Nanostructured Materials and New Processing Strategies Through Polymer Chemistry Professor Christopher J. Ellison McKetta Department of Chemical Engineering and Texas Materials Institute The University of Texas at Austin www.che.utexas.edu/ellison ellison@che.utexas.edu 1
Overview Faculty Collaborators: Ellison Group May 2014 Keith Johnston Brian Korgel C. Grant Willson Benny Freeman Don Paul Roger Bonnecaze Venkat Ganesan Thank you to our sponsors: The Kwanjeong Educational Foundation 2
Ellison Lab Research Theme anionic, RAFT, ATRP, NMRP, new functional monomers 1 Å 100 s nm monomer macromolecular bulk shear and extensional flows electric and magnetic fields mechanical electromagnetic conductive thermal barrier Chemistry Structure Processing / Reactive Processing Properties Our research theme is connecting nanoscale / molecular level detail to macroscopic function for designing next generation materials 3
A Few Topics Ellison Group Research 1. Micro- and Nano-layered Films for High Gas Barrier Membranes 2. Thiol-ene Photopolymerizations for Producing Multifunctional Nonwoven Fibers 3. Carbon Nanotube/Graphene Polymer Nanocomposite Materials (rubber tires or aerogels) 4. Catechol Based Additives for Advanced Polymers 5. Lithography and Patterning with Polymers Nanopatterning with Block Copolymers Nano- and Micro-patterning with Marangoni Flow 6. Polymer-nanoparticle Systems for Oil and Gas Applications 7. etc.. 4
Polymer-Nanoparticle Systems for Oil and Gas Enhanced Water Flood Imaging via Coinjection of Contrast Agent Nanomaterials Electrosteric stabilization in high temperature, high salinity brine. Permanent grafting to withstand infinite dilution in reservoir. Weak adsorption on rock surface for enhanced mobility. poly(2-acrylamido-2- methylpropanesulfonate-co-acrylic acid) w/prof. Johnston 5
Multilayered Liquid Crystalline Polymers (LCPs) for High Gas Barrier Membranes Zhenpeng Li, Tsinghua University Melanie Merrick, Va. Tech. Benny Freeman, University of Texas Eric Baer, Case Western Reserve Univ. 6
Multilayer Coextrusion for Nano- and Micro-layering 1000s of layers, each as thin as 10 nm! 7
Nanoconfinement Effects on Permeability and Structure of Crystalline Polymers EAA PEO EAA 125nm PEO layer 20nm PEO layer PEO EAA Tortuosity of diffusion pathway Bulk PEO Stacked Lamellar Crystals Single Crystal PEO : Polyethylene oxide EAA : Poly(ethylene-co-acrylic acid) Bulk LCP (Vectra) Wang H, Freeman B et al. Science 2009, 323, 757. D. H. WEINKAUF and D. R. PAUL, Journal of Polymer Science: Part B: Polymer Physics, 1992, 817-835 8
High Barrier Materials from LCPs main chain (Ticona Vectra) side chain side chain = rigid, rod-like mesogen Rationale: LCPs (aka molecular composites) have a suite of attractive properties High chemical and thermal resistance Unique optical properties High barrier to gas / liquid transport Brochure of Liquid Crystalline Polymer, Celanese 6
LCPs for Multilayered Film? Multilayered LCPs Reduce the amount of LCPs needed for membrane products Enhance the LC ordering via nanoconfinement Challenge : Melt viscosity of LCPs is very low w/strong T dependence! 10
Thin Film Block Copolymer Patterns for Nanolithography Team of 12 graduate/undergraduate students and visiting scientists C. Grant Willson, University of Texas A Univ. of Texas block copolymer made in the Ellison/Willson labs!!! 11
Advanced Lithography for Magnetic Storage Media Electron Beam Lithography Nanoimprint Lithography Photolithography http://www.patrickcarlberg.dk/lic/intro%20mm/lith_image2.htm Lodder, J.C., Journal of Magnetism and Magnetic Materials, 2004. p. 1692 1697. http://nextbigfuture.com/2009/06/electron-beam-lithography.html http://www.itmweb.com/bimages/mitechnique.jpg 12
Nanoimprint Lithography 50 nm pillars 20 nm lines 2 nm replication (Rogers et al., Illinois) 13
Block Copolymers (BCPs) for Nanoimprint Template Fabrication A-block-B Poly(Styrene-block-Methyl Methacrylate) PS-b-PMMA Thin Film Processing Top Down Scanning Electron Micrographs (SEMs) After Etching By Stephen Sirard, Lam Research (Tilt View) Cochran, E., Garcia-Cervera, C. J., Fredrickson, G. H., Macromolecules (2006) 14
Directed Self-Assembly (DSA) Poly(styrene-block-methyl methacrylate) (PS-b-PMMA) Self Assembly on a Neutral Substrate Guiding Pattern Assembled Polymer Directed Self Assembly (DSA) on a Nanopatterned Substrate ($!!!) 1. Spin Coat PS-b-PMMA 2. Heat S. Ji et al. ACS Nano (2010) 15