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WO2009036579A1 - Appareil pour revêtement appliqué sous plasma de la surface interne de contenants d'emballage tubulaires en matière plastique au moyen d'un faisceau-plasma non thermique à pression ambiante réactive - Google Patents

Appareil pour revêtement appliqué sous plasma de la surface interne de contenants d'emballage tubulaires en matière plastique au moyen d'un faisceau-plasma non thermique à pression ambiante réactive Download PDF

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Publication number
WO2009036579A1
WO2009036579A1 PCT/CH2007/000468 CH2007000468W WO2009036579A1 WO 2009036579 A1 WO2009036579 A1 WO 2009036579A1 CH 2007000468 W CH2007000468 W CH 2007000468W WO 2009036579 A1 WO2009036579 A1 WO 2009036579A1
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WIPO (PCT)
Prior art keywords
plasma
capillary
beam plasma
capillaries
anyone
Prior art date
Application number
PCT/CH2007/000468
Other languages
English (en)
Inventor
Rüdiger FOEST
Klaus-Dieter Weltmann
Peter Ellinger
Manfred Stieber
Eckhard Kindel
Andres Ohl
Gerd Friedrichs
Andreas Huber
Original Assignee
Hoffmann Neopac Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Hoffmann Neopac Ag filed Critical Hoffmann Neopac Ag
Priority to PCT/CH2007/000468 priority Critical patent/WO2009036579A1/fr
Publication of WO2009036579A1 publication Critical patent/WO2009036579A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32816—Pressure
    • H01J37/32825—Working under atmospheric pressure or higher
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/48—Generating plasma using an arc
    • H05H1/486—Arrangements to provide capillary discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32366—Localised processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32532—Electrodes
    • H01J37/32541—Shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/47—Generating plasma using corona discharges
    • H05H1/471—Pointed electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H2245/00—Applications of plasma devices
    • H05H2245/10—Treatment of gases
    • H05H2245/15—Ambient air; Ozonisers

Definitions

  • the invention refers to an apparatus for the treatment of plastics surfaces, in particular for the production of a permeation reducing coating on the inner and/or the outer surface of packaging bodies made of plastics by reactive ambient pressure beam plasma.
  • the treatment of surfaces with low temperature plasma procedures and low temperature plasma appara- tuses can be performed in various embodiments for a broad spectrum of applications in the field of plasma technology.
  • Typical applications of this kind of plasma apparatuses for example comprise the plasma surface activation (control of the features of boundary layers, hydropho- bisation, hydrophilisation) , plasma etching, plasma polymerisation, plasma coating, plasma cleaning and plasma sterilization (see Alfred Rutscher et al . "Wissenschaft- liche Plasmaphysik” VEB horrbuchverlag Leipzig 1983 and H. Conrads, Plasmatechnologie - Stand undroun, Endbericht desggis Fkz 13N61825 1994) .
  • Ambient pressure plasma can for example be generated by the long known corona discharge or barrier discharge (also referred to as silent or dielectric barrier discharge (DBD) ) , spark discharge, arc discharge, torch/flare discharge, as well as micro wave supported discharges (see H . -E . Wagner, R. Brandenburg, K. V. Ko- zlov, A. Sonnenfeld, P. Michel, J. F. Behnke, Vacuum 71, 417-436, 2003) .
  • corona discharge or barrier discharge also referred to as silent or dielectric barrier discharge (DBD)
  • spark discharge arc discharge
  • torch/flare discharge as well as micro wave supported discharges
  • Such plasma can be thermal or nonthermal.
  • Hitherto of technical significance are in particular corona discharges and DBD.
  • the DBD is operated with alternating voltage (AC voltage) and develops in a very narrow discharge gap between two electrodes, whereby at least one dielectric barrier must be placed between the two electrodes.
  • the DBD is the hitherto most used discharge form for ambient pressure plasma methods .
  • Corona discharges function with direct voltage (DC voltage), they are, however, often operated in a pulsed manner and develop - due to the selection of specific arrangements of pointed electrodes - in a very inhomogeneous electri- cal field. In large scale applications, frequently corona discharges are used. From the perspective of surface treatment homogenous, geometrically adapted plasmas are desired. Solutions for such plasmas comprise arrangements of parallelly or memorilly operated micro plasma (see E. Kunhardt, IEEE Trans.
  • ACD Admospheric Glow Discharge
  • S. Kanazawa, M. Kogoma, T. Moriwaki, S. Okzaki, J. Phys . D: Appl . Phys . 21, 838, 1988 The ACD is characterized by the lack of the characteristic discharge filaments and, due to its homogenous glow appearance, strongly reminds of a low pressure DC glow discharge. Similar thereto a low current Townsend mode and a glow mode can be distinguished (see F. Massines, A. Ra- behi, P.
  • micro hollow cathode arrays and plasma capillary electrodes See K. H. Schoenbach, R. Ver- happen, T. Tessnov, F. E. Peterkin, and W. W. Byszewski, Appl. Phys. Lett. 68, 13, 1996) and their application in the treatment of polymer films is described (see A. Ig- natkov, A. Schwabedissen, G. F. Leu and J. Engemann, Contributed Papers Hakone VIII (Puhajarve, Estonia), 1, 58, 2002) .
  • the plasma treatment of small cavities within dielectric materials by DBD is applied in plasma printing (see C. Penache, C. Gessner, T. Betker, V. Bartels, A.
  • Plasma generated by microwave play a role in the surface treatment at enhanced pressure 50-1000 hPa
  • plasma generated by microwave play a role in the surface treatment at enhanced pressure 50-1000 hPa
  • R. Foest, D. Baumann, and A. OhI, Proc. Vth Int. Workshop on Microwave Discharges: Fundam. and Appl . , 201, 2003 One possibility to achieve a plasma that is not limited to a narrow space between the electrodes and with conservation of the necessary homogeneity to a lar- ger extent is to generate a non-thermal beam plasma outside the discharge room by a combination of the electrical field with a directed stream of the working gases.
  • Ambient pressure beam plasma of this type can be generated with arc discharges as well as with spark dis- charges, corona discharges and barrier discharges (see A. Sch ⁇ tze, J. Y. Yeong, S. E. Babayan, J. Park, G. S. Selwyn, and R. F. Hicks, IEEE Trans. Plasma Sci . , 26, (6), 1685, 1998 and the original documents cited therein) .
  • a method for the treatment of fiber material utilizing a single polar high frequency RF- discharge or an electrode less RF-discharge, respectively are described.
  • a rod electrode or a hollow electrode can be used on which the RF- plasma torch starts that, without counter-electrode, un- disturbedly extends freely into the space.
  • an apparatus for the generation of a beam plasma by means of Corona discharge is presented that is suitable for the plasma treatment of surfaces. Thereby a gas stream is guided through the Corona discharge space between a rod like inner electrode and a tube like outer electrode.
  • a further method for the plasma treatment of surfaces that is based on the genera- tion of a plasma beam by means of an arc discharge under supply of a working gas is described in the patent specification DE 19532412.
  • the substrate temperatures remain at room temperature or in a temperature range between 50 0 C and 100 0 C.
  • process gases for atmospheric jets serve gases or their mixtures, respectively, known from low pressure plasma procedures, namely: rare gases (e.g. Ar, He) , oxygen, nitrogen, air, hydrogen, hydrocarbons and silanes or silicon organic compounds as admixtures.
  • a permeation inhibiting coating of surfaces can be achieved by a metallisation, by deposition of amorphous hydrocarbon coatings and by silica layers.
  • gas phase methods such as chemical vapor deposition (CVD) , electron beam methods as well as sol-gel-methods .
  • Thin metal layers can additionally be applied by sputter physical vapor deposition (Sputter-PVD) .
  • the apparatus suitable for the plasma supported coating of inner and/or outer surfaces of packaging containers made of plastics comprises at least one set of capillaries, each set comprising at least two beam plasma capillaries, said beam plasma capillaries being or comprising tubes or forming channels with narrow inner diameter and/or capillaries that are positioned radially within one another, said beam plasma capillaries being axially extending, said beam plasma capillaries comprising a first or inner beam plasma capillary that is the beam plasma capillary positioned closest to the axis, said first beam plasma capillary being made of an electrically conducting material, in particular metal, and forming a first electrode, said first beam plasma capillary being connected to a voltage source leading to an electrical con- nection to which a defined electrical potential is applied, preferably a high frequency generator and more preferably the earth connection of a high frequency generator, said beam plasma capillaries comprising a
  • the apparatus of the present invention has 3 beam plasma capillaries, a first or inner beam plasma capillary, an outer beam plasma capillary and a second beam plasma capillary positioned between the inner and the outer beam plasma capillary.
  • the first and second beam plasma capillaries are in general connected to first and second process gas sup- plies, although connections to only one process gas supply might for some applications be provided, namely if the same gas composition at different velocities should be supplied and provided that suitable velocity regulating valves are positioned between the capillaries and the process gas sources.
  • the part termed outer beam plasma capillary in one embodiment is rather a jacket comprising a plurality of regularly distributed capillaries, in general at least 3 capillaries, whereby the number of capillaries as a rule has to be as high as to ensure a sufficiently homogeneous (in radial-symmetrical respect) and controllable removal of excess and waste gases through said jacket.
  • the outer beam plasma capillary is comprised of two tubes fitted into each other (one of said tubes may be the wall limiting the next inner beam plasma capillary) such that there is a small annular slit between both which acts as channel for removing exhaust gas .
  • a ring with rectangular toroidal cross- section can be fitted tightly into the annular slit, carrying the aforementioned axial holes, thus simplifying the mechanical construction of an alternative to the capillaries.
  • Capillaries or at least a ring are preferred in view of mechanical stability of the plasma beam appara- tus.
  • each of the capillaries extends into a basic body, said basic body providing a connection to a process gas source and/or a pumping device.
  • the connection of the basic body- to the process gas source or the pumping device can e.g. be made by providing the basic body with a bore that tightly fits to a capillary and to a tube serving the connection to a process gas supply/process gas storage container or to the pumping device.
  • the capillary receiving basic bodies also provide a mechanical fixation for their capillary.
  • the first beam plasma capillary is made of an electrically conductive material, in particular a metal, especially molybdenum, tungsten, tantalum or high- grade/stainless steel, most advantageously tungsten.
  • a metal especially molybdenum, tungsten, tantalum or high- grade/stainless steel, most advantageously tungsten.
  • it may be advantageous to protect the metal by applying a protective layer to the inner and/or the outer surface of the first beam plasma capillary, preferably at least to the outer surface, since the more reactive gases are in general provided through the second capillary.
  • Suitable coatings for the surfaces of the inner beam plasma capillary are e.g. coatings made of ceramic oxides or temperature resistant polymers .
  • the second and any further beam plasma capillaries are made of a thermally stable inert insulating material, in particular a material selected from ceramics and duroplastic materials, e.g. polyimides and polyether ketones.
  • the thickness of the total of insulating materials and the gas spaces must be such that ignition and maintenance of the plasma is guaranteed.
  • the wall thick- ness of the walls defining the second and further beam plasma capillaries is not critical. For an apparatus with three beam plasma capillaries intended for coating tubes with a diameter of 13.5 mm, a total wall thickness of about 10 mm has proved to be preferred.
  • the material for the basic bodies is not critical provided that it does not interfere with the plasma generation. In general, for an embodiment with three beam plasma capillaries a basic body consisting of 5 parts is provided.
  • not conducting or semi-conducting areas that can be capacitively loaded in order to get an optimal electric field strength can be provided to ensure that no discharge at an undesired place occurs .
  • the dimensions of the embodiments are not critical, the preferred material is a metal in the case of electrically grounded potential or a non conducting material, preferably polyetheretherketone (PEEK) in case the inner electrode carries high voltage.
  • PEEK polyetheretherketone
  • the outer beam plasma capillary consists of a jacket that in one embodiment tightly abuts the next inner beam plasma capillary and comprises a plurality of at least 3, preferably at least 5, most preferred at least 6 capillaries. Since it is technically complicated to produce long capillaries, it is also possible to form the outer beam plasma capillary as a lumen similar to the second beam plasma capillary. In this embodiment it is also possible and - e.g. for stability reasons preferred - to tightly fit a ring with rectangular toroidal cross section into the annular slit (opening of the outer beam plasma capillary lumen) , wherein such a ring carries axial holes .
  • the inner beam plasma capillary has diameters ranging from about 2 mm to about 3 mm
  • said plurality of capillaries in said outer beam plasma capillary have diameters ranging from about 1 mm to about 2 mm, and preferably have diameters of about 1.5mm
  • said lumen of said second capillary placed between said outer and said inner beam plasma capillary has a width of about 2 mm to about 10 mm.
  • the thickness of the insulating material of the second and further beam plasma capillaries is not critical, however their combined thickness should be at least about 5 mm.
  • the outer beam plasma capillary is formed with a plurality of capillaries or with an annular lumen or with an annular lumen partially closed with a ring is not critical as long as the sum of the cross- sections of the capillaries or the area of the lumen in cross-section or the sum of the cross-sections of the openings in the ring are such that the gas volume to be removed through said outer plasma beam capillary can be regulated through the suction force.
  • the size of the outer diameter of the jacket which carries the capillaries or defines the lumen of the outer beam plasma capillary must be adjusted such that it fits to the diameter of the tube or bottle to be treated.
  • the size of the in- ner beam capillary is enlarged such that a maximal lumen cross section of 10 mm is ensured.
  • the same parameters have to be changed in the opposite direction, i.e. the size of the outer di- ameter of jacket which carries the outer beam capillaries must be adjusted such that it fits to the tube diameter.
  • the size of the inner beam capillary is decreased accordingly such that a radial lumen cross section between inner and 2 n d capillary of 0.5 mm is ensured.
  • the ratio of the active area of the annular cross-section of the lumen of the second beam plasma capillary (Fa) to the active area of the circular cross- section of the inner beam plasma capillary (Fi) is in the range of 0.7-1.4.
  • Fa Fi is preferably about 1.2.
  • the inner capillary When the inner capillary is connected to high voltage, it may act as the only explicit electrode.
  • the substrate that is to be coated acts as a reference electrode.
  • the inventive apparatus comprises a sec- ond electrode.
  • the second electrode is separated from the plasma by the surface to be coated.
  • the inner beam plasma capillary carries high voltage while the second electrode is connected to mass.
  • the second electrode carries high voltage and the inner beam plasma capillary is grounded.
  • the second electrode is preferably a formed body positioned at the upper end of the body to be coated, i.e. the end distal from the capillaries.
  • the form of the second electrode is not necessarily form- fitting, but preferably form-following, whereby a sealing with respect to the gas is necessary.
  • tube or tube-like as used in connection with the container to be surface treated means a container with a cylindrical body part (such as a bottle or a (collapsible) tube) that - if applied to the plasma beam apparatus - in distal direction from said plasma ap- paratus narrows towards an outlet; in general, the tube in distal direction ends in an elongated neck forming part .
  • a cylindrical body part such as a bottle or a (collapsible) tube
  • the hole or bore of said second electrode can be connected to a pumping device for pumping off excess gases and waste gases. This allows to control the back flow of excess gases and waste gases through the outer beam plasma capillary, the pressure in the plasma and the flow of gas through the outlet of the tube as well as the extension of the plasma into said usually elongated neck forming part of said outlet such that also said neck can be plasma treated and/or plasma coated, respectively.
  • the beam plasma capillaries For getting a homogeneous plasma treatment and/or plasma coating of a large inner surface area of a container, in particular a tube, in longitudinal exten- sion, it may be advantageous to arrange the beam plasma capillaries such that they can be moved in axial direction relative to the packaging container.
  • the apparatus described above can also be used for external treatment, in particular for treating the outer surface of a container, such as a bottle and in particular a tube, especially the outer surface in the area around the container mouth, in particular the elongated neck part of a tube.
  • a container such as a bottle and in particular a tube
  • the body to be treated is positioned at an appropriate dis- tance from the distal end of the apparatus, i.e. the end where the plasma beam is generated.
  • a container such as a bottle or tube
  • said container is positioned coaxially with the plasma beam apparatus .
  • both, the distal end of the plasma beam apparatus and the container end to be treated are positioned opposite to each other in a casing, in particular a tubular casing that at least at its ends fits to the container wall and the plasma beam apparatus.
  • said casing can have a larger diameter, in particular a diameter larger than the outer diameter of the container body.
  • This casing preferably is made of insulating material .
  • the container to be coated is too large for being homogeneously coated with one set of concentric capillaries as described above, several such sets of capillaries can be combined for use within one container, e.g. by providing mechanical fixation means such as fitting bores for several sets of concentric capillaries within each basic body.
  • plasma treating and/or coating devices can be provided comprising a plurality of one set apparatuses or multiple set apparatuses as described above. Such apparatuses may be serially or circularly arranged.
  • Several or all of the apparatuses can be connected to a common gas source for a first process gas and/or a common gas source for a second or further process gas and/or common pumping devices and/or common RF generators.
  • modules can be made such that they easily fit to one another, e.g. in that the basic bodies are shaped to together form a circle that can be hold in a circular holder, or in that each of the basic bodies fits to a re- ceptacle within a holder, whereby said holder can provide connections to gas sources, pumping devices, RF generator or mass, etc.
  • the modular embodiment has the advantage of simplified change, be it that one plasma beam apparatus is defect and needs replacement, be it that the whole device shall be changed to another container size.
  • the modular embodiment has the advantage that apparatuses with differently sized capillaries as well as one set and multiple set apparatuses can be provided with identically shaped basic bodies such that one and the same holder - that preferably is connected to the different supply means as well as pumping devices - can be used for coating different container shapes at different times.
  • plasma treating/plasma coating devices wherein at least some of the apparatuses and/or a part of some of them is formed in one common block.
  • Such embodiments comprise embodiments wherein several apparatuses are fixed together, e.g. by joining common basic bodies and/or common second electrodes .
  • Suitable coating materials are those that vaporize below about 200 0 C at ambient pressure (about 1 + 0.1 atmosphere) . Compounds with higher vaporization temperatures can also be used, however, they in general necessitate the use of lower pressures. Such vaporized compounds herein are also referred to as process gases.
  • a method for the beam plasma treatment and/or beam plasma coating of a plastics surface and using an apparatus or device of the present invention comprises the steps of positioning the surface to be treated above the apparatus of the present invention, applying at least one plasma supporting and/or surface treating gas and optionally at least one coating gas at least through the inner beam plasma capillary during high frequency excita- tion applied to the inner capillary or to the second electrode, and applying a suction force to the outer beam plasma capillary.
  • the high frequency electric field applied must be such that it is sufficient to ignite and support/maintain the plasma.
  • the surface to be treated/coated is the inner surface of a packaging container made of plastics.
  • said con- tainer is applied to the outer surface of the outer beam plasma capillary or to the outer surfaces of the outer beam plasma capillaries of a set of beam plasma capillaries, and then at least one plasma supporting and/or surface treating gas and optionally at least one coating gas are applied at least through the inner beam plasma capillary during high frequency excitation applied to either the inner capillary or a second electrode, and applying a suction force to the outer beam plasma capillary.
  • the surface to be treated is the outer surface of a packaging container, such as a bottle and in particular a tube, especially the outer surface in the area around the container mouth, in particular the elongated neck part of a tube.
  • said container is positioned at an appropriate distance from the distal end of the apparatus and coaxially with the apparatus .
  • the distal end of the plasma beam apparatus and the container end to be treated are positioned opposite to each other in a casing, in particular a tubular casing that at least at its ends fits to the container wall and the plasma beam apparatus .
  • At least one plasma supporting and/or surface treating gas and optionally at least one coating gas are applied at least through the inner beam plasma capillary during high frequency excitation applied to ei- ther the inner capillary or a second electrode, and applying a suction force to the outer beam plasma capillary.
  • the other end of the container i.e. the end that is not surface treated, can be connected to a suction apparatus .
  • At least one plasma coating gas besides of the at least one plasma supporting and/or surface treating gas at least one plasma coating gas is provided.
  • the at least one plasma supporting/surface treating gas and the at least one coating gas can be fed through different beam plasma capillaries or, preferred, are fed admixed.
  • a first process gas is fed through the inner capillary
  • a second process gas is fed through a second beam plasma capillary and at least part and preferably only part of the excess gases and the waste gases are removed via the outer beam plasma capil- lary.
  • the first process gas in general comprises gases selected from the group comprising rare gases, oxygen, nitrogen, hydrogen and mixtures thereof. It can be admixed with further compounds such as e.g. alcohols, in particular aliphatic alcohols, aldehydes, silanes, disi- lanes, disiloxanes, disilazanes and mixtures thereof, however, such admixture is less preferred unless the surface of the inner beam plasma capillary is inert (or made inert) to such admixtures.
  • the second process gases in general comprise gases selected from silicon comprising compounds (e.g. silanes) and hydrocarbons, wherein silicon organic compounds are preferred.
  • the compounds are selected from the group comprising alcohols, in particular aliphatic alcohols, aldehydes, silanes, disilanes, disiloxanes, disilazanes and mixtures thereof, optionally in combination with gases as mentioned above.
  • the surface treatment leads to ' a reduced oxygen permeability of the plastics substrate, in particular the tube.
  • silicon comprising compounds are preferred, in particular hexamethyldisilox- ane (CH 3 ) 3 -Si-O-Si- (CH 3 ) 3, hexamethyldisilazane (CH 3 ) 3 -Si- HN-Si- (CH 3 ) 3/ tetramethylsilane (CH 3 ) 4-Si, tetramethydisi- loxane H (CH 3 ) 2 -Si-O-Si- (CH 3 ) 2 H, tetraethoxysilane (C 2 H 5 O) 4 - Si, and mixtures of two or more of these compounds.
  • the method of the present invention is preferably performed at pressures close to atmospheric pressure, in general ambient pressure, although for certain applications reduced pressure can be provided. Besides of about atmospheric pressure, a pressure range of 5 mbar to 800 mbar is preferred.
  • ambient pressure or slightly reduced pressure that can be easily achieved with common pumping devices is much preferred in an inventive method for the plasma treatment/plasma coating of the inner and/or outer surface of tubes since no evacuation prior to plasma treatment is necessary and no vacuum chamber to avoid collapsing of the tubes is neces- sary, thereby saving investment costs and time.
  • Minimum sparking potentials Vs for some gases can be found in Naidu, M.S. and Kamaraju, V., High Voltage Engineering, 2nd ed . , McGraw Hill, 1995, ISBN 0-07-462286-2.
  • Suitable frequences of the voltage applied are from 50 Hz to 10 GHz, preferably from 1 kHz to 9 GHz, much preferred from 5 kHz to 50 MHz, most preferred about 27.12 MHz, and the effective voltage in general ranges from 100 V e ff to 10kV e ff, preferably from 500 V e ff to 5 kV e ff, much preferred from 0.8 kV e ff to 1.5kV e ff.
  • this coating can be and preferably is applied in pulsed mode, most preferably at a frequency of 100 Hz and duty cycle of 0.1 for an operating frequency of 27.12 MHz.
  • said packaging container and/or said beam plasma capillaries can be axially moved with regard to each other either in a stepwise or in continuous mode. The velocity of the relative movement allows the regula- tion of e.g. the surface treatment intensity and the coating thickness.
  • a great advantage of the inventive beam plasma method is that it can be performed at temperatures between 30 0 C and 100 0 C which makes it perfectly suitable for a broad variety of plasties such as polyethylene and polypropylene, polyethylene terephthalate, and polyethylene naphthalate .
  • the regulation of the plasma temperature can be made through the process gas temperature.
  • the inventive plasma treatment and/or plasma coating method can be applied in one step or in consecutive steps.
  • inventive method can be used in combination with chemical methods such as the subsequent or previous application of antifungal/antibacterial coatings, heat sealable layers etc.
  • the inventive method can be used to homogeneously coat the whole circumferential area of a certain extent in axial direction of the container or of the whole container. If for the main body forming part of the container a compound material comprising a diffusion barrier, e.g. an aluminium layer, is used, the plasma treatment/plasma coating can be more intense at the (elon- gated) neck part, the seams etc.
  • a diffusion barrier e.g. an aluminium layer
  • a container with a surface treated according to the present invention can then be filled and closed according to conventional methods .
  • the filling in general is performed from the bottom part prior to sealing it.
  • bottles it is possible to first fill them from the bottom and then seal them by connecting a bottom part to the tube- like side wall, or to first connect a bottom part to the tube-like side wall and then fill the bottle from the top.
  • Figure 1 shows a plasma beam apparatus of the present invention (with a second electrode shown) used for applying a permeation resistant layer to the inner surface of a plastic tube in a section along the longitudinal axis.
  • Figure 2 shows a preferred embodiment of the plasma beam apparatus (with the second electrode not shown) in a section along the longitudinal axis, said beam apparatus having an outer capillary with circular bores fully surrounded by insulator material.
  • Figure 3 is a cross section along line A-A of Figure 2.
  • Figure 4 is another preferred embodiment of the beam apparatus (with the second electrode not shown) in a section along the longitudinal axis, said beam apparatus having an outer capillary with peripheral semicircular bores.
  • Figure 5 is a cross section along line A-A of
  • Figure 6 is a schematic presentation of an apparatus with multiple sets of capillaries within a tube in cross-section perpendicular to the longitudinal axis.
  • Figure 7 shows a device of the present invention with two sets of capillaries joining the same body parts and the same counter electrode in section along the longitudinal axis .
  • Figure 8 is a schematic presentation of a de- vice of the present invention with a circular arrangement of inventive apparatuses in cross-section perpendicular to the longitudinal axis, each apparatus shown in a cut at a position as shown in- Figure 1 by line A-A.
  • Figure 9 is a schematic presentation of a device of the present invention with a circular arrangement of modules of inventive apparatuses, each apparatus shown in a cut at a position as shown in Figure 1 by line B-B.
  • Figure 10 is a schematic presentation of a plasma beam apparatus arranged for the treatment of outer surfaces in a section along the longitudinal axis .
  • FIG. 1 An apparatus 100 with one set of capillaries that is suitable for the plasma treatment/plasma coating of small containers, in particular small bottles or especially small tubes, with two electrodes 9, 12 in an arrangement for the treatment of inner surfaces of containers, especially bottles and in particular tubes, is shown in Figures 1 to 5.
  • the inner beam plasma capillary 9 is at its proximal end hold in a fitting bore in the basic body 6 and extends into a larger bore in basic body 5, said bore in basic body 5 forms part of the gas supply for the first process gas 3.
  • Capillary 9 extends axially from its proximal end, where it extends over the second beam plasma capillary 10, to its distal end, where, in the preferred embodiments shown in Figures 1 to 5, it ends within the second beam plasma capillary 10 thereby ensuring suitable mixing of the first and second process gases.
  • Plasma generation is pre- ferred at the distal end of the second beam plasma capillary 10.
  • Said second beam plasma capillary 10 at its proximal end is hold in a fitting bore in basic body 7 and extends into a larger bore forming part of basic body 6 and of the gas supply for the second process gas 4.
  • the basic bodies 5, 6, 7 and 8 are connected to each other by any suitable connecting means such as a screw and preferably sealed to each other by a gasket.
  • the outer beam plasma capillary 2 is a body of electrically insu- lating material that comprises a plurality of (e.g. 8) capillaries arranged either within and completely bound by said material 2a ( Figures 2, 3) or peripherally 2b ( Figures 4, 5) such that the capillaries are formed by the outer beam plasma capillary in combination with the tube.
  • the outer beam capillary 2 is such that - except for peripheral capillaries 2b - it tightly fits to the tube-like container 1, and the tube-like container 1 is hold in the basic body 8 by any suitable holding or sealing means, preferably by a gasket 17.
  • Body part 6 includes an electrical connection to the inner capillary 9, the capillary made of metal, in particular molybdenum or tungsten, or tantalum or steel, most advantageously tungsten.
  • This electrical connection is either connected to the RF-power supply unit 11a (preferably providing 13.56 MHz or 27.17 MHz) via an impedance adaptation network, or it is connected to ground potential.
  • a second electrode 12 must be present that is connected to the RF-power supply lib.
  • the several body parts 5, 6, 7, 8 can be fixed by e.g. screws and sealed by there between positioned gaskets 18.
  • a second electrode 12 may or must be present. In the case where the second electrode is optional, it is connected to mass lib.
  • Said second electrode 12 comprises a bore fitting the elongated neck of the tube 1 to be coated. Said bore goes through the whole electrode allowing excess and waste gases to leave the apparatus by this way.
  • the distant opening 13 of the bore in the second electrode 12 can be connected and preferably is connected to an exhaust gas line that can be connected to a pumping device.
  • the whole device is provided with valves allowing the regulation of the specific flows and optionally with flow meters and/or pressure indicators.
  • the whole apparatus can in addition be connected to an automatic regulation device regulating the treatment/coating conditions and speeds .
  • Such a plasma apparatus is used as follows: First the tube to be treated is applied to the plasma beam apparatus to provide an arrangement as shown in Figures 1, 2 and 4. The tube body 1 is pushed onto the outer plasma beam capillary 2 such that it forms therewith a gas tight seal. The gas supply occurs via gas support tubes 3, 4 that lead to the disc like basic bodies 5, 6. As described above, the disc-like basic bodies serve the fixation of the beam capillaries 9, 10 that are arranged one within the other.
  • the excess and waste gases of the process on the one hand are guided through capillaries 2a, 2b in the outer plasma beam capillary 2 to the body part 7, on the other hand they exhaust through the shaped/formed part that simultaneously acts as counter electrode 12 and that is connected to mass and to the outlet of the tube-like container in a gas-tight manner. If a vacuum pump is connected to the outlet of the tube-like container, or rather the shaped/formed part tightly connected thereto, the exhaust gas 13 can be sucked off and collected for possible recovery and recycling.
  • the plasma 14 is ignited and extends from the capillaries in a beam-like shape such that it is suitable to treat the inner surface of the container 1 in a defined manner.
  • Such an arrangement can be used with all the above outlined gases and vapors, preferably, however, it is used with argon, oxygen and admixtures of silanes, disilanes and disiloxanes although it can also be used with pure nitrogen or nitrogen-oxygen mixtures.
  • Figure 6 schematically shows an apparatus with multiple sets of capillaries within a tube in cross- section perpendicular to the longitudinal axis.
  • Figure 7 shows a device of the present invention with two sets of capillaries joining the same body parts and the same counter electrode. Both sets of capillaries are simultaneously used. In stead of a linear arrangement more than two such plasma beam apparatuses can also be circularly arranged. Such an arrangement is schematically shown in cross-section perpendicular to the longitudinal axis in Figure 8.
  • the apparatuses of the present invention can also be formed as modules, such that each can easily be replaced, e.g. in case of damage.
  • a modular arrangement is also advantageous if one and the same device shall be used for the treatment of different tube diameters.
  • a device in an intermediate state with two of the six modules exchanged is shown in Figure 9. In view of the different tube lengths in general all modules will be changed from one kind to another. Thus, Figure 9 rather shows an in- termediate state than a final state.
  • Figure 10 shows an arrangement of an apparatus 100 of the present invention for the treatment of the outer surface of a container 1, especially the mouth part of said container 1.
  • the distal end of the capillaries and the container mouth both are positioned in a casing 20 tightly fitting to the outer surface otf the container as well as to the outer surface of the outer capillary of the plasma beam apparatus 100.
  • the container is e.g. a collapsible tube
  • the tube body may be tightly positioned on a preferably hollow holder 21 that at one end is open towards the area defined by casing 20, the mouth end of container 1 and the distal end of apparatus 100 and at the other end connected to a suction device suitable for assisting in the removal of excess and exhaust gases.
  • the modular device preferably comprises totally independent modules, i.e. each module has its own connections to power and gas supplies, although it is also possible that the modules are provided with connect- able bores for gas distribution or power connections . In this case, however, valves must be provided to ensure ho- mogeneous gas and pressure distribution over all apparatuses .

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Chemical Vapour Deposition (AREA)
  • Plasma Technology (AREA)

Abstract

L'invention concerne un appareil (100) approprié au revêtement appliqué sous plasma de surfaces en matière plastique, ledit appareil (100) comportant au moins un ensemble de capillaires (2, 9, 10), chaque ensemble comportant de préférence trois capillaires faisceaux-plasma (2, 9, 10), un premier capillaire faisceau-plasma ou capillaire interne (9) étant fait d'un matériau électroconducteur, un second capillaire faisceau-plasma (10) et un capillaire de faisceau-plasma externe (2), tous les deux faits d'un matériau inerte. Les premier et second capillaires faisceaux-plasma (9, 10) servent à l'alimentation en gaz plasma, tandis que le troisième capillaire sert au transport des gaz de dégagement. L'un ou l'autre du premier capillaire faisceau-plasma (9) ou d'une seconde électrode (12) est connecté à un générateur à haute fréquence ou à une masse (11a, 11b).
PCT/CH2007/000468 2007-09-21 2007-09-21 Appareil pour revêtement appliqué sous plasma de la surface interne de contenants d'emballage tubulaires en matière plastique au moyen d'un faisceau-plasma non thermique à pression ambiante réactive WO2009036579A1 (fr)

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PCT/CH2007/000468 WO2009036579A1 (fr) 2007-09-21 2007-09-21 Appareil pour revêtement appliqué sous plasma de la surface interne de contenants d'emballage tubulaires en matière plastique au moyen d'un faisceau-plasma non thermique à pression ambiante réactive

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PCT/CH2007/000468 WO2009036579A1 (fr) 2007-09-21 2007-09-21 Appareil pour revêtement appliqué sous plasma de la surface interne de contenants d'emballage tubulaires en matière plastique au moyen d'un faisceau-plasma non thermique à pression ambiante réactive

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WO2010129783A1 (fr) * 2009-05-06 2010-11-11 3M Innovative Properties Company Appareil et procédé pour le traitement au plasma de contenants
US20110139751A1 (en) * 2008-05-30 2011-06-16 Colorado State Univeristy Research Foundation Plasma-based chemical source device and method of use thereof
US8304976B2 (en) 2009-06-30 2012-11-06 3M Innovative Properties Company Electroluminescent devices with color adjustment based on current crowding
WO2012163876A1 (fr) * 2011-05-31 2012-12-06 Leibniz-Institut für Plasmaforschung und Technologie e.V. Dispositif et procédé de production d'un plasma froid homogène dans des conditions de pression atmosphérique
US8541803B2 (en) 2009-05-05 2013-09-24 3M Innovative Properties Company Cadmium-free re-emitting semiconductor construction
US8629611B2 (en) 2009-06-30 2014-01-14 3M Innovative Properties Company White light electroluminescent devices with adjustable color temperature
CN103681197A (zh) * 2013-12-11 2014-03-26 苏州市奥普斯等离子体科技有限公司 一种毛细玻璃管内壁等离子体处理装置
EP2716606A4 (fr) * 2011-05-31 2014-11-05 Korea Basic Science Inst Dispositif au plasma de tube capillaire sous-marin doté d'un canal de gaz
US8994071B2 (en) 2009-05-05 2015-03-31 3M Innovative Properties Company Semiconductor devices grown on indium-containing substrates utilizing indium depletion mechanisms
CN104812154A (zh) * 2015-04-22 2015-07-29 西安交通大学 一种三电极介质阻挡放电等离子体发生装置
US9293622B2 (en) 2009-05-05 2016-03-22 3M Innovative Properties Company Re-emitting semiconductor carrier devices for use with LEDs and methods of manufacture
KR20190102462A (ko) * 2018-02-26 2019-09-04 (주)선재하이테크 가스 스트림에 적용되는 인-라인형 정전기 제거장치
WO2021064242A1 (fr) * 2019-10-04 2021-04-08 Leibniz-Institut für Plasmaforschung und Technologie e.V. Système et procédé de commande de configuration de jet de plasma
WO2022207563A1 (fr) * 2021-04-01 2022-10-06 Universiteit Gent Dispositif et procédé de génération d'un jet de plasma
WO2024031118A3 (fr) * 2022-08-09 2024-04-11 Thermal Processing Solutions GmbH Dispositif de préparation d'un plasma

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US9288886B2 (en) * 2008-05-30 2016-03-15 Colorado State University Research Foundation Plasma-based chemical source device and method of use thereof
US20110139751A1 (en) * 2008-05-30 2011-06-16 Colorado State Univeristy Research Foundation Plasma-based chemical source device and method of use thereof
US8994071B2 (en) 2009-05-05 2015-03-31 3M Innovative Properties Company Semiconductor devices grown on indium-containing substrates utilizing indium depletion mechanisms
US8541803B2 (en) 2009-05-05 2013-09-24 3M Innovative Properties Company Cadmium-free re-emitting semiconductor construction
US9293622B2 (en) 2009-05-05 2016-03-22 3M Innovative Properties Company Re-emitting semiconductor carrier devices for use with LEDs and methods of manufacture
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US8304976B2 (en) 2009-06-30 2012-11-06 3M Innovative Properties Company Electroluminescent devices with color adjustment based on current crowding
US8629611B2 (en) 2009-06-30 2014-01-14 3M Innovative Properties Company White light electroluminescent devices with adjustable color temperature
EP2716606A4 (fr) * 2011-05-31 2014-11-05 Korea Basic Science Inst Dispositif au plasma de tube capillaire sous-marin doté d'un canal de gaz
WO2012163876A1 (fr) * 2011-05-31 2012-12-06 Leibniz-Institut für Plasmaforschung und Technologie e.V. Dispositif et procédé de production d'un plasma froid homogène dans des conditions de pression atmosphérique
CN103681197A (zh) * 2013-12-11 2014-03-26 苏州市奥普斯等离子体科技有限公司 一种毛细玻璃管内壁等离子体处理装置
CN104812154A (zh) * 2015-04-22 2015-07-29 西安交通大学 一种三电极介质阻挡放电等离子体发生装置
KR20190102462A (ko) * 2018-02-26 2019-09-04 (주)선재하이테크 가스 스트림에 적용되는 인-라인형 정전기 제거장치
KR102020911B1 (ko) * 2018-02-26 2019-09-11 (주)선재하이테크 가스 스트림에 적용되는 인-라인형 정전기 제거장치
WO2021064242A1 (fr) * 2019-10-04 2021-04-08 Leibniz-Institut für Plasmaforschung und Technologie e.V. Système et procédé de commande de configuration de jet de plasma
US12239843B2 (en) 2019-10-04 2025-03-04 Leibniz-Institut für Plasmaforschung und Technologie e.V. System and method for operating a plasma jet configuration
WO2022207563A1 (fr) * 2021-04-01 2022-10-06 Universiteit Gent Dispositif et procédé de génération d'un jet de plasma
WO2024031118A3 (fr) * 2022-08-09 2024-04-11 Thermal Processing Solutions GmbH Dispositif de préparation d'un plasma

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