ABSTRACT
Anomalous aging in soft glassy materials has generated a great deal of interest because of some intriguing features of the underlying relaxation process, including the emergence of "ultra-long-range" dynamical correlations. An intriguing possibility is that such a huge correlation length is reflected in detectable ensemble fluctuations of the macroscopic material properties. We tackle this issue by performing replicated mechanical and dynamic light scattering (DLS) experiments on alginate gels, which recently emerged as a good model-system of anomalous aging. Here we show that some of the monitored quantities display wide variability, including large fluctuations in the stress relaxation and the occasional presence of two-step decay in the DLS decorrelation functions. By quantifying elastic fluctuation through the standard deviation of the elastic modulus and dynamic heterogeneities through the dynamic susceptibility, we find that both quantities do increase with the gel age over a comparable range. Our results suggest that large elastic fluctuations are closely related to ultra-long-range dynamical correlation, and therefore may be a general feature of anomalous aging in gels.
ABSTRACT
The effect of aging on the mechanical behaviour of ionically cross-linked alginate gels is studied in detail. Relaxation experiments upon both unconfined compression and torsion are performed on samples at different aging times. The elastic moduli of the gel are found to increase with the aging time, whereas the internal (constitutive) mechanism of the relaxation of the solid component of the gel is found to be unaffected by aging. It is demonstrated that the Linear Visco-Elastic Stress/Diffusion Coupling model [D. Larobina, F. Greco, J. Chem. Phys., 2012, 136, 134904], recently developed by two of the present authors, is able to quantitatively reproduce the experimental data for differently aged samples, at early-to-intermediate relaxation times. Moreover, it is shown that the gel always undergoes a spontaneous expulsion of water (syneresis) and some spontaneous deformation for a sufficiently long observation time, even in the absence of any externally imposed strain. The latter phenomenology progressively slows down with increasing of the gel age. By proper time shifting of the late relaxation decays, i.e., by properly defining an "effective time", master curves can be obtained in all cases, with all data pertaining to differently aged samples collapsing on a single relaxation law for each deformation history. The dependence of the shift factors on the aging time is found to follow a power law behavior, with an exponent of 1.39.
ABSTRACT
The mechanical behaviour of ionically cross-linked alginate gels is investigated here in detail. To determine the range of linear response of the materials, uniaxial, unconfined compression and torsional deformation experiments are performed, obtaining both the stress-strain and the viscoelastic behaviour of the gels. On-line measurements of the radii of the cylindrical gel samples in these experiments are also reported. The linearity range in the gel mechanical response is found to be rather limited, up to 6% strain, at most, contrary to more optimistic conclusions usually reported in the literature. We confirm the presence of a stress-diffusion coupling phenomenon in our alginates, i.e., the migration of water from/into the gels in response to the applied deformation. A phenomenon of inner (constitutive) relaxation of the network component of the gels is also clearly identified, and observed to occur, in parallel with solvent diffusion, upon compression. At sufficiently longer times after a deformation step, syneresis is always observed, with concomitant nonstandard viscoelastic effects, such as the growth of a normal force in torsion, and a size dependent decay of the longitudinal force in compression. We applied a two-fluid model, recently developed by two of the present authors [D. Larobina and F. Greco, J. Chem. Phys., 2012, 136(13), 134904], to simulate the relaxation tests upon torsional and compressive deformations, and to fit our own experiments. The model is found to well describe the coupling between constitutive relaxation and diffusion, and to reproduce the available force and radii data before the advent of syneresis.