CN101417789B - Plasma modification processing method of metallic oxide nano powder at atmosphere pressure and normal temperature - Google Patents
Plasma modification processing method of metallic oxide nano powder at atmosphere pressure and normal temperature Download PDFInfo
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- CN101417789B CN101417789B CN2008102022461A CN200810202246A CN101417789B CN 101417789 B CN101417789 B CN 101417789B CN 2008102022461 A CN2008102022461 A CN 2008102022461A CN 200810202246 A CN200810202246 A CN 200810202246A CN 101417789 B CN101417789 B CN 101417789B
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Abstract
The invention relates to a treatment method for modifying metal oxide nanometer powder bodies by using plasma bodies under the atmosphere pressure and the normal temperature, which comprises the steps: the metal oxide nanometer powder bodies are placed on a special transportation device of plasma body treatment equipment, plasma bodies are directly sprayed on the surfaces of the metal oxide nanometer powder bodies under the atmosphere pressure and open environment to lead the metal oxide nanometer powder bodies to move in the plasma body atmosphere, the power for treating the metal oxide nanometer powder bodies is 10W to 5000W, and the time thereof is 0.01s to 6000s, and the surface modification of the metal oxide nanometer powder bodies is carried out. The invention can further improve the surface property, structure and form of the metal oxide nanometer powder bodies under the atmosphere pressure and the normal temperature, is strong in process controllability and simple in modification process, and has small environmental pollution by the dry processing process; the surfaces of the metal oxide nanometer powder bodies obtained by the invention can produce the mutual repulsion effect of the same polarity to reach the possibility for reducing the nanometer particle agglomeration.
Description
Technical field
The invention belongs to the preparation field of nano-powder material, particularly relate to a kind of plasma modification processing method of metallic oxide nano powder at atmosphere pressure and normal temperature.
Background technology
Technology such as normal temperature, atmospheric plasma body chemical vapor phase growing, ion implantation, sputter, plasma spraying, chemical polymerization, anodic oxidation obtain widespread use in fields such as aerospace, electronics, machinery.This new process for treating surface is being brought into play increasing effect in the nanometer engineering technology in recent years.
Normal temperature, atmospheric plasma are meant part or all of Ionized gas, comprise electronics, ion, also comprise high energy activeconstituentss such as radical and photon.Normal temperature, atmospheric plasma have high energy, at a high speed, highly active advantage.Equilibrium relationship in nonequilibrium state normal temperature, the atmospheric plasma between electronic temp and ion temperature is false, and normal temperature, atmospheric plasma can have both effectively to be excited molecule, atom and preserve the characteristic that the material substrate molecule is not damaged; In the material surface improved performance, substrate performance is unaffected; Form the gaseous species and the plasma chemistry condition of plasma body through suitable selection. can carry out the modification of extraordinary purpose to the chemical structure and the physical structure of bill of material surface layer, and can realize the irrealizable reaction of traditional chemical reaction.
Because nano material has characteristics such as dimensional effect, surface effects, quantum effect, macro quanta tunnel effect, thereby shows the notable feature that is different from general macroscopic material at aspects such as optics, mechanics, electricity, magnetics, is developed rapidly in recent years.Metallic oxide nano powder and the nano-sized membrane aspects such as pollutent in the storage of sun power and utilization, opto-electronic conversion, the photochromic and big G&W of photocatalytic degradation have widespread use.Metal oxide nanoparticles is increasingly extensive because of having advantage ranges of application such as light, electricity, suction ripple.In recent years, when the metal oxide nano-material synthesis technique constantly makes further progress, the research of nano-material surface aftertreatment technology has also been received attention.Early stage is through coating certain application performance inorganic or organic cpds raising metal oxide nanoparticles on the metal oxide nano-material surface: weather resisteant, photostabilization, dispersiveness, surfactivity etc.To existing many relevant report and the application of metal oxide nanoparticles surface-treated, the surface modifying method of metal oxide nanoparticles mainly is divided into liquid phase method and vapor phase process two big classes.Inorganic coating is accomplished with liquid-phase coprecipitation, and organic absorption is then accomplished when comminution by gas stream.No matter metallic oxide nano powder is in preparation or the use, all possibly cause reuniting, and wherein drying and calcining process are the master operations that causes hard aggregation between the nano-metal-oxide nanoparticle.For alleviating the reunion degree between metal oxide nanoparticles, Chinese invention patent 03152887.2 at first prepares hydration TiO2 or TiO2 crystal sol with liquid phase method, adds tensio-active agent again, and SURFACTANT ADSORPTION is heat-treated on the nano TiO 2 surface again.Though the liquid phase method synthesis device is simple, technology is time-consuming loaded down with trivial details, pollutes greatly, and batch operation, high-temperature calcination process very easily make hard aggregation or sintering between nanoparticle, and the introducing of additives such as tensio-active agent can reduce product gas purity.
At home and abroad in the document, do not see the research report that the treatment process of utilizing normal atmosphere, normal-temperature plasma modification is improved the metallic oxide nano powder surface property as yet at present.
Summary of the invention
Technical problem to be solved by this invention provides a kind of plasma modification processing method of metallic oxide nano powder at atmosphere pressure and normal temperature; Present method is a dry method modification, in normal atmosphere and room temperature, open environment down can the directly surperficial modification of acquisition metallic oxide nano powder of a step.
Plasma modification processing method of metallic oxide nano powder at atmosphere pressure and normal temperature of the present invention comprises:
Metallic oxide nano powder is placed on the dedicated transmissions device of apparatus for processing plasma; At normal atmosphere, under the open environment, directly that plasma jet is surperficial to metallic oxide nano powder; Metallic oxide nano powder is moved in plasma atmosphere; The power of handling metallic oxide nano powder is 10W-5000W, and the time is 0.01s-6000s, produces the metallic oxide nano powder surface-treated.
Described apparatus for processing plasma (APPJ) is commercially available commodity.
Described MOX is titanium oxide, red stone, aluminum oxide, zinc oxide, iridium oxide, their mixtinite and they and carbon nanotube, cover the mixtinite of holder soil or silicon-dioxide.
Described plasma body is selected from one or more in helium, argon gas or the functional gas, and wherein helium, argon gas mol ratio are 50%-99.99%, and functional gas is 0.001～30%, and the plasma body of flowing through simultaneously forms the district and forms plasma atmosphere.
The purity of described helium or argon gas is 99.99%.
Described functional gas is SO
2, ammonia, oxygen, hydrogen, nitrogen, tetrafluoro-methane, carbonic acid gas, methane CH4, ethane C2H6, propane C3H8, butane C4H10, pentane C5H12, hexane C6H14; Heptane C7H16, octane C8H18, nonane C9H20, decane C10H22, undecane C11H24, dodecyl C12H26; Tridecane C13H28, ethene (C2H4), propylene (C3H6), butylene (C4H8), amylene (C5H10), hexene (C6H12); Propadiene (C3H4), divinyl (C4H6), isoprene (C5H8), hexatriene (C6H8), acetylene (C2H2); Propine (C3H4), butine (C4H6), pentyne (C5H8), hexin (C6H10), heptyne (C7H12); Octyne (C8H14), n-heptylacetylene (C9H16), decine (C10H18), undecyne (C11H20), tetrafluoroethylene and silane, various siloxane gas, vinylformic acid, methylacrylic acid etc. or their composition gas.
Under jet plasma atmosphere prerequisite, Nanosurface is carried out surface-treated by the demand of demands of different.
Improve in the system of metallic oxide nano powder surface property in the treatment process of normal atmosphere, normal-temperature plasma modification, mainly comprise effect by plasma generation high energy active particle, nano-metal-oxide surface are etched or activation, grafting etc. repel each other the nano-metal-oxide surface generation same sex.Under jet plasma atmosphere prerequisite, form radical and cause the surperficial nano-metal-oxide surface-treated that forms the free radical grafting reaction under certain condition with other materials and component and obtain of nano-metal-oxide that further radical causes thus, and because the radical polymerization that the nano-metal-oxide surface free radical that plasma body causes causes is plasma body initiation ATRP (ATRP).The plasma nano metal oxide surface is modified as dry method modification, mainly adopts above-described gas and their mixed gas, and the plasma body that utilizes normal atmosphere, normal-temperature plasma equipment to produce carries out surface treatment to nano-metal-oxide.A common step of plasma surface modifying method accomplishes, and the gaseous fraction, the proportioning that form plasma body through adjustment can realize the raising to the consistency of different rerum natura materials.
Nano-metal-oxide with this method modification can be applicable in polymer modification, polymer composite modification and the fiber.
Beneficial effect
(1) the inventive method process controllability is strong, and change technology is simple, technical process short, need not aftertreatment, and level of automation is high, low, the continuous operations of energy consumption, easy realization of industrial scale operation and little to the pollution of environment;
(2) gained nano-metal-oxide particle surface of the present invention produces the effect that the same sex is repelled each other, and reaches the possibility that reduces nanoparticle agglomerates;
(3) gained metallic oxide nano powder internal structure of the present invention is not destroyed, and its nano crystal particles uniformity coefficient and particle size distribution range narrow down, and the dispersiveness in associated materials improves, and improves with corresponding high molecular bonding properties.
Description of drawings
The transmission electron microscope photo of Fig. 1 gained sample;
The transmission electron microscope photo of Fig. 2 gained sample;
Fig. 3 metallic oxide nano powder surface plasma reforming apparatus synoptic diagram; 1 plasma body carrier gas (helium or argon gas), 2 functional gases, 3 plasma body generation system; 4 plasma generators and shower nozzle; 5 nano-powder e Foerderanlages, 6 surface treating nano powders not, 7 surface-treated nano-powders;
Fig. 4 handles sample: No. 1 is the former powder helium plasma treatment of nano titania sample, and No. 2 is the former powder oxygen plasma treatment of nano titania sample, and No. 3 is the former powder of nano titania
Fig. 5 handles sample: No. 1 is the former powder helium plasma treatment of silica nanometer sample, and No. 2 is the former powder oxygen plasma treatment of silica nanometer sample, and No. 3 is the former powder of silica nanometer.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Get on the dedicated transmissions device that a certain amount of commercialization nano TiO 2 powder is placed on apparatus for processing plasma.Synoptic diagram such as Fig. 3 passage of plasma nozzle (or install additional); This container or carrier place normal pressure 2 centimetres of the spout below specific ranges of normal-temperature plasma sparging unit with interior (design of nozzle segment passage is by particular requirement); Nano-powder lay thickness is by 5 millimeters thickness laies; Under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that nano-titanium dioxide powder obtains handling under helium plasma atmosphere, 40 watts of power and 5 second time.Transmission electron microscope photo such as Fig. 1 of this sample.The water-sol (0.5/1000 nano powder/water) that is formed by this sample leaves standstill 24 hours contrast experiment's photos such as Fig. 4-No. 1 sample.
Embodiment 2
Get on the dedicated transmissions device that a certain amount of commercialization nano TiO 2 powder is placed on apparatus for processing plasma.Synoptic diagram such as Fig. 3 passage of plasma nozzle (or install additional); This container or carrier place normal pressure 2 centimetres of the spout below specific ranges of normal-temperature plasma sparging unit with interior (design of nozzle segment passage is by particular requirement); Nano-powder lay thickness is by 5 millimeters thickness laies; Under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that nano-titanium dioxide powder obtains handling under oxygen gas plasma atmosphere, 40 watts of power and 5 second time.Transmission electron microscope photo such as Fig. 1 of this sample.The water-sol (0.5/1000 nano powder/water) that is formed by this sample leaves standstill 24 hours contrast experiment's photos such as Fig. 4-No. 2 sample.
Get on the dedicated transmissions device that a certain amount of commercialization silicon dioxide nano powder is placed on apparatus for processing plasma.Synoptic diagram such as Fig. 3 passage of plasma nozzle (or install additional); This container or carrier place 2 centimetres of the spout below specific ranges of normal pressure, normal-temperature plasma sparging unit with interior (design of nozzle segment passage is by particular requirement); Nano-powder lay thickness is by 5 millimeters thickness laies; Under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that silicon dioxide nano powder obtains handling under helium plasma atmosphere, 40 watts of power and 5 second time.Transmission electron microscope photo such as Fig. 2 of this sample.The water-sol (0.5/1000 nano powder/water) that is formed by this sample leaves standstill 24 hours contrast experiment's photos such as Fig. 5-No. 1 sample.
Embodiment 4
Get on the dedicated transmissions device that a certain amount of commercialization silicon dioxide nano powder is placed on apparatus for processing plasma.Synoptic diagram such as Fig. 3 passage of plasma nozzle (or install additional); This container or carrier place 2 centimetres of the spout below specific ranges of normal pressure, normal-temperature plasma sparging unit with interior (design of nozzle segment passage is by particular requirement); Nano-powder lay thickness is by 7 millimeters thickness laies; Under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that silicon dioxide nano powder obtains handling under oxygen gas plasma atmosphere, 40 watts of power and 5 second time.Transmission electron microscope photo such as Fig. 2 of this sample.The water-sol (0.5/1000 nano powder/water) that is formed by this sample leaves standstill 24 hours contrast experiment's photos such as Fig. 5-No. 2 sample.
Claims (2)
1. plasma modification processing method of metallic oxide nano powder at atmosphere pressure and normal temperature, form by following steps:
Metallic oxide nano powder is placed on the dedicated transmissions device of apparatus for processing plasma; At normal atmosphere, under the open environment, directly that plasma jet is surperficial to metallic oxide nano powder; Metallic oxide nano powder is moved in plasma atmosphere; The power of handling metallic oxide nano powder is 10W-5000W, and the time is 0.01s-6000s, produces the metallic oxide nano powder surface-treated; Wherein, MOX is titanium oxide or silicon-dioxide.
2. plasma modification processing method of metallic oxide nano powder at atmosphere pressure and normal temperature according to claim 1 is characterized in that: under jet plasma atmosphere prerequisite, Nanosurface is carried out surface-treated by the demand of demands of different.
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| CN102651317B (en) * | 2011-12-28 | 2015-06-03 | 京东方科技集团股份有限公司 | Surface treatment method of metal oxide and preparation method of thin film transistor |
| US8940647B2 (en) | 2011-12-28 | 2015-01-27 | Boe Technology Group Co., Ltd. | Method for surface treatment on a metal oxide and method for preparing a thin film transistor |
| CA2977295A1 (en) * | 2015-02-27 | 2016-09-01 | Imerys Graphite & Carbon Switzerland Ltd. | Nanoparticle surface-modified carbonaceous material and methods for producing such material |
| CN106317714B (en) * | 2016-08-23 | 2018-08-31 | 同济大学 | The low-temperature plasma modified processing method of nano-aluminium oxide |
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| EP3425085A1 (en) * | 2017-07-07 | 2019-01-09 | The Swatch Group Research and Development Ltd | Method for surface treatment of metal powder particles and metal powder particles obtained using said method |
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| CN112723337B (en) * | 2020-12-30 | 2022-11-29 | 电子科技大学 | Plasma modified carbon fluoride anode material, preparation method and application |
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