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The Influence of Substrate on the Formation of Surface Structure of Polymer Film and Its Property

Author: ZhengFanFan
Tutor: WangXinPing
School: Zhejiang University of Technology
Course: Polymer Chemistry and Physics
Keywords: substrate modification dynamic wetting behavior glass transition temperature phase separation
Type: Master's thesis
Year: 2013
Downloads: 57
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With the advances in nanotechnology, the physical properties and performances ofpolymer materials in the nanometer range already attract a great deal of interest in many fieldsof science and technology. The chain structure and dynamic behavior of polymer film wereinfluenced by the interaction between polymer and substrate. The existence ofpolymer/substrate interaction will induce the deviation of chain density, the degree ofentanglement, and ordering from that in bulk. Therefore, the investigation of the influence ofpolymer/substrate interaction on the formation of structure of polymer thin film and its chainmobility is essential to understand the molecule motion mechanism of polymer chain innanoscale and the application of polymer film.In this thesis, the interfacial interaction between PVAc film and substrate, the influenceof interfacial interaction on the glass transition temperature of PS thin film and surfacestructure formation of SBS triblock copolymer thin film were systematically investigated bydynamic contact angle measurement, Sum Frequency Generation Vibrational Spectroscopy(SFG), Ellipsometry and Atomic Force Microscopy (AFM). Some conclusions were obtainedas follows:(1) The interaction between PVAc thin film and substrate was investigated by surfacedynamic wetting behavior. It was shown that the jumping angle decreased with increasing thehydroxyl content on the substrate during the dynamic contact angle measurement when thefilm was thin. The jumping angle increased from0on100%hydroxyl content substrate to8on29%hydroxyl content substrate when the film thickness was about6nm. This wasattributed to that PVAc thin film which spin-coated on high hydroxyl content substratesformed more hydrogen bonding with the substrates, so the thin film became stiffer. Throughvarying the thickness of PVAc film, it was found that the critical thickness, which the jumpingangle showed no difference, increased as the hydroxyl content increased. It was indicated thatthe more hydroxyl on the substrate, the deeper the influence of interfacial interaction on filmproperties.(2) The effect of interfacial interaction on the glass transition of PS thin film was studied.The results showed that the Tgof PS film decreased with increasing film thickness on the substrates modified by XST-R. This was due to the fact that the PS chain permeated throughthe substrate. When the PS film was thin, It was found that the higher the interfacialinteraction between the PS film and substrate, the higher the Tgof PS film. The criticalthickness, the Tgdeviated from the bulk value, increased with increasing the interfacialenergy.(3) The influence of interfacial interaction on the formation of surface structure of SBStriblock thin film was studied. As to the spin-coated film, when the film thickness was lessthan34nm, the SBS film, spin-coated on substrate XST-H and XST-Me, showed dewettingphenomenon after thermal annealing, typical sea-island structure was detected, and phaseseparation showed on the island part. When the film thickness increased to83nm, thedewetting behavior vanished. On the substrate of XST-tBu which had affinity to PB,double-layer microstructure formed on SBS film surface. On the top surface was dot structurewhich was about2.5nm, it was preliminary predicated as PB component, while the secondlayer was typical fingerprint phase separation structure. As to the casting film, when theSBS/toluene solution concentration was low, the film, cast on the XST-H substrate, showedthe sea-island structure on the surface. Further investigation found that the phase separationonly showed on the island structure. However, on the substrate of XST-Me and XST-tBu, theSBS film could not form because of their low surface tension, only increasing the solutionconcentrate could the film form on the substrate.

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