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Partially sulfonated polystyrene-b-poly(dimethylsiloxane) (sPS-b-PDMS) block copolymer membranes were prepared using three different polymers with various molecular weights and block ratios. Eleven different products were obtained with controlled degree of sulfonation (DS) of PS block ranging from 22% to 48%, and they were cast into proton exchange membranes (PEMs). Each PEM was rigorously characterized to see the effect of molecular weight and PS content to PEM for direct methanol fuel cells (DMFC). The first set of sPS-b-PDMS with the highest molecular weight and 50% PS block ratio generally showed high mechanical strength and selectivity (proton conductivity/ methanol permeability), and the second set with medium molecular weight and 60% PS ratio showed high proton conductivity. The last PEM with the lowest molecular weight and 80% PS ratio exhibited a poor tensile strength which is not suitable for PEM application. When the membrane/electrode assemblies (MEAs) were fabricated using the sPS-b-PDMS PEMs with moderately high DS (~40%), one from the second set (moderate molecular weight, 60% PS content) showed the best power performance (90 mW/cm2 at 70 °C) in active mode DMFC operation, which was found to be 20% higher than that of Nafion 115 MEA.

Poly(dimethyl siloxane) (PDMS) was characterized by interaction chromatography using C4-bonded silica and a mixture of THF/CH3OH as the stationary phase and the mobile phase, respectively. Under the separation condition, a commercial PDMS with broad molecular weight distribution was successfully fractionated according to molecular weight into fractions with a very narrow molecular weight distribution. The IC separation could be applied to more rigorous characterization of PDMS, modified PDMS, and block copolymer-containing PDMS. Open image in new window

In this feature article, we briefly review the new methods we have utilized recently in the investigation of morphology and phase behavior of block copolymers. We first describe the chromatographic fractionation method to purify block copolymers from their side products of mainly homopolymers or block copolymer precursors inadvertently terminated upon addition of the next monomer in the sequential anionic polymerization. The chromatographic method is extended to the fractionation of the individual block of diblock copolymers which can yield the diblock copolymer fractions of different composition and molecular weight, which also have narrower distributions in both molecular weight and composition. A more detailed phase diagram could be constructed from the set of block copolymer fractions without the need of acquiring many block copolymers each prepared by anionic polymerization. The fractions with narrow distribution in both molecular weight and composition exhibit better long-range ordering and sharper phase transition. Next, epitaxial relationships between two ordered structures in block copolymer thin film is discussed. We employed the direct visualization method, transmission electron microtomography (TEMT) to scrutinize the grain boundary structure.

High temperature size exclusion chromatography (SEC) has been used widely for the characterization of crystalline polymers, for which high temperature operation above the polymer melting temperature is required to dissolve the polymers. However, this high temperature operation has many advantages in SEC separation in addition to merely increasing polymer solubility. At high temperature the eluent viscosity decreases, which in turn decreases the column backpressure and increases the diffusivity of the analytes. Therefore, many reports on the high temperature operation of high performance liquid chromatography (HPLC) have focused on shortening the analysis time and enhancing the resolution. However, the application of high temperature SEC analysis to exploit the merits of high temperature operation is scarce. In this article, therefore, we report on a new apparatus design for high temperature SEC.

We have studied the surface micelle formation of polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) at the air-water interface. A series of four PS-b-P2VPs were synthesized by anionic polymerization, keeping the PS block length constant (28 kg/mol) and varying the P2VP block length (1, 11, 28, or 59 kg/mol). The surface pressure-area (π-A) isotherms were measured and the surface morphology was studied by atomic force microscopy (AFM) after Langmuir-Blodgett film deposition onto silicon wafers. At low surface pressure, the hydrophobic PS blocks aggregate to form pancake-like micelle cores and the hydrophilic P2VP block chains spread on the water surface to form a corona-like monolayer. The surface area occupied by a block copolymer is proportional to the molecular weight of the P2VP block and identical to the surface area occupied by a homo-P2VP. It indicates that the entire surface is covered by the P2VP monolayer and the PS micelle cores lie on the P2VP monolayer. As the surface pressure is increased, the π-A isotherm shows a transition region where the surface pressure does not change much with the film compression. In this transition region, which displays high compressibility, the P2VP blocks restructure from the monolayer and spread at the air-water interface. After the transition, the Langmuir film becomes much less compressible. In this high-surface-pressure regime, the PS cores cover practically the entire surface area, as observed by AFM and the limiting area of the film. All the diblock copolymers formed circular micelles, except for the block copolymer having a very short P2VP block (1 kg/mol), which formed large, non-uniform PS aggregates. By mixing with the block copolymer having a longer P2VP block (11 kg/mol), we observed rod-shaped micelles, which indicates that the morphology of the surfaces micelles can be controlled by adjusting the average composition of block copolymers.

A poly(ethylene oxide)-b-poly(L-lactide) diblock copolymer (PEO-b-PLLA) is characterized by matrixassisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and a block length distribution map is constructed. Although the MALDI-TOF mass spectrum of PEO-b-PLLA is very complicated, most of the polymer species were identified by isolating the overlapped isotope patterns and by fitting the overlapped peaks to the Schulz-Zimm distribution function. Reconstructed MALDI-TOF MS spectrum was nearly identical to the measured spectrum and this method shows its potential to be developed as an easy and fast analysis method of low molecular weight block copolymers.