TY - JOUR
T1 - Fast and slow components in the crystallization of a model multicomponent system, NaKCa(NO3)
T2 - The role of composition fluctuations
AU - Wen, Ping
AU - Harrowell, Peter
AU - Angell, Charles
PY - 2011/6/16
Y1 - 2011/6/16
N2 - We use calorimetrically detected crystal nucleation and growth studies to broaden the discussion of fluctuation-induced nucleation processes to include composition fluctuations in ionic complex-forming systems. We use the model system Ca-(NO3)2-KNO3 with NaNO3 introduced as a third component, so that crystallization kinetics can be controlled by change of alkali cation at constant mole fraction of Ca(NO 3)2. At fixed NaNO3 content, we find separate and thermodynamically anomalous kinetics for the crystallization of NaNO 3 and Ca(NO3)2,which we attribute to the importance of slow concentration fluctuations in the latter case. The "nose" of the time-temperature- transformation TTT curve for crystallization of the Ca(NO3)2 occurs at much higher temperatures and longer times than that for NaNO3 and the shape of the curve is different. Above the metastable liquidus surface of NaNO 3, supercooled ternary melts can persist for long times. Suppression of the fast NaNO3 crystallization, by replacement of Na+ by K+, is a prerequisite for easy vitrification in this system.
AB - We use calorimetrically detected crystal nucleation and growth studies to broaden the discussion of fluctuation-induced nucleation processes to include composition fluctuations in ionic complex-forming systems. We use the model system Ca-(NO3)2-KNO3 with NaNO3 introduced as a third component, so that crystallization kinetics can be controlled by change of alkali cation at constant mole fraction of Ca(NO 3)2. At fixed NaNO3 content, we find separate and thermodynamically anomalous kinetics for the crystallization of NaNO 3 and Ca(NO3)2,which we attribute to the importance of slow concentration fluctuations in the latter case. The "nose" of the time-temperature- transformation TTT curve for crystallization of the Ca(NO3)2 occurs at much higher temperatures and longer times than that for NaNO3 and the shape of the curve is different. Above the metastable liquidus surface of NaNO 3, supercooled ternary melts can persist for long times. Suppression of the fast NaNO3 crystallization, by replacement of Na+ by K+, is a prerequisite for easy vitrification in this system.
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U2 - 10.1021/jp111835z
DO - 10.1021/jp111835z
M3 - Article
C2 - 21548638
AN - SCOPUS:79959952660
SN - 1089-5639
VL - 115
SP - 6260
EP - 6268
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 23
ER -