Thin Coatings of Polymeric Carbon andThin Coatings of Polymeric Carbon and

Carbon Nanotubes for Corrosion ProtectionCarbon Nanotubes for Corrosion Protection

Zafar IqbalZafar Iqbal

DepartmentDepartment ofof ChemistryChemistry andand EnvironmentalEnvironmental ScienceScienceNewNew JerseyJersey InstituteInstitute ofof TechnologyTechnologyNewark,Newark, NewNew JerseyJersey 0710207102

CollaboratorsCollaborators:: GraduateGraduate studentsstudents:: ChiChi Yu,Yu, AnithaAnitha PatlollaPatlollaFacultyFaculty:: MM.. SosnowskiSosnowski andand HH.. GrebelGrebelARDECARDEC:: JJ.. ZuninoZunino

2009 US Army Corrosion Summit

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1. REPORT DATE FEB 2009 2. REPORT TYPE

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4. TITLE AND SUBTITLE Thin Coatings of Polymeric Carbon and Carbon Nanotubes forCorrosion Protection

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13. SUPPLEMENTARY NOTES 2009 U.S. Army Corrosion Summit, 3-5 Feb, Clearwater Beach, FL

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Outline of talkOutline of talk

IntroductionIntroduction –– new barrier materials and concepts fornew barrier materials and concepts forcorrosion protectioncorrosion protection–– Conjugated/conducting polymersConjugated/conducting polymers–– SmartSmart--active corrosion protection with carbon nanotubeactive corrosion protection with carbon nanotube pp--nn

junctionsjunctions–– Potential corrosion protection in ironPotential corrosion protection in iron--carbon nanotube compositescarbon nanotube composites–– Potential corrosion protection in ironPotential corrosion protection in iron--carbon nanotube compositescarbon nanotube composites

Polyperinaphthalene (PPN) resultsPolyperinaphthalene (PPN) resultsCarbon Nanotube approaches and resultsCarbon Nanotube approaches and resultsThermochromic conjugated polymer conceptsThermochromic conjugated polymer conceptsSummarySummary

Polyperinapthalene (PPN)

Chemical Structures of Coating MaterialsChemical Structures of Coating Materials

Single wall carbon nanotubes

Polydiacetylene: CH3(CH2)11CC-CC-(CH2)8-COOH

Apparatus for Plasma-CVD Synthesis and Deposition of PPN

C. Yu, S. C. Wang, M. Sosnowski, and Z. Iqbal, Synthetic Metals 158, 425 (2008)

Transition from PTCDA precursor to PPN

Crystal structure ofPTCDA precursor

TEM images of PPN

Z.Iqbal, D.M.Ivory, J.Marti, J.L.Bredas and R.H.Baughman, Mol. Cryst. Liq. Cryst.118, 103 (1985)

PPN Coating Characterization

FTIR

Al steel silicon

Al steel

Raman

SEM on differentsubstrates

silicon ITO

silicon ITO

C. Yu, S. C. Wang, M. Sosnowski, and Z. Iqbal, Synthetic Metals 158, 425 (2008)

Potentiodynamic Corrosion Testing Tafel Plots

PPN coatedsteel

uncoated

C. Yu, S. C. Wang, M. Sosnowski, and Z. Iqbal, Synthetic Metals 158, 425 (2008)

Applications:•Corrosion protection for inaccessible device components•Corrosion protection for fuel cell current collecting bipolar flow-fieldplates [“Corrosion Resistant Coated Fuel Cell Plate with GraphiteProtective Barrier and Method of Making the Same”, Z. Iqbal, T.Rehg, J. Guiheen and D. Narasimhan – US Patent 6,864,007 (2005)

Honeywell-GE Power Systems].

-1100

-900

-700

-500

-300

-100

0.0E+00 5.0E-07 1.0E-06 1.5E-06 2.0E-06

I/area [A/cm2]

E[m

V]

Al-Blank

RFPL4/Fe-1

RFPL4/Fe-2

ElectrodesHydrophobic-CNT(optional)

p-n CNT

•Paints of 3 types of carbon nanotubes prepared as paints or inks in polymers•p-n doped layer functions as a transistor to monitor the health of the coating•Top layer functionalized with hydrophobic (e.g. fluorine-containing) groupsfunctions as the barrier layer

Multilayer Smart Carbon Nanotube Coating

Insoluble polymer layer top coating -PMMA

Substrate

Carbon Nanotube Functionalization/DopingCarbon Nanotube Functionalization/Doping

Polyvinylpyrrolidone (PVP)

A) p-Doping C) Polymer WrappingModel

B) n-Doping

Polyethyleneimine(PEI)

SWCNT Paint/Ink for CoatingsSWCNT Paint/Ink for Coatings

SWCNTsUltrasonicationin surfactantand water

SuspensionAdd 1% PVP,incubated at 50ºC for 12 hours

Suspension

High-speedcentrifugation

Disperse inwater

PrecipitateFinal

dispersion Paint/Ink

Multilayer Smart Carbon Nanotube Coating

-200

0

200

Fe/(SWCNT/PVP)

Tafel Plots of Coated and Uncoated Iron

Pot

entia

l(m

V)

0.01 0.1 1 10 100

-800

-600

-400 Fe

Pot

entia

l(m

V)

Current (A)

n-doped SWCNTs PEI

p-doped SWCNTs PVP

Corrosion current decreases with nanotube coating-thus improved corrosion protection

Multilayer Smart Carbon Nanotube Coating

Metal substrate

P-Doped layer N-Doped layer

Electrode

400

Tafel Plots of Coated and Uncoated Iron

TEMs

I V P ro p e r ty o f R e f lu x P E I -P - T _ 2

n-doped SWCNTs PEI

As-prepared SWCNTs

0.01 0.1 1 10 100-400

-200

0

200

400

Fe

Fe/(SWCNT/PVP)

Po

tent

ialt

oE

corr(m

V)

Current Density (A/cm2)- 4 4

- 3 4

- 2 4

- 1 4

-4

6

-3 . 5 -2 .5 -1 .5 -0 .5 0 .5 1 .5 2 .5

V o l t a g e ( V )

Cu

rre

nt(

mA

)

Ar

H2

CO

C2H2

Pellets with catalyst

To Pump

Bubbler

Potentially corrosion-resistant high strength bulk iron-carbon nanotubecomposites

SEM

CVI synthesis set-up

45% increase in yield strength relative to ironTEM

Goyal, Wiegand, Owens, Iqbal Chemical Physics Letters 442 (2007) 365–371

Multilayer Smart Polydiacetylene Paint Coating

185 F

ZnO

PCDA red

•If PCDA red layer isdamaged, oxygen from thecorroding substrate willreact with Zn strip to formZnO•In presence of ZnO PCDAwill undergo red to blue

irreversible

at ambient T

PCDA blue PCDA red

Zn to ZnO if PCDA layer is damaged

SubstratePCDA red paint

will undergo red to blueconversion – Raman datanext slide

Blue

Red

PCDA

PCDA-TiO2

PCDA-ZnO

PCDA-ZrO2

Monitoring blue andred PCDA phases inpresence or absenceof ZnO, ZrO2 and TiO2by Raman scattering

Also note: Red phaseC=C CC

Red

PCDA-ZrO2

PCDA-ZnO

PCDA-TiO2

PCDA

Also note: Red phaseis highly fluorescent C=C CC

SummarySummaryThree types of nanotechnologyThree types of nanotechnology--based passive and smartbased passive and smart

barrier coatings for corrosion protection discussedbarrier coatings for corrosion protection discussed–– PlasmaPlasma--deposited conducting carbon polymer PPN can be used todeposited conducting carbon polymer PPN can be used to

protect small device or engine components and has beenprotect small device or engine components and has beendemonstrated to protect PEM fuel cell current collecting bipolardemonstrated to protect PEM fuel cell current collecting bipolarmetal platesmetal plates

–– Carbon nanotube paints/inks can form smart protective coatings viaCarbon nanotube paints/inks can form smart protective coatings via–– Carbon nanotube paints/inks can form smart protective coatings viaCarbon nanotube paints/inks can form smart protective coatings viapp--n junction layers which can electrically sense coating damagen junction layers which can electrically sense coating damagedue to corrosiondue to corrosion

–– Semiconducting, thermochromic polydiacetylene paints undergoSemiconducting, thermochromic polydiacetylene paints undergoirreversible color changes which can become reversible in theirreversible color changes which can become reversible in thepresence of chemical reactions induced by corrosionpresence of chemical reactions induced by corrosion