Tage Emil Christensen

Time-Temperature Superposition in Viscous Liquids

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

Investigation of the shear-mechanical and dielectric relaxation processes in two monoalcohols close to the glass transition

Shear-mechanical and dielectric measurements on the two monohydroxy (monoalcohol) molecular glass formers 2-ethyl-1-hexanol and 2-butanol close to the glass-transition temperature are presented. The shear-mechanical data are obtained using the piezoelectric shear-modulus gauge method covering frequencies from 1 mHz to 10 kHz. The shear-mechanical relaxation spectra show two processes, which follow the typical scenario of a structural (alpha) relaxation and an additional (Johari-Goldstein) beta relaxation. The dielectric relaxation spectra are dominated by a Debye-type peak with an additional non-Debye peak visible. This Debye-type relaxation is a common feature peculiar to monoalcohols. The time scale of the non-Debye dielectric relaxation process is shown to correspond to the mechanical structural (alpha) relaxation. Glass-transition temperatures and fragilities are reported based on the mechanical alpha relaxation and the dielectric Debye-type process, showing that the two glass-transition temperatures differ by approximately 10 K and that the fragility based on the Debye-type process is a factor of 2 smaller than the structural fragility. If a mechanical signature of the Debye-type relaxation exists in these liquids, its relaxation strength is at most 1% and 3% of the full relaxation strength of 2-butanol and 2-ethyl-1-hexanol, respectively. These findings support the notion that it is the non-Debye dielectric relaxation process that corresponds to the structural alpha relaxation in the liquid.

beta relaxation of nonpolymeric liquids close to the glass transition

Dielectric beta relaxation in a pyridine-toluene solution is studied close to the glass transition. Loss peak frequency and maximum loss both exhibit thermal hysteresis. An annealing-state-independent parameter involving loss and loss peak frequency is identified. This parameter has a simple Arrhenius temperature dependence. The same behavior is found for four other viscous liquids, indicating that the phenomenon is possibly general.

A rheometer for the measurement of a high shear modulus covering more than seven decades of frequency below 50 kHz

A new rheometer is described. It consists of a transducer unit supplied with an electric impedance analyzing unit. The transducer unit converts a mechanical impedance into an electrical impedance by the piezoelectric effect. A detailed quantitative analysis of the interaction between the sample and the transducer is given. The real and imaginary parts of the shear modulus of a viscoelastic sample can be found in the frequency range of 1 mHz–50 kHz, modulus range of 0.1 MPa–10 GPa, and the temperature range of 150–300 K. The sample volume is 0.3 cm3 and the strain amplitude is exceedingly small. The small size of the transducer allows for good temperature control and equilibration. It has a simple construction based on inexpensive components. Results on the supercooled liquid 2‐metyl‐2,4‐pentandiol at the glass transition obtained by the method are included.

Supercooled Liquid Dynamics Studied via Shear-Mechanical Spectroscopy

We report dynamical shear-modulus measurements for five glass-forming liquids (pentaphenyltrimethyltrisiloxane, diethyl phthalate, dibutyl phthalate, 1,2-propanediol, and m-touluidine). The shear-mechanical spectra are obtained by the piezoelectric shear-modulus gauge (PSG) method. This technique allows one to measure the shear modulus (10(5)-10(10) Pa) of the liquid within a frequency range from 1 mHz to 10 kHz. We analyze the frequency-dependent response functions to investigate whether time-temperature superposition (TTS) is obeyed. We also study the shear-modulus loss-peak position and its high-frequency part. It has been suggested that when TTS applies, the high-frequency side of the imaginary part of the dielectric response decreases like a power law of the frequency with an exponent -1/2. This conjecture is analyzed on the basis of the shear mechanical data. We find that TTS is obeyed for pentaphenyltrimethyltrisiloxane and in 1,2-propanediol while in the remaining liquids evidence of a mechanical beta process is found. Although the high-frequency power law behavior w(-alpha) of the shear loss may approach a limiting value of alpha = 0.5 when lowering the temperature, we find that the exponent lies systematically above this value (around 0.4). For the two liquids without beta relaxation (pentaphenyltrimethyltrisiloxane and 1,2-propanediol) we also test the shoving model prediction, according to which the relaxation time activation energy is proportional to the instantaneous shear modulus. We find that the data are well described by this model.

Feasibility of a single-parameter description of equilibrium viscous liquid dynamics

Molecular dynamics results for the dynamic Prigogine-Defay ratio are presented for two glass-forming liquids, thus evaluating the experimentally relevant quantity for testing whether metastable-equilibrium liquid dynamics is described by a single parameter to a good approximation. For the Kob-Andersen binary Lennard-Jones mixture as well as for an asymmetric dumbbell model liquid, a single-parameter description works quite well. This is confirmed by time-domain results where it is found that energy and pressure fluctuations are strongly correlated on the alpha time scale in the constant-volume, constant-temperature ensemble; similarly, energy and volume fluctuations correlate strongly in the constant-pressure, constant-temperature ensemble.

Single-order-parameter description of glass-forming liquids: a one-frequency test.

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

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

\Lambda_{Tp}(\omega)

Mechanical spectra of glass-forming liquids. I. Low-frequency bulk and shear moduli of DC704 and 5-PPE measured by piezoceramic transducers

with the property that

A cryostat and temperature control system optimized for measuring relaxations of glass-forming liquids

\Lambda_{Tp}(\omega)=1