Molecular constitutive equations for a class of branched polymers: The pom-pom polymer

T. C. B. McLeisha)

IRC in Polymer Science and Technology, Department of Physics and Astronomy, University of Leeds, Leeds LS2 9JT, United Kingdom
R. G. Larson

Department of Chemical Engineering, 2300 Hayward, University of Michigan, Ann Arbor, Michigan 48109-2136
(Received 27 May 1997; nal revision received 15 September 1997)

Synopsis
Polymer melts with long-chain side branches and more than one junction point, such as commercial low density polyethylene LDPE, have extensional rheology characterized by extreme strain hardening, while the shear rheology is very shear thinning, much like that of unbranched polymers. Working with the tube model for entangled polymer melts, we propose a molecular constitutive equation for an idealized polymer architecture, which, like LDPE, has multiple branch points per molecule. The idealized molecule, called a pom-pom, has a single backbone with multiple branches emerging from each end. Because these branches are entangled with the surrounding molecules, the backbone can readily be stretched in an extensional ow, producing strain hardening. In start-up of shear, however, the backbone stretches only temporarily, and eventually collapses as the molecule is aligned, producing strain softening. Here we develop a differential/integral constitutive equation for this architecture, and show that it predicts rheology in both shear and extension that is qualitatively like that of LDPE, much more so than is possible with, for example, the K-BKZ integral constitutive equation. 1998 The Society of Rheology. S0148-60559800401-5

I. INTRODUCTION Polymer melts with long-chain branching have rheological properties that differ distinctly from those of linear polymers or polymers with side branches too short to entangle with surrounding polymers Meissner 1972; Laun 1984; McLeish 1995; Larson 1988. For commercial polymer melts, such as polyethylene, these differences show up most strikingly in extensional ows. Melts such as low density polyethylene LDPE, which have multiple, irregularly spaced, long side branches, show a strain-hardening phenomenon in uniaxial extensional ow that differs qualitatively from the behavior of unbranched melts in similar ows. In shearing ows, however, the behavior of LDPE is highly strain-softening, not qualitatively different from the behavior of ordinary unbranched melts. The terms strain-hardening and strain-softening here refer to the behavior of the transient viscosities after start-up of ow. In this context, strain-hardening means that for strain rates in the nonlinear regime, the viscosity during the start-up rises above
a

Corresponding author.

1998 by The Society of Rheology, Inc. J. Rheol. 421, January/February 1998

0148-6055/98/421/81/30/$10.00

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the linear viscoelastic low-strain-rate response, while for strain-softening, the transient viscosity falls below that observed in the linear viscoelastic limit. Examples of strainhardening and strain-softening will be displayed in Secs. III and IV. Ordinary linear polymers typically show predominantly strain-softening characteristics in both shear and extensional ows, while long-chain branched melts are strain-hardening in uniaxial extensional ow and strain-softening in shear. The strain-hardening behavior of long-chain-branched polyethylenes is a desirable feature in certain processing ows dominated by extensional ow, such as ber spinning or lm blowing. If the melt is strain hardening, then regions of the melt that happen to become thinner, and therefore more highly strained, than surrounding regions, are able to support a higher force per unit area without undergoing run-away thinning or necking, leading to rupture. Since for other purposes related to the properties of the nal product long-chain branching is sometimes undesirable, optimal tailoring of branch content has become a major goal of the polyolen industry. Such tailoring may now be possible at the commercial scale, because of the development of metallocene catalysts Vega et al. 1996. It is thus crucial that the effects of long-chain branching on polymer melt rheology, especially extensional rheology, be understood and hopefully even predicted from molecular theory. One would ideally like to develop a constitutive equation relating stress to deformation history that somehow accounts for the effects of long-chain branching. Existing constitutive theories for polymer melt rheology have not really come to grips with the problem of long-chain branching, however. The most robust constitutive theory is the single integral model of K-BKZ type Kaye 1962; Bernstein et al. 1963; Wagner and Laun 1978, given by

dtm1tt, I1 ,I2B t , t m 2 t t , I 1 , I 2 C t , t .

Here B and C are the Finger tensor and the Cauchy tensor, with B C 1 for an incompressible melt. The tensor B is related to the deformation gradient tensor E by B ETE see standard treatments of nonlinear rheology, such as Larson 1988 or Tanner 1985. The invariants of the tensors B and C are given by I 1 trace( B) and I 2 trace( C). In the limit of small strains, for which I 1 I 2 3, the functions m 1 and m 2 reduce to functions of time only which must match the linear viscoelastic behavior; i.e., m 1 ( t t ,3,3) m 2 ( t t ,3,3) ( d / dt ) G ( t t ), where G ( s ) is the linear viscoelastic modulus. At higher strains, outside of the linear viscoelastic regime, the dependences of m 1 and m 2 on the invariants I 1 and I 2 become important and determine the strain-hardening or strain-softening character of the predicted response. The functions m 1 ( t t , I 1 , I 2 ) and m 2 ( t t , I 1 , I 2 ) can, in principle, be measured in step-strain experiments, or can be calculated from start-up experiments such as those mentioned above. Because of the dependences on two invariants, the degree of strain hardening predicted by the model can change from one type of deformation to another, for example from shear to uniaxial extension. For a shearing deformation, I 1 I 2 identically, while for uniaxial extension, I 1 becomes much greater than I 2 for large deformations. Thus, by judiciously choosing dependences of the K-BKZ strain measure on I 1 and I 2 it is possible to t simultaneously highly strain-softening behavior in shear, and highly strain-hardening behavior in uniaxial extension. See, for example, Wagner et al. 1979. However, for planar extension, as for simple shear, I 1 I 2 . This implies that while the strain softening or hardening character of uniaxial extension can in principle diverge arbitrarily far from that in

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simple shear, the behavior in planar extension is of necessity linked to that of simple shear, for the K-BKZ model Samurkas et al. 1989. Thus, although the K-BKZ equation is very exible in its ability to t simultaneously differing ow characteristics as one changes from one type of ow to another for a given material, it is not innitely exible. In particular, when the K-BKZ kernel functions are obtained by tting the highly strain softening behavior in shear, they fail to predict the highly strain-hardening response seen in planar extension for LDPEs. The planar extensional viscosities have been measured for two different long-chainbranched polyethylenes, in one case by Laun and Schuch 1989 and the other by Meissner 1996. For both materials, the dominant planar extensional viscosity was found to be highly strain hardening, nearly as much so as the viscosity in uniaxial extension. As discussed by Samurkas et al. 1989, the K-BKZ equation fails to predict the observed degree of strain hardening in planar extension when the kernel functions are adjusted to t the observed degree of strain softening in shear. This failure of even so robust a model as the K-BKZ equation to describe the rheology of long-chain branched polymers suggests that some new molecular insight is needed into the nonlinear relaxation processes that occur in such melts under ow. The development of a realistic molecular theory for commercial LDPE melts is, however, a daunting task. The branching structures in typical LDPEs are topologically and geometrically irregular, and molecular weights are very polydisperse. Thus, a quantitative molecular theory for commercial branched polymers is at present out of reach. The best way forward would therefore seem to lie in the development of a molecular constitutive theory for the nonlinear rheological properties of an idealized branched melt, one that is simple enough to consider theoretically, but still having the generic properties of LDPEin particular the strain hardening in extension and strain softening in shear. The most important aspect of the branching structure of such molecules is the presence of multiple branch points on the same molecule. Because of the multiple branch points, there are molecular strands that lie between two branch points and hence have no free ends. As described in the following, we believe that such molecular strands produce the strain hardening properties of multiply branched melts such as LDPE in extensional ows. Such molecules differ in a signicant way from molecules with a star architecture; stars have only a single branch point, and each arm of the star has a free end. Under ow, the free end allows the branch to retract quickly, and hence large stresses cannot readily build up. Star architectures are therefore too simple to produce the strain hardening seen in LDPE. The simplest architecture that has a molecular strand with no free end is one with just two branch points. This architecture is therefore the simplest one that might produce the nonlinear rheological characteristics of commercial long-chain branched polymers such as LDPE. II. MOLECULAR RHEOLOGY OF THE POM-POM POLYMER The class of branched polymers chosen for this study can be thought of as a generalization of the H-polymer structure Roovers 1984, McLeish 1988. The molecules contain just two branch points of chosen functionalitya backbone links two pompoms of q arms each see Fig. 1. The attraction of this family of polymers is that the parameter space describing molecular structure is sufciently large to be interesting: variables are the molecular weight of the backbone M b , molecular weight of the arms M a , and the number of arms on each branch point q . The entanglement molecular weight M e is another important molecular parameter, but will serve only as a scale for

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FIG. 1. The structure of a pom-pom polymer with a backbone and 2 q dangling arms, with q 3, under various degrees of stretch. The stretch of the backbone is denoted by the variable ( t ), the path length of arm withdrawn into the backbone tube by the variable s c ( t ).

polymer molecular weight so that we dene the dimensionless partial molecular weights s a M a / M e and s b M b / M e . The quantities s a and s b are also measures of the entangled path lengths of the arms and backbone, respectively. On the other hand, the symmetry of the structure, and the separation of timescales between the backbone and the arms see below will permit a tractable constitutive formulation, valid for an interesting range of shear rates. In this section we introduce the physical features of the model with reference to existing theoretical and experimental work on well-characterized branched polymers. We will see that the structure is indeed complex enough to exhibit the special nonlinear rheology of branched polymers. This is suggested by the application of the tube model Doi and Edwards 1986 to branched polymers: we recall that in this theoretical model of the dynamics of entangled polymers the topological constraints of any given chains neighbors are assumed to be represented by a conning tube along the chain contour. Perpendicular to the tube axis, a chain segment is not permitted to move more than the tube diameter, a , but parallel to the tube a linear polymer chain may freely diffuse and thereby move its center of mass reptation. It may also contract by virtue of its entropic elasticity following an imposed stretch retraction. However in the case of a branched polymer such as the pom-pom, the strand between the two branch points is not free to retract within its tube after a step strain as freely as a chain with a free end. This leads to less strain-softening than in linear polymers, and in particular was shown for the H-architecture to lead to extension-hardening McLeish 1988. In conrmation of the prediction that it is material between branch points that gives rise to the special rheological properties of branched polymer melts, the nonlinear rheology of simple star polymers follows closely that of linear melts Fetters et al. 1993. A. Branch point withdrawal Of course the resistance to retraction in a ow cannot be unlimited even in a highly branched polymerotherwise the response would be that of a network. Fortunately the

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tube model provides a mechanism which naturally limits the curvilinear stretch any segment can support. Once the constraints on every chain by its neighbors are modeled by a tube along its contour of diameter a , the requirement that Gaussian chain statistics are maintained in equilibrium implies a net Brownian force on every free chain end of magnitude kT / a , tending to maintain the curvilinear path of the chain segment within its tube. This means that, for the q 3 pom-pom polymer of Fig. 1, the backbone may be stretched by the three free ends until it sustains a curvilinear tension of 3 kT / a . Since all segments share the same equilibrium tension, this amounts to a maximum allowed stretch of three the primitive path occupied by the backbone segment may be no longer than three times its equilibrium length. Beyond this, the tension in the backbone is sufcient to withdraw the free ends into the tube originally occupied by the backbone see Fig. 1c. This is not prohibited sterically since tube diameters are always much larger than monomer dimensions. Neither are there density nonuniformities penalizing the process, as conjectured to occur in reptation for very high molecular weight polymers Semenov 1997. This is because in a given tube volume there are many of order N 3/2 e / N pompom molecules. Any mismatch between the number of dangling ends leaving and entering the volume may be accommodated by local elastic strain of the entanglement network at an energy cost kT . An alternative way of explaining the effect is to employ an entropy balance: eventually it becomes less costly to lose entropy in the free ends by withdrawing them all into the same contour tube than to lose it by continuing to stretch the backbone and thereby to restrict its own conguration space. This new effect of branch point withdrawal has been used recently to calculate damping functions for a range of molecular topologies Bick and McLeish 1996. The mechanism of branch point withdrawal introduces in a natural way two important dynamical variables which will be necessary to include in any molecular constitutive formulation. The rst of these is the dimensionless stretch ratio, , of the path length of the backbone to its equilibrium length. The second is the path length of arm which is forced to adopt a conguration set by the backbone orientation along with a similar section of all other attached arms due to withdrawal of the branch point along the tube. The latter we measure in units of the tube diameter and denote by s c so that 0 s c M a / M e . Partially withdrawn congurations such as that of Fig. 1 may occur during continuous deformation as well as after a step strain, so both and s c are functions of time. The use of a single stretch parameter for the entire backbone is justied because any local uctuations in stretch very rapidly equilibrate on timescales on the order of the Rouse time of the backbone. As we will see below, these timescales are much shorter than those of rheological interest. The stretch and withdrawal play complementary roles: the congurational entropy balance means that s c 0 whenever q but s c assumes its own dynamics when the ow history is such that q , its maximum value. Conversely we will nd that whenever s c is nonzero the stretch of the backbone is xed at q . The conclusion is that in a general dynamical history at any one time either or s c is changing with time, but not both. We will see that the role of the congurational changes set by s c is to change the effective relaxation times of stretch and orientation of the backbone. In this way the molecules avoid in a natural way the innite extension in elongational ows predicted for Gaussian chains or dumbbells with xed friction. We now turn to the linear stress relaxation of the pom-pom model to see how the various relaxation times arise. B. Linear stress relaxation Before proceeding to general nonlinear deformations, we need to derive the consequences of the tube model for the linear stress relaxation of a pom-pom melt and deduce

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the congurational relaxation times of the various parts of the molecule. The tube model implies no extra terms in the expression for the stress of a polymeric uid than those arising from the rubber-elastic orientational entropy of the chain segments Doi and Edwards 1986. So each segment of a polymer melt contributes to the stress with a time dependence that reects exactly its orientational relaxation. Because the orientation of a segment is in turn constrained by the orientation of the tube segment it occupies, the orientational relaxation times are just the characteristic times for chain ends to visit the corresponding tube segments and thereby destroy all memory of their constraints. We consider how an ensemble of mutually entangled pom-pom polymers recongure the orientations of their segments at t 0 by escaping from their original tube constraints. The rst consequence of the tube model for these branched polymers is that, at early times, the backbone segments do not relax at all beyond the conned motion within the tubesthe branch points are effective pinning points under innitesimal deformation as observed above and therefore no free ends have access to backbone segments. So at rst all relaxation is conned to the arms. These behave in a similar manner to a melt of entangled star polymers, in which it is now well established that tube segments are lost by deep retractions or breathing modes of the arms. These occur by the random formation of unentangled loops Helfand and Pearson 1983 which become exponentially more rare as their size increases. A consequence of this is that the very rapidly relaxing segments at the extremities of the arms behave as unentangled solvent at the longer timescales characterizing the relaxation of segments nearer the branch point Ball and McLeish 1989, Milner and McLeish 1997. This has a very strong accelerating effect on the distribution of timescales for relaxation along the star arms, modifying the result for star arms in a xed tube:

x 0 exp
into the result for a melt of pure stars:

15 4 sa sa 2

1x 2

x 0 exp

15 4

1x 2

1x 3

In both these cases ( x ) is the relaxation time of a tube segment a fraction x from the branch point to the free end. The constant 0 is an attempt time for deep retractions of the entangled dangling arm. In fact 0 carries an additional weak x dependence which has recently been calculated Milner and McLeish 1997 but this is not relevant to the backbone relaxations central to this work. The enormous effect of the cooperative relaxation of the starlike arms can be seen in the different predictions for the terminal times of the modied and unmodied expressionsthe former is faster by a factor of exp(15/12) s a . In the melt of pom-pom polymers, the free arms relax as if they were in a melt of star polymers with the same molecular weight of arms except for one aspectthe backbones remain part of an effective network throughout the relaxation process of the arms, and so give a spectrum of relaxation times for the star arms intermediate to the two extreme forms above. The calculation is equivalent to the case of a blend of star polymers with very long linear polymers studied by McLeish and OConnor 1993. In this case the fraction of effectively xed backbone material b enters into the expression for the pom-pom arm relaxation time spectrum, a ( x ), in a natural way:

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87

ax 0 exp

15 4 sa

1x 2

1b

1x 3

This prediction has been checked recently both in the case of a star-linear blend and for a monodisperse H-polymer Allgaier et al. 1997. The relaxation of occupied tube segments for timescales less than and including a (0) can now be written as a simple integral over the arm segments, with a xed backbone. Following the quadratic dependence of the modulus on concentration of oriented polymer segments, we nd in this regime of timescales: Gt G0 b1b

et/axdx .

Before proceeding to the slower viscoelastic modes originating from the backbones, it is worth noting in anticipation that the exact form of 4 of the distribution of arm relaxation times is not at all essential to the nonlinear rheological properties that are our main concern. The important property of this fast regime of the relaxation spectrum is that the segmental relaxation times should decay rapidly from the branch point towards the free ends of the arms. This requirement is certainly met by the particular exponential form of 4 predicted by the tube model. The physical picture of the pom-pom polymer at timescales longer than the maximum orientational relaxation time of an arm is quite different from the star-arm dynamics outlined above, although it is consistent with it. Now the backbones themselves are the dynamical objects, and all arm material behaves as solvent because of its much more rapid dynamics. The backbones therefore diffuse by reptationthe polymers are now effectively linear objects. However, the tube diameter is larger than it is at high frequency: the only entanglements that are effective in constraining the backbone are those with other backbones, so that the effective number of entanglements along the backbone becomes s b b . This argument was advanced some time ago to explain early rheological data on H-shaped polystyrene melts McLeish 1988 and has been conrmed in recent experiments Allgaier et al. 1997. There is one further difference between the reptation of the pom-pom backbones and that of ordinary linear polymers: in the case of the branched polymers at long times all of the effective friction to curvilinear motion is located at the branch points rather than distributed along the chain. We can see this by calculating the diffusion constant of one of these branch pointsafter a time a (0) the branch point has moved within the constraining tube typically the distance of the tube diameter itself it might be guessed that the diffusive step would explore typically the dilated tube, but here we take a model for the branch point diffusion which relies on the residence time of the completely retracted state, which is much shorter than the terminal time for the arm at which dilation is valid, so a 2 2 D c a (0). Using an Einstein argument and requiring that the drag on a branch point increases linearly with the number of arms q gives a branch-point friction constant b of:

kT Dc

2kT

a0
a2

q.

This is exponentially dependent on the arm molecular weight, whereas the contribution to the total friction of the backbone from the backbone monomers themselves is linear in the backbone molecular weight. The characteristic time for orientational relaxation of the backbone material, b , is therefore the diffusion time of a one-dimensional walker of

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diffusion constant D c /2 there are two branch points on the backbone to traverse a mean square distance of the dilated primitive path between the branch points, L 2 . Assuming the inverse proportionality of the entanglement molecular weight on the concentration of entangled strands which is b in our case, we have effective values for the dilated tube 1/2 2 2 diameter and primitive path of a eff a and s beff s b b so that L 2 s beff a eff b 2 2 a bsb. The nal result for the backbone relaxation time, b , is:

s2 bba0q.

The prefactor, as in the standard reptation theory, comes from the solution of the onedimensional diffusion equation with absorbing boundaries at either end of the linear domain see Appendix A. We could carry the theory of the linear relaxation spectrum to greater renement by including the full reptation spectrum of modes, and incorporating the effect of orientational relaxation by path length uctuation of the backbone. In fact this is done elsewhere in a discussion of experimental results on the H-polymer McLeish 1988, Allgaier et al. 1997. For the purpose of this exercise, which is to develop a workable constitutive equation for this class of polymers in nonlinear ows, it will be sufcient to assign a single relaxation time to the backbone material, so that the full relaxation modulus becomes: Gt G0 bet/b1b

et/axdx .

C. Slow-mode restriction and expression for the stress We will assume that the stress may be calculated as a function of molecular orientation and, as is standard in the tube model, that this in turn may be calculated from the orientation distribution of occupied tube segments Doi and Edwards 1986. For ordinary linear polymers whose distribution of tube-segment orientations u is known, and which are not stretched beyond the equilibrium contour length of chain per tube segment, the stress tensor may be written:

15 4 G0uu ,

where the angular brackets denote an average over the orientation distribution. As usual it is the second moment of the orientation distribution function that governs the stress. At this point we observe that the wide separation of timescales between the spectrum of arm relaxations and the backbone relaxation means that a wide range of deformation rates, 1 1 , give rise to nonlinear response and therefore have Weissenbetween b and a (0) berg numbers greater than one, while only marginally perturbing the conguration of the arm material away from equilibrium. Within this wide window of ow rates, the important contribution to the stress comes from the backbone segments of the moleculesthe arms merely contribute to an effectively Newtonian background viscosity. Therefore we will henceforth work with variables pertaining to the backbone alone orientation distribution and stretch, noting that when s c 0, some arm material essentially becomes part of the backbone. The stress tensor expression will then be valid at timescales longer than all arm relaxations, when the relaxed arm material is acting as solvent. It has long been established as a useful and accurate approximation that the concentration dependence of the shear modulus in theta-solvents or melts is approximately quadratic Ball and

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McLeish 1989, Colby and Rubinstein 1990. Hence, in terms of the high-frequency plateau modulus G 0 , we expect a modied expression for the stress, arising from the backbone alone, given by:

15 4

G02 b uu

with

sb s b 2 qs a

10

One factor of b is simply accounting for the number of elastically active segments; the other accounts for the dependence of the tube diameter on concentration. Further modication of the stress expression is required in the case of ows that produce either backbone stretching ( 1) or branch-point withdrawal ( s c 0). If the backbone is stretched, then it may occupy more than the equilibrium number of tube segments each of length a . Since each occupied and oriented tube segment contributes to the stress, this effect produces a linear dependence of stress on . Moreover, as discussed above, when the backbones are stretched, the thermodynamic tension which they carry grows proportionately with the stretch. The nal result is that the stress contribution from the backbone is quadratic in . Still higher values of the molecular deformation lead to partially withdrawn congurations as illustrated in Fig. 1, when some of the arm material near the branch point is also oriented. This material must also contribute to the stress because it shares the same orientation distribution as the end segments of the linear backbone. At this point we make an approximation by assuming that the orientation distribution is a weak function of position along the backbone, and that in consequence the tensor S uu is the unique measure of orientation also imposed upon the withdrawn arm material. S( t ) becomes the third dynamical variable which we shall require for the molecular rheological model, along with ( t ) and s c ( t ) S is, of course, the variable least surprising to a rheologist. The nal expression for the stress in terms of the dynamic variables becomes

15 4

G 0 b b 2 t

2 qs c t 2 qs a s b

S t

with

sb 2 qs a s b

11

The contribution from the withdrawn arm segments carries just one power of b from the diluted entanglement environment arising from the backbones alone. It might be objected that the inclusion of contributions to the stress from arm material is inconsistent with our restriction to deformation rates much slower than any of the arm segments natural relaxation times. However, there is no inconsistency since the local deformation rate within a tube segment surrounding a withdrawn arm segment is actually much larger than the bulk deformation rate. This will be demonstrated in the next section. On the other hand, the consequence of the rate restriction is indeed reected in the stress formula in that the withdrawn segments do not contribute to the entanglement network which is still controlled by b even though they are oriented. The rapid star-arm retractions are still fast on the timescale of our deformations, so the arms cannot act as topological obstacles for backbone material, even though they may be oriented by it. D. Dynamical equations It is already apparent that the constitutive structure suggested by our molecular model is not a closed equation relating stress to strain, but will instead be cast into a dynamical system of evolution equations for the auxiliary variables S( t ), ( t ), and s c ( t ) which in turn are used to construct the stress. At this stage we make the further assumption that each backbone spans a sufcient number of tube segments to self-average over both the

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orientation and the stretch. This allows us to carry unique values for the dynamical variables within an element of the melt over which the deformation history is constant, rather than work with distribution functions for them in which state the problem was left by McLeish in 1988. In the limit of large s b this approximation will become increasingly accurate. This in contrast with the dilute case, where the serious deciency of preaveraging approximations in dumbbell models has recently motivated highly sophisticated treatments of the full orientational ensemble Feigl et al. 1995. The highly entangled backbone of pom-pom polymers seem to provide a molecular justication of a desirable approximation in the phenomenology which the physics has elsewhere refused to legalize! We take each variable in turn in the following discussion of their dynamical equations.
1. Dynamics of orientation tensor S t

The orientation tensor S measures the distribution of unit vectors describing the orientation of tube segments in the deforming melt. We have made the approximations of a single relaxation time and of a unique orientation distribution for backbone segments. However, as we noted above, an essential aspect of the ow-induced molecular congurations at high strains is that they reduce the effective friction constants of the branch points and in consequence the relaxation time for the tube orientation. In particular, the expression for the backbone relaxation time has a generalization to a ow for which s c 0:

s2 bbaxctq,

12

where x c s c / s a . The essential feature is that the relaxation time is itself in general time-dependent and takes its equilibrium value as an upper bound. It is actually quite straightforward to write an integral expression for the time evolution of S under these conditions, and was done recently in the case of wormlike surfactant micelles for which the approximations are exact under certain circumstances Cates 1990. Tube segments 1 are created at a rate b ( t ) and are thereafter convected and extended by the ow. A segment created with orientation u at time t has an orientation E( t , t ) u/ E( t , t ) u at time t , where E( t , t ) is the local deformation gradient tensor between those times providing it survives. The segment will also increase in length, and therefore in the amount of chain it carries, by E( t , t ) u . Segments created with orientation u at t therefore carry a relative weight of E( t , t ) u / E( t , t ) u in the distribution at time t again the angular brackets denote an average over orientations u. The survival prob1 ability itself is the exponential of the time integral of destruction rates b ( t ) in the interval t t t . The resulting expression for S( t ) is therefore: S t

dt

b t

exp

dt

t bt

E t , t u

E t , t uE t , t u
E t , t u

. 13

In common with tube theories for ordinary linear polymers Doi and Edwards 1986 and entangled wormlike micelle solutions Cates 1990, this has interesting asymptotic properties in extensional and shear ow. In uniaxial extension with x the direction of stretch, the difference in normal components S xx S y y approaches a constant in the limit of innite extension rate, whereas in simple shear with x the ow direction and y the gradient direction S xy goes as the inverse of the shear rate for large shear rates.

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2. Dynamics of stretch t

The molecular dynamics of the backbone stretch is controlled by the local force balance of dissipative drag and elastic recovery. In a ow, the extension of the tube around the backbone tends to drag the backbone segment with itthe coupling is just the effective friction constant of the branch points calculated above. In opposition is the Gaussian elasticity of the backbone whose effective spring constant is kT / s b a 2 . As above, we denote the curvilinear distance of separation of the two branch points along the tube by L ( t ); since the equilibrium separation is just s b a , we have L / s b a . Now the relative velocity of separation of the branch points along their connecting tube is just L / t . However, the velocity of separation of the tube relative to the branch points against which they drag depends on the average rate of extension of the tube segments linking the branch points as they are deformed by the ow. If we dene the deformation rate tensor K such that E( t , t )/ t K.E( t , t ) then the average increase of length per unit length of tube is just K:S, so that the relative curvilinear tube velocity is L K.S. Equating the frictional drag force from the relative velocity to the elastic force restoring L to its equilibrium length, we write:

b K.SL

L t

kT sba2

Lsba .

14

Substituting for the branch point friction constant b from Eq. 6 and re-expressing the force-balance in terms of the dimensionless stretch parameter gives the second evolution equation:

K:S

strictly for q .

15

The stretch relaxation timescale s is given by

s sba0q.

16

This expression is of the form /2 for the relaxation time of a spring of spring constant working against friction at each end of . The effective friction constant of the branch point clearly scales with both the terminal time of the arm, a and the number of arms q . The spring is the Gaussian chain of the backbone, whose elastic constant 1 s b . This time is shorter than the terminal time for orientation relaxation by one power of s b but it is relevant to our declared range of deformation rates because it is longer than the longest arm relaxation time a (0). Relaxations with this timescale only appear in nonlinear deformations.
3. Dynamics of branch-point withdrawal s c t

As discussed above, if ever the melt achieves a local state in which q , the model insists that dynamical evolution of stops in favor of the variable s c describing branchpoint withdrawal. Evolution of recommences if and when s c returns to zero. We may think of the evolution of s c in a similar way to that of , in terms of a balance between an elastic restoring force and a frictional drag force. In this case, however, the drag comes from the parts of the arms that are not withdrawn into the backbone tube the blob of randomly oriented material from the q arms at the extremity of the molecule in Fig. 1 because by its rapid retraction dynamics this material creates dissipation by sliding against the continually extending tube. Using similar arguments to those for b we nd

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blob 2 kT

a x c
a2

q.

17

The relative velocity of the extending tube and the monomer at s c , assuming that the mid-point of the backbone is at rest, is ( qs b /2 s c ) K:S s c / t . The factor qs b /2 enters because the backbone must be stretched by a factor max q before branch-point withdrawal occurs. The drag on this relative velocity is balanced by the equilibrium tensions of the arms qkT / a , since the arms are never stretched at the deformation rates we are interested in. It might be objected that a higher deformation rate must always lead to greater tension in a frictional polymer chain embedded in the deforming medium. But as Ajdari et al. 1994 have shown in the context of chains pulled out of a network, the tube model gives rise to a self-adjusting friction constant by growing or shrinking the blob of disoriented material near the chain end. For all chain velocities for which the chain moves less than a tube diameter in the Rouse time of an entanglement segment, the tension is kept at the equilibrium value. Our theory for s c in a deforming melt contains the same physics that Ajdari et al. applied to chains dragged out of a network. Balancing the drag and elastic tension, and cancelling all dimensional factors of the tube diameter gives our evolution equation for s c :

sc t

sb 2

sc K:S

1 2 a s c ,

when q .

18

We now see how it is that arm material may be aligned by bulk ows at deformation rates far slower than the inverse relaxation times of the armthe bulk deformation rate projected onto the tube orientation distribution K:S is amplied by the typically large factor of the path length, ( qs b /2 s c ), from the center of the molecule to the blob of nearly relaxed material in the driving term for s c ( t ). The three equations for S( t ), ( t ) and s c ( t ), Eqs. 13, 15, and 18 together with the expressions for the self-consistent variable timescales within them Eqs. 12 and 16 and the expression for the stress Eq. 11, constitute the simplied constitutive formulation for a melt of pom-pom polymers. It does not t neatly into any phenomenological category of constitutive equation such as the K-BKZ equation, since it shares both integral in the case of S and differential in the cases of and s c character. Moreover its structure has the ow coupled to auxiliary variables from which the stress is constructed, rather than evolving the stress directly. In the next section we will explore the consequences of the model for a range of viscometric ows. However, we may remark that we anticipate both extension hardening and shear-thinning from the model: before any reduction of relaxation times sets in, the model is essentially an entangled version of a simple Gaussian dumbbell, or Oldroyd model. Such models always exhibit stretches which grow without limit in extension above a critical extension rate. In modeling dilute solution rheology, this problem is usually circumvented by imposing a maximum strain on the molecule at which the force required for further extension diverges. The entangled pom-pom polymers avoid the divergence in a gentler way: by renormalizing their relaxation times, they postpone the divergence to ever higher deformation rates, remaining always in a Gaussian regime. However, we expect to see some growth of the stress in extensional ows just before this renormalization takes place. This is not expected in shear, since for simple dumbbells the driving divergence does not arise.

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To summarize this section, we gather the effective constitutive equation set together: Pom-Pom Equation Set Expression for the stress:

4 2 qs a s b Evolution of orientation: t dt t dt 1 exp S t b t t bt E t , t u

15

G 0 b b 2 t

2 qs c t

S t

with

sb 2 qs a s b

E t , t uE t , t u
E t , t u

Evolution of backbone stretch:

1 strictly for t s Evolution of arm-withdrawal measure s c :

K:S

q,

sc

t 2 2 a x c Timescales: Backbone orientation:

sb

sc K:S

1 strictly for

q.

Arm spectrum:

4
2

s2 b b a x c t q

with

xc

sc sa

this timescales changes

a x 0 exp

Backbone stretch:

15 4 sa

1x 2

1b

1x 3

this timescale changes

s s b a 0 q

this timescale is xed .

III. BEHAVIOR IN STARTUP AND STEADY FLOWS We now explore some consequences of the set of equations derived in the previous section by computing the stress-growth on startup of extensional and shear ows. A representative molecular structure is chosen so that neither the arms nor the backbone dominate the total amount of material. It is of interest to begin with a molecule that has all parts well-entangled, and for which the backbone is permitted to stretch by a signicant amount before the arms begin to withdraw. Finally, we observe that is also of interest to explore the case in which b and s are reasonably well-separated as timescales. When this is not so, the orientation and stretch contributions to the stress meet their respective nonlinearities at the same deformation rates, and the pom-pom polymer would

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be expected to mimic an ensemble of simple elastic dumbbells, albeit with a novel nonlinear softening. Such models do not show the extreme differences in shear and extensional behavior seen in branched melts. On the other hand, if the nonlinearity in stretch is postponed to deformation rates already in the highly nonlinear regime, the aligning effect of the shear ow may suppress the tendency to stretch the K:S term in the stretch equation is small as strong orientation by shear has already begun at shear rates near the inverse orientational relaxation time. Such a separation cannot, however, prevent an extensional ow from exploring the novel features of this model under a strong stretch because in that case the stretch-coupling to the ow K:S remains large. We observe that it is the entangled nature of the effective dumbbell of the pom-pom polymer that generates this separation in timescales:

b s

sbb .

19

The structure specied by the molecular parameters q 5; s a 3; s b 30 was chosen to begin with, in the light of these considerations. In all that follows, we make deformation rates dimensionless in terms of the arm relaxation time a (0). This is not, of course, a terminal time, but stands apart from the two important long times, the orientational relaxation time b and the stretch relaxation time s . For our chosen model s 150 and b 912 in these units. To estimate the signicance of a nonlinearity and b molecular stretch in a ow Weissenberg numbers may be dened in each case by multiplying the deformation rate by the appropriate dimensionless time constant. We also make all stresses dimensionless in terms of the plateau modulus G 0 . The pom-pom equations are solved by a rst-order time integration, using small timesteps. To simplify the calculations, the strain tensors are approximated using formulas derived by Currie 1984, as described in the next section. Figure 2a indicates the growth of extensional stress xx y y , normalized by the extension rate, in start-up of uniaxial extensional ows over a range of deformation rates. In terms of the arm relaxation time, these represent dimensionless deformation rates from 0.0006, corresponding to orientational 0.0003 to 0.04. As expected, the low rates Weissenberg numbers less than 1, exhibit simple stress growth to a steady-state plateau. As the extension rate is increased, a very small amount of extension thinning is observed 0.0025 which is where the stretch Weisbefore the backbones begin to stretch at senberg number begins to approach values of order one. This can be seen Figs. 2b and 2c, which show on the same time-axis the evolution of the molecular dynamical variables and s c . Throughout the range of deformation rates over which the plateau viscosity is growing, the equilibrium value of is also rising. At still higher rates, a marked change of behavior sets in: reaches its maximum value in nite time, and thereafter branch-point withdrawal occurss c rapidly rises and nds its equilibrium value, typically after a small overshoot Fig. 2c. The stress-growth curves Fig. 2a now show a rapid hardening behavior which is cut off, again with a small overshoot, as the maximum sustainable backbone stretch is reached. For still greater extension rates, the extensional viscosity thins again as the steady-state extensional stress is not much altered by further increases in extensional rate. The qualitative similarity with extensional data by Laun for LDPE Laun 1984 is remarkable. The computations for shear ow show very different behavior. Figure 3 shows the growth of shear viscosity and rst normal stress coefcient for the same range of deformation rates as in the extensional ows Fig. 3a, together with the molecular dynami-

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95

on startup of uniaxial extension for the pomFIG. 2. a Time-dependent extensional viscosity ( xx y y )/ pom model with q 5, s a 3, and s b 30. Extension rates are 0.0003, 0.0006, 0.00125, 0.0025, 0.005, 0.01, 0.02, and 0.04 in terms of the arm relaxation time a (0). Weissenberg numbers for orientation and stretch may be obtained by multiplying these rates by 912 and 150, respectively. In this and all gures, times and rates are made dimensionless using a (0) and viscosities are made dimensionless using G 0 a (0). b, c The time evolution of the molecular variables ( t ) and s c ( t ) for the same ows. High stretch correlates with extension hardening; rapid changes in s c with equilibration of stretch.

cal parameters Fig. 3b. Overshoots in both the shear stress xy and the normal stress difference xx y y are evidentin fact the overshoots in the shear stress occur at lower shear rates than in the normal stress. The shear behavior is similar to the results of previous models incorporating molecular stretch in entangled linear polymers Pearson

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FIG. 3. a Time-dependent shear stress and rst normal stress difference for shear startup ows using the same model parameters and deformation rates as in the extentional calculations of Fig. 2. b The time evolution of ( t ) and s c ( t ) in shear.

et al. 1991. Although the backbone may stretch transiently, and even reach its maximum value, no hardening effect occurs, and the shear response is uniformly thinning. The steady-state ow curves for the pom-pom model are shown in Fig. 4 solid lines, where the simultaneous shear-thinning and extension-hardening is manifest. Our suspicion that the shear-ow dynamics never sample the stretching behavior of the molecules is conrmed for this set of structural parametersthe steady-state stretch only occurs in the extensional case, giving rise to the peak in extensional viscosity. The magnitude of the peak and the extension rate at which it occurs may be controlled by varying the molecular structure. Crudely, the maximum stretch sets the height of the peak, and this is in turn determined by q , whereas the extension rate at the peak will be 1 of the order of s . Since the low rate limiting viscosity is approximately G 0 b , and the peak viscosity, from the preceding arguments, is G 0 q 2 s , the ratio of these two is proportional to q 2 s / b . Since q 1 and s / b 1, the existence of an extensional viscosity peak higher than the low rate viscosity is delicatethe separation of the two

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97

FIG. 4. Steady-state shear and extensional viscosities as functions of deformation rate. Note the strong extension hardening and shear thinning. The dashed lines give the prediction of the K-BKZ-type integral equation which ts the step-strain behavior of the pom-pom model exactly.

fundamental timescales s and b must not be so great as to negate the hardening due to stretch. On the other hand, when the timescales are widely separated, a regime of extension thinning will exist before the hardening regime. This constitutes an interesting prediction to be tested by future experiments. A very important prediction of the model is that the response in planar extension falls into the same class as uniaxial extension, not that of shear. This is clear in Fig. 5a where we compare the steady-state uniaxial and planar extensional viscosities as functions of extension rate. At low extension rates the planar and uniaxial viscosities differ by a modest factor of 4/3, but at higher strain rates this difference disappears entirely. Thus, qualitatively, the difference between shear and extension shown in Fig. 4 applies to both uniaxial and planar extension. In Fig. 5b, we plot the transient shear and normalized uniaxial and planar viscosities for a deformation rate of 0.01. Again, the planar and uniaxial viscosities are similar to each other and both greatly differ from the shear viscosity in the nonlinear region at long times. The corresponding experimental data from Laun and Schuch 1989 are represented in Fig. 5c. Again the qualitative agreement with the pom-pom model is striking. The differentiation of ow types arises because both uniaxial and planar extensional ows allow the molecular orientation to couple strongly to stretch, in contrast to the special, softer, behavior in shear. Thus, there is experimental evidence that in branched polymers the two extensional ows fall into the same class, in agreement with the pom-pom model. Generalizations of the molecular model to more randomly branched material are expected to retain this behavior because of the connection between molecular stretch and strain hardening. The ability of integral schemes to mimic the behavior of this model will be further investigated in the next section.

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We next explore the effect of varying molecular structure: keeping s a and s b xed as well as a (0), q is varied from 2 to 8 in extensional ows of low and high rates. The results are shown in Fig. 6 in the same format as the previous calculations. At early times, and uniformly for low deformation rates, the viscosity decreases with increasing q . Of the two competing factors of increasing relaxation times on the one hand and reducing effective modulus because of the diluting effect the arms have on the backbone on the other, the modulus dominates at low extension rates: 0 3G02 bb 12
3 G0s2 b a 0 bq .

20

On the other hand, at high extension rates the stretch introduces a factor of q 2 in the stress so that at any xed high extension rate, plateau 15 4
2 1 . G02 bq

21

When q is not too large, this plateau viscosity increases with increasing q , leading to the cross-over in the ordering of response from early to late times in Fig. 6. Although the pom-pom model is not meant to represent LDPE quantitatively, since it was derived specically for the pom-pom architecture, it does have features in common with LDPE. The structure of LDPE is both random and polydisperse, but it contains the essential feature of signicant material in segments linking two branch points. In Fig. 7 we reproduce data from Meissner 1972 on LDPE in startup of uniaxial extension and shear, together with the behavior of the pom-pom model for the set of structural parameters explored in this article. Many features are common to both. In particular we draw attention to the gentle overshoot in shear lying below the linear response and extension

as functions of extension rate FIG. 5. a Steady-state uniaxial and planar extensional viscosities ( xx y y )/ , where x is the direction of stretch and y the direction of contraction. For planar extension the samples dimension does not change in the z direction. b Transient uniaxial, planar and shear viscosities for deforma 0.01. The uniaxial and planar viscosities have been normalised by dividing by the Trouton tion rate ratios of 3 and 4, respectively, so that all three viscosities match at short times. c Data on transient viscosities 0.05 s1 replotted in the same format in these geometries from Laun and Schuch 1989 on LDPE at as b. The line shows the linear viscoelastic response.

BRANCHED POLYMERS: THE POM-POM MODEL

99

FIG. 5. Continued.

hardening lying above. Also we note the sigmoidal shape of the extensional stress growth curves and the marked difference in the time at which extension and shear responses depart from the linear curves. Data on well-characterized melts of pom-pom polymers are still awaited. However a further qualitative comparison with LDPE is possible by treating the output of the pompom model as data for which a t to a K-BKZ-type integral model. The shortcomings or

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FIG. 6. Start-up ow viscosities in shear and extension for the pom-pom model with structural parameter as for Figs. 2 and 3 but varying the arm number q to 2, 4, 6, and 8. Note the non-monotonic dependence on q in the extensional response.

success of such a t may be compared with the performance of integral models in tting LDPE behavior itself. This is done in the following section. IV. COMPARISON WITH K-BKZ TYPE MODELS In the previous section, we showed that our constitutive model for entangled pompoms captures qualitatively a distinctive attribute of the rheology of long-chain-branched polymer melts, namely strain hardening in extension both uniaxial and planar combined with extreme strain softening in shear. Section I discussed the inability of the K-BKZ equation to describe this behavior. To further illustrate this point, in this section we derive a K-BKZ analog of the pom-pom model: one that reproduces the timedependent stresses of the pom-pom model exactly for all step deformations, both shear and extension. Since a K-BKZ equation is completely specied by its predictions in these deformations, this procedure uniquely determines the appropriate K-BKZ analog of the pom-pom model. We then show that this K-BKZ analog, while matching the stepstrain behavior of the pom-pom model by construction, predicts behavior in start-up of steady shear that is not as softening as that of the pom-pom model, while in start-up of extension is not as strain hardening as the pom-pom model. We derive the K-BKZ analog from a version of the pom-pom model that is simplied, but still qualitatively and quantitatively almost identical to the model described in Sec. II. First, as alluded to in Sec. III, we replace the strain measure of the K-BKZ equation by an analytic form proposed by Currie 1984. That is, in Eq. 13, we replace

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101

FIG. 7. a Start-up transient viscosities in uniaxial extension and shear for the LDPE melt IUPAC A studied by Meissner 1972 at 150 C; b Start-up viscosities for the q 5, s a 3, s b 30 pom-pom model in shear and extension Deformation rates are given in the caption to Fig. 2.

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FIG. 8. Comparison of the ow curves in extension and shear predicted by the full equation set solid line and by the approximation of no branch-point withdrawal except for the consequence of the crucial upper limit to the backbone stretchshown as a dashed line. In shear, no branch-point withdrawal occurs even in the full pom-pom model for the parameter values considered here.

15 4 E t , t u by Q with

E t , t uE t , t u
E t , t u

22

5 J1 B

5
J 1 I 2 13/4 1/2

23

J I12I213/4 1/2.

24

This analytic expression by Currie has been found to be a very accurate representation of the tensor given in Eq. 22 for both shear and extensional deformations. In fact we used this representation already in all calculations of Sec. III. Second, we neglect all the consequences of the withdrawal of the branch point into the central tube except the limit on the stretch, . This approximation may seem drastic, but in fact makes little difference in the predicted stresses, at least for the parameter values considered here. Figure 8, for example, shows the steady-state shear and extensional viscosities versus deformation rate for s b 30, s a 3, and q 5 predicted by the pom-pom equations with the Currie tensor Q in Eq. 23, with and without this approximation. In the former case the second contribution to the stress tensor in Eq. 11 is zero since s c 0 , and the relaxation time b is a constant. Nevertheless, it is evident from

BRANCHED POLYMERS: THE POM-POM MODEL

103

Fig. 8 that the neglect of this consequence of branch point withdrawal makes little difference in the predictions of the theory. This is because withdrawal only occurs when q , when the factor of 2 in the rst term of Eq. 11 makes it then the dominant contribution for q 3. In addition, when branch-point withdrawal is allowed, the backbone relaxation time is reduced, which allows the backbone to disorient somewhat, reducing its contribution to the stress, and so off-setting the small stress contributions from the retracted arms. In fact the amount of arm material required to stabilize the backbone stretch at q is typically rather small even over a wide range of deformation rates. This is a consequence of the well-attested exponential dependence of entangled arm relaxation times. So the exact form of this relaxation-time spectrum Eq. 4 is not essential to the nonlinear response of the model, which merely requires a very strong dependence of a ( x ) on x . When the effect of branch point withdrawal is approximated in this manner, the KayeBKZ analog of the pom-pom model is easily constructed. At a time t after a step strain, the stress tensor predicted by the pom-pom model is

t Gt, I1 , I2Q,
where Gt,I1 ,I2 G0et/bI1 ,I21et/s12.

25 26

Here is a function of the strain invariants I 1 and I 2 . This function can be computed for a shear or a uniaxial deformation by solving the pom-pom equation set in a step strain i.e., a very fast strain, and the results stored in a table to be read in by the computer program that solves the K-BKZ equation. The K-BKZ constitutive equation that yields the pom-pom results of the tabulated equations in section II in a step strain is just

t G0
where mt, I1 , I2 d

dtmtt, I1 , I2Q t , t ,

27

dt 1

Gt, I1 , I2 G0et/b1et/s1
1et/s1

1et/s .

28

With this KBKZ analog of the pom-pom model, we can compute the stresses in steady shear and extensional ows. Figure 4 shows the viscosities in these ows versus strain rate, compared to those for the pom-pom model with branch-point withdrawal approximated. Note that at high strain rates, there are large divergences of the Kaye-BKZ analog model from the behavior of the true pom-pom model. The direction of these deviations is highly signicant. In uniaxial extensional ow, the K-BKZ model shows hardly any strain hardening; it fails nearly completely to predict the maximum in extensional viscosity. The deviation in shearing ow is almost as large, but in the opposite direction! The K-BKZ equation fails to predict the level of shear thinning shown by the pom-pom model. Thus, as expected, the K-BKZ model is unable to show simultaneously severe strain hardening in extension and extreme shear strain softening in shear. Hence, the mathematical structure of the pom-pom equations permits a difference between shear and extensional-ow rheology that is much greater than can be supported by the K-BKZ single integral. Note that this distinction is not restricted to uniaxial

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extension versus shear; in planar extension the strain hardening is almost the same as in uniaxial extension see Fig. 5. The large distinction between shearing and extensional ows emerges from the equation for backbone stretch, Eq. 15. In an extensional ow planar or uniaxial, the velocity gradient tensor K is diagonal and the term K:S in Eq. 15 remains large as the molecules are oriented, and the tensor S asymptotically approaches a limit in which only S xx does not approach zero. In shear, however, K is skew; as the molecules are oriented and all components of S approach zero except S xx , the term K:S becomes small, since K does not couple to S xx . Hence, it is the vorticity in shearing that leads to its extreme strain softening in the pom-pom model. The K-BKZ model contains only strain tensors and the dominating effect of vorticity is absent. An important difference between the predictions of the pom-pom model and the observed rheological behavior of many commercial long-chain branched polymers is in the approximate time-scale factorability of the latter. Factorability means that after imposition of a step-strain, the stress can be represented as a product of separate functions of time and strain. Such behavior has been observed for branched LDPE Laun 1978. In the pom-pom model, however, the stress after a step-strain is not factorable into strainand time-dependence functions. Instead, there are two characteristic timescales, the retraction time and the backbone reorientation time. Factorability is only achieved on time scales longer then the retraction time. Even monodisperse entangled melts of linear molecules show nonfactorability at time scales shorter than the retraction time Einaga et al. 1971. Thus we believe that the factorability observed in the much more complex polydisperse, branched polymers must be the result of an averaging process that smears out the nonfactorability that would be observed in monodisperse branched or linear melts, making it less noticeable. Indeed, very recent experiments on the nonlinear response of a monodisperse H-shaped polymer melt do show nonfactorability Allgaier et al. 1997. An example that shows how smearing due to a broad spectrum of relaxation times resulting from polydispersity can transform an intrinsically nonfactorable response at the level of individual components into an apparently factorable response is the Leonov equation, which is nonfactorable when only one relaxation time is included, but is nearly factorable when a spectrum of relaxation times, characteristic of polymer melts, is used Larson 1987. Indeed, it can be shown that if a power-law distribution of relaxation times is incorporated into a nonfactorable constitutive equation, the step-strain response will be factorable Larson 1987. Thus, we believe that if the pom-pom model were generalized to allow for molecular polydispersity, its step-strain response would be nearly factorable. V. APPROXIMATE DIFFERENTIAL MODEL We have already seen in the previous section that some of the more subtle features of the molecular model may be discarded with impunity, providing one keeps the essential features of two distinct relaxation times for orientation and stretch as well as the maximum limiting stretch of the backbone. The smaller equation set still reects quantitative features of molecular structure, while retaining great simplicity the dynamical equation for s c ( t ) and the arm relaxation spectrum are not needed. However, there remains considerable computational complexity in the integral equation for the orientation tensor S( t ) Eq. 13. Carrying out the full double integral at every timestep requires a computational time which grows quadratically with the ow time. This is feasible for the calculation of viscometric homogenous ows, but becomes prohibitive when spatially inhomogeneous ows are considered. It would, however, be very desirable to explore the consequences of the pom-pom model in spatially varying

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105

ows such as contraction ows, because of the special behavior of LDPE observed in ow visualizations. This would be possible if a differential dynamical equation could be found for S( t ) which would approximate the integral form. Since the important aspects of the model all touch on the way the stretch couples to the ow via the orientation, we expect that the important aspects of S( t ) to get right are the asymptotic forms of its components in extension and shear. This rules out the simplest candidate for the evolution of a tensor of unit trace in a ow:

S t K.S S.KT 2 S:K S

S 1 3

I .

30

Although the shear-response S xy of Eq. 30 does have a maximum as a function of shear 2/3 rather than as rate, it does not exhibit the right asymptotic form; it decreases as 1 for the integral equation. The latter shares this highly shear thinning behavior with that of the strain measure in standard DoiEdwards theory for linear polymers. The less steep shear-rate dependence of Eq. 30 does not ensure the shear-thinning response of 1/3 rather than the model, since the important coupling term K:S then grows as reaching a plateau value, as it does when the integral equation is used for S. So with the differential form of 30 stretch is observed in steady-state shear as well as in the startup transient. More complex forms of differential equations akin to Eq. 30 exist Hinch et al. 1976, but may have multiple solutions which threaten instabilities when used in numerical ow-solvers. Instead, we shall retain the simplicity and stability of Eq. 30 while ensuring the correct asymptotics by using the convection equation for line elements embedded in the ow, and then dividing by the trace of their second moment tensor at the each time the tensor S is required, rather than insisting on working with a single tensor of unit trace. We are grateful to Dr. Oliver Harlen for this suggestion. The recipe for calculating S( t ) is therefore:

A t KA AKT

1 3

I ,

S t

A t trace A t

31

In Fig. 9 we show a comparison of startup ows in extension and shear of the differential version of the pom-pom equations. In this case all other variables including s c are kept i.e., all consequences of branch-point withdrawal are kept. Comparing Fig. 9 to Fig. 7b, it can be seen that, at least in these ows, the behavior of the differential approximation is qualitatively similar to that of the integral form. For readers who would prefer to avoid the mouthfulls of integral-version pom-pom and differential-version pom-pom the abbreviations Ron-Pom and Tom-Pom, respectively have been suggested, in accordance with the respective computational competance of the authors.

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FIG. 9. Start-up transient viscosities in uniaxial extension and shear computed using the differential equation for S given in Sec. VI. Deformation rates are given in the caption to Fig. 2. The results should be compared with those of the full model in Fig. 7b.

For ease of reference, we summarize the drastic but unproblematic simplications of the full pom-pom model discussed in the last two sections in the following table: Simplied Pom-Pom Equation Set Expression for the stress:

4 Evolution of orientation:

15

2 G02 b t S t

with

sb 2 qs a s b

A t KAAKT

1 3

I ;

S t

A t trace A t

Evolution of backbone stretch:

t
Timescales:

K:S

strictly for

Backbone orientation: Backbone stretch:

s2 0 q 2 b b a s s b a 0 q

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107

We defer further discussion of the pom-pom equations in complex ow geometries to another paper Bishko et al. 1997. VI. CONCLUSION We have derived a molecular constitutive equation for the dominant backbone stresses for an ideal multi-branched polymer, the pom-pom. The pom-pom was contrived as the simplest branching architecture whose nonlinear rheological properties are qualitatively like those of long-chain branched commercial melts, such as low density polyethylene LDPE. By neglecting rapidly relaxing branch motions and concentrating on the slow backbone relaxation, we derived a tractable integro-differential constitutive equation that predicts rheological properties in shear and extensional ow remarkably similar to those of typical LDPEs. In particular, the pom-pom constitutive equation shows strain hardening in extension, but extreme strain softening in shear. Furthermore, the predicted behavior in extensional ow is not sensitive to whether the extension is uniaxial or planar, in agreement with recent data and with intuitive expectations. This last feature is unattainable even in the versatile K-BKZ equation, which can only predict strong strain hardening in uniaxial extension and strong strain softening in shear if the kernel function is chosen in such a way that the behavior in uniaxial extension differs markedly from that in planar extension. Thus, the pom-pom model not only provides a constitutive equation for an unusual branched architecture, but also suggests that generalized integro-differential equations of this type might be good candidates for phenomenological constitutive equations for commercial branched melts. The key physics of the model survives, even quantitatively, in a number of approximations to the full equation set, including a fully differential set which holds promise as an algorithm for the calculation of the non-Newtonian stress in numerical ow-solvers. ACKNOWLEDGMENTS The authors would like to thank D. Bick, G. Bishko, R. Keunings, O. Harlen, S. Milner, and M. Wagner for stimulating discussions, and the Isaac Newton Institute for the Mathematical Sciences, where much of this work was done. APPENDIX A: DERIVATION OF THE BACKBONE RELAXATION TIME The stress-relaxation of the backbone is assumed to be dominated by reptationat long times the pom-pom polymers renormalize to linear chains in tubes whose diameters are given be entanglements between the backbones only. Stress from occupied tube segments is lost when a free end in this case a branch point diffuses to the segment. The total stress is then just the sum of the survival probabilities p ( s , t ) at time t of a tube segment originally at a curvilinear distance s from one of the free ends. This obeys a linear diffusion equation with absorbing boundaries and has the initial condition p ( s ,0) 1 Doi and Edwards 1986.

ps,t Dc

2 s2

ps,t;

p0,t p L , t 0.

A1

By an Einstein argument, the curvilinear diffusion constant D c is just given by Dc a2 4a0q A2

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from the arguments preceding Eq. 6 and from the recognition that two branch points 2 hinder the diffusion of the backbone. We recall from Sec. II that L 2 s 2 ba b . The partial differential equation is solved in terms of the eigenfunctions sin(ns/L), labeled by the integer value n . The lowest eigenfunction carries the dominant part of the total probability p ( s , t ) over most of the chain, so we need only its time-constant for the level of approximation of our treatment. Substituting the n 1 eigenfunction into A1 yields for its amplitude a 1 ( t ) the ordinary differential equation d dt a1t

2Dc
L2

a1t.

A3

This gives exponential decay with the time constant b of

b
which is Eq. 7.

L2

Dc

s2 bb0q,

A4

APPENDIX B: NOMENCLATURE

B C E I1 ,I2 G(t) a q sa
sb k T (t) sc(t) a(x)

0 b G0 Dc b L S( t ) xc K blob 0

viscoelastic stress tensor Finger tensor Cauchy tensor deformation gradient tensor rst and second invariants of E time-dependent linear viscoelastic modulus tube diameter number of dangling arms on each branch point molecular weight of dangling arms in terms of the entanglement molecular weight molecular weight of backbone segment in terms of the entanglement molecular weight Boltzmanns constant absolute temperature stretch ratio of the backbone number of entanglement segments of arms drawn into the backbone tube relaxation time of an arm-segment a fraction x from the branch point to the free end attempt time for deep retractions of the entangled dangling arm volume fraction of backbone material plateau modulus curvilinear diffusion constant of a branch point effective friction constant of a branch point entangled primitive path length of the backbone segments second moment of the orientation distribution of backbone segments fraction of arm withdrawn into a backbone tube deformation rate tensor renormalized friction constant of a branch point when some arm is withdrawn extension rate zero-extension rate limit of extensional viscosity shear rate

BRANCHED POLYMERS: THE POM-POM MODEL

109

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