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HUChi-chang HUChi-chang


The optimal sulfonation condition of self-doped sulfonated polyaniline(prepared from leucoemeraldinebase;denoted as LEB-SPANI) with a high electronic conductivity was obtained by experimental strategies,includingthe fractional factorial design(FFD) and central composite design(CCD).From the FFD experiment,the self-doped LEB-SPANI prepared at a lowtemperature(4oC),a short reaction time(1 h),and a small volume of fumingsulfuric acid(10 mL) showed a better conductivity(ca.127 mS/cm).In the CCD study coupled with a confirmationtest,the highest conductivity(ca.141 mS/cm) of the LEB-SPANI film was obtained under a sulfonation temperatureof 4oC,a sulfonation time of75 minutes,and a volume of8 mLof30% fuming sulfuric acid.The textural cha-racter-istics of self-doped LEB-SPANI were characterized by Fourier transform infrared(FTIR) spectroscopy,four-pointprobe method,and X-ray photoelectron spectroscopy(XPS).The sulfonation rate and degree of LEB-SPANI werefound to be dependent upon the acid used in the polymerization step of PANI.


Self-doped polyaniline, Sulfonation, Conductivity, Fractional factorial design, Central composite de-sign

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[1]Skotheim TA.Handbook of Conducting Polymers Vol.1and 2[M].New York:Marcel Dekker,Inc.,1988.
[2]Patil A Q,Heeger A J,Wudl F.Optical properties ofconducting polymers[J].Chem.Rev.,1988,88:183.
[3]Bredas J L,Chance R R.Conjugates Polymeric Materi-als:Opportunities in Electronics,Optoelectronics andMolecular Electronics[M].Dordrecht:KluwerAcadamic Pub.,1990.
[4]Skotheim TA.Electroresponsive Molecular and Polymer-ic Systems Vol.II[M].New York:Marcel Dekker,Inc.,1992.
[5]Yamamoto H,Oshima M,Fukuda M,et al.Characteris-tics of aluminium solid electrolytic capacitors using aconducting polymer[J].J.Power Sources,996,60:173.
[6]Yue J,Epstein A J,Zhong Z,et al.Thermal stabilitiesof polyanilines[J].Synth.Met.,1994,41:765.
[7]Yue J,Wang Z H,Cromack KR,et al.Effect of sulfo-nic acid group on polyaniline backbone[J].J.Am.Chem.Soc.,1991,113:2 665.
[8]Wei X L,Wang Y Z,Long S M,et al.Synthesis andphysical properties of highly sulfonated polyaniline[J].J.Am.Chem.Soc.,1996,118:2 545.
[9]Hu C C,Lin J Y.Effects of the loading and polymeriza-tion temperature on the capacitive performance of polya-niline in NaNO3[J].Electrochim.Acta,2002,47:4055.
[10]Hu C C,Chu C H.Electrochemical impedance charac-terization of polyaniline-coated graphite electrodes forelectrochemical capacitors-effects of film coverage/thickness and anions[J].J.Electroanal.Chem.,2001,503:105.
[11]Lampert C M,Granqvist C G.Large-Area Chromoge-nics:Materials and Devices for Transmittance Control[M].Washington:SPIE Optical Engineering Press,1990.
[12]Barbero C,Miras MC,Calvo E J,et al.A probe beamdeflection study of ion exchange at poly(vinylferro-cene)films in aqueous and nonaqueous electrolytes[J].Langmuir,2002,18:2756.
[13]Hwang K S,Lee C W,Yoon T H,et al.Fabricationand characteristics of a composite cathode of sulfonatedpolyaniline and Ramsdellite MnO2for a new recharge-able lithium polymer battery[J].J.Power Sources,1999,79:225.
[14]Ferreira M,Rubner M F.Molecular-level processingof conjugated polymers.1.layer-by-layer manipu-lation of conjugated polyions[J].Macromolecules,1995,28:7107.
[15]Box G E P,Hunter W G,Hunter J S.Statistics for Ex-periments[M].New York:Wiley,1978.374.
[16]Montgomery D C.Design and Analysis of Experiments,5th ed.,[M].Singapore:Wiley,2001.303.
[17]Cornell J A.How to Apply Response Surface Methodo-logy,vol.8[M].Wisconsin:ASQC,1990.3.
[18]Tsay P,Hu C C.Non-anomalous codeposition of iron-nickel alloys using pulse-reverse electroplatingthrough means of experimental strategies[J].J.Elec-trochem.Soc.,2002,149:C 492.
[19]Hu C C,Tsay C H,Bai A.Optimization of the hydro-gen evolution activity of zinc-nickel deposits using ex-perimental strategies[J].Electrochim.Acta,2003,48:907.
[20]Li Y J,Chang C C,Wen TC.Application of statisticalexperimental strategies to H2O2production on Au/graphite in alkaline solution[J].I&EC Research,1996,35:4 767.
[21]Hsu C H,Peacock P M,Flippen R B,et al.Molecularweight of sulfonic acid ring-substituted polyaniline bylaser light scattering[J].Synth.Met.,1993,60:223.
[22]Mu S,Kan J.Energy density and IR spectra of polyani-line synthesized electrochemically in the solutions ofstrong acids[J].Synth.Met.,1998,98:51.
[23]Lim V W L,Kang E T,Neoh K G,et al.Determina-tion of pyrrole aniline copolymer compositions by X-ray photoelectron spectroscopy[J].Applied SurfaceScience,2001,181:317.
[24]Trivedi D C.Handbook of Organic Conductive Mole-cules and Polymers,vol.2[M].New York:H.S.Nalwa,Wiley,1997.Chapter 12.
[25]Anand J,Palaniappan S,Sathyanarayana D N.Hand-book of Organic Conductive Molecules and Polymers,vol.2[M].New York:H.S.Nalwa,Wiley,1997.Chapter 13.
[26]Wang X H,Li J,Wang LX,et al.Structure and prop-erties of self-doped polyaniline[J].Synth.Met.,1995,69:149.
[27]John McMurry.McMurry Organic Chemistry,4th ed.,[M].Brooks/Cole,1996.Chapter 16.
[28]Kang E T,Neoh K G,Tan K L.Handbook of OrganicConductive Molecules and Polymers,vol.3[M].NewYork:H.S.Nalwa,Wiley,1997.
[29]Yue J,Epstein A J.XPS study of self-doped conduc-ting polyaniline and parent systems[J].Macromole-cules,1991,24:4 441.
[30]Wei X L,Fahlman M,Epstein AJ.XPS study of high-ly sulfonated polyaniline[J].Macromolecules,1999,32:3 114.



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