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c) Figure 6-8. a) Triangular concentration diagram showing the composition of the various ternary HDPE/PS/PMMA blends examined in this study, b) various morphological states for ternary HDPE/PS/PMMA, and c) triangular concentration diagram showing the various regions of in the morphological states for ternary HDPE/PS/PMMA 190
6.4.6 Continuity, Co-continuity, and Tri-continuity of Phases One very important issue in the selection of a ternary blend for a particular application is the continuity level of each phase. In this part of the work the effect of the composition of phases on continuity levels is examined. The same 30 samples examined in the previous section above for morphology are also examined here for their quantitative PS and PMMA continuity. It was not possible to obtain the continuity of the HDPE phase since HDPE could not be selectively extracted. Triangular continuity plots are introduced(Figures 6-9a and 6-9b) to show the continuity of the PS and PMMA phases respectively. In this HDPE/PS/PMMA system, the continuity levels of PS and PMMA phases are identified through the selective solvent extraction/gravimetry of PMMA by acetic acid(Figure 6-9a) and of PS by cyclohexane(Figure 6- 9b). The axes in Figures 6-9a and 6-9b represent the volume fraction of PMMA and PS. Note that the volume fraction of HDPE for these plots can be estimated by subtracting the combined volume fractions of PS and PMMA from 100%. For example, in the sample comprising 40%PS and 40%PMMA the remaining 20% would be HDPE. Figures 6-9a and 6-9b reveal the various continuity levels for both PS and PMMA in the ternary system. These diagrams show that increasing the concentration of phases results in increased continuity levels until that phase becomes the matrix and continuity achieves 100%. In Figure 6-9b there are two regions with a 100% continuity level of the PS phase representing tri-continuous morphologies type I (low PS concentration) and type II (high PS concentration). In a binary blend the continuity percolation threshold is only one point. In a ternary blend it becomes a line due to the simultaneously changing concentration of two of the phases in the blend. The percolation threshold lines for PS and PMMA are represented in both Figures 6-9a and 6-9b where the colour changes from purple to blue. The data from the continuity diagrams for PS and PMMA in Figures 6-9a) and 6-9b), can be combined with the morphological study shown in the triangular diagram of Figure 6-8c) in order to produce even more well defined continuity boundaries for the various morphological states. The new 3-axes triangular diagram is shown in Figure 6-9c). Since it is impossible to selectively extract HDPE without also extracting PS and PMMA, the upper border of region 191
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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
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
Page 209 and 210: close together. It is interesting t
Page 211 and 212: Figure 5-9. Mass increase (%) indic
Page 213 and 214: In this work the conductance of the
Page 215 and 216: deposited PANI layers increases unt
Page 217 and 218: (52) Guo, H. F.; Packirisamy, S.; G
Page 219 and 220: 6.2 Introduction It is well-known t
Page 221 and 222: modified version of Harkins theory(
Page 223 and 224: 6.3 Experimental 6.3.1 Materials Co
Page 225 and 226: Complex voscosity (Pa.s) 1,0E+04 1,
Page 227 and 228: 6.3.5.2 Focused Ion Beam (FIB) and
Page 229 and 230: 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: a) b) HDPE : black PS : grey PMMA :
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
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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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