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allows for a method to tailor the processability of sulfonic acid-doped PANI(Hartikainen, et al., 2001; Ruokolainen, et al., 2000). It has been observed that for polymer blends containing PANI, a range of conductivity between 10 -10 S cm -1 to 10 -1 S cm -1 (melt processing) and 10 -10 S cm -1 to 10 S cm -1 (solution processing) can be achieved(Panipol, 2000). The blending of PANI with a variety of classical polymers to improve the mechanical properties of PANI and also to decrease the percolation threshold of the conductive polymers has been extensively studied. Conductive binary polymer blends can demonstrate good mechanical properties with conductivity varying from 10 −11 S cm -1 (almost insulating) to 300 S cm -1 . It should be noted that different techniques including melt-blending, solution blending, in-situ polymerization, and dispersion mixing have different influence on PANI morphology and subsequently on properties. For instance, in the case of a PS/PANI blend, although melt-blending results in a higher PANI percolation threshold than dispersion mixing, a significant improvement in mechanical properties is achieved via the melt blending approach(Segal, et al., 2001). Most studies of polymer blends containing PANI have been performed in solution and only a few melt-blending studies have been reported(Ikkala et al., 1995; Narkis, Zilberman, & Siegmann, 1997; Shacklette, et al., 1993; Zilberman, et al., 1997). Polystyrene(PS)(Woo Jin, et al., 2003), Cellulose acetate(Planes, et al., 1998), Polymethylmethacrylate(PMMA)(Morgan, et al., 2001), Polyethylene(PE), Polypropylene(PP), Polyamide(PA)(Qinghua, et al., 2002), Polyimide(PI)(Moon Gyu & Seung Soon, 2001), Polyvinyl chloride(PVC)(Chipara, et al., 1998), Polyurethane(PU)(Rodrigues & Akcelrud, 2003), and a wide variety of thermoplastic elastomers(Dong-Uk, et al., 2001; Ong, et al., 1997) have been blended with PANI using a variety of techniques other than melt-blending(Ikkala, et al., 1995; Narkis, et al., 1997; Segal, et al., 2001; Shacklette, et al., 1993; Zilberman, et al., 1997). A conductivity value of 0.1 S cm -1 for 20 wt% of PANI is observed for PS/PANI blend prepared by in-situ polymerization(Woo Jin, et al., 2003). Using a polymer solution blending approach, Cao et al.(Cao, Smith, & Heeger, 1992) developed a processing method for a host polymer of PMMA and polyaniline optimally doped with camphor sulfonic acid. Using this method the value of electrical conductivity could be increased to 1 S cm -1 for loading levels of polyaniline as low as 0.3% (vol/vol)(Yang, Y. Cao, P. Smith, & Heeger, 1993b). The solution blending of PANI and its derivatives with poly(vinylidene fluoride)(PVDF) have attracted significant interest due to some of the special properties of PVDF, namely, excellent mechanical properties, 100
chemical and weathering resistance, piezo-electric properties and good flexibility(Bliznyuk et al., 2005; Privalko, et al., 2005). Fraysse et al(Fraysse, et al., 2000) were able to decrease the percolation threshold of PANI sharply in a PANI/PMMA solution blend to 0.5 wt% of PANI. Although the above methods using in-situ polymerization and polymer solution blending can result in very low percolation thresholds of conductive polymer, they suffer from serious disadvantageous such as poor mechanical properties. In addition, clearly the environmental and health related issues associated with solvents and solvent removal are critical concerns. A melt blending approach, from this point of view, is potentially a much more robust and environmentally friendly approach. In the case of melt-processing, Shacklette et al.(Shacklette, et al., 1993) reported percolation thresholds in a range of 6-10% for PANI dispersed in polar polymers such as polycaprolactone and poly(ethylene terphthalate glycol). Zilberman et al.(Zilberman, et al., 2000d) have reported percolation thresholds of PS/PANI and linear low-density polyethylene(LLDPE)/PANI of about 30 wt% of PANI. They reported a lower percolation value of 20 wt% PANI for the binary blend composed of CoPA/PANI. Levon et al.(Levon, et al., 1993) were the first to suggest the concept of double percolation in a ternary polymer blend consisting of a conductive polymer. This double percolated system was comprised of a connected path within a connected path, the latter of which is conducting. Zilberman et al.(Zilberman, et al., 2000d) observed a high-quality conductive PANI network in a CoPA/LLDPE/PANI ternary blend and a poor-quality PANI network in a (PS+DOP)/LLDPE/PANI blend. Narkis and coworkers(Haba, et al., 2000; Narkis, et al., 2000a; Segal, et al., 2001)extended and developed these previous works by blending PANI with other homopolymers via different methods mostly by using the methodology of a double percolated morphology to decrease the percolation threshold and increase mechanical properties. They showed that for several melt processed PANI/polymer blends, the conductivity results reveal a percolation threshold of approximately 20%. That work also shows that, in ternary blends consisting of PANI and two immiscible polymers, the PANI is preferentially located in one of the constituting polymers. They found that PANI always prefers to locate in one phase rather than situating at the interface(Zilberman, et al., 2000d). In all previous works performed on PANI, the percolation threshold concentration of PANI was determined based on the onset of increase in the conductivity as a function of composition. In most of those cases, the sample 101
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© Sepehr Ravati, 2010. UNIVERSITÉ
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DEDICATED To my parents iii
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RÉSUMÉ Cette thèse présente, po
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devenir une structure hiérarchique
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ABSTRACT This thesis presents, for
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system can be increased from 10 -15
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CONDENSÉ EN FRANÇAIS Dans ce trav
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deuxième coquille de PS. Les phase
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structures à percolation multiple
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autre sous-type de morphologie dans
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TABLE OF CONTENTS DEDICATION.......
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xxiii 2.4.1.1.1 Charged Polymer Ads
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5.3.4 Annealing Test ..............
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xxvii REFERENCES ..................
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LIST OF FIGURES xxix Figure 1-1. a)
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Figure 2-12. SEM photomicrograph of
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Figure 2-34. Schematic view of diff
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Figure 4-8. SEM micrographs of vari
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Figure 5-6. a),b) Scanning electron
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and c) triangular concentration dia
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n number of moles p concentration o
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AFM atomic force microscopy LIST OF
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PS-co-PMMA copolymer of PS and PMMA
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1.1 Introduction CHAPTER 1 - INTROD
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Figure 1-2. Human heart, longitudin
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One of the applications for porous
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On the other hand, a novel tri-cont
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2.1 Polymer Blends CHAPTER 2 - LITE
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Based on Sterling’s approximation
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Antonoff’s rule (Equation 2-13) i
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2.1.2.1 Binary Polymer Blends 2.1.2
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Some other studies(Everaert, Aerts,
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where the parameter z is dependent
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“compatibilization” was suggest
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a) λ BC A and B are matrices, b) C
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Reignier & Favis, 2000, 2003a; Reig
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measure the interfacial tension of
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a) b) Figure 2-6. Dependence of the
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Omonov et al. found double percolat
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2.1.2.2.3 Effect of Composition on
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a) b) C B A c) Figure 2-12. SEM pho
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In the case where PS is the matrix,
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Posthuma de Boer, 1999) (Kumin & Ch
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lattice, such as square lattice, wi
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magnetization, which is a function
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Polymers have long been thought of
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epoxy as a function of nanotube wei
Page 95 and 96: Figure 2-19. Approaching the percol
Page 97 and 98: Figure 2-21. Transmission electron
Page 99 and 100: Figure 2-22: Dependence of PE conti
Page 101 and 102: Figure 2-24. Plot of the total numb
Page 103 and 104: chain provides the conductive path
Page 105 and 106: 2.3.1.2.1 Polyaniline One of the mo
Page 107 and 108: CoPA/LLDPE/PANI blend and a poor-qu
Page 109 and 110: Narkis and co-workers extended and
Page 111 and 112: Figure 2-31: Conductivity of PVDF/P
Page 113 and 114: organic thin films, a novel and str
Page 115 and 116: on the topic have been reported in
Page 117 and 118: succeeded in creating thin films wi
Page 119 and 120: Addition of salt to the solution of
Page 121 and 122: different from that of linear homop
Page 123 and 124: Figure 2-39. Macromolecule with a)
Page 125 and 126: polyanion such as hyaluronan (HA)(P
Page 127 and 128: 2.4.1.1.7 Effect of Salt on Multila
Page 129 and 130: 2.4.1.1.8 Overcompensation of the M
Page 131 and 132: important factors determining the g
Page 133 and 134: As shown in Figure 2-44, swelling a
Page 135 and 136: increasing the pH value due to a de
Page 137 and 138: CHAPTER 3 - ORGANIZATION OF THE ART
Page 139 and 140: discussed above, HDPE, PS, PMMA, an
Page 141 and 142: CHAPTER 4 - LOW PERCOLATION THRESHO
Page 143 and 144: or model which predicts where the p
Page 145: concentration threshold for the ons
Page 149 and 150: Table 4-1. Material Characteristics
Page 151 and 152: filled with blend pellets. To facil
Page 153 and 154: 4.3.6 Conductivity Measurements DC
Page 155 and 156: experimentally in this research gro
Page 157 and 158: a) b) c) d) Figure 4-4. Schematic i
Page 159 and 160: microstructure of the quaternary bl
Page 161 and 162: a) b) c) d) Figure 4-6. SEM microgr
Page 163 and 164: a) b) PVDF PS PMMA c) d) e) HDPE PS
Page 165 and 166: Uniform layers of PS and PMMA situa
Page 167 and 168: the concentration of HDPE is increa
Page 169 and 170: a) b) c) e) Figure 4-11. SEM microg
Page 171 and 172: melt-processable and contains 25 wt
Page 173 and 174: One question that should be address
Page 175 and 176: Conductivity(S/cm) Ternary Blend 1,
Page 177 and 178: phase(PMMA), the concentration of P
Page 179 and 180: (6) Virgilio, N.; Desjardins, P.; L
Page 181 and 182: ONION MORPHOLOGY HDPE PVDF PS Contr
Page 183 and 184: work described above has focused on
Page 185 and 186: thermodynamic explanation to predic
Page 187 and 188: four-point probe increases continuo
Page 189 and 190: in the rheology tests were compress
Page 191 and 192: 5.3.6 Layer-by-Layer Deposition The
Page 193 and 194: prepare a polymer blend structure w
Page 195 and 196: a) b) c) Figure 5-3. Scanning elect
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spontaneously self-assembled. After
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a) b) c) d) e) f) g) h) Figure 5-5.
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Since the ultra-low surface area va
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c) a) b) Figure 5-6. a),b) Scanning
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salt to a PSS polyelectrolyte solut
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A relationship between macropore si
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close together. It is interesting t
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Figure 5-9. Mass increase (%) indic
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In this work the conductance of the
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deposited PANI layers increases unt
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(52) Guo, H. F.; Packirisamy, S.; G
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6.2 Introduction It is well-known t
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modified version of Harkins theory(
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6.3 Experimental 6.3.1 Materials Co
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Complex voscosity (Pa.s) 1,0E+04 1,
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6.3.5.2 Focused Ion Beam (FIB) and
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a) c) b) d) e) f) PMMA PMMA HDPE HD
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y Harkins theory, PS will always si
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a) b) c) d) e) f) PS Figure 6-6. a)
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a) b) HDPE : black PS : grey PMMA :
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6.4.6 Continuity, Co-continuity, an
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c) V III II I VII I IV VI Figure 6-
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Continuity Scheme (a) Figure 6-10.
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Addition of a low concentration of
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Addition of small amounts of HDPE t
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icontinuous network with the HDPE.
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Three examples are shown in Figure
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(9) Mekhilef, N.; Verhoogt, H. Poly
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structures are formed due to the co
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CONCLUSION AND RECOMMENDATIONS In t
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REFERENCES A. K. Gupta, K. R. S. (1
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Caruso, F. (2003). Hollow Inorganic
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Domenech, S. C., Bortoluzzi, J. H.,
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Geuskens, G., Gielens, J. L., Geshe
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Hou, S., Harrell, C. C., Trofin, L.
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Krass, H., Papastavrou, G., & Kurth
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Macdiarmid, A. G., Jin-Chih, C., Ha
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Niziol, J., & Laska, J. (1999). Con
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Reghu, M., Yoon, C. O., Yang, C. Y.
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Shirakawa, H., Louis, E. L., MacDia
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Utracki, L. A. (1991). On the visco
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Yasuda, K., Armstrong, R., & Cohen,
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literature has examined factors inf
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(Reignier & Favis, 2000, 2003a; Rei
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Table A-1.2. Interfacial tensions a
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acquisition of images with a very h
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Table A-1.3. Continuity of the PMMA
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(17) Reignier, J.; Favis, B. D., Ma
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PANI. Theoretically, the extent of
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Equation A-2.7 0( ) 0 1. 5 σ = σ
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Cumulative Mass × 10 5 (g) dipping
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of PANI, and an increase in the con
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Resistance(ohm) 1.0E+12 1.0E+11 1.0
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esistance value. Samples containing
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The results of resistance for PS/PE
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Caruso, F., & Schuler, C. (2000). E
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