CN100518430C - Plasma generating electrode assembly - Google Patents
Plasma generating electrode assembly Download PDFInfo
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- CN100518430C CN100518430C CNB2004800031038A CN200480003103A CN100518430C CN 100518430 C CN100518430 C CN 100518430C CN B2004800031038 A CNB2004800031038 A CN B2004800031038A CN 200480003103 A CN200480003103 A CN 200480003103A CN 100518430 C CN100518430 C CN 100518430C
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Abstract
A plasma glow discharge and/or dielectric barrier discharge generating assembly (1) comprising at least one pair of substantially equidistant spaced apart electrodes (2), the spacing between the electrodes being adapted to form a plasma zone (8) upon the introduction of a process gas and enabling passage, where required, of gaseous, liquid and/or solid precursor(s) characterized in that at least one of the electrodes (2) comprises a housing (20) having an inner (5) and outer (6) wall, wherein the inner wall (5) is formed from a non-porous dielectric material, and which housing (20) substantially retains an at least substantially non-metallic electrically conductive material.
Description
The present invention relates to produce the assembly of plasma, it is made of the electrode that at least one pair of separates, and wherein at least one electrode is nonmetal basically.
If provide energy to material continuously, its temperature rises and changes into liquid from solid usually, changes into gaseous state then.Continue to provide energy can cause the further variation of system status, neutral atom in the gas or molecule produce electronegative electronics owing to energy impact divides, the ion of positively charged or negative electricity and other material.This mixture that presents the charged particle of gathering behavior is called as " plasma ".Because their electric charge, plasma is easy to be subjected to the influence of external electromagnetic field, and this makes plasma be easy to control.In addition, their high-energy makes them can not or be difficult to realize handling by other physical form, such as passing through liquid or gas treatment.
Term " plasma " comprises very large-scale system, and its density and temperature have the variation of a plurality of orders of magnitude.Some plasmas are very warm and its all microscopic species (ion, electronics etc.) is approaching is in heat balance, and the energy that enters system extensively distributes by the collision of atom/molecule level.Yet the particulate in the other plasma is in low pressure (as 100 handkerchiefs), and it collides less relatively generation, and such plasma has the very different component of temperature, is called as " thermal nonequilibrium " plasma.In the plasma of these thermal nonequilibriums, free electron is very warm, and its temperature is thousands of Kelvins, and atom and ionic species keep cooling simultaneously.Because the free electron quality can be ignored, therefore low the and plasma of the thermal capacitance of whole system need not apply the heat load that causes damaging and just can handle temperature-sensitive material, such as plastics or polymer near room temperature-operating on sample.Yet, produced hot electron by energetic encounter (this be have a very high chemical potential energy chemistry and the free radical of physical change and the abundant source of excited species can take place).Cold operation makes nonthermal plasma extremely important technically with combining of high degree of reaction just, and for manufacturing and material processed is a kind of very effective instrument, it can realize handling, if using plasma not, this processing will need very high temperature or harmful and have an invasive chemicals.
For the commercial Application of plasma technique, conventional method is that energy of electromagnetic field is coupled in a large amount of processing gas, and these gases may be gas and steam mixture, and wherein pending workpieces/samples is submerged or passes through.This is to realize by the space between the adjacent electrode that the giant electric potential difference is arranged by handling gas (such as helium).By potential difference effect excited gas atom and the molecule between the electrode, a plasma (after this is called the plasma zone) and forms in the space.The gas ionization that in plasma, becomes, the excited atom and the ion that produce chemical based, ultraviolet ray, react with sample surfaces.Along with the aura of plasma generation is to be caused by the light that excited species is sent when getting back to low excited state more.Handle the component of gas, the frequency of driving power, coupled modes, pressure and other the Control Parameter of energy by correct selection, plasma process can customize according to the specific (special) requirements of manufacturer.
Because chemistry that plasma is huge and heat rating, they are fit to many technology of constantly extending and use.The plasma of thermal nonequilibrium is especially effective for surface active, cleaning surfaces, material surface etching and coating.
The surface active of polymeric material is widely used in the industrial plasma technology that auto industry advocates.Therefore, for instance, be used for the general polyolefin of recyclable purpose,, have nonpolar surface and relatively poor coating or adhesiveness as polyethylene and polypropylene.But, can form high wettable surface polarity group after handling by oxygen gas plasma, therefore metal, coating, adhesive or other coatings there are excellent spreadability and adhesiveness.Therefore, for instance, the plasma surface engineering is necessary for industry such as element assembling such as the manufacturing of the vehicles, instrument board, buffer etc., toys.In printing, coating, adhesion, layering and common coatings, many other application are arranged also in the component of polymer, plastics, pottery/inorganic matter, metal and other materials.
Generality and dynamics that the global environment legislation is constantly risen form substantial pressure to industrial quarters, require to reduce or eliminate solvent and other wet chemical substances in manufacture process, especially for component/cleaning surfaces.Especially, the clean operation based on CFC is replaced in a large number by the plasma cleaning technology with oxygen, air and the operation of other non-toxic gas.In conjunction with precleaning based on water, plasma even can clean the component of heavily contaminated, and the surface nature that obtains is better than the surface nature that produces from conventional method.The pollution on any organic surface can enough room temperatures the plasma rapid cleaning and change into the carbon dioxide and the water of gaseous state, this can safety dumping.
Plasma also can be used for the etching of bulk material, that is to say, removes unwanted material.Therefore, for instance, based on the plasma etching polymer of oxygen, this is a technology that is used for productions such as circuit board.These different materials of metal, pottery and inorganic matter are etched by the chemical composition of choosey precursor gases and concern plasma.Reducing to the standard-sized structure of nanometer produces with plasma etching technology now.
A kind of plasma technique that enters the main flow industrial quarters fast is plasma coating/thin film deposition.Typically, realize high level polymerizate by plasma being used for pure gas and steam.Therefore, a kind of film that is connected with three-dimensional intensive, that combine closely can form, and it has thermal stability, very high chemical stability and mechanically stable.Such film even can deposit on complex surfaces, its temperature guarantees that the heat load on substrate is very low.Therefore for meticulous, temperature-sensitive and firm material coating, plasma is desirable.Even in thin layer, plasma has been broken away from micropore.The optical characteristics of coating such as color, usually can customize, and plasma coating even for non-polar material, and such as polyethylene, and adhesiveness such as steel (as the anticorrosive film on the metallic reflection thing), pottery, semiconductor, fabric is fine.
In all these technologies, Plasma Engineering is produced a surface effect or the product that does not at all influence basis material according to the application of expectation.Plasma process therefore offer one of manufacturer general and be that powerful instrument allows to select material, according to its basic fundamental and the independence and freedom surface of handling it the commercial characteristic that meets multiple different needs.Therefore plasma technique has improved function, performance, life-span and the quality of product very bigly, and gives the very important additional benefit of production capacity of manufacturing enterprise.
These characteristics are impelled the technology of industrial quarters employing based on plasma, and by microelectronics circle leader, it has made the low pressure glow discharge plasma be developed as a kind of technology and the instrument that is used for the high fund cost engineering of semiconductor, metal and dielectric technology of superelevation to this trend since nineteen sixties.Since the 1980s, the plasma that has more and more infiltered the same low pressure glow discharge type of other industrial circles provides cost, the technology of appropriateness more, for example is the polymer surfaces activation that strengthens adhesion/bond strength, high-quality degreasing/cleaning and high performance coating deposition.Therefore, plasma technique has had substantial development.Glow discharge both can also can under atmospheric pressure realize in vacuum.In the glow discharge situation under atmospheric pressure, gas, as helium or argon gas, as diluent (processing gas), under atmospheric pressure pass through the Penning ionization effect mechanism (for instance with the power supply that adopts high-frequency (such as greater than 1kHz), referring to Kanazawa et al, J.Phys.D:Appl.Phys.1988
21, 838, Okazaki et al, Proc.Jpn.Symp.Plasma Chem.1989,
2, 95, Kanazawa et al, Nuclear Instruments and Methods in PhysicalResearch 1989, B37/38,842, and Yokoyama et al/, J.Phys.D:Appl.Phys.1990,
23, 374) and produce uniform glow discharge.
Yet the employing of plasma technique is limited by most of industrial plasma system, that is to say, they need be operated under low pressure.The vacuumizing of part means the periphery of a sealing, and airtight reactor assembly only provides the batch processing of discrete workpieces off-line.Production capacity is low or moderate, and need provide additional finance and operating cost for vacuum.
But atmospheric pressure plasma provides open port or perimeter systems to industrial quarters, and it is by network freedom turnover plasma zone, and therefore continuous online big or little regional network, the perhaps discrete net of transport tape delivery handled.The production capacity height, and by having obtained reinforcement from the following high mass flow-rate that obtains of hyperbar operation.Many industrial departments such as textile, encapsulation, paper, medical treatment, automobile, aviation or the like, almost completely rely on continuous, online processing, and therefore under atmospheric pressure the plasma of open port/peripheral structure provides a kind of new industrial treatment ability.
Corona and flame (also being a kind of plasma) treatment system provides a kind of finite form of atmospheric plasma treatment ability for industrial quarters over 30 years.Although they are convenient to large-scale production, these systems fail under industrial rank is ultra-large.This is because corona/flame system has great defective.They are operated in the air around, and it provides a single surface activating process, and to a lot of materials, effect can be ignored, and major part is had only very weak effect.This handle often be non-homogeneous and corona technology be incompatible for thick net or three dimensional network, and flame technology is incompatible for heat sensitive substrates.This is clear and definite, and atmospheric pressure plasma techniques must more deeply develop into atmospheric pressure plasma and compose the system that develops the advanced person, satisfies industrial requirement.
Under atmospheric pressure plasma-deposited obtained great progress.There has been a large amount of work the stable aspect of Atomospheric pressure glow discharge, Satiko Okazaki, MasuhiroKogoma, Makoto Uehara and Yoshihisa Kimura " under atmospheric pressure using source steady glow electric discharge phenomena in air, argon gas, oxygen and nitrogen of a 50Hz " on J.Phys.D:Appl.Phys.26 (1993) 889-892 set forth.In addition, U.S. Patent No. 5414324 people such as () Roth also set forth under the atmospheric pressure with one 1 to 100kHz, radio frequency (R.F.) energy that 1 to 5kV root mean square current potential comes energy supply is in a pair of generation that separates to 5 centimetres metal plate electrode stable state glow discharge plasma.U.S. Patent No. 5414324 has been discussed using of electric isolating metal plate electrode and observed problem and the necessity that stops the electrical breakdown of eletrode tip during with plate electrode.It has further set forth the use of a copper flat type electrode and a water-cooling system, and water-cooling system is supplied with by the flow of liquid pipeline that links to each other with electrode, so water can directly not contact with any electrode surface.
In U.S. Patent No. 5185132, set forth a kind of atmospheric pressure plasma reaction method, wherein used the metal plate electrode of vertical stratification.But the electrode in vertical stratification seldom is used to provide plasma, and plasma is from deriving between the flat board under the electrode of positioned vertical on the horizontal surface.
An atmospheric plasma assembly is provided in EP0431951, and the material of using the mixing by plasma treatment inactive gas/active gas to produce is handled substrate.Parallel placement of the metal electrode of partial coating and vertical alignment at least in dielectric are so they are vertical with the substrate that passes through under the slit between the electrode.This assembly requires an integrated surface treatment unit, and it can limit the width of any pending substrate effectively by the width of surface treatment unit, itself makes systems bulky.
Adopt coating or adhere to the metal plate of dielectric substance and/or during mesh electrode, main problem is the uniformity between electrode surface and the dielectric substance.Even between very little metallic plate and dielectric, guarantee that uniformity almost is impossible completely, this is because especially have blemish on the metal surface at one or another.Therefore the electrode that makes up this suitable commercial Application type is difficult unusually, and this is a subject matter of exploitation atmospheric pressure plasma technology on the commercial scale.
WO 02/35576 has set forth the use of the metal electrode that is attached to the dull and stereotyped back side of vertical dielectric, and the limited conductor that has sprayed a kind of liquid state on it provides two kinds of functions of heat treatment and electrode passivation.The liquid of the partially conductive that use such as water is such can help to alleviate micro discharge, and it may be from coarse " projecting point " in metal surface and by providing a conductive path that passes through the gap portion between relatively poor inhomogeneity electrode and dielectric to improve the uniformity of metal electrode to dielectric surface.The water of partially conductive can make at dielectric ammeter face level and smooth, therefore sets up an approximate uniform surface potential.This technology is subject to the complexity that makes up a suitable spraying distribution system and guarantees enough or even from the difficulty of each electrode assemblie draining.
Although the use of direct and the contacted cooling water of metal electrode has alleviated inhomogeneities, it does not have the cost of eliminating but having rolled up complexity and desired plasma apparatus.For the engineer, a perfect metal electrode that had not both had remaining rough surface also not have the edge pollutant and can be attached to big dielectric surface very safe and closely is very difficult.The such partially conductive liquid of use such as water can alleviate micro discharge, it may be from metal surface coarse " projecting point ", and by providing a conductive path that passes through the gap portion between relatively poor inhomogeneity electrode and dielectric to improve the uniformity of metal electrode to dielectric surface.The water of partially conductive can make at dielectric ammeter face level and smooth, therefore sets up an approximate consistent surface potential.
The water electrode that the front is described as producing the power supply of direct current (D.C) in the literature is the plasma between electrode and water surface or water column.For example people such as P.Andre (J.of Physics D:Applied Physics (2001) 34 (24) 3456-3465) has set forth the generation of D.C. discharge between two post flowing water.
A.B.Saveliev and G.J.Pietsch (the international symposium of Hakone VIII ConferenceProcessings-high pressure low temperature plasma characteristic, July 21-252002, Puhajarve Estonia.) has also set forth the application that water electrode produces surface discharge.Surface discharge is different with above-mentioned parallel-plate glow discharge, comprise one as device and be attached to the dielectric plane electrode with the bar-shaped surface electrode that directly contacts with the dielectric substance face, discharge exists as the point discharge along dielectric surface then.In the example that Saveliev describes, water electrode is mainly used in provides transparency electrode.
People such as T.Cserfavi (J.Pys.D:Appl.Phys.26,1993,2184-2188) set forth a kind of generation of discharge, this discharge is described as at metal anode and as the glow discharge between the open containers water surface of negative electrode by them.Yet these are different with previously defined glow discharge, do not place dielectric between electrode, and what see in such system will be the discharge of " beating " between metal anode and water surface.Discharge in the air void between water surface and anode is determined salt decomposition in water by the optical emitting spectroanalysis instrument.
In US 6232723, the porous non-metallic electrode is used to produce plasma by scattering the hole that conductor fluid passes nonmetal electrode.Between electrode, do not place dielectric substance outwardly, yet, mean and between electrode, may take place because the problem that short circuit causes.
In US4130490 and JP 07-220893, set forth by using by the stream of forming the system of electrode by the dielectric substance of conductor fluid.US4130490 has set forth a kind of device that removes by the pollutant oxidation from the air or oxygen environment, this device is made up of an interior metal hollow edged electrode, such as the such cooling agent of current by flowing to away from the cooling agent accumulator tank of electrode or from described storage concentrated flow.Outside electrode is made up of the shell of dielectric substance, and it has an entrance and exit, and a kind of conduction liquid coolant from accumulator tank passes through described entrance and exit.Be defined as gas compartment in gaps between electrodes, inside pollutant is oxidized.
The application attempts adopting a kind of conducting medium, it is consistent with dielectric surface, therefore the metal electrode that needed originally can save, this will cause the dielectric surface of even electric charge and the heat treatment that produces heat with conducting medium by plasma, and it has shown the long-term adhesion at inner and exterior wall interface/contact.
According to the present invention, an assembly that produces plasma glow discharge and/or dielectric layer discharge is provided, comprise the electrode that at least one pair of substantially equidistantly separates.Under introduce handling gas and allowing situation that gas, liquid and/or solid precursor pass through when needed, the interval of electrode is suitable for forming a plasma zone, it is characterized in that at least one electrode comprises a shell, it has an inwall and an outer wall this shell, wherein inwall is to be formed by a kind of non-porous dielectric material at least, and shell keeps a kind of basic at least nonmetallic electric conducting material that is substantially.
Plasma is interpreted as the zone between the right relative wall of adjacent electrode (after this being called inwall), can produce a plasma there when having potential difference between the electrode.
Each electrode preferably is made up of a shell, described shell has an inner and outer wall, wherein inwall is by forming from dielectric substance at least, and described shell comprises a kind of direct and contacted basic at least nonmetallic electric conducting material that is of inwall, has replaced the metallic plate or the mesh electrode of " routine ".Kind electrode is more suitable, can produce uniform glow discharge because the inventor has realized that by adopting the electrode consistent with the present invention to produce glow discharge, and compare with the system that adopts the metal plate electrode, has reduced heterogeneity.In the present invention, a metal plate never directly is fixed on the inwall of an electrode, and non-metallic conducting material preferably directly contacts with electrode inner wall.
Can constitute by any suitable dielectric according to dielectric substance of the present invention, for example including but not limited to Merlon, polyethylene, glass, flass, flass and similar material that epoxy is filled.Preferably, in order to prevent any bending or because the dielectric strain that causes of electric conducting material in the electrode, dielectric will have enough intensity.Preferably, the dielectric of use can be processed with machine, and provides and mostly be 50 millimeters thickness most, is preferably and mostly is 40 millimeters thickness most, preferably the thickness of 15-30 millimeter.Under the transparent inadequately situation of the dielectric of selecting, can with a glass or similarly window observe the plasma of generation.
Electrode can be kept apart by pad or similar thing, and it is preferably made with dielectric substance, therefore makes whole dielectric intensity of system get a promotion by the discharge potential of eliminating between the conducting liquid edge.
Electrode pair according to assembly of the present invention can be made of any suitable geometry and size.Very clear, simple geometric shape is that the parallel flat that surpasses 1 per square meter of surface area is arranged, therefore can form and be fit to the large-scale plasma zone that industrial plasma is used for network or similar processing, but they also can with concentric tube or tubulose or similarly form handle Powdered and liquid or analog.
Being essentially nonmetallic electric conducting material can be liquid, and as polar solvent, for example water, alcohol and/or ethylene glycol or water-soluble salt solution and composition thereof still preferably adopt water-soluble salting liquid.When making water separately, preferably form by running water or mineral water.Better, this water comprises the most multiple about 25% water soluble salt, as alkali metal salt, and for example sodium or potassium or chloride or alkali salt.The conductivity that improves liquid with above-mentioned ion salt can obviously reduce heterogeneity, has therefore shown the unnecessary of front plate electrode.This is because the electric conducting material that occurs in electrode of the present invention has good homogeneous, therefore at dielectric surface a more uniform surface potential is arranged, can observe characteristics in the use, because the plasma that influenced by electrode of the present invention has sent more uniform aura, and can not produce since weak plasma form than black region.Further the fact has been supported this conclusion, does not observe local point discharge here in the plasma that produces between the electrode of Miao Shuing.Change the kind of conducting liquid intermediate ion material and electric capacity and the resistance that concentration can be controlled electrode of the present invention at an easy rate.Such control can be used for being reduced in the requirement of the radio freqnency generator and the impedance matching circuit in the voltage transformer system that are used for producing plasma between the electrode.
If be used in the electrode of the present invention basic at least for nonmetallic electric conducting material be a kind of polar solvent, such as the water within the dielectric restricted area, alcohol and/or ethylene glycol or water miscible salting liquid, according to selected dielectric, electrode may be transparent, therefore make and carry out optical diagnostics easily, and itself help from such as removing heat load the such plasma apparatus of glow discharge apparatus for nonmetallic electric conducting material substantially.The spray technology of describing among the present invention and the WO02/35576 is compared, and this has simplified covering and electric passivation that heat removes problem and improved electrode greatly.The use of conducting liquid has further improved the uniformity of electromotive force on the dielectric side by guaranteeing that fixed charge distributes, yet metal electrode can not guarantee the uniformity of dielectric side.The uniformity of conducting liquid can make the inwall of electrode and/or outer wall surface have fixing and contact closely.
Alternatively, be that nonmetallic electric conducting material can be with the form of one or more conductive polymer composition substantially, the form with paste provides typically.At present such paste is applied in the electronics industry, is used to adhere to the heat treatment with electronic devices and components, such as the microprocessor chip group.Typically, these pastes have enough mobilities to flow and comply with the scrambling on surface.
Suitable polymers according to conductive polymer composition of the present invention can comprise siloxanes, epoxy polyolefin elastomer, a kind of hot-melt object based on wax, such as siloxane wax, resin/polyblend, siloxanes-polyamide copolymer or other siloxanes-organic substance copolymer or analog or epoxy resin, polyimides, acrylate, amido formate or based on the polymer of isocyanates.Typically, polymer will comprise conductive particle, be typically silver but as an alternative conductive particle also can adopt gold, nickel, and copper, metal oxide that mixes and/or carbon comprise carbon nano-tube or metallized bead or ceramic bead.The specific example of spendable polymer is included in electro-conductive glass polymer of describing among the EP240648 or the composition based on organopolysiloxane of filling with silver, as the Dow that is sold by Dow Corning company
DA6523, Dow
DA6524, Dow
DA6526BD and Dow
The polymer that DA6533 or silver are filled based on epoxy resin, as from
H20E-PFC or
E30's (Epoxy Technology Inc)
8175 (AblestikElectrinic Materials﹠amp; Adhesives).
As above mentioned, a main advantage of the present invention is a uniformity, by adopt have between inner and outer wall that a liquids/guarantees electrode and the interface one fixing and contact closely/adhere to.Can obtain contact/adhesion such as liquid or the so flowable medium of paste by using, it also can be absorbed in mechanical stress those surfaces, that can cause delamination and the conducting medium of thermal stress obtains by physical adherence on the inner and outer wall surface of electrode.Like this, the adhesion elastomer with thermal conductivity and conductivity can use as the medium between the electrode inside and outside wall surface.A kind of paste of conduction can be laid on dielectric surface, and chemical bond forms the medium of a rubber-like, conduction, it can conduct electricity and heat conduction, by providing structural strength in conjunction with restricted flat board on dielectric and the structure, it also can absorb the stress of the delamination that will cause firmer adhesion.A main advantage of uniformity of the present invention aspect be by adopt have between inner and outer wall that liquids/guarantees electrode and the interface one fixing and contact closely/adhere to, provide a chance for making large-area electrode.Consider under commercial scale and use that this is a main advantage, wherein need large-area electrode system for substrate with suitable rate processing industrial scale.
For example, the kind electrode assembly can comprise an inwall of being made by dielectric substance, linked a combination electrode that comprises metal fin thereon, it provides the integration on the global structure, an elastomer heat conduction, conduction, that fill is provided between them, and it forms an adhesion, resilient interface.
Hot removing is a main problem in plasma assembly, especially for the electrode that uses the metal plate type.But in electrode as described above, because the heat energy convection effect by liquid, this problem obviously reduces.In addition, by the convection current of conducting liquid, the projecting point of electricity is removed.It should be noted that the heat that is produced by electrode for example can be distributed by adopting cooling coil, utilize the device of electrode outer wall as heat radiation, so outer wall is made of suitable fin preferably when adopting one or more as discussed above during electrode.Fin preferably adopts metallic forms and comprises outwards outstanding fin, can use cooling fluid, typically strengthens cooling processing as air or outside cooling coil.
At present a subject matter that faces such as the such plasma system of atmospheric pressure glow discharge systems that adopts the metal plate electrode be not the way by the physical replacement electrode change the passage length of the substrate in the plasma zone by activation.There is individual scheme to need over time, in this scheme, by speed substrate is fixed in the plasma zone by changing substrate.The sort of electrode of Chan Shuing provides a kind of more simple proposal in the above.Preferably adopt a kind of polar solvent, for example each electrode of salting liquid of water, alcohol and/or ethylene glycol or water and composition thereof has comprised an inlet, and preferably includes an inlet and an outlet.Entrance and exit all comprises valve, can introduce and remove polar solvent, for example water, alcohol and/or ethylene glycol or water-soluble salt solution and composition thereof.These valves can comprise any suitable form, and are particularly useful for changing the plasma treatment zone itself that passage length and substrate pass through.By having the entrance and exit of valve, can change the passage length of electrode system at an easy rate, by opening outlet valve and inlet valve, allow liquid to flow out still and stop liquid to enter inlet, perhaps introduce the effective dimensions that the liquid of more liquid and the original quantification of introducing improves electrode by opening inlet valve by outlet valve.Mean in turn that so successively the user can control the reaction time of plasma better, thereby by using one or more electrodes of the present invention to come ex vivo treatment such as substrate carry out, especially when the relative velocity of substrate by plasma is difficult to change.
Do not need as setting forth among US4130490 and the JP07220895, circulation makes polar solvent continuously, as water, alcohol and/or ethylene glycol or water-soluble salt solution and composition thereof, flow to an accumulator tank or analog by electrode system, and flow through next from accumulator tank or analog, this means that the required equipment complexity of electrode system according to the present invention obviously reduces owing to no longer require passing through of Continuous Flow.
Can be separated out by using ribs according to each electrode of the present invention, ribs is that design is used for shell is divided into two or more parts.This split plot design provides extra advantage in the mode of assisting plasma zone passage length to change, if for example continuous electric field is not set up between different parts, then each independent parts will be as an independently electrode job, makes the passage length in plasma zone can be easy to change and purpose as requested is optimized.Ribs can be attached in the inner and outer wall any one or on the two, connects or keep the electric field continuity by the existence of the continuous conduction fluid passage between each part under the situation of using conducting liquid by single line.By the in succession inner and outer wall of ribs of protection, zone above it is reduced by the maximum pressure that the non-metallic conducting material internal pressure causes, thereby has reduced to cause potentially the power of inwall and/or outer wall distortion.Make the passage length in plasma zone can be easy to change and optimize by introducing ribs.
According to electrode of the present invention, this example that can be used for plant-scale assembly provides an atmospheric pressure plasma assembly that comprises first and second pairs according to the electrode of parallel spaced apart of the present invention, each forms the first and second plasma zones to the spacing between the inside flat board of electrode, and wherein assembly comprises that also one is transmitted continuously substrate and makes its device by the described first and second plasma zones and one be used for introducing fog-like liquid or solid cladding makes material be applied to the sprayer in one of described first or second plasma zone.The basic conception of such equipment is described among the application WO 03/086031 undetermined in the applicant, and it will be announced after priority date of the present invention and here combine as a reference.In the embodiment of a first-selection, electrode is vertical setting.
Set forth as the front, liquid is the liquid that every pair of electrode can have varying number as a main advantage of electric conducting material, causes the plasma zone, passage length of different sizes and different reaction time when substrate passes through between different electrode pairs.This means when a coating is laid on the substrate and relevant reactions change is only arranged, have the conducting liquid of varying number to introduce different electrode pairs, the reaction time of the cleaning course in the first plasma zone can be different from passage length and/or the reaction time in the second plasma zone.Preferably, use the liquid of equal number at each electrode of an electrode pair as indicated above.
Electrode of the present invention can be used in any suitable plasma system, such as pulsed plasma system, but especially is useful in glow discharge or the dielectric layer discharge assembly, and it can be worked under any suitable air pressure.Especially, they can be integrated in low pressure or the Atomospheric pressure glow discharge assembly, and the assembly of thermal nonequilibrium type is preferably used in the atmospheric pressure system especially like that.
Being used to use the processing gas of the plasma-treating technology of electrode of the present invention can be any suitable gas, but inert gas or preferably based on the mist of inert gas, for example helium, helium argon mixture gas, based on the mist that contains ketone and/or relevant composition in addition of argon.These handle that gases can use separately or with other potential reacting gas, be used in combination as oxidation and reducing gas, as nitrogen, ammonia, ozone, oxygen, water, nitrogen dioxide, air or hydrogen.But, handle gas and can comprise one or more so-called potential reaction gas.Handle gas and preferably only be combining of helium or helium and a kind of oxidation or reducing gas.The selection of gas depends on the plasma process that will carry out.When handling the such potential reaction gas of gas such as a kind of oxidation or reduction and need combine with helium or any other mist based on inert gas, the inert gas or the inert gas mist that in mist, preferably contain 90-99%, the oxidation of 1-10% or reducing gas.
Under the condition of oxidation, this method can be used for forming on substrate and contain oxygen coating.For instance, can form material by vaporific silica containing coating based on the coating of silicon dioxide forms on substrate surface.Under reducing condition, can be used to provide the substrate of no oxygen coating according to assembly of the present invention, for example, can form material and form by the vaporific silicon coating that contains based on the coating of silicon carbon compound.
In a nitrogen containing atmosphere, nitrogen can be combined in substrate surface, and in the atmosphere of nitrogenous and oxygen, nitrate can combination and/or formation on substrate surface.Such gas also can be used for the pre-processed substrate surface before forming material being exposed to coating.For instance, substrate contains oxygen plasma treatment and can improve adhesion to the coating of laying subsequently.Containing oxygen plasma is to produce such as oxygen or the such oxygen material that contains of water by introducing in plasma.
Can obtain various plasma treatment at present, comprise the electrode of the present invention that surface active, cleaning surfaces, material etching and coating lay and be even more important.Substrate can be activated and/or handle through a series of plasmas zone with any suitable combinations thereof, drive by a series of plasma systems, in plasma zone separately, can obtain to comprise a pair of or many at least one plasma system according to electrode of the present invention, that required additional component is provided.For instance, under the situation of substrate by a series of plasmas zone, substrate can be cleaned in first plasma zone and/or activate, in second plasma zone by surface active, and in the 3rd plasma zone coated or etching.
Alternatively, substrate surface be cleaned and/or be activated in first plasma zone can by the plasma treatment of carrying out with the helium plasma, second plasma zone can be used to lay the coating of precursor gases material, for example passed through a sprayer or an atomizer described in the patent application WO 02/028548 undetermined as the applicant time and laid a kind of gaseous precursors or a kind of liquid or solid spraying precursor.As another selectable scheme, first plasma zone can be used as oxidation unit (for example handling in the gas in a kind of oxygen/helium) or be used to lay coating, and second plasma zone is used to lay second coating of different precursor gases.As an example with preliminary treatment and subsequent processing steps, following technology is suitable for providing SiO
xBarrier layer, it has the outer surface of an antipollution/burning, it can be used as solar cell or automobile, and wherein substrate at first carries out preliminary treatment by the helium cleaning/activation of substrate, then in first plasma zone by SiO from methyl silicon ketone precursor
xDeposit.Further helium plasma treatment provides SiO
xLayer is extra crosslinked, and finally lays coating with a kind of precursor of fluoridizing.Can carry out any appropriate pretreatment, such as substrate can be cleaned, dry, clean or use processing gas to come Purge gas such as helium.
In another embodiment, substrate is coated, wherein not many group plasma assemblies, and single plasma assembly can be as the device that changes by the material in the plasma zone that forms between electrode.For example, the only material by described plasma zone can be to handle gas at first, and as helium, it is excited by apply electromotive force between the electrode that forms the plasma zone.Resulting helium plasma can be used for cleaning and/or activation substrate, its pass or relatively and the plasma zone pass through.One or more precursor material that forms coating can be introduced into and be activated by plasma zone and processing substrate.In most of the cases, substrate can pass or move with respect to the plasma zone, thereby influence a plurality of layerings, the suitable ingredients that forms the precursor material of coating can be by replacing, increase or stop to introduce the precursor material that one or more for example forms coating, changes as reacting gas or liquid or solid.
Be used to utilize precursor material substrate to be carried out under the situation of coating in system, the precursor material that forms coating can make it atomizing with any traditional method, such as a ultrasonic nozzle.Sprayer preferably produces the droplets of material that forms coating, from 10 to 100 microns of sizes, preferably from 10 to 50 microns.The suitable sprayer that uses among the present invention is the ultrasonic nozzle from the Lechler company in the Sono-Tek company of USA New York Milton or German Mai Qingen city.Device of the present invention can comprise a plurality of nozzles, it is used for multiple use, for example described device be used as form on the substrate that two different coatings form materials one copolymer coated, monomer wherein is immiscible or in different phases, for example first be solid-state and second be gaseous state or liquid state.
Should be appreciated that, substrate and plasma zone can relatively move each other, that is to say, substrate can physically pass through between adjacent electrode pair, can pass through adjacent to electrode pair, suppose the plasma zone of thinking that described substrate influences by the electrode pair that is subjected to the combination of employed processing gas.Under latter event, should understand plasma zone and substrate and move relative to each other, that is to say that electrode assemblie passes a fixing substrate or substrate can move with respect to a fixing electrode system.In another embodiment, electrode system can be away from substrate, and substrate is with the material coating that is excited like this, and these materials that are excited are by a plasma, but influence that needn't subject plasma.
Be integrated under the situation about being fit to the assembly of backing coating at electrode of the present invention, the sort of coating that forms on substrate is by the used precursor material decision that forms coating.The precursor material that forms coating can be organic or inorganic, solid-state, liquid state or gaseous state or its mixture.Suitable organic formation coating precursor material comprises carbonyl compound, methacrylate, acrylates, styrene, isopropene cyanide, alkene and alkadienes, methyl methacrylate for example, the ethyl methacrylate, the propyl group methacrylate comprises the methacrylate and the acrylates of organic functions, comprise methyl propenoic acid glycidyl ether, trimethoxy silane propyl group acrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate, dialkylamino alkyl methacrylate and fluoro-alkyl (network) acrylate, methacrylic acid, acrylic acid, fumaric acid and ester, methylene-succinic acid (and ester), maleic acid, acid anhydrides, AMS, the alkene of halogenation, for example, vinyl halide, fluoridize thing such as vinyl chlorination thing and vinyl, with the alkene of fluoridizing, for example, perfluoroolefine, acrylonitrile, isopropene cyanide, ethene, propylene, allyl amine, vinylidene halide, butadiene, acrylamide, such as the N-N-isopropylacrylamide, Methacrylamide, epoxy compounds, for example, the glycerine propyl trimethoxy silicane, glycidol, styrene oxide, butadiene monoxide, ethylene glycol is to diglycidyl ether, glycidyl methacrylate, bisphenol-A be to diglycidyl ether (with its oligomer), VCH oxide and based on the polyethylene oxide of polymer.Also can use such as such conducting polymer of pyrroles and thiophene and their derivative, and dimethylallyl phosphoric acid phosphorus-containing compound for example.The material of suitable inorganic formation coating comprises metal and metal oxide, comprises colloidal metal.For the material that forms coating, organo-metallic compound also is suitable, comprises metal alcoholate, as titanate, and tin alcoholates, the alcoholates of zirconates and germanium and erbium.
Substrate also can provide with the coating based on silicon dioxide or siloxanes, and it has used the component that forms the material of coating.But suitable material comprises and is not limited only to silane (silane for example, alkyl silane alkyl silane salt, alkoxy silane, epoxy silane and or the silane of amino functional group) and linear (such as dimethione) and periodic siloxanes (such as Octamethylcyclotetrasiloxane), comprise the linearity of organic functional group and periodically siloxanes (such as siliceous hydrogen, salt functional group, epoxide function group, the ammonia functional group and the linearity alkylhalide group functional group and periodic siloxanes are such as tetramethyl-ring tetrasiloxane and three (non-fluorine butyl) methyl cyclotetrasiloxane).Also can use the different silicon-containing mixtures of material, as physical property for specific demand (for example hot property, optical property is as refraction coefficient and viscoelastic property) tailored substrate coating.
Coated substrate can comprise any material, and its enough softness can be transmitted by electrode assemblie as previously described, such as plastics, thermoplastics for example, as polyolefin, for example polyethylene and polypropylene, Merlon, Polyurethane, polyvinyl chloride, polyester (for example poly-inferior hydrocarbon terephthalate, especially polyethylene terephthalate), polymethacrylates (for example polymer of polymethyl methacrylate and poly hydroxy ethyl acrylate), polyepoxide, poly-sulfo group, polyphenylene, polytrimethylene ether ketone, polyimides, polyamide, polystyrene, dimethione, phenol, epoxy and melamine formaldehyde resin, and composition thereof and copolymer.Preferred organic polymer materials is a polyolefin, especially polyethylene and polypropylene.Alternatively, coated substrate also can be the thin metal forming of one deck, by making such as aluminium, copper, iron or steel or metal film.The coated substrate of the sort of type of foregoing system of the present invention preferably is used as handles hard substrate, as glass, metallic plate and pottery and analog.
The substrate of handling by assembly according to the present invention can be artificial synthetic and/or natural fiber, weaving or non-woven fibre, powder, siloxanes, fabric, weaving or non-woven fibre, natural fiber, artificial composite fibre materials and powder or organic polymer materials and contain organosilyl adhesive, and it is blendable or as in can not mix with organic polymer materials described in applicant's the patent application WO01/40359 co-pending.The size of substrate is subjected to producing the size restrictions of the volume of atmospheric plasma discharge, promptly according to the distance between the inwall of electrode of the present invention.For typical plasma generating equipment, plasma produces in 3 to 50 mm clearance, for example 5 to 25 millimeters.Therefore, the present invention has special purposes for coated film, fiber and powder.
The generation of stable state glow discharge under atmospheric pressure is preferably between the adjacent electrode and obtains, and adjacent electrode is according to 5 centimetres at most at interval of employed processing gases.Electrode is penetrated uncle's energy supply with 1 to 100 kilovolt root mean square (rms) electromotive force, and preferably between 4 to 30 kilovolts, frequency is 1 to 100 KHz, preferably 15 to 40 KHz.The voltage typical case who is used to form plasma is between 2.5 to 30 kilovolts, and preferably between 2.5 to 10 kilovolts, still actual value depends on the selection and the zone of the plasma between the electrode size of chemistry/gas.
Simultaneously, the Atomospheric pressure glow discharge assembly can be worked under any suitable temperature, is preferably in room temperature (20 ℃) and works between 70 ℃, is typically and is used in 30 to 40 ℃ of temperature in the scope.
The electrode of preparing according to the present invention with respect to as the design that applicant's PCT co-pending applies for setting forth among the WO02/35576, metal electrode and cooling system combined more simple and cheap during fabrication.For example,, can reduce the distance between the inside and outside wall of electrode of the present invention, therefore reduce the space of required electric conducting material, reduce the weight of assembly by removing the requirement of the flow of liquid on the electrode surface described in the WO02/35576.
Also reduced to guarantee desirable equidistant with parallel complexity between the adjacent electrode according to electrode of the present invention, this is a special problem in metal electrode.And further can use a kind of dielectric, it can be a printing opacity, allows to observe at an easy rate and diagnose plasma.
In addition, such assembly has reduced to guarantee the inhomogeneity complexity at the interface of electrode and dielectric substance, and when using the metal plate electrode as similar application, this is a prior problem.
From the description of more following embodiments of the present invention, can more be expressly understood the present invention.Its general only provides in the mode of example with reference to the accompanying drawings:
Fig. 1 is the view that comprises the atmospheric pressure plasma system of two nonmetal electrodes;
Fig. 2,3,4,5a, 5b and 5c are the sectional arrangement drawings of the optional embodiment of assembly as shown in Figure 1;
Fig. 6 is the sectional arrangement drawing of an atmospheric pressure plasma system, and wherein electrode is the concentric pipe form;
Fig. 7 is the sectional arrangement drawing of the atmospheric pressure plasma assembly of a Fig. 6, and it is suitable for powder or liquid are carried out plasma treatment;
Fig. 8 is the sectional arrangement drawing of another optional atmospheric pressure plasma assembly;
Fig. 9 a still is the sectional arrangement drawing of another optional atmospheric pressure plasma assembly;
Fig. 9 b is the plane graph of a pair of dielectric tube electrode, and it is used for the described atmospheric pressure plasma assembly as Fig. 9 a;
Figure 10 is with the parallel view to the elastic pipeline that combines of opposite voltage, and it forms the flat thin sheet and is bent to adapt to surface profile;
Figure 11 is the component view that the present invention is used to handle the substrate of process between electrode pair; And
Figure 12 is the chart that shows the plasma products of glow discharge type.
Provide an atmospheric pressure plasma assembly 1 with reference to Fig. 1, it has a pair of nonmetal electrode, represents with Reference numeral 2.Each electrode 2 is the forms with shell 20, and a chamber 11 is arranged, and at the one end inlet 3 is arranged, and at its other end outlet 4 is arranged, and a kind of supporting electrolyte can be introduced into or shift out by described inlet or outlet.Under the situation of Fig. 1, electrode is fully by the salting liquid submergence.Inlet 3 and outlet 4 all comprise a valve, and they are to be used for controlling entering and shifting out of supporting electrolyte.Each electrode 2 has an inwall 5 of being made by dielectric substance and by dielectric substance or metal outer wall 6.The adjacent end that escapement 7 is kept electrode 2 separates with a predetermined distance.When using, the gap 8 between the inwall 5 of adjacent electrode 2 forms plasma zone 8.Power supply 9 is connected to each inlet 3 by cable 10.In Fig. 2 to 5b, will use identical Reference numeral.
In use, valve 3a and 4a open, and a kind of conducting liquid is introduced in the chamber 11 by the inlet 3 of shell 20, and flow out by outlet 4. Valve 3a and 4a close then, stop any solution to enter or shift out when electrode system uses.Liquid is both as the current-carrying part of electrode 2, with the interface shape unanimity of inner and outer wall 5,6, also as a kind of device of the temperature heat management of each electrode 2.Conducting liquid 3 was cooled before introducing chamber 11 by entering the mouth, because because the use of voltage in the system, liquid is often stayed the possible elevated temperature in there.When flowing out electrode by outlet 4, conducting liquid is received the cooling device (not being shown) of an outside, can reuse in electrode system in the future by being introduced once more by inlet 3 then.
For plasma of initialization in plasma zone 8, on electrode 2, apply electrode potential.In case a suitable electrode potential is arranged on electrode 2, handle gas (being typically helium) and passed through plasma zone 8, and the formation plasma that is excited.The ideal uniform electric field of generation at the interface between it and the inwall 5 made by dielectric substance of each electrode 2 as shown in Figure 1, this is because at the interface uniformity and the transverse conduction of liquid between conducting liquid and inwall 5.
Fig. 2 to 5 has shown various alternative execution mode of Fig. 1.They are particularly useful for reducing, preferably eliminating the distortion of the inwall of being made by dielectric substance 5, as because internal pressure and optionally/additional be used for caused bending of device of cooling electrode assembly or the like.These optionally design that is to say in particular for electrodes of inwall 5 with high surface area, be used to have the system in big plasma zone 8,1 square metre or the plasma zone of heavy in section area are more for example arranged.
In Fig. 2, each electrode 2 utilizes ribs 15 by separated, and it is with shell 20 separated into two parts 22,23.Ribs 15 is attached on the inner and outer wall 5,6, and by the existence of the continuous conduction fluid passage 18 between two parts continuous electric field is kept.By inside and outside wall 5,6 is fixed on the ribs 15, the area that has applied maximum pressure is reduced, and therefore having reduced may the potential power that causes distortion.The electrode that " separates " among Fig. 2 provides the advantage of extra changeable channel length, if each part as independently electrode work, the passage length in plasma zone can be easy to change and optimize.In this case, the height of the conducting liquid in the electrode is controlled by the action of valve 3a and 4a.When as shown in Figure 2, chamber 11,22,23 when being full of conductor fluid, and conductor fluid enters by inlet 3a and by shifting out as the outlet 4a that describes among Fig. 1.But, when passage length changes, that is to say, when chamber 11,22,23 when not being full of conducting liquid, and liquid enters and shifts out by inlet 3a, outlet 4a is used for stoping that 11,22, the 23 air bag places that do not comprise the zone of conducting liquid form vacuum in the chamber.
In another execution mode as shown in Figure 3, outlet 4 (perhaps entering the mouth for 3 (not showing)) was both also used for export as inlet, unless and electrode is by submergence fully, valve 4a always remains on the enable possition, makes liquid in use owing to reasons such as temperature and/or pressure variation discharge from chamber 11.In Fig. 3 a, used a plane coldplate 6a as the capacity border, back in the chamber 11 that comprises conducting liquid, so conducting liquid is limited between the dielectric surface and the dull and stereotyped 6a of cooling of inwall 5.Heat conducting liquid internally flows through dull and stereotyped 6a and flow to outer surface, and it is cooled off by second source, and under the situation of the part 22 of the chamber 11 of Fig. 3, second source is the stream that one cold quenching is crossed, as water or the air by cooling coil 25.
If second cooling media is a kind of liquid, that is to say, a kind of liquid as shown in Figure 3 by cooling coil 25, so dull and stereotyped 6a is designed so that the fluid pressure in cooling coil 25 is unlikely the dull and stereotyped 6a of distortion, and shift on the conducting liquid of this pressure in the chamber 11, thereby cause the harmful distortion on inwall 5, especially the interface between conducting liquid and inwall 5.In a low-angle distortion on the dull and stereotyped 6a can the sub-fraction 60 by the gap between inwall 5 and dull and stereotyped 6a, leave free fluid and in conducting liquid, adapt to.For example, such gap 60 can be sealed and empty, or fills arbitrarily with a kind of inert gas of not exerting pressure or air, perhaps opens to air simply.Distortion in dull and stereotyped 6a can adapt to along with the conducting liquid weight change in chamber 11 then.
Another optional heat removes processing as shown in Figure 4, its midplane coldplate 6a has a fin-shaped outer surface 30, it cools off with nature or forced convertion, for example, under latter event, a kind of cooling fluid (being typically air) Be Controlled (by blowing) on fin 30 and dull and stereotyped 6a with cooling electrode.
In use, because conducting liquid is retained or is retained in basically within each electrode, electrical connection must be within electrode 2 and not near pipe-line system, just as the situation of passing through system at stream.This is achieved in the following manner very effectively: by applying the electrode potential that passes dull and stereotyped 6a (Fig. 3), it provides an extraordinary method to transmit the conducting liquid of electric charge to the chamber 11.Therefore in Fig. 3, we can say electrode 2 be one by metal plate 6a with forms the electrode that the conducting liquid 11 of composite electrode synthesizes.In addition, dull and stereotyped 6a is that the conducting liquid in the chamber 11 forms a limiting surface, and so design is in order to provide structural integrated for electrode assemblie 2.
For heat be by conducting liquid by dull and stereotyped 6a rather than by the inner derivative design of cooling coil, the thickness of conducting liquid (apart from d) can reduce, further to reduce the weight in assembly 2.Electrode as illustrated in fig. 1 and 2, dull and stereotyped 6 and inwall 5 between apart from d (Fig. 1), just the thickness of conducting liquid layer is typically in 5 to 45 millimeters scope, is preferably between 5 to 30 millimeters.But such thickness only is the capabilities limits that is subjected to liquid diffusion internal field scrambling, and its surface of passing flat board 6 is positioned at the surface of outer wall 6, makes uniform electric charge be passed to inwall 5.In practice, avoid the cooling system in chamber 11, the conducting liquid of making by dense saline solution apart from d even can be below 1 millimeter.In the electrode of little d value (less than 10 millimeters), the potential electrode of shown in Fig. 3 and 4 those, conducting liquid has utilized surface tension, and it has the effect that attracts liquid to enter gap 60 and cause tangible drop under the fluid pressure within the conducting liquid.Therefore this drop in hydrostatics has reduced to act on the power on the inwall, and has reduced the distortion that the dielectric substance as inwall 5 takes place owing to conducting liquid weight.Conducting liquid becomes the oneself effectively to be supported, and this is useful for the interior wall construction of being made by dielectric substance 5 with the surface area that surpasses 1 square metre.
Under little d value (less than 10 millimeters), thermal convection part is delivered to dull and stereotyped 6 from the dielectric substance of inwall 5, and perhaps 6a becomes and ignores and heat conduction is occupied an leading position.Therefore this is favourable for the thermal conductivity of optimizing conducting liquid, because the mobility of liquid in nonfluid combination electrode gap is no longer crucial, the viscosity of conducting liquid no longer is a constraint.The mobility of conducting liquid is necessary for the uniformity of the conducting liquid that guarantees dielectric and surface of metal electrode only.
All execution modes of describing in Fig. 1 to 4 have been avoided being increased by the pressure that the demand of getting liquid by the electrode pump of setting forth in the prior art produces.The hydrostatic head that removes the only left liquid height that in assembly, comprises from the pump pressure power of system, and therefore reduced the possibility of the distortion of electrode wall, it will reduce the efficient of electrode system, and can produce the homogeneous plasma that spreads all over the plasma zone.
Fig. 5 a has shown an electrode assemblie, previous employed conducting liquid is replaced by the adhesive 40 of conduction, heat conduction in chamber 11, and it had both influenced uniform electric field and has also influenced the effective transmission of heat from inwall 5 to the dull and stereotyped 6a of the cooling with cooling fin or analog 30.Fig. 5 b has shown the electrode assemblie that uses a slice dielectric 67, and it has a chamber 11b that main body processed by dielectric 67.In this embodiment, dielectric is used to admit the dull and stereotyped 6a with cooling fin 30 and encases conducting liquid.Typically, dielectric substance hollows out, and adopts or do not adopt ribs 15, and described ribs is formed by the remaining part that does not hollow out when adopting ribs.Employed typical dielectric material be engineering plastics (polyethylene, polypropylene, Merlon or such as the suitable material of PEEK) or engineering ceramics thin slice.Each electrode 2 can be assembled by the conducting liquid among the 11b of chamber then, the metal plate 6a sealing of cooling off with fin 30 and available air or cooling liquid.In the execution mode of describing in Fig. 5 b, electric conducting material is normally a kind of such as the such conducting liquid of salting liquid.
In Fig. 5 c, the demand of the chamber 11b that hollows out can by with one between inwall 5 and dull and stereotyped 6a the curing that is fit to or electroconductive binder 62 floor of non-curing replace avoiding.Adhesive can keep non-curing, but preferably solidifies, to improve the degree of adhesion to dull and stereotyped 6a and dielectric 61.Dull and stereotyped 6a is again by air or cooling liquid cooling.At Fig. 5 a, among the embodiment described in 5b and the 5c, electromotive force is added on the metal plate 6a, and is distributed to equably on the rear surface of inwall 5 by the adhesive in conducting liquid and the chamber 11.
In another embodiment of the present invention, conducting liquid is enclosed in the inside and outside zone of two concentric pipe designs shown in Fig. 6 and 7, wherein externally the gap between pipeline 32 and the internal pipeline 34 forms a plasma zone 36, and it produces between pipeline in use.This execution mode can be used for handling material, such as gas, and the liquid aerosol, powder, fiber, thin slice, foam or the like, it can be transmitted to be used for plasma treatment by this pair of concentric pipe design.Under the situation of solid material, such as powder, for example pipeline can be used in a vertical substantially position as shown in Figure 7.In the execution mode shown in Fig. 6 and 7, a kind of cooling liquid can enter, pass through and outflow internal pipeline 34 by inlet 3a and outlet 4a, and the cooling coil 25a of an outside can as at least basically around external pipe 32, to remove by influencing the heat that plasma produces.
In another execution mode of the present invention as shown in Figure 8, in the time need carrying out plasma treatment to the inner surface 40 of container 38, described container 38 parts are immersed in the charged conducting liquid 42.The liquid form of electrode has guaranteed the crash consistency of the complex surface structures of outer electrode and container 38.Alternatively, can make an on all four mould of shape, remain in position with the method for introducing charge air conditioning 50 with the dielectric film 44 or the analog of a softness.Reverse potential can provide by the reverse electrode in the container that influences the plasma zone on the inner surface, and internal electrode has dielectric coating to avoid partial discharge.Internal electrode can be a solid probe, itself also can be that shape is on all four, has therefore guaranteed local parallel being kept between the electromotive force surface, has improved the condition of glow discharge plasma thus.Alternatively, it also can be a liquid electrode 51, and it has inlet 3c and one an outlet 4c, is used for introducing and remove conducting liquid by valve (not showing) and enters and flow out electrode 51.Under these circumstances, plasma zone 8 keeps its gap by using escapement 7a.(such as bottle or container) be opened or partly be closed to the article that are used for handling can in manifold.Closing under the situation of object in part, the on all four surface of the shape of an inside can produce by the balloon of an expansion, and balloon is that the gas by conducting liquid or a kind of introducing comes supercharging, and the surface of conducting liquid is hunted down around it.Such notion also can be used bottle or similar containers are being carried out in the plasma treatment, wherein bottle is partially immersed in the supporting electrolyte, perhaps be introduced in a kind of rubber-like dielectric mould, its be used for increase pressure with keep shape to conform to the exterior contour of bottle surface, come together to keep conforming to inner surface configuration with the expansion of an interior dielectric balloon simultaneously, the polarity of inside and outside liquid electrode is opposite.
As an atmospheric pressure plasma assembly 100 is provided in the described another embodiment of the invention of Fig. 9 a, form by an atmospheric pressure plasma generating unit 107, it has one and is columniform main body 117 substantially, it has the basic circular cross section that is, comprise the inlet (not showing) that an introducing acts on the processing gas of plasma, one produces ultrasonic nozzle (not having to show) and a pair of electrode 104 that comprises liquid that vaporific liquid and/or solid-state coating forms material, and these two electrodes all comprise conducting liquid in the shell of being made by dielectric material 103.Described electrode keeps one section predetermined distance by pair of electrodes spacer assembly 105.Electrode 103,104 is protruding from atmospheric pressure plasma generating unit 107.Gaps between electrodes forms a plasma zone 106.Atmospheric pressure plasma generating unit 107 can be designed so that unique being used to handled gas and introduced the outlet of the reaction reagent of unit 107 can be by by the plasma zone 106 between the electrode 103,104 of dielectric coating.This atmospheric pressure plasma generating unit 107 is fixed, and in any form transmission method of substrate 101 (not showing) assembly below by, transmission method can change to be fit to processed substrate, considers that wherein transport tape does not form the part of assembly.
Similar with atmospheric pressure generating unit 107, extractor unit 108 normally has substantially and is the cylinder of circular cross section, by making such as polypropylene or the such dielectric substance of PVC.Unit 107 and 108 is concentric, and extractor unit 108 has bigger diameter.Extractor unit 108 comprises edge 105, and it surrounds electrode 103,104 and form raceway groove 109 between them, and remaining processing gas, reactant and byproduct are extracted by raceway groove.As the pedestal of electrode 103,104, it is equidistant with substrate 1 that the tip designs at edge 116 becomes, but can be nearer.Extractor 108 also comprises an outlet to pump (not having to show), and it is used for extracting residual process gas, reaction reagent and byproduct from assembly.The outside offers the air that the restriction bar 102 at edge 116 is used for minimizing from atmosphere and enters extraction unit 109.The restriction bar can be the edge strip of paper used for sealing of contact substrate 101; or rely on processed substrate; they also can be antistatic that is used in the plastic film industry, eliminate static and spray elimination dust granule or anlistatig carbon brush with air alternatively from substrate surface with high electrostatic potential.
Electrode of the present invention can be used at electrode 103, form a narrow plasma zone in 104 between the adjacent conductive liquid channel, it generates in the following manner: (Fig. 9 a) to reduce dielectric surface to the low height of parallel flat assembly, perhaps simpler, and non-conductive dielectric tube equidistant isolation placed side by side from two forms opposite electrode pair and reduces their length (Fig. 9 b).Plasma gas between this pipe in the zone removes by extractor unit 108.This no metal electrode design causes crossing over any surface roughness of narrow gap micro discharge by elimination and an electric field more uniformly is provided between electrode.
Another embodiment of the invention (Figure 10) keeps conducting liquid by resilient pipe, and these pipes can combine in to 130,132 in the opposite voltage parallel connection, and form as shown in figure 10 can be agley the fixing flat board of contour surface.Above electric field between the alternating voltage pipe has been expanded and below flat board, therefore can be in these zones in the suitable processing gas componant known to the industrial quarters plasma zone of formation.So the flat board that forms can wind up along the contour of object surface.This is for the surface, processing section or handle those large-sized objects that are not easy to pass conventional atmospheric plasma treatment system and will be particularly useful.Another kind of optionally scheme is that opposite voltage pipe tangle up is right as a spiral winding, and it can form the pipe of a wide diameter.A plasma zone can form on the outer surface of this winding pipe, but more usefully forms on inner surface, satisfies the processing to light-wall pipe or bottle.
Example
With reference to Figure 11 and Figure 12 and table 1, the use example following elaboration of electrode of the present invention in an atmospheric pressure glow discharge systems:
It is that the assembly of describing among the applicant's that how to use the to comprise electrode of the present invention patent application WO 03/086031 co-pending carries out plasma treatment that Figure 11 has described a rubber-like substrate.Each electrode pair is the type of describing in Fig. 5 b as before, 1.2 meters wide 1 meter long, the saline solution (weight is 2% sodium chloride) near 24 millimeters thickness (d) is housed between inwall 67 and rear wall 6a (Fig. 5 b).Form with guide roller 170,171 and 172 provides a device that makes the assembly transmission by substrate.Processing 175, one the assembly lids 176 in gas access and a ultrasonic nozzle 174 of being used for fog-like liquid is introduced plasma zone 160 are provided.Handle gas access 175 and also may be arranged in assembly lid 176, to replace side as shown in figure 11.
In use, the rubber-like substrate is transferred to guide roller 170 tops, and above guide roller 170, therefore is directed by the plasma zone 125 between salt water electrode 120a and 126a.Plasma in plasma zone 125 is the helium plasma of cleaning, that is to say do not have reactant directly to enter plasma zone 125.Helium is 175 to enter system by entering the mouth.Lid 176 is placed on the system top to prevent that helium from leaking, because its lta.When leaving plasma zone 125, by the substrate of plasma cleaning by guide roller 171 and directly be passed down through plasma zone 160, between electrode 126b and the 120b and above guide roller 172, further handle by other unit of the same type then.Yet plasma zone 160 is that substrate produces a coating by introducing reacting precursor.This reacting precursor can comprise gas, liquid and/or solid cladding manufactured materials, but preferably introduces the coating manufactured materials of liquid and solid with the liquid or solid form by sprayer 174.An important fact is that coated reactant is liquid or solid, described vaporific liquid or solid pass plasma zone 160 and keep isolating with plasma zone 125 under action of gravity, therefore do not have coating and exist in plasma zone 125.Substrate that then will coating is by plasma zone 160, and transmission is collected subsequently or for example further handles with other plasma by guide roller 172 after coating.
The fog-like liquid precursor is introduced plasma zone 160 from nozzle 174, nozzle can produce vaporific precursor droplet under the situation of liquid, precursor droplet and plasma and substrate interact and produce coating, and its chemical constitution and precursor have directly and concern closely.Nozzle 174 is used ultrasonic activation, and flow of liquid is controlled with matter stream controller (MFCs).By apply one big pass through adjacent electrode between the electromotive force in space produce plasma.Provide a high pressure from a variable frequency generator that has high-tension transformer at output to electrode.From the maximum power of this generator is 10 kilowatts, and maximum voltage is 4 kilovolts of RMS (root mean square) and the frequency in the 10-100 kilohertz range.The electrical measured value that writes down in processing procedure obtains from generator itself, and is obtained by the voltage and current probe on the installing electrodes.Each electrode has 1.2 meters wide, and 1 meter long.Use the pressure-air cutter that is connected with cooling fin to come the rear wall of cooling electrode, guarantee that electrode temperature remains on below 80 degrees centigrade.
Glow-discharge characteristic
The dielectric layer discharge exists with thread or glow discharge form.Cause the local gas ionization and when becoming localization and in very short time (approximately continues the 2-5 nano-seconds) at interval, causing the current discharge of high concentration, thread discharge takes place when the electric field gesture of part or charge density are inhomogeneous.The discharge of these types is because the local violent characteristic of thread discharge can produce coating heterogeneous or destruction substrate.Having guaranteed with the composition of suitable electrode geometry, gas and power/frequency condition that the discharge of atmospheric pressure dielectric layer can be crossed under the glow discharge pattern that the width of electrode evenly forms at plasma according to the selection of electrode of the present invention takes place.This can cause continuing 2-10 nanosecond than the thread discharge current discharge of longer time, and it causes the formation of much even coating.
In this example, immediately following being to follow the tracks of and measure after the current discharge in the atmospheric pressure assembly.The light that emits from plasma receives with high-speed photodiode.Figure 12 has shown under the following condition output with the photodiode of plasma generation: 1000 watts, and 10 liters of helium of per minute.The output result has shown the current peak between 1 to 3 microsecond, and it has clearly illustrated that the glow discharge pattern that is operated in.
Waterproof coating
Aforesaid device is used in combination with tetramethyl-ring tetrasiloxane, and when by plasma zone 160, it is deposited on a polyethylene terephthalate (PET) the non-woven lining basal surface.This PET was waterproof extremely before handling.
Anti-water-responsive is to utilize the different densities of isopropyl acetone (IPA) in water to measure with detecting probe method in the subsequent treatment.With the whole precursor flow rate of about 400-1000 mul/min, power between 2 to 10 meters/minute of the substrate speed, obtains 5 grades anti-water-responsive between 5 to 9 kilowatts, to the physical property of substrate without any adverse influence.
Table 1. is used to measure the grade of the anti-water-responsive of PET substrate
| Probe liquid | Classification of waterproof |
| Water | 1 |
| 98% water/2 |
2 |
| 95% water/5 |
3 |
| 90% water/10 |
4 |
| 80% water/20 |
5 |
Claims (18)
1. assembly (1) that produces the discharge of plasma glow discharge and/or dielectric layer, comprise at least one pair of electrode that equidistantly separates basically (2), handle gas and allow gaseous state when introducing, under the situation that liquid state and/or solid precursor are passed through, spacing between the electrode is suitable for forming a plasma zone (8), it is characterized in that, at least one electrode in the electrode (2) comprises a shell (20), described shell has an inwall (5) and an outer wall (6), wherein inwall (5) is to be formed by a kind of non-porous dielectric substance, and shell (20) keeps at least a basic nonmetallic electric conducting material that is basically.
2. according to the assembly of claim 1, it is characterized in that, provide many electrode (2).
3. according to the assembly of claim 1 or 2, it is characterized in that, comprise a kind of polar solvent for nonmetallic electric conducting material substantially.
4. according to the assembly of claim 3, it is characterized in that described polar solvent is water, alcohol and/or ethylene glycol.
5. according to the assembly of claim 3, it is characterized in that described non-metallic conducting material is a kind of salting liquid.
6. according to the assembly of claim 1 or 2, it is characterized in that, describedly select from conducting polymer paste and electroconductive binder for nonmetallic electric conducting material at least substantially.
7. according to the assembly of claim 6, it is characterized in that described conducting polymer paste and electroconductive binder are curable.
8. according to the assembly of claim 1 or 2, it is characterized in that, each shell (20) has an inlet (3) or has an inlet (3) and outlet (4), makes non-metallic conducting material be introduced into and to remove by described inlet (3) and/or outlet (4) from electrode (2).
9. according to the assembly of claim 1 or 2, it is characterized in that described outer wall (6) is a fin.
10. according to the assembly of claim 1 or 2, it is characterized in that the functional dimension of each electrode changes by introducing and removing described non-metallic conducting material.
11. assembly according to Claim 8 is characterized in that, one or more cooling coil (25) or cooling fin (30) be fixed on outer wall (6,6a) on, with cooling conducting liquid and assembly (1).
12. the assembly according to claim 1 or 2 is characterized in that, electrode (2) is the shape of concentric pipeline (32,34).
13. assembly according to claim 1 or 2, it is characterized in that, each electrode (2) is cuboidal, comprise a shell, described shell has one and is applicable to that admittance is the chamber of nonmetallic electric conducting material (11b) at least substantially, and described electrode (2) is making away from a single part that is suitable as the flat board (6a) of fin by dielectric substance (67).
14. assembly according to claim 1 or 2, comprise first and second couples of parallel plane electrode (120a that separate, 126a and 126b, 120b), interval between every pair of electrode in the first and second pairs of electrodes forms first and second plasma zones (125,160), it is characterized in that, described assembly comprises that also a continuous substrate that transmits makes it pass described first and second plasma zones (125,160) device, and a nozzle (174) that is applicable to that guiding gas or vaporific liquid and/or solid cladding manufacturing materials enter the described first and second plasma zones.
15. the assembly according to claim 1 or 2 is characterized in that, has controlled the electric capacity and the resistance of electrode in the variation of the kind of conducting liquid intermediate ion material and concentration.
16. use to come powder and granular materials are handled according to the assembly in claim 1 or 2.
17. a pair of electrode that equidistantly separates basically, it is characterized in that, at least one electrode in the electrode (2) comprises a shell (20), described shell has an inwall (5) and outer wall (6), wherein inwall (5) is formed by non-porous dielectric substance, and described shell (20) has kept a kind of nonmetallic electric conducting material that is essentially basically.
18. utilize the method for coming substrate is carried out plasma treatment according to the assembly of generation plasma glow discharge described in claim 1 or 2 and/or dielectric layer discharge, described method comprises the plasma zone (8) that substrate is formed by the plasma that influences between the electrode (2).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0302265A GB0302265D0 (en) | 2003-01-31 | 2003-01-31 | Plasma generating electrode assembly |
| GB0302265.4 | 2003-01-31 | ||
| GB0304094.6 | 2003-02-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1745607A CN1745607A (en) | 2006-03-08 |
| CN100518430C true CN100518430C (en) | 2009-07-22 |
Family
ID=9952209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800031038A Expired - Fee Related CN100518430C (en) | 2003-01-31 | 2004-01-28 | Plasma generating electrode assembly |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100518430C (en) |
| GB (1) | GB0302265D0 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20070350A1 (en) * | 2007-02-23 | 2008-08-24 | Univ Milano Bicocca | ATMOSPHERIC PLASMA WASHING METHOD FOR THE TREATMENT OF MATERIALS |
| PL2564412T3 (en) * | 2010-04-30 | 2018-08-31 | Agc Glass Europe | Electrode for dbd plasma process |
| GB2501933A (en) * | 2012-05-09 | 2013-11-13 | Linde Ag | device for providing a flow of non-thermal plasma |
| CN103255467A (en) * | 2012-10-25 | 2013-08-21 | 北京太禹天工科技有限公司 | Novel material surface modification method and apparatus |
| JP6584787B2 (en) * | 2015-02-13 | 2019-10-02 | 株式会社日立ハイテクノロジーズ | Plasma ion source and charged particle beam device |
| CN105101603B (en) * | 2015-08-04 | 2018-06-08 | 昆山禾信质谱技术有限公司 | A kind of dielectric barrier discharge plasma fluidic device |
| CN105944523B (en) * | 2016-06-08 | 2022-06-21 | 上海盛剑环境系统科技股份有限公司 | Plasma gas waste gas treatment device |
| EP3478327A4 (en) * | 2016-06-30 | 2020-04-01 | 3M Innovative Properties Company | Plasma sterilization system and methods |
| WO2020124264A1 (en) * | 2018-12-20 | 2020-06-25 | Mécanique Analytique Inc. | Electrode assemblies for plasma discharge devices |
| CN109772248A (en) * | 2019-03-25 | 2019-05-21 | 安吉润风空气净化科技有限公司 | A kind of dielectric barrier plasma discharge reactor with refrigerating function |
| EP3748745A1 (en) * | 2019-06-03 | 2020-12-09 | Total Se | Eco-electrode, device storing electrical energy and process for preparation thereof |
| CN113731325B (en) * | 2021-09-03 | 2022-05-13 | 重庆大学 | Device for synthesizing nitrogen oxide by air plasma |
| CN115475498A (en) * | 2022-08-25 | 2022-12-16 | 大连海事大学 | Waste heat recovery system of ship exhaust gas plasma removing device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899685A (en) * | 1972-03-23 | 1975-08-12 | Electricity Council | Ozonisers |
| CN1060117A (en) * | 1990-09-27 | 1992-04-08 | 机械电子工业部第四十九研究所 | The isolation technology of metallic surface dielectric film |
| RU2159520C1 (en) * | 1999-04-30 | 2000-11-20 | Камский политехнический институт | Plasma generator which has liquid electrodes |
| CN1379144A (en) * | 2001-04-10 | 2002-11-13 | 中国科学院化学研究所 | Antishrinking method for wool fibre products |
-
2003
- 2003-01-31 GB GB0302265A patent/GB0302265D0/en not_active Ceased
-
2004
- 2004-01-28 CN CNB2004800031038A patent/CN100518430C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899685A (en) * | 1972-03-23 | 1975-08-12 | Electricity Council | Ozonisers |
| CN1060117A (en) * | 1990-09-27 | 1992-04-08 | 机械电子工业部第四十九研究所 | The isolation technology of metallic surface dielectric film |
| RU2159520C1 (en) * | 1999-04-30 | 2000-11-20 | Камский политехнический институт | Plasma generator which has liquid electrodes |
| CN1379144A (en) * | 2001-04-10 | 2002-11-13 | 中国科学院化学研究所 | Antishrinking method for wool fibre products |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1745607A (en) | 2006-03-08 |
| GB0302265D0 (en) | 2003-03-05 |
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