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May 15, 1975The Journal of Chemical Physics92 citations

Study of the low-temperature ’’transition’’ in ice Ih by thermally stimulated depolarization measurements

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GJG. P. JohariSJSheila J. Jones

Key Points

  • To determine whether low-temperature electrical peaks in polycrystalline H2O and D2O ice indicate a thermodynamic ferroelectric phase transition or molecular orientation relaxation.
  • Measured thermally stimulated depolarization (TSD) currents in polycrystalline H2O and D2O ice across 77–260 K at pressures of 1 bar and 1.2 kbar using a heating rate of 0.0023 K s⁻¹.
  • Calculated equilibrium dielectric permittivity and relaxation times between 98–119 K after charging ice samples across multiple days.
  • Observed three depolarization current peaks at 1 bar, with the lowest-temperature peak emerging at 110.4 K in H2O and 123.8 K in D2O ice, shifting to higher temperatures with increasing heating rate or pressure.
  • Identified that the low-temperature current peak originates from the relaxation of frozen-in molecular orientation polarization rather than a transition to a ferroelectric phase.
  • Demonstrated that equilibrium dielectric permittivity between 98–119 K shows no evidence of approaching ferroelectric ordering at 98 K.

Abstract

Thermally stimulated depolarization (TSD) current has been measured in polycrystalline H2O and D2O ice in the temperature range 77–260 K and at pressures of about 1 bar and 1.2 kbar. Three peaks in current have been observed at about 1 bar at a heating rate of 0.0023 K sec−1, the smallest of which appears at 110.4 K and 123.8 K in H2O and D2O ice, respectively. An increase in heating rate shifts the current peaks to higher temperatures, as does an increase in pressure. From an analysis of the current–temperature plots, the dielectric permittivity and the relaxation times have been obtained. It is shown that the current peak occurring at the lowest temperature is due to the relaxation of frozen-in orientation polarization of water molecules in ice and does not indicate a thermodynamic transformation to a ferroelectric phase. The equilibrium dielectric permittivity of H2O ice has been measured in the range 98–119 K by charging the ice for many days and then obtaining the stored charge by TSD technique. The equilibrium dielectric permittivity shows no approach to a ferroelectric ordering at 98 K. The heterocharge in an ice electret of ∼ 105 C V−1⋅F−1 is largely due to the polarization which gives rise to the high-temperature TSD current peaks. Aging reduces the magnitude of this polarization substantially. The mechanism of this polarization is not clear. The homocharge was seen in one sample of ice as a negative depolarization current. It is proposed that the TSD technique should be useful for the detection of very slow phase transformation in dipolar materials.

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Cite This Study

Johari et al. (1975) studied this question.

synapsesocial.com/papers/6a1d507573c56dd1bd2f82d7https://doi.org/10.1063/1.430303
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