X. Chelsea Chen

Structure of thin film polymer/nanoparticle systems: polystyrene (PS) coated-Au nanoparticle/tetramethyl bisphenol-A polycarbonate mixtures (TMPC)

The morphologies of thin film blends of polystyrene (PS)-brush coated Au nanoparticles with tetramethyl bisphenol-A polycarbonate (TMPC) were investigated. Our results reveal that entropic effects, associated with the brush/host chain interactions, nanoparticle diameter, D, and asymmetries in monomer sizes of the host and grafted chains, can play a more important role than the favorable PS/TMPC enthalpic interactions toward determining the phase miscibility of the system. A diagram of states is constructed to show the phase separated and dispersed regimes as a function of D, N, the degree of polymerization of the grafted chains, and P, the degree of polymerization of the host chains, at a constant grafting density. These results have important implications on the design of brush coated nanoparticle/homopolymer mixtures for various applications.

Effect of Morphology of Nanoscale Hydrated Channels on Proton Conductivity in Block Copolymer Electrolyte Membranes

Hydrated membranes with cocontinuous hydrophilic and hydrophobic phases are needed to transport protons in hydrogen fuel cells. Herein we study the water uptake and proton conductivity of a model fuel cell membrane comprising a triblock copolymer, polystyrenesulfonate-block-polyethylene-block-polystyrenesulfonate (S-SES), as a function of water activity in both humid air and liquid water. We demonstrate that the water uptake and proton conductivity of S-SES membranes equilibrated in liquid water are fundamentally different from values obtained when they were equilibrated in humid air. The morphological underpinnings of our observations were determined by synchrotron small-angle X-ray scattering and cryogenic scanning transmission electron microscopy. A discontinuous increase in conductivity when nearly saturated humid air is replaced with liquid water coincides with the emergence of heterogeneity in the hydrated channels: a water-rich layer is sandwiched between two polymer-rich brushes. While the possibility of obtaining heterogeneous hydrated channels in polymer electrolyte membranes has been discussed extensively, to our knowledge, this is the first time that direct evidence for the formation of water-rich subdomains is presented.

Design of a humidity controlled sample stage for simultaneous conductivity and synchrotron X-ray scattering measurements.

We report on the design and operation of a novel sample stage, used to simultaneously measure X-ray scattering profiles and conductivity of a polymer electrolyte membrane (PEM) surrounded by humid air as a function of temperature and relative humidity. We present data obtained at the Advanced Light Source and Stanford Synchrotron Radiation Laboratory. We demonstrate precise humidity control and accurate determination of morphology and conductivity over a wide range of temperatures. The sample stage is used to study structure-property relationships of a semi-crystalline block copolymer PEM, sulfonated polystyrene-block-polyethylene.

Orientation mapping of semicrystalline polymers using scanning electron nanobeam diffraction.

We demonstrate a scanning electron nanobeam diffraction technique that can be used for mapping the size and distribution of nanoscale crystalline regions in a polymer blend. In addition, it can map the relative orientation of crystallites and the degree of crystallinity of the material. The model polymer blend is a 50:50w/w mixture of semicrystalline poly(3-hexylthiophene-2,5-diyl) (P3HT) and amorphous polystyrene (PS). The technique uses a scanning electron beam to raster across the sample and acquires a diffraction image at each probe position. Through image alignment and filtering, the diffraction image dataset enables mapping of the crystalline regions within the scanned area and construction of an orientation map.

Simulation of local ion transport in lamellar block copolymer electrolytes based on electron micrographs

Author(s): Chintapalli, M; Higa, K; Chen, XC; Srinivasan, V; Balsara, NP | Abstract:

Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes

In this work, we examine the swelling of nanostructured block copolymer electrolytes immersed in liquid water. A series of sulfonated polystyrene-b-polyethylene-b-polystyrene (S-SES) membranes having the same nominal chemical composition but two different morphologies are prepared by systematic changes in processing. We start with a membrane comprising a mixture of homopolymer polystyrene (hPS) and a polystyrene-b-polyethylene-b-polystyrene (SES) copolymer. hPS is subsequently selectively removed from the membrane and the polystyrene domains are sulfonated to give S-SES membranes. The morphology of the membranes is controlled by controlling ϕ v, the volume fraction of hPS in the blended membrane. The morphology of the membranes was studied by small angle X-ray scattering (SAXS), cryogenic scanning transmission electron microscopy (cryo-STEM), and cryogenic electron tomography. The overall domain swelling measured by SAXS decreases slightly at ϕ v = 0.29; a crossover from lamellar to bicontinuous morphology is obtained at the same value of ϕ v. The bicontinuous morphologies absorb more water than the lamellar morphologies. By contrast, the nanodomain swelling of the bicontinuous membrane (120%) is slightly less than that of the lamellar membrane (150%). Quantitative analysis of the STEM images and electron tomography was used to determine the swelling on the hydrophilic and hydrophobic domains due to exposure to water. The hydrophilic sulfonated polystyrene-rich domain spacing increases while the hydrophobic polyethylene domain spacing decreases when the membranes are hydrated. The extent of increase and decrease is not a strong function of ϕ v.

Nanobeam Scanning Diffraction for Orientation Mapping of Polymers

1. National Center for Electron Microscopy, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, USA. 2. Department of Materials Science and Engineering, University of California, Berkeley, USA. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, USA. 5. Photon Sciences, Stanford University, Menlo Park, USA.

Development of Diffraction Scanning Techniques for Beam Sensitive Polymers.

1. National Center for Electron Microscopy, Molecular Foundry, and Materials Sciences Division; Lawrence Berkeley National Laboratory, Berkeley, CA, USA. 2. Department of Materials Science and Engineering and Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, USA. 3. Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA, USA.