Comparison of methods for estimating continuous distributions of relaxation times

The nonparametric estimation of the distribution of relaxation times approach is not as frequently used in the analysis of dispersed response of dielectric or conductive materials as are other immittance data analysis methods based on parametric curve fitting techniques. Nevertheless, such distributions can yield important information about the physical processes present in measured material. In this letter, we apply two quite different numerical inversion methods to estimate the distribution of relaxation times for glassy \lila\ dielectric frequency-response data at 225 \kelvin. Both methods yield unique distributions that agree very closely with the actual exact one accurately calculated from the corrected bulk-dispersion Kohlrausch model established independently by means of parametric data fit using the corrected modulus formalism method. The obtained distributions are also greatly superior to those estimated using approximate functions equations given in the literature.Comment: 4 pages and 4 figure

Glassy dynamics in thin films of polystyrene

Glassy dynamics was investigated for thin films of atactic polystyrene by complex electric capacitance measurements using dielectric relaxation spectroscopy. During the isothermal aging process the real part of the electric capacitance increased with time, whereas the imaginary part decreased with time. It follows that the aging time dependences of real and imaginary parts of the electric capacitance were primarily associated with change in volume (film thickness) and dielectric permittivity, respectively. Further, dielectric permittivity showed memory and rejuvenation effects in a similar manner to those observed for poly(methyl methacrylate) thin films. On the other hand, volume did not show a strong rejuvenation effect.Comment: 7 pages, 7 figures. Phys. Rev. E (in press

Ion and polymer dynamics in polymer electrolytes PPO-LiClO4: II. 2H and 7Li NMR stimulated-echo experiment

We use 2H NMR stimulated-echo spectroscopy to measure two-time correlation functions characterizing the polymer segmental motion in polymer electrolytes PPO-LiClO4 near the glass transition temperature Tg. To investigate effects of the salt on the polymer dynamics, we compare results for different ether oxygen to lithium ratios, namely, 6:1, 15:1, 30:1 and infinity. For all compositions, we find nonexponential correlation functions, which can be described by a Kohlrausch function. The mean correlation times show quantitatively that an increase of the salt concentration results in a strong slowing down of the segmental motion. Consistently, for the high 6:1 salt concentration, a high apparent activation energy E_a=4.1eV characterizes the temperature dependence of the mean correlation times at Tg < T< 1.1T_g, while smaller values E_a=2.5eV are observed for moderate salt contents. The correlation functions are most nonexponential for 15:1 PPO-LiClO4, whereas the stretching is reduced for higher and lower salt concentrations. A similar dependence of the correlation functions on the evolution time in the presence and in the absence of ions indicates that addition of salt hardly affects the reorientational mechanism. For all compositions, mean jump angles of about 15 degree characterize the segmental reorientation. In addition, comparison of results from 2H and 7Li NMR stimulated-echo experiments suggests a coupling of ion and polymer dynamics in 15:1 PPO-LiClO4.Comment: 14 pages, 12 figure

History Memorized and Recalled upon Glass Transition

The memory effect upon glassification is studied in the glass to rubber transition of vulcanized rubber with the strain as a controlling parameter. A phenomenological model is proposed taking the history of the temperature and the strain into account, by which the experimental results are interpreted. The data and the model demonstrate that the glassy state memorizes the time-course of strain upon glassification, not as a single parameter but as the history itself. The data also show that the effect of irreversible deformation in the glassy state is beyond the scope of the present model. Authors' remark: The title of the paper in the accepted version is above. The title appeared in PRL is the one changed by a Senior Assistant Editor after acceptance of the paper. The recovery of the title was rejected in the correction process.Comment: 4 pages, 4 figure

Loading rate and contraction type effects on the human Achilles tendon force-elongation relationship

IntroductionWhile it is accepted that tendons are viscoelastic, the loading rate of contractions is often not strictly controlled when assessing human tendon mechanical properties in vivo. Given the potential benefits of sustained constant load isometric contractions for in vivo tendon property assessment, we aimed to determine if sustained submaximal isometric plantarflexion contractions result in a similar force-elongation relationshipand stiffness of the Achilles tendon (AT) to other loading methods.MethodsThe AT mechanical properties (elongation and stiffness) of the dominant leg inten male adults (26.5±5.5y) were assessed during isometric plantarflexion contractions by integrating dynamometry and ultrasonography (Aloka α7, Tokyo, Japan).Measurements were taken on two consecutive days and the results from all participants on day one and seven participants on day two (three excluded due to measurement problems) were pooled for the analysis. Maximum voluntary contractions (MVC; high loading rate), ramp maximum force contractions with three seconds loading (RAMP; lower loading rate), and sustained contractions (held for three seconds) at forces of 25%, 50% and 80% of the maximal tendon force with the lower loading rate (SUS) were conducted.ResultsA two way repeated measures ANOVA with method and tendon force level as factors revealed a significant method (P<0.001) effecton tendon elongation. Post hoc tests with Bonferroni corrections revealed significantlygreater tendon elongation in SUS compared withMVC (P=0.001) and RAMP(P=0.002),but no differences in tendon elongationbetween MVC and RAMP(P=0.077).A one way ANOVA with method as a factor did not reveal a significant method effect on tendon stiffness(P=0.079; MVC: 653.6±220.9 N/mm; RAMP: 694.8±190.3 N/mm; SUS: 564.2±148.1 N/mm).ConclusionSustained plantarflexion contractions appear to lead to an increased AT elongation for a given force, presumably due to the reduced influence of the loading rate on the viscoelastic behaviour of the tendon during the sustained contractions. However,AT stiffness was not significantly different between methods, suggesting that the differences in the rate of elongation occurred prior to the linear region of the force elongation relationship. Sustained isometric contractions appear to be appropriate for assessing AT stiffness in vivo, although potential differences in tendon elongation should be considered when comparing results with other methods

Extracting spectral density function of a binary composite without a-priori assumption

The spectral representation separates the contributions of geometrical arrangement (topology) and intrinsic constituent properties in a composite. The aim of paper is to present a numerical algorithm based on the Monte Carlo integration and contrainted-least-squares methods to resolve the spectral density function for a given system. The numerical method is verified by comparing the results with those of Maxwell-Garnett effective permittivity expression. Later, it is applied to a well-studied rock-and-brine system to instruct its utility. The presented method yields significant microstructural information in improving our understanding how microstructure influences the macroscopic behaviour of composites without any intricate mathematics.Comment: 4 pages, 5 figures and 1 tabl

Free volume dilatation in polymers by ortho-positronium

The possibility of positronium induced free volume cavity expansion in some polymers above the glass transition temperature was investigated using experimental positron annihilation lifetime data from the literature for polydimethylsiloxane, polyisobutylene, and polybutadiene as function of temperature. The results suggest that free volume sites can expand towards an equilibrium size, determined as the equilibrium Ps-bubble size defined earlier for low-molecular-weight liquids. The expansion can be explained by the increase of molecular mobility and hence decrease of relaxation times, which at the higher temperatures approach the o-Ps lifetimes. Nanoscale viscosities were estimated using Navier-Stokes equation and were found to be several orders of magnitude lower than the macroscopic viscosity at the same temperature

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.Comment: Phys. Rev. Lett. (in press

Loading rate and contraction duration effects on in vivo human Achilles tendon mechanical properties.

Tendons are viscoelastic, which implies loading rate dependency, but loading rates of contractions are often not controlled during assessment of human tendon mechanical properties in vivo. We investigated the effects of sustained submaximal isometric plantarflexion contractions, which potentially negate loading rate dependency, on the stiffness of the human Achilles tendon in vivo using dynamometry and ultrasonography. Maximum voluntary contractions (high loading rate), ramp maximum force contractions with 3 s loading (lower loading rate) and sustained contractions (held for 3 s) at 25%, 50% and 80% of maximal tendon force were conducted. No loading rate effect on stiffness (25-80% max. tendon force) was found. However, loading rate effects were seen up to 25% of maximum tendon force, which were reduced by the sustained method. Sustained plantarflexion contractions may negate loading rate effects on tendon mechanical properties and appear suitable for assessing human Achilles tendon stiffness in vivo

Additive Manufacturing and Performance of Architectured Cement-Based Materials

There is an increasing interest in hierarchical design and Additive Manufacturing (AM)of cement-based materials. However, the brittle behavior of these materials and the presence of interfaces from the additive manufacturing process represent the current major challenges. Our work focuses on harnessing the heterogeneous interfaces by employing clever designs from bio-inspired Bouligand architectured materials. In this paper, we aim to demonstrate some key mechanisms that can allow brittle hardened cement-based materials to gain flaw-tolerant properties. Mechanisms such as cracktwisting at the interfaces have been previously observed in naturally-occurring orsynthetic composite Bouligand architectures. In this paper, a heterogeneous interface with porous characteristics in 3D-printed solid hardened cement paste (hcp)architectures were characterized. We hypothesize that the presence of heterogeneous interface in 3D-printed hardened cement paste (hcp) elements, in conjunction with clever architectures, promote key damage mechanisms such as interfacial cracking and crack twisting that lead to damage delocalization. This delocalization can be energetically favorable and allow energy dissipation and promote toughening and flaw-tolerant properties. We found that these architectures can enhance the properties from the typical strength-porosity relationship, classically known for brittle hcp materials