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pairs within a ternary polymer blend and is related to the minimization of the interfacial free energy. In Equation A-1.1, Equation A-1.1 λ = γ − γ − γ ij jk λij is defined as the spreading coefficient describing the tendency of component i to encapsulate or spread around component j in a matrix of component k. γjk, γik and γij are the interfacial tensions of the different polymer pairs. In blends of one major constituent (polymer A) and two minor ones (polymers B and C, the dispersed phases), four different morphologies are possible (Figure A-1.1) : a) separate dispersions; b) partial encapsulation and c), d) two possibilities of complete wetting (composite droplets). Each morphology has a distinct set of spreading coefficients. Figure A-1.1. Morphologies of ternary polymer blends containing one major phase (polymer A (white)) and two minor ones (polymers B (gray) and C (black)): (a) separate dispersions; (b) partial encapsulation; (c and d) composite droplets (complete wetting) Recently, in our group, studies have been conducted on ternary immiscible polymer blends of high-density polyethylene (HDPE), polystyrene (PS) and poly(methyl methacrylate) (PMMA) ik ij 236
(Reignier & Favis, 2000, 2003a; Reignier, et al., 2003). When PS and PMMA are dispersed in a HDPE matrix, composite droplets constituted of a well-segregated PMMA core and PS shell are formed. By controlling the relative amounts of PS and PMMA, it is possible to control the thickness of the PS shell down to 30-40 nm, near the range of a molecular layer of PS. Furthermore, virtually all of the PMMA is present as sub-inclusions within the PS dispersed phase after approximately 2 minutes of mixing. This paper reports on the development of ternary percolated co-continuous systems in HDPE/PS/PMMA blends in which HDPE and PMMA form two continuous networks, while the PS forms a continuous sheath structure at the HPDE/PMMA interface (Figure A-1.2). By controlling the relative amounts of HDPE, PS and PMMA, it will be shown that it is possible to decrease the percolation threshold of the PS layer down to less than 3%, resulting in a PS continuous network of ultra low composition. Figure A-1.2. Schematic of the HDPE/PS/PMMA multiple percolated structure. a) Threedimensional view of the blend structure, showing the thin PS layer at the HDPE/PMMA interface. b) Section showing the relative position of the different phases. 237
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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
Page 231 and 232: y Harkins theory, PS will always si
Page 233 and 234: a) b) c) d) e) f) PS Figure 6-6. a)
Page 235 and 236: a) b) HDPE : black PS : grey PMMA :
Page 237 and 238: 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: literature has examined factors inf
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 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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