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conductive polymer, the applicability of these original morphologies is confirmed mostly by conductivity results. It is shown that the order of phases in a complete wetting case such as a multi-percolated structure is dependent only on the thermodynamic properties; although viscosity and composition of phases play a major role in the determination of the morphology, they do not change the order of phases. In this case, addition of the copolymer of adjacent phases in a multipercolated structure induces a reduction in the phase size of the other phases, lowering the percolation threshold of phases, which leads to higher conductivity of the samples. Though the order of phases in multi-percolated structures is determined by the interfacial tension between phases, it is shown that the viscosity of phases significantly influences the distribution of interfacial energy between phases, and ultimately, the morphology. It is shown that fully interconnected porous materials are prepared via the production of a multipercolated structure followed by selective phase extraction. These porogens are used as substrates for alternate deposition of PSS and PANI. A detailed study on the behaviour of polyelectrolytes in the deposition process is carried out. This thesis presents a systematic technique for study and prediction the morphology of quaternary and quinary blends. To date, there is no theory for prediction of the morphology and order of the phases in hierarchical self-assembled systems prepared by melt-blending. This is the first study which begins to develop some mechanism and methods to predict the morphology of multi-component blends. 210
REFERENCES A. K. Gupta, K. R. S. (1993). Melt rheology and morphology of PP/SEBS/PC ternary blend. Journal of Applied Polymer Science, 47(1), 167-184. Adjari, A., Brochard-Wyart, F., de Gennes, P.-G., Leibler, L., Viovy, J.-L., & Rubinstein, M. (1994). Slippage of an entangled polymer melt on a grafted surface. Physica A: Statistical Mechanics and its Applications, 204(1-4), 17-39. Al-Saleh, M. H., & Sundararaj, U. (2008). An innovative method to reduce percolation threshold of carbon black filled immiscible polymer blends. Composites Part A: Applied Science and Manufacturing, 39(Copyright 2008, The Institution of Engineering and Technology), 284-293. Alexander, S. (1977). Polymer adsorption on small spheres. A scaling approach Journal de Physique (Paris), 38(8), 977-981. Anand, J., Palaniappan, S., & Sathyanarayana, D. N. (1998). Conducting polyaniline blends and composites. Progress in Polymer Science (Oxford), 23(6), 993-1018. Andreatta, A., Cao, Y., Chiang, J. C., Heeger, A. J., & Smith, P. (1988). Electrically-conductive fibers of polyaniline spun from solutions in concentrated sulfuric acid. Synthetic Metals, 26(4), 383-389. Angappane, S., Rajeev Kini, N., Natarajan, T. S., Rangarajan, G., & Wessling, B. (2002). PAni- PMMA blend/metal Schottky barriers, Singapore, Singapore. Antonoff, G. (1942). On the Validity of Antonoff's Rule. The Journal of Physical Chemistry, 46(4), 497-499. Antonoff, G. N. (1907). J Chim Phys 5, 364-371. Avgeropoulos, G. N., Weissert, F. C., Biddison, P. H., & Boehm, G. G. A. (1976). Hetrogeneous Blends of Polymers Rheology and Morphology. Rubber Chemistry and Technology, 49(1), 93-104. Baba, A., Kaneko, F., & Advincula, R. C. (1999). Adsorption properties of polyelectrolytes in ultrathin multilayer assemblies: Investigations using the quartz crystal microbalance (QCM) technique, Anaheim, CA, USA. Baradie, B., & Shoichet, M. S. (2003). Insight into the Surface Properties of Fluorocarbon−Vinyl Acetate Copolymer Films and Blends.. Macromolecules, 36(7), 2343-2348. doi: 10.1021/ma0216019 Bashforth, F., & Adams, J. C. (1883). An Attempt to Test the Theories of Capillary Action. Cambridge: Cambridge Univ. Press and Deighton Bell & Co. Bauhofer, W., & Kovacs, J. Z. (2009). A review and analysis of electrical percolation in carbon nanotube polymer composites. Composites Science and Technology, 69(10), 1486-1498. Berger, W., Kammer, H. W., & Kummerlowe, C. (1984). Makromol Chem Suppl B, 8, 101. 211
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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
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2.4.1.1.7 Effect of Salt on Multila
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2.4.1.1.8 Overcompensation of the M
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important factors determining the g
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As shown in Figure 2-44, swelling a
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increasing the pH value due to a de
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CHAPTER 3 - ORGANIZATION OF THE ART
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discussed above, HDPE, PS, PMMA, an
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CHAPTER 4 - LOW PERCOLATION THRESHO
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or model which predicts where the p
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concentration threshold for the ons
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chemical and weathering resistance,
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Table 4-1. Material Characteristics
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filled with blend pellets. To facil
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4.3.6 Conductivity Measurements DC
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experimentally in this research gro
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a) b) c) d) Figure 4-4. Schematic i
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microstructure of the quaternary bl
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a) b) c) d) Figure 4-6. SEM microgr
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a) b) PVDF PS PMMA c) d) e) HDPE PS
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Uniform layers of PS and PMMA situa
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the concentration of HDPE is increa
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a) b) c) e) Figure 4-11. SEM microg
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melt-processable and contains 25 wt
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One question that should be address
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Conductivity(S/cm) Ternary Blend 1,
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phase(PMMA), the concentration of P
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(6) Virgilio, N.; Desjardins, P.; L
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ONION MORPHOLOGY HDPE PVDF PS Contr
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work described above has focused on
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thermodynamic explanation to predic
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four-point probe increases continuo
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in the rheology tests were compress
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5.3.6 Layer-by-Layer Deposition The
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prepare a polymer blend structure w
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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
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
Page 229 and 230: a) c) b) d) e) f) PMMA PMMA HDPE HD
Page 231 and 232: y Harkins theory, PS will always si
Page 233 and 234: a) b) c) d) e) f) PS Figure 6-6. a)
Page 235 and 236: a) b) HDPE : black PS : grey PMMA :
Page 237 and 238: 6.4.6 Continuity, Co-continuity, an
Page 239 and 240: c) V III II I VII I IV VI Figure 6-
Page 241 and 242: Continuity Scheme (a) Figure 6-10.
Page 243 and 244: Addition of a low concentration of
Page 245 and 246: Addition of small amounts of HDPE t
Page 247 and 248: icontinuous network with the HDPE.
Page 249 and 250: Three examples are shown in Figure
Page 251 and 252: (9) Mekhilef, N.; Verhoogt, H. Poly
Page 253 and 254: structures are formed due to the co
Page 255: CONCLUSION AND RECOMMENDATIONS In t
Page 259 and 260: Caruso, F. (2003). Hollow Inorganic
Page 261 and 262: Domenech, S. C., Bortoluzzi, J. H.,
Page 263 and 264: Geuskens, G., Gielens, J. L., Geshe
Page 265 and 266: Hou, S., Harrell, C. C., Trofin, L.
Page 267 and 268: Krass, H., Papastavrou, G., & Kurth
Page 269 and 270: Macdiarmid, A. G., Jin-Chih, C., Ha
Page 271 and 272: Niziol, J., & Laska, J. (1999). Con
Page 273 and 274: Reghu, M., Yoon, C. O., Yang, C. Y.
Page 275 and 276: Shirakawa, H., Louis, E. L., MacDia
Page 277 and 278: Utracki, L. A. (1991). On the visco
Page 279 and 280: Yasuda, K., Armstrong, R., & Cohen,
Page 281 and 282: literature has examined factors inf
Page 283 and 284: (Reignier & Favis, 2000, 2003a; Rei
Page 285 and 286: Table A-1.2. Interfacial tensions a
Page 287 and 288: acquisition of images with a very h
Page 289 and 290: Table A-1.3. Continuity of the PMMA
Page 291 and 292: (17) Reignier, J.; Favis, B. D., Ma
Page 293 and 294: PANI. Theoretically, the extent of
Page 295 and 296: Equation A-2.7 0( ) 0 1. 5 σ = σ
Page 297 and 298: Cumulative Mass × 10 5 (g) dipping
Page 299 and 300: of PANI, and an increase in the con
Page 301 and 302: Resistance(ohm) 1.0E+12 1.0E+11 1.0
Page 303 and 304: esistance value. Samples containing
Page 305 and 306: The results of resistance for PS/PE
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Caruso, F., & Schuler, C. (2000). E
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