The effect of the network-to-molecular structural transformation with increasing phosphorus content in P x Se 100− x (30 ≤ x ≤ 67) supercooled liquids on their shear-mechanical response is investigated using oscillatory shear rheometry. While network liquids with 30 ≤ x ≤ 40 are characterized by shear relaxation via a network bond scission/renewal process, a Maxwell scaling of the storage (G′) and loss (G″) shear moduli, and a frequency-independent viscosity at low frequencies, a new relaxation process emerges in liquids with intermediate compositions (45 ≤ x ≤ 50). This process is attributed to an interconversion between network and molecular structural moieties. Predominantly molecular liquids with x ≥ 63, on the other hand, are characterized by a departure from Maxwell behavior as the storage modulus shows a linear frequency scaling G′(ω) ∼ ω over nearly the entire frequency range below the G′–G″ crossover and a nearly constant ratio of G″/G′ in the terminal region. Moreover, the dynamic viscosity of these rather fragile molecular liquids shows significant enhancement over that of network liquids at frequencies below the dynamical onset and does not reach a frequency-independent regime even at frequencies that are four orders of magnitude lower than that of the onset. Such power-law relaxation behavior of the molecular liquids is ascribed to an extremely broad distribution of relaxation timescales with the coexistence of rapid rotational motion of individual molecules and cooperative dynamics of transient molecular clusters, with the latter being significantly slower than the shear relaxation timescale.
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Molecular origins of bulk viscosity in liquid water
The rapid equilibrium fluctuations of water molecules are intimately connected to the rheological response; molecular motions resetting the local structure and stresses seen as flow and volume changes. In the case of water or hydrogen bonding liquids generally, the relationship is a non-trivial consideration due to strong directional interactions complicating theoretical models and necessitating clear observation of the timescale and nautre of the associated equilibrium motions. Recent work has illustrated a coincidence of timescales for short range sub-picosecond motions and the implied timescale for the shear viscosity response in liquid water. Here, neutron and light scattering methods are used to experimentally illustrate the timescale of bulk viscosity and provide a description of the associated molecular relaxation. Brillouin scattering has been used to establish the timescale of bulk viscosity; and borrowing the Maxwell approach, the ratio of the bulk viscosity, ζ , to the bulk modulus, K , yields a relaxation time, τ B , which emerges on the order of 1–2 ps in the 280 K to 303 K temperature range. Inelastic neutron scattering is subsequently used to describe the motions of water and heavy water at the molecular scale, providing both coherent and incoherent scattering data. A rotational (alternatively described as localized) motion of water protons on the 1–2 ps timescale is apparent in the incoherent scattering spectra of water, while the coherent spectra from D 2 O on the length scale of the first sharp diffraction peak, describing the microscopic density fluctuations of water, confirms the relaxation of water structure at a comparable timescale of 1–2 ps. The coincidence of these three timescales provides a mechanistic description of the bulk viscous response, with the local structure resetting due to rotational/localized motions on the order of 1–2 ps, approximately three times slower than the relaxations associated with shear viscosity. In this way we show that the shear viscous response is most closely associated with changes in water network connectivity, while the bulk viscous response is associated with local density fluctuations.
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- Award ID(s):
- 1836556
- NSF-PAR ID:
- 10300504
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 22
- Issue:
- 17
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 9494 to 9502
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0cp01560a
