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Shearing Flows

VIJAY R. MHETAR, L. A. ARCHER

Department of Chemical Engineering, Texas A & M University, College Station, Texas 77843

ABSTRACT: Beginning with a recently proposed expression for the drag force on a single

macromolecule pulled with constant velocity through a fluid of long-entangled molecules (V. R. Mhetar and L. A. Archer, Macromolecules 1998, 31, 6639), we investigate

the effect of entanglement loss on polymer dynamics in steady shearing flows. At

steady-state, a balance between the elastic restoring force and viscous drag acting on

entangled polymer segments reveals a critical molecular strain g m,c beyond which the

drag force exerted on polymer molecules by their neighbors is insufficient to support

arbitrarily small orientation angles. Specifically, we find that in fast steady shear flows

t 21

, g , t 21

d

Rouse, polymer orientation in the shear plane approaches a limiting angle

x c ' atau(1/(1 1 g m,c )) beyond which flow becomes incapable of producing further

molecular alignment. Shear flow experiments using a series of concentrated polystyrene/diethyl phthalate solutions with fixed entanglement spacing, but variable polymer

molecular weight 0.94 3 10 6 # M w # 5.48 3 10 6 , reveal a limiting steady-state

orientation angle between 6 and 9 over a range of shear rates; confirming the

theoretical result. Orientation angle undershoots observed during start-up of fast

steady shearing flows are also explained in terms of a transient imbalance of elastic

restoring force and viscous drag on oriented polymer molecules. Our findings suggest

that the DoiEdwards affine orientation tensor (Q) is not universal, but rather depends

on deformation type and deformation history through a balance of elastic force and

viscous drag on polymer molecules. 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys

38: 222233, 2000

theory; entanglement loss; partial retraction; convected constraint release; viscous drag

INTRODUCTION

The DoiEdwards (D-E) theory contends that in

melts and solutions of entangled macromolecules

translational motion of individual molecules is

confined to tube-like regions surrounding the molecular contour. When an entangled polymer is

subjected to sudden straining, the tube and chain

deform affinely. Stresses induced by the deformation relax on two time-scales. At short times of

Correspondence to: L. A. Archer (E-mail: laa@unix.

tamu.edu)

Journal of Polymer Science: Part B: Polymer Physics, Vol. 38, 222233 (2000)

2000 John Wiley & Sons, Inc.

222

polymer, t Rouse, stretched chain segments are assumed to retract along their respective tubes to

restore the equilibrium contour length. Following

equilibration of contour length, affine orientation

of chain segments relax by reptation. For t

. t Rouse the instantaneous stress in the material

is then,

(1)

polymer network; E the deformation gradient

tensor; Q(E) the second moment tensor of seg-

z u)(E z u)/uE z uu&; and c (t) a reptation relaxation function, c (t) 5 p;odd 8/p 2 p 2 exp(2p 2 t/ t d ),

where t d0 is the terminal orientation relaxation

or reptation time.1

Equation 1 predicts that for t . t Rouse stress is

factorizable into time-dependent, G N c (t), and

strain-dependent, Q(E), parts. For a shear strain

of magnitude g, the strain-dependent shear stress

contribution may be approximated as Q xy ( g ) '

4/15g 2

. Experimental results using weak to

~1 1 g2 /5!

moderately entangled solutions of narrow molecular weight distribution poly(styrene) provide

support for the latter result.3,4 This functional

form of Q xy ( g ) has nonetheless been the source of

a long-standing paradox in the D-E theory. Specifically, the prediction for Q xy ( g ) implies that for

shear strains g . =5 a larger imposed strain

yields a smaller shear stress, s xy ( g ) ; 1/ g at high

strains. This unusual result follows directly from

the assumption that polymer chain segments orient affinely in response to an imposed strain,

regardless of the size of that strain. Monotonic

decrease in the second moment tensor Q xy ( g ) at

high shear strains reflects enhanced segment

alignment parallel to the direction of shear, x,

compared with alignment parallel to the direction

of the shear gradient, y.

The multivalued shear stress result observed

in step shear flows carries over to D-E stress

predictions in all time-dependent shearing flows.

In these flows, the shear stress at any instant in

time is taken to be the affine stress accumulated

over the history of the deformation, weighted by

the materials memory ( c (t 2 t9)) of that stress,

t

s xy ( g ) 5 15/4 G (0)

N * 2` Q xy (E(t, t9)) c (t 2 t9)/t9

1

dt9. Thus, a continuous shearing deformation

imposed at a rate g , t 21

Rouse is assumed to orient

polymer chain segments in proportion to the effective strain accumulated by molecular segments

at steady-state. The orientation of polymer segment vectors is therefore anticipated to monotonically approach the direction of shear as shearing

becomes progressively faster. The consequent decrease in shear stress with increasing rate yields

the unusual prediction that at high rates apparent steady-state viscosity h 5 ( s xy ( g )/ g ) scales

with shear rate as h ; g 23/2. Thus, the very same

DoiEdwards orientation tensor Q that provides

favorable predictions in step-shear deformations

yields unrealistic levels of shear thinning in

steady shear flow. Any attempt to fix Q to improve predictions in steady shearing has the un-

223

step-strain predictions.

Several proposals have been advanced in the

literature to correct the D-E steady shear predictions without changing Q. All but one,5,6 achieve

this by including more realistic descriptions of

shear stress contributions due to flow-induced

changes in polymer contour length. Reviews outlining the successes and shortcomings of each of

these proposals are available,5,7,8 and will not be

discussed here. Instead, a different approach for

evaluating polymer orientation dynamics in

steady flows is addressed. In this approach the

orientation of entangled polymer chain segments

in a deformation field is contended to be determined by a balance between the elastic restoring

force due to molecular alignment parallel to the

direction of shear and viscous drag exerted on

chain segments by their neighbors, which retards

restoration of the equilibrium random distribution of molecular segment vectors. Specifically, we

propose that arbitrarily small orientation angles

x between entangled polymer segments and a

macroscopic flow are possible only if the viscous

drag force on segments is sufficiently large to

balance the entropic, elastic restoring force that

continually attempts to return segments to their

equilibrium orientation distribution.

This approach is different from that taken in

the DoiEdwards theory, where orientation of

polymer segments in any flow field is completely

described by the affine orientation tensor, Q, for

that flow field. A consequence of the new proposal

is that at moderate shear rates, in a steady shear

flow, the orientation of polymer chain segments

approaches a limiting angle beyond which the

flow becomes incapable of inducing further molecular alignment. Our result appears to resolve the

long-standing discrepancy between good agreement between DoiEdwards step-strain predictions and experimental results, and the unusually

high levels of shear thinning predicted in steady

shearing flows.1,5 Experimental support for the

proposal is discussed in the Results and Discussion section of the article.

Theory

Consider a homogeneous melt of flexible, entangled macromolecules each with degree of polymerization N and entanglement spacing N e0 . At equilibrium, each of the N-mer molecules will on average entangle with (N/N e0 2 1) surrounding

224

flow. At low shear rates, g ! 1/t d0 (N), the primitive

(N-mer) chain is essentially a Gaussian coil. The polymer chain moves with an average curvilinear velocity,

V T , which is related to its center of mass velocity V c by,

V C 5 V T R/L c (N).

the system (N-mer chain and surrounding mole21

cules at equilibrium), such that g ! t d0

, the

frictional drag force experienced by each N-mer is

identical to the force that would arise if the molecule is pulled by its center of mass with a directed velocity V c 5 R g through a sea of chemically identical, but stationary molecules (P-mers),

(see Fig. 1).

Recently, Mhetar and Archer,9 showed that a

pulled macromolecule (N-mer) will not instinctively follow a curvilinear path around entanglement points. These authors contended, as did

Bueche almost half a century ago,10 that the Nmer will instead continually attempt to drag surrounding molecules entangled with it (P-mers) as

it translates through the entangled polymer network. Because P-mers are themselves entangled

and the N-mer is here free at both its ends the

pulled N-mer cannot drag P-mers indefinitely as

argued by Bueche,10 rather the N-mer will on

average only induce P-mer translation over a

short distance, of order the mean entanglement

spacing a 5 =N e0 b. Beyond that point, the large

frictional resistance offered by polymer molecules

entangled with the P-mer arrests its motion and,

thereby, compels the pulled N-mer to slide

through its entanglement with the P-mer to maintain the applied velocity. This sliding motion

traces out a curvilinear (tube-like) path around

the N-mer contour with diameter equal to the

mesh size of the entanglement network =N e0 b.

The frictional resistance the N-mer experiences

per entanglement site is therefore P z m , the drag

coefficient per N-mer molecule caused by the combined dragging and sliding motions is then,

zN 5

N

N z m,

N e0

(2)

the N-mer, and we have assumed P 5 N.

The predicted halting curvilinear motion of the

N-mer molecule progresses at an average speed

V T that is related to the induced center of mass

velocity V c by L c (N)/V T 5 R/V c , where L c (N) and

R are the N-mers mean contour length and radius of gyration, respectively. The total drag force

offered by the surrounding molecules to the Nmers motion is therefore not the usual Rouse

drag assumed for polymer chains sliding intuitively through monomer-filled tubes: fdrag

5 V T z Rouse 5 V T N z m , rather f drag 5 V T z N .

Before proceeding, it is useful to derive the

limiting Newtonian viscosity h0 and terminal molecular relaxation time t d0 predicted by eq 2 for

an entangled melt of equal-sized molecules. In a

slow steady shear flow, the rate of viscous dissipation per unit volume is h0g 2. The dissipation

due to a single N-mer is z C V 2C 5 z C R 2 g 2 , where z C

is the center of mass friction coefficient. The rate

of dissipation per unit volume is therefore

z C R 2 g 2 /Nb 3 , yielding h 0 5 z C /b where b is the

monomer size. When the N-mer moves by L c (N)

along its curvilinear path, its center of mass

translates a distance R. Equating dissipation

rates yields,

zC 5 zN

S D S D

VT

VC

5 zN

L c~N!

R

<

N3

2 zm

N e0

(3)

Thus, for well entangled polymers N/N e0 @ 1, the

limiting Newtonian shear viscosity is predicted to

2

2

be h 0 5 5 ( z m /b) N 3 /N e0

5 h m N 3 /N e0

, which is

similar to the result obtained by integrating the

relaxation modulus predicted by the DoiEdwards theory.1

Thermal fluctuations in the N-mer contour

length modify L c (N) in eq 3 by its fluctuating

equivalent, L c (N) 5 L c (N)(1 2 b ( =N e0 /N)). 11

The limiting shear viscosity then becomes, h 0

2

5 h m N 3 /N e0

(1 2 b ( =N e0 /N)) 2 ; where b is a

constant of order unity. The shear modulus of the

network is just G N ' 3 kT/(N e0 b 3 ). These two

results define a terminal molecular relaxation

time, td0 [ (h0/GN) ' tm(N3/Ne0(1 2 b(=Ne0/N))2).

Here h m ' ( z m /b) and t m 5 h m /(3 kT/b 3 ) are the

monomeric viscosity and segment jump time, respectively.

The frictional drag force acting on the N-mer

21

molecule at low shear rates, ( g ! t d0

), is

f drag 5 z NV T <

S D

S D

N2

z V

Ne m T

5

N2

N3

z m L cg < 3/2 z mb g

Ne

Ne

(4)

where, for simplicity, we have ignored the fluctuation correction to L c (N). Substituting z m

5 3 t m kT/b 2 yields,

f drag 5

225

3kT

N eb

S D

tm

N3

3kT

t g .

g <

Ne

N eb d0

(5)

At steady-state, this frictional drag force is balanced by an entropic elastic restoring force,

f elastic. The elastic force results from flow-induced

orientation of polymer chain segments and may

be estimated as follows. Consider a N-mer molecule under the influence of a shear strain g m . The

strain is taken to be sufficiently small that deviations from Gaussian coil statistics are minimal.

The elastic force acting on the molecule is then,

f elastic 5

3 kT

3kT

g

2 L c~N! g m <

Nb

N e0b m

at equilibrium, average orientation angle x 5 45, (b)

oriented primitive N-mer segment subjected to a shear

strain g m . Here, L x and L y are the projections of the

primitive chain segment length in the shear ( x) and

shear gradient ( y) directions, respectively.

Again, let g m be the effective molecular shear

strain at steady-state. Also, let l x and l y be the

projection of a N-mer segment of unit length in

the shear ( x) and shear-gradient ( y) directions,

respectively (see Fig. 2). At steady-state, the average orientation of the N-mer segment in the

shear plane can then be estimated in terms of l x ,

l y , and g m as

(6)

simply states that at steady-state the effective

shear strain experienced by polymer molecules is

proportional to the product of their terminal relaxation time and the imposed deformation rate; a

result that is supported by experiment. Thus, unlike the imposed strain g 5 g t, g m is a timeindependent molecular strain that reflects the

balance between flow-induced deformation and

molecular relaxation at steady-state.

The preceding slow-flow analysis can be ex21

tended to higher shear rates, g . t d0

. For the

sake of simplicity, the analysis will be restricted

to shear rates less than the reciprocal longest

Rouse relaxation time of the N-mer (g , t21

Rouse). It

is further assumed that complete retraction of the

N-mer contour length is achieved in a time tRouse

following sudden imposition of strain. Though the

second restriction is not expected to hold strictly,9

it allows us to argue that the curvilinear length of

the N-mer chain is independent of deformation

21

rate in the range ( t d0

, g , t 21

Rouse). Shear rates

in this range are, however, large enough that the

equilibrium configuration distribution of polymer

segment vectors is significantly perturbed by

shearing. Thus, to estimate the viscous drag acting on the N-mer molecule at a shear rate g , we

L x 5 L Cl x < L C

1 1 gm

1 1 ~1 1 g m! 2

L y 5 L Cl y < L C

1 1 ~1 1 g m! 2

The mean center of mass velocity of the polymer molecule is then V C 5 L y g . Since V T /L C

5 V C /L x the curvilinear, tube velocity is V T

5 L C g (L y /L x ). The convective constraint release

(CCR) renewal time introduced by Ianniruberto

and Marrucci8 is then t CCR 5 L C /V T 5 L x /(L y g ).

21

Thus, at low shear rates ( g ! t d0

), where L x

' L y , the CCR process yields a tube renewal time

tCCR 5 g 21, which is eclipsed by the faster renewal process due to simple reptation. At high

shear rates where CCR is anticipated to dominate, we find tCCR 5 g m / g . Thus, in the absence of

some other process for accelerating reptation at

higher shear rates, tube renewal by convective

constraint release should therefore occur on a

characteristic timescale ( t CCR ' t d0 ), at best.

In steady shear flow at rates g , t21

Rouse, retraction of the primitive N-mer molecule to maintain

its equilibrium contour length reduces the number of entanglements the N-mer makes with surrounding molecules (see Fig. 3). In the simplest

case, the surrounding temporary network could

be assumed to deform affinely and the N-mer to

226

constraint release) should lower the level of molecular orientation possible in a steady-shear flow

compared to the D-E prediction.

To quantify this, we first estimate the viscous

drag on a N-mer molecule at steady-state,

network of chemically identical molecules at equilibrium. Dots represent network constraints. (b) Retracted N-mer molecule in a deformed network. The

number of network constraints exerted on the N-mer is

seen to be lower than at equilibrium.

tRouse. The steady-state entanglement density can

therefore be computed from, N/N e ( g m ) 5 N/

N e0 =2/(1 1 (1 1 g m ) 2 ). For well-entangled

polymer liquids, tRouse is much shorter that any

other timescale of rheological significance. Entanglement loss should therefore begin essentially

upon start-up of steady shearing and persist at

steady-state, where its fundamental effect is to

reduce frictional drag between entangled macromolecules and their neighbors.

Material properties, such as network modulus,

viscosity, and orientation relaxation time, that

depend either directly on entanglement density,

or indirectly through their dependence on the molecular drag coefficient, will clearly be altered by

entanglement loss. Mead et al., for example, have

recently shown that the effect of entanglement

loss on polymer orientation relaxation can be captured phenomenologically in the DoiEdwards

constitutive model if a strain-dependent rate of

entanglement loss k is introduced.12 Mhetar and

Archer have proposed that the combination of

partial chain retraction and entanglement loss in

flow yields a strain-dependent stretch relaxation

time, t s ' t d0 /^uE z uu 1/ 2 &, in entangled polymer

21

liquids.8 At shear rates t d0

, g , t 21

Rouse, both

approaches remove the downturn in shear stress

predicted by the DoiEdwards constitutive equation. Viewed in terms of the required balance

between viscous drag and elastic restoring force

at steady-state, extra orientation relaxation produced by lost entanglements can be thought of as

a means for lowering the elastic restoring force

per molecule, so that at steady-state this force

remains in balance with the lower drag force

caused by entanglement loss. Thus, either consequence of entanglement loss (reduction of drag

force, or acceleration of molecular relaxation by

f drag~ g ! 5 z NV T <

<

S D

Ly

N2

z mL cg

Ne

Lx

2

1 1 ~1 1 g m! 2

1/2

g m 3 kT

L,

1 1 g m Nb 2 c

(7)

5 g . Equation 7 indicates that at high shear

rates, or equivalently at large g m , the viscous

drag on the primitive chain, f drag, decreases with

increasing shear rate roughly as g 21. At shear

rates in the range of interest, the elastic restoring

force on the primitive N-mer chain is here taken

to be determined by its orientation only. The force

is directed along the chain contour and can be

estimated from,

f elastice T 5

3 kT

L $@l ~ g ! 2 l x~0!#e x

Nb 2 c x m

1 @l y~ g m! 2 l y~0!#e y%.

(8)

restoring force parallel to the direction of shear is

more important,

f elastic <

3 kT

L @l ~ g ! 2 l x~0!#

Nb 2 c x m

5

3 kT

L

Nb 2 c

1 1 gm

1 1 ~1 1 g m!

(9)

force increases in proportion to the accumulated

molecular shear strain at low strains, but eventually saturates at large shear strain.

In a steady shear flow, this restoring force

must be balanced by the drag force component

parallel to the direction of shear if the molecular

orientation causing the restoring force is to be

maintained at steady-state. Herein we believe lies

the source of the aforementioned step-shear/

steady-shear contradiction in the D-E theory. In

both deformation types, the theory contends that

(l y /l x ) 3 0 monotonically with increasing strain

or strain rate. This prediction is reasonable for

step shear because in a suddenly imposed defor-

mation the instantaneous orientation of a primitive N-mer molecule is entirely determined by its

affine deformation. The macroscopic stress developed by an ensemble of such molecules is therefore unsurprisingly elastic. The D-E prediction is

unrealistic for steady shear flow, however, because there the viscous drag required to maintain

the high levels of molecular orientation predicted

at steady-state decrease with increasing shear

strain [see Fig. 4(a)].

Equations 7 and 9 in fact indicate that in

21

steady-shearing flows at rates t d0

, g , t 21

Rouse,

shear-induced entanglement loss ultimately

causes the frictional drag force on polymer molecules to become insufficient to sustain arbitrarily

low orientation angles at steady-state. Thus, if

polymer chains are long enough to entangle, the

steady-state molecular orientation in a steady

shear flow is predicted to approach and become

locked to a limiting/plateau angle x c '

atan(1/(1 1 g m,c )), regardless of the strain rate

and molecular details of the polymer. At higher

shear rates g . t21

Rouse, retraction becomes impossible and shear-induced entanglement loss

ceases. The molecular orientation angle should

then resume its descent to 0 at shear rates exceeding t21

Rouse. A similar result is predicted by the

theory of Mead et al. (see Figure 14 of ref. 12),

except there the entanglement densities considered are too small to allow a clear distinction

between the plateau orientation angle regime and

the high shear regime, g . t21

Rouse, where molecules eventually align parallel to the direction of

flow.

Strain-dependent drag, f drag and restoring

forces f el , estimated from eqs 7 and 9 are presented in Figure 3(a). A critical molecular strain

g m,c ' 2.75 (strain corresponding to minimum

allowed steady-state orientation angle), can be

identified from the figure. The corresponding limiting orientation angle is x c ' 16.6. If the assumption that molecules completely recover their

equilibrium contour length after tRouse is replaced

by L c u t5 t Rouse 5 L c ^uE z uu& 1/ 2 which supports only

partial contour length recovery,8 a much smaller

number of entanglements are lost under shear,

N/N e ( g m ) ' N/N e0 (2/1 1 (1 1 g m ) 2 ) 1/4 . In that

case, comparison of elastic and drag force components parallel to the direction of shear [Fig. 4(a)],

yields g m,c ' 13.2 and x c ' 4.5.

Before concluding this section, it is useful to

consider the critical strain and limiting orientation angle estimates provided by variants of eqs 7

and 9, modified to produce a smooth crossover

227

f drag and elastic restoring force ( f el ) parallel to the

direction of shear. f drag is computed under the assumption that molecules recover their equilibrium contour

length in a time tRouse following imposition of a step

strain. f drag,PSE is computed under the assumption that

only partial recovery of contour length occurs in tRouse,

21

L c u t5 t Rouse 5 L c ^uE z uu& 1/ 2 . At low shear rates ( g , t d0

)

both f drag and f el increase linearly with molecular

21

strain g m 5 g t d0 . However, at high shear rates ( t d0

21

, g , t Rouse), the viscous drag force decreases with

molecular strain f drag ; g 21

m , while the elastic force

becomes independent of molecular f el ; g 0m . (b) Components of the viscous drag force f drag and elastic restoring force ( f el ) parallel to the direction of shear

predicted by eqs 10 and 11. Except for differences in the

limiting orientation angles predicted, f drag and f el show

the same qualitative behavior at low and high shear

rates as those predicted by eqs 7 and 9.

flow rates. Again assuming complete retraction,

the amended drag and elastic restoring force estimates are,

228

Table I. Structural and Linear Viscoelastic Data for Poly(styrene)/Diethyl Phthalate Solutions

Used in the Study

Polymer

Sample #

#

M

w

3 10 26

PI

h0 [Pa z s]

J 0e [Pa21]

t d0 [s]

l d0 [s]

G N [Pa]

PS-P93M

PS-1P8M

PS-2P9M

PS-3P8M

0.935

1.810

2.890

3.840

1.01

1.03

1.09

1.04

7.05 3 102

7.46 3 103

5.41 3 104

1.38 3 105

6.8 3 1024

7.6 3 1024

7.9 3 1024

7.7 3 1024

0.5

5.7

42.8

106.3

2.5

11.7

99.5

198.4

4.8 3 103

4.6 3 103

4.6 3 103

4.7 3 103

1/2

gm

1 1 Qgm

fdrag~gm ! 5

3 kT

2

2 Lc

Nb

1 1 ~1 1 gm !2

f elastice T 5

3 kT

L $@l ~ g ! 2 l x~0!#e x

Q 2Nb 2 c x m

1 @l y~ g m! 2 l y~0!#e y%,

(10)

(11)

these equations are compared in Figure 4(b).

Again a critical molecular strain g m,c is observed,

beyond which further molecular orientation cannot be sustained by viscous drag at steady-state.

The corresponding limiting orientation angle x c

5 atan(1/(1 1 Q g m,c )) is estimated to be x c ' 33

(assuming complete retraction) and x c ' 15.6

(assuming only partial retraction). Thus, the refined estimates of f el and f drag support the prediction that a nonzero, limiting steady-state orientation angle exists in steady shear flow, but suggest

that this angle could be reached at even lower

shear rates than predicted by eqs 7 and 9.

EXPERIMENTAL

Materials and Methods

Several high molecular weight, narrow molar

mass distribution polystyrenes (PS) were purchased from Tosoh Corp., Japan and from Aldrich

Chemicals. Weight-averaged molecular weights,

polydispersity indices, and abbreviated names

are provided in Table I for all polymers used in

the study. Solutions containing 18%, by weight,

poly(styrene) in diethyl phthalate (Aldrich) were

made up using the following procedure. First, the

required amounts of polymer and diethyl phthalate (DEP) were weighed and placed into a labelled glass container, the weight of the container

(including its contents) was recorded. A large excess of dichloromethane [methylene chloride] (Al-

drich) cosolvent was added to the PS/DEP mixture to accelerate dissolution. The container containing the PS/DEP/methylene chloride mixture

was then sealed and agitated for two days using a

room-temperature (24.5C) laboratory stirrer/

shaker device. For all polymers used in the study

this time was sufficient to produce transparent,

well-mixed solutions. Subsequent exposure of the

PS/DEP/methylene chloride mixture to air, at

room temperature, resulted in complete evaporation of the cosolvent within a week.

Linear viscoelastic properties of the PS/DEP

solutions were studied using a Paar Physica

UDS-200 mechanical rheometer. Frequency-dependent polymer behavior in low-amplitude oscillatory shear and polymer relaxation following

small amplitude step strain measurements g

5 0.2 were investigated using the rheometer. The

rheometer was equipped with 25-mm diameter)

6-mm thick, bead-blasted, stainless steel cone

(cone angle, 4) and plate fixtures. Using a Stylus

profilometer (Surfanalyzer 5000), the root-mean

square surface roughness of the bead-blasted fixtures was determined to be 3.1 mm. In highly

entangled polymers, clean surfaces with micrometer-size roughness have been shown to reduce

apparent slip at low shear stresses and to delay

the transition from weak (rheometrically insignificant), to strong slip at high stresses.13

Frequency-dependent storage G9( v ) and loss

G0( v ) moduli for the PS/DEP solutions used in

the study are presented in Figure 5(a, b). Complex shear viscosities uh*u(v) deduced from the

dynamic moduli are presented in Figure 5(c). Except for sample PS-3P8M, all measurements were

performed at a fixed temperature of 25.5C; a

recirculating oil bath facilitated temperature control. Data presented for PS-3P8M was obtained

by superimposing G9( v ) 2 G0( v ) data at two

temperatures (25.5 and 65.5C) to 25.5C by horizontal shifting alone. It is noteworthy that the

moduli G0( v ), and complex viscosities uh*u(v) for the 18

wt % poly(styrene)/diethyl phthalate solutions used in

the study. Low-amplitude oscillatory shear flow measurements on the lower molecular weight poly(styrene)

(PSP93M, PS1P8M, and PS2P9M) were performed at

25.5C using bead-blasted, stainless steel cone-andplate rheometer fixtures. Data presented for the high

229

G9( v ), and uh*u(v) curves for all solutions converge at high frequencies. This behavior is expected for narrow molecular weight distribution polymers of differing molecular weights,

but with the same entanglement spacing. Material properties deduced from the frequencydependent moduli are presented in Table I. The

following definitions were used in extracting this

2

data: h0 5 uh*u(v)uv30; J 0e 5 h 22

0 (G9( v )/ v u v 30 );

0

t d0 5 h 0 J e ; G N 5 G9( v m ), where v m is the

frequency at which G0( v ) has a local minimum.

Values of G N and J 0e deduced in this way are

related as follows, G N ' 3.5 6 0.2 ( J 0e ) 21 . Terminal relaxation times l d0 determined from the

long-time slope of semilogarithmic plots of shear

stress versus time following linear step strains

are also included in the table. Except for the lowest molecular weight polymer studied PS-P93M,

relaxation times obtained from step strain measurements are seen to be related to those from

oscillatory shear by, l d0 ' (2.0 6 0.2) t d0 .

Steady shear flow rheological measurements

were also performed on the PS/DEP solutions using the UDS-200 rheometer. These measurements were conducted at 25.5C with the same

bead-blasted, stainless steel cone-and-plate rheometer fixtures employed in the oscillatory shear

experiments. In addition to the possibility of slip

violations at the cone/plate surface, edge fracture

presents a well-known challenge to cone-andplate, steady shear rheology measurements on

highly entangled polymers. In this work, a combination of procedures proved successful in delaying edge fracture. First, prior to each test the cone

and plate were thoroughly cleaned using methylene chloride and acetone, and the cone edge lubricated using a fluoropolymer lubricant. During

steady shear measurements, the cone was submersed to a depth of about 4 mm in a small

puddle of the polymer solution under study. Second, at the highest shear rates studied, experiments were actively monitored and stopped

shortly after steady-state was achieved. This last

procedure was motivated by the observation that

edge fracture requires a shear-rate dependent

critical strain for its onset; interrupting experiments before this strain was achieved proved suc-

by superimposing G9( v ) 2 G0( v ) data at two temperatures (25.5 and 65.5C) to 25.5C by horizontal

shifting.

230

this combination of procedures steady shear measurements were possible up to shear rates of 3 s21

without any visible appearance of edge lacerations or transient shear stress decay normally

associated with edge fracture and wall slip.

For each material studied, time-dependent

shear stress, s xy (t) and first normal stress differences N 1 (t) were collected over three decades of

shear rate. In every case, steady-state stresses

were deduced from this information by taking the

average of twenty instantaneous stress values at

long times where s xy (t) and N 1 (t) were both independent of time. The averaging procedure minimizes errors caused by inevitable transient

stress fluctuations about the mean, steady-state

value. It is significant that the steady-state

stresses reported here were determined directly

from the respective time-dependent stress data

measured at constant shear rate, rather from

shear rate sweeps at long times. The former approach facilitates steady-state stress measurements under conditions where transient artifacts

due to slip at the walls, rheometer compliance,

and edge fracture can be safely ruled out. Averaging over several repeat experiments also permitted confidence intervals (error bars on plots) to

be defined, run-to-run repeatability of steadystate stresses is therefore guaranteed within the

defined intervals.

Plots of steady-state shear stress s ss and first

normal stress differences N 1,ss versus dimensionless shear rate are presented in Figure 6(a). The

dimensionless shear rate or Weissenberg number

is defined by, Wi 5 g t d0 . The similarity of the s ss

versus Wi and N 1,ss versus Wi plots for PS/DEP

solutions with varying PS molecular weight is

remarkable, but nevertheless well known.1,2 The

near-perfect overlap of the steady-state data at

Wi , 10 suggests that for the studied materials,

the terminal molecular relaxation time is more

accurately determined from zero shear viscosity

and steady-state creep compliance, than from

longtime stress relaxation data. It is significant

21

that at high rates g . t d0

, the experimental

steady-state shear stress and normal stress differences exhibit a virtual lack of dependence on

shear rate over a fairly broad range of rates. As

discussed in the previous section of the paper,

were determined directly from time-dependent

data measured at fixed shear rate. No evidence of

unstable flow or unusual transient stress behavior was observed in the range of experimental

shear rates and times for which data are reported,

indicating that the observed dependencies are

real. Plateaus in steady-state shear stress and

first normal stress differences have also been reported by Bercea et al.15 from cone-and-plate

shearing experiments using solutions of high molecular weight poly(methylmethacrylate) M w 5

23.8 3 10 6 in toluene (N/N e0 5 42 and 125). As

in the present study, these authors observed that

the range of shear rates over which the plateau is

seen in N 1,ss is shorter than the range of rates at

which a plateau in shear stress is observed. Cates

et al. have suggested that plateaus in steadystate shear stress and first normal stress differences are expected in entangled polymers when

the finite lateral size of the tube is taken into

account in stress calculations.16 Specifically,

these authors contend that because of its finite

cross section, slight differences in flow velocity

are experienced by different lateral sections of the

tube. This effect yields a contribution to shear

stress that increases linearly with rate and balances the down-turn in shear stress that would be

21

predicted at g . t d0

, if the only source of stress

was molecular orientation.

To investigate the steady shear behavior of

entangled polymers further, it is advantageous to

recast the two sets of data presented in Figure

6(a) in terms of steady-state orientation angles

x ss [ 0.5 3 atan(2 s ss /N 1,ss ) [see Fig. 6(b)]. For

all solutions investigated, a defined dependence

on Wi is clearly apparent from the data at Wi

, 10, indicating that the steady-state orientation

angle is set by g and t d0 only, in this range of

shear rates. At higher Wi, x ss is observed to become nearly independent of Wi over a range of

values that becomes larger with increasing polymer molecular weight. A limiting orientation angle x c may be deduced from the experimental

results. The limiting angle is found to lie in the

range of 6 and 9 for a nearly four-fold increase

in polymer molecular weight, confirming that x c

is indeed insensitive to polymer molecular

weight.

Steady-state orientation angles for entangled

poly(butadiene)/Flexon391 solutions, high molecular weight poly(methylmethacrylate)/toluene solutions, a poly(styrene)/tricrecyl phosphate solution, and PS-1P8M are provided in Figure 6(c) for

231

Figure 6. (a) Steady-state shear stress s ss (open symbols) and first normal stress

difference N 1,ss (filled symbols) versus dimensionless shear rate Wi 5 g t d0 . Error bars

define confidence intervals in which run-to-run repeatability of the steady-state

stresses are guaranteed. For all the polymers studied, both sets of data ( s ss and N 1,ss )

are observed to overlap over a rather wide range of dimensionless shear rates, indicating a dependence of steady-state polymer material properties on Wi only. (b) Steadystate orientation angle x 5 0.5 atan((2 s ss )/N 1,ss ) versus dimensionless shear rate for

various 18 wt % PS/DEP solutions. (c) Steady-state orientation angle x 5 0.5

atan((2 s ss )/N 1,ss ) versus dimensionless shear rate for various poly(butadiene)/

Flexon391 (PBA-PBD) [from Menezes and Graessley18]; ultra-high molecular weight

poly(methylmethacrylate)/toluene (HPMMA1 and HPMMA2) [from Bercea et al.15];

poly(styrene)/tricrecyl phosphate (PS/TCP) [Hua et al.17]; and poly(styrene)/diethylphthalate (PS-1P8M) solutions. (d) Plot of orientation angle x versus shear strain g t

at various Wi during start-up of steady shearing. The data are for an 18 wt % solution

of PS-2P9M in DEP.

variable Wi. The poly(butadiene) orientation angles were recovered from time-dependent shear

and normal stress measurements by Menezes and

Graessley obtained using a stiffened Weissenberg

Rheogoniometer.17 Narrow distribution polybutadienes M w /M n , 1.05) of variable molar mass

(PBA-Mw 5 200,000, N/Ne ' 7; PBB-Mw 5 350,000,

PBD-M w 5 813,000, N/N e ' 29), but fixed polymer volume fraction (f 5 0.0755) were used in the

study. It is noteworthy that while s ss (Wi) results

for the two most highly entangled poly(butadiene)/Flexon solutions (PBC and PBD) manifest

a regime of very weak to no shear stress depen-

232

plateau in N 1,ss is not observed in these solutions.

Orientation angle data for the high molecular

weight poly(methylmethacrylate)/toluene samples (HPMMA1, f ' 0.023 and HPMMA2, f

' 0.07) studied by Bercea et al., was determined

from s ss vs. g and N 1,ss vs. g results reported by

the authors. Data for the PS/TCP solution was

obtained from orientation angle results reported

by Hua et al.18 for solutions of a high molecular

weight poly(styrene), M w 5 1.9 3 10 6 , in tricrecyl phosphate ( f 5 0.13; N/N e ' 13), with the

exception that a terminal time t d0 ' 7.5 s (exactly one-half the value reported), was used to

compute Wi. Orientation angle data for PS-1P8M

were obtained from the present study.

Several features of the orientation angle results in Figure 6(c) are noteworthy. First, for Wi

, 10 the Wi-dependent orientation angles for the

PB/Flexon391, PS/tricrecyl phosphate solutions,

are qualitatively similar to those found for the

PS/DEP solutions investigated in the present

study. Furthermore, as was the case for the PS/

DEP solutions, orientation angles for the PB and

PS/TCP solutions are observed to superimpose

well when plotted as a function of Wi; confirming

that in this shear rate range g and t d0 are the

dominant dynamic parameters that set the level

of molecular orientation at steady-state. Second,

for Wi . 10, the PB/Flexon391 and PS/TCP solutions both manifest a regime of Wi values

where x ss shows a rather weak dependence on

Wi. As pointed out already, a similar flattening of

the Wi dependence of x is observed for PS/DEP in

the same Wi range. Remarkably, the limiting orientation angle projected for the poly(butadiene)/

Flexon 391 and poly(styrene)/diethylphthalate solutions, x c ' 7 is in the same range as the

plateau orientation angles observed for the PS/

DEP solutions.

These results are, however, quite different

from orientation angles observed for the two high

molecular weight PMMA/toluene solutions. In

these solutions two orientation angle plateau regions are apparent. Beginning at Wi value

around 2, a first plateau between 35 and 30

is observed for HPMMA1 and HPMMA2. In

HPMMA2, this first plateau region is followed by

a high-Wi regime where the orientation angle

decreases with Wi in a manner strikingly similar

to the initial decrease observed for the PS/DEP,

PS/TCP, and PB/Flexon solutions. The finding of

two orientation angle plateaus, rather than one,

in the PMMA/toluene solutions could be rational-

section of the paper, if the transition from complete contour length retraction to partial retraction is taken into account.8 Flow birefringence

experiments using polymer solutions of comparable entanglement density to the materials studied

by Bercea et al. could help resolve the source of

the orientation angle differences between PMMA/

toluene and the other polymer solutions.

Additional support for the proposal is provided

by transient orientation angle measurements following start-up of steady shearing [Figure 6(d)].

Specifically, at high shear rates, the orientation

angle is observed to undergo an undershoot before

ultimately approaching x c . This behavior was

seen in all the PS/DEP solutions investigated in

this study, but is not predicted by the DoiEdwards theory. Time-dependent birefringence

measurements during start-up of circular Couette

shear of a 3% solution of PS-8P42M in tricrecyl

phosphate also reveal similar transient undershoots of orientation angle.19 A limiting steadystate orientation angle between 10 and 14 is

suggested by the birefringence data. An undershoot in orientation angle during start-up of

steady shearing is not predicted by the recent

theory of Mead et al.,12 but is expected if the

required balance between entropic elastic restoring force and viscous drag at steady-state is enforced. Specifically, at Wi $ 1, the network and

N-mer strands trapped in it initially orient affinely. The elastic restoring force created by the

high levels of affine molecular orientation is initially larger than the viscous drag force exerted

on molecules by their neighbors. The force imbalance causes polymer segments to relax the excess

orientation until the elastic and viscous drag

forces balance at steady-state.

CONCLUSION

In this article a simple, new proposal has been

presented for polymer dynamics in fast steady

shearing flows. Specifically, we contend that in

steady shear flow a balance between the viscous

drag on polymer segments and the entropic elastic restoring force due to primitive chain orientation and stretch must be met at steady-state.

Thus, the level of molecular orientation achievable at steady-state is determined both by the

direct effect of flow on molecular orientation and

by the indirect effect of flow-induced orientation

molecules by their neighbors. For entangled polymers, the second effect is dominated by entanglement loss due to contour length retraction. Its

consequence is quantified by a new expression for

entanglement friction between molecules under

action of a directed external force.9

In a simplified analysis enforcing the proposed

balance of forces, we find that at high shear rates

21

t d0

, g , t 21

Rouse in a steady shear flow the

steady-state orientation of polymer molecules approach a limiting value x c ' atan(1/(1 1 g m,c ))

beyond which flow becomes incapable of producing further molecular orientation. If molecules

are assumed to retain their equilibrium contour

length at shear rates g , t21

Rouse, the limiting orientation angle is found to be x c ' 33. This angle

changes to x c ' 15.6 when shear-induced

changes in polymer contour length at rates below

t21

Rouse are taken into account. The latter prediction is higher than limiting orientation angles

determined from steady shear rheological measurements using poly(styrene)/diethyl phthalate,

poly(butadiene)/Flexon391, poly(methylmethacrylate)/toluene, and poly(styrene)/tricresylphosphate

solutions. These solutions show limiting orientation angles in the range of 6 to 9 over a wide

range of polymer molecular weight and monomer

chemistries. Orientation angle undershoots deduced from flow birefringence measurements during start-up of steady shearing are confirmed by

our PS/DEP experiments. Both sets of results are

consistent with relaxation of extra molecular orientation induced by a transient imbalance of viscous drag, and elastic restoring force acting on

polymer molecules during start-up of steady

shearing.

The authors are grateful to the National Science Foundation Grants number DMR9816105 and CTS9624254,

233

Board, Advanced Technology Program for supporting

this study.

1. Doi, M.; Edwards, S. F. The Theory of Polymer

Dynamics; Oxford Science Publications: New York,

1986.

2. Larson, R. G. Constitutive Equations for Polymer

Melts and Solutions, Butterworths: London, 1988.

3. Osaki, K.; Nishizawa, K.; Kurata, M. Macromolecules 1982, 15, 1068.

4. Osaki, K. Rheol Acta 1993, 32, 429.

5. Marrucci, G. J Non-Newtonian Fluid Mech 1996,

62, 279.

6. Ianniruberto, G.; Marrucci, G. J Non-Newtonian

Fluid Mech 1996, 65, 241.

7. Archer, L. A.; Mhetar, V. R. Rheol Acta 1998, 37,

170.

8. Mhetar, V. R.; Archer, L. A. J Non-Newtonian

Fluid Mech 1999, 81, 71.

9. Mhetar, V. R.; Archer, L. A. Macromolecules 1998,

31, 6639.

10. Bueche, F. J Chem Phys 1952, 20, 1959.

11. Doi, M. J Polym Sci Polym Phys Ed 1983, 21, 667.

12. Mead, D. W.; Larson, R. G.; Doi, M. Macromolecules 1998, 31, 7895.

13. Mhetar, V. R.; Archer, L. A. Macromolecules 1998,

31, 8617.

14. Crawley, R. L.; Graessley, W. W. J Rheol 1977, 21,

19.

15. Bercea, M.; Peiti, C.; Simionescu, B.; Navard, P.

Macromolecules 1993, 26, 7075.

16. Cates, M. E.; McLeish, T. C. B.; Marrucci, G. Europhys Lett 1993, 21, 451.

17. Menezes, E. V.; Graessley, W. W. J Polym Sci

Polym Phys 1982, 20, 1817.

18. Hua, C. C.; Schieber, J. D.; Venerus, D. C. J Rheol

1999, 43, 701.

19. Oberhauser, J. P.; Leal, G. L.; Mead, D. W. J Polym

Sci Polym Phys Ed 1998, 35, 265.

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