| 41. |
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| 42. |
- Andersson, Ove, et al.
(författare)
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Effect of pressure on thermal conductivity and pressure collapse of ice in a polymer-hydrogel and kinetic unfreezing at 1 GPa
- 2011
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 134:12, s. 124903-
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Tidskriftsartikel (refereegranskat)abstract
- We report a study of aqueous solutions of poly(vinylalcohol) and its hydrogel by thermal conductivity,κ, and specific heat measurements. In particular, we investigate (i) the changes in the solution and the hydrogel at 0.1 MPa observed in the 350-90 K range and of the frozen hydrogel at 130 K observed in the range from 0.1 MPa to 1.3 GPa, and (ii) the nature of the pressure collapse of ice in the frozen hydrogel and kinetic unfreezing on heating of its high density water at 1 GPa. The water component of the polymer solution on cooling either first phase separates and then freezes to hexagonal ice or freezes without phase separation and the dispersed polymer chains freeze-concentrate in nanoscopic and microscopic regions of the grain boundaries and grain junctions of the ice crystals in the frozen state of water in the hydrogel. The change in κ with temperature at 1 bar is reversible with some hysteresis, but not reversible with pressure after compression to 0.8 GPa at 130 K. At high pressures the crystallized state collapses showing features of. and specific heat characteristic of formation of high density amorphous solid water. The pressure of structural collapse is 0.08 GPa higher than that of ice at 130 K. The slowly formed collapsed state shows kinetic unfreezing or glass-liquid transition temperature at 140 K for a time scale of 1 s. Comparison with the change in the properties observed for ice shows that κ decreases when the polymer is added.
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| 43. |
- Andersson, Ove, et al.
(författare)
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Effects of pressure and temperature on the thermal conductivity of Sn2P2S6
- 2011
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 83:13
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Tidskriftsartikel (refereegranskat)abstract
- The thermal conductivity kappa of the ferroelectric, paraelectric, and incommensurate phases of polycrystalline Sn2P2S6 has been measured in the 0.1-0.7 GPa range. The thermal conductivity kappa of the ferroelectric phase decreases with increasing pressure p. This unusual behavior, which is found in only a few other phases, is attributed to a negative Gruneisen parameter. The temperature T dependence of kappa for the ferroelectric phase (kappa similar to T-1) is well described by the Debye model for kappa, with three-phonon Umklapp scattering serving as the dominant scattering mechanism near and above the Debye temperature (similar to 100 K) up to a few tenths of degrees below the ferro- to paraelectric phase transition, where kappa(T) gradually changes and becomes temperature independent upon further heating. The thermal conductivity of the paraelectric and incommensurate phases was temperature independent and indistinguishable. Possible causes for the unusually weak T dependence at high temperatures and implications of the p dependence of kappa are discussed.
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| 44. |
- Andersson, Ove, et al.
(författare)
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Evidence suggesting kinetic unfreezing of water mobility in two distinct processes in pressure-amorphized clathrate hydrates
- 2022
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 24:34, s. 20064-20072
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Tidskriftsartikel (refereegranskat)abstract
- Type II clathrate hydrates (CHs) with tetrahydrofuran (THF), cyclobutanone (CB) or 1,3-dioxolane (DXL) guest molecules collapse to an amorphous state near 1 GPa on pressurization below 140 K. On subsequent heating in the 0.2-0.7 GPa range, thermal conductivity and heat capacity results of the homogeneous amorphous solid show two glass transitions, first a thermally weak glass transition, GT1, near 130 K; thereafter a thermally strong glass transition, GT2, which implies a transformation to an ultraviscous liquid on heating. Here we compare the GTs of normal and deuterated samples and samples with different guest molecules. The results show that GT1 and GT2 are unaffected by deuteration of the THF guest and exchange of THF with CB or DXL, whereas the glass transition temperatures (Tgs) shift to higher temperatures on deuteration of water; Tg of GT2 increases by 2.5 K. These results imply that both GTs are associated with the water network. This is corroborated by the fact that GT2 is detected only in the state which is the amorphized CH's counterpart of expanded high density amorphous ice. The results suggest a rare transition sequence of an orientational glass transition followed by a glass to liquid transition, i.e., kinetic unfreezing of H2O reorientational and translational mobility in two distinct processes.
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| 45. |
- Andersson, Ove
(författare)
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Glass-liquid transition of water at high pressure
- 2011
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Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 108:27, s. 11013-11016
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Tidskriftsartikel (refereegranskat)abstract
- The knowledge of the existence of liquid water under extreme conditions and its concomitant properties are important in many fields of science. Glassy water has previously been prepared by hyperquenching micron-sized droplets of liquid water and vapor deposition on a cold substrate (ASW), and its transformation to an ultraviscous liquid form has been reported on heating. A densified amorphous solid form of water, high-density amorphous ice (HDA), has also been made by collapsing the structure of ice at pressures above 1 GPa and temperatures below approximately 140 K, but a corresponding liquid phase has not been detected. Here we report results of heat capacity C(p) and thermal conductivity, in situ, measurements, which are consistent with a reversible transition from annealed HDA to ultraviscous high-density liquid water at 1 GPa and 140 K. On heating of HDA, the Cp increases abruptly by (3.4 ± 0.2) J mol-1 K-1 before crystallization starts at (153 ± 1) K. This is larger than the Cp rise at the glass to liquid transition of annealed ASW at 1 atm, which suggests the existence of liquid water under these extreme conditions.
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| 46. |
- Andersson, Ove, et al.
(författare)
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Glass Transitions in Pressure-Collapsed Ice Clathrates and Implications for Cold Water
- 2012
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Ingår i: Journal of Physical Chemistry Letters. - Washington : American Chemical Society (ACS). - 1948-7185 .- 1948-7185. ; 3:15, s. 1951-1955
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Tidskriftsartikel (refereegranskat)abstract
- Ice is known to collapse to amorphous ice upon pressurization at low temperatures and shows the unusual feature of multiple distinct solid amorphous water states, which have inspired models of liquid water’s structure and unusual properties.Here, we use heat capacity Cp measurements to show that similarly collapsed ice clathrates display identical glass behavior as amorphous ice but that crystallization above the glass transition temperature Tg of ∼140 K at 1 GPa is inhibited. This effect of the homogeneously distributed “guest molecules” in water reveals a relatively strong reversible Cp increase above Tg but no further transition before crystallization at ∼190 K.This is consistent with a glass−liquid transition of water at Tg, which suggests a new path to study an ultraviscous liquid water network and evaluate water models
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| 47. |
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| 48. |
- Andersson, Ove, et al.
(författare)
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Nature of the pressure-induced collapse of an ice clathrate by dielectric spectroscopy
- 2008
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Ingår i: Journal of Chemical Physics. - : American Institute of Physics (AIP). - 0021-9606 .- 1089-7690. ; 129:23
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Tidskriftsartikel (refereegranskat)abstract
- Collapse of an ice clathrate of type II structure containing tetrahydrofuran as guest molecules has been studied at different pressures by dielectric spectroscopy. The sample was pressurized to 1.3 GPa at 130 K and the resulting collapsed state was pressure cycled. The dielectric relaxation time increases at a progressively rapid rate during pressurizing and then decreases slowly on depressurizing, but the dielectric relaxation time does not reach the value of the original state. With increase in pressure, the limiting high frequency permittivity due to orientation of H2O molecules first increases by about 5% until 0.75 GPa and then decreases slightly until 1 GPa, and finally it increases until ~1.2 GPa. The decrease is attributed to the loss of contribution from the reorientational motion of tetrahydrofuran molecules and the increase to densification as the structure mechanically collapses completely in the 1–1.25 GPa range. The relaxation time of the collapsed state is comparable with that of the high-density amorph formed on pressure collapse of ice.
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| 49. |
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| 50. |
- Andersson, Ove, et al.
(författare)
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Phase behavior and thermal conductivity of urea at pressures up to 1 GPa and at temperatures in the range 50–370 K
- 1994
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Ingår i: International journal of thermophysics. - : Plenum Publishing. - 0195-928X .- 1572-9567. ; 15:3, s. 513-524
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Tidskriftsartikel (refereegranskat)abstract
- The thermal conductivity of the solid phases I and III of urea was measured at temperatures in the range 50-370 K for pressures up to 1 GPa. Phase III, previously detected only at pressures above 0.5 GPa, was observed here at low pressures (< 0.07 GPa) below about 230 K. Extrapolation of the I-III phase line indicates that phase III might be obtained at 218 K at atmospheric pressure and, consequently, that urea might exhibit two solid phases at atmospheric pressure. The temperature dependence of the thermal conductivity of both phase I and phase III could be described by the Debye model for thermal conductivity assuming phonon scattering by three phonon umklapp processes only. Despite a volume decrease at the I --> III transition, the thermal conductivity decreased by about 20%. Normally, thermal conductivity increases at a phase transition at which volume decreases. This rather unusual behavior of urea might be due to an increase in the nearest-neighbor distance at the I --> III transition.
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