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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
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
(1)
223
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
zN 5
N
N z m,
N e0
(2)
zC 5 zN
S D S D
VT
VC
5 zN
L c~N!
R
<
N3
2 zm
N e0
(3)
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
(6)
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,
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)
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)
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)
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
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)
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
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-
230
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,
232
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
233