dorsal/arxiv
View SchemaElectrospray techniques for the study of liquid energetics by hyperquenched glass calorimetry
| Authors | Li-Min Wang, Steve Borick, C. Austen Angell |
|---|---|
| Categories | |
| ArXiv ID | physics/0211030 |
| URL | https://arxiv.org/abs/physics/0211030 |
Abstract
We describe an electrospray technique for in situ preparation, for differential scanning calorimetry study, of samples of molecular liquids quenched into the glassy state on extremely short time scales (hyperquenched). We study the case of propylene glycol PG in some detail. Using a fictive temperature method of obtaining the temperature dependence of enthalpy relaxation, we show that the electrospray method yields quenching rates of ~105 K/s, while the more common method, dropping a sealed pan of sample into liquid nitrogen, yields only 120 K/s. Hyperquenched samples start to relax exothermically far below the glass temperature, at a temperature where the thermal energy permits escape from the shallow traps in which the system becomes localized during hyperquenching. This permits estimation of the trap depths, which are then compared with the activation energy estimated from the fictive temperature of the glass and the relaxation time at the fictive temperature. The trap depth in molar energy units is compared with the "height of the landscape" for PG, the quasi-lattice energy of the liquid based on the enthalpy of vaporization, and the single molecule activation energy for diffusion in hydrogen bonded crystals. The implications for the topography of the energy landscape and the mechanism of its exploration, are considered.
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"abstract": "We describe an electrospray technique for in situ preparation, for\ndifferential scanning calorimetry study, of samples of molecular liquids\nquenched into the glassy state on extremely short time scales (hyperquenched).\nWe study the case of propylene glycol PG in some detail. Using a fictive\ntemperature method of obtaining the temperature dependence of enthalpy\nrelaxation, we show that the electrospray method yields quenching rates of ~105\nK/s, while the more common method, dropping a sealed pan of sample into liquid\nnitrogen, yields only 120 K/s. Hyperquenched samples start to relax\nexothermically far below the glass temperature, at a temperature where the\nthermal energy permits escape from the shallow traps in which the system\nbecomes localized during hyperquenching. This permits estimation of the trap\ndepths, which are then compared with the activation energy estimated from the\nfictive temperature of the glass and the relaxation time at the fictive\ntemperature. The trap depth in molar energy units is compared with the \"height\nof the landscape\" for PG, the quasi-lattice energy of the liquid based on the\nenthalpy of vaporization, and the single molecule activation energy for\ndiffusion in hydrogen bonded crystals. The implications for the topography of\nthe energy landscape and the mechanism of its exploration, are considered.",
"arxiv_id": "physics/0211030",
"authors": [
"Li-Min Wang",
"Steve Borick",
"C. Austen Angell"
],
"categories": [
"physics.chem-ph"
],
"title": "Electrospray techniques for the study of liquid energetics by hyperquenched glass calorimetry",
"url": "https://arxiv.org/abs/physics/0211030"
},
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