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increasing mixing time, this interval gets narrow and finally shrinks to one point. Veenstra et al.(Veenstra, Norder, van Dam, & Posthuma de Boer, 1999) observed a direct correlation between the width of the co-continuity interval under shear flow and the capillary number. The above mentioned factors influence the width of the co-phase area, whereas several factors affect the position of the phase inversion. The most important one is phase viscosities and their ratio. Investigations have shown that for a binary blend consisting of components of equal viscosity, phase inversion occurs around a volume fraction of 0.5(Miles & Zurek, 1988b). Several works(Jordhamo, Manson, & Sperling, 1986; Mekhilef & Verhoogt, 1996) showed that when component viscosities differ significantly, the phase inversion point is shifted towards compositions richer in the high viscosity component. Several authors have proposed semiempirical equations based on rheological properties, particularly viscosity, in order to predict cocontinuity point. Paul and Barlow(Paul & Barlow, 1980b), according to the observations made by Avgeropolous(Avgeropoulos, Weissert, Biddison, & Boehm, 1976) and the work developed by Jordhamo et al.(Jordhamo, et al., 1986), suggested a model for blends prepared at low shear rates as follows: Equation 2-18. [ φ I 1 = whereφ and η are volume fraction and zero shear viscosity of each phase, respectively, at the I phase inversion point. Miles et al.(Miles & Zurek, 1988a) argued that the point of phase inversion should be more precisely related to the effective viscosity ratio. φ I 2 η η Equation 2-19. φ η( & γ ) I 1 1 = φ η( & γ ) 2 Most of the researchers have acknowledged that Equation 2-18 and Equation 2-19 are valid for predicting the phase inversion concentration in many binary blend systems with a viscosity ratio near unity(Mekhilef & Verhoogt, 1996; Miles & Zurek, 1988a). It has been demonstrated that they are invalid for the ones that exhibit viscoelastic asymmetry between the melt components(Favis & Chalifoux, 1988). I 2 01 0 2 16
Some other studies(Everaert, Aerts, & Groeninckx, 1999; Ho, Wu, & Su, 1990) developed Equation 2-18 and added excess factors for given blend systems to correlate their results with a semi-empirical model. A model was derived by Metelkin et al.(Metelkin & Blekht, 1984) based on theory of filament instability described by Tomotika (Tomotika, 1935a) in terms of viscosity ratio: Equation 2-20. where λ is viscosity ratio and f(λ) is defined as : 1 φ = I 2 1+ λf ( λ) 2 Equation 2-21. f ( λ ) = 1. 25 log( λ ) + 1. 81(log( λ )) with λ being the viscosity ratio of the blend components at the blending shear rate. Again all of these equations can predict the phase inversion point with a very good accuracy when both components have approximately equal viscosity. Results of samples with high viscosity ratio demonstrate that these models are unable to predict the phase inversion point and significant errors appear. For such cases, some authors used the percolation threshold definition to develop an equation based on maximum packing volume fraction. Utracki(Utracki, 1991) proposed a model based on theory for mono-dispersed hard spheres(Krieger & Dougherty, 1959). Equation 2-22. where 1 [ η ] φ ⎛η ⎞ 1 φ + ( 1− φ ) ⎜ ⎟ m m ⎝η 2 φ = ⎠ I 2 1 [ η ] φm ⎛η ⎞ 1 ⎜ ⎟ + 1 ⎝η 2 ⎠ φ is the phase inversion point, φ I 2 m is the maximum packing volume fraction, [η] is intrinsic viscosity, and indices refer to components. For polymer blends, φ is defined as m φ − m = 1 φc , where c φ stands for the percolation threshold and amounts to 0.156 for dispersions of spheres. The definition of the percolation threshold is explained in detail in the next sections. This equation explains that the addition of the first component to second one leads to an increase m 17
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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
Page 11 and 12: system can be increased from 10 -15
Page 13 and 14: CONDENSÉ EN FRANÇAIS Dans ce trav
Page 15 and 16: deuxième coquille de PS. Les phase
Page 17 and 18: structures à percolation multiple
Page 19 and 20: autre sous-type de morphologie dans
Page 21 and 22: TABLE OF CONTENTS DEDICATION.......
Page 23 and 24: xxiii 2.4.1.1.1 Charged Polymer Ads
Page 25 and 26: 5.3.4 Annealing Test ..............
Page 27 and 28: xxvii REFERENCES ..................
Page 29 and 30: LIST OF FIGURES xxix Figure 1-1. a)
Page 31 and 32: Figure 2-12. SEM photomicrograph of
Page 33 and 34: Figure 2-34. Schematic view of diff
Page 35 and 36: Figure 4-8. SEM micrographs of vari
Page 37 and 38: Figure 5-6. a),b) Scanning electron
Page 39 and 40: and c) triangular concentration dia
Page 41 and 42: n number of moles p concentration o
Page 43 and 44: AFM atomic force microscopy LIST OF
Page 45 and 46: PS-co-PMMA copolymer of PS and PMMA
Page 47 and 48: 1.1 Introduction CHAPTER 1 - INTROD
Page 49 and 50: Figure 1-2. Human heart, longitudin
Page 51 and 52: One of the applications for porous
Page 53 and 54: On the other hand, a novel tri-cont
Page 55 and 56: 2.1 Polymer Blends CHAPTER 2 - LITE
Page 57 and 58: Based on Sterling’s approximation
Page 59 and 60: Antonoff’s rule (Equation 2-13) i
Page 61: 2.1.2.1 Binary Polymer Blends 2.1.2
Page 65 and 66: where the parameter z is dependent
Page 67 and 68: “compatibilization” was suggest
Page 69 and 70: a) λ BC A and B are matrices, b) C
Page 71 and 72: Reignier & Favis, 2000, 2003a; Reig
Page 73 and 74: measure the interfacial tension of
Page 75 and 76: a) b) Figure 2-6. Dependence of the
Page 77 and 78: Omonov et al. found double percolat
Page 79 and 80: 2.1.2.2.3 Effect of Composition on
Page 81 and 82: a) b) C B A c) Figure 2-12. SEM pho
Page 83 and 84: In the case where PS is the matrix,
Page 85 and 86: Posthuma de Boer, 1999) (Kumin & Ch
Page 87 and 88: lattice, such as square lattice, wi
Page 89 and 90: magnetization, which is a function
Page 91 and 92: Polymers have long been thought of
Page 93 and 94: epoxy as a function of nanotube wei
Page 95 and 96: Figure 2-19. Approaching the percol
Page 97 and 98: Figure 2-21. Transmission electron
Page 99 and 100: Figure 2-22: Dependence of PE conti
Page 101 and 102: Figure 2-24. Plot of the total numb
Page 103 and 104: chain provides the conductive path
Page 105 and 106: 2.3.1.2.1 Polyaniline One of the mo
Page 107 and 108: CoPA/LLDPE/PANI blend and a poor-qu
Page 109 and 110: Narkis and co-workers extended and
Page 111 and 112: 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.
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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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