arXiv subjects

Niels Boye Olsen

Publications and source records attributed to Niels Boye Olsen.

At least 19 recordsLinked to original sources

arXiv2022

Rheological model for the alpha relaxation of glass-forming liquids and its comparison to data for DC704 and DC705

Dynamic shear-modulus data are presented for the two silicone oils DC704 and DC705 for frequencies between 1 mHz and 10 kHz at temperatures covering more than five decades of relaxation-time variation. The data are fitted to the alpha part of a phenomenological model previously shown to describe well the dynamic shear modulus of squalane, which has a large beta process [Hecksher \textit{et al.}, J. Chem. Phys. \textbf{146}, 154504 (2017)]; that model is characterized by additivity of the alpha and beta shear compliance and by a high-frequency decay of the alpha process in proportion to $ω^{-1/2}$ in which $ω$ is the angular frequency. The fits of the alpha part of this model to the DC704 and DC705 data are compared to fits by a Havriliak-Negami type model, the Barlow-Erginsav-Lamb model, and a Cole-Davidson type model. At all temperatures the best fit is obtained by the alpha part of the squalane model. This strengthens the conjecture that so-called $\sqrt{t}$-relaxation, leading to high-frequency decays proportional to $ω^{-1/2}$, is a general characteristic of the alpha relaxation of supercooled liquids [Dyre, Phys. Rev. E {\bf 74}, 021502 (2006); Nielsen \textit{et al.}, J. Chem. Phys. \textbf{130}, 154508 (2009); Pabst \textit{et al.}, J. Phys. Chem. Lett. \textbf{12}, 3685 (2021)].

cond-mat.soft↗

arXiv2017

Model for the alpha and beta shear-mechanical properties of supercooled liquids and its comparison to squalane data

This paper presents data for supercooled squalane's frequency-dependent shear modulus covering frequencies from 10 mHz to 30 kHz and temperatures from 168 K to 190 K; measurements are also reported for the glass phase down to 146 K. The data reveal a strong mechanical beta process. A model is proposed for the shear response of supercooled liquids. The model is an electrical equivalent-circuit characterized by additivity of the dynamic shear compliances of the alpha and beta processes. The nontrivial parts of the alpha and beta processes are represented by a "Cole-Cole retardation element", resulting in the Cole-Cole compliance function well-known from dielectrics. The model, which assumes that the high-frequency decay of the alpha shear compliance loss varies with angular frequency as $ω^{-1/2}$, has seven parameters. Assuming time-temperature superposition for the alpha and the beta processes separately, the number of parameters varying with temperature is reduced to four. From the temperature dependence of the best-fit model parameters the following conclusions are drawn: 1) the alpha relaxation time conforms to the shoving model; 2) the beta relaxation loss-peak frequency is almost temperature independent; 3) the alpha compliance magnitude, which in the model equals the inverse of the instantaneous shear modulus, is only weakly temperature dependent; 4) the beta compliance magnitude decreases by a factor of three upon cooling in the temperature range studied. The final part of the paper briefly presents measurements of the dynamic adiabatic bulk modulus covering frequencies from 10 mHz to 10 kHz in the temperature range 172 K to 200 K. The data are qualitatively similar to the shear data by having a significant beta process. A single-order-parameter framework is suggested to rationalize these similarities.

cond-mat.soft↗

arXiv2016

Thermalization Calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This "Thermalization Calorimetry" technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat conduction through an insulating material, i.e., is proportional to the temperature difference between sample and surroundings. The monitored signal reflects the sample's specific heat and is sensitive to exo- and endothermic processes. The technique is useful for studying supercooled liquids and their crystallization, e.g., for locating the glass transition and melting point(s), as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition.

cond-mat.soft↗

arXiv2015

Direct tests of single-parameter aging

This paper presents accurate data for the physical aging of organic glasses just below the glass transition probed by monitoring the following quantities after temperature up and down jumps: the shear-mechanical resonance frequency (around 360 kHz), the dielectric loss at 1 Hz, the real part of the dielectric constant at 10 kHz, and the loss-peak frequency of the dielectric beta process (around 10 kHz). The setup used allows for keeping temperature constant within 100 micro Kelvin and for thermal equilibration within a few seconds after a temperature jump. The data conform to a new simplified version of the classical Tool-Narayanaswamy aging formalism, which makes it possible to calculate one relaxation curve directly from another without any fitting to analytical functions.

cond-mat.soft↗

arXiv2012

Identical temperature dependence of the time scales of several linear-response functions of two glass-forming liquids

The frequency-dependent dielectric constant, shear and adiabatic bulk moduli, longitudinal thermal expansion coefficient, and longitudinal specific heat have been measured for two van der Waals glass-forming liquids, tetramethyl-tetraphenyl-trisiloxane (DC704) and 5-polyphenyl-4-ether. Within the experimental uncertainties the loss-peak frequencies of the measured response functions have identical temperature dependence over a range of temperatures, for which the Maxwell relaxation time varies more than nine orders of magnitude. The time scales are ordered from fastest to slowest as follows: Shear modulus, adiabatic bulk modulus, dielectric constant, longitudinal thermal expansion coefficient, longitudinal specific heat. The ordering is discussed in light of the recent conjecture that van der Waals liquids are strongly correlating, i.e., approximate single-parameter liquids.

cond-mat.soft↗

arXiv2010

Beta relaxation in the shear mechanics of equilibrium viscous liquids: Phenomenology and network modeling of the alpha-beta merging region

The phenomenology of the beta relaxation process in the shear-mechanical response of glass-forming liquids is summarized and compared to that of the dielectric beta process. Furthermore, we discuss how to model the observations by means of standard viscoelastic modeling elements. Necessary physical requirements to such a model are outlined, and it is argued that physically relevant models must be additive in the shear compliance of the alpha and beta parts. A model based on these considerations is proposed and fitted to data for Polyisobutylene 680.

cond-mat.soft↗

arXiv2010

Frequency Dependent Specific Heat from Thermal Effusion in Spherical Geometry

We present a novel method of measuring the frequency dependent specific heat at the glass transition applied to 5-polyphenyl-4-ether. The method employs thermal waves effusing radially out from the surface of a spherical thermistor that acts as both a heat generator and thermometer. It is a merit of the method compared to planar effusion methods that the influence of the mechanical boundary conditions are analytically known. This implies that it is the longitudinal rather than the isobaric specific heat that is measured. As another merit the thermal conductivity and specific heat can be found independently. The method has highest sensitivity at a frequency where the thermal diffusion length is comparable to the radius of the heat generator. This limits in practise the frequency range to 2-3 decades. An account of the 3omega-technique used including higher order terms in the temperature dependency of the thermistor and in the power generated is furthermore given.

cond-mat.soft↗

arXiv2008

Physical ageing studied by a device allowing for rapid thermal equilibration

Ageing of organic glasses to the equilibrium liquid state is studied by measuring the dielectric loss utilizing a microregulator where temperature is controlled by means of a Peltier element. Compared to conventional equipment the new device adds almost two orders of magnitude to the span of observable ageing times. Data for five organic glass-forming liquids are presented. The existence of an "inner clock" is confirmed by a model-free test showing that the ageing of structure is controlled by the same material time that controls the dielectric properties. At long times relaxation is not stretched, but simple exponential, and there is no "expansion gap" between the limits of the relaxation rates following up and down jumps to the same temperature.

cond-mat.soft↗

arXiv2007

Approximate square-root-time relaxation in glass-forming liquids

We present data for the dielectric relaxation of 43 glass-forming organic liquids, showing that the primary (alpha) relaxation is often close to square-root-time relaxation. The better an inverse power-law description of the high-frequency loss applies, the more accurately is square-root-time relaxation obeyed. These findings suggest that square-root-time relaxation is generic to the alpha process, once a common view, but since long believed to be incorrect. Only liquids with very large dielectric losses deviate from this picture by having consistently narrower loss peaks. As a further challenge to the prevailing opinion, we find that liquids with accurate square-root-time relaxation cover a wide range of fragilities.

cond-mat.soft↗

arXiv2007

Glass-forming liquids: One or more "order" parameters?

We first summarize the classical arguments that the vast majority of glass-forming liquids require more than one "order" parameter for their description. Critiques against this conventional wisdom are then presented, and it is argued that the matter deserves to be reconsidered in light of recent experimental developments. Out of the eight basic thermoviscoelastic frequency-dependent response functions, there are generally three independent functions. For stochastic dynamics we show that there are only two independent response functions; for this case it is shown how analytic continuation may be utilized to express the third response functions in terms of two others. Operational criteria are presented for the linear thermoviscoelasticity being described by a single "order" parameter, in which case there is just one independent thermoviscoelastic response function. It is shown that a single "order" parameter description applies to a good approximation whenever thermal equilibrium fluctuations of fundamental variables like energy and pressure are strongly correlated. Results from computer simulations showing that this is the case for a number of simple glass-forming liquids, as well as a few exceptions, are briefly presented. Finally, we discuss a new conjecture according to which experiments at varying temperature and pressure follow the density-scaling expression for the relaxation time, $τ=F(ρ^x/T)$ ($ρ$ and $T$ are density and temperature), if and only if the liquid is "strongly correlating," i.e., to a good approximation is described by a single "order" parameter.

cond-mat.soft↗

arXiv2007

Can the frequency-dependent specific heat be measured by thermal effusion methods?

It has recently been shown that plane-plate heat effusion methods devised for wide-frequency specific-heat spectroscopy do not give the isobaric specific heat, but rather the so-called longitudinal specific heat. Here it is shown that heat effusion in a spherical symmetric geometry also involves the longitudinal specific heat.

cond-mat.soft↗

arXiv2007

Conventional methods fail to measure c_p(omega) of glass-forming liquids

The specific heat is frequency dependent in highly viscous liquids. By solving the full one-dimensional thermo-viscoelastic problem analytically it is shown that, because of thermal expansion and the fact that mechanical stresses relax on the same time scale as the enthalpy relaxes, the plane thermal-wave method does not measure the isobaric frequency-dependent specific heat c_p(omega). This method rather measures a "longitudinal" frequency-dependent specific heat, a quantity defined and detailed here that is in-between c_p(omega) and c_v(omega). This result means that no wide-frequency measurements of c_p(omega) on liquids approaching the calorimetric glass transition exist. We briefly discuss consequences for experiment.

cond-mat.soft↗

arXiv2006

Elastic models for the non-Arrhenius viscosity of glass-forming liquids

This paper first reviews the shoving model for the non-Arrhenius viscosity of viscous liquids. According to this model the main contribution to the activation energy of a flow event is the energy needed for molecules to shove aside the surrounding, an energy which is proportional to the instantaneous shear modulus of the liquid. Data are presented supporting the model. It is shown that the fractional Debye-Stokes-Einstein relation, that quantitatively expresses the frequently observed decoupling of, e.g., conductivity from viscous flow, may be understood within the model. The paper goes on to review several related explanations for the non-Arrhenius viscosity. Most of these are also "elastic models," i.e., they express the viscosity activation energy in terms of short-time elastic properties of the liquid. Finally, two new arguments for elastic models are given, a general solid-state defect argument and an Occam's razor type argument.

cond-mat.soft↗

arXiv2004

A single-frequency test for one-parameter models of the linear thermo-visco-elastic response of glass-forming liquids

A master equation description of the inherent dynamics is used to calculate the frequency-dependent linear thermo-visco-elastic response functions of a glass-forming liquid. From the imaginary parts of the isobaric specific heat, isothermal bulk modulus, and isobaric thermal expansion coefficient, we define a quantity $Λ_{Tp}(ω)$ with the property that $Λ_{Tp}(ω)=1$ is equivalent to having a one-parameter description of the linear thermo-visco-elastic response. This provides an alternative to the well-known criterion based on the Prigogine-Defay ratio.

cond-mat.stat-mech↗

arXiv2003

Minimal model for beta relaxation in viscous liquids

Contrasts between beta relaxation in equilibrium viscous liquids and glasses are rationalized in terms of a double-well potential model with structure-dependent asymmetry, assuming structure is described by a single order parameter. The model is tested for tripropylene glycol where it accounts for the hysteresis of the dielectric beta loss peak frequency and magnitude during cooling and reheating through the glass transition.

cond-mat.soft↗

arXiv2003

Landscape equivalent of the shoving model

It is shown that the shoving model expression for the average relaxation time of viscous liquids follows largely from a classical "landscape" estimation of barrier heights from curvature at energy minima. The activation energy involves both instantaneous bulk and shear moduli, but the bulk modulus contributes less than 8% to the temperature dependence of the activation energy. This reflects the fact that the physics of the two models are closely related.

cond-mat.soft↗

arXiv2001

Testing models for structural relaxation of viscous liquids by temperature jump experiments

Based on the Tool-Narayanaswami formalism for structural relaxation we propose an experiment which independent of the relaxation time distribution determines the structural relaxation rate by subtracting relaxations following two different temperature jumps. In particular, the experiment makes it possible to evaluate the relaxation rate immediately following a temperature jump - thus allowing one to distinguish the entropy model from others.

cond-mat.soft↗

arXiv2000

Time-temperature superposition in viscous liquids

Dielectric relaxation measurements on supercooled triphenyl phosphite show that at low temperatures time-temperature superposition (TTS) is accurately obeyed for the primary (alpha) relaxation process. Measurements on 6 other molecular liquids close to the calorimetric glass transition indicate that TTS is linked to an $ω^{-1/2}$ high-frequency decay of the alpha loss, while the loss peak width is nonuniversal.

cond-mat.soft↗