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- All Subjects: Materials
- Creators: Nofen, Elizabeth
- Creators: Adams, James
Description
Iodide-based ionic liquids have been widely employed as sources of iodide in electrolytes for applications utilizing the triiodide/iodide redox couple. While adding a low-viscosity solvent such as water to ionic liquids can greatly enhance their usefulness, mixtures of highly viscous iodide-containing ILs with water have never been studied. Thus, this paper investigates, for the first time, mixtures of water and the ionic liquid 1-butyl-3-methylimidazolium iodide ([BMIM][I]) through a combined experimental and molecular dynamics study. The density, melting point, viscosity and conductivity of these mixtures were measured experimentally. The composition region below 50% water by mole was found to be dramatically different from the region above 50% water, with trends in density and melting point differing before and after that point. Water was found to have a profound effect on viscosity and conductivity of the IL, and the effect of hydrogen bonding was discussed. Molecular dynamics simulations representing the same mixture compositions were performed. Molecular ordering was observed, as were changes in this ordering corresponding to water content. Molecular ordering was related to the experimentally measured mixture properties, providing a possible explanation for the two distinct composition regions identified by experiment.
ContributorsNgan, Miranda L (Author) / Dai, Lenore (Thesis director) / Nofen, Elizabeth (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
Description
The story of graphene truly began in what was simply a stub in the journal Physical Review not two years after the end of World War II. In 1947, McGill University physicist P.R. Wallace authored “The Band Theory of Graphite” and attempted to develop a foundation on which the structure-property relationship of graphite could be explored; he calculates the number of free electrons and conductivity of what he describes as “a single hexagonal layer” and “suppos[es] that conduction takes place only in layers” in bulk graphite to predict wave functions, energies at specific atomic sites in the hexagonal lattice, and energy contours using a tight binding approximation for a hypothesized version of what we now call ‘armchair-style’ graphene. While Wallace was the first to explore the band structure and Brillouin Zones of single-layer graphite, the concept of two-dimensional materials was not new. In fact, for years, it was dismissed as a thermodynamic impossibility.
Everything seemed poised against any proposed physical and experimental stability of a structure like graphene. “Thermodynamically impossible”– a not uncommon shutdown to proposed novel physical or chemical concepts– was once used to describe the entire field of proposed two-dimensional crystals functioning separately from a three-dimensional base or crystalline structure. Rudolf Peierls and Lev Davoidovich Landau, both very accomplished physicists respectively known for the Manhattan Project and for developing a mathematical theory of helium superfluidity, rejected the possibility of isolated monolayer to few-layered crystal lattices. Their reasoning was that diverging thermodynamic-based crystal lattice fluctuations would render the material unstable regardless of controlled temperature. This logic is flawed, but not necessarily inaccurate– diamond, for instance, is thermodynamically metastable at room temperature and pressure in that there exists a slow (i.e. slow on the scale of millions of years) but continuous transformation to graphite. However, this logic was used to support an explanation of thermodynamic impossibility that was provided for graphene’s lack of isolation as late as 1979 by Cornell solid-state physicist Nathaniel David Mermin. These physicists’ claims had clear and consistent grounding in experimental data: as thin films become thinner, there exists a trend of a decreasing melting temperature and increasing instability that renders the films into islands at somewhere around ten to twenty atomic layers. This is driven by the thermodynamically-favorable minimization of surface energy.
Everything seemed poised against any proposed physical and experimental stability of a structure like graphene. “Thermodynamically impossible”– a not uncommon shutdown to proposed novel physical or chemical concepts– was once used to describe the entire field of proposed two-dimensional crystals functioning separately from a three-dimensional base or crystalline structure. Rudolf Peierls and Lev Davoidovich Landau, both very accomplished physicists respectively known for the Manhattan Project and for developing a mathematical theory of helium superfluidity, rejected the possibility of isolated monolayer to few-layered crystal lattices. Their reasoning was that diverging thermodynamic-based crystal lattice fluctuations would render the material unstable regardless of controlled temperature. This logic is flawed, but not necessarily inaccurate– diamond, for instance, is thermodynamically metastable at room temperature and pressure in that there exists a slow (i.e. slow on the scale of millions of years) but continuous transformation to graphite. However, this logic was used to support an explanation of thermodynamic impossibility that was provided for graphene’s lack of isolation as late as 1979 by Cornell solid-state physicist Nathaniel David Mermin. These physicists’ claims had clear and consistent grounding in experimental data: as thin films become thinner, there exists a trend of a decreasing melting temperature and increasing instability that renders the films into islands at somewhere around ten to twenty atomic layers. This is driven by the thermodynamically-favorable minimization of surface energy.
ContributorsShulman, Neal Arthur (Author) / Adams, James (Thesis director) / Islam, Rafiqul (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
The problem of catastrophic damage purveys in any material application, and minimizing its occurrence is paramount for general health and safety. We have successfully synthesized, characterized, and applied dimeric 9-anthracene carboxylic acid (Di-AC)-based mechanophores particles to form stress sensing epoxy matrix composites. As Di-AC had never been previously applied as a mechanophore and thermosets are rarely studied in mechanochemistry, this created an alternative avenue for study in the field. Under an applied stress, the cyclooctane-rings in the Di-AC particles reverted back to their fluorescent anthracene form, which linearly enhanced the overall fluorescence of the composite in response to the applied strain. The fluorescent signal further allowed for stress sensing in the elastic region of the stress\u2014strain curve, which is considered to be a form of damage precursor detection. Overall, the incorporation of Di-AC to the epoxy matrix added much desired stress sensing and damage precursor detection capabilities with good retention of the material properties.
ContributorsWickham, Jason Alexander (Co-author) / Nofen, Elizabeth (Co-author, Committee member) / Koo, Bonsung (Co-author) / Chattopadhyay, Aditi (Co-author) / Dai, Lenore (Co-author, Thesis director) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05