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A-1.4. Conclusions Through a combination of composite droplet and co-continuous blend morphology preparation methodologies, a continuous shell structure of polystyrene has been situated at the interface of a co-continuous polyethylene/poly(methyl methacrylate) blend. This multiple percolated, interfacial tension driven structure results in a dramatic <strong>de</strong>crease in the percolation threshold volume fraction of the encapsulating PS component. As little as 3% polystyrene is shown to generate a continuous PS network. The encapsulation effect follows the prediction based on the spreading coefficient theory. This approach could be used as a route to generate novel cocontinuous structures and also as a technique to significantly reduce percolation thresholds in multiphase blends. A-1.5. References (1) Favis, B. D., In Polymer Blends: Formulation and Performance, Paul, D. R.; Bucknall, C. B., Eds. John Wiley & Sons, Inc: New York, 2000; Vol. 1, pp 239-289. (2). Potschke, P.; Paul, D. R., Journal of Macromolecular Science - Polymer Reviews 2003, 43, (1), 87-141. (3) Yuan, Z.; Favis, B. D., Journal of Polymer Science, Part B: Polymer Physics 2006, 44, (4), 711-721. (4) Yuan, Z.; Favis, B. D., Biomaterials 2004, 25, (11), 2161-2170. (5) Soares, B. G.; Gubbels, F.; Jerome, R.; Teyssie, P.; Vanlathem, E.; Deltour, R., Polymer Bulletin (Berlin) 1995, 35, (1-2), 223. (6) Gubbels, F.; Jerome, R.; Teyssie, P.; Vanlathem, E.; Deltour, R.; Cal<strong>de</strong>rone, A.; Parente, V.; Bredas, J. L., Macromolecules 1994, 27, (7), 1972-1974. (7) Lyngaae-Jorgensen, J.; Utracki, L. A., Polymer 2003, 44, (5), 1661-9. (8) Zilberman, M.; Siegmann, A.; Narkis, M., Journal of Macromolecular Science - Physics 2000, B39, (3), 333-47. (9) Narkis, M.; Haba, Y.; Segal, E.; Zilberman, M.; Titelman, G. I.; Siegmann, A., Polymers for Advanced Technologies 2000, 11, (8-12), 665-673. (10) Omonov, T. S.; Harrats, C.; Groeninckx, G., Polymer 2005, 46, (26), 12322-12336. (11) Reignier, J.; Favis, B. D., AIChE Journal 2003, 49, (4), 1014-1023. (12) Reignier, J.; Favis, B. D.; Heuzey, M.-C., Polymer 2003, 44, (1), 49-59. (13) Berger, W.; Kammer, H. W.; Kummerlowe, C., Makromol Chem Suppl B 1984, 8, 101. (14) Van Oene, H. J., Colloid Interface Sci. 1972, 40, 448-467. (15) Torza, S.; Mason, G., J. Coll. Interface Sci. 1970, 33, (1), 67-83. (16) Hobbs, S. Y.; Dekkers, M. E. J.; Watkins, V. H., Polymer 1988, 29, (9), 1598-1602. 244
(17) Reignier, J.; Favis, B. D., Macromolecules 2000, 33, (19), 6998-7008. (18) Valera, T. S.; Morita, A. T.; Demarquette, N. R., Macromolecules 2006, 39, (7), 2663- 2675. (19) Steinmann, S.; Gronski, W.; Friedrich, C., Polymer 2001, 42, (15), 6619-6629. (20) Virgilio, N.; Favis, B. D.; Pepin, M.-F.; Desjardins, P.; L'Esperance, G., Macromolecules 2005, 38, (6), 2368-2375. 245
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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
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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
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 and 256: 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
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: Table A-1.3. Continuity of the PMMA
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
Page 307 and 308: Caruso, F., & Schuler, C. (2000). E
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