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Award Detail

Doing Business As Name:University of Minnesota-Twin Cities
  • Marc A Hillmyer
  • (612) 625-7834
Award Date:04/27/2010
Estimated Total Award Amount: $ 480,000
Funds Obligated to Date: $ 726,000
  • FY 2013=$120,000
  • FY 2014=$246,000
  • FY 2011=$120,000
  • FY 2010=$120,000
  • FY 2012=$120,000
Start Date:06/01/2010
End Date:05/31/2016
Transaction Type:Grant
Awarding Agency Code:4900
Funding Agency Code:4900
CFDA Number:47.049
Primary Program Source:040100 NSF RESEARCH & RELATED ACTIVIT
Award Title or Description:Block Polymer Routes to Robust Nanostructured Membrane Materials
Federal Award ID Number:1006370
DUNS ID:555917996
Parent DUNS ID:117178941
Program Officer:
  • Andrew Lovinger
  • (703) 292-4933

Awardee Location

Street:200 OAK ST SE
Awardee Cong. District:05

Primary Place of Performance

Organization Name:University of Minnesota-Twin Cities
Street:200 OAK ST SE
Cong. District:05

Abstract at Time of Award

TECHNICAL SUMMARY: Polymeric membranes are widely used in technologies ranging from municipal water treatment to food processing to industrial gas separations. The separation efficiency and flux across the membrane are two of the key factors that determine their ultimate utility. These figures of merit are closely tied to the nanoscale morphology of the membrane in many cases. Two strategies that utilize block polymers as the principal components for the preparation of various nanostructured membranes with tunable attributes are proposed. Block polymer self-assembly coupled with the integration of functional attributes into these hybrid macromolecules is a powerful and versatile platform for the preparation of advanced membrane materials. The proposed research activities build on the principal investigator's past efforts with functional block polymers that have resulted in efficient ultrafiltration, gas separation, and proton exchange membranes for applications in water purification, ammonia purification, and direct methanol fuel cells. Specific targets in the proposed work include nanostructured high-density polyethylene membranes by a self-assembly approach and nanostructured thermoset membranes by a reaction induced phase separation approach. The complete characterization of the resultant materials will be undertaken using a bevy of modern techniques and the implementation and testing of new membranes derived from these materials will be accomplished. The target materials described have tremendous potential to impact a broad swath of important technologies. The basic research and development emphasis will be aimed at new materials for water purification, battery, and fuel cell applications. NON-TECHNICAL SUMMARY: Membranes are thin sheets of material that can be used to purify a wide variety of heterogenous mixtures. Many industrially relevant membranes are made from polymers. Such polymeric membranes are currently used in technologies ranging from municipal water treatment to food processing to industrial gas separations. Membranes with higher efficiency and overall performance are targeted in this proposal. Strategies that rely on precision design and synthesis of innovative hybrid polymeric materials that can adopt complex but controlled nanostructures will be undertaken. The membranes generated in this work will be thoroughly characterized, evaluated, and compared to currently available materials. The technological implications of the proposed work are far-reaching and promise societal benefit. Water purification, lithium-ion battery and fuel cell technologies are far from maturity but are extremely important for global sustainability mandates. The basic research described in this proposal will provide the necessary fundamental underpinnings for the development of next-generation technologies in these areas. In addition to the basic research efforts, several outreach activities will be integrated into the overall program. As one example, a chemical demonstration show called "Energy and U" that emphasizes the important topic of energy (where it comes from, how it's used, and how it's converted) will be performed annually to over 3000 K-12 students.

Publications Produced as a Result of this Research

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Pitet, L. M.; Hillmyer, M. A. "Carboxy-Telechelic Polyolefins by ROMP Using Maleic Acid as a Chain Transfer Agent" Macromolecules, v.44, 2011, p.2378. doi:10.1021/ma102975r 

Seo, M.; Moll, D., Silvis, C.; Roy, A.; Querelle, S.; Hillmyer, M. A. "Interfacial Polymerization of Reactive Block Polymers for the Preparation of Composite Ultrafiltration Membranes?" Ind. Eng. Chem. Res., v.53, 2014, p.18575. doi:10.1021/ie5032259 

Pitet, LM; Chamberlain, BM; Hauser, AW; Hillmyer, MA "Synthesis of Linear, H-Shaped, and Arachnearm Block Copolymers By Tandem Ring-Opening Polymerizations" MACROMOLECULES, v.43, 2010, p.8018. doi:10.1021/ma101432  View record at Web of Science

Pitet, LM; Amendt, MA; Hillmyer, MA "Nanoporous Linear Polyethylene from a Block Polymer Precursor" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.132, 2010, p.8230. doi:10.1021/ja100985  View record at Web of Science

Jackson, EA; Hillmyer, MA "Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration" ACS NANO, v.4, 2010, p.3548. doi:10.1021/nn101400  View record at Web of Science

Baruth, A.; Seo, M.; Lin, C. H.; Walster, K.; Shankar, A. Hillmyer, M. A.; Leighton, C. "Optimization of Long-Range Order in Solvent Vapor Annealed Poly(styrene)-block-poly(lactide) Thin Films for Nanolithography" ACS Appl. Mater. Interfaces, v.6, 2014, p.13770. doi:10.1021/am503199d 

Schulze, M. W.; McIntosh, L. D.; Hillmyer, M. A.; Lodge, T. P. "High-Modulus, High-Conductivity Nanostructured Polymer Electrolyte Membranes via Polymerization-Induced Phase Separation" Nano Lett., v.14, 2014, p.122. doi:10.1021/nl4034818 

Chopade, Sujay A. and So, Soonyong and Hillmyer, Marc A. and Lodge, Timothy P. "Anhydrous Proton Conducting Polymer Electrolyte Membranes via Polymerization-Induced Microphase Separation" ACS Applied Materials & Interfaces, v.8, 2016, p.. doi:10.1021/acsami.5b12366 Citation details  

Seo, M.; Kim, S.; Oh, J.; Kim, S. -J.; Hillmyer, M. A. "Hierarchically Porous Polymers from Hyper-cross-linked Block Polymer Precursors" J. Am. Chem. Soc. 2015, 137, 600?603., v.137, 2015, p.600. doi:10.1021/ja511581w 

Jackson, E. A.; Lee, Y.; Hillmyer, M. A. "ABAC Tetrablock Terpolymers for Tough Nanoporous Filtration Membranes" Macromolecules, v.46, 2013, p.1484?1491. doi:10.1021/ma302414w 

Myungeun Seo, Christopher J. Murphy, Marc A. Hillmyer "One-step Synthesis of Crosslinked Block Polymer Precursor to a Nanoporous Thermoset" ACS Macro Letters, v.2, 2013, p.617. doi:10.1021/mz400192f 

Jackson, Elizabeth A. and Lee, Youngmin and Radlauer, Madalyn R. and Hillmyer, Marc A. "Well-Ordered Nanoporous ABA Copolymer Thin Films via Solvent Vapor Annealing, Homopolymer Blending, and Selective Etching of ABAC Tetrablock Terpolymers" ACS Applied Materials & Interfaces, v.7, 2015, p.. doi:10.1021/acsami.5b08856 Citation details  

Saba, Stacey A. and Mousavi, Maral P. and Bühlmann, Philippe and Hillmyer, Marc A. "Hierarchically Porous Polymer Monoliths by Combining Controlled Macro- and Microphase Separation" Journal of the American Chemical Society, v.137, 2015, p.. doi:10.1021/jacs.5b04992 Citation details  

Vayer, M; Nguyen, TH; Grosso, D; Boissiere, C; Hillmyer, MA; Sinturel, C "Characterization of Nanoporous Polystyrene Thin Films by Environmental Ellipsometric Porosimetry" MACROMOLECULES, v.44, 2011, p.8892. doi:10.1021/ma201497  View record at Web of Science

Jackson, E. A.; Lee, Y.; Radlauer, M. R.; Hillmyer, M. A. "Well-ordered nanoporous ABA copolymer thin films via solvent vapor annealing, homopolymer blending, and selective etching of ABAC Tetrablock Terpolymers." ACS Appl. Mater. Interfaces, v.7, 2015, p.27331. doi:10.1021/acsami.5b08856 

Seo, M; Amendt, MA; Hillmyer, MA "Cross-Linked Nanoporous Materials from Reactive and Multifunctional Block Polymers" MACROMOLECULES, v.44, 2011, p.9310. doi:10.1021/ma201394  View record at Web of Science

Saba, S. A.; Mousavi, M. P. S.; Buhlmann, P.; Hillmyer, M. A. "Hierarchically porous polymer monoliths by combining controlled macro- and microphase separation" J. Am. Chem. Soc., v.137, 2015, p.8896. doi:10.1021/jacs.5b04992 

Seo, M.; Hillmyer, M. A. "RAFT copolymerization of acid chloride-containing monomers" Polym. Chem., v.5, 2014, p.213. doi:10.1039/c3py00867c 

Amendt, M. A.; Pitet, L. M.; Moench, S.; Hillmyer, M. A. "Reactive triblock polymers from tandem ring-opening polymerizations for nanostructured vinyl thermosets" Polymer Chemistry, v.3, 2012, p.1827-1837. doi:10.1039/C1PY00450F 

Chopade, S. A.; So, S.; Hillmyer, M. A.; Lodge, T. P. "Anhydrous proton conducting polymer electrolyte membranes via polymerization-induced microphase separation." ACS Appl. Mater. Interfaces, v.8, 2016, p.6200. doi:10.1021/acsami.5b12366 

Bertrand, A.; Hillmyer, M. A. "Nanoporous Poly(lactide) by Olefin Metathesis Degradation" J. Am. Chem. Soc., v.135, 2013, p.10918. doi:10.1021/ja4050532 

McIntosh, L. D.; Schulze, M. W.; Irwin, M. T.; Hillmyer, M. A.; Lodge, T. P. "Evolution of Morphology, Modulus, and Conductivity in Polymer Electrolytes Prepared via Polymerization-Induced Phase Separation" Macromolecules, v.48, 2015, p.1418. doi:10.1021/ma502281k 

Seo, M.; Hillmyer, M. A. "Reticulated Nanoporous Polymers by Controlled Polymerization-Induced Microphase Separation" Science, v.336, 2012, p.1422-1425. doi:10.1126/science.1221383 

Jason Engbrecht, David Green, Marc A. Hillmyer, David Olson, Eric M. Todd "Positron Lifetime Spectroscopy in ordered nanoporous polymers" Journal of Polymer Science Polymer Physics, v.51, 2013, p.1157. doi:10.1002/polb.23114 

Rodwogin, M. D.; Baruth, A.; Jackson, E. A.; Leighton, C.; Hillmyer, M. A. "Nanoscale Rings from Silicon-Containing Triblock Terpolymers" ACS Applied Materials and Interfaces, v.4, 2012, p.3550-3557. doi:10.1021/am300603x 

Nasiri, M.; Bertrand, A.; Reineke, T. M.; Hillmyer, M. A. "Polymeric Nanocylinders by Combining Block Copolymer Self-Assembly and Nanoskiving" ACS Appl. Mater. Interfaces, v.6, 2014, p.16283. doi:10.1021/am504486r 

Crossland, EJW; Cunha, P; Ludwigs, S; Hillmyer, MA; Steiner, U "In situ Electrochemical Monitoring of Selective Etching in Ordered Mesoporous Block-Copolymer Templates" ACS APPLIED MATERIALS & INTERFACES, v.3, 2011, p.1375. doi:10.1021/am200050  View record at Web of Science

Sarah E. Querelle, Elizabeth A. Jackson, Edward L. Cussler, and Marc A. Hillmyer "Ultrafiltration membranes with a thin poly(styrene)-b-poly(isoprene) selective layer" ACS Applied Materials and Interfaces, v.5, 2013, p.5044. doi:10.1021/am400847m 

Amendt, MA; Roerdink, M; Moench, S; Phillip, WA; Cussler, EL; Hillmyer, MA "Functionalized Nanoporous Membranes from Reactive Triblock Polymers" AUSTRALIAN JOURNAL OF CHEMISTRY, v.64, 2011, p.1074. doi:10.1071/CH1113  View record at Web of Science

Christophe Sinturel, Marylène Vayer, Michael Morris, Marc A. Hillmyer "Solvent vapor annealing of block polymer thin films" Macromolecules, v.46, 2013, p.5399. doi:10.1021/ma400735a 

Project Outcomes Report


This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

Membranes are critical materials that play important roles in a wide variety of separation applications. Most membranes for water purification, battery separators, fuel cells, and gas separations are comprised of polymers, the molecules of plastic. We focused our research efforts under this award on the design, discovery and development of new nanostructured membrane materials using a special class of polymers called block polymers. Block polymers are hybrid materials that readily assemble into a variety of nanoscopic structures that enable the integration of disparate components into one a single material. This is important for application in membrane separations, because it is increasingly difficult to expand the range of potential applications and improve efficiencies in various technologies. Under this award we prepared new membrane materials that achieved record combination of modulus (stiffness) and ion conductivity for applications that include advanced batteries for energy storage. We also discovered a new method for the generation of nanostructure membrane materials using a simple process that involved the concurrent synthesis of block polymers and their self-assembly into various nanostructures. This process has greatly simplified the ability to incorporate a wide range of components into the polymerization media and precisely control the resultant nanoscopic structure. Using this technique we were able to achieve a range of porous materials that are useful for water purification applications as an example. Our advances and the practical relevance of the work has led to partnerships with industry. Moreover, our work advanced the important area of membrane materials for applications in water purification and energy storage that both have direct societal benefit. The researchers working under this grant were broadly trained in polymer science (with emphasis on the synthesis, characterization, and applications of block polymers) and have gone on to become academics or leaders in industry. Integrated into our work were outreach initiatives and numerous activities aimed at encouraging youth to become interested and engaged in science and technology.

Last Modified: 08/26/2016
Modified by: Marc A Hillmyer

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