Conductive polymer metal composites preparation methods on bulk and nano scales

CONDUCTIVE POLYMER-METAL COMPOSITES: PREPARATION METHODS ON BULK AND NANO SCALES WANG JINGGONG NATIONAL UNIVERSITY OF SINGAPORE 2004 CONDUCTIVE POLYMER-METAL COMPOSITES: PREPARATION METHODS ON BULK AND NANO SCALES WANG JINGGONG (B. Eng., Tianjin University) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMICAL & BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2004 ACKNOWLEDGEMENT I would like to express my heart-felt gratitude to the following people for their help and support in the completion of this thesis: — to my supervisors, Professor Neoh Koon Gee and Professor Kang En-Tang, for their constant guidance and invaluable advices throughout my research. I am indebted to them for their supports and patience by introducing me into this exciting field of research; — to the faculty and staff of Department of Chemical and Environmental Engineering, and National University of Singapore for rendering me help of one kind or another to facilitate my research, with special thanks to Dr. Zhang Yan and Dr. Li Sheng for their help in running the XPS measurements; — to my dear mother, father, sister and my wife Wang Xiu for their unfailing encouragement and spiritual support. I TABLE OF CONTENTS ACKNOWLEDGEMENTS I SUMMARY VII NOMENTCLATURE X LIST OF FIGURES XI CHAPTER INTRODUCTION CHAPTER LITERATURE REVIEW 2.1 Overview of Conductive Polymers 10 2.1.1 General Information of Conductive Polymers 10 2.1.2 Polyaniline, Polypyrrole and Polythiophene 13 2.2 Synthesis and Characterization of Polyaniline-Metals Systems 17 2.2.1 Polyaniline-Palladium Systems 19 2.2.2 Other Polyaniline-Metals (Gold, Copper, Iron etc.) Systems 21 2.3 Synthesis of Nanosized Conductive Polymers 23 2.3.1 Synthesis of Nanosized Conductive Polymers by Template Method 24 2.3.2 Other Popular Methods in the Synthesis of Nanosized Conductive Polymers (or Composites) 26 2.4 Plasma Polymerization of Conductive Polymers 28 2.4.1 Plasma Polymerized Aniline Systems 30 2.4.2 Plasma Polymerized Pyrrole Systems 31 2.4.3 Plasma Polymerized Thiophene Systems 32 2.5 Characterization of Conductive Polymers 33 2.5.1 Surface and Interface Analysis of Conductive Polymers 33 II 2.5.1.1 X-ray Photoelectron Spectroscopy (XPS) 34 2.5.1.2 Microscopic Techniques Applied in Surface Characterization 38 2.5.2 39 Spectroscopic Measurements Applied in Conductive Polymers Characterization CHAPTER CHEMICAL DEPOSITION OF PALLADIUM ON LEUCOEMERALDINE FROM SOLUTIONS: STATE AND DISTRIBUTION OF PALLADIUM SPECIES 41 3.1 Introduction 42 3.2 Experimental Section 42 3.2.1 Preparation of Polyaniline 42 3.2.2 Uptake of Pd from Solutions 43 3.2.3 Measurement of Metal Ion Concentration and Film Characterization 43 3.3 Results and Discussion 45 3.3.1 Pd Uptake from PdCl2, Pd(NO3)2 and Their Mixed Solutions 45 3.3.2 Pd Uptake from Mixed Solutions of PdCl2 and AuCl3 55 3.4 Conclusion 64 CHAPTER PREPARATION OF NANOSIZED METALLIC PARTICLES IN POLYANILINE 65 4.1 Introduction 66 4.2 Experimental Section 66 4.2.1 Preparation of Polyaniline 66 4.2.2 Reactions of EM with AuCl3 in NMP (Method 1) 66 4.2.3 Reactions of EM with AuCl3 in Water (Method 2) 67 4.2.4 Reactions of LM with Pd(NO3)2 in Acid (Method 3) 67 4.2.5 Dispersion of Metal Particles in Polyaniline 68 4.2.6 Characterization 68 III 4.3 Results and Discussion 70 4.3.1 Synthesis of Nanosized Particles by Method 70 4.3.2 Synthesis of Nanosized Particles by Method and 78 4.4 Conclusion 88 CHAPTER POLYANILINE-PALLADIUM COMPOSITE COATINGS FOR METALLIZATION OF POLYETHYLENE SUBSTRATE 92 5.1 Introduction 93 5.2 Experimental Section 93 5.2.1 Preparation of AAc-graft Copolymerized LDPE 93 5.2.2 Preparation of Polyaniline 94 5.2.3 Reactions of LM Thin Films with Pd(NO3)2 (Method 1) 94 5.2.4 Reactions of LM Powder with Pd(NO3)2 Followed by Film Casting (Method 2) 95 5.2.5 Characterization 95 5.3 Results and Discussion 96 5.3.1 AAc-graft Copolymerization with LDPE 96 5.3.2 Reactions of LM Thin Films with Pd(NO3)2 (Method 1) 99 5.3.3 Reactions of LM Powder with Pd(NO3)2 Followed by Film Casting (Method 2) 104 5.3.4 Adhesion and Conductivity of Polyaniline-Palladium Films 111 5.4 Conclusion 115 CHAPTER THIN FILMS OF CONDUCTIVE POLYMERS VIA PLASMA POLYMERIZATION 117 6.1 Plasma Polymerization of Aniline on Different Surface Functionalized Substrates 118 6.1.1 Introduction 118 IV 6.1.2 Experimental Section 118 6.1.2.1 AAc-graft Copolymerized LDPE (AAc-g-LDPE) 118 6.1.2.2 PSSA Coated LDPE (PSSA-c-LDPE) 118 6.1.2.3 Viologen-graft Copolymerized LDPE (viologen-g-LDPE) 119 6.1.2.4 Plasma Polymerization of Aniline 120 6.1.2.5 Reactions of Plasma Polymerized Aniline 120 6.1.2.6 Film Characterization 121 6.1.3 122 Results and Discussion 6.1.3.1 Characterization of Plasma Polymerized Aniline 122 6.1.3.2 Reactions Carried Out with Plasma Polymerized Aniline 130 6.1.4 Conclusion 141 6.2 Comparative Study of Chemically Synthesized and Plasma Polymerized Pyrrole and Thiophene Thin Films 143 6.2.1 Introduction 143 6.2.2 Experimental Section 143 6.2.2.1 AAc-graft Copolymerized LDPE (AAc-g-LDPE) 143 6.2.2.2 Chemical Synthesis of Polypyrrole and Polythiophene 143 6.2.2.3 Plasma Polymerization of Pyrrole and Thiophene 144 6.2.2.4 Doping of Plasma Polymerized Monomers with Iodine 145 6.2.2.5 Film Characterization 145 6.2.3 146 Results and Discussion 6.2.3.1 Characterization of Plasma Polymerized Pyrrole and Thiophene 146 6.2.3.2 Stability of Chemically Synthesized and Plasma Polymerized Pyrrole and Thiophene 159 6.2.4 168 Conclusion V CHAPTER ELECTROACTIVE POLYMER PATTERNS WITH METAL INCORPORATION ON POLYMERIC SUBSTRATE 169 7.1 Introduction 170 7.2 Experimental Section 170 7.2.1 Preparation of Polyaniline-Viologen Film 170 7.2.2 Plasma Treatment of Polyaniline-Viologen Film 171 7.2.3 Pattern Formation via Plasma Polymerization of Aniline 171 7.2.4 Incorporation of Metals/Metal Ions 171 7.2.5 Sample Characterization 172 7.3 Results and Discussion 172 7.3.1 Plasma Treatment of PANI-Viologen Film 172 7.3.2 Plasma Polymerized Aniline System 177 7.3.3 Incorporation of Metals/Metal Ions 179 7.4 Conclusion 179 CHAPTER CONCLUSION 182 CHAPTER REFERENCES 186 PUBLICATIONS 209 VI SUMMARY This thesis is a graduate study on the synthesis of nanosized conductive polymers and its metal composites. The two purposes of the study are first, to investigate the reactions between polyaniline and metals, and second, to synthesize nanosized composites of conductive polymers and metals by different methods. The reactions of polyaniline in leucoemeraldine (LM) state with palladium ions in PdCl2, Pd(NO3)2, mixed solutions of PdCl2 and Pd(NO3)2 and mixed solutions of PdCl2 and AuCl3 were investigated. The results showed that a much faster and more complete reduction of Pd ions to Pd0 occurred in the Pd(NO3)2 solution as compared to the PdCl2 solution. The mixing of Pd(NO3)2 with PdCl2 appears to affect the Pd coordination states in solution which in turn affects the Pd uptake rate and the manner in which the Pd is deposited on the LM surface. In mixed solutions of PdCl2 and AuCl3, it was clearly seen that the presence of a small amount of AuCl3 (molar ratio of AuCl3/PdCl2 of 0.1) can greatly accelerate the uptake of Pd and complete removal of Pd ions from PdCl2 can be accomplished. When the reduction of AuCl3 was carried out in N-methylpyrrolidinone (NMP) solutions of polyaniline, the Au particles were of the order of 20 nm. The reduction of AuCl3 or Pd(NO3)2 by polyaniline in the powder form in aqueous media resulted in the accumulation of the elemental Au or Pd on the surface of the polyaniline particles. Subsequent dissolution of the polyaniline in NMP resulted in metal particles of about 50 to 200 nm being dispersed in the NMP solution of polyaniline. The rate of metal salt reduction and the size of the metal particles were found to be strongly dependent on the medium used, the initial ratio of metal ions to polyaniline and the reaction time. VII The coating of acrylic acid grafted low-density polyethylene (AAc-g-LDPE) films with a polyaniline-palladium composite layer was investigated. In the first method, polyaniline was first deposited on the AAc-g-LDPE, followed by reaction with Pd(NO3)2. This resulted in a layer of palladium being deposited on the polyaniline surface. In the second method, polyaniline powder was first reacted with Pd(NO3)2 and the powder was then treated with NMP and coated on the AAc-g-LDPE. In both methods, the amount of palladium deposited can be varied by controlling the reaction time and the proportion of palladium to polyaniline used. In the second method, nanosized palladium metal particles are distributed in the polyaniline coating rather then confined to the surface of the polyaniline layer. In both cases, the palladium metal particles confer surface conductivity to the LDPE substrate even with the polyaniline in the undoped state. The adhesion of the polyaniline-palladium coating to the AAc-g-LDPE substrate is excellent at low palladium content but is significantly weakened when a high palladium content interferes with the interactions between the polyaniline and the AAc-graft copolymerized chains. 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Wang, J.G., K.G. Neoh and E.T. Kang. Comparative Study of Chemically Synthesized and Plasma Polymerized Pyrrole and Thiophene Thin Films, Thin Solid Films, 446, pp.205-217. 2004. 6. Zhao, L.P., K.G. Neoh, J.G. Wang and E.T. Kang. Electroactive Polymer Patterns with Metal Incorporation on a Polymeric Substrate, Polym. Eng. Sci., 44, pp.20612069. 2004. 209 [...]... interactions between conductive polymers and metal ions are essential from both a theoretical and application point of view The conductive polymers are more suitable for hosting metallic microparticles than the fixed redox-site polymers because conductive polymers have multi-coordination sites to give multi-nuclear complexes (Tourillon and Garnier, 1982) 17 Complexation of transition metals to a conjugated... applications such as secondary batteries and display devices 2.2 Synthesis and Characterization of Polyaniline-Metals Systems In the recent years, one can observe a growing interest in conductive polymermetal systems since such incorporation of metals is known to enhance conductivity of the polymer, be applied as novel catalysts for a great number of synthetic reactions and allow metal- ligand interactions... recombine rapidly, and this results in changes in the plasma polymer network over time (Hynek and Yoshihito, 1992) As reported earlier, the chemical structures of plasma polymerized conductive polymers are rather different from conventional polymers and are dependent on the plasma polymerization conditions (Cruz et al., 1999; Cruz et al., 1997; Bhat and Wavhal, 1998) Although detailed information on the structures... containing metal particles include the use of templates for arranging the nanoscopic metal and conductive polymer clusters into spatially well-defined structures (Marinakos et al., 1999), and the 2 incorporation of the metal clusters during electrosynthesis of the polymer (Rajeshwar and Bose, 1994; Vork et al., 1986; Noufi, 1983) There are also a number of investigations on the electrodeposition of metal. .. investigations, the commonly recognized conclusions are: the deposition rate and film thickness are dependent on the carrier gas and plasma power, and hence the thickness of layer can be controlled; the molecular structures are different from counterparts synthesized via conventional methods; conductivity in plasma polymerized aniline, pyrrole and thiophene can be induced with I2 doping but the conductivity level... spectroscopy 6 (XPS) for monitoring the changes in the chemical states of the polymer and metal species, and laser light scattering and electron microscopy for particle size determination The synthesis of polyaniline-palladium composite coatings for the metallization of an inert substrate is described in Chapter 5 The effects of reaction conditions on the particle size and distribution in such systems are... Chapter 7 is on the selective surface deposition of polyaniline via plasma polymerization through a mask By utilizing the special characteristics of plasma polymerization, patterns on the micro and nanoscale can be conveniently fabricated on surfaces of polymeric substrates through a photomask Furthermore, metal incorporation on the electroactive patterns was applied to the assynthesized plasma polymerized... theoretical chemists and physicists 2.1.1 General Information of Conductive Polymers The structures of all conductive polymers have the same signature Each atom along the backbone is involved in a π bond which is much weaker than the σ bonds that hold the atoms in the polymer chain together Placed side by side, these π bonds can delocalize over all the atoms The extent of delocalization of an electron in an extended... interpretation and debate: although every electronic wave function is defined for any point in space, the majority of electron density is smeared over a relatively small volume (Tolbert and Ogle, 1990) A polaron is a type of “electronic 10 defect” that occurs within those π orbitals and is the charge carrier responsible for the conductivity of conductive polymers Thus, the mechanism for charge transport in conductive. .. interaction of polyaniline with transition metal ions with the subsequent reduction of these ions to produce metal nanoparticles with high surface areas (Huang et al., 1998) The selection of a substrate for the conductive polymers -metal systems (and for the subsequent work) is an issue of concern Low-density polyethylene (LDPE) is a useful substrate for many experiments in the laboratory and for many . CONDUCTIVE POLYMER-METAL COMPOSITES: PREPARATION METHODS ON BULK AND NANO SCALES WANG JINGGONG NATIONAL UNIVERSITY OF. UNIVERSITY OF SINGAPORE 2004 CONDUCTIVE POLYMER-METAL COMPOSITES: PREPARATION METHODS ON BULK AND NANO SCALES WANG JINGGONG (B. Eng., Tianjin University) . of nanosized conductive polymers and its metal composites. The two purposes of the study are first, to investigate the reactions between polyaniline and metals, and second, to synthesize nanosized