Thin Coatings of Polymeric Carbon and Thin Coatings of Polymeric Carbon and Carbon Nanotubes for Corrosion Protection Carbon Nanotubes for Corrosion Protection Zafar Iqbal Zafar Iqbal Department Department of of Chemistry Chemistry and and Environmental Environmental Science Science New New Jersey Jersey Institute Institute of of Technology Technology Newark, Newark, New New Jersey Jersey 07102 07102 Collaborators Collaborators: Graduate Graduate students students: Chi Chi Yu, Yu, Anitha Anitha Patlolla Patlolla Faculty Faculty: M. Sosnowski Sosnowski and and H. Grebel Grebel ARDEC ARDEC: J. Zunino Zunino 2009 US Army Corrosion Summit
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Thin Coatings of Polymeric Carbon and Carbon Nanotubes for ... · •Corrosion protection for inaccessible device components •Corrosion protection for fuel cell current collecting
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Thin Coatings of Polymeric Carbon andThin Coatings of Polymeric Carbon and
Carbon Nanotubes for Corrosion ProtectionCarbon Nanotubes for Corrosion Protection
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1. REPORT DATE FEB 2009 2. REPORT TYPE
3. DATES COVERED 00-00-2009 to 00-00-2009
4. TITLE AND SUBTITLE Thin Coatings of Polymeric Carbon and Carbon Nanotubes forCorrosion Protection
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6. AUTHOR(S) 5d. PROJECT NUMBER
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7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) New Jersey Institute of Technology,Department of Chemistry andEnvironmental Science,Newark,NJ,07102
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12. DISTRIBUTION/AVAILABILITY STATEMENT Approved for public release; distribution unlimited
13. SUPPLEMENTARY NOTES 2009 U.S. Army Corrosion Summit, 3-5 Feb, Clearwater Beach, FL
14. ABSTRACT
15. SUBJECT TERMS
16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT Same as
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Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18
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)
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
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