Tribology Letters 3 (1997) 133^138

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Modeling the rheology of polymer solutions by dissipative particle dynamics

Y. Kong a , C.W. Manke a , W.G. Madden a and A.G. Schlijper b
a

Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI 48202, USA b Shell Research and Technology Centre Thornton, PO Box 1, Chester CH1 3SH, UK

Dissipative particle dynamics (DPD), a new simulation technique that focuses on intermediate time and length scales, is evaluated for systems in which polymers are used as viscosity index improvers. Model studies of simple non-Newtonian fluids show that DPD reveals the expected shear thinning. DPD solutions confined between solid surfaces, predict anisotropic conformational relaxation dynamics. In addition, the effects of thermodynamic solvent quality on the configurations and rheological behavior of dissolved polymers, essential to the performance of multigrade lubricants, are represented by the DPD model. Keywords: computer simulation, polymer solutions, polymer solution rheology, dissipative particle dynamics (DPD)

1. Introduction Dilute solutions of polymer additives in oil-based lubricants are of great utility as viscosity index (VI) improvers and as anti-wear additives. These applications depend not only on how the polymer affects the rheological properties of the bulk solution, but also ^ and perhaps more importantly ^ on how the solution behaves in very thin layers, when confined between lubricated surfaces. To design new polymers targeted at specific applications, it is necessary to understand the link between microscopic fluid characteristics (i.e. the detailed chemical structures of both the polymer and the base lubricant) and the macroscopic rheological and tribological behavior. Because the former involves distances at the atomic level and the latter time scales of mechanical motion e.g. in automobile engines, no single simulation method is adequate to this task. Traditional rheological simulations are based on continuum mechanics and focus on the longer time scales. The lubricant is represented as an undifferentiated substance whose properties enter the calculation as simple property parameters and as complex, empirical constitutive equations. The origin of these parameters and the form of constitutive equations is beyond the scope of the approach. At the other extreme, the molecular dynamics (MD) methods of chemists and physicists allow one to explore the motion of individual atoms and molecules by integrating Newton's equations of motion subject to realistic intermolecular forces. While some attempts have been made to apply the MD method to the dynamics of bulk polymer solutions, these have generally been limited to isolated studies on highly idealized molecules and require months of supercomputer CPU time to execute. Even so, they do not extend to time scales at which continuum mechanics simulations become applicable. The difficulty is that the time step in J.C. Baltzer AG, Science Publishers

ordinary MD is constrained to values much smaller than the shortest characteristic relaxation time of the smallest mobile entity in the system. For atoms, molecules or chemical groups, this is short indeed (measured in femtoseconds). If continuum mechanics simulations are thought to apply at some macroscopic level and MD simulation at a microscopic level, what is needed is an intermediate simulation method that operates at some mesoscopic level with its associated time scales. This is particularly important for polymer solutions, since a coarse graining in space and time that eliminates individual solvent molecules and their irrelevant short time scale motions does not eliminate the essential chain character of high molecular weight polymers. Indeed, nearly all approximate theories for the dynamics of polymers in solution are based on a mesoscopic viewpoint that dates to the classic theories of Rouse and Zimm [1,2]. In these theories, the solvent is represented as a continuum fluid but the polymer molecule is represented as an explicit chain, not of individual atoms or mers, but of ``blobs'' representing collections of mers. The problem with these approximate theories is that they are unable to properly incorporate the effects of neighboring velocity fields on one another or to include the presence of solid^fluid interfaces in a self-consistent fashion. In this work we investigate the applicability of a new mesoscopic simulation method, dissipative particle dynamics (DPD) [3,4], to polymer solutions of interest as lubricants. The level of coarse graining is such that atoms or mers are not represented individually, but are collected into more massive particles. For the polymer, these beads are the blobs of the standard classical theories, linked together into chains of appropriate topological character. For the solvent, they are collections of molecules analogous to the polymer blobs. Essentially these are local ``packets'' of fluid, able to move indepen-

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dently. They influence one another (and are influenced by the polymer beads) through a set of interaction rules guaranteed to give rise to the standard fluid mechanical equations of motion at sufficiently long times. The interactions are sufficiently soft and the density sufficiently high that there is substantial interpenetration of particles and near continuity of mass. The particles move by rules that are analogous to the simplest algorithms for ordinary molecular dynamics but use a time step that is two orders of magnitude larger. Complex velocity fields are represented by the local velocities of individual solvent or polymer particles. Only basic parameters are required, and no constitutive equations are needed. For application to polymer solutions, DPD employs a much more consistent coarse graining than has been used in the past. Unlike the standard theories, it is designed for numerical implementation and contains no approximations motivated by purely mathematical concerns inserted into the theory merely to produce an ultimately analytic equation. DPD is precisely the kind of mesoscopic theory required to bridge the gap between the molecular viewpoint and that of continuum mechanics. It fills an intermediate role in a hierarchy that starts with the quantum mechanics of individual molecules or a few molecules at a time. This effort predicts the intermolecular forces that serve as input to ordinary molecular dynamics for shorttime averaging and simple thermodynamics. The MD results are then mapped onto the parameters of DPD, which can in turn be used to suggest appropriate constitutive equations and transport parameters for introduction into macroscopic continuum mechanics simulations. In such a hierarchical approach, one may have full detail in the fundamental model without having to carry that detailed information along when it is no longer relevant at the time scales of interest. This enables one to envision the computer aided design of new lubricants in which molecular structure of the lubricant's constituents can be directly translated into the ultimate rheological and tribological consequences. If this scenario seems ambitious, it is also directly analogous to the computer design of drugs, which seemed equally ephemeral a mere 15 years ago. Today, computer design is standard practice in the pharmacological industry, not so much because these simulations unerringly predict the winning formulations, but rather because they focus expensive laboratory investigations on the most promising lines of research. The dissipative particle dynamics (DPD) technique, developed by Hoogerbrugge and Koelman [3], was motivated by the highly efficient lattice^gas automata methods for the simulation of complex fluid flow. DPD extends lattice^gas automata to motion of particles in continuous space, ensuring Galilean invariance and spatial isotropy. The motion of the DPD particles involves both stochastic and dissipative terms that guarantee evolution of the system toward equilibrium and long-term

consistency with macroscopic fluid mechanical equations of motion (see Bird et al. [5]). Because ineffectual high-frequency motion is eliminated, the DPD particles move relatively large distances in a single time step. As a result, the method probes long-time behavior two orders of magnitude more efficiently than ordinary MD [3]. It is easy to introduce bead-and-spring-type polymer chains into the basic simulation scheme, which results in a suitable model for a dilute polymer solution. Schlijper et al. [4] have examined the static and dynamic scaling relationships for this DPD polymer solution model. For athermal solutions at rest, they have shown that the dependence of both radius of gyration and relaxation times on molecular weight follow the classical Zimm model [1,2] closely. DPD has not yet been employed in realistic simulations of lubricating flows of fluids containing polymeric VI-improvers. However, a number of fundamental studies relevant to this objective have been performed. In what follows, we present features of the DPD polymer model that would be needed for realistic mesoscopic representations of lubrication flows. DPD predictions of bulk solution rheological properties are presented, and the ability of the model to represent rheological responses to solvent^polymer thermodynamic interactions is examined. Finally, the DPD representation of the static and dynamic behavior of linear polymer chains in the presence of confining walls is reviewed. Except for the confined chain study, the DPD simulations presented here are new calculations that have not been reported previously in the literature. Our purpose is to provide an overview of promising new results of DPD polymer simulations relevant to lubrication. Complete details of these simulations, which are far too lengthy to include in the present letter, will be presented in subsequent full-length publications. 2. Bulk rheological properties of polymer solutions Steady shear flow of solutions of rigid dumbbells models represents an important category of rheological behavior where both non-Newtonian viscosity and shear-thinning first normal stress behavior is known to occur, and where the stress tensor components have been predicted by standard kinetic theory [6]. Moreover, the rheological behavior of rigid dumbbell solutions is known to be sensitive to the presence of inter-bead hydrodynamic interaction. Thus the known kinetic theory results for this flow can serve as an important benchmark for comparison with DPD rheological predictions. Rigid dumbbells can be modeled by connecting pairs of DPD particles with a Fraenkel spring connector having a very large spring constant [4], which effectively constrains the DPD dumbbells to a fixed length. Viscosity predictions are shown in fig. 1 for DPD strong

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Fig. 1. Viscosity of DPD strong Fraenkel spring dumbbells is shown as a function of reduced shear rate. The case where the beads are separated by 1X0rc (rg 1) compares very well with the rigid rod kinetic theory predictions of Stewart and Sorensen [6] for the comparable case with interbead hydrodynamic interaction h 3a8. For reference, the kinetic theory case for h 0 (no hydrodynamic interaction) is also dis , 0 is the played. In the axes labels,  denotes viscosity at shear rate  viscosity at zero shear rate, and s is the viscosity of the solvent. ! is the principal relaxation time for the polymer in solution, measured at zero shear rate.

Fig. 2. First normal stress predictions for the cases shown in fig. 1. The DPD predictions for rg 1 are in very good agreement with the comparable rigid rod kinetic theory results for h 3a8. In the axes labels 21 is the first normal stress coefficient; other symbols are as defined in fig. 1.

Fraenkel spring dumbbells with radius of gyration rg 1X0rc , where rc is the interaction radius of the DPD particles forming the two beads of the dumbbell. Thus the calculations are performed for dumbbells with beads that are just touching each other. This corresponds to the case of complete hydrodynamic interaction in conventional polymer kinetic theory treatments, and Stewart and Sorensen [6] have made corresponding kinetic theory predictions for solutions of rigid dumbbells employing a hydrodynamic interaction parameter h 0X38. The DPD predictions for rg 1X0rc agree very well with the rigid dumbbell predictions for h 3a8. Comparison of the rigid dumbbell curves for h 0 (no hydrodynamic interaction) and h 3a8 shows that shear-thinning becomes less pronounced as hydrodynamic interaction increases. Hydrodynamic interaction is an intrinsic feature of the DPD polymer model, because the flow of the solvent is modeled explicitly. Variations of the first normal stress coefficient with shear rate are shown in fig. 2 for the same cases displayed in fig. 1. Like the rigid dumbbell kinetic theory, the DPD strong Fraenkel spring model predicts shear-thinning of 21 . The DPD results for rg 1X0rc are again very close to the rigid-dumbbell predictions for h 3a8. The excellent comparison of the DPD strong Fraenkel spring dumbbell with rg 1X0rc to the comparable Stewart and Sorensen rigid dumbbell with h 3a8 demonstrates that the rheological behavior predicted by DPD is directly comparable to results given by standard kinetic theory for a case where the model features are similar. Moreover, the comparison suggests that the

hydrodynamic interaction effects that emerge naturally from the explicit DPD representation of the solvent flow field are comparable to hydrodynamic interaction effects predicted by conventional bead^connector models, such as the rigid dumbbell kinetic theory, that model interbead hydrodynamic interaction through an Oseen tensor. These comparisons generally strengthen confidence in the rheological predictions of the DPD beadand-spring polymer model and provide a rational basis for extending DPD predictions to multi-bead polymer chains and other more realistic polymer architectures where direct comparisons with kinetic theory are not possible. 3. Effects of thermodynamic solvent quality In multigrad lubricants, the improvement with increasing temperature of the thermodynamic solvent quality of a base oil produces increased thickening power of dissolved polymeric VI improvers that partially counteracts the decrease in base oil viscosity with temperature. This increase in the thickening power of polymeric components arises from expansions of macromolecular configurations with increasing solvent power. These effects can be modeled in DPD simulations by modifying the repulsive interactions between solvent particles and polymer beads to make the repulsive forces either stronger (poor solvent case) or weaker (good solvent case) than repulsions between like particles. We have employed this DPD solvent^polymer interaction model to calculate the radius of gyration of chains of different length at different solvent qualities. The predicted scaling exponents for the variation of radius of gyration with

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Fig. 3. Simulation snapshot of instantaneous configuration of a ten-bead linear polymer in a sea of DPD solvent particles. Open circles denote the centers of solvent particles and filled circles denote beads of the polymer structure. The solid lines connecting polymer beads represent strong Fraenkel spring connectors. DPD interparticle repulsions between solvent particles and polymer beads have been set stronger than like-particles repulsions to represent the case of a poor solvent, which produces the tightly collapsed polymer configuration shown. The rectangular grid denotes the periodic box of the DPD simulation and its surrounding image boxes.

Fig. 4. Simulation snapshot of instantaneous configuration on the same ten-bead linear polymer solution depicted in fig. 3, but with DPD parameters set to model the good solvent case. Here the DPD interparticle repulsions between solvent particles and polymer beads are weaker than likeparticles repulsions, resulting in a favorable solvent^polymer interaction. Note that the polymer structure expands into the solvent under these conditions. (See fig. 3 for complete explanation of symbols and lines.)

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Fig. 5. Intrinsic velocity () of ten-bead linear polymer is shown as a function of shear rate  for the theta solvent and good solvent cases. The expanded configuration of the polymer in the good solvent produces higher intrinsic viscosity values. Intrinsic viscosity is reported in units of r3 c /particle, and shear rate is in inverse time step units. (The points at the lowest shear rates, near 0.0001, suffer high statistical uncertainty.)

chain is collapsed into a very tight configuration, in which thermodynamically unfavorable contacts between polymer chain beads and solvent particles are minimized. The good solvent case, fig. 4, produces a highly expanded chain configuration, in which contacts between the polymer chain beads and solvent particles, now thermodynamically favorable, are promoted. The effects of solvent-induced configurational changes on rheological properties are examined in figs. 5 and 6. The polymer in good solvent shows higher viscosities and higher first normal stress coefficients than the polymer in a theta solvent, where polymer^solvent repulsions are identical to solvent^solvent and polymer^polymer repulsions. (The poor solvent case leads to precipitation of high molecular weight polymers from solution, and is not shown here.) The expected shear-thinning behavior for both viscosity and first normal stress coefficient is observed in both solvents. 4. Dynamics of confined polymer chains The effect of wall confinement on the rheological properties of lubricant films with dissolved polymers is another key problem that can be approached by mesoscopic modeling. Here DPD is employed to examine the effect of wall confinement on the relaxation times of dissolved polymer solutes. In this study, mobile solvent and polymer particles are confined between two impenetrable walls made up of ``frozen'' (immobile) DPD particles. The roughness of these glassy walls is less than a single particle diameter. The effect of the confining walls on the conformation and dynamics of the chain becomes significant as the gap approaches the radius of gyration of the polymer chains in bulk solution. We have shown previously [8] that the behavior of

molecular weight vary from 0.32 for DPD poor solvents to 0.60 for DPD good solvents, values which are in nearly perfect agreement with known experimental and theoretical scaling behavior [7] for polymer solutions. Thus the DPD polymer solution simulations model polymer^solvent interactions with remarkable accuracy, even though DPD is not intrinsically a thermodynamic modeling technique. Figs. 3 and 4 illustrate the predicted effects of solvent quality on the configuration of a ten-bead linear polymer chain. In the case of the poor solvent, fig. 3, the polymer

Fig. 6. First normal stress coefficient 21 divided by polymer concentration & for a ten-bead linear polymer solution is shown as a function of shear rate for the theta solvent and good solvent cases. The first normal stress coefficient is higher for the good solvent case due to the expansion of the polymer chain in the solvent. (The points at the lowest shear rates, below 0.001, suffer high statistical uncertainty.)

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porated in hierarchical models for lubrication flow described by Coy [10]. 5. Conclusions We have investigated the applicability of dissipative particle dynamics (DPD) as a mesoscopic simulation tool for polymer solutions. From studies of model solutions, we find that it predicts shear thinning and changes in first normal stress consistent with known theory and available experimental data. We have demonstrated that the method can be used to study the changing effects of solvent quality on polymer dynamics in solutions. Finally, the dynamics of the chain in the vicinity of confining walls have been analyzed. In each case, DPD either predicts correctly the accepted results or provides the first calculation of any sort of the microscopic relaxation investigated. We conclude that DPD is a very promising simulation tool for polymer solutions that focuses directly on the length scales and time scales which are difficult to probe experimentally and which cannot be easily addressed by more conventional simulation tools. Acknowledgement The authors are grateful to Shell Research Ltd. for financial support of this work. References
[1] P.E. Rouse Jr., J. Chem. Phys. 21 (1953) 1272. [2] B.H. Zimm, J. Chem. Phys. 24 (1956) 269. [3] P.J. Hoogerbrugge and J.M.V.A. Koelman, Europhys. Lett. 19 (1992) 155. [4] A.G. Schlijper, P.J. Hoogerbrugge and C.W. Manke, J. Rheol. 39 (1995) 567. [5] R.B. Bird, W.E. Stewart and E.N. Lightfoot, Transport Phenomena (Wiley, New York, 1960). [6] W.E. Stewart and J.P. Sorensen, Trans. Soc. Rheol. 16 (1972) 1. [7] P.-G. de Gennes, Scaling Concepts in Polymer Science (Cornell University Press, Ithaca, 1979). [8] Y. Kong, C.W. Manke, W.G. Madden and A.G. Schlijper, Int. J. Thermophys. 15 (1994) 1093. [9] C.M. Lastoskie and W.G. Madden, in: Computer Simulation of Polymers, ed. R.J. Roe (Prentice Hall, Englewood Cliffs, 1991). [10] R.C. Coy, Modeling of boundary lubrication and its application to industrially important systems, Limits of Lubrication Conference, Williamsburg, 14^18 April 1996.

Fig. 7. Variation of principle relaxation time for parallel component of configurational autocorrelation function with gap dimension in 3D simulations of ten-bead chains. Principal relaxation time in parallel direction is scaled by its value in bulk solution, see Kong et al. [8].

the components of the radius of gyration of the polymer chain behave as expected as the gap decreases. DPD simulations of five- and ten-bead polymer chains show that the component of the radius of gyration in the direction perpendicular to the confining walls begins to collapse as the gap is reduced to about five times the unperturbed radius of gyration. The component of the radius of gyration parallel to the walls remains essentially unaffected by confinement, however, even when the gap approaches the unperturbed radius of gyration. This result is consistent with other statistical mechanical results from the literature [9]. What is new from the DPD simulations is the capability to analyze the dynamical response of the polymer chains to wall confinement, as well as the configurational response detailed above. This is accomplished by calculating the decay curve for a configurational autocorrelation function [3,7], which is initially equal to the square of the radius of gyration, and decomposing this decay curve into components representing the decay of configurational correlations in the directions parallel and perpendicular to the confining walls (see Kong et al. [8]). These decay curves are well represented as sums of exponentials, with each exponential decay contributing a characteristic relaxation time. Fig. 7 represents the behavior of the principal relaxation time for the decay of the perpendicular component of the configurational autocorrelation function for five- and ten-bead polymer chains. As the gap is decreased, a strong enhancement of this relaxation time is observed. This DPD-predicted effect has important consequences for the rheological behavior of thin lubricating layers that have been incor-