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Dans la dernière partie de cette étude, des mélanges polymères ternaires montrent un comportement de mouillage complet. Conceptuellement, il s’agit de l’état où un des composants aura toujours tendance à séparer les deux autres complètement, et du point de vue thermodynamique, deux des trois coefficients d’étalement binaires sont négatifs et l’autre est positif, selon la théorie d’étalement de Harkins. Ce travail couvre l’étendue totale des états morphologiques possibles pour un tel système préparé à l’état fondu, sur tout le diagramme de composition ternaire. Un mélange polymère ternaire composé de HDPE, de PS et de PMMA est choisi comme système modèle montrant un mouillage complet, alors que le coefficient d’étalement positif λPS/PMMA = 2,6 mN/m indique que le PS sépare les phases de HDPE et de PMMA. Quatre sous-catégories de morphologie peuvent être identifiées : a) matrice/phase dispersée coeur-coquille; b) tricontinuité; c) bicontinuité/phase dispersée; d) matrice/deux phases dispersées distinctes. La microscopie électronique, de même qu’une technique basée sur l’irradiation par faisceau ionique focalisé combinée à la microscopie par force atomique, est utilisée afin d’illustrer clairement et d’identifier les différentes phases. L’extraction par solvant et la gravimétrie sont utilisées pour mesurer le degré de continuité des systèmes afin d’identifier efficacement les régions de haute continuité. Les diagrammes de composition triangulaires sont utilisés pour distinguer ces différentes régions morphologiques et les résultats sont interprétés à la lumière des tensions interfaciales des différentes paires et de leurs coefficients d’étalement subséquents. L’effet de la masse moléculaire et du ratio de viscosité sur la taille des phases des différentes structures est également considéré. Il est démontré que typiquement, un plus haut ratio de viscosité, de même qu’une plus haute tension interfaciale, mène à une plus grande taille de phases. viii
ABSTRACT This thesis presents, for the first time, a comprehensive survey on the subject of self-assembled, multi-encapsulated structures for ternary, quaternary, and quinary polymer blends demonstrating complete wetting. The work targets the development of novel conductive devices possessing low percolation threshold concentrations of conductive polymer. The blends studied are comprised of conductive polyaniline and four commercial polymers: HDPE, PS, PMMA, and PVDF. A complete wetting morphology is an interfacial tension driven structure which can be thermodynamically predicted by the Harkins spreading theory. This type of microstructure in a ternary polymer blend is formed when one of the spreading coefficients, as calculated from the interfacial tensions of polymer pairs in the system, has a positive value. Conceptually, for a ternary blend, complete wetting is the state where one of the components will always tend to completely separate the other two. The development of similar thermodynamic definitions to quaternary and quinary systems results in the prediction and construction of hierarchically ordered multi-encapsulated, multi-component blends. Controlling the compositions of components in such hierarchically ordered systems in ternary, quaternary, and quinary blends allows for the preparation of multi-percolated structures in which all phases are fully interconnected and interpenetrated. This approach is employed to attain the goal of this research which is to build a foundation of methods to reduce the percolation threshold of components in multi-component blends. The percolation threshold of phases is defined as the formation of longrange connectivity in random systems. The geometrical restriction of phases in self-assembled systems, for example in interfacial tension driven structures such as a multi-percolated morphologies, can significantly reduce the percolation threshold of phases. Another part of the work has focused on the preparation of ultra-low surface area porous substrates derived from multi-percolated polymer blends, followed by the deposition of polyanilene conductive polymer (PANI) on the internal porous surface using a layer-by-layer technique. Polymer blends comprising various components including HDPE, PS, PMMA, PVDF, and PANI, and in some cases PP, PEMA, and PS-co-PMMA are prepared in an internal mixer. Discshaped samples for conductivity testing are compression molded in a hot press. Some of the samples, after melt processing, are compression molded in a hot press to perform quiescent ix
Page 1 and 2: © Sepehr Ravati, 2010. UNIVERSITÉ
Page 3 and 4: DEDICATED To my parents iii
Page 5 and 6: RÉSUMÉ Cette thèse présente, po
Page 7: devenir une structure hiérarchique
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
Page 55 and 56: 2.1 Polymer Blends CHAPTER 2 - LITE
Page 57 and 58: Based on Sterling’s approximation
Page 59 and 60:
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
Page 257 and 258:
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.
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
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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
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
Page 307 and 308:
Caruso, F., & Schuler, C. (2000). E
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