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Table A-4.1. Interfacial Tensions for Polymer Pairs Theoretical data(Harmonic mean equation) γ (mN/m) HDPE/PEMA 8.3 PEMA/PANI 10.6 HDPE/PANI 26.9 PS/PANI 15.1 PEMA/PANI 10.6 PS/PEMA 1.3 Ternary polymer blends comprised of HDPE/PEMA/PANI with various compositions of PANI are prepared. In such samples, the ratios of HDPE and PEMA concentrations are changed while constant volume fractions of PANI (10%, 20%, and 30%) were selected. Figure A-4.2 shows the results of resistance for various compositions of HDPE/PEMA/PANI. It is observed that the binary blend of HDPE and PANI has the highest value of resistance, which is attributed to droplet-matrix morphology, because of the high interfacial tension between HDPE and PANI. A percolation threshold of 25% PANI can be detected for this binary blend, as at 25% of PANI, the value of resistance starts to decrease. It is found that addition of PEMA to the HDPE/PANI binary blend decreases the resistance of the blend. It is proposed that the interfacial tension between PEMA and PANI is low, leading to a reduction in the size of the PANI phases in the blend. Connection of such small phases of PANI and the presence of large branches of continuous HDPE in the blend result in the formation of small connected pathways, and subsequently helps to reduce the total percolation threshold. Consequently, addition of PEMA to the binary blend reduces both the percolation threshold of PANI and the resistance of the blend for samples with PANI compositions more than 20%. For concentrations of less than 10% PANI, due to lack of sufficient PANI to form tclusters, other components and morphology play a major role in determining the value of resistance. 254
Resistance(ohm) 1.0E+12 1.0E+11 1.0E+10 1.0E+09 1.0E+08 1.0E+07 1.0E+06 1.0E+05 1.0E+04 1.0E+03 1.0E+02 0 5 10 15 20 25 30 35 40 45 Volume fraction of PANI (%) HDPE/PANI PEMA/PANI 255 PANI/(HDPE8/PEMA1) PANI/(HDPE6/PEMA3) PANI/(HDPE5/PEMA5) PANI/(HDPE3/PEMA6) PANI/(HDPE1/PEMA8) Figure A-4.2. Resistance values for ternary blends of HDPE/PEMA/PANI with various compositions as a function of volume fraction of PANI Figure A-4.3 represents the same results as Figure A-4.2 from another point of view, since the resistance has been plotted against volume fraction of one of the components (PEMA). As expected, Figure A-4.3 shows higher values of resistance for samples comprising 10% of PANI compared with samples containing 20% or 30% of PANI. Resistance values of samples containing 10% PANI are represented in the first curve in Figure A-4.3, revealing that increasing the concentration of PEMA decreases the resistance value of the blend, up to 45% of PEMA. Further increase of PEMA leads to an increase in the resistance value. This experiment clearly illustrates the dependence of the conductivity percolation threshold to sample morphology. The conductivity value decreases when morphology of matrix-droplet for 90/10 HDPE/PANI changes to matrix/core-shell morphology for the 80/10/10 HDPE/PEMA/PANI ternary blend. At a composition of 60/30/10 HDPE/PEMA/PANI, shells of PEMA coalesce with each other and make several connected pathways. The relatively high interfacial tension between HDPE and PEMA (γPEMA/HDPE = 8.3 mN/m) results in a lower interfacial area value, demonstrating the
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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.
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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.
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 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: of PANI, and an increase in the con
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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