Dynamic oscillatory shear tests are common in rheology and have been used to investigate a wide range of soft matter and complex fluids including polymer melts and solutions, block copolymers, biological macromolecules, polyelectrolytes, surfactants, suspensions, emulsions and beyond. More specifically, Small Amplitude Oscillatory Shear (SAOS) tests have become the canonical method for probing the linear viscoelastic properties of these complex fluids because of the firm theoretical background [1][2][3][4] and the ease of implementing suitable test protocols. However, in most processing operations the deformations can be large and rapid: it is therefore the nonlinear material properties that control the system response. A full sample characterization thus requires well-defined nonlinear test protocols. Consequently there has been a recent renewal of interest in exploiting Large Amplitude Oscillatory Shear (LAOS) tests to investigate and quantify the nonlinear viscoelastic behavior of complex fluids. In terms of the experimental input, both LAOS and SAOS require the user to select appropriate ranges of strain amplitude (γ 0 ) and frequency (ω). However, there is a distinct difference in the analysis of experimental output, i.e. the material response. At sufficiently large strain amplitude, the material response will become nonlinear in LAOS tests and the familiar material functions used to quantify the linear behavior in SAOS tests are no longer sufficient. For example, the definitions of the linear viscoelastic moduli G΄(ω) and G˝(ω) are based inherently on the assumption that the stress response is purely sinusoidal (linear). However, a nonlinear stress response is not a perfect sinusoid and therefore the viscoelastic moduli are not uniquely defined; other methods are needed for quantifying the nonlinear material response under LAOS deformation. In the present review article, we first summarize the typical nonlinear responses observed with complex fluids under LAOS deformations. We then introduce and critically compare several methods that quantify the nonlinear oscillatory stress response. We illustrate the utility and sensitivity of these protocols by investigating the nonlinear response of various complex fluids over a wide range of frequency and amplitude of deformation, and show that LAOS characterization is a rigorous test for rheological models and 3 advanced quality control.

The strongly enhanced cooperative influence of medium polarity and organic structural design on the first hyperpolarizability beta of a novel family of highly polarizable azinium-(CH=CH-thienyl)-dicyanomethanido chromophores 1-3 is described. The dyes can be efficiently synthesized by regioselective protonation/alkylation of the corresponding bidentate anion precursors. Consecutive annelation of the pyridyl ring of 1 (pyridine-->quinoline-->acridine) and medium polarity effects are responsible for an extraordinarily variable range of intramolecular charge transfer (ICT), leading to a large set of pi-electron distribution patterns. Accordingly, systems with remarkably different zwitterionic/quinoid character in the ground and excited states present beta values in a broad range, eventually switching from negative to positive. Our investigation is based on a combination of experimental (UV/Vis spectroscopy, multinuclear NMR spectroscopy, and electrooptical absorption measurements) and computational (ab initio) approaches. It is shown that: 1) beta and mubeta are dramatically influenced, even by orders of magnitude, by a complex, non-monotonic interplay of structure and medium action, which in turn affects molecular ICT and bond length alternation (BLA), 2) the computations, validated by different experimental data, are to be recommended as an extremely useful tool in the search for a greatly improved set of molecular nonlinear optical (NLO) responses (in the case of 1-3 they show that such conditions may be attained only in a narrow and limited range of dielectric constants in which the annelation effect operates most efficiently), and 3) the search for the most favorable molecular NLO response of a highly polarizable chromophore both in solution and in solid matrices should simultaneously take into account not only the molecular design supplemented by annelation effects but also the polarity of the medium.

Water-based dispersions and emulsions are used as model systems for a new rheological data analysis. The application of large amplitude oscillatory shear can be used to generate a high nonlinear response, which is analyzed by Fourier transform (FT)-rheology. The individual higher harmonics appearing in the shear stress response do not have a simple physical interpretation. Furthermore, in the FT analysis used so far the focus was mainly on the third harmonic relative to the fundamental I 3 /I 1 , even if multiple higher harmonics appear, as in the polystyrene dispersions examined here. As a consequence, we propose a new and simple method that considers the whole overtone spectra as a superposition of different overtone spectra of typical nonlinear rheological effects, like strain hardening, strain softening, and shear bands or wall slip. This novel analysis of FT-rheology experiments thus separates the nonlinear mechanical response into the underlying physical phenomena.

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Desalination of a sodium chloride solution is achieved by the incorporation of salt depleted water into an acrylic acid based hydrogel and the subsequent deswelling of the gel by mechanical force to gain water with a lower salt content. This is a new approach towards the problem of desalination of seawater that has, to the best of our knowledge, not been presented before. In a proof-of-principle experiment the salt content of a 10 g/L NaCl solution could be reduced by 35% in one cycle. The influence of main chemical parameters, e.g. degree of crosslinking, degree of neutralization and experimental parameters like particle size and salt concentration on the desalination process are examined. Possible optimum conditions for the desalination using a poly(acrylic acid) network are discussed and the construction of a simple apparatus for deswelling by mechanical force is described.

Poly(acrylic acid)‐based hydrogels can swell up to 100–1000 times their own weight in desalinated water due to osmotic forces. As the swelling is about a factor of 2–12 lower in seawater‐like saline solutions (4.3 wt% NaCl) than in deionized water, cyclic swelling, and shrinking can potentially be used to move a piston in an osmotic motor. Consequently, chemical energy is translated into mechanical energy. This conversion is driven by differences in chemical potential and by changes in entropy. This is special, as most thermodynamic engines rely instead on the conversion of heat into mechanical energy. To optimize the efficiency of this process, the degree of neutralization, the degree of crosslinking, and the particle size of the hydrogels are varied. Additionally, different osmotic engine prototypes are constructed. The maximum mean power of 0.23 W kg−1 dry hydrogel is found by using an external load of 6 kPa, a polymer with 1.7 mol% crosslinking, a degree of neutralization of 10 mol%, and a particle size of 370–670 µm. As this is achieved only in the first round of optimization, higher values of the maximum power average over one cycle seem realistic.

Here, the development of an adhesive is reported – generated via free radical polymerization – which can be degraded upon thermal impact within minutes. The degradation is based on a stimuli responsive moiety (SRM) that is incorporated into the network. The selected SRM is a hetero Diels‐Alder (HDA) moiety that features three key properties. First, the adhesive can be degraded at relatively low temperatures (≈80 °C), second the degradation occurs very rapidly (less than 3 min), and third, the degradation of the network can readily be analyzed and quantified due to its self‐reporting nature. The new reversible self‐reporting adhesion system is characterized in detail starting from molecular studies of the retro HDA reaction. Moreover, the mechanical properties of the network, as well as the adhesion forces, are investigated in detail and compared to common methacrylate‐based systems, demonstrating a significant decrease in mechanic stability at elevated temperatures. The current study thus represents a significant advance of the current state of the art for debonding on demand adhesives, making the system interesting for several fields of application including dental adhesives.

Reachability testing is an approach to verifying concurrent programs. During reachability testing, every partially ordered synchronization sequence of a program with a given input is exercised exactly once. In this paper, we present the design and implementation of a distributed reachability testing algorithm for a cluster of workstations. This algorithm allows different test sequences to be exercised concurrently by different workstations without any synchronization, and without any duplication of sequences among workstations. Dynamic load balancing is performed using a work‐stealing scheme. A novel aspect of this scheme is that work‐stealing requests progress in rounds. This round‐based structure identifies overloaded workstations to target for work stealing. Empirical studies show good speedup for four benchmark Java programs and one Lotos specification. Copyright © 2010 John Wiley & Sons, Ltd.