CN1488462A - Nano particle surface physicochemical structure cutting and coating method - Google Patents
Nano particle surface physicochemical structure cutting and coating method Download PDFInfo
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- CN1488462A CN1488462A CNA031504582A CN03150458A CN1488462A CN 1488462 A CN1488462 A CN 1488462A CN A031504582 A CNA031504582 A CN A031504582A CN 03150458 A CN03150458 A CN 03150458A CN 1488462 A CN1488462 A CN 1488462A
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Abstract
The invention is a cutting and coating method for surface physical and chemical structure of nano particles. Through confecting the radio frequency plasma to control pulse ratio, time, power, and furthermore control the kind, content, sediment layer thickness the coarse rate of packing film of functional group, it can cut and coat the special monomer molecular functional group film on the surface of the nano particles, and adjusts the thickness, surface coarse rate and so on, gets the coating film with special physical and chemical structure, changes the physical and chemical structure of nano particles.
Description
Technical field
The present invention relates to utilize the plasma discharge method to coat the method for thin film in nanoparticle surface.Concrete is about a kind of nanoparticle surface physical chemistry cutting pattern method for coating, be by the pulsed radio frequency plasma body being carried out the modulation of discharge parameter under the vacuum plasma concrete conditions in the establishment of a specific crime, according to the difference that coats object, the chemical physics structure of optionally cutting design packet overlay film, thus reach the purpose that cutting designs the Surface Physical Chemistry structure of nanoparticle.
Background technology
At present, the research of various structure classes and function class nanometer particle material is just causing increasing concern with application.When forming nano composite material, have only to reach below 100 nanometers or when lower, the exceptional function that its small size is brought could embody when the size of arbitrary phase wherein.But this moment, surface atom accounts for the ratio of total atom number and increases sharply, and surface energy increases rapidly, and the agglomeration of particle is serious further, thereby it is very difficult to make nanoparticle reach nano level dispersion in matrix.
Because the nano material dispersing property is subjected to the nanoparticle surface performance impact to a great extent, thereby surface modification is one of method of the improvement nanoparticle dispersiveness used always, and it is most important that nano material is embodied its exceptional function.Various liquid methods are as coupling agent, tensio-active agent, organic oligomer etc., mainly by changing the dispersiveness that surface chemical structure improves nanoparticle.But exist use temperature low in using, coat process need and carry out deficiencies such as solid-liquid separation operation repeatedly.Gaseous process such as laser splash, plasma body coating etc. can coat by simple single stage method.The plasma body coating is the monomer by discharge all kinds of polymerizations of cracking or non-polymerization, and the vapour phase polymerization deposition is by the physics and the Chemical bond of reactive behavior kind and nanoparticle surface, at a nanoparticle surface coating skim as thin as a wafer.Just beginning the research of this respect at present both at home and abroad, as application radio frequency continuous wave plasma polymerization methods such as D Shi, at the Al of size 10nm to 150nm
2O
3With ZnO nanoparticle surface acquisition uniform thin film (D Shi etal., Appl.Physics Letter, 2001,78 (9): 1243-1245) as thin as a wafer; Dorothee V.Szabo etc. use microwave plasma at Fe
3O
4Nanoparticle surface coats polymethylmethacrylate (PMMA) film (Dorothee V.Szabo et al., Advanced Materials, 1999,11 (15): 1313-1316).The plasma body of above-mentioned nanoparticle coats and mostly uses radio frequency continuous wave plasma method, and it destroys greatly the monomer original structure, cannot say for sure to stay original monomer to contain oxygen, nitrogenous etc. functional group, as COOH, OH, NH
2Deng, polymerization coats the rete that obtains very high degree of crosslinking, so perviousness is very low, and insoluble not molten, and handiness is little aspect regulation and control deposited film chemical structure.The pulsed radio frequency plasma body that latest developments are got up is aspect material surface modifying, can be by modulation that radio-frequency plasma is pulsed, discharge is intermittently carried out between "on" and "off", produce free radical when " opening ", at the intermittence of " pass ", can carry out conventional radical polymerization, thereby optionally " cutting " keeps the certain monomers molecule functional group.Use it for the film deposition of perfluoroalkyl benzene on flat glass or silicon chip as people such as Licheng M.Han, heat-resisting phenyl ring and to the contributive CF of insulating property functional group in the selective retention monomer, obtain functional membrane coating (the Licheng M.Han of low-k and high thermal stability, et al., 1997, Langmuir, 13:5941).Zhang Jing etc. in the research of vinylacetic acid pulsed radio frequency plasma polymerization, when pulsation when reducing, the content of carboxyl, hydroxyl (Zhang Jing etc., Acta Physica Sinica, 2003,52 (7): 1707-1712) in rising trend in the polymeric membrane structure on the slide
Yet, utilize the plasma polymerization method to carry out nanoparticle and coat and how also to exist single particle but not the difficult problem that the particle cluster aggressiveness coats.Owing to the very high reason of the surface energy of aforementioned nanoparticle, nanoparticle very easily produces reunion, be at one nanoparticle but not the coacervate surface of particle coat and just seem difficult unusually.And when the plasma polymerization method was carried out the nanoparticle coating, optionally " cutting " reservation certain monomers molecule functional group also was that problem to be solved is arranged.
Therefore need seek at these two difficult problems and improve one's methods, improving the single particle cladding uniformity, and at the different application purpose more neatly cutting change the surface physics and the chemical structure of coating film.
Summary of the invention
Easily produce the problem of reuniting when overcoming nanoparticle and coat, to improve the single particle cladding uniformity, and according to different application purpose two purposes of Surface Physical Chemistry structure of cutting coating film more neatly, the present invention proposes a kind of nanoparticle surface physical chemistry cutting pattern method for coating.Its action principle is: at first make nanoparticle charged, particle produces the plasma sheath current potential of the same sex, utilize the effect of repelling each other of particle same sex sheath current potential, and apply tangential force by fluidisation or shearing action, soft-agglomerated being easy to destroyed, nanoparticle is dynamically brought in constant renewal in and is exposed in the plasma polymerization atmosphere, and the gaseous monomer spike is easy to infiltrate between particle and produces uniform deposition and coat.Regulate and control the plasma polymerization discharging condition simultaneously, compare etc. as time, power, the pulsation of discharge, the physical chemistry structure of regulation and control coating film obtains the nanoparticle surface of physical chemistry structurally variable, to be applicable to different application purposes.
Nanoparticle surface physical chemistry cutting pattern method for coating of the present invention may further comprise the steps:
(1) by the clad nano particle in advance through the HV generator effect, make it charged.Can adopt commercially available HV generator, 1-20 minute discharge time, voltage 10-100KV inserts after the taking-up on the plasma reactor perforated distributor of (as shown in Figure 1) immediately;
(2) reactor is evacuated to base vacuum degree≤10Pa, monomer is mixed in proportion into mixed gas with carrier gas, by perforated distributor with certain velocity flow to importing plasma reactor, make particle be in fluidized state, and by electrostatic repulsion effect between particle, soft-agglomerated being easy to destroyed by fluidisation or shearing action, and gaseous monomer atom or group are easy to infiltrate uniform deposition coating between particle.Monomer is 1-10 with the mixed volume ratio of carrier: 1-95, and control mixed gas flow velocity 5-150sccm (per minute standard cube liter), reactor vacuum tightness reaches 15-300Pa.
(3) open pulsed radio frequency plasma generator and agitator.In reactor, form discharge by the condenser coupling coil, make the monomer discharge polymerisation of importing, and be coated on nanoparticle surface.Pulsed radio frequency plasma generator frequency 13.56MHz, peak power 600W.The reactor modulation of can pulsing, discharge is intermittently carried out between "on" and "off", pulsation is 1-100% than (time of " opening " is divided by the temporal summation of " opening " and " pass "), the time range of " opening " is 1 μ s-50ms, electrode for plasma reactor is a capacitance coupling type, discharge power 2-500W, the polymerization coating time needs to decide on coating thickness, can be 0.1-15 hour.After reaction finished, the nanoparticle after the coating can filter the collector collection or collect at reactor lower part.Agitator in the plasma reactor is that 0-45 ° the right knife-edge blade of 1-40 is formed by gradient, the wide 0.5-2.0cm of blade, pass through driven by motor, stirring velocity 50-2000 rev/min, agitator mounting height 10-50cm to improve soft-agglomerated destructiveness, upgrades particle surface, it dynamically is scattered in the plasma atmosphere, reaches the effect that single particle evenly coats.
Described monomer can be under the normal temperature and pressure or after the decompression can form gasiform compound (rare gas element and oxygen, nitrogen, except non-polymeric deposition class such as the hydrogen gas), can be selected from L-Ala, glycine, Methionin, acrylamide, vinylacetic acid, vinylformic acid, methyl methacrylate, tetrafluoro-methane, R 1216, hexamethyldisiloxane, ethene, acetylene, methane, ethanol, acetone, four hydroxyethyl titaniums, tetramethoxy-silicane, zinc ethyl, tin tetramethide or copper sulfate etc., carrier gas can be the non-polymerization gas of band certain pressure, as argon, nitrogen, oxygen, hydrogen, pressurized air etc.
Perforated distributor as shown in Figure 2 in the plasma reactor.The lower diameter d in the hole on the perforated distributor
1: the upper diameter d in hole
2=1: 1-5, the height of the lower diameter in hole: the total height=1-4 in hole: 5, hole area accounts for 1/10～8/10 of plate area, d
2Be 1～50mm.Be coated with aperture 50-600 purpose stainless steel filtering net or filter paper on the perforated distributor.Arrangement can make gas distribution even like this, thereby the gas impulse force that suited of nanoparticle and be in good fluidized state.
The present invention has following characteristics and effect:
1, the inventive method is charged owing to nanoparticle when coating, can utilize the effect of repelling each other between the plasma sheath current potential of the same sex that particle produces, and apply tangential force by air-flow fluidisation and shearing action, soft-agglomerated being easy to destroyed, nanoparticle is dynamically brought in constant renewal in and is exposed in the plasma polymerization atmosphere, and the gaseous monomer spike is easy to infiltrate between particle and produces uniform deposition and coat.
2, radio-frequency plasma is pulsed modulation is used for monomeric polymerization, can improve the retention rate of functional groups such as containing oxygen, nitrogenous, sulfur-bearing in the aggregate packet overlay film largely, the consistency of regulation and control coating particles and matrix polymer.Also but the coating particles surface has the functional group that can further react.Overcome common insoluble molten, the highly cross-linked defective of radio frequency continuous wave plasma body coating film, the chemical structure of regulation and control coating film, thus but form the nanoparticle surface that the chemical structure cutting is controlled.
3, regulating and controlling pulsed radio frequency condition of plasma as power, pulsation ratio, flow velocity, monomer ratio, time etc., can be regulated controlling packet coating thickness, surface topology, changes the particle surface physical structure.Thereby change coating particles flowability, proportion, with body material combine tightness degree, adsorptivity etc.Like this, space physics steric hindrance by coating, can stop nanoparticle to be agglomerated into bigger particle, physics roughness by chemical compatibility and coating etc., promote dispersiveness with matrix polymer, reduce the agglomeration of nanoparticle, to embody special effects that small size brings to nanoparticle etc.
4, coating reaction is carried out in the normal temperature dry state, applicable to the coating of solvability and non-solubility nanoparticle, and the coating of thermally sensitive particle.And overcome operations such as solvent repeated isolation, environmental pollution is little, and cladding process is simple relatively.
5, coating monomer range of choice is wide, can carry out coating organic and inorganic, metallic film, is used for the development of all kinds of nano-complex particles and nanometer/polymer composites, nanometer/metal composite etc.Also can be used for the development of all kinds of Nano composite granules etc., form nano-complex particles such as inorganic/organic and inorganic/metal, metal/organic and inorganic/metal/organic.
Description of drawings
Fig. 1 is a plasma body coating reaction apparatus synoptic diagram.
Fig. 2 is the perforated distributor synoptic diagram in the plasma reactor
D wherein
1The lower diameter h in hole
1The height of hole lower diameter
d
2The upper diameter h in hole
2The total height in hole.
Fig. 3 is TiO before and after plasma body vinylformic acid coats
2The HRTEM figure of nanoparticle
After wherein a does not coat the coating of b plasma body.
Fig. 4 is plasma body TiO before and after vinylformic acid coats
2The EDS spectrogram of nanoparticle
After wherein a does not coat the coating of b plasma body.
Fig. 5 is the Cr that the plasma body hexamethyldisiloxane coats
2O
3The HRTEM figure of nanoparticle.
Fig. 6 is the AFM figure of plasma body hexamethyldisiloxane film
Wherein a pulsation is than 3%, and the time of pulsation " opening " is 15ms, discharge power 3W
The b continuous wave, discharge power 30W.
Fig. 7 is the AFM section roughness comparison diagram of plasma body hexamethyldisiloxane film
Wherein a pulsation is than 3%, and the time of pulsation " opening " is 15ms, discharge power 3W
The b continuous wave, discharge power 30W.
Fig. 8 is the TiO under the not equal daughter coating condition
2The infrared spectrogram of nanoparticle
Wherein a does not coat
B vinylformic acid coats, and pulsation is than 2%
C vinylformic acid coats, and pulsation is than 40%.
Fig. 9 is that different coating conditions are to TiO
2The influence of nanoparticle ultraviolet light absorption.
Embodiment
Adopt plasma body coating reaction apparatus shown in Figure 1 to coat test.At first will coat object TiO nanoparticle, about median size 30nm, through 50KV HV generator effect 5 minutes, make it charged in advance, insert immediately after the taking-up on the perforated distributor 3 (detailed structure is referring to Fig. 2) of plasma reactor 6 bottoms.Reactor 6 is evacuated to base vacuum degree 5Pa by vacuum system 7.Respectively by under meter 1 metering, is 1: 50 with monomer vinylformic acid and carrier gas argon gas by volume, in gas mixer 2 behind the uniform mixing, by perforated distributor 3, flow velocity with 10sccm imports plasma reactor 6, makes particle be in fluidized state, and vacuum tightness drops to 150Pa.Open pulsed radio frequency plasma generator 5 and agitator 4.Producer 5 forms discharge by the condenser coupling coil in reactor 6, make the monomer discharge polymerisation of importing, and be coated on nanoparticle surface.Pulsed radio frequency plasma generator 5 frequency 13.56MHz, peak power 600W.Reactor 6 modulation of pulsing, the pulsation of discharge is than 100%, and the time of " opening " is 1ms, and be 4 hours discharge time, and discharge power is 20W.Agitator 4 is to be that 30 ° the 30 pairs of knife-edge vane group become the wide 1cm of blade, 1000 rev/mins of stirring velocitys by gradient, agitator mounting height 20cm, to improve soft-agglomerated destructiveness, upgrade particle surface it dynamically is scattered in the plasma atmosphere, reach the effect that single particle evenly coats.After reaction finishes, coat the back particle and collect or collect in reactor 6 bottoms at filtration collector 8.
Coat the back sample and detect (Fig. 3), the not TiO of Bao Fuing through high-resolution-ration transmission electric-lens (HRTEM)
2Visible its crystalline laminate structure of nanoparticle (among Fig. 3 a), but outside surface is not seen the coating layer of translucent amorphous organic coating layer or other layered crystal structure, and the TiO that coats through the vinylformic acid plasma polymerization
2Except that visible its crystalline laminate structure, the organic coating layer of the translucent amorphous propene acid plasma polymer of the visible one deck in outer ring evenly is coated on TiO
2Layered crystal outer ring, thickness are about (b among Fig. 3) about 5nm.X-ray energy dispersive spectrum (EDS) shows, the titanium peak intensity is higher before the coating (a), coats back titanium peak intensity and drops to zero (b among Fig. 4) among Fig. 4, oxygen peak, the rising of carbon peak intensity, illustrate that the plasma body polyacrylic acid film that coats is quite effective and even, so titanium elements no longer is detected.
Adopt plasma body coating reaction apparatus shown in Figure 1, operation steps is with reference to embodiment 1.
With Cr
2O
3Nanoparticle is for coating object, median size 150nm, made it charged in 1 minute through the effect of 20KV HV generator, insert immediately in the plasma reactor 6, be evacuated to base vacuum degree 4Pa, feed the mixed gas of hexamethyldisiloxane and nitrogen, the volume ratio of two kinds of gases is 10: 50, flow velocity 60sccm, vacuum tightness drops to 200Pa.Open plasma generator 5 and agitator 4, the power of control discharge is 40W, and be 8 hours discharge time, and the pulsation of discharge is than 50%, and the time of pulsation " opening " is 2ms, 500 rev/mins of stirring velocitys.
Coat the back sample and detect (see figure 5) through high-resolution-ration transmission electric-lens (HRTEM), the result shows that particle surface all evenly coats the hexamethyldisiloxane film that a layer thickness is about the plasma polymerization about 25nm.
Adopt plasma body coating reaction apparatus shown in Figure 1.
In order to observe the relation of pulsed radio frequency plasma body coating condition and coating film surfaceness, selecting smooth sheet glass is the coating object, after cleaning up, insert in the plasma reactor 6, be evacuated to base vacuum degree 4Pa, feed the mixed gas of hexamethyldisiloxane and argon gas, the volume ratio of two kinds of gases is 10: 90, flow velocity 10sccm makes vacuum tightness drop to 30Pa.Open plasma generator 5, discharge polymerisation.Be 1 hour discharge time, and polymerization finishes, and takes out sample and do atomic force microscope (AFM) analysis, and the atomic force microscope figure of gained sample sees Fig. 6.The a discharge power is that the time of 3w, pulsation ratio 3%, pulsation " opening " is 15ms among Fig. 6, and the b discharge power is 30w among Fig. 6, continuous wave.Brightness is big more, represents level high more.A and b are the sectional view of a and b sample among Fig. 6 among Fig. 7.Curve is just represented the fluctuating of film section.From the detected result of this AFM as can be known, low pulsation than under, the lower powered condition (among Fig. 6 among a, Fig. 7 a), coating is that nano level membrana granulosa is formed, coating fluctuating roughness is the number nanometer; Under the continuous wave superpower situation (among Fig. 6 among b, Fig. 7 b), coating is that micron-sized macrobead film is formed, and coating fluctuating roughness is several microns.Change the coating condition, can effectively change the roughness of coating.
Embodiment 4 coats condition influence TiO
2The test of nanoparticle surface chemical structure
Adopt plasma body coating reaction apparatus shown in Figure 1, operation steps is with reference to embodiment 1.
Adopt plasma body coating reaction apparatus shown in Figure 1, operation steps is with reference to embodiment 1.
Coat object TiO
2Nanoparticle, about median size 30nm, TiO
2Nanoparticle is in advance through 35KV HV generator effect 3 minutes, make it charged, insert immediately in the plasma reactor 6, be evacuated to base vacuum degree 3Pa, feed the mixed gas of vinylformic acid and argon gas, the volume ratio of two kinds of gases is 5: 50, and flow velocity 35sccm makes vacuum tightness drop to 85Pa.Open plasma generator 5 and agitator 4, the power of control discharge is 20w, and be 2 hours discharge time, 1000 rev/mins of stirring velocitys, and the pulsation ratio of discharge is 2%, 40%.
Coat the TiO after handling
2Nanoparticle sample and the blend according to a certain percentage of the KBr powder compressing tablet of milling, the NEXUS-670 type Fourier spectrometer of producing through Nicolet company are measured and are coated TiO
2The infrared spectra of nanoparticle coats TiO with test
2The chemical structure of nanoparticle as shown in Figure 8.(a) is uncoated TiO among Fig. 8
2The infrared spectrogram of nanoparticle is among Fig. 8 (b) and (c) be respectively the TiO that pulsation coat to be handled than 2%, 40% o'clock
2The infrared spectrogram of nanoparticle.Because coating layer is thin, also not only reflection is surperficial for the structure of infrared transmission spectrum test, so among Fig. 8 (a) (b) (c) as seen, the 400-700cm-1 scope all has very strong absorption peak, this is the charateristic avsorption band of Ti-O-Ti key, near 3300cm-1, all have broad since the absorption of water etc. cause-stretching vibration peak of OH.Near the 1631cm-1 absorption peak also is because surface hydroxylation produces-stretching vibration peak of OH.Through pulsation coat than 2% vinylformic acid plasma body handle after, a new acromion has appearred near 1433cm-1, pulsation was than 40% o'clock, this acromion develops into a new absorption peak.Because the absorption and the CH of this position
3-O-or CH
2The CH formation vibration is relevant in the groups such as-O-, and the height of this peak relative intensity illustrates different pulsation than under the condition, similar CH in the coating film
3-O-or CH
2The content of the ester group of-O differs.Different coating conditions can change the content of group in the coating chemical structure even kind.
Adopt plasma body coating reaction apparatus shown in Figure 1, operation steps is with reference to embodiment 1.
Coat object TiO
2Nanoparticle, about median size 30nm, TiO
2Nanoparticle is inserted in the plasma reactor 6 immediately through 100KV HV generator effect 1 minute.Be evacuated to base vacuum degree 3Pa, feed the mixed gas of hexamethyldisiloxane and argon gas, the volume ratio of two kinds of gases is 5: 95, and flow velocity 50sccm makes vacuum tightness drop to 150Pa.Open plasma generator 5 and agitator 4, the power of control discharge is 60w, and be 4 hours discharge time, 2000 rev/mins of stirring velocitys, and the pulsation ratio of discharge is 5%, 15%, 40%.
Handle the back sample and be made into 0.015% suspension, pour in the quartz colorimetric utensil of 0.5cm, with its absorption value of 752 spectrophotometric instrumentations at ultraviolet one visible light through ethylene glycol.The gained result as shown in Figure 9.Different pulsation is than down, owing to the physical chemistry structure difference of coating layer, the TiO of coating
2Nanoparticle light absorptive in ethylene glycol solution is just different.Because good dispersity, aggregated particle size is little, and is good to the absorptivity of UV-light.So the quality of light absorptive has also been represented dispersed quality.From Fig. 9 as seen, although pulse than the TiO that coats under the condition in difference
2Nanoparticle is the light absorptive difference in ethylene glycol solution, but all than not coating TiO
2The light absorptive of the ethylene glycol solution of nanoparticle is good, also the TiO of explanation coating
2Nanoparticle is dispersed than not coating TiO in ethylene glycol solution
2The good dispersity of nanoparticle.
Claims (6)
1, a kind of nanoparticle surface physical chemistry cutting pattern method for coating is characterized in that this method may further comprise the steps:
(1) made it charged by the clad nano particle, insert after the taking-up in the plasma reactor;
(2) reactor is evacuated to base vacuum degree≤10Pa, imports the mixed gas of monomer and carrier, and flow velocity is 5-150sccm, and monomer is 1-10 with the mixed volume ratio of carrier gas: 1-95, reactor vacuum tightness reaches 15-300Pa.
(3) open pulsed radio frequency plasma generator and agitator, in reactor, form discharge, the monomer discharge polymerisation that imports also is coated on nanoparticle surface, the reactor modulation of pulsing, make pulsation than being 1-100%, the time range of opening is 1 μ s-50ms, discharge power 2-500W, 0.1-15 hour discharge time, the agitator stirring velocity is 50-2000 rev/min.
2, method for coating as claimed in claim 1, it is characterized in that described monomer is selected from L-Ala, glycine, Methionin, acrylamide, vinylacetic acid, vinylformic acid, methyl methacrylate, tetrafluoro-methane, R 1216, hexamethyldisiloxane, ethene, acetylene, methane, ethanol, acetone, four hydroxyethyl titaniums, tetramethoxy-silicane, zinc ethyl, tin tetramethide or copper sulfate.
3, method for coating as claimed in claim 1 is characterized in that described carrier gas is argon, nitrogen, oxygen, hydrogen, pressurized air.
4, method for coating as claimed in claim 1 is characterized in that being placed on the perforated distributor in the plasma reactor by the clad nano particle, and imports the mixed gas of monomer and carrier gas by perforated distributor.
5, method for coating as claimed in claim 4, the lower diameter that it is characterized in that hole on the described perforated distributor: the upper diameter in hole=1: 1-5, the height of the lower diameter in hole: the total height=1-4 in hole: 5, hole area accounts for 1/10～8/10 of plate area, and the upper diameter in hole is 1～50mm.
6, method for coating as claimed in claim 1 is characterized in that described agitator is that 0-45 ° the right knife-edge blade of 1-40 is formed the wide 0.5-2.0cm of blade, agitator mounting height 10-50cm by gradient.
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| CN112652751B (en) * | 2020-12-23 | 2022-01-11 | 荆门市格林美新材料有限公司 | Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method |
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