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(spreading coefficients 2, 6, 7, and 9); and PS|PMMA|PVDF|PANI (spreading coefficients 4, 8,9, and 10. Finally, from the above, the quinary blend should have the hierarchical ordering of HDPE|PS|PMMA|PVDF|PANI. Table 4-4. Spreading Coefficients in Different Ternary Blends and Predicted Order of Phases in Blends Spreading coefficients λ (mN/m) Ternary blend and order of phases in the blend Spreading coefficients λ (mN/m) 112 Ternary blend and order of phases in the blend 1 λPS/PMMA = 2.6 mN/m HDPE|PS|PMMA 6 λPS/PANI = 7.1mN/m HDPE|PS|PANI 2 λPS/PVDF = 3.8 mN/m HDPE|PS|PVDF 7 λPVDF/PANI = 7.3 mN/m HDPE|PVDF|PANI 3 λPMMA/PVDF = 2.5 mN/m HDPE|PMMA|PVDF 8 λPMMA/PANI = 4.7 mN/m PS|PMMA|PANI 4 λPMMA/PVDF = 1.3 mN/m PS|PMMA|PVDF 9 λPVDF/PANI = 4 mN/m PS|PVDF|PANI 5 λPMMA/PANI = 9.2mN/m HDPE|PMMA|PANI 10 λPVDF/PANI = 0.6 mN/m PMMA|PVDF|PANI After a theoretical determination of the order of all phases, morphology experiments for the binary, ternary, and quaternary blends comprised of the previously mentioned components confirm the theoretical ordering. Some examples are shown in Figure 4-5. The binary blend of 80/20 PMMA/PS with matrix-droplet morphology is shown in Figure 4-5a. A ternary blend of 30/10/60 HDPE/PS/PMMA blends has already been shown in Figure 4-3a and confirms the situation of PS at the interface of PE and PMMA which corresponds to the positive value of λPS/PMMA(2.6 mN/m) (Case 1 from Table 4-4) as already discussed. Another ternary blend of 60/20/20 HDPE/PMMA/PVDF is shown in Figure 4-5b. In that case the PMMA has been selectively extracted showing clearly a core/shell structure where PMMA is the shell and PVDF is the core. This HDPE/PMMA/PVDF ternary blend corresponds to λPMMA/PVDF(2.5 mN/m) (Case 3 from Table 4-4) which predicts an encapsulation of PMMA about PVDF. The morphology observed for a quaternary blend of 50/20/10/20 HDPE/PS/PMMA/PVDF, shown in Figure 4-5c, is also consistent with the theoretical ordering discussed above. Figure 4-5c shows the onion-like
microstructure of the quaternary blend after selective dissolution of PMMA. The selective dissolution of PMMA allows for the clear identification of the other phases. There is a core of PVDF encapsulated in a first shell of PMMA, encapsulated in second shell of PS, all of which are encapsulated by the HDPE matrix. a) c) HDPE Figure 4-5. SEM micrograph of a) matrix-droplet morphology of 80/20 PMMA/PS, b) PVDF core-PMMA shell morphology in an HDPE matrix for 60/20/20 HDPE/PMMA/PVDF (PMMA extracted), and c) onion morphology in an HDPE matrix for 60/13/13/13 HDPE/PS/PMMA/PVDF (PMMA extracted) Theoretically, the addition of PANI as a fifth component to the quaternary blend above, creates a five-component onion droplet structure with PANI as the inner phase and HDPE as the matrix. b) PMMA PMMA PS PVDF PVDF HDPE 113
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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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Page 109 and 110: Narkis and co-workers extended and
Page 111 and 112: Figure 2-31: Conductivity of PVDF/P
Page 113 and 114: organic thin films, a novel and str
Page 115 and 116: on the topic have been reported in
Page 117 and 118: succeeded in creating thin films wi
Page 119 and 120: Addition of salt to the solution of
Page 121 and 122: different from that of linear homop
Page 123 and 124: Figure 2-39. Macromolecule with a)
Page 125 and 126: polyanion such as hyaluronan (HA)(P
Page 127 and 128: 2.4.1.1.7 Effect of Salt on Multila
Page 129 and 130: 2.4.1.1.8 Overcompensation of the M
Page 131 and 132: important factors determining the g
Page 133 and 134: 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
Page 139 and 140: discussed above, HDPE, PS, PMMA, an
Page 141 and 142: CHAPTER 4 - LOW PERCOLATION THRESHO
Page 143 and 144: or model which predicts where the p
Page 145 and 146: concentration threshold for the ons
Page 147 and 148: chemical and weathering resistance,
Page 149 and 150: Table 4-1. Material Characteristics
Page 151 and 152: filled with blend pellets. To facil
Page 153 and 154: 4.3.6 Conductivity Measurements DC
Page 155 and 156: experimentally in this research gro
Page 157: a) b) c) d) Figure 4-4. Schematic i
Page 161 and 162: a) b) c) d) Figure 4-6. SEM microgr
Page 163 and 164: a) b) PVDF PS PMMA c) d) e) HDPE PS
Page 165 and 166: Uniform layers of PS and PMMA situa
Page 167 and 168: the concentration of HDPE is increa
Page 169 and 170: a) b) c) e) Figure 4-11. SEM microg
Page 171 and 172: melt-processable and contains 25 wt
Page 173 and 174: One question that should be address
Page 175 and 176: Conductivity(S/cm) Ternary Blend 1,
Page 177 and 178: phase(PMMA), the concentration of P
Page 179 and 180: (6) Virgilio, N.; Desjardins, P.; L
Page 181 and 182: ONION MORPHOLOGY HDPE PVDF PS Contr
Page 183 and 184: work described above has focused on
Page 185 and 186: thermodynamic explanation to predic
Page 187 and 188: four-point probe increases continuo
Page 189 and 190: in the rheology tests were compress
Page 191 and 192: 5.3.6 Layer-by-Layer Deposition The
Page 193 and 194: prepare a polymer blend structure w
Page 195 and 196: a) b) c) Figure 5-3. Scanning elect
Page 197 and 198: spontaneously self-assembled. After
Page 199 and 200: a) b) c) d) e) f) g) h) Figure 5-5.
Page 201 and 202: Since the ultra-low surface area va
Page 203 and 204: 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
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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
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Caruso, F. (2003). Hollow Inorganic
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Domenech, S. C., Bortoluzzi, J. H.,
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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
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Macdiarmid, A. G., Jin-Chih, C., Ha
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Niziol, J., & Laska, J. (1999). Con
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Reghu, M., Yoon, C. O., Yang, C. Y.
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Shirakawa, H., Louis, E. L., MacDia
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Utracki, L. A. (1991). On the visco
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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
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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
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esistance value. Samples containing
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The results of resistance for PS/PE
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Caruso, F., & Schuler, C. (2000). E
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