Unidimensional Approximation of the Diffuse Electrical Layer in the Inner Volume of Solid Electrolyte Grains in the Absence of Background Ions

In this paper we continue working on our theory of electrical double layers resulting exclusively from dissociation of a solid electrolyte, which we previously proposed as a medium for catalytic interaction between solid cellulose and solid acid catalysts of hydrolysis. Two theoretical unidimensional models of the inner grain volume are considered: an infinitely long cylindrical pore, and a gel electrolyte near a grain outer surface. Despite the model simplicity, the predictions for the cylindrical pore case are in semi-quantitative agreement with literature data on electroosmotic experiments, adequately explaining high proton selectivity of sulfonic membranes, and decline of such selectivity at high background acid concentration. The gel model predicts less concentrated diffuse layer in comparison to electrolytes with impenetrable skeleton (e. g., sulfonated carbons). This suggests limited suitability of gel electrolytes as catalysts if a substrate cannot diffuse into the gel bulk and the reaction is thereby spatially limited to the near-surface region, for example if a substrate is solid like aforementioned cellulose.     

A new instrument for measuring the viscoelastic properties of dilute polymer solutions

A new oscillating capillary viscometer has been developed and used for measuring viscoelastic flow properties of dilute polymer solutions. These flow properties are determined from measurements of the pressure to volume flow relationships for sinusoidal flow in cylindrical glass capillaries. The theory for this measurement procedure is based upon the known theory for oscillatory flow of a viscoelastic fluid in circular tubes and which is presented with a few supplementations in this paper.The oscillatory flow is generated by a piezoelectric driver which is dipped directly into the aqueous solution. The advantage of this driver is that the excitation voltage for the piston is a direct measure of the motion of the piston. Changes in pressure are measured with a sensitive low-pressure quartz tranducer.The viscometer was tested with aqueous glycerol solutions and a gelatin gel. The viscoelastic flow properties of dilute polymer solutions (gelatin, gelatin/color-coupler, polyacrylamide) were then investigated in the frequency range 5 Hz to 150 Hz at very small volume flow amplitudes. The results presented illustrate the suitability of the method. The results are also evaluated with regard to the stabilizing action of slightly viscoelastic gelatinous coating liquids in the high-speed coating process in the manufacture of photographic materials.     

The evolution of viscoelasticity near the gel point of end-linking poly(dimethylsiloxane)s

The linear viscoelasticity of polymers near the gel point can be described by two scaling laws. The material at the gel point has a power-law linear viscoelastic relaxation modulus, and the relaxation exponent has been found to vary with the composition of the precursor materials, i.e., it is not universal for gelation. A second scaling law describes the evolution of the linear viscoelastic properties through the gel point. The rate of change of the dynamic mechanical modulus/viscosity is observed to scale as a power-law function of frequency. This power-law function defines a dynamic critical exponent, and this has been found to be independent of precursor composition for end-linking poly(dimethylsiloxane) polymers and equal to κ = 0.21 ± 0.02. This exponent may be a universal measure of gelation. The technique of Time Resolved Mechanical Spectroscopy is used to observe the evolution of linear viscoelastic properties of crosslinking polymers in situ in the rheometer. A stretched exponential relaxation modulus describes the evolution of mechanical properties in the vicinity of the gel point very well. The exponents which characterize the divergence of the zero-shear viscosity and the equilibrium modulus are not universal, since they are related to the relaxation exponent and the dynamic critical exponent.     

Linear viscoelastic behavior of chitosan films as influenced by changes in the biopolymer structure

Films were prepared via solvent casting from different deacetylated and depolymerized chitosans obtained from β‐chitin. The linear viscoelastic behavior of the chitosan films was studied with uniaxial tensile stress–relaxation tests. All stress–relaxation profiles exhibited an asymptotically decaying trend, with a residual value different from zero, thus pointing out a solid‐like, viscoelastic behavior. The decay of the tensile modulus with time was phenomenologically described by a generalized Maxwell model consisting of three exponential functions and an equilibrium elastic modulus. Films prepared from chitosans with higher molecular weights showed higher residual elastic moduli and longer relaxation times. Within the range of the degrees of acetylation analyzed (0–27%), chitosans with the lowest and highest degrees of acetylation exhibited more pronounced solid‐like character. This behavior is explained on the basis of a complex balance between steric effects, types of intermolecular interactions, and aggregation of the chitosan samples. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1907–1915, 2007     

Effect of surface tension on the relaxation of a viscoelastic half-space perturbed by a point load

We study the effect of surface tension on the flattening of a surface perturbed by a point load subsequent to its removal. The surface bounds an infinite isotropic linear viscoelastic incompressible half space. The point load is initially applied for a sufficiently long time so that the half space is fully relaxed before the load removal. An exact solution is obtained assuming small deformation. We then specialize our theory to the case of a standard viscoelastic solid. There is an initial reduction of the surface displacement immediately after load removal that is found to be directly proportional to the ratio of applied load to surface tension. This is followed by a temporal decay of the surface profile that depends only on the relaxation time and the long and short time moduli of the viscoelastic solid. Our work also provides the Green's function for a suddenly applied point load on the surface of a viscoelastic half space. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 274–280     

A nonlinear uniaxial stress-strain constitutive model for viscoelastic membrane materials

Membrane materials with the excellent thermal, optical, electrical and chemical properties have attracted significant attention in numerous research fields recently. However, while being used to construct the membrane structures, the mechanical behaviors of membrane materials are more foundational than the other properties in evaluating the structure safety. This paper thus proposes a nonlinear stress-strain constitutive model for revealing the viscoelastic behaviors of membrane materials under uniaxial tensile loading. To this end, the constitutive equations for expressing the uniaxial tensile stress-strain relationships of viscoelastic materials are established gradually from the kinematic equations of the generalized Maxwell model that includes several basic Maxwell models and one basic spring element. Meanwhile, the uniaxial tensile tests of two typical viscoelastic membrane materials were carried out in order to examine the proposed constitutive model. The constitutive model parameters of the stress-strain properties of both membrane materials are accurately identified using the least square method. By comparing the true stress-strain curves between experimental results and constitutive models, good agreements with the maximum differences of 4.67% and 3.41% are acquired for the two employed viscoelastic membrane materials, respectively. These observations are able to validate the accuracy and efficiency of this proposed constitutive model in predicting the uniaxial stress-strain behaviors of viscoelastic membrane materials, which are significant in the nonlinear structural analysis of membrane structures.     

Viscoelasticity of mono- and polydisperse inverse ferrofluids

We report on measurements of a magnetorheological model fluid created by dispersing nonmagnetic microparticles of polystyrene in a commercial ferrofluid. The linear viscoelastic properties as a function of magnetic field strength, particle size, and particle size distribution are studied by oscillatory measurements. We compare the results with a magnetostatic theory proposed by De Gans et al. [Phys. Rev. E 60, 4518 (1999)] for the case of gap spanning chains of particles. We observe these chain structures via a long distance microscope. For monodisperse particles we find good agreement of the measured storage modulus with theory, even for an extended range, where the linear magnetization law is no longer strictly valid. Moreover we compare for the first time results for mono- and polydisperse particles. For the latter, we observe an enhanced storage modulus in the linear regime of the magnetization.     

Thermal expansion of a viscoelastic gel

It was previously shown [J. Non-Cryst. Solids, 130, 157 (1991)] that the permeability of a saturated gel can be determined from a measurement of its rate of expansion during a change in temperature. The existing analysis assumes that the solid network of the gel behaves elastically, but in many cases the gel is likely to be viscoelastic, especially when the gel exhibits syneresis. In this paper, the expansion kinetics are determined for a gel with a viscoelastic (VE) network. Sample calculations for a silica gel containing ethanol indicate that a naive application of the elastic analysis could result in errors exceeding a factor of two in the estimate of the permeability of a VE gel. However, in such cases, there are qualitative features in the experimental data that alert the experimenter to the existence of significant VE relaxation. Therefore, it is possible to avoid errors by careful examination of the data.     

Evidences of non-linear short-term stress relaxation in polymers

Back in 1986, investigating the Space Shuttle Challenger disaster, famous physicist Richard Feynman clearly showed how viscoelastic behavior of a polymeric material is of paramount importance in practical engineering. At present day a definitive universal rheological law is not yet available for polymers, as a consequence both theoretical models and experimental investigations of viscoelastic behavior must be necessarily focused independently on each single polymer or, at least, on well-defined classes of polymers. Accurate experimental evidences are needed in order to properly evaluate the mechanical properties of a polymeric material, as a function of its particular applications. In this paper measurements of the stress relaxation behavior of six polymeric materials under uniaxial tension and uniaxial unconfined compression tests, are performed and experimental results are modelled using a stretched exponential function, known as Kohlraush-Williams-Watts time-decay function. In particular the short-term stress relaxation is investigated, as a function of typical environmental temperature range, in order to assess viscoelastic behavior of tested polymeric materials for peculiar industrial and biomedical applications.     

New method to determine the viscoelastic properties of admicelles around the stick-slip transition

We report on a new method by which, for the first time, the viscoelastic properties of an adsorbed surfactant layer on a solid surface are measured. It is based on an analysis of the amplitude and the phase angle of the pressure fluctuations induced by a pulsating flow of a Newtonian surfactant solution through cylindrical pores. This method is subsequently used to determine the viscoelastic properties of an admicelle, formed when flushing surfactant solutions through nanopores, around the stick-slip transition. We find that the admicelle responds elastically for flow strengths below the transition and beyond the viscous. This is in agreement with the hypothesis formulated earlier (Cheikh, C.; Koper, G. J. M. Phys. Rev. Lett. 2003, 91, 156102).     

Physical gelation of binary mixtures of hydrocarbons mediated by n-lauroyl-L-alanine and characterization of their thermal and mechanical properties

Fatty acid amides, such as n-lauroyl-L-alanine, gelate both aliphatic and aromatic hydrocarbon solvents efficiently. In addition this compound is found to gelate the binary solvent mixtures comprised of aromatic hydrocarbon, e.g., toluene and aliphatic hydrocarbons, e.g., n-heptane. Scanning electron microscopy and atomic force microscopy show that the fiber thickness of the gel assembly increases progressively in the binary mixture of n-heptane and toluene with increasing percentage of toluene. The self-assembly patterns of the gels in individual solvents, n-heptane and toluene, are however different. The toluene gel consists of predominantly one type of morphological species, while n-heptane gel has more than one species leading to the polymorphic nature of the gel. The n-heptane gel is thermally more stable than the toluene gel as evident from the measurement using differential scanning calorimetry. The thermal stability of the gels prepared in the binary mixture of n-heptane and toluene is dependent on the composition of solvent mixture. Rheology of the gels shows that they are shear-thinning material and show characteristic behavior of soft viscoelastic solid. For the gels prepared from binary solvent mixture of toluene and n-heptane, with incorporation of more toluene in the binary mixture, the gel becomes a more viscoelastic solid. The time sweep rheology experiment demonstrates that the gel made in n-heptane has faster gel formation kinetics than that prepared in toluene.     

Predictive/fitting capabilities of differential constitutive models for polymer melts—reduction of nonlinear parameters in the eXtended Pom-Pom model

A phenomenological modification of the eXtended Pom-Pom (XPP) model is proposed with the aim to reduce the number of free nonlinear parameters. The modified XPP model includes three parameters per mode in total (two linear viscoelastic parameters—linear relaxation time λ and shear modulus G, and one nonlinear parameter). The original XPP model contains five parameters (two linear viscoelastic parameters and three nonlinear ones, one nonlinear parameter participates in the second normal stress difference prediction). The predictive/fitting capabilities of the modified model are compared with the Giesekus, eXtended Pom-Pom, and modified Leonov models using various low-density PE materials in steady and transient shear and uniaxial elongational flows. It has been found that the modified model is capable of predicting/fitting the rheological properties, with the exception of the second normal stress difference, for studied LDPE materials with sufficient accuracy, including strain hardening in uniaxial elongational flow.     

Relaxation of a viscoelastic gel bar: I. theory

When a rod of gel is deflected in 3-point bending, two types of relaxation process occur: hydrodynamic relaxation caused by flow of liquid within the gel network, and viscoelastic relaxation of the network itself. The kinetics of load relaxation have previously been analyzed for the case of hydrodynamic relaxation within a perfectly elastic network. That analysis describes, for example, the behavior of silica gel in a nonreactive solvent, such as acetone. When the liquid can attack the gel network, then true viscoelastic relaxation is superimposed on hydrodynamic relaxation, and that situation is examined in the present paper. To a very good degree of approximation, the total relaxation is equal to the product of the hydrodynamic and viscoelastic relaxation functions. In Part II, it will be shown that the present analysis describes the behavior of silica gel in an aqueous solvent and in an alcohol/amine solution.     

Thickness, stability and contact angle of liquid films on and inside nanofibres, nanotubes and nanochannels

While the stability of liquid films on substrates is a classical topic of colloidal science, the availability of nanostructured materials, such as nanotubes, nanofibres and nanochannels, has raised the question of how the stability of liquid films and their wetting behaviour is affected by nanoscale confinement. This paper will present the conditions for the stability of liquid films on and inside cylindrical solid substrates with nanometre scale characteristic dimensions. It is shown that the stability is determined by an effective disjoining/conjoining pressure isotherm which differs from the corresponding disjoining/conjoining pressure isotherm of flat liquid films on flat solid substrates. From the former, the equilibrium contact angles of drops on an outer or inner surface of a cylindrical capillary have been calculated as a function of surface curvature, showing that the expressions for equilibrium contact angles vary for different geometries, in view of the difference in thickness of the film of uniform thickness with which the bulk liquid (drops or menisci) is at equilibrium. These calculations have been extended to the case of glass nanocapillaries and carbon nanotubes, finding good agreement with experimental results in the literature.     

Flow,high-elastic (recoverable) deformation,and rupture of uncured high molecular weight linear polymers in uniaxial extension

The behavior of narrow molecular weight distribution polymers has been investigated under uniaxial extension at constant deformation rate and at constant stress. It has been established that up to rupture these polymers behave as linear viscoelastic bodies. A detailed investigation of the rupture phenomenon has shown that the rupture of fluid polymers is due to their transition to the rubbery state at critical deformation rates, with the result that they disintegrate like quasi-cured rubbers. The effect of the temperature and the molecular weight on the critical conditions of rupture has been described in terms of viscoelastic relaxation.     

Dielectric and Viscoelastic Study of Entanglement Dynamics: A Review of Recent Findings

This article gives a review of the results of recent dielectric and viscoelastic studies for entangled binary blends of linear cis-polyisoprenes to explain the current understanding of the equilibrium entanglement dynamics on the basis of the molecular picture of dynamic tube dilation (DTD). Comparison of dielectric and viscoelastic properties reveals that the full-DTD picture regarding the relaxed portions of the chains as a solvent fails for the high molecular weight component chain in the blends at intermediate times. This failure is related to insufficient constraint release (CR) equilibration of the entanglement segments of this chain. A partial-DTD picture properly considering this CR equilibration successfully describes the linear relaxation behavior of the blends. The dielectric and viscoelastic properties of PI under fast flow, being affected by the flow-activated CR/DTD mechanism, are also presented in order to demonstrate the usefulness of the comparison of these properties in both equilibrium and non-equilibrium states.     

Nonlinear evolution of thin liquid films dewetting near soft elastomeric layers

The nonlinear evolution of thin liquid films dewetting near soft elastomeric layers is examined in this work. Evolution equations are derived by applying the lubrication approximation and assuming that van der Waals forces in the liquid cause the dewetting and that the solid can be described as a linear viscoelastic material. Two cases are examined: (i) a liquid layer resting on an elastomer bounded from below by a rigid substrate, and (ii) an elastomer overlying a thin liquid film bounded from below by a rigid substrate. Linear stability analysis is carried out to obtain asymptotic relations which are then compared against solutions of the full characteristic equations. In the liquid-on-solid case, numerical solutions of the evolution equations show that van der Waals forces cause thinning of the liquid film and thickening of the elastomeric solid beneath film depressions. Inclusion of a short-range repulsive force suggests that regular patterns may form in which ridges of fluid rest on depressions in the solid. In the solid-on-liquid case, the van der Waals forces cause the solid layer to break up before the liquid film can dewet. The results presented here support the idea that the dewetting of thin liquid films might be exploited to create topographically patterned surfaces on soft polymeric solids.     

A slender-body micromechanical model for viscoelasticity of magnetic colloids: comparison with preliminary experimental data

The storage modulus, G', together with the yield stress, is an essential quantity characterizing the rheological properties of magnetic field-responsive suspensions (magnetorheological fluids or MRF). In this work, we present both experimental and theoretical results on the viscoelastic properties of MRFs. Two MRFs are used: In one the solid phase consists of cobalt ferrite particles + silica gel, with silicone oil as liquid phase. The second system is formed by carbonyl iron + silica gel also dispersed in silicone oil. The cobalt ferrite particles are synthesized as monodisperse colloidal spheres with an average diameter of 850 nm. We describe a new model based on the slender-body approach for hydrodynamic interactions. The predictions of the model are compared to preliminary experimental G' data obtained in a controlled stress plate-plate rheometer. It is found that the model gives the correct order of magnitude for the highest fields in iron suspensions, but underestimates the experimental results obtained in ferrite ones. In the case of high permeability materials such as carbonyl iron, by the inclusion of high-order multipolar interactions and saturation effects we also predict the order of magnitude of the experimental results. When dealing with low permeability cobalt ferrite based MRFs, other effects, such as remanence (at low fields) and saturation (at high fields), must be considered.