CN100437884C - An atmospheric pressure plasma assembly - Google Patents
An atmospheric pressure plasma assembly Download PDFInfo
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- CN100437884C CN100437884C CNB038081369A CN03808136A CN100437884C CN 100437884 C CN100437884 C CN 100437884C CN B038081369 A CNB038081369 A CN B038081369A CN 03808136 A CN03808136 A CN 03808136A CN 100437884 C CN100437884 C CN 100437884C
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Abstract
A method of forming a coating on a powdered substrate, which method comprises introducing an atomized liquid and/or solid coating forming material and separately transporting a powdered substrate to be coated into an atmospheric plasma discharge and/or an ionized gas stream resulting therefrom, and exposing the powdered substrate to the atomized liquid and/or solid coating forming material.
Description
Technical field
The method that the present invention relates to atmospheric pressure plasma assembly and handle a substrate with described assembly.
Background technology
When material was continued to energize, its temperature raise and typically is transformed into liquid from solid, becomes gas then.Be continuously applied energy and cause system to experience further state variation, wherein the neutral atom of gas or molecule are smashed by energetic encounter, generate electronegative electronics, plus or minus ion and other material.The collective behavior that the mixture of this charge species demonstrates is called " plasma ", i.e. the 4th attitude of material.Because their electric charge, plasma can be subjected to the very big influence of external electromagnetic field, makes their easy control.In addition, can allow other state that they can treated substance in they high, this to use liquid or gas treatment be impossible or very difficult.
Term " plasma " comprises the system of huge range, and its density and temperature have the variation of many orders of magnitude.Some plasmas are very warm, their all microscopic species (ion, electronics, etc.) approximate thermal equilibrium, the energy that is input in the system distributes widely by the collision of atom/molecule level.Yet, other plasma, the less relatively generation of (for example 100Pa) collision especially under low pressure has component under very wide different temperatures, be called " thermal nonequilibrium " plasma.In these non-thermal plasmas, free electron heat very, temperature are several thousand thermodynamic temperatures (K) and neutral and ionic species remains cold.Because free electron almost has negative mass, the enthalpy of whole system is lower, and plasma is operated in and approaches room temperature, allow like this to handle to temperature-sensitive material, and for example plastics or polymer, and it is not added that damaging heat loads.By energetic encounter, hot electron causes abundant free radical and excites substance source that they have the high chemical potential energy that is suitable for deep chemistry and physical activity.This just low-temperature working adds that highly active combination makes non-thermal plasmas extremely important technically, and be a strong instrument that is used to make with material processed, be suitable for handling needs are very high when not having plasma the temperature or the occasion of harmful and aggressive chemicals.
For the commercial Application of plasma technique, one easily method be electromagnetic power to be coupled into handle in the gas, it can be gas and steam mixture, pending workpieces/samples immerses therein or passes through.Gas is ionized and becomes plasma, generates chemical free radical, ultraviolet ray and ion with the sample surfaces reaction.Handle gas component by selection correctly, the driving power frequency, power coupled mode pressure and other Control Parameter, plasma treatment can be designed to satisfy the required concrete application of producer.
Because huge chemistry and the heat rating of plasma, they are suitable for many technology and use.Nonthermal plasma is especially effective to surface activation, surface clean, material etching and overlay coating.
The surface activation of polymeric material is a kind of industrial plasma technology of the extensive use of at first being used by auto industry.Like this, for example the polyolefin that receives an acclaim owing to the recirculation purposes as polyethylene and polypropylene, is difficult to coating or bonding thereby have nonpolar surface.Yet, cause forming the surface polarity base with oxygen plasma treatment, cause high wettability, thereby have metallic paint., adhesive or other coating has excellent covering and adherence.Therefore, in the manufacturing of Vehicular instrument panel, instrument board, bumper bar etc., and in the assembling of the assembly in toy and similar industrial, it is more and more important that the plasma surface engineering is just becoming.In to the printing of the assembly of all geometries of polymer, plastics, pottery/inorganic, metal and other material, japanning, bonding, lamination and conventional coating, can obtain many other application.
The infiltration of environmental legislation and the increase of intensity in the world wide are used solvent and other wet chemistry goods to industrial reducing or eliminating in manufacture process, especially concerning assembly/surface clean, just producing immense pressure.Especially, based on the degreasing operation of CFC in large quantities by etc. the gas ions cleaning technique of use oxygen, air and other non-toxic gas work replace.In conjunction with pre-cleaning operation and plasma application based on water, allow to clean even the unusual assembly of severe contamination, the surface that obtains is better than the surface that conventional method obtains.Any organic surface contamination is removed rapidly by room-temperature plasma, change into can safety dumping gas CO
2And water.
Plasma can also be realized etching body material, for example is used for removing therefrom undesired material.Like this, for example a kind of plasma based on oxygen is with etch polymers, and this is a kind of processing that is applied to make wiring board etc.Different materials, for example metal, pottery and inorganic matter come etching by careful selection initial gas and attention plasma chemistry.Little structure to nanometer critical dimension is now by plasma etching technology and made.
The plasma technique that occurs rapidly and become main flow industry is plasma coating/thin film deposition.Typically, realize that the high energy polymerization is by plasma application is arrived monomer gas and steam.Like this, can form the film of densification, firm joint and three-dimensional combination, it has thermally-stabilised, chemical anticorrosive, mechanical firm.Such film can be deposited on guarantor's type in addition complex surface on, and be in and can guarantee under the heat load temperature low on the substrate.So plasma is used to apply accurate and thermo-responsive and robust metallic is very desirable.Plasma coating even in thin layer, also do not have micropore.The optical characteristics that usually can customize coating is color for example, and plasma coating even very good with the non-polar material adhesion, for example polyethylene, and steel (for example anticorrosive film on the solid metal reflector), pottery, semiconductor, textile etc.
In these all processing, Plasma Engineering has been made the surface effect of the hope application of customization, has perhaps made the product that influences material monolithic in no instance.Plasma treatment provides general and a powerful instrument for the producer like this, permission is for overall technology and nature of business and select material, freedom is provided simultaneously, make it possible to the independent design surface to satisfy diverse needs, and functional, the performance that has given greatly that product strengthens, life-span and quality, offering the important added value of user to properties of product.
These character have promoted the processing of industrial employing based on plasma consumingly, guided this promotion from nineteen sixty generation, by microelectronics group the low pressure glow discharge plasma has been developed into and be used for supertech and the high capital cost engineering tools that semiconductor, metal and dielectric are handled.The low pressure glow discharge type plasma same since the 1980's has been penetrated into other industrial department day by day, provide processing with appropriate more cost, for example be used to increase the polymer surfaces activation of adhesion/bond strength, high-quality degreasing/cleaning and depositing high-quality coating.Like this, accepted plasma technique basically.Glow discharge can obtain under vacuum and atmospheric pressure.Under the Atomospheric pressure glow discharge situation, for example helium and argon gas are as diluent for gas, and a high frequency (for example greater than 1kHz) power source is used under atmospheric pressure producing uniform glow discharge, according to Penning ionization mechanism, (for example see Kanazawa etc., J.Phys.D:Appl.Phys.1988
21, 838, Okazaki etc., Proc.Jpn.Symp.PlasmaChem.1989,
2, 95, Kanazawa etc., Nuclear Instr μ ments and Methods inPhysical Research 1989, B37/38,842, and Yokoyama etc., J.Phys.D:Appl.Phys.1990,
23, 374).
Yet the using plasma technology has been confined to the main constraint of most of industrial plasma systems, that is, they need under low pressure be worked.Partial vacuum work means closed perimeter, and sealed reaction system only provides off-line, the discrete work package of batch processing.Output is lower or medium and need vacuum to increase capital and operating cost.
Yet atmospheric pressure plasma provides opening port or perimeter systems for industry, provides by work package/nethike embrane to enter and withdraw from ion plasma freely, therefore can the big small size nethike embrane of online, continuous processing or transmission carry discrete nethike embrane.The reinforcement of the high flow of material that is obtained by high-pressure work, output is very high.Many industrial departments, for example textile, packing, paper, medicine, automobile, aviation etc. almost completely depend on continuous on-line and handle, and make that opening port/circumferential arrangement plasma provides new industrial treatment ability under the atmospheric pressure.
Corona discharge and flame (also being a kind of plasma) treatment system provides the atmospheric plasma treatment performance of limited form about 30 years for industry.Yet although they have high manufacturability, these systems fail to penetrate into market, perhaps fail to reach picture low pressure, electrolytic treatments plasma type in industrial occupied degree.Reason is that corona discharge/flame system has significant limitations.They are operated in the surrounding air, provide single surface activation to handle, and many materials are not almost had effect and most of materials are only had faint effect.It usually is uneven handling, and Corona discharge Treatment and thick nethike embrane or 3D nethike embrane are incompatible, and flame treatment and thermo-responsive substrate are incompatible.Be perfectly clear, atmospheric pressure plasma techniques must enter in the darker atmospheric pressure plasma field, to develop the AS that satisfies industrial needs.
The atmospheric pressure plasma deposit has obtained major progress.On stabilisation of atmospheric pressure glow discharges, carried out suitable work, for example the description among J.Phys.D:Appl.Phys.26 (1993) 889-892 such as Okazaki.More, US Patent specification No.5414324 has described under atmospheric pressure, at a pair of interval 5cm, between the metallic plate electrode that insulate on the electricity, and the excitation of the 1-100kHz radio frequency (RF) of 1-5kV root mean square (rms) current potential generates the stable state glow discharge plasma down.The U.S. 5414324 has also discussed the problem of battery lead plate and has stoped the needs of electrical breakdown at the electrode tips place, and has described a water-cooling system of implementing by the fluid flow conduit that is bonded on the electrode, and water does not wherein directly contact with any electrode surface.
In US Patent specification No.5185132, an atmospheric pressure plasma reaction method has been described, wherein plate electrode is used for arranged perpendicular.Yet they only are used in the arranged perpendicular with the preparation plasma, and plasma is directly on the horizontal plane under the electrode that injects to vertical arrangement between two pole plates then.
Among the common pending application WO02/28548 of applicant that after the application's priority date, announces, an atmospheric pressure plasma glow discharge device is provided, has been designed to liquid or solid by the plasma treatment substrate in the introducing plasma flows such as atomizer.
In JP 07-0062546 and US 6086710, plasma processing apparatus is provided, the method for several alternative removal plasmas through processing gas, gaseous reactant and accessory substance etc. later described.
In EP 0431951, provide an atmospheric pressure plasma device, the mass treatment substrate that uses a kind of rare gas of plasma treatment/reaction gas mixtures to generate.Plate dielectric electrode to small part and place side by side mutually, their perpendicular alignmnets make that substrate passes through perpendicular to substrate under interelectrode slit.This device needs a complete surface treatment unit, and the width by this surface treatment unit can limit the width of any pending substrate effectively, and this makes system very heavy.
In the WO02/40742 that the application's priority was announced after the date, a method and apparatus of atmospheric pressure plasma using gases processing substrate has been discussed.JP 2002-57440 has described an atmospheric plasma treatment method of using gases treatment circuit plate, the surface treatment of using pulse voltage to come the intensifier circuit plate.Do not discuss in these documents and as disclosed among the present invention, introduce in a kind of liquid or solid coating to one equipment.
Summary of the invention
The present inventor has confirmed a device that overcomes many problems of existing equipment now, in the present invention promptly, does not need a complete surface treatment unit, and plasma treatment no longer is only limited to using gases processing substrate.Many other improvement will be confirmed in the following description.
In the first embodiment of the present invention, an atmospheric pressure plasma formation component is provided, an atmospheric pressure plasma generator that contains a fuselage comprises a reactant introducing device, handle gas introducing apparatus for one, electrode arrangement arranged side by side with one or more suitable plasmas generations, each electrode arrangement comprises the electrode of at least one part dielectric coated, described device is suitable for making a kind ofly introduces processing gas in the described device and the unique method of solid reactants discharging is by the plasma zone between the former electrodes, described device is suitable for moving relative to a substrate, described substrate basically near former electrodes from described unit end points farthest, it is characterized in that the reactant introducing device is an atomizer, be used for forming the form atomizing reactant of material with liquid and/or solid cladding.
Atmospheric pressure plasma generation unit fuselage can be any suitable geometry, but preferably elongate, and have square, circle, rectangle or elliptic cross-section basically, wherein optimum is circular.Preferably, fuselage is made by dielectric material, and as distribution process gas with reactant enters and through a kind of method of the plasma slab between the parallel pole of electrode arrangement.Atmospheric pressure plasma generation device fuselage can be the length of any needs, although preferred length is not less than 0.5 meter.Alternatively, fuselage can be for variable-length (depending on the width of the substrate of handling) but 20 meters of preferred maximum length, and more excellent length is 10 meters, and optimum maximum length is 5 meters.Therefore wherein this length is approximately the length of each electrode, also is the length of the plasma slab that produces between this is to the adjacent parallel electrode.In the time will handling size greater than the substrate of device fuselage, this can take by single treatment part substrate perhaps to use a plurality of assemblies by providing up to all processed method of entire substrate, is once handling entire substrate in the running.Under the situation of back, can preferably have a plurality of assemblies and place, to guarantee to handle entire substrate with offset row.
The reactant introducing device preferably includes an atomizer or sprayer or the type described etc. in the common pending application application of applicant WO02/28548, the content of this patent is quoted at this.The material of fog-like liquid and/or solid cladding formation simultaneously can use any suitable atomizer or aerosol form to atomize, and a preferred embodiment is a ultrasonic nozzle.
Atomizer preferably produces film formation material and drips, big or small 10-100 μ m, preferred 10-50 μ m.Be used for suitable atomisers of the present invention and comprise Sono-Tek Corporation, Milton, New York, or German Lechler GmbH, the ultrasonic nozzle of Metzingen from the U.S..Equipment of the present invention can comprise a plurality of atomizers, particular utility can be arranged, for example, this equipment can be used for forming co-polymer membrane by two kinds of different film formation materials on a substrate, wherein each monomer cannot not be fused or homophase not, for example first is that solid phase and second are gas phase or liquid phase.
Can use any suitable method will handle gas introduces in the assembly.Any suitable transfer approach may be used to be transported to plasma slab between adjacent electrode with handling gas and reactant.Under the situation of single processing gas introducing apparatus of utilization and single reaction agent introducing device, electrode can separate by the method for an electrode pad.Electrode pad makes along providing equal flow rates to arrive plasma slab on the plasma section length as a kind of variable slit process gas/reactive agent distributor.As selecting the electrode pad can a kind of porous pole plate etc., along providing equal flow rates to arrive plasma slab on the plasma section length.The kind electrode liner can be a kind of slit that has wedge shape section simply, makes that slit is the wideest, and the solstics is away from processing gas/reactive agent introducing device, and the narrowest point is near handling the gas/reactive agent introducing device.As selection, can provide a processing gas/reactive agent introducing device array that is suitable for along fuselage length.Can use strut if necessary in each case, with along keeping a preset distance between the electrode of every bit on the length of plasma slab.
By ullrasonic spraying mouth introduce atomized liquid will need a frequency produce cable and can so that be suitable for atomized liquid directly introduce (i.e. directly injection) or by carrier gas for example air enter nozzle.For effective plasma treatment, guarantee that the even distribution of spraying is very important.This can realize by suitable method, yet, be preferably as follows option:
I. handle gas and introduce, make when air-flow is redirected along the main direction of shaft length overdraught, generate turbulent flow near the outlet of ullrasonic spraying mouth perpendicular to fuselage axis.This is suitable for higher flow velocity most, and this can see when using low-cost processes gas such as air and nitrogen.
Ii. introduce turbulent flow by in the flow of process air field of ultrasonic spray nozzle tip upstream, placing the throttling dish.Turbulent flow will exist in the dish diameter of 6 in disk downstream, therefore guarantee the uniformity (be approximately based on the fuselage that contains circular cross-section and dish diameter fuselage half) of liquid spray.
Iii. as selection, the ullrasonic spraying mouth can be installed in the afterbody of main pipe, makes it keep flat along axle.On this position, preferred carrier gas side enters.
Alternatively, can additionally use a gaseous reactant, handling gas introducing apparatus in this case can be the same or different with the gaseous reactant introducing device.When gaseous reactant introducing device of extra needs, handle gas introducing apparatus and can apply to introduce the place of handling gas and needing gaseous reactant.
Be suitable for producing each of at least one many electrode arrangement side by side of plasma, contain the electrode that one or more is the part dielectric coated at least.To the preferred two kinds of special electrode arrangement of the present invention, to non-conductive substrate, and comprise one or more to being in a predetermined distance of separation, and to the electrode of small part dielectric plated film, especially preferred first kind of arrangement.
Second kind of particularly preferred arrangement be in particular for conductive substrates, and comprise one three electrode system arranged side by side, and a central electrode is the part dielectric coated at least.Two other electrode is positioned at one of central electrode on one side with predetermined distance of separation, and two all are not coated with dielectric and ground connection all basically, make that in use they are as the short circuit between the conductive substrates that prevents central electrode and processing.Preferably, central electrode is suitable for having adjustable distance between electrode and substrate surface.Preferably, central electrode is by dielectric enclosed, and more preferably, and dielectric is thicker in the electrode tips of the most close substrate surface.
Be appreciated that term conduction and non-conductive referring to relate in particular to conduction (metal) and non-conductive (plastics) substrate.
Each electrode can be made into suitable form, for example, only gives an example, and the pole plate of a metal or grid electrode are made by any suitable metal such as stainless steel, copper or brass, but is preferably made by stainless steel and have a suitable geometry.Preferably, electrode is made by the bar that stainless steel elongates.Preferably, suitable dielectric at least two limits of each electrode and the central electrode in three electrode arrangement cover in two electrode arrangement; Optimally, electrode is sealed by a kind of dielectric substance.Electrode is preferably protruding from fuselage, and purpose is the minimum range of guaranteeing between each electrode tip and the substrate surface.
Dielectric substance is used for covering an electrode to small part according to the present invention, can be any suitable dielectric substance, and example includes, but are not limited to, Merlon, polyethylene, glass, glass laminate, epoxy filling glass laminate, pottery etc.Metal electrode can be by adhesive bonds to dielectric substance, and perhaps some heating is bonded to dielectric substance with the welding electrode metal.Simply, electrode can be sealed in the dielectric substance.
The generation of stable state glow discharge plasma under atmospheric pressure preferably obtains between the parallel pole that equals 5cm is at interval arranged, and depending on is the processing gas of usefulness.Electrode is the RF excited of 1-100kV by root mean square (rms) electromotive force, preferably between the 4-30keV under the 1-100kHz, preferably under 15-40kHz.The voltage typical case who forms plasma is at 2.5-30kV, and optimum 2.5-10kV selects and interelectrode plasma region size yet actual value will depend on chemistry/gas.
The applicant finds that the plasma of electrode arrangement generation as described above extends beyond the reflecting surface of electrode at least between 0.5-2.0cm.Therefore, for example, if each electrode limit vis-a-vis is a rectangle, be of a size of 5cm * 10cm, the plasma slab that uses such electrode to produce is 6cm * 11cm with minimum, and as noted, if the beeline between electrode tips and substrate surface is not more than about 2cm, substrate surface can be described as in plasma slab rather than its downstream (as the description among the EP0431951).When electrode package in dielectric, for the reason of back, preferred dielectric sleeve thickness is not more than 2mm, at least about electrode tips near substrate surface.
This assembly preferably is suitable for moving with respect to a substrate, described substrate basically near former electrodes from described unit end points farthest, make the atmospheric plasma treatment substrate surface realize in the downstream of described electrode.Relatively moving of assembly and substrate can be got the form of a fixation kit and a removable substrate, and by a roller system mode, substrate is a reel-to-reel net or a form such as conveyer belt.As selection, relatively moving may be thought of as the form that has a stationary substrate and a movable-component of getting.The layout of back can the most suitable especially big seat shape substrate, for example steel and aluminium sheet, and preferably by computer operation control, the motion of its predefined components is to guarantee that entire substrate can uniform treatment in the motion of assembly in this case.
Although the preferred electrode vertical arrangement, and substrate moves along horizontal plane.This is not an essence, and this assembly can be suitable for handling the substrate surface of any needs, for example the body of an aircraft or wing.Be to be understood that the vertical meaning of term is to consist essentially of vertically, and should only not to be confined to electrode position and level be 90 to spend.
When needs, can add in system that additional assemblies is to form the further continuous plasma tagma that will pass through by its substrate.Additional unit can be positioned at the front or the back of above-described assembly, makes substrate can experience pre-treatment or post-processing step.The processing that applies in the plasma slab that is formed by additional assemblies can be identical or different with the processing carried out in the above-described assembly.
Can work under any suitable temperature according to assembly of the present invention simultaneously, will preferably work under room temperature (20 ℃) and the temperature between 70 ℃, the typical case uses 30-50 ℃ temperature province.
Preferably, additionally comprise an extractor unit according to assembly of the present invention.This extractor unit preferably includes an extractor body, gets the guard shield form, is suitable for plasma and outside atmosphere are isolated when using.Extractor unit further comprises useless gas, reactant and an accessory substance removal device handled, and they enter extractor unit after through plasma slab and electrode low side and substrate surface gap.Useless gas, reactant and the accessory substance removal device handled is arranged in extractor body, pump etc. preferably, or only be an extraction tube, processing gas, reactant are removed to collect then from extractor unit with accessory substance and are used to separate, and handle and/or reuse.Especially preferably recycle gas, its typical case comprises for example essential part of helium or argon gas of one or more valuable rare gas.As selection, a kind of gas is typically for example nitrogen of a kind of inert gas, can be incorporated into extractor unit, be used for direct process gas, reactant and accessory substance and wait until useless gas, reactant and the accessory substance removal device handled, stop it to enter plasma slab physically by flange or a selectable suitable geometry simultaneously.
Preferably, extractor body is shaped, and makes to form an open channel around plasma generation assembly fuselage, make in use, the edge of extractor body is near substrate surface, and bonded substrate forms a chamber around electrode basically, thereby forms the sealing to atmosphere basically.
Extractor body can be any suitable cross-section, but preferred basically with the identical cross sectional shape of cross sectional shape of atmospheric pressure plasma generation unit fuselage, but its sectional dimension is bigger, making has a gap at atmospheric pressure plasma generation unit fuselage outer wall and extractor body inner surface, to form above-described open channel.In use substrate surface and extractor body form the chamber around atmospheric pressure plasma generation unit fuselage.The escape that provides this chamber to stop basically to handle gas, reactant and accessory substance rather than by extractor unit, and from atmosphere, isolated atmospheric pressure plasma generation unit fuselage basically.
Near to or in contact with can be by any suitable material to the extractor unit edge of substrate surface, and if they touch substrate, must be selected from and will not destroy the material of substrate surface basically.Can be flange forms, stretch out from the extractor unit fuselage near to or in contact with extractor unit edge to substrate surface.Flange is preferably designed to equidistant with substrate surface as electrode tips basically, more preferably, near to or in contact with to the extractor unit edge of substrate surface more than electrode tips near substrate surface, perhaps contact with substrate surface, provide this contact will be not can negative effect to the plasma treatment of substrate surface.
Extractor body is preferably made by dielectric substance, for example polyvinyl dichloride (PVC) or polypropylene.Extractor body is not only as extracting above-mentioned gas, and by bucking electrode as security mask, and the area that an increase is provided is used for the heat management of electrode, make and to avoid overheated (and the destruction that causes), when aerial plasma generation for example, need and/or run in the process of high pressure and heat load to produce.
In use, in admission passage behind processing gas, reactant and the accessory substance process plasma slab, they have cooled off assembly effectively makes that using the bright assembly of this law to carry out the plasma treatment substrate is operated under the above-described low temperature, and temperature preferably is not more than about 50 ℃.This is used for being even more important at processing gas at air, because voltage and heat load are than the height when using helium as processing gas.Escape of gas minimum and preferred nontoxic that extractor unit of the present invention is suitable for guaranteeing to be caused by plasma treatment is in atmosphere.
One or more adjustment rods can be arranged in withdrawal device flange outside.These are adjusted rod and preferably are suitable at substrate by contact before and after the plasma treatment or near substrate surface.Provide and adjust rod and be used for restriction/deaeration etc. and from atmosphere, enter withdrawal device.They can be applicable to the static that uses high electrostatic potential to remove substrate surface, and choose wantonly and remove grit with air jet for flange seal form contact substrate surface and/or the antistatic rod of using in plastic film industry.Also can use antistatic carbon brushes and electrostatic barrier guns.Under the situation of electrostatic barrier guns, based on the equipment of corona type electrode for example in US6285032, describe especially preferred, as a barrier means, the prevention air enters withdrawal device and stops the processing gas loss to enter in the atmosphere, makes described processing gas to be collected and to reuse.
In an alternate embodiments, be particularly suitable for handling substrate, handle gas and reactant and trend towards through for example non-weaving and textile web etc., rather than around this assembly fuselage.Extractor unit can make below substrate that substrate transmits between assembly fuselage and extractor unit.Extractor unit can be suitable for extracting processing gas and reactant from substrate, causes the substrate of a uniform treatment.
In a further embodiment of the present invention, a method of handling a substrate surface is provided, the assembly of type is described above using, comprise: with a kind of processing gas and a kind of atomized liquid and/solid cladding forms material and introduces in the atmospheric pressure plasma generation component fuselage and influences plasma, plasma use consequent active material handle atomized liquid and/solid cladding forms material and handles a substrate surface.
At one further among the embodiment of the present invention, an atmospheric pressure plasma generation component is provided, be suitable for applying a substrate, contain an atmospheric pressure plasma generation unit, its fuselage comprises a reactant introducing device, handle gas introducing apparatus for one, be fit to the electrode arrangement one or more arranged side by side that plasma generates, each electrode arrangement comprises the electrode of at least one part dielectric coated, described device is suitable for making a kind ofly introduces processing gas in the described device and the unique method of solid reactants discharging is by the plasma zone between the former electrodes, it is characterized in that the reactant introducing device is an atomizer, be used for forming the form atomizing reactant of material with liquid and/or solid cladding.
Preferred in the present embodiment suitable substrate can be a kind of powder, can introduce in the assembly by the 3rd introducing device, and it can comprise a for example powderject rifle etc. of a suitable powder introducing device.According to the embodiment of the invention, the back introducing mixing of the powder preferably use carrier gas with top the 27th section description is consistent to the device of atomized liquid or solid cladding formation material introducing and mixing.In handling gas and atomized liquid or solid cladding formation material, guarantee that the even distribution of powder is very important.
The powdered substrate that applies can be collected on any suitable device or in the device, for example handles powder and can collect on an electrostatic transfer belt.
As selection, plasma assembly of the present invention can be fixed on or near the open substrate of a powder container, for example funnel or skewed slot, a narrow opening during powder converges through substrate therein, can use a kind of fluidizing gas fluidisation thus, make the powder that penetrates container cause Venturi effect, processing gas/the atomized liquid that from plasma assembly, penetrates or the conveying of solid cladding material blends have been caused, make powder particle enter atmospheric plasma discharge and/or ionizing air, caused there when leaving assembly of the present invention, being coated with and be covered with atomized liquid or solid cladding and form material.
Embodiments of the invention are particularly useful for relating to the coating powders shape substrate to other coating processing sensitivity, for example to for example coating powders shape substrate of heat, temperature and ultraviolet light sensitivity.The powdered substrate that applies can comprise any material, for example metal, metal oxide, silica, carbon, organic dust shape substrate, comprise polymerization, dyestuff, fragrance, flavor enhancement, the powdered substrate of pharmacy is penicillin and antibiotic for example, and biologically active cpds, for example based on the material and the enzyme of protein.
The various plasma treatment of present available very wide scope, those the particularly important is surface activation, surface clean, material etching and application to the present invention.Typically, substrate can stand to use any suitable processing of one or more assemblies.For example, first assembly can be used for cleaning substrate surface, and second assembly can be used for surface activation, coating or etching.The surface that can use additional assemblies activate to apply applies the surface then again, apply one deck or further more overbrushing cover etc., depend on the application that substrate is planned.For example, the coating that forms on a substrate can reprocessing in the condition of plasma scope.For example, the siloxanes film of deriving can be with containing the further oxidation of oxygen plasma treatment.Contain the oxygen material for example oxygen or water produce and contains oxygen plasma by in plasma, introducing.
Can use any suitable combination of plasma treatments, for example first plasma slab is by using a kind of helium plasma, can clean substrate surface with plasma treatment, second plasma slab is used to coat a skim, for example a kind of liquid or solid spray applications by above-described atomizer or sprayer.
As selection, first assembly can be used as a kind of oxidation unit (for example handling in the gas at oxygen/helium) or as the application of a skim, second plasma slab is used to use different precursors to coat second tunic.As an example, following processing contains preliminary treatment and post-processing step, is suitable for preparing a SiO who contains antipollution/fuel outer surface
xPotential barrier can be used for solar cell or automobile and use, and substrate at first by the preliminary treatment of He cleaning/activation substrate, is followed from dimethyl silicone polymer precursor deposit SiO at first plasma slab
x, further use the helium plasma treatment then so that SiO to be provided
xLayer is extra crosslinked, uses perfluorinated precursor to coat a skim at last.
The present invention can be used to form many dissimilar substrate films.The type that is formed on the film on the substrate is by the film formation material decision of using, and this method can form monomer material with (being total to) polymeric membrane and be used for substrate surface.Film formation material can be organic or inorganic, solid, liquid or gas, or their mixture.Suitable organic film formation material comprises carboxylate, methacrylate fat, acrylate, styrene, methacrylonitrile, alkene and diene, methyl methacrylate for example, EMA, propyl methacrylate, butyl methacrylate, and other alkylmethacrylate, and corresponding acrylate, the methacrylate and the acrylate that comprise organic functions, comprise epihydric alcohol methylpropenoic acid ester, trimethoxy monosilane propyl methacrylate, the allyl methyl acrylate, hydroxyethyl meth acrylate, the hydroxypropyl methyl acrylate, dialkyl aminoalkyl methacrylate, and fluoroalkyl (methyl) acrylate, methacrylic acid, acrylic acid, fumaric acid and ester, methylene succinic acid (and ester), maleic acid, styrene, AMS, the halo alkene, perfluor alkene for example, acrylonitrile, methacrylonitrile, ethene, propylene, allyl amine, vinylidene halide, butadiene, acrylamide, N-N-isopropylacrylamide for example, Methacrylamide, epoxy compounds, glycidyl trimethoxy silane (glycidoxypropyltrimethoxysilane) for example, epoxy prapanol, styrene oxide, butadiene monoxide, the ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, glycidyl methacrylate, diglycidyl ethers of bisphenol-A (and its oligomer,), ethylene propylene hexene oxide, conducting polymer, for example pyrroles and thiophene and their derivative, and phosphorus-containing compound, for example dimethyl propylene phosphonate ester.Suitable inorganic film formation material comprises metal and metal oxide, comprises colloidal metal.Organo-metallic compound also can be suitable for film formation material, comprises metal alcoholate, for example the alcoholates of titanate, tin spirit, zirconates and germanium and erbium.
As selection, substrate can provide with silica or siloxanes basement membrane, uses the film that comprises material to form synthetic.Suitable material comprises silane (for example silane, alkyl silane, alkyl halogen silanes, alkoxy silane) and wire (for example dimethyl silicone polymer) and annular siloxane (for example octamethylcy-clotetrasiloxane), comprise that organic functional line shape and annular siloxane (for example contain H-silicon, halogen function and alkylhalide group function wire and annular siloxane, for example tetramethyl-ring tetrasiloxane and three (non-fluorine butyl) trimethyl cyclotrisiloxane (tri (nonofluorobutyl) trimethylcyclotrisiloxane)).Can use the different silicon-containing mixtures of material, for example the physical characteristic of design substrate film is used for special requirement (for example thermal characteristic, optical characteristics, for example refractive index and viscoelastic property).
An advantage of the invention is that with respect to prior art liquid and solid atomizing film formation material may be used to form substrate film, because method of the present invention occurs under the atmospheric pressure.In addition, film formation material can be incorporated under not having the situation of carrier gas in plasma discharge or the plasma flow, and promptly they can be introduced directly into by for example directly injecting, and directly are injected in the plasma by its film formation material.
The processing gas that uses in plasma treatment procedure with electrode of the present invention can be any suitable gas, but preferably a kind of inert gas or based on the mixture of inert gas, helium for example, the mixture of helium and argon gas additionally comprises ketone and/or related compound based on the mist of argon gas.These processing gases can use separately or use in conjunction with figure's reactant, for example nitrogen, ammonia, O
2, H
2O, NO
2, air or hydrogen.Optimally, handling gas will be separately helium or in conjunction with a kind of oxidation or the gaseous reactant that reduces.The selection of gas depends on the plasma treatment that will carry out.When a kind of oxidation of needs or reduction gaseous reactant, it will preferably use with the mixture that comprises 90-99% rare gas and 1-10% oxidation or reducing gas.
In assembly, do not want under the situation of oxidation or reducing gas, can be before starting plasma, with inert gas or processing gas bleed assembly.Typically, inert gas can be for example nitrogen.
Under oxidizing condition, can contain the oxygen film on the substrate as being formed on according to assembly of the present invention.For example, can be by the siliceous film formation material of atomizing, at the film of substrate surface formation based on silica.Under reducing condition, this method can for example by the siliceous film formation material of atomizing, can form the film based on carborundum as forming oxygen-free films.
In nitrogenous atmosphere, nitrogen can be combined in substrate surface, and in the atmosphere that contains nitrogen and oxygen, nitrate can in conjunction with and/or be formed on the substrate surface.This gaseous reactant also can be used for the pre-processed substrate surface before being exposed to liquid or solid coating formation material.For example, contain the oxygen plasma treatment substrate improved adhesion can be provided the film of coating.For example oxygen or water enter plasma and produce by containing the oxygen material to contain oxygen plasma.
The substrate that will apply can comprise any suitable material, glass for example, metal is steel for example, aluminium, copper, titanium and their alloy, plastics, thermoplastics for example, for example, polyolefin is polyethylene for example, polypropylene, Merlon, polyurethane, polyvinyl chloride, polyester (polyolefin terephthalate for example, especially polyethylene terephthalate), polymethacrylates (for example polymer of polymethyl methacrylate and hydroxyethyl meth acrylate), polyepoxide, polysulfones, polyphenylene, polyketone ether, polyimides, polyamide, polystyrene, phenol, epoxy and melamine formaldehyde resin, and their mixture and copolymer, siloxanes, fabric, weaving or non-textile fiber, natural fiber, synthetic fibers cellulosic material and powder, and a kind of organic polymer material and the mixture that contains organosilyl additive, it is miscible or do not mix with organic polymer basically, and WO01/40359 is described as the common pending application application of applicant.Have enough distinct interaction parameters and make and under equilibrium condition, do not mix for avoiding query " not mix basically " meaning containing organosilyl additive and organic material.This will be typically, but not be exclusively, when the solubility parameter that contains organosilyl additive and organic material has different situation greater than 0.5MPa1/2.The present invention especially is fit to handle rigidity and unbending thin plate etc., for example uses three electrode arrangement to handle sheet metal, and uses two electrode arrangement to handle plastics.
Use is carried out substrates coated according to assembly of the present invention can various uses.For example, the film based on silica that produces in oxidizing atmosphere can strengthen stopping and/or diffusion property of substrate, and can strengthen the ability of additional materials adhesion substrate surface; Organic or the silicone film of a halogen function (for example perfluor alkene) can increase hydrophobicity, oleophobic property, anti-fuel and the pollution of substrate, and/or release characteristics; A dimethyl silicone polymer film can strengthen the water-resistance and the release characteristics of substrate, and can strengthen the flexibility of contact fiber; An acrylic acid polymer film can be used as adhesive layer with the adhesion of promotion with substrate surface, or as the part laminated construction; Comprise that in film the colloidal metal grain can provide the conductivity with substrate surface, or strengthen its optical characteristics.Polythiophene and polypyrrole provide conductive polymer membrane, and it can also provide the corrosion resistance on the metal substrate.
Description of drawings
Only by the example reference accompanying drawing, will more be expressly understood the present invention to the description of the following embodiment, wherein:
Fig. 1 is the assembly cross-sectional view that two electrode arrangement used according to the invention are used for non-conductive substrate,
Fig. 2 is the assembly cross-sectional view that three electrode arrangement used according to the invention are used for conductive substrates,
Fig. 3 is the equidistant perforation of the assembly according to the present invention,
Fig. 4 a and 4b are preferred atomized liquid drawing-in system figure,
Fig. 5 is as the atomizing drawing-in system figure that selects,
Fig. 6 is as the processing gas drawing-in system figure that selects,
Fig. 7 is the enforcement illustration that equipment of the present invention is used to handle a kind of powder.
Embodiment
With reference to figure 1 and 3, an atmospheric pressure plasma assembly 100 is provided, has comprised a plasma generation unit 7, contained the fuselage body 17 of cylinder basically, basically contain circular cross-section, comprise a processing gas access 12 and be used for processing gas is entered unit 7.Handle gas and be used to influence plasma.Provide a ultrasonic nozzle 10 to be used to introduce a kind of reactant.Unit 7 comprises that also 4, two of pair of electrodes all are coated with or seals with a kind of dielectric substance 3.Electrode keeps a preset distance that separates by pair of electrodes liner 5.Dielectric coated electrode 3,4 is protruding from atmospheric pressure plasma generation unit 7.Atmospheric pressure plasma generation unit 7 is designed so that to introduce the processing gas of unit 7 and unique outlet of reactant is by the plasma slab 6 between the electrode 3,4 of dielectric coated.
As atmospheric pressure plasma generation unit 7, extractor unit 8 is the cylindrical of a circular cross-section basically generally, is made by a kind of dielectric substance, for example polypropylene or PVC.Unit 7 and 8 is concentric, and extractor unit 8 has than major diameter.Extractor unit comprises a flange 15, and it surrounds dielectric coated electrode 3,4 and form a passage between electrode 3,4 and flange 15, is extracted by its residual process gas, reactant and accessory substance.It is equidistant with substrate 1 that the tip designs of flange 16 becomes, as dielectric coated electrode 3,4 benchmark but it can be more recently.Extractor unit 8 also comprises one to delivery side of pump 18 (not marking), is used for extracting residual process gas, reactant and accessory substance from assembly 100.Adjustment rod 2 is provided in flange 15 outsides, makes the air minimum that from atmosphere, enters extractor unit 9.Adjust the sealing of rod 2 or lip ring shape and contact substrate 1, perhaps depend on the antistatic rod that pending substrate is as uses in plastic film industry, use high electrostatic potential to get rid of the static of substrate surface, and can choose wantonly and use air to spray the removal grit.Adjustment rod as depicted in figs. 1 and 2 is an antistatic carbon brushes.
In an embodiment of the present invention, atmospheric pressure plasma generation unit 7 is fixed on the appropriate location, substrate 1 process below it, load mode (not shown) in any form, do not form the fact of the part of assembly based on conveyer, it can change to adapt to processed substrate.Depend on the substrate of processing from the end points 23 of each electrode 3,4 to the distance of substrate, but typically, the distance of several millimeters weak points with end points 23 and substrate 1 separately.
In use, the placement of this assembly is near a non-conductive substrate 1, makes the end 16 of the end points 23 of electrode 3,4 and flange 15 from the distance of substrate surface 1 millimeter soon.Substrate 1 combines the chamber that forms around dielectric coated electrode 3,4 with extractor unit 8.This chamber is suitable for stoping basically the escape of residual process gas, reactant and accessory substance, rather than passes through passage 9 via pump.A kind of processing gas 12 enters unit 7 by entering the mouth, and a kind of atomized liquid or powder are introduced unit 7 by ultrasonic nozzle 10.Handle gas and atomized liquid or powder and in unit 7, mix,, cause the preferred option of turbulent flow below with reference to figure 3 and Fig. 4 discussion by influencing turbulent flow.Unique outlet of handling gas/atomized liquid or mixture of powders is the plasma slab that forms by by electrode pad 5 and dielectric coated electrode 3,4.When helium process plasma slab 6, when plasma when obtaining suitable electrical potential difference between the dielectric coated 3,4 is affected.The processing that atomized liquid or solid are subjected to plasma forms active material, and by the 6 guiding substrates 1 of the plasma slab between the dielectric coated 3,4, with described substrate effect, this also is as discussed above in plasma slab thus then.Then residual helium gas reactive agent and any accessory substance upwards are drawn into the passage 9 below electrode tips 23, and extract out from exporting 18.
In Fig. 2, provide an assembly identical, except electrode with the above-described Fig. 1 of contact.Assembly shown in Figure 2 is particularly useful for for example metal of conductive substrates, but also can be used for non-conductive metal substrate.In this three electrode arrangement, provide a central electrode 34, by a kind of dielectric 33 sealings.Each limit 33,34 of the electrode of this sealing is two grounding electrodes 37, and the purpose that provides is to guarantee can avoid in the substrate of enclosed-electrode 38 and the short circuit between the substrate 1.In this arrangement, central electrode 33,34 hang in by the gap of double aperture slit electrode pad between grounding electrode 37, enclosed- electrode 33,34 the base of dielectric 38 and the distance of substrate 1 must be greater than the distances of dielectric and grounding electrode 37, to guarantee between enclosed- electrode 33,34 and substrate 1 surface, avoiding electric arc.
In use, therefore in the plasma slab 36 between enclosed- electrode 33,34 and each grounding electrode 37, produce plasma, handle gas and reactant this district of process before transmitting extractor unit 8 by passage 9.
Fig. 4 a and 4b pointed out a kind of liquid and/solid cladding forms two kinds of selectable methods that material (reactant) and processing gas enter unit 7, and guaranteed before the plasma slab 6 or 36 of the electrode assemblie of mixture by depending on use the equally distributed device of spraying.
In Fig. 4 a ultrasonic nozzle 10 contain frequency produce cable 13 and air intake 14 (air can be used as liquid that a kind of carrier gas is used to atomize and/solid cladding forms material).Handle gas and introduce perpendicular to the main shaft of fuselage 7, make when air-flow during the outlet of the close nozzle 10 of the turbulent flow of generation the reorientation of main flow axle by inlet 12.This mixed process is suitable for the high processing gas flow rate most, and this can be used for handling cheaply gas for example air or nitrogen.In Fig. 4 b, ultrasonic nozzle 10 is fixed on the end of fuselage 7, makes to arrange along its main shaft, and carrier gas is introduced fuselage 7 by inlet 12.
Fig. 3 and Fig. 5 show the equally distributed device of guaranteeing to handle gas/liquid and/or solid cladding formation material that is further used as selection.This is by using a throttling dish 11 to induce turbulent flow to obtain before nozzle 20 immediately in handling gas flowfield.Turbulent flow will exist in 6 disk diameters that (be half of diameter of fuselage 7 when the diameter of disk, the uniformity of the liquid jet has been guaranteed in the downstream of 1/2 conduit diameter of disk 11 therefore.
Fig. 6 shows further device, air is used to handle gas if desired, can introduce in the fuselage 7 by it, because variable-ratio fan 40 is used for extracting air and enters fuselage 7 and influence turbulent flow simultaneously, make the liquid that causes the atomizing introducing air and introduce fuselages 7 by ultrasonic nozzle 10 or the mixing between the powder.
In Fig. 7, an assembly as shown in Figure 2 is provided, it is positioned at the narrow outlet 48 near a powder skewed slot 50.Fluidizing gas is introduced in the skewed slot at inlet 52 places, directly arrives in the powder to assist its flowability.Because to narrowing down of outlet 48, the obstruction that causes by assembly 100 and handle gas/liquid and/or solid cladding forms material and leaves assembly 100 at a high speed, handle gas/liquid or caused Venturi effect from the coating material mixture that assembly 100 leaves, cause taking away powder/gas and left powder skewed slot 50, make powder enter atmospheric plasma discharge and/or ionizing air, caused there in assembly 100 of the present invention, being coated with and be covered with atomized liquid or solid cladding and form material.Can use any suitable collection plasma treatment powder unit.
Claims (26)
1. atmospheric pressure plasma generation component, contain an atmospheric pressure plasma generation unit that has fuselage, described fuselage comprises the reactant introducing device, handle gas introducing apparatus for one, with the one or more many electrode arrangement side by side that are used to generate plasma, each many electrode arrangement side by side comprises partly by at least one electrode of dielectric coated, make to introduce processing gas in the described assembly and reactant from unique outlet of described assembly by the plasma zone between the former electrodes, the relative substrate of described assembly is removable, described substrate near from the outstanding former electrodes of fuselage from described unit end points farthest, it is characterized in that the reactant introducing device is an atomizer, be used for atomizing and introducing liquid and/or solid reactants to form coating.
2. according to the assembly of claim 1, wherein many electrode arrangement side by side comprise one or more pairs of at least in part by dielectric coated and electrode arranged side by side, and each is located with a predetermined distance of separation electrode.
3. according to the assembly of claim 1, wherein many electrode arrangement side by side are one three parallel pole system, this three parallel poles system has a central electrode and two grounding electrodes, central electrode is at least partially by dielectric coated, and two grounding electrodes to be to be positioned at one of central electrode on one side at a distance of the predetermined distance of central electrode.
4. according to each assembly among the claim 1-3, wherein atmospheric pressure plasma generation component fuselage length is between 0.5 meter-5 meters.
5. according to each assembly among the claim 1-3, wherein provide around the extractor unit of atmospheric pressure plasma generation unit, be used for atmospheric pressure plasma unit and outside atmosphere are isolated, described extractor unit comprises the useless gas of handling, reactant and accessory substance removal device, described extractor unit is formed such that described extractor unit comprises an open channel, make in use, the edge of open channel is shaped as bonded substrate and forms a chamber around electrode, thereby form sealing to atmosphere, thus, the useless processing gas of chamber, reactant and accessory substance are extracted.
6. according to each assembly among the claim 1-3, wherein atomizer is a ultrasonic nozzle.
7. according to each assembly among the claim 1-3, wherein handle the main shaft location of gas introducing apparatus perpendicular to atmospheric pressure plasma generation component fuselage, relative or vertical with the atomizer in described atmospheric pressure plasma generation component fuselage, make when handling gas flow when the air-flow principal direction along the main axis length direction of atmospheric pressure plasma generation component fuselage redirects, the outlet turbulization of close atomizer.
8. according to the assembly of claim 7, one of them throttling dish is arranged in the flow field of handling gas.
9. according to the assembly of claim 5, wherein handle gas, reactant and any accessory substance and be extracted cooling agent as assembly by extractor unit.
10. according to each assembly among the claim 1-3, this assembly comprises one or more adjustment rods.
11., wherein adjust rod and be selected from carbon brush and electrostatic barrier guns according to the assembly of claim 10.
12. according to each assembly among the claim 1-3, described assembly makes the atmospheric plasma treatment of substrate surface implement in the downstream of described electrode with respect near removable from the substrate of the outstanding former electrodes outermost end points of fuselage.
13. according to each assembly among the claim 1-3, wherein substrate arrangement is shaped as a wall of assembly, produces plasma in assembly, described wall is used for stoping after plasma activates and discharges processing gas, reactant and/or accessory substance.
14. use the method for handling a substrate surface according to each assembly among the claim 1-3, comprise: introduce liquid and/or the solid cladding of handling gas and atomizing and form material in atmospheric pressure plasma generation component fuselage, influence plasma, use consequent active material that atomized liquid and/or solid cladding formation material are carried out plasma treatment and thus a substrate surface carried out plasma treatment.
15. according to the method for claim 14, wherein the processing of substrate surface realizes in the electrode downstream.
16., wherein handle gas and be a kind of inert gas or based on the mixture of inert gas according to the method for claim 14 or 15.
17., wherein handle gas and be used in combination with gaseous reactant according to the method for claim 16.
18. according to the method for claim 14, atmospheric pressure plasma generation component pre-processed substrate wherein.
19. according to the method for claim 14, wherein the atmospheric pressure plasma generation component is used for the reprocessing substrate.
20. according to the method for claim 14, wherein a kind of gaseous reactant is additionally used.
21. according to the method for claim 14, wherein substrate is next pretreated by substrate being carried out He cleaning and/or activation, follows at one first plasma slab from dimethyl silicone polymer precursor deposit SiO
xLayer further uses the helium plasma treatment so that SiO to be provided then
xIt is crosslinked that layer adds, and uses the further coated of fluoridized precursor at last.
22. atmospheric pressure plasma generation component that is used for coated substrate, comprise an atmospheric pressure plasma generation unit that contains fuselage, fuselage comprises the reactant introducing device, handle gas introducing apparatus, with the one or more many electrode arrangement side by side that are used to generate plasma, each many electrode arrangement side by side comprises partly by at least one electrode of dielectric coated, make to introduce processing gas in the described assembly and reactant from unique outlet of described assembly by the plasma zone between the former electrodes, it is characterized in that the reactant introducing device is an atomizer, be used for atomizing and introduce reactant, this reactant is the form that liquid and/or solid cladding form material.
23. according to the atmospheric pressure plasma generation component of claim 22, wherein coated substrate is Powdered.
24. method of in the assembly of claim 22 or 23, handling powdered substrate.
25. the use according to the assembly of claim 2 is used to handle non-conductive substrate.
26. the use according to the assembly of claim 3 is used to handle conductive substrates.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0208259A GB0208259D0 (en) | 2002-04-10 | 2002-04-10 | An atmospheric pressure plasma assembly |
| GB0208259.2 | 2002-04-10 | ||
| GB0208263.4 | 2002-04-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1698176A CN1698176A (en) | 2005-11-16 |
| CN100437884C true CN100437884C (en) | 2008-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038081369A Expired - Fee Related CN100437884C (en) | 2002-04-10 | 2003-04-08 | An atmospheric pressure plasma assembly |
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| CN (1) | CN100437884C (en) |
| GB (1) | GB0208259D0 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108624845B (en) * | 2017-03-22 | 2024-03-29 | 杭州朗旭新材料科技有限公司 | Plating device for organic hardening coating film of plastic |
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|---|---|---|---|---|
| EP0431951A2 (en) * | 1989-12-07 | 1991-06-12 | Research Development Corporation Of Japan | An atmospheric plasma reaction method and a device therefor |
| EP0617142A1 (en) * | 1993-03-26 | 1994-09-28 | Shin-Etsu Chemical Co., Ltd. | Preparation of silica thin films |
| WO1995018249A1 (en) * | 1993-12-24 | 1995-07-06 | Seiko Epson Corporation | Method and apparatus for processing surface with plasma under atmospheric pressure, method of producing semiconductor device and method of producing ink-jet printing head |
| CN1150327A (en) * | 1995-07-05 | 1997-05-21 | 索尼公司 | System and method for plasma etching |
| DE19546187A1 (en) * | 1995-12-11 | 1997-06-12 | Fraunhofer Ges Forschung | Plasma-aided surface treatment at atmospheric pressure |
| WO1998010116A1 (en) * | 1996-09-05 | 1998-03-12 | Talison Research | Ultrasonic nozzle feed for plasma deposited film networks |
-
2002
- 2002-04-10 GB GB0208259A patent/GB0208259D0/en not_active Ceased
-
2003
- 2003-04-08 CN CNB038081369A patent/CN100437884C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0431951A2 (en) * | 1989-12-07 | 1991-06-12 | Research Development Corporation Of Japan | An atmospheric plasma reaction method and a device therefor |
| EP0617142A1 (en) * | 1993-03-26 | 1994-09-28 | Shin-Etsu Chemical Co., Ltd. | Preparation of silica thin films |
| WO1995018249A1 (en) * | 1993-12-24 | 1995-07-06 | Seiko Epson Corporation | Method and apparatus for processing surface with plasma under atmospheric pressure, method of producing semiconductor device and method of producing ink-jet printing head |
| US6342275B1 (en) * | 1993-12-24 | 2002-01-29 | Seiko Epson Corporation | Method and apparatus for atmospheric pressure plasma surface treatment, method of manufacturing semiconductor device, and method of manufacturing ink jet printing head |
| CN1150327A (en) * | 1995-07-05 | 1997-05-21 | 索尼公司 | System and method for plasma etching |
| DE19546187A1 (en) * | 1995-12-11 | 1997-06-12 | Fraunhofer Ges Forschung | Plasma-aided surface treatment at atmospheric pressure |
| WO1998010116A1 (en) * | 1996-09-05 | 1998-03-12 | Talison Research | Ultrasonic nozzle feed for plasma deposited film networks |
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|---|---|
| CN1698176A (en) | 2005-11-16 |
| GB0208259D0 (en) | 2002-05-22 |
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