A simple chemical fixation method for the fabrication of layer-by-layer (LbL) polyelectrolyte multilayer (PEM) has been developed to create a large area, highly uniform film for various applications. PEM of weak polyelectrolytes, i.e., polyallylamine hydrogen chloride (PAH) and poly(acrylic acid)(PAA), was assembled on polymer substrates such as poly(methyl methacrylate)(PMMA) and polycarbonate (PC). In the case of a weak polyelectrolyte, the fabricated thin film thickness of the polyelectrolyte multilayers was strongly dependent on the pH of the processing solution, which enabled the film thickness or optical properties to be controlled. On the other hand, the environmental stability for device application was poor. In this study, we utilized the chemical fixation method using glutaraldehyde (GA)-amine reaction in order to stabilize the polyelectrolyte multilayers. By simple treatment of GA on the PEM film, the inherent morphology was fixed and the adhesion and mechanical strength were improved. Both surface tension and FT-IR measurements supported the chemical cross-linking reaction. The surface property of the polyelectrolyte films was altered and converted from hydrophilic to hydrophobic by chemical modification. The possible application to antireflection coating on PMMA and PC was demonstrated.
Phase behavior of a PEO-PPO-PEO (Pluronic P103) triblock copolymer in water is investigated using small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and rheology. Pluronic P103 shows apparent two gel states in different temperature regions. The first sol-to-gel transition at a lower temperature (i.e., the hard gel I state) turns out to be the hexagonal microphase as evidenced by the combined SANS and SAXS and the frequency dependence of both G' and G'' in rheology. In contrast to the hard gel I, the second sol-to-gel transition (i.e., the hard gel II state) at a higher temperature represents the block copolymer micelles in somewhat disordered state rather than the ordered state seen in the hard gel I. Moreover, turbidity change depending only on the temperature with four distinct regions is observed and the large aggregates with size larger than 5,000 nm are detected with DLS in the turbid solution region. Based upon the present study, two different gelation mechanisms for aqueous PEO-PPO-PEO triblock copolymer solutions are proposed.
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