Hydrogen Bonding Aggregation in Acrylamide: Theory and Experiment
| Autor: | Elena Patyukova, Robert Evans, Taylor Rottreau, Paul D. Topham, M. J. Greenall |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Materials science
Polymers and Plastics Dimer Polyacrylamide Infrared spectroscopy Thermodynamics Cooperativity 02 engineering and technology 010402 general chemistry 01 natural sciences Inorganic Chemistry chemistry.chemical_compound Materials Chemistry Bond energy chemistry.chemical_classification Quantitative Biology::Biomolecules Hydrogen bond Organic Chemistry Polymer 021001 nanoscience & nanotechnology Block (periodic table) 0104 chemical sciences Condensed Matter::Soft Condensed Matter chemistry F320 Chemical Physics 0210 nano-technology |
| Zdroj: | Macromolecules |
| ISSN: | 0024-9297 1520-5835 |
| DOI: | 10.1021/acs.macromol.8b01118 |
| Popis: | Hydrogen bonding plays a role in the microphase separation behavior of many block copolymers, such as those used in lithography, where the stronger interactions due to hydrogen bonding can lead to a smaller period for the self-assembled structures, allowing the production of higher resolution templates. However, current statistical thermodynamic models used in descriptions of microphase separation, such as the Flory–Huggins approach, do not take into account some important properties of hydrogen bonding, such as site specificity and cooperativity. In this combined theoretical and experimental study, a step is taken toward the development of a more complete theory of hydrogen bonding in polymers, using polyacrylamide as a model system. We begin by developing a set of association models to describe hydrogen bonding in amides. Both models with one association constant and two association constants are considered. This theory is used to fit IR spectroscopy data from acrylamide solutions in chloroform, thereby determining the model parameters. We find that models with two constants give better predictions of bond energy in the acrylamide dimer and more realistic asymptotic behavior of the association constants in the limit of high temperatures. At the end of the paper, we briefly discuss the question of the determination of the Flory–Huggins parameter for a diblock copolymer with one self-associating hydrogen bonding block and one non-hydrogen bonding block by means of fitting the scattering function in a disordered state. |
| Databáze: | OpenAIRE |
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