Designing new materials depends upon understanding the properties of today's materials. One such material, Nafion , is a polymer that efficiently conducts ions (a polymer electrolyte) and water through its nanostructure, making it important for many energy-related industrial applications, including in fuel cells, organic batteries, and reverse-osmosis water purification.

But since Nafion was invented 50 years ago, scientists have only been able to speculate about how to build new materials because they have not been able to see details on how the molecules come together and work within Nafion.

Now, two Virginia Tech research groups have combined forces to devise a way to measure Nafion's internal structure and, in the process, have discovered how to manipulate this structure to enhance the material's applications.

The research is published in the June 19 issue of Nature Materials in the Letters article, "Linear coupling of alignment with transport in a polymer electrolyte membrane," by Jing Li, Jong Keun Park, Robert B. Moore, and Louis A. Madsen, all with the chemistry department in the College of Science and the Macromolecules and Interfaces Institute at Virginia Tech.

Nafion is made up of molecules that combine the non-stick and tough nature of Teflon with the conductive properties of an acid, such as battery acid. A network of tiny channels, nanometers in size, carries water or ions quickly through the polymer.

"But, due to the irregular structure of Nafion, scientists have not been able to get reliable information about its properties using most standard analysis tools, such as transmission electron microscopy," said Madsen, assistant professor of physical, polymer, and materials chemistry.

Madsen and Moore, professor of physical and polymer chemistry; Madsen's post-doctoral associate Jing Li; and Moore's Ph.D. student Jong Keun Park, of Korea, were able to use nuclear magnetic resonance (NMR)to measure molecular motion, and a combination of NMR and X-ray scattering to measure molecular alignment within Nafion.

"We were looking at water molecules inside Nafion as internal reporters of structure and efficiency of conduction," said Madsen. "The new feature we discovered is the locally aligned aggregates of polymer molecules in the material. The molecules align like strands of dry spaghetti lined up in a box. We can measure the speed (diffusion) of the water molecules and the direction they travel within those structures, which relates strongly to the alignment of the polymer molecule strands."

The researchers observed that the alignment of the channels influenced the speed and preferential direction of water motion. And a startlingly clear picture presented itself when the scientists stretched the Nafion and measured its structure and water motion.

"Stretching drastically influences the degree of alignment," said Madsen. "So the molecules move faster along the direction of the stretch, and in a very predictable way. These materials actually share some properties with liquid crystals - molecules that line up with each other and are used in every LCD television, projector, and screen."

These relationships have not been previously recognized in a polymer electrolyte, Madsen said.

The ability to observe motion and direction, and understand what is happening within Nafion, has implications for using the material in new ways, and for designing new materials, the researchers write in the Nature Materials article. Ion-based applications could include actuator devices such as artificial muscles, organic batteries, and more energy efficient fuel cells. A water-based application would be improved reverse osmosis membranes for water purification.

Madsen and Moore started this collaborative project shortly after they arrived at Virginia Tech (Madsen in 2006, Moore in 2007), and they are furthering their work together by investigating new polymeric materials using their unique combination of analysis techniques.

"Alignment provides for a better flow of the molecules through the polymer," Madsen said.

The research is supported by Madsen's National Science Foundation Faculty Early Career Development (CAREER) Award. His research focuses on improving advanced polymers for fuel cells and reverse-osmosis water purification by combining detailed analysis of these materials with theoretical understanding. The research is also supported by the US Army Research Office under Ionic Liquids in Electro-Active Devices (ILEAD) Multidisciplinary University Research Initiative (MURI) grant. Moore is also associate director for research of the Institute for Critical Technology and Applied Science at Virginia Tech.

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