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ACKNOWLEDGEMENTS I would like to express my gratitude to my advisor Professor Basil D. Favis for all our insightful conversations. His thoughtful advice and enthusiasm for science have always inspired me. All what I learned from him, not only academically but in ways to do research, is priceless. There are many other people I need to thank who contributed to the success of this dissertation in different ways. Among them, special thanks to François Normandin from IMI for his direct help on assembling a particular setup to measure conductivity throughout the sample for my project. Thanks to Carol and Jacques for technical help in providing the particular equipments for both the layer-by-layer and blending process parts. Thanks also to Mélina for her assistance and discussions on the rheological part. I would also like to thank Patricia Moraille for her assistance in AFM, Éric Duchesne for introducing SEM to me and Jean-Philippe Masse for helping me with FIB equipment and for helpful discussions. My sincere thanks to my friends Sina Mortazy, Reza Shirazi, Nick Virgilio, Pierre Sarazin, and Mehdi Maziane for their assistance and useful discussions in this thesis. This thesis and all of my past academic success is due in large part to the support of my brothers: Shahrooz, Babak, and Sasan, without whom I could not have this glorious moment in my life. My deepest gratitude goes to my parents for their unconditional love and support. They taught me the right way to live and no rewards without hard working by their own life. iv
RÉSUMÉ Cette thèse présente, pour la première fois, une étude complète des morphologies de contact interfacial (engloutissement complet) pour des mélanges ternaires, quaternaires et quinaires de polyaniline (PANI) avec quatre polymères commercialement disponibles : le polyéthylène à haute densité (HDPE), le polystyrène (PS), le poly(méthyl méthacrylate) (PMMA) et le polyfluorure de vinylidène (PVDF). La morphologie d’engloutissement complet est une structure dictée par la tension interfaciale et est thermodynamiquement prévisible selon la théorie d’étalement de Harkins. Ce type de microstructure est formé dans un mélange polymère ternaire quand un des coefficients d’étalement, tel que calculé par les tensions interfaciales des paires de polymères dans le système, a une valeur positive. L’extension aux systèmes quaternaires et quinaires de définitions thermodynamiques similaires mène à la prédiction et à la formation de mélanges à plusieurs composants ordonnés hiérarchiquement. Le contrôle de la composition des composants de tels systèmes ordonnés hiérarchiquement, dans le cas des mélanges binaires, ternaires, quaternaires et quinaires, permet de produire des structures à percolation multiple, dans lesquelles toutes les phases sont pleinement interconnectées et interpénétrées. Cette approche est utilisée pour atteindre l’objectif de ce travail de recherche qui est d’échafauder un ensemble de techniques pour réduire le seuil de percolation des composants dans les mélanges. Le seuil de percolation des phases est défini comme étant la formation de connectivité sur une longue distance dans un système aléatoire. Les restrictions géométriques des phases dans des systèmes auto-assemblés, par exemple dans des structures dictées par la tension interfaciale telles les morphologies à percolation multiple, peuvent réduire le seuil de percolation des phases de manière significative. Une autre partie de ce travail visait la préparation de substrats poreux à très petite surface provenant de mélanges polymères à percolation multiple, suivie par la déposition de PANI, un polymère conducteur, sur la surface interne poreuse par une technique couche par couche. Des mélanges polymères constitués de plusieurs composants, dont le HDPE, le PS, le PMMA, le PVDF et le PANI, et, dans certains cas, le PP, le PEMA, et le PS-co-PMMA, ont été préparés dans un mélangeur interne. Des échantillons en forme de disque ont été préparés dans une presse v
Page 1 and 2: © Sepehr Ravati, 2010. UNIVERSITÉ
Page 3: DEDICATED To my parents iii
Page 7 and 8: devenir une structure hiérarchique
Page 9 and 10: ABSTRACT This thesis presents, for
Page 11 and 12: system can be increased from 10 -15
Page 13 and 14: CONDENSÉ EN FRANÇAIS Dans ce trav
Page 15 and 16: deuxième coquille de PS. Les phase
Page 17 and 18: structures à percolation multiple
Page 19 and 20: autre sous-type de morphologie dans
Page 21 and 22: TABLE OF CONTENTS DEDICATION.......
Page 23 and 24: xxiii 2.4.1.1.1 Charged Polymer Ads
Page 25 and 26: 5.3.4 Annealing Test ..............
Page 27 and 28: xxvii REFERENCES ..................
Page 29 and 30: LIST OF FIGURES xxix Figure 1-1. a)
Page 31 and 32: Figure 2-12. SEM photomicrograph of
Page 33 and 34: Figure 2-34. Schematic view of diff
Page 35 and 36: Figure 4-8. SEM micrographs of vari
Page 37 and 38: Figure 5-6. a),b) Scanning electron
Page 39 and 40: and c) triangular concentration dia
Page 41 and 42: n number of moles p concentration o
Page 43 and 44: AFM atomic force microscopy LIST OF
Page 45 and 46: PS-co-PMMA copolymer of PS and PMMA
Page 47 and 48: 1.1 Introduction CHAPTER 1 - INTROD
Page 49 and 50: Figure 1-2. Human heart, longitudin
Page 51 and 52: One of the applications for porous
Page 53 and 54: 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
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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
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
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Hou, S., Harrell, C. C., Trofin, L.
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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,
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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
Page 289 and 290:
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
Page 303 and 304:
esistance value. Samples containing
Page 305 and 306:
The results of resistance for PS/PE
Page 307 and 308:
Caruso, F., & Schuler, C. (2000). E
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