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theory. Through the control of the composition of the inner(HDPE) and outer(PVDF) layers in the onion structure, the morphology can be transformed to a highly elongated onion morphology and subsequently to a multi-percolated structure in which all HDPE, PS, PMMA, and PVDF phases are continuous and percolated throughout the system. It is shown that the addition of PANI results in a 5-component multi-encapsulated, multi-percolated blend with the PANI situated in the core of the system. The addition of an interfacial modifier for the PS and PMMA components results in the diminished phase sizes of those particular components which, due to the encapsulated nature of the morphology, has the effect of reducing the phase size for all other phases as well. The conductivity is measured for a wide range of the above systems as a function of the number of phases and as a function of the PANI concentration. It is shown that increasing the number of components in the blend with a multi-percolated structure from ternary to quaternary to quinary and finally to an interfacially modified quinary blend results in a several orders of magnitude increase in the conductivity of the system. In this way, the percolation threshold of the PANI can be reduced to below 5 vol%. The conductivity of the quinary blend system, for example, can be increased from 10 -15 S cm -1 (pure PE) to 10 -5 S cm -1 at 5 % PANI and up to 10 -3 S cm -1 for 10% PANI. These are the highest conductivity values ever reported for these PANI concentrations in melt processed systems. 4.6 Acknowledgements The authors express appreciation to the Natural Sciences and Engineering Research Council of Canada for supporting this work. They also thank F. Normandin from the Institut des matériaux industriels for his assistance with the conductivity measurements of the samples. 4.1. References (1) Moussaif, N.; Jérôme, R. Polymer 1999, 40, 3919. (2) Reignier, J.; Favis, B. D. Macromolecules 2000, 33, 6998. (3) Reignier, J.; Favis, B. D. AIChE Journal 2003, 49, 1014. (4) Zhang, J.; Ravati, S.; Virgilio, N.; Favis, B. D. Macromolecules 2007, 40, 8817. (5) Virgilio, N.; Marc-Aurele, C.; Favis, B. D. Macromolecules 2009, 42, 3405. 132
(6) Virgilio, N.; Desjardins, P.; L'Esperance, G.; Favis, B. D. Macromolecules 2009, 42, 7518. (7) Torza, S.; Mason, S. G. J. Coll. Interface Sci. 1970, 33, 67. (8) Hobbs, S. Y.; Dekkers, M. E. J.; Watkins, V. H. Polymer 1988, 29, 1598. (9) Reignier, J.; Favis, B. D. Polymer 2003, 44, 5061. (10) Zilberman, M.; Siegmann, A.; Narkis, M.; 1 ed.; SAMPE: Anaheim, CA, USA, 1998; Vol. 43, p 528. (11) Zilberman, M.; Siegmann, A.; Narkis, M. Journal of Macromolecular Science - Physics 2000, B39, 333. (12) Pud, A.; Ogurtsov, N.; Korzhenko, A.; Shapoval, G. Progress in Polymer Science (Oxford) 2003, 28, 1701. (13) Anand, J.; Palaniappan, S.; Sathyanarayana, D. N. Progress in Polymer Science (Oxford) 1998, 23, 993. (14) Bhattacharya, A.; De, A. Journal of Macromolecular Science - Reviews in Macromolecular Chemistry and Physics 1999, C39, 17. (15) Scher, H.; Zallen, R. The Journal of Chemical Physics 1970, 53, 3759. (16) Gubbels, F.; Blacher, S.; Vanlathem, E.; Jerome, R.; Deltour, R.; Brouers, F.; Teyssie, P. Macromolecules 1995, 28, 1559. (17) Gubbels, F.; Jerome, R.; Teyssie, P.; Vanlathem, E.; Deltour, R.; Calderone, A.; Parente, V.; Bredas, J. L. Macromolecules 1994, 27, 1972. (18) Jagur-Grodzinski, J. Polymers for Advanced Technologies 2002, 13, 615. (19) Bridge, B.; Tee, H. International Journal of Electronics 1990, 69, 785. (20) Carmona, F. Physica A: Statistical and Theoretical Physics 1989, 157, 461. (21) Munson-McGee, S. H. Physical Review B (Condensed Matter) 1991, 43, 3331. (22) Sumita, M.; Sakata, K.; Asai, S.; Miyasaka, K.; Nakagawa, H. Polymer Bulletin (Berlin) 1991, 25, 265. (23) Burroughes, J. H.; Jones, C. A.; Friend, R. H. Nature 1988, 335, 137. (24) Paul, R. K.; Vijayanathan, V.; Pillai, C. K. S. Synthetic Metals 1999, 104, 189. (25) Macdiarmid, A. G.; Jin-Chih, C.; Halpern, M.; Wu-Song, H.; Shao-Lin, M.; Somasiri, L. D.; Wanqun, W.; Yaniger, S. I. In Proceedings of the International Conference on the Physics and Chemistry of Low-Dimensional Synthetic Metals (ICSM 84), 17-22 June 1984; 1-4 ed. UK, 1985; Vol. 121, p 173. (26) Andreatta, A.; Cao, Y.; Chiang, J. C.; Heeger, A. J.; Smith, P. Synthetic Metals 1988, 26, 383. (27) Ruokolainen, J.; Eerikainen, H.; Torkkeli, M.; Serimaa, R.; Jussila, M.; Ikkala, O. Macromolecules 2000, 33, 9272. (28) Hartikainen, J.; Lahtinen, M.; Torkkeli, M.; Serimaa, R.; Valkonen, J.; Rissanen, K.; Ikkala, O. Macromolecules 2001, 34, 7789. (29) Panipol http://www.azom.com/details.asp?ArticleID=1197 2000. (30) Segal, E.; Haba, Y.; Narkis, M.; Siegmann, A. Journal of Polymer Science, Part B: Polymer Physics 2001, 39, 611. (31) Shacklette, L. W.; Han, C. C.; Luly, M. H. Synthetic Metals 1993, 57, 3532. (32) Ikkala, O. T.; Laakso, J.; Väkiparta, K.; Virtanen, E.; Ruohonen, H.; Järvinen, H.; Taka, T.; Passiniemi, P.; Österholm, J. E.; Cao, Y.; Andreatta, A.; Smith, P.; Heeger, A. J. Synthetic Metals 1995, 69, 97. 133
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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
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Figure 2-19. Approaching the percol
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Figure 2-21. Transmission electron
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Figure 2-22: Dependence of PE conti
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Figure 2-24. Plot of the total numb
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chain provides the conductive path
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2.3.1.2.1 Polyaniline One of the mo
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CoPA/LLDPE/PANI blend and a poor-qu
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Narkis and co-workers extended and
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Figure 2-31: Conductivity of PVDF/P
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organic thin films, a novel and str
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on the topic have been reported in
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succeeded in creating thin films wi
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Addition of salt to the solution of
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different from that of linear homop
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Figure 2-39. Macromolecule with a)
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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 and 146: concentration threshold for the ons
Page 147 and 148: chemical and weathering resistance,
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: phase(PMMA), the concentration of P
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
Page 197 and 198: spontaneously self-assembled. After
Page 199 and 200: a) b) c) d) e) f) g) h) Figure 5-5.
Page 201 and 202: Since the ultra-low surface area va
Page 203 and 204: c) a) b) Figure 5-6. a),b) Scanning
Page 205 and 206: salt to a PSS polyelectrolyte solut
Page 207 and 208: A relationship between macropore si
Page 209 and 210: close together. It is interesting t
Page 211 and 212: Figure 5-9. Mass increase (%) indic
Page 213 and 214: In this work the conductance of the
Page 215 and 216: deposited PANI layers increases unt
Page 217 and 218: (52) Guo, H. F.; Packirisamy, S.; G
Page 219 and 220: 6.2 Introduction It is well-known t
Page 221 and 222: modified version of Harkins theory(
Page 223 and 224: 6.3 Experimental 6.3.1 Materials Co
Page 225 and 226: Complex voscosity (Pa.s) 1,0E+04 1,
Page 227 and 228: 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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