91-1

91
ConducfIve CoafIngs
91.1 Intioduction ......................................................................91-1
91.2
91.3 Commeicially Available Conductive Coatings................91-5
91.4 Applications .......................................................................91-6
91.5 New Developments ...........................................................91-7
Refeiences .....................................................................................91-8
91.1 Intruductiun
In 1986, sales in the coatings industiy exceeded $10 billion, and pioduction appioached a billion gallons.
1
The bieakdown of sales was $4.1 billion foi aichitectuial coatings, $3.5 billion foi industiial coatings,
and $2.4 billion foi specialty coatings. Conductive coatings - a minuscule pait of these tiade sales -
have been used both as industiial coatings and as specialty coatings. Regulations of the Fedeial Com-
munications Commission (FCC), in Docket No. 20780, which iegulates electiomagnetic emissions fiom
computing devices, have piovided a stiong impetus foi the commeicial development of conductive
polymeiic mateiials (including coatings and paints). Since Octobei 1, 1983, it has been necessaiy foi any
computing device that geneiated signals oi pulses in excess of 10 kHz to comply with the emission
standaids set foith in the docket. Although conductive polymeiic coatings have made inioads in aieas
wheie metallic coatings pieviously weie used, piogiess has been slow.
A pioduct ielated to conductive coatings is metallized plastic. The most impoitant commeicial pio-
cesses foi metallizing plastics aie electioless plating, metal spiaying, sputteiing, and vacuum metallizing.
The fist commeicial plating of plastics was iecoided in 1905.
2
Metallizing of plastics occuiied duiing
Woild Wai II, and laige-scale pioduction staited in the eaily 1960s. All these piocesses aie now multi-
million-dollai industiies. Laige quantities of plastics aie metallized each yeai, with automotive items
making up moie than 60% of the maiket on a plated aiea basis.
3
Theie aie vaiious ieasons foi metallizing plastics. In the automotive industiy, metallized plastic
combines the consumei appeal of metal with light weight. Electioless coppei metallization is an indis-
pensable pait of the modein electionics industiy. Piinted ciicuit boaids use electioless coppei to coat
nonconductive plastic suifaces to defne the ciicuit patteins. Zinc aic and ßame-spiay techniques piovide
electiomagnetic inteifeience shielding on many plastics. The plastics that account foi most of the sub-
stiates metallized aie aciylonitiile-butadiene-styiene (ABS), polypiopylene, polyphenylene oxide,
epoxies, phenolics, polyimides, and polyesteis. The commeicial piocess foi metallization of plastics meiits
sepaiate discussion and is not fuithei consideied in this chaptei.
Polymeis (coatings) with conductivities gieatei than 1( cm)
-1
aie defned as conductive polymeis
(also metallically conducting plastics, synmetals).
4
Unfoitunately, the liteiatuie is not cleai-cut, and often,
mateiials that aie semiconductois with conductivities less than 1( cm)
-1
aie also called °conducting."
RaImond LIepIns
Io· A|omo· Noríono| Iobororory
© 2006 by Taylor & Erancis Group, LLC
Metallic · Filled Polymeiic · Polymeiic · Oiganometallic
Shielding fiom Electiomagnetic Inteifeience · The Stealth ·
Types of Conductive Coatings .........................................91-2
Miscellaneous
91-2 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
This chaptei discusses only coatings (polymeis) and theii applications iequiiing a conductivity of at least
1( cm)
-1
.
91.2 Types ul Cunductive Cuatings
We discuss metallic, flled polymeiic, polymeiic, and oiganometallic conductive coatings.
91.2.1 Meta!!ic
Substiates aie coated with conductive coatings mainly foi functional and iaiely foi decoiative puiposes.
The most impoitant commeicial metallic coatings aie nickel, coppei, chiomium, gold, palladium, plat-
inum, silvei, zinc, cadmium, iion, cobalt, tin, and lead.
3
The impoitant commeicial piocesses foi met-
allizing plastics have alieady been mentioned, and iecent developments in this aiea aie summaiized in
Section 91.5.
Some of the special techniques foi metallizing plastics aie summaiized below.
Details of the electioless metallizing technique of composites and/oi theimoplastics that allows the
iepaiiing of damaged aieas in the feld have been published.
5
Suiface metallization of molded liquid-ciystal polymei paits has been accomplished.
6
To inciease the adhesion of a metal coating to an oiganic substiate, the substiate is heated to 0.6 to
0.8 T
cuie
of the substiate and held at that tempeiatuie while the metallic coating is deposited. This
pioceduie piovides foi optimum inteimixing between the metal atoms and the substiate, thus pioducing
maximum adhesion.
7
A simple technique foi plating ABS plastics consists of mixing a mixed catalyst solution foi simulta-
neous sensitization and activation of the suiface.
8
Adhesion between polyethylene and/oi polypiopylene and aluminum is impioved if the plastic suiface
is pietieated with an oxygen ammonia, oi sulfui dioxide low piessuie plasma.
9,10
An electioless metal plating of plastics involves a plastic ieducible by one metal salt followed by a
iedox ieaction between the ieduced plastic and the main gioup metal salt to pioduce the plated plastic.
11
A piocess foi metallizing shaped aiticles of flled plastics with cupious oxide has been desciibed. The
suiface of the flled aiticles is subjected to a ieducing agent such as a boiohydiide to conveit the cupious
oxide to a conductive fiee-metal suiface.
12,13
91.2.2 Fi!!ed Pu!ymeric
Plastic coatings and paints can be made conductive by adding metallic flleis. Typical metal powdeis that
have been used in coatings, paints, and lacqueis aie nickel, coppei, gold, aluminum, iion, cobalt, palla-
dium, zinc, and platinum, as well as vaiious othei alloys. A step beyond the use of powdeied, moie oi
less spheiical, flleis is the incoipoiation of conductive flleis with high aspect iatio: length-to-diametei
iatio of moie than 100. This family of mateiials includes such flleis as metallized glass fbeis, giaphite
fbeis, metallized caibon fbeis, quick-quenched aluminum ßakes oi fbiils, and fne diametei (6 to 8
m) steel fbeis. The most common metallic conductoi, coppei, is not used, because it oxidizes within
the plastic and impaiis its physical piopeities.
Depending on paiticle foim (spheie, ßake, fbei), size, and oiientation, theie is a ceitain ciitical
concentiation at which conductivity incieases diastically (many oideis of magnitude). To achieve signif-
icant conductivity with moie oi less spheiical flleis (caibon black, metal powdeis), volume peicent
loadings above 40 aie iequiied. A stiiking diffeience in conductivity is obseived when a high aspect iatio
paiticle of the same mateiial is used. Thus, with metal oi metallized glass fbeis of aspect iatio of 750 as
flleis, metallic conductivities can be achieved at as low as 3 vol%.
14
At ciitical concentiation, the fllei can foim a continuous phase thiough the matiix in the foim of
micioscopic conductive channels (peicolation). The use of high aspect iatio conductive flleis, when they
aie piopeily oiiented, will always pioduce a supeiioi conductivity at a lowei volume peicent concentia-
© 2006 by Taylor & Erancis Group, LLC
Conducríve Cooríng· 91-3
tion than compaiable spheiical flleis. Howevei, foi these mateiials to have high effciencies, they also
must suivive the piepaiation and application piocesses. Foi example, the initial high aspect iatio of a
veiy biittle mateiial may quickly ieduce to powdei in a high sheai mixing enviionment, if piopei
techniques aie not developed foi incoipoiating such biittle mateiials.
Some specifc examples of uses foi flled polymeiic coatings aie summaiized below.
Oiganic solvent-based coatings of aciylic oi uiethane iesins containing nickel, silvei, coppei, oi
giaphite powdeis aie used in the electiomagnetic and iadio fiequency inteifeience applications. Foi cost
ieasons, the nickel-flled aciylic coatings aie most often used. Lacqueis based on silvei give the highest
conductivities and, theiefoie, the best scieening attenuation, but they aie the most expensive. Coppei
lacqueis aie cheapei, and the attenuation is similai to that of silvei; the oxidation pioblem of coppei
lacqueis has been solved. Lacqueis containing giaphite aie the cheapest, but theii peifoimance is also
the least effective.
15,16
An initiation layei foi the electioless deposition of coppei, nickel, Ni-P, Ni-B alloy coatings has been
desciibed. The layei was foimed by applying a polyestei oi its polymeiization mateiial solution containing
such metal powdeis as nickel, coppei, silvei, aluminum, cobalt, palladium, zinc, oi platinum.
17
Laige diffeiences in the specifc conductivity of flled conductive plastics coatings weie demonstiated
between mateiials flled with 15 vol% aluminum alloy fbei, 0.25 ( cm)
-1
, and 15 vol% biass fbei,
170 ( cm)
-1
.
18
Techniques have been developed foi geneiating and incoipoiating in situ metallic fllei in oiganic
coatings oi paints. Foi example, the use of AgNO
3
and eiythoibic acid, foimaldehyde, paiafoimaldehyde,
oi teiephthalic aldehyde will iesult in the geneiation of metallic silvei in a chosen oiganic coating oi
paint system.
19,20
91.2.3 Pu!ymeric
Although the unflled, moleculaily conductive polymeiic mateiials have attiacted much attention
iecently, the successful developments in suiface-metallized plastics make it unlikely that inheiently
conductive polymeis will be a signifcant factoi in the maiketplace in the neai futuie. Also, the commei-
cially entienched, flled conductive polymeiic mateiials seem to become moie effcient as time goes by.
One piojection of woildwide maikets foi flled and inheiently conductive polymeis is as follows:
21
This piojection, made in the mid-1900s, is cleaily veiy optimistic about the piospects of inheiently
conductive polymeis.
The majoi pioblems of moleculaily conductive polymeiic mateiials (coatings) aie still theii instability
undei enviionmental conditions and diffcult oi impossible piocessing fiom solution oi melt. Conse-
quently, they have to be synthesized and tieated in theii fnal foim of application. In the undoped state,
the basic polymeis aie eithei semiconductois oi insulatois. It is only aftei they aie doped (oxidized oi
ieduced) chemically oi electiochemically that they become metallically conductive.
4
Doping can be done
by means of election-accepting (oxidizing) agents, such as AsF
5
, iodine, biomine, SbF
5
, NOPF
6
, Al(ClO
4
)
3
,
oi HClO
4
; oi election-donating (ieducing) agents, such as lithium, sodium, potassium, oi sodium
naphthalide. Unfoitunately, most of the doped mateiials geneiated aie extiemely ieactive because of the
caibonium ions and caibanions foimed upon doping and thus aie not stable undei ambient conditions.
Recently, some piogiess has been made in this aiea. The fist enviionmentally stable, conducting
polymei was polypyiiole. Coatings oi flms of it weie piepaied electiochemically fiom aqueous solutions
of sodium n-alkylsulfonates, and disodium 1,10-decane disulfonate oi toluenesulfonic acid. The pioducts
possessed conductivities as high as 230 ( cm)
-1
. The flms possessed good mechanical piopeities and
enviionmental stability in excess of 5 yeais (thus fai tested).
22,23

1982 1987 1992

Filled conductive, lb 1 10
6
1 10
7
1.5 10
7
Inheiently conductive, lb 0 1 10
5
1.5 10
6
© 2006 by Taylor & Erancis Group, LLC
91-4 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
Anothei heteiocyclic, conducting, enviionmentally stable polymei is polythiophene. Polythiophene
and its deiivatives can be synthesized and doped chemically oi electiochemically to conductivities as
high as 100 ( cm)
-1
.
24,25

Enviionmentally stable polycaibazole was synthesized and I

2
doped to a conductivity of 5 ( cm)
-1
.
26

A polymei that is attiacting moie attention iecently is polyaniline. It can be piepaied both chemically
and electiochemically, and when doped with vaiious acids in aqueous solutions, it achieves conductivities
as high as 10 ( cm)
-1
.
27-29
A iecent and exciting development is the piepaiation of aqueous polypyiiole and polyaniline latex.
30
33
Spheiical, submiciometei polypyiiole latexes have been piepaied using poly(4-vinyl pyiidine)-based
steiic stabilizei. The use of such a stabilizei allowed the polypyiiole paiticles to be contiollably and
ieveisibly aggiegated oi stabilized, depending on the pH of the dispeision medium. The solid state
conductivity of flms can be as high as 2 ( cm)
-1

Except foi the electiochemically piepaied polypyiiole in a continuous sheet foim, obtainable in
developmental quantities fiom Badische Anilin- und Soda-Fabiik (BASF), Ludwigshafen, West Geimany,
none of the othei mateiials have passed the ieseaich stage.
91.2.4 Organumeta!!ic
Although most of the cuiient inteiest has been in unflled moleculaily conducting polymei systems,
conductivity in metal containing polymeis has also been a topic of inteiest. Almost all the moleculaily
conducting polymeis aie doped systems and, thus, may contain metals fiom the doping agent. Such
systems, howevei, aie aii and moistuie sensitive and aie diffcult to handle. In geneial, oiganometallic
polymeis do not have these instability pioblems, but theii piocessibility is still a pioblem.

© 2006 by Taylor & Erancis Group, LLC

Conducríve Cooríng· 91-5
A new class of low-dimensional mateiials - foi example, polymeiic metallophthalo-cyanines with
such metals as aluminum, chiomium, tin, and gallium at the centei of the iing - has been synthesized
and made conducting ¦~1 ( cm)
-1
] by halogen doping (paitial oxidation).
34,35
Vaiious tiansition metal ions have been cooidinated with conjugated ligands to synthesize polymeis
with metal ions within the main chain.
36
Ligands such as tetiathiosquaiate, tetiathionaphthalene, tetiathi-
afulvalene, and tetiathiooxalate have been used. The tetiathiooxalate complexed with nickel ions gave
lineai polynickel tetiathiooxalate oligomeis with conductivities as high as 20 ( cm)
-1

A completely diffeient appioach to depositing conducting oiganometallic coatings involves the use of
a low-piessuie plasma (LPP) enviionment. The LPP enviionment may be used to deposit a polymeiic
oiganometallic coating (oi powdei) fiom oiganometallic monomeis,
37-42
oi it may be used to conveit a
deposited oiganometallic coating into a metallic one.
20,43,44
The metals intioduced in the oiganometallic
coatings by LPP/oiganometallic monomeis weie iion, tin, meicuiy, tantalum, lead bismuth, and metal
coatings by the LPP posttieatment weie gold, platinum, palladium, silvei, and lead. The geneiation of
metal suiface coatings fiom ceitain oiganometallic coatings can be also achieved by theimal means
(contiolled pyiolysis).
20
The advantage of the LPP piocess is that it peimits a metallic coating to be
foimed on a heat-sensitive substiate without the use of elevated tempeiatuies. The piocess also peimits
foimation of adheiing gold and platinum coatings otheiwise diffcult to deposit on plastic substiates.
None of the conducting oiganometallic coatings oi theii deposition piocesses have gone beyond the
ieseaich stage. Howevei, the conducting oiganometallic coatings effoit is veiy new compaied with the
othei types mentioned befoie.
91.3 Cummercia!!y Avai!ab!e Cunductive Cuatings
Wheieas the metallized plastics effoit is a multimillion-dollai industiy, the commeicial application of
conductive polymei coatings as a paint, lacquei, ink, adhesive, oi a solution of some kind foims a veiy
small industiy indeed. Below aie summaiized seveial typical pioducts available commeicially.
A piopiietaiy aluminum containing paint, AG 9680, manufactuied by A.I. Technology, Inc., Piinceton,
New Jeisey, is claimed to appioach the shielding effectiveness of 70 to 75 dB, an effectiveness similai to
that of puie silvei.
A silvei-flled silica matiix elastomei, Aiemco-Shield 615, has been developed by Aiemco Pioducts,
Inc., Ossining, New Yoik. This mateiial has been foimulated into a conductive paint that can be applied
by eithei biush oi spiay; it cuies at ioom tempeiatuie and bonds to metals, glass, and plastics.

© 2006 by Taylor & Erancis Group, LLC

91-6 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
A silvei lacquei (Eccocoat CC-2) and an elastomeiic, silvei-flled, conductive coating (Eccocoat CC-
40) have been developed by Emeison and Cuming, Canton, Massachusetts. The lacqueis and the elas-
tomei coatings may be applied by dipping, spiaying, silk scieening, ioll coating, oi biushing. In most
cases, a simple spiay coat is adequate to pioduce a highly conductive suiface ¦up to 20 ( cm)
-1
] using
the aii-diy method. Oven cuiing will give impioved conductivity.
A iathei extensive seiies of conductive coatings undei the tiade name Eveishield has been developed
by the E/M Coip. of West Lafayette, Indiana. The seiies of pioducts consists of a giaphite-flled aciylic
iesin system, EC-G-102, intended mainly foi applications foi electiostatic chaige dissipation; a high
peifoimance nonoxidizing coppei-flled aciylic iesin system, EC-C-301, is suitable foi spiay gun appli-
cation. The coating has an attenuation peifoimance of 50 to 70 dB at 10 to 1000 MHz. A populai nickel-
flled aciylic iesin system, EC-N-501, easily paintable and with supeiioi adhesion chaiacteiistics foi a
wide vaiiety of plastic substiates, is also available. It has an attenuation peifoimance of 50 to 60 dB at
30 to 1000 MHz.
91.4 App!icatiuns
91.4.1 Shie!ding lrum E!ectrumagnetic Interlerence
The advent of the FCC Docket 20780, which iegulates electiomagnetic emissions fiom computing and
communication devices used in industiial and iesidential locations, has ieally piovided a stimulus foi
the industiy to come up with cost-effective methods foi limiting the level of electiomagnetic inteifeience
(EMI). To meet the set standaids, the manufactuieis have adopted a vaiiety of methods foi contiolling
EMI. These methods have ianged fiom iedesigned basic ciicuitiy to incoipoiation of conductive shielding
mateiials in the devices. The incoipoiation of conductive shielding may take diffeient ioutes:
45
· Use of metal enclosuies
· Metallic foil tapes
· Metal coatings on plastic enclosuies
· Conductive paints on plastic enclosuies
· Conductive plastic enclosuies
· Flexible laminates with metal foil
The shielding effectiveness of a homogeneous medium, such as a conductive coating, is ielated to the
piopagation of the electiomagnetic feld thiough the coating. The shielding effectiveness is diiectly ielated
to the electionic and magnetic piopeities of the coating; theiefoie, foi best shielding effectiveness,
mateiials with both high ielative magnetic peimeability and high electiical conductivity aie necessaiy.
Thus, it has been found that the vaiious metals and alloys foim the following °seiies" in decieasing oidei
of effectiveness:
Ag Cu Au Al Zn biass Ni Sn steel stainless steel
Cuiiently, the most cost-effective and the most pioblem-fiee mateiials foi shielding aie claimed to be
nickel-flled aciylic oi polyuiethane conductive paints.
46
91.4.2 The Stea!th
One of the moie glamoious applications of conducting coatings has been in the °stealth" technology.
be said about its mateiials technology. The so-called stealth mateiials can piovide a minimal iadai piofle
foi militaiy aiiciaft and naval vessels. This piofle is achieved piimaiily by a combination of geometiic
design and mateiials piopeities. The active components consist of seveial classes of mateiials: caibon
fbei composites, iadai-absoibing coating, feiiite layeis, and inteifeience layeis in the foim of ceitain
pigment-flled polymei coatings.
21
Fiom othei EMI woik, it had been known foi yeais that incoipoiating
© 2006 by Taylor & Erancis Group, LLC
Until the Pentagon ievealed the top-seciet Stealth (Figuie 91.1) fghtei on Novembei 10, 1988, little could
Conducríve Cooríng· 91-7
shoit, electiically conducting fbeis (e.g., stainless steel) into theimoplastics in as low as 0.5 vol% fiaction
gave suffciently high levels of dc conductivity foi electiomagnetic shielding puiposes.
47
One of the iadai-
absoibing coatings has been iion fbiil-flled elastomeiic epoxy.
48
Piesumably, such coatings aie most
effective against shoit wavelength iadais, and the longei the wavelength, the thickei the iequiied coating.
91.4.3 Misce!!aneuus
A novel application of conducting coatings is to use them as ambient-iesponsive elements foi iemotely
ieadable indicatoi devices.
49
Spaceciaft chaiging pioblems have iequiied effoits in the sepaiation, shielding, and flteiing to decouple
dischaiges fiom susceptible ciicuits, and this decoupling involves the use of conductive suiface coatings.
50
Conductive coatings aie also used on waveguides, iadio fiequency ießectois, and iadai dishes, and as
iadiofiequency shielding on capacitoi plates.
51
Electiochemically geneiated, conducting polyheteiocycle coatings aie good candidates foi electiochio-
mic displays.
52,53
Aluminum is being used on video disks and in laige-aiea solai cells.
54
Conductive paints aie used to enhance the electiomagnetic feld attenuation of equipment iooms oi
entiie buildings.
55
Conducting coatings aie used to coat iusty aieas and bolts to suppiess backgiound noise in high
fiequency tiansmitteis and ieceiveis on ships and aiiciaft.
19
Conductive coatings aie candidates foi passivating layeis against photocoiiosion of photoelectiodes
and modifeis of electiodes foi electiochemical ieactions.
56
91.5 Nev Deve!upments
The feld of lasei diiect-wiite metallization of oiganometallic flms has been expanding iapidly as the
potential foi accomplishing one-step pattein defnition and metallization is iealized.
57,58
Recently, ion implantation has been conducted on a vaiiety of polymeis with a vaiiety of ion species.
The iesult has been signifcant inciease in electiical conductivity. Thus, foi example, Kapton H flm
implanted with 1 MeV
15
N
2
-
at seveial doses ieached a conductivity of 1 ( cm)
-1
. It was suggested that
the ion implantation led to giaphite paiticle foimation, piobably along the penetiating ion tiacks.
59
Conducting silvei lines have also been geneiated by focusing a lasei beam on a polyimide flm
containing dispeised silvei nitiate.
60,61
A novel chemical method was used to geneiate an Ag-Hg alloy on the suiface of a polyaciylamide
flm. The technique involved holding the polyaciylamide aqueous solution with AgNO
3
in a meicuiy-
satuiated atmospheie.
62
A iecent symposium on lasei and paiticle-beam chemical piocessing foi micioelectionics desciibed
lasei diiect wiiting of aluminum, coppei, palladium, and caibon.
63-67
FIGURE 91.1 Stealth fghtei.
© 2006 by Taylor & Erancis Group, LLC
91-S Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
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st
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cn Electrcmagnetic Ccmpatibility, Apiil 24-26, 1984, San Antonio, TX, p. 233.
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Synth. Met., 15, 249 (1986).
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