DE19640528A1 - Method and apparatus for treatment of components by vacuum technology processes - Google Patents

Method and apparatus for treatment of components by vacuum technology processes

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Publication number
DE19640528A1
DE19640528A1 DE1996140528 DE19640528A DE19640528A1 DE 19640528 A1 DE19640528 A1 DE 19640528A1 DE 1996140528 DE1996140528 DE 1996140528 DE 19640528 A DE19640528 A DE 19640528A DE 19640528 A1 DE19640528 A1 DE 19640528A1
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Germany
Prior art keywords
arrangement according
parts
vacuum
processes
treatment
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Withdrawn
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DE1996140528
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German (de)
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Roland Dr Gesche
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Priority to DE1996140528 priority Critical patent/DE19640528A1/en
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/14—Plasma, i.e. ionised gases
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Public Health (AREA)
  • Plasma & Fusion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The method and apparatus for treatment of components by processes of vacuum technology are characterised by the following facts: a) the components are introduced into an airtightly closable container; b) this container is either vacuumised or is filled with a process gas at a low pressure; c) the components in the container are subjected to vacuum technology processes.

Description

Die Anmeldung beschreibt eine Verfahren zur vakuumtechnischen Behandlung von Teilen, insbesondere mit Niederdruck-Gasentladungen (Plasmen). Diese Verfahren sind in der Beschichtungstechnik (PVD, CVD) weit verbreitet und gewinnen zuneh­ mend Bedeutung in der Oberflächenbehandlung. Wichtige Anwendungen sind hier­ bei die Reinigung und Entfettung von Teilen, die Aktivierung von Kunststoffoberflä­ chen und die Sterilisation im medizinischen Bereich. Die Anmeldung beschreibt ein Verfahren, bei dem die zu behandelnden Teile nicht in stationären Vakuumkessel behandelt werden, sondern vielmehr in vakuumtaugliche Verpackungsbehälter ein­ gebracht und in diesen sowohl behandelt als auch gelagert werden.The application describes a process for the vacuum treatment of Parts, especially with low pressure gas discharges (plasmas). This procedure are widely used in coating technology (PVD, CVD) and are gaining in popularity Importance in surface treatment. Important applications are here when cleaning and degreasing parts, activating plastic surfaces chen and sterilization in the medical field. The registration describes a Process in which the parts to be treated are not in stationary vacuum vessels are treated, but rather in vacuum-compatible packaging containers brought and both treated and stored in these.

Stand der TechnikState of the art

Vakuumtechnische Prozesse werden derzeit in stationären Vakuumkesseln durch­ geführt, die fest mit den vakuumtechnischen Komponenten (Pumpen, Meßgeräte, Gasversorgungen) verbunden sind und mit den erforderlichen Behandlungsein­ richtungen (Stromquellen, Antennen, Kathoden, Verdampfer, etc.) ausgerüstet sind. Vacuum technology processes are currently carried out in stationary vacuum boilers which are firmly connected to the vacuum components (pumps, measuring devices, Gas supplies) and associated with the required treatment directions (power sources, antennas, cathodes, evaporators, etc.) are equipped.  

Je nach Anwendung können auch Manipulatoren zur Be- und Entladung vorgese­ hen sein. Für viele plasmatechnische Anwendungen (Reinigung, Entfettung, Aktivie­ rung, Sterilisation, CVD-Beschichtung) ist diese Technologie zu aufwendig und zu teuer, obwohl sich hochwertige Ergebnisse mit guter Umweltverträglichkeit erzielen lassen.Depending on the application, manipulators for loading and unloading can also be provided hen. For many plasma technology applications (cleaning, degreasing, activation tion, sterilization, CVD coating), this technology is too complex and too expensive, although high-quality results with good environmental compatibility are achieved to let.

Bei vielen Anwendungen weiterhin das technische Problem auf, daß Prozeßergeb­ nisse bei und nach der Entladung solcher Anlagen beeinträchtigt werden. Entfettete Teile oxidieren schnell, die Aktivierung von Kunststoffoberflächen wird schwächer und sterile Teile verlieren ihre Sterilität.In many applications, the technical problem that process results nisse during and after the unloading of such systems. Degreased Parts oxidize quickly, the activation of plastic surfaces becomes weaker and sterile parts lose their sterility.

Aufgabenstellung für die vorliegende Erfindung war es, ein neues Verfahren zur schaffen, welches kostengünstige Plasmabehandlungen erlaubt und die behandel­ ten Teile anschließend hermetisch abgeschlossen hält.The task for the present invention was to develop a new method create, which allows inexpensive plasma treatments and the treated then holds the hermetically sealed parts.

Beschreibung der VerfahrensDescription of the procedure

Die Aufgabenstellung wird erfindungsgemäß dadurch gelöst, das die zu behandeln­ den Teile (2) in vakuumtaugliche Verpackungsbehälter (1) eingebracht werden. Diese Behälter werden mit einer Vakuumpumpe (4) verbunden und evakuiert. An­ schließend wird ggfs. das benötigte Prozeßgas (5) eingelassen. Zur Behandlung, die typischerweise durch eine Plasmaanregung erfolgt, wird der Behälter mit den Werkstücken einem elektromagnetischen Wechselfeld (6) ausgesetzt, daß die Energie für die Ionisierung liefert. Nach dem Prozeß verbleibt das Werkstück unter Vakuum im Behälter (7) und kann so unter Vakuum gelagert werden.According to the invention, the object is achieved by introducing the parts ( 2 ) to be treated into vacuum-compatible packaging containers ( 1 ). These containers are connected to a vacuum pump ( 4 ) and evacuated. Finally, the required process gas ( 5 ) is let in. For the treatment, which is typically carried out by plasma excitation, the container with the workpieces is exposed to an alternating electromagnetic field ( 6 ) that supplies the energy for the ionization. After the process, the workpiece remains in the container ( 7 ) under vacuum and can thus be stored under vacuum.

Alternativ kann auch im Behälter während der eigentlichen Behandlung ein Gas kontinuierlich zugeführt und abgesaugt werden.Alternatively, a gas can also be in the container during the actual treatment continuously fed and suctioned off.

Es ist ebenfalls möglich, das Prinzip für reine Vakuumbehandlungen und für thermi­ sche Vakuumbehandlungen zu verwenden. It is also possible to use the principle for pure vacuum treatments and for thermi to use vacuum treatments.  

Wenn die Behälter aus nichtleitendem Material gefertigt sind, wird für die Plasmaan­ regung lediglich eine äußere Energieversorgung mit einem Wechselfeld benötigt. Dies kann eine Nieder-, Mittel-, oder Hochfrequenzquelle ebenso sein wie eine Mikrowellenversorgung. Es ist denkbar, kleine Teile in einem handelsüblichen Mikrowellenherd zu behandeln.If the containers are made of non-conductive material, the plasma is used excitation only requires an external energy supply with an alternating field. This can be a low, medium or high frequency source as well as one Microwave supply. It is conceivable to have small parts in a commercial Treat microwave oven.

In metallischen Lagerbehältern müssen zu Plasmaanregung Elektroden vorgese­ hen sein. Diese können auch mit Gleichspannung betrieben werden.Electrodes have to be preadjusted in plasma storage containers for plasma excitation hen. These can also be operated with DC voltage.

Die Lagerung unter Vakuum verhindert, daß die behandelten Teile an Atmosphäre beeinträchtigt werden. Die Behälter können erst kurz vor dem nächsten Behand­ lungsschritt (Lackieren, Beschichten, Löten, etc.) geöffnet werden, was einen Pro­ duktionsablauf vereinfacht.Storage under vacuum prevents the treated parts from getting into the atmosphere be affected. The containers can only be used shortly before the next treatment opening step (painting, coating, soldering, etc.), which is a pro production process simplified.

Besonders interessant ist das Verfahren in der Medizintechnik. Die Sterilisation mit Plasma ist möglich, jedoch ist die anschließende sterile Verpackung bei der her­ kömmlichen Technologie nicht zu gewährleisten. Die Plasmasterilisation von ver­ packten Gegenständen erfordert jedoch spezielle Prozeßgase. Mit dem hier be­ schriebenen Verfahren sind diese Probleme gelöst. Die Gegenstände werden im Aufbewahrungsbehälter plasmasterilisiert und im Vakuum keimfrei aufbewahrt. Das Vakuum liefert dabei eine sichere Indikation über den andauernden Abschluß, wei­ terhin können Indikatoren für die Plasmabehandlung vorgesehen werden.The process is particularly interesting in medical technology. Sterilization with Plasma is possible, but the subsequent sterile packaging is from here not guarantee conventional technology. The plasma sterilization of ver packed items, however, requires special process gases. With this one written procedures, these problems are solved. The objects are in the Storage containers are plasma sterilized and kept germ-free in a vacuum. The Vacuum provides a reliable indication of the ongoing closure, white indicators for plasma treatment can also be provided.

Claims (13)

1. Verfahren und Anordnung zur Behandlung von Teilen mit vakuumtechnischen Prozessen, dadurch gekennzeichnet, daß die Teile in luftdicht verschließbare Behälter eingebracht werden, diese evakuiert und ggfs. mit Prozeßgas niedri­ gen Druckes beaufschlagt werden, und die Teile in den Behältern den vaku­ umtechnischen Prozessen unterzogen werden.1. The method and arrangement for treating parts with vacuum processes, characterized in that the parts are introduced into airtight closable containers, these are evacuated and possibly pressurized with process gas low pressure, and the parts in the containers subjected to the vacuum engineering processes will. 2. Verfahren und Anordnung nach Anspruch 1, dadurch gekennzeichnet, daß die Teile vor oder nach den vakuumtechnischen Prozessen in den verschlossenen Behältern unter Abschluß von der Atmosphäre zur Aufbewahrung verbleiben.2. The method and arrangement according to claim 1, characterized in that the Parts before or after the vacuum processes in the closed Containers should be kept away from the atmosphere for storage. 3. Verfahren und Anordnung nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei den vakuumtechnischen Prozessen um Plasmaprozesse handelt.3. The method and arrangement according to claim 1, characterized in that it the vacuum technology processes are plasma processes. 4. Verfahren und Anordnung nach Anspruch 3, dadurch gekennzeichnet, daß die Plasmaprozesse zur CVD-Beschichtung verwendet werden.4. The method and arrangement according to claim 3, characterized in that the Plasma processes can be used for CVD coating. 5. Verfahren und Anordnung nach Anspruch 3, dadurch gekennzeichnet, daß die Plasmaprozesse zur Aktivierung für Kunststoffoberflächen verwendet werden. 5. The method and arrangement according to claim 3, characterized in that the Plasma processes can be used for activation for plastic surfaces.   6. Verfahren und Anordnung nach Anspruch 3, dadurch gekennzeichnet, daß die Plasmaprozesse zur Reinigung von Teilen verwendet werden.6. The method and arrangement according to claim 3, characterized in that the Plasma processes can be used to clean parts. 7. Verfahren und Anordnung nach Anspruch 3, dadurch gekennzeichnet, daß die Plasmaprozesse zur Entfettung von Teilen verwendet werden.7. The method and arrangement according to claim 3, characterized in that the Plasma processes for degreasing parts can be used. 8. Verfahren und Anordnung nach Anspruch 3, dadurch gekennzeichnet, daß die Plasmaprozesse zur Sterilisation von Teilen verwendet werden.8. The method and arrangement according to claim 3, characterized in that the Plasma processes can be used to sterilize parts. 9. Verfahren und Anordnung nach Anspruch 2, dadurch gekennzeichnet, daß Teile aus dem medizinischen Bereich sterilisiert und steril aufbewahrt werden.9. The method and arrangement according to claim 2, characterized in that Parts from the medical field are sterilized and kept sterile. 10. Verfahren und Anordnung nach Anspruch 1, dadurch gekennzeichnet, daß das Prozeßgas niedrigen Druckes in den evakuierten Behälter eingelassen wird, dieser dann verschlossen und anschließend der vakuumtechnischen Behand­ lung unterzogen wird.10. The method and arrangement according to claim 1, characterized in that the Process gas of low pressure is admitted into the evacuated container, this then closed and then the vacuum treatment treatment. 11. Verfahren und Anordnung nach Anspruch 1, dadurch gekennzeichnet, daß das Prozeßgas dem Behälter während der vakuumtechnischen Behandlung beauf­ schlagt wird.11. The method and arrangement according to claim 1, characterized in that the Process gas to the container during the vacuum treatment is struck. 12. Verfahren und Anordnung nach Anspruch 1, dadurch gekennzeichnet, daß die Behälter aus nichtleitenden Materialien gefertigt sind.12. The method and arrangement according to claim 1, characterized in that the Containers are made of non-conductive materials. 13. Verfahren und Anordnung nach Anspruch 12, dadurch gekennzeichnet, daß die Behälter zur Behandlung der Teile elektromagnetischen Wechselfeldern ausgesetzt werden.13. The method and arrangement according to claim 12, characterized in that the containers for the treatment of the parts of alternating electromagnetic fields get abandoned.
DE1996140528 1996-10-01 1996-10-01 Method and apparatus for treatment of components by vacuum technology processes Withdrawn DE19640528A1 (en)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19814865A1 (en) * 1998-04-02 1999-10-07 Fraunhofer Ges Forschung Process for plasma treatment in hollow bodies
DE19944631A1 (en) * 1999-09-17 2001-03-22 Aurion Anlagentechnik Gmbh Unit for treating hollow body in vacuum recipient is useful for sterilization and/or surface modification, e.g. of plastics or glass bottle for food, cosmetics or pharmaceuticals
DE10202311B4 (en) * 2002-01-23 2007-01-04 Schott Ag Apparatus and method for the plasma treatment of dielectric bodies
DE102006025736A1 (en) * 2006-05-31 2007-12-06 RUHR-UNIVERSITäT BOCHUM sterilization procedures
WO2010116191A1 (en) * 2009-04-07 2010-10-14 Malcolm Robert Snowball Sterilisation of packaged articles
US8641977B2 (en) 2011-05-09 2014-02-04 Ozonica Limited Disinfection of packaged articles

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3116040C2 (en) * 1981-04-22 1983-04-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München Biocompatible carbon layers for coating flexible materials and methods for applying the layers
GB2155862A (en) * 1984-03-03 1985-10-02 Standard Telephones Cables Ltd Plasma surface processing
DE3801998C1 (en) * 1988-01-23 1989-05-18 Schertler, Siegfried, Haag, Ch
DE4031770A1 (en) * 1990-10-06 1992-04-09 Leybold Ag Dust prevention appts. for CVD chamber - has process gas feed and suction openings near plasma forming electrode
EP0503820A1 (en) * 1991-03-12 1992-09-16 The Boc Group, Inc. Plasma enhanced chemical vapour deposition device
EP0507547A2 (en) * 1991-04-01 1992-10-07 General Electric Company Improved irradiation resistant functionally endcapped polycarbonate
DE4112459A1 (en) * 1991-04-12 1992-10-15 Naum Dr Goldstein METHOD AND DEVICE FOR PRODUCING DEFINED IONIZED GASES OR. GAS MIXTURES
DE9213333U1 (en) * 1992-03-18 1993-03-18 Kiener, Hannelore, 7089 Lauchheim Airtight sealable freshness container
EP0593315A2 (en) * 1992-10-12 1994-04-20 Nihon Seiki Co. Ltd. Air-exaustible bag for storing articles
US5308649A (en) * 1992-06-26 1994-05-03 Polar Materials, Inc. Methods for externally treating a container with application of internal bias gas
DE4318084A1 (en) * 1993-06-01 1994-12-08 Kautex Werke Gmbh Process and device for producing a polymeric outer layer in plastic blow mouldings
DE4320098A1 (en) * 1993-06-17 1994-12-22 Groninger & Co Gmbh Decanting process
US5413758A (en) * 1990-08-31 1995-05-09 Abtox, Inc. Apparatus for plasma sterilizing with pulsed antimicrobial agent treatment
RU2037320C1 (en) * 1992-03-20 1995-06-19 Виктор Николаевич Коровин Method for sterilizing packed things
GB2287473A (en) * 1994-03-15 1995-09-20 Dr Joseph Franks Diamond coated polymer devices for biomedical applications
EP0679407A2 (en) * 1994-04-28 1995-11-02 JOHNSON & JOHNSON MEDICAL, INC. Vapor sterilization using a non-aqueous source of hydrogen peroxide
US5472509A (en) * 1993-11-30 1995-12-05 Neomecs Incorporated Gas plasma apparatus with movable film liners
DE4437269C1 (en) * 1994-10-18 1996-02-22 Balzers Hochvakuum Cleaning workpiece surfaces
EP0708185A1 (en) * 1994-10-17 1996-04-24 Leybold Aktiengesellschaft Apparatus for treating the surface of an object, especially the internal surface of fuel tanks
DE69208743T2 (en) * 1991-06-14 1996-07-25 France Telecom Process for cleaning oxidized metallic surfaces in the manufacture of interconnection networks and circuit boards for such networks
DE19502133A1 (en) * 1995-01-25 1996-08-01 Tiller Hans Juergen Sterilising metallic medical instruments, esp. dental instruments

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3116040C2 (en) * 1981-04-22 1983-04-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München Biocompatible carbon layers for coating flexible materials and methods for applying the layers
GB2155862A (en) * 1984-03-03 1985-10-02 Standard Telephones Cables Ltd Plasma surface processing
DE3801998C1 (en) * 1988-01-23 1989-05-18 Schertler, Siegfried, Haag, Ch
US5413758A (en) * 1990-08-31 1995-05-09 Abtox, Inc. Apparatus for plasma sterilizing with pulsed antimicrobial agent treatment
DE4031770A1 (en) * 1990-10-06 1992-04-09 Leybold Ag Dust prevention appts. for CVD chamber - has process gas feed and suction openings near plasma forming electrode
EP0503820A1 (en) * 1991-03-12 1992-09-16 The Boc Group, Inc. Plasma enhanced chemical vapour deposition device
EP0507547A2 (en) * 1991-04-01 1992-10-07 General Electric Company Improved irradiation resistant functionally endcapped polycarbonate
DE4112459A1 (en) * 1991-04-12 1992-10-15 Naum Dr Goldstein METHOD AND DEVICE FOR PRODUCING DEFINED IONIZED GASES OR. GAS MIXTURES
DE69208743T2 (en) * 1991-06-14 1996-07-25 France Telecom Process for cleaning oxidized metallic surfaces in the manufacture of interconnection networks and circuit boards for such networks
DE9213333U1 (en) * 1992-03-18 1993-03-18 Kiener, Hannelore, 7089 Lauchheim Airtight sealable freshness container
RU2037320C1 (en) * 1992-03-20 1995-06-19 Виктор Николаевич Коровин Method for sterilizing packed things
US5308649A (en) * 1992-06-26 1994-05-03 Polar Materials, Inc. Methods for externally treating a container with application of internal bias gas
EP0593315A2 (en) * 1992-10-12 1994-04-20 Nihon Seiki Co. Ltd. Air-exaustible bag for storing articles
DE4318084A1 (en) * 1993-06-01 1994-12-08 Kautex Werke Gmbh Process and device for producing a polymeric outer layer in plastic blow mouldings
DE4320098A1 (en) * 1993-06-17 1994-12-22 Groninger & Co Gmbh Decanting process
US5472509A (en) * 1993-11-30 1995-12-05 Neomecs Incorporated Gas plasma apparatus with movable film liners
GB2287473A (en) * 1994-03-15 1995-09-20 Dr Joseph Franks Diamond coated polymer devices for biomedical applications
EP0679407A2 (en) * 1994-04-28 1995-11-02 JOHNSON & JOHNSON MEDICAL, INC. Vapor sterilization using a non-aqueous source of hydrogen peroxide
EP0708185A1 (en) * 1994-10-17 1996-04-24 Leybold Aktiengesellschaft Apparatus for treating the surface of an object, especially the internal surface of fuel tanks
DE4437269C1 (en) * 1994-10-18 1996-02-22 Balzers Hochvakuum Cleaning workpiece surfaces
DE19502133A1 (en) * 1995-01-25 1996-08-01 Tiller Hans Juergen Sterilising metallic medical instruments, esp. dental instruments

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19814865A1 (en) * 1998-04-02 1999-10-07 Fraunhofer Ges Forschung Process for plasma treatment in hollow bodies
DE19814865C2 (en) * 1998-04-02 2000-09-07 Fraunhofer Ges Forschung Process for plasma treatment in hollow bodies
US6171450B1 (en) 1998-04-02 2001-01-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for plasma treatment in hollow bodies
DE19944631A1 (en) * 1999-09-17 2001-03-22 Aurion Anlagentechnik Gmbh Unit for treating hollow body in vacuum recipient is useful for sterilization and/or surface modification, e.g. of plastics or glass bottle for food, cosmetics or pharmaceuticals
DE10202311B4 (en) * 2002-01-23 2007-01-04 Schott Ag Apparatus and method for the plasma treatment of dielectric bodies
DE102006025736A1 (en) * 2006-05-31 2007-12-06 RUHR-UNIVERSITäT BOCHUM sterilization procedures
WO2010116191A1 (en) * 2009-04-07 2010-10-14 Malcolm Robert Snowball Sterilisation of packaged articles
CN102438661A (en) * 2009-04-07 2012-05-02 奥唑尼卡有限公司 Sterilisation of packaged articles
US10178874B2 (en) 2009-04-07 2019-01-15 Ozonica Limited Sterilisation of package articles
US8641977B2 (en) 2011-05-09 2014-02-04 Ozonica Limited Disinfection of packaged articles
US9597422B2 (en) 2011-05-09 2017-03-21 Ozonica Limited Disinfection of packaged articles

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