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Reignier et al.(Reignier, et al., 2003) studied the effect of different factors on the composite droplet formation. They showed the influence of elasticity on composite droplet formation by introducing the dynamic interfacial tension term taken from VanOene(Vanoene, 1972) in the free energy model developed by Guo et al.(Guo, Packirisamy, et al., 1997), and developed new equations for the interfacial free energies in conditions of dynamic mixing: Equation 2-35. Equation 2-36. Equation 2-37. 2 ⎡ Ri ⎤ 2 ⎡ Ri ( ∑ Aγ ) = 4πR γ + ( N − N ) + 4πR γ + ( N − N ) i ⎢ ⎣ 2 ⎡ Re ⎤ 2 ⎡ Ri ( ∑ Aγ ) = 4πR γ + ( N − N ) + 4πR γ + ( N − N ) i ij B+ C ij B C ⎢ ⎣ 2 ⎡ Re ⎤ 2 ⎡ Ri ⎤ ( ∑ Aiγ ij ) C = 4πRe ⎢γ CA + ( N1, C − N1, A ) ⎥ + 4πRi ⎢γ BC + ( N1, B − N1, C ) ⎥⎦ B e i ⎣ BA BA Normal stress differences for the phases A, B, and C are referred to by N1, γ ij is the interfacial tension between the components i and j, and the internal and external radius of the core-shell droplets are shown by Ri and Re, respectively. Reignier et al.(Reignier, et al., 2003) indicated that the viscosity ratio estimated at a constant shear stress rather than at a constant shear rate is accurate to study the effect of viscosity ratio on the morphology because shear stress is more continuous at the interface between the dispersed phase and the matrix phase. The effect of molecular weight of phases on the encapsulation process was investigated(Reignier, et al., 2003). The equilibrium morphology for HDPE/low molecular weight PS/low molecular weight PMMA illustrates that PS encapsulates PMMA (Figure 2-6a). When components were replaced by high molecular weight PS and high molecular weight PMMA, an inversion in encapsulation occurred and PMMA encapsulated PS (Figure 2-6b). They related this discrepancy to the high viscosity of PS that does not allow PMMA to be encapsulated. Finally, considering all the observations, they concluded that interfacial energy reduction is the main driving force controlling encapsulation effects and that the viscosity ratio and the absolute viscosity have little influence on encapsulation phenomena in composite droplets. 6 6 6 1, B 1, B 1, A 1, A ⎥ ⎦ ⎥ ⎦ ⎦ i i ⎢ ⎣ ⎢ ⎣ ⎣ CA CB 6 6 6 1, C 1, C 1, A 1, B 28 ⎤ ⎥ ⎦ ⎤ ⎥ ⎦
a) b) Figure 2-6. Dependence of the composite dispersed morphology on PS and PMMA molecular weights. SEM photomicrographs of (a) HDPE/L-PS/L-PMMA; PMMA is extracted by acetic acid and (b) HDPE/H-PS/H-PMMA; PS is extracted by cyclohexane. The white bar denotes 1 μm(Reignier, et al., 2003). This section showed that many parameters can affect the simplest morphology of ternary polymer blends, which is composite droplet morphology. The question is: which theory can correctly predict the morphology, and which theory can give similar results to reality in the fastest time? In some work, different theories mentioned above are compared by (Valera, Morita, & Demarquette, 2006) work. In this work, the morphology of the PMMA/PP/PS ternary blend with different compositions was comprehensively studied. PMMA, PS, and PP are selected as the matrix and the composition of the minor phases was changed to find which model is able to predict a wide range of compositions. It has been reported that the predictions of the minimal surface free energy theory were verified by experimental observations only when PS was the matrix, and in the other cases the minimal surface free energy theory was unsuccessful to predict the morphology. The spreading coefficient model and the dynamic interfacial tension model can predict most of the experimental results. Finally, it is concluded that the fastest way to predict the morphology of the ternary polymer blend with a great accuracy still remains the spreading coefficients. 29
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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.......
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 and 62: 2.1.2.1 Binary Polymer Blends 2.1.2
Page 63 and 64: Some other studies(Everaert, Aerts,
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: measure the interfacial tension of
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
Page 113 and 114: organic thin films, a novel and str
Page 115 and 116: on the topic have been reported in
Page 117 and 118: succeeded in creating thin films wi
Page 119 and 120: Addition of salt to the solution of
Page 121 and 122: different from that of linear homop
Page 123 and 124: 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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