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2.1.2.2 Ternary Polymer Blends ................................................................................... 22 2.1.2.2.1 Composite Droplet Morphology ................................................................. 25 2.1.2.2.2 Double-Percolated Systems ......................................................................... 30 xxii 2.1.2.2.3 Effect of Composition on Ternary Blends with Complete Wetting Morphology................................................................................................................... 33 2.1.2.2.4 Interfacially Modified Ternary Polymer Blends ......................................... 34 2.1.2.3 Quaternary Polymer Blend Systems ................................................................. 35 2.1.3 Porous Polymeric Substrates Prepared by Melt-Blending ........................................ 37 2.1.3.1 Controlling the Pore Size in the Substrate ........................................................ 37 2.1.3.1.1 Coarsening of Binary and Ternary Polymeric Systems .............................. 38 2.2 Percolation Theory ........................................................................................................ 40 2.2.1 Universality Systems ................................................................................................ 42 2.3 Conductive Materials .................................................................................................... 43 2.3.1 Electrically Conductive Polymers and Composites .................................................. 45 2.3.1.1 Conducting Polymer Composite Materials (CPCM) ........................................ 46 2.3.1.1.1 Parameters Influencing the Percolation Threshold of Conductive Fillers .. 49 2.3.1.1.2 Percolation Threshold of Carbon-Nanotube Polymer Composites ............. 54 2.3.1.1.3 Disadvantages of Conductive Fillers, Especially Carbon Black ................. 54 2.3.1.2 Intrinsically Conductive Polymers .................................................................... 56 2.3.1.2.1 Polyaniline ................................................................................................... 59 2.3.1.2.1.1 Binary PANI/Polymer or Ternary PANI/Polymer/Polymer Blends .... 59 2.4 Self-assembly Processes in Material Science ............................................................... 66 2.4.1 Layer-by-Layer Self-Assembly Technique ............................................................... 66 2.4.1.1 Fabrication of Conductive Multilayers by the LbL Method ............................. 70
xxiii 2.4.1.1.1 Charged Polymer Adsorption ...................................................................... 71 2.4.1.1.2 Polymer Adsorption on the Surface ............................................................ 73 2.4.1.1.3 Adsorption of Polyelectrolytes on the Surface of a Substrate ..................... 75 2.4.1.1.4 Various Mechanisms of Film Growth ......................................................... 78 2.4.1.1.5 Effect of Polyelectrolyte Concentration on Multilayers ............................. 79 2.4.1.1.6 Effect of Molecular Weight on Multilayers ................................................ 80 2.4.1.1.7 Effect of Salt on Multilayers ....................................................................... 81 2.4.1.1.8 Overcompensation of the Multilayer/Solution Interface ............................. 83 2.4.1.1.8.1 Overcompensation due to Difussion of Polyelectrolytes insi<strong>de</strong> Multilayers 83 2.4.1.1.8.2 Overcompensation due to the Addition of Salt .................................... 85 2.4.1.1.9 LbL Deposition on Curved Surfaces ........................................................... 88 2.4.1.1.10 Effect of Roughness on the Multilayer Thickness .................................... 88 2.4.1.1.11 Important Views on PANI/PSS LbL Adsorption ...................................... 89 2.4.1.1.12 Characterization Techniques for LbL Deposited Layers .......................... 90 CHAPTER 3 - ORGANIZATION OF THE ARTICLES ....................................................... 91 CHAPTER 4 - LOW PERCOLATION THRESHOLD CONDUCTIVE DEVICE DERIVED FROM A FIVE-COMPONENT POLYMER BLEND ........................................ 95 4.1 Abstract ......................................................................................................................... 95 4.2 Introduction ................................................................................................................... 95 4.3 Experimental Methods ................................................................................................ 102 4.3.1 Materials ................................................................................................................. 102 4.3.2 Rheological Analysis .............................................................................................. 103 4.3.3 Sample Preparation ................................................................................................. 104 4.3.4 Solvent Extraction ................................................................................................... 105
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 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: TABLE OF CONTENTS DEDICATION.......
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
Page 61 and 62: 2.1.2.1 Binary Polymer Blends 2.1.2
Page 63 and 64: Some other studies(Everaert, Aerts,
Page 65 and 66: where the parameter z is dependent
Page 67 and 68: “compatibilization” was suggest
Page 69 and 70: a) λ BC A and B are matrices, b) C
Page 71 and 72: Reignier & Favis, 2000, 2003a; Reig
Page 73 and 74:
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
Page 135 and 136:
increasing the pH value due to a de
Page 137 and 138:
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
Page 181 and 182:
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
Page 217 and 218:
(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
Page 231 and 232:
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
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
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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
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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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