Mesoscale modeling of the rheology of pressure sensitive adhesives through inclusion of transient forces

For optimal application, pressure-sensitive adhesives must have rheological properties in between those of a viscoplastic solid and those of a viscoelastic liquid. Such adhesives can be produced by emulsion polymerisation, resulting in latex particles which are dispersed in water and contain long-chain acrylic polymers. When the emulsion is dried, the latex particles coalesce and an adhesive film is formed. The rheological properties of the dried samples are believed to be dominated by the interface regions between the original latex particles, but the relation between rheology and latex particle properties is poorly understood. In this paper we show that it is possible to describe the bulk rheology of a pressure-sensitive adhesive by means of a mesoscale simulation model. To reach experimental time and length scales, each latex particle is represented by just one simulated particle. The model is subjected to oscillatory shear flow and extensional flow. Simple order of magnitude estimates of the model parameters already lead to semi-quantitative agreement with experimental results. We show that inclusion of transient forces in the model, i.e. forces with memory of previous configurations, is essential to correctly predict the linear and nonlinear properties.Comment: 29 pages, 8 figure

Direct conversion of rheological compliance measurements into storage and loss moduli

We remove the need for Laplace/inverse-Laplace transformations of experimental data, by presenting a direct and straightforward mathematical procedure for obtaining frequency-dependent storage and loss moduli ($G'(\omega)$ and $G"(\omega)$ respectively), from time-dependent experimental measurements. The procedure is applicable to ordinary rheological creep (stress-step) measurements, as well as all microrheological techniques, whether they access a Brownian mean-square displacement, or a forced compliance. Data can be substituted directly into our simple formula, thus eliminating traditional fitting and smoothing procedures that disguise relevant experimental noise.Comment: 4 page

Cross-slot extensional rheometry and the steady-state extensional response of long chain branched polymer melts

Stress-optical measurements at a flow stagnation point in confined geometries such as the cross-slot provide an elegant way to perform extensional testing for polymer melts. This technique is especially useful for samples which have a steady-state that cannot be reached (easily) in standard elongational rheometry, for example, highly branched polymers which show a non-homogeneous deformation that occurs in stretching experiments for Hencky strains above 4. In contrast to filament stretching, the cross-slot provides one point at which steady-state extensional flow may be sustained indefinitely. In this study, a Cambridge multi-pass rheometer [ Coventry, K. D., and M. R. Mackley, J. Rheol. 52, 401–415 (2008) ] is used to generate planar elongational flow in a cross-slot geometry for different polyethylene melts. The experimental results are compared to finite element flow simulations using the multi-mode Pompom constitutive equations. The steady-state elongational viscosity at the stagnation point is computed from the flow-induced stress birefringence and the strain-rate determined from numerical calculations of the flow field. We apply this technique to a range of different branched high- and low-density polyethylene melts. This demonstrates both the effectiveness of this technique and shows how the stress distribution in a complex flow depends on molecular structure. Cross slot extensional rheometry therefore provides a very promising technique for parameterizing molecular constitutive equations for LCB melts

Transient overshoot extensional rheology of long-chain branched polyethylenes: Experimental and numerical comparisons between filament stretching and cross-slot flow

This work analyses the high-strain extensional behavior of long-chain branched polyethylenes, employing two novel extensional rheometer devices, the filament stretching rheometer and the cross-slot extensional rheometer. The filament stretching rheometer uses an active feedback loop to control the imposed strain rate on a filament, allowing Hencky strains of around 7 to be reached. The cross-slot extensional rheometer uses optical birefringence patterns to determine the steady-state extensional viscosity from planar stagnation point flow. The two methods probe different strain-rate regimes and in this paper we demonstrate the agreement when the operating regimes overlap and explore the steady-state extensional viscosity in the full strain-rate regime that these two complimentary techniques offer. For long-chain branched materials, the cross-slot birefringence images show a double cusp pattern around the outflow centre line (named W-cusps). Using constitutive modeling of the observed transient overshoot in extension seen in the filament stretching rheometer and using finite element simulations we show that the overshoot explains the W-cusps seen in the cross-slot extensional rheometer, further confirming the agreement between the two experimental techniques. © 2013 The Society of Rheology

Structure and dynamics of ring polymers: entanglement effects because of solution density and ring topology

The effects of entanglement in solutions and melts of unknotted ring polymers have been addressed by several theoretical and numerical studies. The system properties have been typically profiled as a function of ring contour length at fixed solution density. Here, we use a different approach to investigate numerically the equilibrium and kinetic properties of solutions of model ring polymers. Specifically, the ring contour length is maintained fixed, while the interplay of inter- and intra-chain entanglement is modulated by varying both solution density (from infinite dilution up to \approx 40 % volume occupancy) and ring topology (by considering unknotted and trefoil-knotted chains). The equilibrium metric properties of rings with either topology are found to be only weakly affected by the increase of solution density. Even at the highest density, the average ring size, shape anisotropy and length of the knotted region differ at most by 40% from those of isolated rings. Conversely, kinetics are strongly affected by the degree of inter-chain entanglement: for both unknots and trefoils the characteristic times of ring size relaxation, reorientation and diffusion change by one order of magnitude across the considered range of concentrations. Yet, significant topology-dependent differences in kinetics are observed only for very dilute solutions (much below the ring overlap threshold). For knotted rings, the slowest kinetic process is found to correspond to the diffusion of the knotted region along the ring backbone.Comment: 17 pages, 11 figure

i-Rheo: Measuring the materials' linear viscoelastic properties “in a step”!

A new analytical technique for determining a materials' linear viscoelastic properties from a simple step-strain measurement is reported. The technique avoids the need for idealisation of real measurements. The technique involves evaluating the Fourier transforms of raw experimental data describing both the time-dependent stress and strain functions. A comparison with conventional linear oscillatory measurements for a diverse range of complex materials is made and the technique is shown to be superior to existing linear oscillatory measurements in all cases

Scale-free static and dynamical correlations in melts of monodisperse and Flory-distributed homopolymers: A review of recent bond-fluctuation model studies

It has been assumed until very recently that all long-range correlations are screened in three-dimensional melts of linear homopolymers on distances beyond the correlation length $\xi$ characterizing the decay of the density fluctuations. Summarizing simulation results obtained by means of a variant of the bond-fluctuation model with finite monomer excluded volume interactions and topology violating local and global Monte Carlo moves, we show that due to an interplay of the chain connectivity and the incompressibility constraint, both static and dynamical correlations arise on distances $r \gg \xi$. These correlations are scale-free and, surprisingly, do not depend explicitly on the compressibility of the solution. Both monodisperse and (essentially) Flory-distributed equilibrium polymers are considered.Comment: 60 pages, 49 figure

Arrested spinodal decomposition in polymer brush collapsing in poor solvent

We study the Brownian dynamics of flexible and semiflexible polymer chains densely grafted on a flat substrate, upon rapid quenching of the system when the quality of solvent becomes poor and chains attempt collapse into a globular state. The collapse process of such a polymer brush differs from individual chains, both in its kinetics and its structural morphology. We find that the resulting collapsed brush does not form a homogeneous dense layer, in spite of all chain monomers equally attracting each other via a model Lennard-Jones potential. Instead, a very distinct inhomogeneous density distribution in the plane forms, with a characteristic length scale dependent on the quenching depth (or equivalently, the strength of monomer attraction) and the geometric parameters of the brush. This structure is identical to the spinodal-decomposition structure, however, due to the grafting constraint we find no subsequent coarsening: the established random bundling with characteristic periodicity remains as the apparently equilibrium structure. We compare this finding with a recent field-theoretical model of bundling in a semiflexible polymer brush.This work was funded by the Osk. Huttunen Foundation (Finland) and the Cambridge Theory of Condensed Matter Grant from EPSRC. Simulations were performed using the Darwin supercomputer of the University of Cambridge High Performance Computing Service provided by Dell Inc. using Strategic Research Infrastructure funding from the Higher Education Funding Council for England.This is the accepted manuscript. The final version is available at http://pubs.acs.org/doi/abs/10.1021/ma501985r