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Now, as the conductivity of HDPE, air, and PSS polyelectrolytes are very low, it is assumed that the entire sample, except the PANI network, is void. This implies that the HDPE substrate and PSS network are considered as porous parts in order to propose a model to predict the conductivity of the PANI network. Thus, porosity of the sample, including HDPE, voids, and the PSS network can be calculated as follows: Equation A-2.3 Vvoid ( 3. 5 − 0. 0076) Θ = V total = 3. 5 Therefore, a total porosity of 99.78% for this sample is observed. = 0. 9978 The oldest and most well-known theory of low porosity levels was devised by Maxwell and predicts the conductivity of CPPD as follows: Equation A-2.4 ⎛ 2 − 2Θ ⎞ σ = σ 0⎜ ⎟ = 0. 00147σ 0 ⎝ 2 + Θ ⎠ where σ is the conductivity of the porous material, σ0 is the conductivity of the pure material, and Θ is value of porosity. The porosity of a porous system ranges from 0 to 1. Fricke (Fricke, 1924) in 1924 added a shape factor due to the geometry of pores in the expression: Equation A-2.5 ⎛ 1− Θ ⎞ ⎛ 0. 0022 ⎞ σ = σ 0⎜ ⎟ = ⎜ ⎟σ 0 ⎝1 − ( 1− f ) Θ ⎠ ⎝ 0. 0022+ 0. 9978f ⎠ f varies from 1.5 for spherical pores to infinity for thin, disc-shaped pores. Koh (Koh & Fortini, 1973) developed the following equation for highly porous materials with porosity ranging from 0.38 to 0.9: Equation A-2.6 ⎛ 1 − Θ ⎞ σ = σ 0 ⎜ = 0. 0002 σ 2 ⎟ 0 ⎝ 1 + 10 Θ ⎠ Skorokhod (Skorokhov, 1972) found that for porous bodies with wide porosity, the equation would become: 248
Equation A-2.7 0( ) 0 1. 5 σ = σ 1− Θ = 0. 0001σ Hence, these semi-empirical relations predict the conductivity of porous sample A as low as 0.00147 to 0.0001 times that of pure PANI. Since in our case there is a PANI network with ultra- high porosity (> 99%), an equation based on measured conductivity data should be developed. Knowing that the conductivity of pure PANI is around 10 S.cm, and assuming that samples A and B have similar mass deposition behaviours, from the measured conductivity data the following equation for the deposition of 38 layers of PSS/PANI (after reaching the stable plateau) can be given: Equation A-2.8 σ = 0. 000002 σ The coefficient obtained from the plot is 50 times less than that of the equation suggested by Skorokhod (Skorokhov, 1972), due to the disconnection of some clusters in the PANI network. Skorokhod (Skorokhov, 1972) corrected equation A-2.9 by introducing a relative linear dimension of contact (ξ) to account for the effect of the imperfection of particle contacts: Equation A-2.9 ( ) ξ 1. 5 σ = σ − 0 1 Θ A value of 1.43 was calculated for ξ of sample B through the comparison of equations A-2.8 and A-2.9. Consequently, the specific relation for the calculation of the conductivity of 3D CPPD on substrate B can be presented as: Equation A-2.10 ( ) 14 . 2 σ =σ − 0 1 Θ 0 249
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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
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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.
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 and 290: Table A-1.3. Continuity of the PMMA
Page 291 and 292: (17) Reignier, J.; Favis, B. D., Ma
Page 293: PANI. Theoretically, the extent of
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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