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InnovativeandConventionalAntistaticSolutions
SpecialChem|MichelBironMar26,2012
AntistaticStrategies
OrganicNonblackAdditives
ReadytouseSolutions:SpecialVersionsofPlasticsandAntistaticMasterbatches
ConductiveFillersandAdditives:ConductiveCarbonBlacks,GraphiteandMetals
NewSolutions:CNTs,MetalplatedCarbonFibers,ICPsorIDPs,Graphene
CombineOldestandNewestTechnologiestoMaketheMost
BeGreen:UseNaturalsourcedAntistaticPlasticsandAdditives
IfYouCannotModifyYourPlastic:SolvetheIssueNeutralizingStaticElectricity
Introduction
Usual plastics are insulating materials subjected to electrostatic buildup and discharge depending on the surface resistivity of the
part.
Ingeneral,dissipativeorESDpolymershave:
Asurfaceresistivityinarangefrom10
5
or10
6
upto10
12
ohms.
Astaticdischargehalflifegenerallyinferiorto60seconds.
Accordingtothetargetedapplication,bewareoftoolowresistivityleadingtoconductivepolymersandinherentrisks.Problemsareof
veryvariousseriousness,fromminortoveryseriousandevendreadfulones:
Dustandotherpollutantsattractionwithmarketing,useandprocessingproblems
Electrostaticbuildupordischargeswhentouchingtheplasticparts:syntheticcarpets,knobs,carhandles
Paintingandprintingdefects
Fireorexplosionofinflammableorexplosiveenvironment,organicpowders
TV,radio,electronicinterferences
Electrostaticbuildupanddischargesarewidespreadin:
Continuousprocessingofplasticssuchasfilms
Electronicmanufacturing,handlingandrepairing
Electronicapplications
Packagingofdustyorganicmaterials
Aeronautics:lightningandinterferences
Automotive:Electrostaticdischargeoffuellinesleadingtofires
Inflammableandexplosiveenvironments:healthcare,operatingtheatre,paintingshops
Useincleaningofrooms
AntistaticStrategies
Itisadifficultproblemandthereisnotanyuniversalstrategybutmultiplewaysareused,sometimesincombination.Amongseveral
routes(seeFigure1'AntistaticWays')usedtominimizethestaticbuildupletusquote:
Choiceofantistaticgrades
Additionofantistaticagentstoconventionalplasticgrades:
Organicnonblackadditives
Conductivefillers:carbonblacks,fibers,graphites,carbonnanotubes
Alloyingwithinherentlyconductiveplastics
Coatingwithapermanentconductivesurfacelayer
Useoftemporaryexternalantistaticagents
To end, if polymer modification is not desired, use antistatic equipment neutralizing electric charges to proceed to a processing
phaseforexample.
0 0 More
Table1:ConductivePlasticsConsumption(billion$)
2005 2010 2011 2016 AAGR2016/2011
ConductivePlastics 0.7 1.7 1.8 2.4 6
WorldPlastics
Consumption
700 1000 1054 1370 5.4
%ConductivePlastics 0.1 0.17 0.17 0.18
Plastics&Elastomers
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Pgina1de6 InnovativeandConventionalAntistaticSolutions Article
04/04/2012 http://www.specialchem4polymers.com/resources/articles/article.aspx?id=7272&lr=m...
Thispaperonlydealswithinternalsolutions.
OrganicNonblackAdditives
The nonblack antistatics have been used for a long time but their action depends on the hygrometry. New generations such as
H2Stat(byTeknorApex)aremarketedwithoutthisdrawbackandareefficientwithanhygrometryaslowas15%.Theymigrateto
thesurfaceandinteractwithatmosphericmoisturereducingsurfaceresistivityandhencedissipatinghigh electricchargedensities,
togivealonglastingantistaticeffecttotheplasticpart.
Theprincipleoftheactionofanamphiphilicantistaticadditive,forexampleanesteroffattyacid,followsthistheoreticalway:
AlipophilicsegmentmadeofalongchainofCH
2
lovesthepolymer
Ahydrophilicendchain,theesterfunctioninthatexampleattractsthewaterorthemoistureoftheenvironment.
The moisture trapped by the hydrophilic end of molecules forms a thin conductive film at the surface of the plastic if the
atmosphericmoistureissufficient.Ifthemoisturelevelistoolow,theantistaticbecomesinefficient.
Theantistaticagentmigratesslowlytothesurfaceatacontrolledratetomaintainlonglastingconductivity.
Theusedadditivelevelsinthepolymeraretypicallyinarangeoflessthan1%tofewpercents.
Theantistaticadditivesoftenare:
Alkanessulfanates
Amides
Amines
Esters
Esteramines
Quaternaryammoniumsalts
Soapsoffattyacids
Severalchemicalfunctionscanbecombinedinthesamemolecule.
NumerousproprietaryantistaticadditivesaremarketedandTable2showssomeexampleswithoutclaimingtobeexhaustive.
ReadytouseSolutions:SpecialVersionsofPlasticsandAntistaticMasterbatches
Figure1:AntistaticWays
Table2:ExamplesofAntistaticAdditives
Company TradeName Website
AkzoNobelAkcrosChemicals Lankrostat http://www.akcros.com/
Baerlocher Baerostat http://www.baerlocher.com/
BASF
Larostat
Irgastat
http://worldaccount.basf.com/
Clariant Hostastat http://www.clariant.com
Colortech Antistatconcentrate http://www.colortech.com/
Croda Atmer http://www.croda.com/
Danisco DIMODAN http://www.danisco.com/
Evonik TEGIN http://corporate.evonik.com/
Lanxess StatexanK1 http://lanxess.com/
Momentive NiaxAntistat http://www.momentiveperformancematerials.com/
NissanChemical
Celnax
Aluminasol
http://nissanchemusa.com/
PCCChemax Chemstat http://www.pccchemax.com/
Rhodia
Catafor
Alkamuls
http://www.rhodia.com/
Stepan
DREWPLAST
MERPOL
NINOL
Zelec
http://www.stepan.com/en/
TeknorApex H2Stat http://www.teknorapex.com/
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Pgina2de6 InnovativeandConventionalAntistaticSolutions Article
04/04/2012 http://www.specialchem4polymers.com/resources/articles/article.aspx?id=7272&lr=m...
Producersorcompoundersmarketantistaticversionsormasterbatchesusableforalmostallpolymerfamilies,forexample:
CommodityplasticssuchasPS,PP
EngineeringplasticssuchasABS,PA6/6,PA6,PC,POM,PBT,PPO,PPS
SpecialtyplasticssuchasPEI,PEEK
AlloyssuchasPC/PMMA,PC/ABS
For ESDgrades,propertiesandrheologycanbe slightlydifferentfrom standardgradesas wecansee inTable3concerningABS
andaTPE.Thissolutionisthesimplestone.
TheBreakthroughofMasterbatches
Antistatic masterbatches are developing because of the easy use and the technical benefits. They are based on polyolefins,
polystyrenes,polyesters,acrylics,ABS,polycarbonate,nylons,acetals.Thesurfaceresistivityisroughlyinarangeof10
7
10
8
Ohms.
NumerousproprietaryantistaticmasterbatchesaremarketedandTable4showssomeexampleswithoutclaimingtobeexhaustive.
ConductiveFillersandAdditives:ConductiveCarbonBlacks,GraphiteandMetals
Thesesolutionslead tovolumeconductiveplasticsthatcanactasconductorsreceivingelectronsfromotherelectrostaticmaterials
withtheknownrisksofelectrostaticdischarges.
AllsuitablyfilledplasticscanbeusedforESD,EMIorRFIshieldings:
CommodityplasticssuchasPE,PS,PP
EngineeringplasticssuchasABS,PA6/6,PA6,PC,POM,PBT,PPO,PPS
SpecialtyplasticssuchasPEI,PEEK
AlloyssuchasPC/PMMA,PC/ABS
FortheESDpolymers,itisdifficulttocontroltheresistivityoverthepercolationthresholdoffillers:Theresistivitycanbesolowthat
thepolymerbecomesconductive.
CarbonBlacks
Theresistivityofthefinalmaterialdependson:
Thesurfaceareaofthecarbonblackandtheionlevelonitssurface
Thelevelofcarbonblack
Thegradeofthepolymeror,eventually,thealloyofpolymers
Themixingmethod
Therearespecificgradesandmasterbatchesofcarbonblacksespeciallymarketedasadditivesforconductiveplasticsandrubbers.
Itwillbenotedthatthecarbonblacksmodifytheotherpropertiesofthepolymerespeciallyitscolor.
ConductiveFibers
The carbon and steel fibers are industrially used to make the plastics and composites conductive but other fibers such as a
conductivecellulosefiberhighlyfilledwithconductivecarbonblacksaredevelopedforexamplebyTITK(http://www.titk.de).
Theresistivityofthefinalmaterialdependson:
Thesize,theaspectratio,thechemicalnatureofthefibers
Theleveloffibers
Themixingmethod
There are specific grades especially marketed as additives for conductive plastics and rubbers. The other properties of the final
material,color,modulus,impactstrengthetc.aremodified.
Graphites
Theresistivityofthefinalmaterialdependson:
Table3:ExamplesofPropertiesofESDandStandardABS
Property ESD Standard
Resistivity,Ohms 6*10
11
4*10
14
MeltIndex(220C,10kg),g/10min 25 16
HDTA(1.8MPa),C 84 83
NotchedIzod@23C,kJ/m
2
21 23
NotchedIzod@40C,kJ/m
2
5 7
Stress@yield,MPa 41 46
ESDTPE
VolumeResistivity,ohmcm 10
3
10
9
SurfaceResistivity,ohm/sq 10
6
10
11
SpecificGravity 1.02
TensileStrength,MPa 2
Elongation@break,% 300
Hardness,ShoreA 65
Table4:ExamplesofReadytouseAntistaticSolutions
Company TradeName Website
Ampacet http://www.ampacet.com/
Cabot Cabelec http://www.cabotcorp.com/
Chrostiki MasteradAntistatic http://www.chrostiki.gr/
Clariant CesaStat http://www.clariant.com/
KineticPolymers AntiStaticMasterbatches http://www.kineticpolymers.in/
PMCGroup Durastat http://www.polymerproductscompany.com/
Premix PREElec http://www.premixgroup.com/
RTP Permastat http://www.rtpcompany.com/
A.Schulman Polystat http://www.aschulman.com/
TeknorApex ViduxConductiveCompounds http://www.teknorapex.com/
Tosaf http://www.tosaf.com/
Viba Vibatan http://www.vibagroup.com/
Pgina3de6 InnovativeandConventionalAntistaticSolutions Article
04/04/2012 http://www.specialchem4polymers.com/resources/articles/article.aspx?id=7272&lr=m...
Thetypeofgraphite:somegradesarespeciallydevelopedfortheirelectricconductivity
Theaspectratio
Thelevelofgraphite
Thegradeofthepolymer
Themixingmethod
Furthermore graphite haslubricatingproperties. Itisclaimed bycertain producersthatthe resistivities canbe in the order ofthose
obtainedwithconductivecarbonblacks,lowerorhigheraccordingtotheusedgrades.
MetalPowdersorFlakes
Aluminium,copper,nickel,silverpowdersorflakesareusedtoincreasetheelectricalconductivity.
Theresistivityofthefinalmaterialdependson:
Theparticlesizeandformofthemetal
Thelevelofmetal
Themixingmethod
There are specific grades especially marketed as additives for conductive plastics and rubbers. The polymer influences the metal
choice. The sulphur vulcanisation canparticularly cause sometroubles with metals such as copper and silver attacked by sulphur.
Theotherproperties,color,modulus,impactstrengthetc.aremodified.
NewSolutions:CNTs,MetalplatedCarbonFibers,ICPsorIDPs,Graphene
CarbonNanotubes(CNT),TitanatesandZirconates
Among new solutions, CNTs are fast growing for massproduced or specific devices. CNTs, relatively well known, are expensive
despiteacontinuouscostdrop.Theverylowresistivityofcarbonnanotubes(CNT)allowsobtainingEMIpolymerswithlevelsofCNT
inferiorto1%,farlowerthanusedlevelsofconventionalandconductivecarbonblacks.
Table5displaysexamplesofcompaniesinvolvedintheCNTmarket
MetalplatedCarbonFibers
Electriplast(IntegralTechnologies,Inc.)hasannouncedtheavailabilityofElectriPlastTMCF66,anewelectricallyconductive,resin
based material that has been engineered to meet demanding electromagnetic shielding, thermal requirements and mechanical
propertiesforautomotive,marineandaerospaceapplications.
ComposedofPA66andnickelplatedcarbonfiber,EPCF66offerslightweightsolutionsatcosteffectivenessforharshenvironments
in a wide range of industries. Its high mechanical strength withstands high temperatures, corrosivity of main fluids, and high
frequencyvibrations. Parts molded withElectriPlastTMCF66 outperformed aluminum at certainfrequencieswhiledeliveringa50to
60%percentreductioninweight.
InherentlyConductivePolymers(ICP)
Amongthenewsolutions,ICPsarethemostexcitingopportunitiesformassproducedorspecificdevices.Nowtheyarerarelyused
but some industrial breakthroughs open the door to massproduced goods notably for transparent electronics, TCF (transparent
Conducting Films) and photovoltaic. So, PEDOT (Poly(3,4ethylenedioxythiophene): poly(styrenesulfonate) and polyaniline are
proposedbyseveralcompanies(seeTable6)suchasEeonyxCorp.,Enthone,FibronTechnologies,IntegralTechnologies,Heraeus
Clevios, SigmaAldrichAgfa Materials joint venture. ICPs can be alloyed with various conventional plastics including, for example,
ABS,acrylics,composites,polyamides,polycarbonate,polyesters,rubbers,andTPEs.
figure2:PolymerresistivityVsCarbonLoading
Table5:ExamplesofTradeNamesandCompaniesInvolvedintheCNTMarket
Company TradeName Website
Arkema Graphistrength http://www.arkema.com/
Bayer Baytubes http://www.baytubes.com/
BuckyUSA http://www.buckyusa.com/
CarbonNanotechnologies http://www.cnanotech.com/
HyperionCatalysis FIBRIL http://www.hyperioncatalysis.com/
NanoC http://www.nanoc.com/
Nanocyl http://www.nanocyl.com/
NanoDynamics http://www.nanodynamics.com/
Nanoledge Graphistrength http://www.nanoledge.com/
RaymorNanotech http://www.raymor.com/
SESResearch http://sesres.com/Nanotubes.asp
ThomasSwan&Co Elicarb http://www.thomasswan.co.uk/
Timesnano TimesTub http://www.timesnano.com/
Zyvex NanoSolve http://www.zyvexpro.com/
Company TradeName Website
AldrichMaterialsScience AgfaMaterials Orgacon http://www.sigmaaldrich.com/
EeonyxCorp Eeonomer http://www.eeonyx.com/
ElectriplastCorp(IntegralTechnologies) Electriplast http://www.electriplast.com/
Enthone http://www.enthone.com/
FibronTechnologies http://fibrontech.com/
Heraeus(formerlyClevios) http://heraeus.com/
Lubrizol StatRite http://www.lubrizol.com/ConductivePolymers/
SanyoChemicals Pelestat http://www.sanyochemical.co.jp/
Pgina4de6 InnovativeandConventionalAntistaticSolutions Article
04/04/2012 http://www.specialchem4polymers.com/resources/articles/article.aspx?id=7272&lr=m...
TitanatesandZirconatesasAntistaticAgents
Somegradesspecially developedforapplicationsinpolymerstoobtainESDandotherantistatic materialsare usedintonumerous
plasticssuchasABS,EVA,polyethylene,polypropylene,PVC,PETG,polyamide,polyethersulfone,acrylics,polyurethane.Theshort
followinglistshowssomeexamplesofsurfaceresistivity(Ohm/sq)withoutclaimingtobeexhaustive.
ABS10
10
to10
13
Acrylic10
8
to10
13
EVA10
9
to10
11
HDPE10
10
to10
13
LLDPE10
9
to10
13
PES10
10
to10
13
CombineOldestandNewestTechnologiestoMaketheMost
Oldestandnewesttechnologiescanbecombinedforanoptimizationoftheproducedparts.Forexample,EeonyxCorp.proposesits
Eeonomeradditivesmadeoutofcarbonblackscoatedwithinherentlyconductivepolypyrroleorpolyaniline.AccordingtoEeonyx,in
situpolymerizationoftheresinonthecarbonblackprovidesmuchgreaterthermalstability(upto300C)thantypicalICPsalone.In
someresins (ABS, nylon,polyesters)the used levelcanbe half of theusualcarbonblack levels. colorsevolve betweenlightgray,
greenandlightbrown.
The same company offers EeonTex, conductive fabrics of glass, quartz, or Kevlar coated with polypyrrole, polyaniline, or
polythiophene.ThosecanbeusedtomanufacturecompositesforapplicationslikelowradarprofileantennasfortheNavy.
BeGreen:UseNaturalsourcedAntistaticPlasticsandAdditives
Gaalene (http://www.gaialene.com/) is claimed having inherently antistatic properties, preventing electrical charge and dust
accumulation. Gaalene shows more than 50% plant based content and can be processed with conventional equipment at lower
temperature,leadingtoenergyandcostsavings.FromamanufacturingstandpointGaaleneresinsbring40%CO
2
emissioncuts
comparedtopolyolefinsandonemusttakeintoaccounttheCO
2
usedtogrowtheplantsusedasrawmaterials.
InjectiongradesofMaterBicanbemouldedusingstandardinjectionpresses,withcoldrunnersorhotchamberinjectionsystems.
Parts have the advantage of being antistatic, eliminating the accumulation of electrical charges. Hybrid compounds combining
Thermoplastics Starch and commodity resins such as Polyolefins and Polystryrene can lead to intrinsically antistatic materials.
Followingthisway,TeknorApex(http://www.teknorapex.com/)proposesTerraloygradeswithabiobasedcontentupto40%made
of TPS and a biodegradable polyester. Certain grades can have an antistatic behaviour. Table 7 shows an example of Terraloy
properties.
Danisco (http://www.danisco.com/) markets the DIMODAN range of antistatic additives based on sunflower, rapeseed, palm or
soyabeanoil.
CrodaPolymerAdditives(http://www.croda.com/)proposesantistaticproductsbasedupto100%onvegetablerawmaterialssuitable
forfossilandbioplastics,forexample:
Atmer110
Atmer129VExpectedtobebiodegradable
Atmer190
Atmer191
Atmer1013VExpectedtobebiodegradable
IfYouCannotModifyyourPlastic:SolvetheIssueNeutralizingStaticElectricity
Staticelectricitycanbeneutralizedthankstomoreorlesssophisticatedequipment(Figure'AntistaticEquipmentExamples'Courtesy
BousseyControl http://www.bousseycontrol.com/en/) from simple Antistatic carbon brushes or Copper tinsels up to Antistatic
Ionisation bars, ESD Ionised Air Blowers, Ionised air guns, Large Air blowers, Corona surface treatments including mini Corona,
Dielectricsleeves,Plasmasurfacetreatments.
Conclusion
Usual plastics are insulating materials subjected to electrostatic buildup and discharge depending on the surface resistivity of the
part.Numerousantistatic solutionsare examinedfromoldestonessuchnonblack organicadditives orcarbonblacksuptonewest
onessuchasCNTs,Metalplatedcarbonfibers,ICPsorIDPs,Graphene.
Amongnewsolutions,CNTsarefastgrowingandexpensivedespiteacontinuouscostdropbutpercolationlevelscanbeinferiorto
1%. The offer is spreading as displayed by quoted examples. Metalplated carbon fibers are now available allowing to meet
demanding electrical, mechanical, thermal and chemical requirements of automotive, marine and aerospace applications. For
example, parts molded with metalplated carbon fiber reinforced polyamides outperform aluminum at certain frequencies while
deliveringa50to60%percentreductioninweight.
Inherentlyconductivepolymers(ICP)arethemostexcitingopportunities.ForexamplePEDOT,polyaniline andsoonareproposed
byseveral companiestobealloyedwithconventional plasticsincluding ABS as wellas composites, polyamidesor TPEs. Greener
Table6:ExamplesofICPorIDPProducers
Table7:ExamplesofPropertiesofTerraloy
Property MachineDirection TransverseDirection
TensileStrength,MPa 26 20
Elongation@break 520 500
Modulus,MPa 86 82
OTR,cm
3
/m
2
/24hr 410
Figure3:AntistaticEquipmentExamples
Pgina5de6 InnovativeandConventionalAntistaticSolutions Article
04/04/2012 http://www.specialchem4polymers.com/resources/articles/article.aspx?id=7272&lr=m...
solutionsusenaturalsourcedantistatic polymersandadditives,forexampleGaalene, MaterBi,hybridcompounds, andnatural
antistatic specialities. Of course, oldest antistatic systems remain operational and, in addition, can be combined with innovative
solutions to optimize answers to harshest requirements. Organic nonblack additives can be Amides, Amines, Esters, Quaternary
ammoniumsalts,Soapsoffattyacidsmigratingtothesurfaceandabsorbingatmosphericmoisturetoreducesurfaceresistivity.
Conventional and Conductive carbon blacks, Conductive fibers (carbon and steel fibers), graphite, metal powders or flakes
(Aluminium, copper, nickel, silver etc.) are industrially used to make the plastics and composites conductive. The resistivity of the
final material depends on the chemical nature, size, aspect ratio and loading level of the used filler, the mixing and processing
methods, and the natureofthe polymer. The properties ofthe final material, color, modulus, impact strength can be altered. If the
plastic cannot be modified, neutralization or elimination of static electricity can be achieved thanks to more or less sophisticated
equipmentfromsimpleAntistaticcarbonbrushesuptoCoronasurfacetreatments.
References
Technicalbooksandguides,papers,websites:AkcrosChemicals,ALAChemicals,AldrichMaterialsScience AgfaMaterials,AlfaAesar,Ampacet,
Arkema, Baerlocher, BASF, Bayer, BousseyControl, Bucky USA, Cabot, Carbon Nanotechnologies, Chemax Group, Chrostiki, Clariant, Cognis,
Colortech, Croda, Crompton, CromptonWitco, Danisco, DegussaGoldschmidt, DuPont, Eeonyx Corp, Electriplast Corp (Integral Technologies),
Enthone, Evonik, Fibron Technologies, Graphit Kropfmuehl GmbH, Heraeus, Hyperion Catalysis, Kenrich Petrochemicals, Kinetic Polymers,
Lanxess,MGChemicals,Momentive,NanoC,Nanocyl,NanoDynamics,Nanoledge,NissanChemical,Orion,PCCChemax,PMCGroup,Precision
Painting,Premix,RaymorNanotech,Rhodia,Rohm&Haas,RTP,SchlegelBvBa, Schulman,SESResearch,ShinEtsu,Stepan,Struktol,Teknor
Apex,ThomasSwan&Co,Timesnano,TITK,Tosaf,Uniqema,Viba,Zyvex
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Pgina6de6 InnovativeandConventionalAntistaticSolutions Article
04/04/2012 http://www.specialchem4polymers.com/resources/articles/article.aspx?id=7272&lr=m...