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FILM A BARRIERA rende i film barriera trasparenti molto importanti per l'industria del packaging.
TRASPARENTI Ci sono molti modi di produrre questi film, con diversi esiti di successo.
In questo articolo discuteremo il rivestimento dei film barriera mediante l'uso del plasma
By Rory Wolf, Enercon Industries Corporation, Menomonee Falls, Wisconsin, USA, Amelia Sparavigna, Dipartimento di Fisica, Politecnico di
Torino, Torino, Italy, Richard Ellwanger, Sigma Technologies International, Tucson, Arizona, USA
less than 1% for more than a step process for deposition and after creation of a plasma of the thousands of K, equivalent to
year. Other products incorpo- polymerization of clear barrier reacting gases, essentially at several eV average energy -
rate a barrier layer of ethylene coatings. The use of plasma in room temperatures. while the neutral atoms remain
vinyl alcohol (EVOH) to protect coating is known as PECVD, pla- Plasma is any gas in which a at the ambient temperature.
pharmaceutical products re- sma enhanced chemical vapor significant percentage of the These energetic electrons can
quiring protection from both deposition. PECVD is a process atoms or molecules are ioni- induce many processes that
moisture and oxygen. To pro- to deposit very thin films from a zed. A plasma can be created would otherwise be very
tect UV-sensitive products, vapor state to a solid state on by an AC discharge between improbable at low temperatu-
where it is desirable to have a substrates. In this process, spe- two electrodes where the in- res, such as dissociation of
clear package, an ultraviolet cies to be deposited are genera- between place can be filled precursor molecules and the
(UV) inhibitor can be added to ted in the plasma discharge. As with gases. Plasmas with low creation of large quantities of
the packaging film. a result, deposition using the fractional ionization are of free radicals.
We have discussed in our pre- same source gases is taking great interest for material pro- Because electrons are more
vious papers the role of surface place at lower temperatures cessing because the energy mobile than ions, plasma is
treatments in enhancing the sur- than in conventional CVD which exchange between the elec- normally more positive than
face film properties, in particular requires high temperature to trons and neutral gas is very any object it is in contact with.
the role of corona and plasma break bonds and to release desi- inefficient. In this plasma, the- Ionized atoms or molecules
treatments. We want to discuss red species from input gases. refore, the electrons can be feel then an electrostatic force
in this paper the use of atmo- The chemical reactions involved maintained at very high equi- and are accelerated towards
spheric plasma treatments as a in the process are occurring valent temperatures - tens of the neighboring surface.
Thus all surfaces exposed to pla- Clear barrier typically means silicon compounds are a logical stic sheet as a successful anti-
sma receive energetic ion bom- inorganic oxides or nitrides of choice. These materials are fog coating. It is not thick
bardment. This bombardment metals deposited on substra- easily selectable as liquids at enough to be a barrier coating
removes contaminants and tes. While deposition of inorga- room temperature and are con- but it is a significant step on
changes the film surface proper- nic oxides at reduced pressure sidered good candidates for the path to clear barrier.
ties. When the ion density is high is fairly routine, such processes thermal evaporation into the The reduction in moisture
enough, a significant sputtering and equipments are expensive. plasma gas stream. Producers transmission rate observed in
of a deposited film occurs. By The prospect of being able to of atmospheric plasma treaters experiments tells that the
inserting in the plasma the desi- add value by depositing an inor- are now working to develop the research is moving in the right
red precursor, a coating of the ganic oxide barrier layer using equipment and process metho- direction and we can tell that
surface is obtained. an inline, inexpensive, atmo- dology for deposition of a thin to get good barrier we will
spheric pressure process is functional coating of SiOx on need the procedural capability
extremely attractive. Much of plastic sheet that will display to perform multi-stage plasma
CLEAR BARRIER COATINGS
the current development effort barrier functionalities. polymerizations.
The continuing and growing is directed toward plasma poly- In the following section we will
interest in clear barrier for flexi- merization and oxidation of discuss Enercon plasma equip- THE PLASMA TUNNEL
ble packaging inevitably led us organo-silicon compounds to ment (see Fig.2) currently in
to investigate the opportunities yield a thin functional layer of place at one of the customer’s Figure 3 shows the schematic
of the use of plasma processes SiOx on a substrate such as a pilot facilities that is able to diagram of the atmospheric
in producing barrier coatings. plastic film or sheet. Organo- deposit a very thin SiOx on pla- PECVD reactor of Enercon, used
trattamento al plasma senza il piano di su un substrato di poliestere e imme- (WVTR) è misurabile con sistemi com-
scarica rivestito di dielettrico. Un gene- diatamente esposto a un “curing” di merciali (un sistema WVTR è prodotto
ratore RF produce la scarica. plasma di elio con la stessa potenza e da MOCON Inc., PERMATRAN-W-700).
I gas sono forniti alla linea di tratta- frequenza del plasma di deposizione. Un rivestimento di 35 nm su un film di
mento con un flusso controllato e pos- Tra le tante caratteristiche del film poliestere spesso 0.5 µm riduce la tra-
sono venire miscelati in una camera di depositato, una importante per la smissione del vapore acqueo da un
turbolenza e poi inviati al sistema di shelf-life dei prodotti è la permeabilità valore di 46 g/(m2-giorno) ad un valore
trattamento al plasma. La miscela dei al vapore acqueo del film. Il fattore di di 33 g/(m2-giorno).
gas, comprendente il tetrametildisilos- trasmissione del vapore d'acqua L'insieme dei trattatori al plasma può
sano (TMDSO) e aria com-
pressa, è usata per ottenere il
deposito di SiOx. I flussi rela-
tivi di TMDSO, elio e aria
compressa sono scelti per
ottimizzare la deposizione
del film di ossido di silicio.
Il coating di SiOx è depositato
For instance, polyester sub- bic and/or oleophobic proper- collected from experiments The multi-stage atmospheric
strates can be coated by vapor ties (Fig.5). Chlorine-based show that the production of plasma system that we have
deposition in a helium plasma precursors (chloro-carbons, plasma-enhanced coated sub- discussed is flexible enough to
at atmospheric pressure using chloro-silicones) produce bar- strates at atmospheric-pressu- allow the investigation of seve-
vaporized silicon-based mate- riers with biocide properties; re conditions is possible with ral processes. Due to its high
rials (siloxanes, alkyl silanes, and organo-metallic complex properties comparable to than modularity, it is also possible
silazanes, silsesquioxanes) precursors (silver, copper or previously obtained under to move this system toward a
mixed with the plasma-gas aluminum complex) produce vacuum plasma conditions. true industrial equipment.
stream and diffused into the barriers with electrostatic, dis- The plasma tunnel design can T a b l e - Three procedures to
treatment area. The resulting sipative, conductive, biocidal be used for treating and modif- obtain hydrophobicity/oleo-
products exhibited improved properties. ying the surface properties of phobicity, hydrophilic/anti-fog,
surface properties with regard Three examples illustrate the organic as well as inorganic biocide/anti-bacterial results.
to moisture- and oxygen-bar- combination of process steps substrates without vacuum The same procedures were
rier characteristics, scratch that can be produced in the equipment or material-thick- applied to polyester, poly-
and abrasion resistance, che- plasma tunnel (see Table). ness limitations. Based on the propylene, polyethylene, poly-
mical resistance, and low fric- The tests in the Table have the collected experimental data, it carbonate, polyamide, polyi-
tion. Positive results are obtai- same substrate material (PET is possible to tell that a large mide and cellulose derivative
ned with fluorine-based pre- film), the plasma gas is helium variety of other compounds films, paper and fabrics (wo-
cursors (fluorocarbons, fluoro- and the precursor is fed in with can be used as precursors with ven and nonwoven) with simi-
silicones) to provide hydropho- a varying proportion. The data related new methodologies. lar results.