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stable zipping of the micelles. Multilayer micelles’ assemblies were also obtained by increasing themicelle concentration through the solvent evaporation. The system showed impressive reversibility asproved by simple wash-off step carried out in cyclohexane. The reorganization of PODMA block uponheating while conserving the overall morphology further presents an oppourtunity to obtain atemperature mediated self-healing coating system. The aforementioned concept of zipping-assembly ofmicelles combines a self-assembly stage following “classical” rules and a reversible lock-in of the globalmorphology through a zipper mechanism.122
REFERENCES1 Zhao, B. & Brittain, W. J. Polymer brushes: surface-immobilized macromolecules. Progress in PolymerScience 25, doi:10.1016/s0079-6700(00)00012-5 (2000).2 Yoshida, T. et al. Electrodeposition of Inorganic/Organic Hybrid Thin Films. Advanced Functional Materials19, doi:10.1002/adfm.200700188 (2009).3 Marichy, C., Bechelany, M. & Pinna, N. Atomic Layer Deposition of Nanostructured Materials for Energyand Environmental Applications. Advanced Materials 24, doi:10.1002/adma.201104129 (2012).4 Hiller, J., Mendelsohn, J. D. & Rubner, M. F. Reversibly erasable nanoporous anti-reflection coatings frompolyelectrolyte multilayers. Nature Materials 1, doi:10.1038/nmat719 (2002).5 de Vos, W. M., de Keizer, A., Stuart, M. A. C. & Kleijn, J. M. Thin polymer films as sacrificial layers for easiercleaning. Colloids and Surfaces a-Physicochemical and Engineering Aspects 358,doi:10.1016/j.colsurfa.2009.12.022 (2010).6 Tyagi, P. et al. Dynamic Interactive Membranes with Pressure-Driven Tunable Porosity and Self-HealingAbility. Angewandte Chemie-International Edition 51, 7166-7170, doi:10.1002/anie.201201686 (2012).7 Ariga, K. et al. Challenges and breakthroughs in recent research on self-assembly. Science and Technologyof Advanced Materials 9, doi:10.1088/1468-6996/9/1/014109 (2008).8 Moulin, E., Cormosw, G. & Giuseppone, N. Dynamic combinatorial chemistry as a tool for the design offunctional materials and devices. Chemical Society Reviews 41, doi:10.1039/c1cs15185a (2012).9 Quemener, D. et al. Free-Standing Nanomaterials from Block Copolymer Self-Assembly. Macromolecules43, doi:10.1021/ma100809v (2010).10 Landschulz, W. H., Johnson, P. F. & McKnight, S. L. The leucine zipper - a hypothetical structure common toa new class of dna-binding proteins. Science 240, doi:10.1126/science.3289117 (1988).11 Oshea, E. K., Klemm, J. D., Kim, P. S. & Alber, T. X-ray structure of the gcn4 leucine zipper, a 2-stranded,parallel coiled coil. Science 254, doi:10.1126/science.1948029 (1991).12 Landon, P. B. et al. DNA Zipper-Based Tweezers. Langmuir 28, doi:10.1021/la201267e (2012).13 Zhang, X., Bera, T., Liang, W. & Fang, J. Longitudinal Zipping/Unzipping of Self-Assembled Organic Tubes.Journal of Physical Chemistry B 115, doi:10.1021/jp2064276 (2011).14 Kim, H. W. et al. One-Dimensional Molecular Zippers. Journal of the American Chemical Society 133,doi:10.1021/ja2031486 (2011).15 Porus, M. et al. Zipper and Layer-by-Layer Assemblies of Artificial Photosystems Analyzed by CombiningOptical and Piezoelectric Surface Techniques. Langmuir 27, doi:10.1021/la2007815 (2011).16 Zeng, J. et al. Interplay of Olefin Metathesis and Multiple Hydrogen Bonding Interactions: Covalently CrosslinkedZippers. Organic Letters 13, doi:10.1021/ol201282d (2011).17 Li, S., Ge, Y., Piletsky, S. A. & Turner, A. P. F. A Zipper-Like On/Off-Switchable Molecularly ImprintedPolymer. Advanced Functional Materials 21, doi:10.1002/adfm.201100593 (2011).18 Goldburt, E., Shvartsman, F., Fishman, S. & Krongauz, V. Intramolecular interactions in photochromicspiropyran merocyanine polymers. Macromolecules 17, doi:10.1021/ma00136a020 (1984).19 Wismontskiknittel, T. & Krongauz, V. Self-assembling of spiropyran polymers by zipper crystallization.Macromolecules 18, doi:10.1021/ma00153a009 (1985).20 de Vos, W. M., Meijer, G., de Keizer, A., Stuart, M. A. C. & Kleijn, J. M. Charge-driven and reversibleassembly of ultra-dense polymer brushes: formation and antifouling properties of a zipper brush. SoftMatter 6, doi:10.1039/b926017j (2010).21 Whitesides, G. M. & Grzybowski, B. Self-assembly at all scales. Science 295, doi:10.1126/science.1070821(2002).22 Qin, S. H., Matyjaszewski, K., Xu, H. & Sheiko, S. S. Synthesis and visualization of densely grafted molecularbrushes with crystallizable poly(octadecyl methacrylate) block segments. Macromolecules 36,doi:10.1021/ma021472w (2003).23 Gitsas, A., Floudas, G., Butt, H. J., Pakula, T. & Matyjaszewski, K. Effects of Nanoscale Confinement andPressure on the Dynamics of pODMA-b-ptBA-b-pODMA Triblock Copolymers. Macromolecules 43,doi:10.1021/ma902639g (2010).123
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THESISPRESENTED ATNATIONAL GRADUATE
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As the human civilization progress
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CHAPTER - 1 SELF-HEALING POLYMERIC
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8.1.5 Atomic Force Microscopy …
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Synthetic engineering materials in
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esponse to a specific external stim
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The first work based on this approa
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een prepared from urea-formaldehyde
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monomer systems. The addition of EN
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Figure - 1.10: Self-healing process
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was required to reach healing effic
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In addition to above works, some ot
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that have been identified to be tak
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part of the chapter, these material
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Figure - 1.17: Self-healing of the
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commercialized under tradenames; Nu
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joined together at temperature high
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Inspired by these findings, the fir
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temperature greater than 80 o C in
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Figure - 1.27: Sulfur chemistry bas
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A different kind of sulfur chemistr
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Figure - 1.29: Dynamic covalent che
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cracks. The recovered droplets afte
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23 White, S. R. et al. Autonomic he
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65 Taber, D. F. & Frankowski, K. J.
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107 Kushner, A. M., Vossler, J. D.,
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148 Park, J. S., Kim, H. S. & Hahn,
Page 58 and 59:
The value of subscripts “n”,
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The formation of spherical micelles
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the micelle assembly showed the pre
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gain onto the electrodes by buildin
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The resistance R can be further exp
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empty-tower velocity U only depends
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This apparent morphological switchi
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In a further qualitative analysis,
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noteworthy and though its feasibili
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Furthermore within this range, lowe
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Figure - 2.22: Scanning Electron Mi
Page 80 and 81:
While the resistance measurements g
Page 82 and 83: In conclusion, a self-healing membr
Page 84 and 85: 23 Giacomelli, F. C., Riegel, I. C.
Page 86 and 87: micelles enabled the membrane to se
Page 88 and 89: The second class is represented by
Page 90 and 91: To avoid the probable clogging of t
Page 92 and 93: 181614SP2 - iNumber of Particles121
Page 94 and 95: 1000900800y = 3E+06xR² = 0,9911y =
Page 96 and 97: very high value of 1.5 g.l -1 . Thi
Page 98 and 99: Since the only change in the membra
Page 100 and 101: 100Retention (%)8060400,100,20,40,6
Page 102 and 103: Figure - 3.18: Scanning Electron Mi
Page 104 and 105: (Figure - 3.20). A cursory look at
Page 106 and 107: When compared to poly(styrene) NPs,
Page 108 and 109: Figure - 3.24: Scanning Electron Mi
Page 110 and 111: REFERENCES1 Metzler, R. & Klafter,
Page 112 and 113: 46 Bemporad, D., Luttmann, C. & Ess
Page 114 and 115: In this chapter, preparation of 3D
Page 116 and 117: obtain complex macromolecular archi
Page 118 and 119: The polymerization was conducted at
Page 120 and 121: proceeds, lesser monomer is availab
Page 122 and 123: mg/ml),the micelles’ hydrodynamic
Page 124 and 125: Figure - 4.15: The monolayer and mu
Page 126 and 127: monolayer of micelles and topmost l
Page 128 and 129: The presence of the dispersed micel
Page 130 and 131: Heating the multilayer micelle asse
Page 134 and 135: 24 Moad, G., Rizzardo, E. & Thang,
Page 136 and 137: The concept of nano-gel based self-
Page 138 and 139: Figure - 5.4: Size distribution of
Page 140 and 141: In a typical process, the two compo
Page 142 and 143: Figure - 5.10: 1HNMR spectra obtain
Page 144 and 145: The 1 HNMR spectrum obtained for th
Page 146 and 147: REFERENCES1 White, S. R. et al. Aut
Page 148 and 149: healing ability shown by the membra
Page 150 and 151: 7. PERSPECTIVESBeing the first such
Page 153 and 154: 8. MATERIALS & METHODSThis chapter
Page 155 and 156: 8.1.3 PEG Filtration MeasurementsTh
Page 157 and 158: addition of TEOS due to formation o
Page 159 and 160: solution was ultrasonicated for 15
Page 161 and 162: Triethylamine (TEA) (Sigma-Aldrich
Page 163 and 164: To prepare the monolayer assembly o
Page 165 and 166: was added followed by addition of 0
Page 168 and 169: ELABORATION OF SELF-HEALING POLYMER
Page 170 and 171: ELABORATION DES MEMBRANES POLYMERES
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