in 5 minutes of situation.
Above technical scheme is preferred embodiment among the present invention, the present invention is not done any pro forma restriction, and every foundation technical spirit of the present invention is done the technology equivalent variations, and ratio modification etc. all belongs to the scope of the invention.
Claims (7)
1. multi-substance straggling effect nano structure liquid membrane coating is characterized in that this coating is evenly distributed on in the film activity dispersed substance by composite nano-powder to constitute:
Composite nano-powder accounts for the 0.1-2% of coating gross weight, composite nano-powder is all mixed after fluorocarbon surfactant modified less than the 100nm nano-powder material by granularity, described nano-powder material comprises: nano anti-biotic material, nano catalytic material, nanometer decomposing material, nano-interface material and Nanosurface power consumption material, and each compositions in weight percentage is as follows:
Nano anti-biotic material 20-30%;
Nano catalytic material 15-25%;
Nanometer decomposing material 20-30%;
Nano-interface material 15-25%;
Nanosurface power consumption material 15-20%;
Wherein: nano anti-biotic material is selected the different phthalonitrile tensio-active agent of tetrafluoro for use, nano catalytic material is selected fluorine carbon silane surface active agent for use, the nanometer decomposing material is selected perfluor base fluorine polymeric silicon tensio-active agent for use, the fluoroalkylation compound tensio-active agent of nano-interface material and Nanosurface power consumption material selection 5%;
Become the film activity dispersed substance to comprise filmogen, functional agent and water dispersion medium, filmogen is a perfluoro alkyl sulfonic acid acyl alkyl acrylic fat, and filmogen accounts for the 2-10% of coating gross weight; Functional agent is a fatty alcohol-polyoxyethylene ether, and functional agent accounts for the 0.05-0.1% of coating gross weight; Surplus is a water dispersion medium;
It is the metal ion anti-biotic material of carrier that above-mentioned nano anti-biotic material is selected silicon-base oxide for use; Nano catalytic material is selected titanium dioxide or yttrium oxide for use; The nanometer decomposing material is selected zinc oxide or zinc dichloride for use; Nano-interface material selection aluminium sesquioxide or samarium sesquioxide; Nanosurface power consumption material selection titanium dioxide or neodymium sesquioxide.
2. multi-substance straggling effect nano structure liquid membrane coating according to claim 1 is characterized in that nano anti-biotic material selects for use the silicon-dioxide of particle diameter 30nm to carry ag material, 23%; Nano catalytic material is selected the titanium dioxide of particle diameter 20nm, 20% for use; The nanometer decomposing material is selected the zinc oxide of particle diameter 60nm, 22% for use; The aluminium sesquioxide of nano-interface material selection particle diameter 50nm, 20%; Nanosurface power consumption material selection is the titanium dioxide of particle diameter 10nm, 15%.
3. multi-substance straggling effect nano structure liquid membrane coating according to claim 1 is characterized in that nano anti-biotic material selects for use the silicon-dioxide of particle diameter 30nm to carry ag material, 23%; Nano catalytic material is selected the yttrium oxide of particle diameter 20nm, 20% for use; The nanometer decomposing material is selected the zinc dichloride of particle diameter 60nm, 22% for use; The samarium sesquioxide of nano-interface material selection particle diameter 50nm, 20%; Nanosurface power consumption material selection is the neodymium sesquioxide of particle diameter 10nm, 15%.
4. multi-substance straggling effect nano structure liquid membrane coating according to claim 1, it is characterized in that by weight percentage composite nano-powder is 2%, perfluoro alkyl sulfonic acid acyl alkyl acrylic fat is 4%, fatty alcohol-polyoxyethylene ether is 0.1%, and deionized water is 93.9%.
5. the preparation method of multi-substance straggling effect nano structure liquid membrane coating according to claim 1 is characterized in that comprising the steps:
1) above-mentioned nano-powder material is disperseed in dispersion medium respectively, be that 1: 0.005～1: 0.01 ratio is added corresponding fluorocarbon surfactant in the dispersion medium in the ratio of the amount between nano-powder material and the fluorocarbon surfactant respectively then, nano-material surface hydroxyl and fluorocarbon surfactant are fully reacted, remove dispersion medium, obtain various nano modified material powders through super-dry;
2) the above-mentioned nano modified material powder mixing and stirring that makes is respectively made composite nano-powder;
3) under 50～70 ℃, the above-mentioned functions auxiliary agent is joined in the water dispersion medium, stirring makes functional agent be dissolved in the water dispersion medium uniformly, then the above-mentioned composite nano-powder that makes is joined in the above-mentioned solution, stir, emulsification makes the nano material composite granule be dispersed in the liquid phase uniformly;
4) with filmogen joining in the scattered nanometer liquid phase slowly, stirring makes described coating.
6. the preparation method of multi-substance straggling effect nano structure liquid membrane coating according to claim 5 is characterized in that dispersion medium adopts toluene or dimethylbenzene.
7. the application of multi-substance straggling effect nano structure liquid membrane coating according to claim 1 in handling cloth, fabric, glasswork, car body, tables and metope.
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| CN102536890A (en) * | 2010-12-15 | 2012-07-04 | 上海宝钢工业检测公司 | Impeller capable of preventing ash sticking of converter primary fan |
| CN103053617A (en) * | 2012-09-14 | 2013-04-24 | 方孝贤 | Preparation method and application antimicrobial liquid |
| CN107011781A (en) * | 2017-05-19 | 2017-08-04 | 张伟 | A kind of super transparent hydrophobic oleophobic films and preparation method |
| CN107680727A (en) * | 2017-09-30 | 2018-02-09 | 四会市启德信息咨询服务有限公司 | A kind of cable cover(ing) of cloudy surface oil resistant and preparation method thereof |
| CN113663829A (en) * | 2020-05-13 | 2021-11-19 | 山东清沂山石化科技有限公司 | Technological method for spraying dustproof oil on calcined coke device product |
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| EP1431352A1 (en) * | 2002-12-20 | 2004-06-23 | Nanosolutions GmbH | In fluorine-containing media homogeneously dispersible nanoparticles and media containing the same |
| CN1712478A (en) * | 2004-06-14 | 2005-12-28 | 中国科学院过程工程研究所 | Nanometer multifunctional composite thin-membrane, its production and use |
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| EP1431352A1 (en) * | 2002-12-20 | 2004-06-23 | Nanosolutions GmbH | In fluorine-containing media homogeneously dispersible nanoparticles and media containing the same |
| CN1712478A (en) * | 2004-06-14 | 2005-12-28 | 中国科学院过程工程研究所 | Nanometer multifunctional composite thin-membrane, its production and use |
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