11/18/2016 Applicationsofcoldplasmatechnologyinfoodpackaging

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Highlights
TrendsinFoodScience&Technology
Introduction Volume35,Issue1,January2014,Pages517
Plasma physics and chemistry
Modification of food packaging poly
Ageing effect
Applications Review
In-package plasma technology
Conclusions
Applicationsofcoldplasmatechnologyinfoodpackaging
Future trends
S.K.Pankaja,C.BuenoFerrera,N.N.Misraa,V.Milosavljevi a,b,C.P.O'Donnellb,P.Bourkea,K.M.
Acknowledgements
References Keenera,c ,P.J.Cullena, ,

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http://dx.doi.org/10.1016/j.tifs.2013.10.009 Getrightsandcontent
Figures and tables

Highlights
Table 1 Overviewofcoldplasmatheoryandequipment.
Table 2
Applicationsofcoldplasmaforfoodpackaging.
Table 3
Applicationsofcoldplasmaformodificationofsurfaceenergy,enhancementof
Table 4
adhesionandprintability.
Packagingdecontamination.
Newtrendsinthedevelopmentofinpackagedecontamination.

Coldplasmatechnologyisanemerging,greenprocessofferingmanypotential
applicationsforfoodpackaging.Whileitwasoriginallydevelopedtoincreasethesurface
energyofpolymers,enhancingadhesionandprintability,ithasrecentlyemergedasa
powerfultoolforsurfacedecontaminationofbothfoodstuffsandfoodpackaging
materials.Newtrendsaimtodevelopinpackagedecontamination,offeringnonthermal
ADVERTISEMENT
treatmentoffoodspostpackaging.Thispaperprovidesanoverviewofcoldplasma
theory,equipmentandsummarisesrecentadvancesinthemodificationofpolymeric
foodpackagingmaterialsalongwithpotentialapplicationsinthefoodindustry.

Introduction
Forthepastfewdecadesthetrendofreplacingtraditionalmaterialssuchasglass,
metalsandpaperbypolymericmaterialshasbeengrowingcontinuallywithinthevarious
processindustries,includingthefoodindustry.Thisisduetothefactthatphysicaland
chemicalcharacteristicsofpolymersareonaparwithconventionalmaterialsintermsof
functionality.Inaddition,polymericpackagingmaterialsprovidegreaterflexibility,
transparency,adequatechemicalinertness,havelowspecificweightsandtypicallycost
less.However,inmostcasespolymericsurfacesarehydrophobicinnatureandareoften
characterisedbyalowsurfaceenergy(Mdardetal.,2002aandVeselandMozetic,
2012).Thisimpliesthatthesedonotpossessthespecificsurfacepropertiesdemanded
invariousapplications.Moreover,theproductionofmultilayerstructuredfoodpackaging
polymersiseconomicallydemanding.Inordertoobtainpolymerswiththedesired
properties,inmostinstancesvarioussurfacetreatmentsareemployed.
Surfacetreatmentsofpackagingcanservevariouspurposesincludingsurface
functionalisation,surfacecleaningoretching,andsurfacedeposition.Surface
functionalisationreferstotheintroductionofspecificfunctionalgroupsontothesurface

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layerofapolymer.Surfacefunctionalisationofpolymersisusuallycarriedouttoimprove
itswettability,sealability,printability,dyeuptake,resistancetoglazing,oradhesionto
otherpolymersormaterials,withoutcompromisingthedesiredbulkpropertiesofthe
polymer(ChouandChang,1994andOzdemiretal.,1999a).Surfacefunctionalisation
hasadditionallybeenusedtoenhancebarriercharacteristicsoffoodpackaging
polymersandtoimpartantimicrobialproperties(Ozdemir,Yurteri,&Sadikoglu,1999b).
Surfacetreatmentscanalsobeemployedtocleanoretchpolymersurfacesbyremoving
unwantedmaterialsandcontaminantsfrompolymersurfacelayers.Additionallysurface
treatmentscanbeusedforthedepositionofthinlayersofcoatingsonpolymersurfaces
orforsterilisation.

Surfacemodificationofpolymerscanbeperformedeitherbychemicalorphysical
methods.Physicalmethodshavegainedpreferenceoverchemicaltechniques,offering
greaterprecision,easeofprocesscontrol,andenvironmentfriendliness.Classical
physicochemicalmethodsformodifyingpolymersurfacesincludeflameandcorona
treatment,ultravioletlight,gammaray,ionbeamtechniques,lowpressureplasmaand
lasertreatment(Adleretal.,1999).However,flameandcoronatreatmentsarenotwell
suitedtopolymersduetothelimitedtimescaleoftheimprovedproperties.
Coldplasma(CP)inducesseveralchemicalandphysicalprocesseswithintheplasma
volumeandontheplasmapolymerinterface,whichmodifythesurfaceproperties.This
phenomenaisexploitedinsurfacefunctionalisationtoimpartselectiveandtuneable
surfaceenergiestothepackagingpolymersforpromotingadhesionorsometimesanti
adhesion(PoncinEpaillard,Brosse,&Falher,1999),improvedprintability,sealability,
impartingantimistpropertiesandimprovingthepolymer'sresistancetomechanical
failure.Usingplasmadepositionofbarrierlayers,thebarrierpropertiesofthepackaging
materialstowardsgases(oxygen,carbondioxide)andchemicalsolventscanbe
improved(Schneideretal.,2009).Gasplasmareactionsalsoestablishefficient
inactivationofmicroorganisms(bacterialcells,spores,yeastsandmoulds)adheringto
polymersurfaceswithinshorttreatmenttimes.Packagingmaterialssuchasplastic
bottles,lidsandfilmscanberapidlysterilisedusingcoldplasma,withoutadversely
affectingtheirbulkpropertiesorleavinganyresidues(Muranyi,Wunderlich,&Heise,
2007).
Thispaperreviewsthestateoftheartforcoldplasmaapplicationsformodificationand
surfacesterilisationofpolymersofimportancetofoodpackaging,followingabrief
overviewofthephysicsandchemistryofcoldplasmas.Thepolymersconsideredinclude
polyethylene(PE),polypropylene(PP)andpolyethyleneterephthalate(PET),which
altogetheraccountformorethan80%offoodpackagingpolymers(PlasticstheFacts,
2012).Thereviewalsoidentifiesresearchgapsandoutlinesthedirectionforfuture
researchworkinthisarea.

Plasmaphysicsandchemistry
Thetermplasmareferstoaquasineutralionisedgas,primarilycomposedofphotons,
ionsandfreeelectronsaswellasatomsintheirfundamentalorexcitedstateswithanet
neutralcharge.Plasmadischargesarewidelyusedforprocessingandareindispensable
formanytechnologicalapplications(Milosavljevi,Karkari,&Ellingboe,2007).Through
theirwidevarietyofoperationalconditions,plasmasourcesofferatremendousfreedom
inthegenerationofradiationandthecreationofchemicalcompositions.Asaresultthe
fieldoftechnologicalandindustrialplasmaapplicationsisexpandingstrongly.Several
plasmaapplicationshavebeenidentifiedinliterature:highefficiencylightsources(the
richplasmaUVsourceforsurfacesterilisation),materialprocessing,suchasdeposition,
cleaningandsurfacemodification(Lawetal.,2012),spectrochemicalanalysis
(analyticalchemistryplasmaspectralemissioncanbeusedforelementdetectionwith
verylowdetectionlimits)(Milosavljevi,Ellingboe,&Daniels,2011),wastetreatment
(e.g.detoxificationuseofthermalplasmatorches,cascadedarcplasmas,or
microwaveplasmasfortheproductionofnegativeions).

Theionsandelectronsfromtheplasmaaregeneratedatanelectrodebymeansofa
radiofrequency(RF),microwave(MW)ordielectricbarrierdischarge(DBD)power

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source,andabiasingpowersourceisappliedtoanother(packagingholding)electrode
tocreateasignificantionbombardment(removecleandeposit)componentduring
plasmatreatment(Breen,Milosavljevi,&Dowling,2011).Theplasmaprocessisa
simultaneousdeposition/removingprocessinwhichlooselydepositedspeciesover
planarortopographicalsurfacesaresputteredoffbyreactiveionsandradicalsduring
deposition.
Plasmaisaneffective,economical,environmentallysafemethodforcriticalcleaning.
Thevacuumultraviolet(VUV)energyisveryeffectiveinthebreakingmostorganicbonds
(i.e.,CH,CC,CC,CO,andCN)ofsurfacecontaminants.Thishelpstobreakapart
highmolecularweightcontaminants(Donegan,Milosavljevi,&Dowling,2013).A
secondcleaningactioniscarriedoutbytheoxygenspeciescreatedintheplasma(O2+,
O2,O3,O,O+,O,ionisedozone,metastablyexcitedoxygen,andfreeelectrons).
ThesespeciesreactwithorganiccontaminantstoformH2O,CO,CO2,andlower
molecularweighthydrocarbons.Theresultingsurfaceisultraclean/sterilised.The
plasmaactivatedatomsandionscausemolecularsandblastingandcanbreakdown
organiccontaminants.
Mostofthecleaningprocessbyproductsaresmallquantitiesofgasessuchascarbon
dioxide,andwatervapourwithtraceamountsofcarbonmonoxideandother
hydrocarbons(Prysiazhnyi,Zaporojchenko,Kersten,&ernk,2012).Toputthisin
perspective,10minofautomobileexhaustisapproximatelyequivalenttooneyearof
plasmacleaning/sterilisationexhaust.Whetherornotorganicremovaliscompletecan
beassessedbycontactanglemeasurements.Whenanorganiccontaminantispresent,
thecontactangleofwaterwiththedevicewillbehigh.Aftertheremovalofthe
contaminant,thecontactanglewillbereducedtothecharacteristicofcontactwiththe
puresubstrate.Plasmacleaningrequiresoptimisationofanumberofinterrelated
variables,mostnotablygasspecies,pressure,timetreatment,natureofsubstrate,and
power.Thus,aseriesofexperimentsdesignedtooptimiseprocessingconditionsshould
becarriedout.Thenetresultisahighdegreeofdaytodayrepeatabilityandimproved
yields.
Differenttreatmentsystemsarebeingstudiedforapplicationtofoodpackagingsurfaces
(Kowalonek,Kaczmarek,&Dbrowska,2010).Acapacitycoupledplasma(CCP)
sourcesisoneofthemostcommontypesoftechnologicalplasmasources
(Milosavljevic,Ellingboe,Gaman,&Ringwood,2008).Itessentiallyconsistsoftwometal
electrodesseparatedbyasmalldistance,placedinachamber.Thegaspressureinthe
chambercanbelowerorequaltoatmospheric.AtypicalCCPsystemisdrivenbya
singleRFpowersupply,typicallyat13.56MHz.Oneoftwoelectrodesisconnectedtothe
powersupply,andtheotheroneisgrounded.Asthisconfigurationissimilarinprincipleto
acapacitorinanelectriccircuit,theplasmaformedinthisconfigurationiscalleda
capacitivelycoupledplasma.CCPshavewideapplicationincludingdeposition,
sputteringandcleaning(Ryan,O'Farrell,&Ellingboe,2011).

Aninductivecoupledplasma(ICP)isatypeofplasmasourceinwhichtheenergyis
suppliedbyelectricalcurrentswhichareproducedbyelectromagneticinduction,thatis,
bytimevaryingmagneticfields(Milosavljevic,Faulkner,&Hopkins,2007).Therearetwo
typesofICPgeometries:planarandcylindrical.Intheplanargeometry,theelectrodeisa
coilofflatmetalwoundlikeaspiral.Incylindricalgeometry,itislikeahelicalspring.
Whenatimevaryingelectriccurrentispassedthroughthecoil,itcreatesatimevarying
magneticfieldaroundit,whichinturninducesazimuthalelectriccurrentsintherarefied
gas,leadingtobreakdownandformationofplasma.ThebenefitofICPdischargesisthat
theyarerelativelyfreeofcontaminationbecausetheelectrodesarecompletelyoutside
thereactionchamber.InaCCP,incontrast,theelectrodesareoftenplacedinsidethe
reactorandarethusexposedtotheplasmaandsubsequentreactivechemicalspecies
(Bauer,Schmuki,vonderMark,&Park,2013).
Anelectroncyclotronresonance(ECR)plasmasourcehasamicrowaveinputat
2.45GHzandamagnetrongeneratesplasma(Milosavljevi,Macgearailt,Daniels,&
Turner,2013).Electronstrajectoryisspiralverticallyalongthemagneticfieldlines.
Magneticfieldstrengthis875Gausswithadomeshapedcontour.Theelectrodewhich
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holdsfoodpackagingcouldbeaRFpowersuppliedandisusedtogeneratedirect
current(DC)biasindependentlyofplasmaionisation.InECRelectronstravelfarenough
togainsufficientenergytostrikegasmoleculesandcauseionisation.Electrondensity
(ionflux)isoveranorderofmagnitudehigherthanforCCPorICPplasmatools,and
thereforemaybemoreefficientforsurfacetreatmentsofpackaging,i.e.surface
functionalisation,surfacecleaning,etching,and/orsurfacedeposition.

Dielectricbarrierdischarge(DBD)istheelectricaldischargebetweentwoelectrodes
separatedbyaninsulatingdielectricbarrier(O'Connor,Milosavljevic,&Daniels,2011).
Theprocessuseshighvoltagealternatingcurrent,oftenatlowerRFfrequencies,but
recentlyevenatmicrowavelevels.DBDdevicescanbeemployedinmany
configurations,typicallyplanar,usingparallelplatesseparatedbyadielectricor
cylindrical,usingcoaxialplateswithadielectrictubebetweenthem.Inacommoncoaxial
configuration,thedielectricisshapedinthesameformascommonfluorescenttubing.It
isfilledatatmosphericpressurewitheitherararegasorraregashalidemix,withthe
glasswallsactingasthedielectricbarrier.Duetotheatmosphericpressurelevel,such
processesrequirehighenergylevelstobesustained.Commondielectricmaterials
includeglass,quartz,ceramicsandpolymers(Liang,Jensen,Pappas,&Palmese,
2011).

Modificationoffoodpackagingpolymers
Polyethylene(PE)
StructurallyPEisoneofthesimplestpolymersusedinfoodpackaging.PEofvarying
densities,characterizedbydifferentWVTR(watervapourtransmissionrate),GTR(gas
transmissionrate),tensilestrength,heatsealingandotherpropertiesarecommercially
available.Thisprovidesfreedomtofoodmanufacturerstochoosethepackagetype
optimumfortheirneeds(Pankaj,Kadam,&Misra,2011).However,thelowsurface
energyofPE,hasdrivenmostoftheresearchincoldplasmatowardssurface
modificationsofPE.SurfacecharacterisationofPEwithCO2,H2OandCO2/H2Oplasma
hasbeenreportedbyMdardetal.(2002a)andtheproposedmechanismofCO2plasma
isdescribedinFig.1(Medard,Soutif,&PoncinEpaillard,2002b).Table1summarises
thekeyfindingsfromimportantstudiesconductedonPEusingcoldplasma.

Fig.1.
Mechanismsofdegradation,crosslinkingandfunctionalisationoccurringonpolyethylenetreatedbyCO2
coldplasma.
AdaptedfromMedardetal.(2002b),withpermission.

Figureoptions

Table1.
Summaryofreportedstudiesoncoldplasmaprocessingofpolyethylene(PE).

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Polymeric Plasmasource Treatmentconditions Keyfindings References

packaging
material
LDPEfilm RFdischarge Arplasma(1590s, Contactangle(), Ataeefard,Moradian,
(13.56MHz, 25100W,15ml/min) Crystallinity(), Mirabedini,Ebrahimi,
100W) Roughness() andAsiaban(2009)
LDPEfilm RFdischarge O2plasma(1590s, Contactangle(), Ataeefardetal.(2009)
(13.56MHz, 25100W,15ml/min) Crystallinity(),
100W) Roughness()
HDPEfilm RFdischarge Ar:O2=9:1(150W, Contactangle() Baniketal.(2002)
(13.56MHz) 30sccm,0.01torr)
HDPEfilm RFdischarge Ar:O2=1:9(150W, Contactangle() Baniketal.(2002)
(13.56MHz) 30sccm,0.01torr)
LDPEfilm RFdischarge O2plasma(150W, Contactangle() Bronco,Bertoldo,
(13.56MHz) 0.02torr) Taburoni,Cepek,and
Sancrotti(2004)
LDPEfilm RFdischarge N2plasma(150W, Contactangle() Broncoetal.(2004)
(13.56MHz) 0.02torr)
LDPEfilm RFdischarge Ar(2sccm),Ar:O2 Contactangle() GilliamandYu(2006)
(8W,50mTorr) (1:1sccm),Ar:H2O
(1:1sccm)plasma
PEfilm Microwave Airplasma(140mA, Contactangle() Kamiskaetal.(2002)
plasma 0.04mbar,1560s)
(2860MHz)
LDPEfilm RFdischarge O2,N2andAirplasma Surfaceenergy() Novketal.(2007)
(2kV,0.1mA, (60s,26Pa)
13.56MHz)

Tableoptions

Polypropylene(PP)
PPisaversatilepolymerusedinfoodpackaging.Itslowdensity,lowcost,highmelting
point,goodheatsealabilityandchemicallyinertnaturehavemadeitanobviouschoice
asapackagingmaterialfordifferentfoodproducts(Pankajetal.,2011).Thelowsurface
tensionofPPposesproblemsinprinting,coatingandlamination,therebyrequiringsome
additionalsurfacetreatmenttoincreaseitssurfaceenergy.PPisasaturated
hydrocarbonpolymerwithacarbonbackbonecontaininghydrogenandmethyl(CH3)
groupsarrangedinanalternatingfashion.Thereactivityofthehydrogengroupsfor
surfacereactionsinPPdependsonthenatureoftheCatomtowhichtheyareattached
andingeneralitvariesasHtert>Hsec>HpriwhereHtertreferstoHatombondedtothreeC
atoms,HsecreferstoHatombondedtotwoCatomsandHpriwhichisbondedtoonlyone
C.ExhaustiveworkonmodellingofmodificationofPPfilmsinatmosphericpressure
plasmadischargeshasbeendonebyDoraiandKushner(2003)andWangandHe
(2006).ThereactionmechanismforPPtreatmentbyairplasmahasbeendescribedby
Akishevetal.(2008).Thedegradationofpolypropyleneuponplasmatreatmentismainly
duetobranchscissions,formationoflowmolecularweightorganicmolecules(LMWOM)
andthedegradationorderisasfollows:N2<He<AirO2(PoncinEpaillardetal.,
1999).NotableresultsofselectedstudiesincoldplasmaprocessingofPPhavebeen
summarisedinTable2.

Table2.
Summaryofreportedstudiesoncoldplasmaprocessingofpolypropylene(PP).

Polymeric Plasmasource Treatment Keyfindings References

packaging conditions
material
PPfilm ACdischarge Airplasma Contactangle(),Adhesion() Carrino,Moroni,
(50Hz,2 (30kV, andPolini(2002)
electrodes, 20dm3/h,
1000Pa) 120s)

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Polymeric Plasmasource Treatment Keyfindings References
packaging conditions
material
PPfilm JetplasmaDC Airplasma Contactangle() Akishevetal.
discharge(35W, (20m/s, (2008)
diffusive 6W/cm2)
filamentary
mode)
PPfilm JetplasmaDC Nitrogen Contactangle() Akishevetal.
discharge(35W, plasma (2008)
diffusive (15m/s,3
filamentary 5W/cm2)
mode)
Isotactic Microwave CO2plasma Degradationyield(), Bertrandand
PPfilm plasma (60W, Roughness(),Totalsurface PoncinEpaillard
(433MHz,0 20sccm, energy() (2003)
250W) 0.75mbar)
PPfilm Aircorona Airplasma Contactangle(),InkAdhesion Dixonand
(30kHz, () Meenan,
1.7J/cm2) 2012andStrobel
etal.,1991
PPfilm RFplasma CH4O2 Contactangle(),Increasein Garciaetal.,
(13.56MHz, plasma weight,Oxygencontent(), 2008andLpez
150W) [80:20] Nitrogencontent(), etal.,2009
(100cm3/min, Roughness()
3132Pa)
PPfilm RFplasma Arplasma Contactangle(),Roughness Gomathiand
(13.56MHz, (20sccm, () Neogi(2009)
155W) 23.33Pa,
8min)
Biaxially Aircorona Airplasma Contactangle(),Roughness Guimondetal.
Oriented (1kHz) () (2002)
PP
(BOPP)
film
BOPP APGD N2plasma(1 Contactangle(),Roughness Guimondetal.
film 6kHz) () (2002)
BOPP RFplasma Arplasma Contactangle(),Roughness Mirabedinietal.
film (13.56MHz,10 (15ml/min, () (2007)
50W) 0.35bar,0
300s)
BOPP RFplasma O2plasma Contactangle(),Roughness Mirabedinietal.
film (13.56MHz,10 (15ml/min, () (2007)
50W) 0.35bar,0
300s)
PPfilm Glowdischarge Airplasma Contactangle(),Adhesion Navaneetha
(DC)(400V, (0.2mbar,2 work(),Polarity(), Pandiyarajetal.
10W,25mA) 20min) Degradationyield(),Oxygen (2008)
content(),Roughness()
PPfilm Diodeplasma Arplasma Contactangle(),Oxygen Slepikaetal.
discharge(3.1, (10Pa,0 content(),Roughness() (2010)
8.3W) 240s)
PPfilm DCplasma(1 O2plasma(5 Contactangle() Sorrentino,
30kV) 120s,0.5 Carrino,and
2kPa) Napolitano
(2007)
PPfilm DBDplasma(3 Airplasma Contactangle(),O/Cratio Sorrentinoetal.
20kV,25 (upto (andthensaturates) (2007)
50kHz) 6.7J/cm2)
PPfilm Microwave Airplasma Contactangle() Kamiskaetal.
plasma (140mA, (2002)
(2860MHz) 0.04mbar,
15135s)

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Polymeric Plasmasource Treatment Keyfindings References
packaging conditions
material
PPfilm DBDplasma Airplasma Contactangle(),(),O/Cratio Leroux,
(15kV,300 (1.2 (andthensaturates), Campagne,
1000W,30kHz) 60kJ/m2) Roughness() Perwuelz,and
Gengembre
(2008)

Tableoptions

Poly(ethyleneterephthalate)(PET)
PEThasmanydesirableproperties,includinggoodstrength,rigidity,highstrengthto
weightratio,transparency,thermalstability,gasbarrierproperty,chemicalresistance
andformabilitywhichmakeitapackagingmaterialofchoiceforawiderangeoffood
products(Pankajetal.,2011).However,PET,likeothersyntheticpolymershaslower
surfaceenergy,whichnecessitatessurfacemodificationforgoodadhesion,printingand
dyeingproperties.ThecrystallinityofPETfilmisanimportantfactorwhichdetermines
thechangesinsurfaceenergyuponCPtreatments(Jacobsetal.,2011).Surface
characterisationstudiesforplasmatreatedPETfilmusingoxygen,carbondioxide,
nitrogenandheliumplasmahavebeenreportedbyAlmazanAlmazanetal.,2005,
AlmazanAlmazanetal.,2006andInagakietal.,2004.Table3summarisesthekey
findingsofvariousstudiesconductedonPETusingcoldplasma.

Table3.
SummaryofreportedstudiesoncoldplasmaprocessingofPET.

Polymeric Plasmasource Treatment Keyfindings References

packaging conditions
material
PETfilm JetplasmaDC Airplasma Contactangle() Akishevetal.
discharge(35W, (20m/s, (2008)
diffusive 6W/cm2)
filamentarymode)
PETfilm JetplasmaDC Nitrogen Contactangle() Akishevetal.
discharge(35W, plasma (2008)
diffusive (15m/s,3
filamentarymode) 5W/cm2)
PETfilm Microwave CO2plasma Surfaceenergy(),Roughness Almazan
plasma(200W) (4and () Almazanetal.
15min, (2005)
1.33mbar)
PETfilm Microwave O2plasma Surfaceenergy(),Roughness Almazan
plasma(200W) (4and () Almazanetal.
15min, (2005)
1.33mbar)
PETfibre RFplasma O2plasma Contactangle(),Averagetensile Cioffi,Voorwald,
(13.56MHz, (40Pa,5 strength() andMota(2003)
50W) 100s)
PETfilm DBDplasma(3 Airplasma Contactangle(),O/Cratio() Cui,Upadhyay,
20kV,4080kHz) (9.6,14, Anderson,
21.9W/cm2) Meenan,and
Brown(2007)
PETfilm RFplasma(150 Airplasma Reflectivity(),Roughness() Esena,Zanini,
300W,15kV, (43.4,73.4, andRiccardi
30kHz) 105.4J/cm2) (2007)
PETfilm Jetplasma Airplasma Contactangle() Gotoh,
(biaxially (285V,6A, (0.16 Yasukawa,and
oriented) 16kHz) 0.81m/s) Taniguchi(2011)
PETfilm Microwave Airplasma Contactangle() Kamiskaetal.
plasma (140mA, (2002)
(2860MHz) 0.04mbar,
15135s)

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Polymeric Plasmasource Treatment Keyfindings References
packaging conditions
material
PETfilm Glowdischarge Airplasma Contactangle(),Adhesionwork Navaneetha
(DC)(400V, (0.2mbar, (),Polarity(),Degradationyield Pandiyarajetal.
10W,25mA) 220min) (),Oxygencontent(), (2008)
Roughness()
PETfilm Coronadischarge Airplasma Contactangle(),Oxygen O'Hareetal.
(0.141kW) (5 content(), (2002)
25m/min)
PETfilm Glowdischarge Airplasma Contactangle(),Degradation Pandiyarajetal.
(400V) (0.2mbar, yield(),Roughness(), (2008)
225min) Crystallinity(),Oxygencontent
()

Tableoptions

Ageingeffect
Themodificationofpackagingsurfaceswithcoldplasmaprocessingmaynotbe
permanentoverextendedperiods.Becauseoftheminimisationofthefreesurface
enthalpy,dynamicprocessesareobservedonallfunctionalisedsurfaceswhichfadethe
initialmodificationeffect(Adleretal.,1999).Thelossofbeneficialattributesderivedfrom
CPprocessingofpolymersovertimeisoftencalledageing.Forexample,alossin
hydrophilicityisobservedforCPtreatedpolymericfilmswhenstored.Thisisreferredto
ashydrophobicrecovery.Sucheffectsareattributedprimarilytoinwarddiffusion,
agglomerationorsublimationofLMWOMs,thereorientationorreptationofpolymer
chains,wherebycovalentlybondedpolargroupsbecomeburiedbeneaththeouter
surfaceandmigrationofadditivesfromthebulktowardsthesurface(Garciaetal.,2008,
Guimondetal.,2002,PoncinEpaillardetal.,1999andStrobeletal.,1991).Ageing
effectsaresignificantwhenthepowerinputtotheplasmaandprocesstimesareboth
low.Fortheaforementionedexample,thissignifiesinsignificantchangesinthesurface
roughness,i.e.lessetching(Carrinoetal.,2004andMirabedinietal.,2007).Conversely,
whereintermediatetohighdosesofplasmadischargesareemployed,afurtherpost
processingdecreaseincontactangleoccurs(Kamiskaetal.,2002andUpadhyayetal.,
2004).Selectionofsuitableoperatinggasmixturesforplasma,suchasuseofanorganic
gas(CH4)withahighlyreactivegas(O2)canconsiderablyreducetheageingprocess
withrespecttohydrophobicrecovery(Garciaetal.,2008).Themechanismofageingand
approachestodelaythehydrophobicrecoveryisasubjectofactiveresearch.Table4
providesasummaryoftheresearchworksconductedtostudytheageingeffectsincold
plasmatreatedpolymericsurfaces.Theageingbehaviourofplasmatreatedpolymers
dependsondifferentparameters,suchasthemedium,temperature,crystallinityand
humidity(Vesel&Mozetic,2012).

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