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Nanosize Surface Electromodification of Carbon Fibers by Conductive Polymers and Their Characterizations. Prof.Dr.A. Sezai.S ARAÇ Istanbul Technical University Department of Chemistry & Polymer Science and Technology Maslak 80626 Istanbul,Turkey. 5-7 μ. C arbon fiber reinforcement
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Nanosize Surface Electromodification of Carbon Fibers by ConductivePolymers and Their Characterizations Prof.Dr.A.Sezai.SARAÇ Istanbul Technical University Department of Chemistry & Polymer Science and Technology Maslak 80626 Istanbul,Turkey
5-7μ Carbon fiber reinforcement of polymeric composites • Carbon fibers(CF) are used in composites(i.e.,PAN based CF) in order to produce materials of lower density and greater strength. advanced structural materials:aircraft, spacecraft, and suspension bridges – • The most widely used composite material in tactical aircraft is a carbon fibre/epoxy • A polymeric ‘interface’ acting as a coupling agent, improve the interfacial properties between reinforcing (carbon) fibers and the polymeric matrix . A.S. Sarac, A. Bismarck, E. Kumru, J. Springer,Synth. Met. 123 (2001) 411-423 E.Kumru,J.Springer,A.S.Sarac,A.Bismarck., Synth. Met. 123(2001)391-402
Biosensor Appl. • Electromodified carbon fibers also have potential for biosensor applications as microelectrodes -working in small volumes of solutions- • HomogeneousConductive Polymer coated -surface functionalitiesis suitable for the miniaturization of electrode system for a particular analyte. • Several copolymer and polymer coated electrodes(Cz based) were shown to be an effective disposable microelectrode system for the determination of p-aminophenolat low detection limits M. Jamal, E. Magner, A.S.Sarac, Sensors and Actuators 97 (2004)59-66
Carbon Fiber Reinforcementapplying force to a composite material, the brittle matrix cracks at low stress levels > fibres take over Woven fiber Epoxy resin –polymer matrix
The structure & comp. of copolymeric films, plays an important role on the final properties of modified carbon surfaceThe coating parameters & characterization of these functionalised thin filmsareimportant.Improving the interfacial adhesionAdvanced Composites- Interfacial adhesioncontrol the level of fiber/matrix adhesion • A.S.Sarac,M.Serantoni,,A.M.T.Syed,V.J.Cunnane ,Appl.Surface Sci.,(2004) 229,13-18 • A.S.Sarac,A.M.T.Syed,M.Serantoni,,V.J.Cunnane J.Mater.Sci.Lett.(2004) 39,2945-2950
Surface Analysis (the characterizations ofelectrografted thin polymeric film ~10-50nm film characterizations-Fast and simple for org. thin film coating & charac. -Nanosize Change of functionality of surface) • Spectroscopic Functionalities • FTIR-ATR • Raman Composition - XPS,EDX,FIBSIMS Electrochemical Impedance Spectroscopic studies • Morphological • SEM • AFM
AFM of Electrogrowth of P[Cz-co-AAm] onto HOPG Graphite Higher scan rates (100 mV/s) : thin (hf 22 nm) coatings .Lower scan rates (≤ 50 mV/s) ~50 nm A.Bismarck,A.Menner,J.Barner,A.F.Lee,K.Wilson, J.Springer,J.P.Rabe,A.S.Sarac, Surface Coat .Tech. 145(2001)164-175
Current density vs cycle number (▪): 1.53V (●): 1.04 Vand the coating thickness (▫) from the ellipsometric angles
Galvanostatic vs.Cyclic voltammetry polymerization ratevs.film growth. • CV : • Galvanostatic process thin coating (hf15nm) & smoother (RMS=13nm),
AFM of Untreated Carbon fiber(r~5.6 μ) polyethylenedioxythiophene(PEDOT)
Electrocoating of polytetrathiophene onto carbon fiber by cyclic voltammetry10mM TEABF4/MeCN. 10 cycles at 100mVs-1 2 mM Polytetrathiophene in 10 mM TEABF4 / PC , 20 mV/s ,RMS 50 nm (1mm2)5 scan SARAC,A.S.,EVANS,U.,SERANTONI,M.,CUNNANE,V.J.,Carbon 41,14 (2003) 2725-2730
Poly[MPy-co-MCz] on CFME in 0.1 M NaClO4 in PC at 100 mV/s, [MPy]& [MCz]=0.001 M
Poly[MPy-co-MCz] in monomer-free solution.a) 10 mV/s, b) 20 mV/s, c) 50 mV/s, d) 100 mV/s, e) 200 mV/s in a 0.1 M NaClO4 / PC solution. All samples were subsequently cycled 8 times
Scan rate dependence of the copolymer film :Plots of anodic and cathodic peak currents vs. the square root of scan rate Inset: : change in anodic and cathodic peak currents with scan ratein monomer free solution of 0.1M NaClO4/PC Randles Selvic ip = (2.69 x 108) n3/2 A C D1/2ν1/2
Effect of feed ratio of monomers on current ,solid state conductivity and yield.
Comparison the peak current densities of electro-growth of the copolymer films obtained by CV and solid state conductivity in differentmonomer ratios
Anodic peak current densities of Poly[MPy-co-MCz] in different electrolytes using multiple (50 cycles) in monomer-free solution at 100 mV/s, [MPy] &[MCz]=0.001 M.
Poly(N-vinylcarbazole-co-Vinylbenzenesulfonic acid) Element Element NVCzVBSA2 NVCzVBSA2 NVCzVBSA3 NVCzVBSA3 C C 76.57 76.57 85.83 85.83 N N 2.843 2.84 3.76 3.76 O O 15.2 15.20 9.033 9.03 S S 2.83 2.825 0.15 0.147 • Ungrafted CF, • P[NVCz-co-VBSA] grafted CF • 100 mA 4 hrs • 200mA 2 hrs
(b) (c) Poly[NVCz-coVBSA] NVCzVBSA3
Reflectance FTIR & EDX of electrografted P[MeTh-co- Cz] thin copolymer film • A.S.Sarac, J.Springer., Surface Coat.Tech.(2002) 160,227-238
XPS C=S C-N C=O P[Cz-co-MeTh] Carbon fiber at different initial comonomer feed ratios • A.S.Sarac, M.Serantoni, T.Syed, J.Henry, V.J.Cunnane, J.B.McMonagle, Appl.Surface Sci.. 243(1-4)( 2005) 183-198 • A.S.Sarac, A.MT.Syed, M.Serantoni, J.Henry, V.J.Cunnane, J.B.McMonagle. • Appl.Surface Sci. Sci.222,1-4(2004) 148-165
Electrocoated carbon fibre single fibre pull-out test. a)The fibre was partially pulled-out of the electrodepositedcoating. b) fibre completely pulled-out of the electrodeposited coating. The adhesive strength CF/PMMA matrix resulted in 100% improved in thin and homogeneous PMMA coatings. (the interfacial shear strength not so good in thicker coatings) So, electrocoating of MMA can improve the interfacial performance of a carbon fibre reinforced PMMA model composite.
% concentration (determined from XPS ) versus cps (determined from FIBSIMS measurements ) P[NVCz-co-MeTh] M.Serantoni,A.S.Sarac,D.Sutton,V.J.Cunnane, Surface Coat.Tech..( 2005) (in press)
Nanosize Surface chemistry & Morphology of CP electrografting onto Carbon Foam & CF surface &Electrochemical ImpedanceTheir Applications • Thin conductive polymer films can be covalently electrografted onto the CF • Surface structure and composition can be analysed in nanoscale (> 20 nm)(XPS,Raman ,FTIRATR) • Surface morphology (SEM,AFM) • improve the interfacial shear strength • reinforcement appl. • biosensor applications
Istanbul BosphorousAsia-Europe sarac@itu.edu.tr http://atlas.cc.itu.edu.tr/~sarac/ http://www.kimya.itu.edu.tr/saraca/