scholarly journals Comparative analysis of dielectric, shear mechanical and light scattering response functions in polar supercooled liquids

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
K. L. Ngai ◽  
Z. Wojnarowska ◽  
M. Paluch
Keyword(s):  
Molecular Dynamics ◽  
Dielectric Permittivity ◽  
Relaxation Times ◽  
Frequency Dispersion ◽  
Correlation Spectroscopy ◽  
The Other ◽  
Molecular Motions ◽  
Dynamic Heterogeneity ◽  
Relaxation Strength ◽  
Β Relaxation

AbstractThe studies of molecular dynamics in the vicinity of liquid–glass transition are an essential part of condensed matter physics. Various experimental techniques are usually applied to understand different aspects of molecular motions, i.e., nuclear magnetic resonance (NMR), photon correlation spectroscopy (PCS), mechanical shear relaxation (MR), and dielectric spectroscopy (DS). Universal behavior of molecular dynamics, reflected in the invariant distribution of relaxation times for different polar and weekly polar glass-formers, has been recently found when probed by NMR, PCS, and MR techniques. On the other hand, the narrow dielectric permittivity function ε*(f) of polar materials has been rationalized by postulating that it is a superposition of a Debye-like peak and a broader structural relaxation found in NMR, PCS, and MR. Herein, we show that dielectric permittivity representation ε*(f) reveals details of molecular motions being undetectable in the other experimental methods. Herein we propose a way to resolve this problem. First, we point out an unresolved Johari–Goldstein (JG) β-relaxation is present nearby the α-relaxation in these polar glass-formers. The dielectric relaxation strength of the JG β-relaxation is sufficiently weak compared to the α-relaxation so that the narrow dielectric frequency dispersion faithfully represents the dynamic heterogeneity and cooperativity of the α-relaxation. However, when the other techniques are used to probe the same polar glass-former, there is reduction of relaxation strength of α-relaxation relative to that of the JG β relaxation as well as their separation. Consequently the α relaxation appears broader in frequency dispersion when observed by PCS, NMR and MR instead of DS. The explanation is supported by showing that the quasi-universal broadened α relaxation in PCS, NMR and MR is captured by the electric modulus M*(f) = 1/ε*(f) representation of the dielectric measurements of polar and weakly polar glass-formers, and also M*(f) compares favorably with the mechanical shear modulus data G*(f).

Is there Universality in the Dielectric Response of Polar Glass Formers?

2021 ◽  
Author(s):  
K. L. Ngai ◽  
Zaneta Wojnarowska ◽  
Marian Paluch
Keyword(s):  
Dielectric Permittivity ◽  
Shear Modulus ◽  
Electric Modulus ◽  
Frequency Dispersion ◽  
Correlation Spectroscopy ◽  
The Other ◽  
Dynamic Heterogeneity ◽  
Relaxation Strength ◽  
Cooperative Dynamics ◽  
Β Relaxation

Abstract The frequency dispersion of structural α-relaxation obtained from broadband dielectric spectroscopy measurements is relatively narrow in many polar glass-formers. On the other hand, it becomes much broader when probed by other techniques, including photon correlation spectroscopy (PCS), nuclear magnetic resonance (NMR), and mechanical shear modulus. Therefore, the dynamics of glass-formers observed by dielectric permittivity spectroscopy (DS) is called into question. Herein we propose a way to resolve this problem. First, we point out an unresolved Johari-Goldstein (JG) β-relaxation is present nearby the α-relaxation in these polar glass-formers. The dielectric relaxation strength of the JG β-relaxation is sufficiently weak compared to the α-relaxation so that the narrow dielectric frequency dispersion faithfully represents the dynamic heterogeneity and cooperativity of the α-relaxation. However, when the other techniques are used to probe the same glass-former, there is a reduction of relaxation strength of α-relaxation relative to that of the JG β-relaxation. Additionally, the separation between the α and the JG β relaxations in dielectric permittivity) decreases when probed by mechanical shear modulus. These changes in relation of α- to JG β-relaxation, when examined by the other techniques, engender the non-negligible contribution of the latter to the former. Hence the apparent α-relaxation is broader than observed by the dielectric permittivity. The broadening is artificial because it is due to a confluence of the α and JG β relaxations with a disparity in their relaxation strengths much less when the other techniques than by dielectric permittivity are used. This explanation is supported by showing the α-relaxation of polar glass-formers becomes broader when the dielectric data are represented in terms of the electric modulus instead of permittivity. The broadening, in this case, is again due to a reduction of the relaxation strength of the α-relaxation relative to that of the JG β-relaxation in the electric modulus representation. A corollary of the explanation applicable to weakly polar glass-formers having JG β-relaxation widely separated from the α-relaxation is the prediction that the frequency dispersion of dielectric α-relaxation is nearly the same as that of the electric modulus, and there is no significant additional broadening when probed by the other techniques. A host of experimental data from the literature and our new measurements are given to support the explanation for polar glass-formers and the ancillary prediction for weakly polar glass-formers. Thus the narrow frequency dispersion of the intense relaxation in polar glass-formers observed by dielectric permittivity is real and genuinely represents the dynamically heterogeneous and cooperative dynamics of α-relaxation. By contrast, the broad dispersion found by the other techniques is artificial and misleading.

scholarly journals Enhancement of the Physical Stability of Amorphous Sildenafil in a Binary Mixture, with either a Plasticizing or Antiplasticizing Compound

Pharmaceutics ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 460
Author(s):  
Justyna Knapik-Kowalczuk ◽  
Krzysztof Chmiel ◽  
Justyna Pacułt ◽  
Klaudia Bialek ◽  
Lidia Tajber ◽  
...  
Keyword(s):  
Molecular Dynamics ◽  
Physical Stability ◽  
The Other ◽  
Recrystallization Process ◽  
Polymer Content ◽  
Molecular Motions ◽  
Constant Relaxation Time ◽  
High Concentrations ◽  
Amorphous Drug ◽  
The Impact

The main purpose of this paper was to evaluate the impact of both high- and low-Tg polymer additives on the physical stability of an amorphous drug, sildenafil (SIL). The molecular mobility of neat amorphous SIL was strongly affected by the polymeric excipients used (Kollidon VA64 (KVA) and poly(vinylacetate) (PVAc)). The addition of KVA slowed down the molecular dynamics of amorphous SIL (antiplasticizing effect), however, the addition of PVAc accelerated the molecular motions of the neat drug (plasticizing effect). Therefore, in order to properly assess the effect of the polymer on the physical stability of SIL, the amorphous samples at both: isothermal (at constant temperature—353 K) and isochronal (at constant relaxation time—τα = 1.5 ms) conditions were compared. Our studies showed that KVA suppressed the recrystallization of amorphous SIL more efficiently than PVAc. KVA improved the physical stability of the amorphous drug, regardless of the chosen concentration. On the other hand, in the case of PVAc, a low polymer content (i.e., 25 wt.%) destabilized amorphous SIL, when stored at 353 K. Nevertheless, at high concentrations of this excipient (i.e., 75 wt.%), its effect on the amorphous pharmaceutical seemed to be the opposite. Therefore, above a certain concentration, the PVAc presence no longer accelerates the SIL recrystallization process, but inhibits it.

Poly(methyl phenyl siloxane) in Random Nanoporous Glasses: Molecular Dynamics and Structure

2003 ◽  
Vol 790 ◽  
Author(s):  
Andreas. Schönhals ◽  
Harald. Goering ◽  
Christoph Schick ◽  
Bernhard. Frick ◽  
Reiner Zorn
Keyword(s):  
Molecular Dynamics ◽  
Neutron Scattering ◽  
Pore Size ◽  
Relaxation Times ◽  
Modulated Dsc ◽  
Length Scale ◽  
Molecular Motions ◽  
Temperature Modulated Dsc ◽  
Quasielastic Neutron ◽  
Methyl Phenyl

ABSTRACTThe effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel / Fulcher / Tammann like behavior to an Arrhenius one. At the same pore size Δcp vanishes. These results give strong evidence that the glass transition has to be characterized by an inherent length scale of the relevant molecular motions. Quasielastic neutron scattering experiments reveal a strong change even in the microscopic dynamic.

Dynamical Behavior and Flow Mechanism of Fluid in Nanochannel by Molecular Dynamics Simulation

2009 ◽  
Author(s):  
Juanfang Liu ◽  
Chao Liu ◽  
Qin Li
Keyword(s):  
Molecular Dynamics ◽  
Molecular Dynamics Simulation ◽  
Dynamical Behavior ◽  
Velocity Profiles ◽  
The Other ◽  
Dynamics Simulation ◽  
Nonequilibrium Molecular Dynamics ◽  
Interfacial Region ◽  
Flow Mechanism ◽  
Bulk Fluid

The flow properties and dynamical behavior of fluid in a nanochannel were investigated by nonequilibrium molecular dynamics simulation. First of all, the locale distribution of molecules in the channel is found to be strongly inhomogeneous compared to the bulk fluid. In the vicinity of the wall, portion of the fluid molecules are absorbed on the surface of wall due to the strong interaction of the atoms between the wall and liquid, so that the fluid density in the contact region would be much larger than one of the bulk fluid. But in the other region, the local density value approaches one of the bulk fluids with the increasing distance from the wall. This oscillatory behavior of density resulted in different motion behavior of molecules in the different region of nanochannel. The molecular behavior in the interfacial region is remarkably different from those of fluid atoms in the center of channel and wall atoms, which posses both the motion properties of bulk liquids and a solid atom. At the molecular level, macroscopic continuum hypothesis failed, that is, the results predicted by the Navier-Stoke equations deviate from the simulation data adopted by molecular dynamics simulation. In the paper, the velocity profiles for the channels with different width were plotted, which demonstrated that the time-averaged velocity profiles was not quadratic when the channel width was less than 10 molecular diameters. But on the other cases, the velocity profiles will agree well with the analytical solution based on the NS theory. The molecular dynamics simulation method can withdraw the important microscopical information from the simulation process, which benefit to analyze the flow mechanism at such length scale channel.

Pb-DOPING EFFECTS ON THE DIELECTRIC AND PYROELECTRIC PROPERTIES OF (Sr,Pb)TiO3 SYSTEM

2012 ◽  
Vol 02 (01) ◽  
pp. 1250005 ◽  
Author(s):  
Y. P. JIANG ◽  
X. G. TANG ◽  
Y. C. ZHOU ◽  
Q. X. LIU
Keyword(s):  
Dielectric Permittivity ◽  
Frequency Dispersion ◽  
X Ray Diffraction ◽  
Pyroelectric Properties ◽  
Doping Effects ◽  
Pyroelectric Sensors ◽  
Diffraction Patterns ◽  
Perovskite Type ◽  
Pb Doping ◽  
Perovskite Type Structure

Lead strontium titanate ( Sr 1-x Pb x) TiO 3 (0.20 ≤ x ≤ 0.45,step = 0.05) ceramics were prepared by conventional mixed oxide method. The X-ray diffraction patterns indicate that the prepared samples have perovskite-type structure. With the increase of Pb content, there is a tendency from the cubic to tetragonal structure. The scanning electron microscopy micrographs reveal that the addition of Pb can affect microstructure. The dependent temperature dielectric permittivity and dielectric loss were investigated in the frequency range from 100 Hz to 1 MHz. The maximum peak of the dielectric permittivity versus temperature curve was broadened and a frequency dispersion of the dielectric permittivity was observed for the (Sr0.8Pb0.2)TiO3 ceramics. The results obtained at the frequency of 10 kHz reveal the Curie temperature linearly increased with the lead content. The fitted curves of temperature versus inverse dielectric permittivity at 10 kHz for ( Sr 1-x Pb x) TiO3 ceramics are consistent with Curie–Weiss law. The Pyroelectric properties were also investigated. The high pyroelectric coefficients and figure of merits indicate that the SPT ceramics are potential materials for pyroelectric sensors.

scholarly journals Electrical Behaviour of Finely Divided Ice

1978 ◽  
Vol 21 (85) ◽  
pp. 173-191 ◽  
Author(s):  
J. G. Paren ◽  
J. W. Glen
Keyword(s):  
Relaxation Times ◽  
Surface Adsorption ◽  
Frequency Dispersion ◽  
Polar Regions ◽  
Electrical Behaviour ◽  
Heterogeneous Nature ◽  
Glacier Ice ◽  
Bulk Relaxation ◽  
Adsorption Of Co ◽  
The Mean

Abstract The electrical behaviour of ice which has been finely ground and compressed was investigated during ageing in air and over a range of temperatures. The dielectric behaviour may be accurately represented as the sum of two elliptical relaxation spectra. The behaviour eventually stabilizes with similar activation energies for the mean relaxation time of each spectrum c. 0.25 eV, and the ratio of the relaxation times is ten in samples of density c. 0.42 Mg m-3. Arguments are presented on whether the higher-frequency dispersion is a consequence of the heterogeneous nature of the samples or is a bulk relaxation process. The similarities between the behaviour of such finely ground ice and of deposited snow and polar glacier ice are discussed. The extent to which the results may be attributed to surface adsorption of CO2 are examined by reference to measurements of the CO2 content of finely divided ice and ice from polar regions.

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