Rheology
H. MAVRIDIS and R.N. SHROFF
INTRODUCTION Lem (1) and Harrel and Nakajima (2) discuss the
1778 POLYMER ENGINEERING AND SCIENCE, MIDDECEMBER 1992, Vol. 32, NO. 23
Temperature Dependence of PolyoleBnMelt Rheology
The purpose of this paper is to develop a unified ular structure on the flow activation energy of poly
framework to treat both dynamic and steady rheologi mer melts and concluded that long chain branching
cal data and apply it to polyolefin melts. in LDPE is responsible for the anomalous behavior of
activation energy of LDPE. Similar observations and
TEMPERATURE DEPENDENCE OF experimental confirmation of “thermorheological
RHEOLOGY complexity” in LDPE have been reported repeatedly
Background (9, 1619).
Graessley and coworkers (10,2022) found indica
The temperature dependence of rheology has tions of thermorheological complexity” in model
mainly been discussed in the literature either in the branched polymer melts. Graessley (11, 12) exam
context of linear viscoelasticity or in terms of steady ined theroetically the effect of long branches on the
shear viscosity. In the latter case the shear stress (T, temperature dependence of rheology and suggested
the shear rate y, and the viscosity 77. are related two reasons for the observed.behavior. One has to do
through: with the temperature dependence of the entangle
u = 77.j (1) ment density; the other is related to the differences in
the paths of conformational relaxation of linear and
Mendelson (3) showed how to extract the tempera branched chains. Linear chains rearrange by repta
ture dependence from steady shear viscosity data by tion. The presence of long branches blocks reptation;
plotting the shear stress (vertical) vs. the shear rate the long chain branches themselves rearrange by
(horizontal) data at different temperatures. passing through relatively compact conformational
A review of the literature shows that it was estab states that may have different energies, depending on
lished early on that polymer melts are thermorheolog the temperature coefficient of chain dimension in the
ically simple. According to Markovitz (41, the term species ( 12).
“thermorheological simplicity” was originated by Verser and Maxwell ( 19) examined the temperature
Schwarzl and Staverman (5) as the “assumption of dependence of linear viscoelastic data (frequency re
uniform temperature dependence for all relaxation sponse). They found that when the classical treat
elements.” The modulus is usually only weakly de ment of timetemperature superposition (6) was a p
pendent on temperature (6). and thus thermorheo plied to the data, then the resulting activation energy
logical simplicity has come to signify the ability to was modulus dependent (in fact their data show the
superpose data from different temperatures by a hori activation energy to increase with complex modulus,
zontal shift on a shear stress vs. shear rate graph (for Fig. 19 in Ref. 19, an unusual result for LDPE). The
steady shear data) or on a modulus vs. frequency modulus dependence was removed when a modulus
graph (for linear viscoelastic data). The temperature shift was also applied to the data (“vertical” as well as
shift is expressed in terms of a flow activation energy “horizontal” shift). Verser and Maxwell (19) obtained
for polyolefin melts. When the flow activation energy the vertical shift from the temperature dependence of
shows a stress dependence (for stress vs. shear rate the steadystate compliance. However, most commer
data) or a modulus dependence (for modulus vs. fre cial polyethylenes are so broad that the terminal
quency data), then this is characterized as “thermo region (i.e., the low frequency region where G‘ a w 2 ,
rheological complexity.” Long chain branched G” a w , and J,“ = G’/G” 2, is not accessible and there
polyethylene (LDPE) exhibits thermorheological com fore the steadystate compliance J,“ would have to be
plexity (in contrast to the behavior of linear polyeth calculated through data extrapolation, which may
ylenes) as was pointed out repeatedly in the literature introduce large errors. I t is an objective of the present
(7 13). paper to develop procedures for obtaining the vertical
I t will be shown in this paper that LDPE may still shift from data available over the experimentally ac
be considered “thermorheologically simple” in the cessible range (thus not involving any extrapolation).
sense that all relaxation times have the same temper In what follows we will deal mainly with the temper
ature dependence and all relaxation moduli have the ature dependence of linear viscoelastic data for two
same temperature dependence (characterized by a reasons: (i) the steady shear data should have the
“vertical” or modulus temperature shift). However, same temperature dependence as the linear vis
neglect of the “vertical” or modulus shift leads to coelastic data (41, and (ii) linear viscoelastic data
a modulus (or stress) dependent flow activation ener include both the viscous and the elastic response of
gy, and thus to an apparent thermorheological the material and are therefore more complete. (Steady
complexity. shear data usually involve the viscous response only.
Early experimental observations that: (a)long chain The elastic response, i.e., normal stresses, is very
branched polyethylene (LDPE) has a higher flow acti difficult to measure.)
vation energy than linear polyethylene (HDPE), and The temperature dependence of linear viscoelastic
(b) the flow activation energy of LDPE depends on data is usually discussed in terms of the relaxation
shear stress (for shear stress vs. shear rate data, spectrum H ( T ) ,where H ( T )is the relaxation strength
shifted horizontally) were reported by Sabia (7) and of the material at relaxation time T . All other linear
Mendelson (8). Porter and coworkers (9, 14, 15) ex viscoelastic properties can be derived from the relax
amined the effects of polymer composition and molec ation spectrum. For completeness and ease of refer
POLYMER ENGINEERING AND SCIENCE, MIDDECEMBER 1992, VOl. 32, NO. 23 1779
H. Mauridis and R. N . Shroff
ence we summarize the most common of them below: reference temperature. The horizontal shift factor a ,
reflects essentially the temperature dependence of
Storage Modulus: relaxation time :
Loss Tangent:
G ( w )
tan 6 ( w ) = 
a,=exp
[?
 ___
(T+;73 To+ 273
1780 POLYMER ENGINEERING AND SCIENCE, MIDDECEMBER 1992, Vol. 32, NO. 23
Temperature Dependence of PolyoleBn Melt Rheology
entanglements varies as (from Eqs 6 and 10): level of loss tangent provides equally acceptable scal
ing parameters), i.e. plotting G'/G, or G / G , vs.
w / w , results in a temperature independent graph.
The temperature dependence of some commonly
referred to viscoelastic properties is given by:
POLYMER ENGINEERING AND SCIENCE, MIDDECEMBER 1992, VOl. 32, NO. 23 1781
H. Mavridis and R. N . Shrofl
form: from:
Ez
Such a shift factor is indeed appropriate for most tion energy Esup as:
linear polymers (as will be shown later).
To examine the magnitude of vertical shift factor
predicted by Eq 9, we select a HDPE, for which the
melt density was determined a s a function of temper
[ (
~ 1 , , ~ = e x
p ~
T+;73 To+ 273
POLYMER ENGINEERING AND SCIENCE, MIDDECEMBER 7992, VOl. 32, NO. 23 1783
H. Mavridis and R. N . Shroff
where ciT is given by Eq 8, b, is given by Eq 12, rn is Step 3: Using the computed activation energies, shift
the order of the fitting polynomial, and ( c k , k = 0, rn) the raw data to a reference temperature for
are the polynomial coefficients. The nonlinear least visual inspection of the goodness of superpc
squares fit would now involve (rn+ 3) parameters: sition.
+
( rn 1) polynomial coefficients, the horizontal activa
RESULTS AND DISCUSSION
tion energy E H ,and the vertical activation energy E,.
Note that in this case the estimates of two activation Dynamic data (frequency response in the linear
energies will be statistically correlated (23). This is to viscoelastic region) were obtained with the Rheomet
be contrasted with the estimation obtained from rics Mechanical Spectrometer (RMS) and the Rhec
dynamic data from which the two activation ener metrics Dynamic Analyzer I1 (RDA2) operating in the
gies are obtained independently and therefore parallel plate mode, while steadyshear viscosity data
uncorrelated. were obtained with a gas extrusion rheometer (25).
In the present paper we extracted activation ener All sample plaques for use in RMS and RDA2 were
gies from the dynamic data and then used these stabilized with additional antioxidants to avoid chain
activation energies to shift the steady,shear data and extension and scission during measurement.
check whether steadyshear data superimpose. We Some of the data (HDPE1 in Table I , and LDPE1
could have done it another way; we could have ex and LDPE3 in Table 5) were obtained on solution
tracted activation energies from steady shear data (as dissolved samples. The polymer was dissolved in xyl
discussed above) and compared them with those ex ene, the xylene was allowed to evaporate, and the
tracted from dynamic data. We pursued the first a p final sample was dried in vacuum for 72 h. Polymer
proach because dynamic data are complete (include samples were solution dissolved in order to eliminate
both the viscous and elastic response) and are more effects of any shear prehistory (e.g., during pelletiz
accurate than steadyshear data. ing). Shear prehistory is known to affect the rheologi
cal behavior and its temperature dependence, espe
METHODOLOGY cially for LDPE ( 17).
The theory outlined in the previous section is a p
plied practically a s follows. HDPE
Tabulated results for HDPE are given in 'fable 1 for
Step 0: Collect dynamic data measured at different five different resins. In all cases the horizontal activa
temperatures. The larger the number of tem tion energy turns out to be about 6 kcal/mole, and
peratures at which data is available and the the vertical activation energy is zero. The value of 0.8
wider the temperature range, the better the kcal/mole for HDPE1 must be treated with caution,
estimation of the activation energies will be. due to the fact that the material was xylene dissolved.
Step 1: Perform a preliminary screening of the data. Also the value of 0.14 kcal/mole for HDPE5 is
The plot of log,,(tan 6 ) vs. log,,(G*) is partic marginally significant. These results are in accord
ularly helpful. with those of the literature (3).
1.1 If the data from different temperatures in
the above plot of log,,(tan 8 ) vs. log,,(G*) LLDPE
superimpose (within experimental error),
Tabulated results for LLDPE are given in Table 2,
then a vertical shift is not required and
for three different resins. The horizontal activation
a n E,= 0 should be expected.
energy varies in the range 7 to 8 kcal/mole, which is
1.2 If the data from different temperatures in
the plot of log,,(tan 6 ) vs. log,,(G*) do
not superimpose but fall onto parallel Table 1. Results for HDPE.
curves, then a vertical shift is required
P MI** EH EV
and a nonzero E , should be expected. Resin g/cm3 g/10 min kcal/mole kcal/mole
1.3 If the data from different temperatures in
HDPE1* 0.96 1.o 6.60 & 0.44 0.80 & 0.33
the plot of log,,(tan 6 ) vs. loglo(G*) do HDPE2 0.96 0.8 5.80 k 0.52 0.0
not superimpose and do not fall onto par HDPE3 0.96 0.8 5.94 f0.58 0.0
allel curves, then we cannot handle this HDPE4 0.96 0.9 6.28 f 0.49 0.0
case within the present theoretical HDPE5 0.96 0.2 6.10 f0.22 0.14 f 0.13
framework. Although rare, this case is * = Xylene dissolved sample.
"=190'C12.16 Kg.
indicative of relaxation times (or moduli)
having nonuniform temperature depen
dence, and does occur in practice (e.g., Table 2. Results for LLDPE.
certain multiphase systems). MI
Step 2: Calculate the horizontal and vertical activa 9/10 P EH E"
tion energies, as described above. Examine Resin Comonomer min g/cm3 kcal/mole kcal/mole
the confidence intervals of the vertical activa LLDPE1 Butene 1.0 0.918 7.27f0.19 0.61 ko.14
tion energy and discard if found to be statisti LLDPE2 Butene 1.0 0.918 7.07 & 0.14 0.0
cally insignificant (23). LLDPE3 Octene 1.O 0.920 7.77 k 0.24 0.25 k 0.18
in agreement with literature results. The highest acti rial, and are plotted in Fig. 5 (three temperatures) as
vation energy (7.77 kcal/mole) is for LLDPE3, a n shear stress vs. shear rate. Shifting these data (as
octene based LLDPE (as opposed to LLDPE1 and explained earlier) gives the graph of Fig. 6, which
LLDPE2, which are butene based LLDPEs). This re shows good superposition, i.e. steadyshear data were
sult was expected since the activation energy in superposed with the activation energies determined
creases with the molar volume of the repeating unit from linear viscoelastic data.
of the polymer (1 5).
Polypropylene
The vertical activation energy is nearly zero for
LLDPE2 and LLDPE3. For LLDPE1 it is 0.61 Tabulated results for PP are given in Table 3 for
kcal/mole, which represents a vertical shift factor of seven different resins. Averaging out the horizontal
only 10% between 150 and 2 10°C. activation energies gives a value of 9.4 kcal/mole,
As a typical example consider the LLDPE 1; a graph again close to values reported in the literature (9 10
of log,,(tan 6) vs. log,,(G*) is given in I?g. 2. Raw kcal/mole). The vertical activation energy turns out
data of storage modulus and dynamic viscosity vs. to be zero, or very small and marginally significant.
frequency at different temperatures are plotted in
EVOH
Fig. 3. These same data upon shifting give the graph
of Fig. 4. The good superposition is a verification that Results for EVOH (ethylenevinyl alcohol copoly
the activation energies used for the shifting (listed in mer) are given in Table 4 for two different resins. The
Table 2, and in Fig. 4 ) are adequate. average horizontal activation energy is 14.6kcal/mole
Steadyshear data were also available for this mate and the vertical activation energy is zero.
It is not clear why the vertical activation energy
turns out to be zero, given that EVOH is produced
Shi'!ed t o 190°C
t,=7,270 cal/rnole
Ev 610 cal/rnole
a" lI
?210 2  4
I,
U
10' 105
Complex Modulus, d y n j c m
a
2 I I ,,q
,
I I I llllil
.
it 10 1  10
I Shifted Frequency
Fg. 2. Loss tangent us. complex modulus data a t differ I/)
ent temperatures superimpose for a linear polyethylene Rg. 4 . Shijted data of storage modulus and dynamic uiscos
( L D P E 1). ity us. frequency, showing superposition (LLDPE1).
LLDPE 1


4 T= 170°C
T= 1 9 0 ° C
r 1 0 5 4
t +
w i LLDPE 1 i

_++

150°C
T=
T= 170°C
Capillary Data
Bagley & Rablnowitch
 T=190°C
T=210°C
corrections applied
FTg. 3. Storage modulus and dynamic uiscosity us. frequency FTg. 5. Steadyshear data (shear stress us. shear rate) a t
a t different temperatures (LLDPE1). different temperatures (LLDPE1).
POLYMER ENGINEERING AND SCIENCE, MIDDECEMBER 1992, VOl. 32, NO. 23 1785
H. Mavridis and R. N . Shroff
through the hydrolysis of VAE (Vinyl acetateEthyl EVOH may have a value of d In( r z > / d T , such that
ene copolymer). VAE, in turn, does have long chain the effect of long chain branches on the temperature
branching and does require a vertical shift. Part of dependence of rheology is minimal. More work on
the reason may be that all branches through the this matter is in progress.
acetate group in VAE are lost after hydrolysis and,
therefore, EVOH is expected to have substantially LDPE
less long chain branching than its predecessor VAE Results for LDPE (long chain branched) are tabu
(26).A second possible reason relates to the tempera lated in Table 5: invariably, the vertical activation
ture coefficient of unperturbed chain dimensions energy is nonzero and around 2 kcal/mole (with the
d In( r:)/dT. As was pointed out by Graessley (12). exception of the model starHPBs).
"species where long branches have little effect on the Let us consider in some detail a typical LDPEthe
temperature coefficient of viscosity also have small LDPE4. Raw data from different temperatures are
temperature coefficients of chain dimensions." For plotted a s log,,(tan 8 ) vs. loglo(G*)in Fig. 7. Obvi
polyethylene this coefficient is d In( r z > / d T = ously the data do not superimpose, but they fall onto
 1 . 1 * l o p 3" C  (12, 27, 28). Stars of polystyrene, parallel curves, an indication that a vertical shift is
polybutadiene, and polyisoprene have positive and the necessary and sufficient step to superpose the
small temperature coefficients of chain dimensions data. Indeed, the effect of vertical superposition is
and do not show the anomalous behavior due to long shown in Fig. 8. Now the data superimpose and they
chain branching as polyethylene does (12). Therefore, form a master curve. It is important to note that the
two shifts (horizontal and vertical) are sufficient to
superpose all viscoelastic properties. As is shown in
Shifted to
EH=7.270 cal/rnole
190°C
E,,=610 c a l / r n o l e *B
db % 1 Fig. 11, both the storage modulus vs. frequency data
(Fig. 9 ) and loss modulus vs. frequency data (Fig.10)
superimpose after a horizontal and vertical shift are
applied to the data.
The importance of the vertical shift will be further
illustrated by examining the problems resulting from
a horizontalonly shift. Traditionally, the data are
shifted horizontally only. As was shown for HDPE,
LLDPE, PP, and EVOH (and for a wide variety of other
systems) a horizontalonly shift is adequate for linear
I
m 1 Bagley '& Rabinowitch materials. When we attempt to apply a horizontalonly
A
2 4
I corrections applied
shift for long chain branched materials we see the
I
72
following: Fig. 12 shows a horizontalonly shift for
:4
a,
+I g o
10 e7YTr
1 1 I I
7,
6 7 8 9 ' 2
,
J
7
I 5
'T'T
6,113
p7 storage modulus vs. frequency data. The superposi
m 1 10 10 tion is indeed good for the storage modulus data. This
Shifted Sbeor Rate ( s e c  ) superposition was made possible by allowing the acti
Fig. 6. The data of FUJ. 5, shijted at 190°C (LLDPE1). vation energy to become a function of storage modu
lus. Specifically, the requirement of a horizontalonly
shift produces a set of temperature shift factors at
Table 3. Resultsfor Polypropylene. every level of storage modulus, from which set of shift
MFR* EH EV factors we compute a n activation energy at every level
Resin Comments g/10 min kcal/mole kcal/mole of storage modulus.
PP1 Homopolymer 37 8.95 k 0.23 0.29 & 0.17 When the temperature shift resulting from Fig. 12
PP2 Homopolymer 26 9.94 k 0.32 0.24 k 0.19 is applied to the loss modulus data we get Fig. 13,
PP3 Random 2 8.74 & 0.22 0.36 & 0.16 which shows that the data do not superimpose very
Copolymer well. (One must be very critical and demanding on
PP4  0.33 10.74 f 0.22 0.0
PP5 Homopolymer 42 8.79 k 0.26 0.0 the goodness of superposition. If the nonsuperposi
PP6 Copolymer 0.2 9.90 k 0.55 0.0 tion of the data in Fig. 1 3 is dismissed as simple
PP7 Copolymer 13.4 8.51 f 0.66 0.0 scatter, then one would totally miss the problem. In
25.9% CF fact this is what has happened in the literature, and
* = 2 3 O C / 2 . 1 6 Kg it was pointed out earlier by Verser and Maxwell (19).
Moreover, the activation energy required for shifting
the data in Fig. 12 is now a function of storage
Table 4. Resultsfor EVOH.
modulus, a s shown in Fig. 14 (solid line), decreasing
MI En EV with increasing modulus.
Resin Comments g/10 min kcal/mole kcal/mole Similarly, when we apply a horizontalonly shift to
EVOHI 32% mole C; 1.3 15.45 k 0.96 0.0 the loss modulus data (by allowing the activation
I.19 g/cm3 energy to become a function of loss modulus), we get
EVOH2 44% mole C; 5.5 13.78 k 0.60 0.0 good superposition for loss modulus a s shown in
1. I 4 g/cm3
Fig. 15. But applying this temperature shift to the
Mi P EH E"
Resin Comments g/10 min glcm3 kcailmole kcal/mole
LDPE1 Xylene  0.931 14.67 k 0.30 2.31 f 0.26
(NBS 1476*) Dissolved
LDPE2 Pellet 1.2 0.931 16.02 ?C 0.38 2.47 + 0.31
(NBS 1476)
LDPE3n Xylene 
0.919 15.27 f 0.28 2.44 f 0.17
Dissolved
LDPE4n Pellets 1 .I 0.919 16.01 f 0.15 2.28 f 0.09
LDPE5 Pellets 2.9 0.926 15.78 +_ 0.20 1.45 0.13
LDPE6 Pellets 1.8 0.923 14.62 k 0.17 1.77 f 0.13
3Star HPB M, = 98,000   15.31 f 0.31 1.01 f 0.32
Data from (10)
4Star HPB M, = 133,000   16.47 ?C 1.43 0.97 f 0.37
Data from (10)
*=Shift at constant modulus performed.
=Same LDPE.

 T= 130°C
i
I
I
LD P E . 4

I
I
0 % .
*
TL150"C
T 1 7 0 ° C
T ' 90°C
I \ i
=.
 * a .
r 1
Shifted t o T=15OoC i
1
i
€,=I 6,010 cal/mole
E,= 2,280 c al / mo l e
Fg. 7. Loss tangent us. complex modulus data at dlfferent R g . 8. The data of Fg. 7, superimpose after a "vertical"
temperatures fall onto parallel curves for a long chain (modulus) shift has been applied to the data (LDPE4).
branched polyethylene (LDPE4), illustrating the need for a
modulus shift with temperature ("vertical" shifi.
Shifted t o 1=150"C
a t c o n s t a n t G'
with EH=EH(C)
Ftg. 10. Loss modulus us. frequency at different tempera Ftg. 12. The storage modulus data of Fig. 9 (LDPEE~),
shlfled
tures (LDPE4). horizontally only, with an activation energy as afunction of
storage modulus.
LDPE4 * 0 4
0 0 :
'1
Shifted t o T=15O0C
E,=16,010 col/rnole 3
Ev= 2,280 col/mole
Ji
Lr
a0 I
7
0.0'7
:t> ~
no
m r T T  71, , 7m
10 r,
7 +
10'
'0 '0
STIfteo F r e q J e T c j
Ftg. 1 I. The storage and loss modulus data of Fqs. 9 and 10
after horizontal and vertical shifting, showing good superpe Ftg. 13. The temperature shift from Fig. 12 applied to the
sitwn (LDPE4). loss modulus data (LDPE4).
LDPEs in Fig. 19 we expect a n ordering in the level of Naturally, the question arises as to what makes
LCB a s LDPEG/LDPE5/LDPE4, with LDPE4 hav long chain branched materials to require a vertical
ing the highest level of LCB. The E, values of Table 5 shift. One potential answer can be provided with
do not follow this order. One might expect a better reference to Eq I I and the concept of molecular
correlation of E , with other LCB parameters such as weight between entanglements (suggested also by
branch length and distribution. Unfortunately, this Graessley in his discussions of the effect of long
type of information was not available for the LDPEs chain branches on the rheology and polymer melts
studied in this work. I t appears that the EH and E, and its temperature sensitivity (11 , 12)). For a verti
values within the LDPE group of resins do not corre cal activation energy of 1.0 kcal/mole and greater,
late with the level of LCB present in these resins. Eq 1 1 predicts that the molecular weight between
It is interesting that even Graessley's model star entanglements decreases with increasing tempera
branched polybutadienes (lo) show the necessity of a ture. This means that the entanglement density in
vertical shift (HPB in Table 5). In fact, Ref. 10 dis creases with increasing temperature, although it is
cussed the anomaly observed when shifting the data not clear why would the entanglement density in
horizontally only (i.e., the modulus dependence of crease (with increasing temperature) for long chain
activation energy, see Fig. 9 in Ref. 10). As was branched and not for linear polymers.
mentioned repeatedly above, a graph of log,,(tan 8 ) As noted by Graessley (12). the temperature depen
vs. log,,( G*) can immediately identify the necessity dence of entanglement spacing is one of two con
(or absence thereof) of a vertical shift. The graph for tributing factors. The second relates to the suppres
the 3star HPB in Fig. 20 clearly shows parallel sion of reptation in branched polyethylenes (12).
curves that require vertical shift. Linear chains rearrange by reptation; long chain
co
O f
~~
Ftg. 14. Activation energy as a function qf storage modulus Fig. 16. The temperature shlft from F ~ J . 15 applied to the
Cfor horizontalonlyshijt at constant G') and as afunction of storage modulus data (LDPE4).
loss modulus (for horizontalonlyshtft at constant G").
r TT ~ 1 m r . .~
ci
P
i
' ,./
Fig. 17. Steadyshear data (shear stress us. shear rate) at
Frg. 15. The loss modulus data of Fig. 10 (LDPE4),shtfted di'erent temperatures (LDPE4).
horizontally only, with an activation energy as a function of
loss modulus.
dence (characterized by a "horizontal activation en
ergy") and all relaxation moduli have the same tem
branches block reptation and rearrange by a process perature dependence (characterized by a "vertical
of "path breathing" (12). Both mechanisms have an activation energy"). Procedures were outlined for ex
impact on the temperature dependence of rheology, tracting these activation energies for rheological data.
but it is not clear how to separate the two effects. The recommended (and adopted) approach was to
EVA extract the temperature dependence from linear vis
coelastic data: in this case the two activation energies
Results for EVA (ethylenevinyl acetate copoly can be estimated independently (and statistically un
mers) are tabulated in Table 6 for two resins. The correlated).
horizontal activation energy for EVA 1 is higher than I t was also shown theoretically (and demonstrated
that for EVA2, presumably due to its higher VA experimentally) that neglect of the vertical shift leads
content. As expected, a vertical activation energy of to a stress (or modulus) dependent activation energy
similar level as that of LDPE was found, thus further and makes impossible the superposition of both loss
reconfirming that the necessity of the vertical shift is and storage modulus data. The long standing prob
associated with long chain branching. lem of a stressdependent activation energy in long
chain branched LDPE was identified as originating
CONCLUDING REMARKS
from the neglect of the vertical shift.
The fundamentals of the temperature dependence The theory was applied successfully to many poly
of rheology were reviewed. We considered the case (by olefin melts, including HDPE, LLDPE, PP, EVOH,
far the most common in polymer melts) where all LDPE, and EVA. Linear polymers (HDPE, LLDPE, PP)
relaxation times have the same temperature depen and EVOH do not require a vertical shift, but long
POLYMER ENGINEERING AND SCIENCE, MIDDECEMBER 1992, VOI. 32, NO. 23 1789
H. Mavridis a n d R. N . Shroff
;;A' T
2 : ; ; ; ; ;  : m B
105 10
FKJ. 18. The data of Fg. 17 shLJed at 150°C. using the Co m p 1 e x M o d u I u s ( d y n / c rri *)
activation energies computed from dynamic data (LDPE4). Fg. 20. Rheological data f o r 3Star HPB (datafrom (10)).
,'
i Table 6. Resultsfor EVA.
r\
.. 
1
MI Weight E, E"
1 .
 . P
Resin g/cm3 g/10 rnin %VA kcal/mole kcal/rnole
EVA1 0.98 3.5 51 17.63 f 0.30 1.65 k 0.15
EVA2 0.932 28 14.8 14.30 0.53 2.04 f 0.36
1790 POLYMER ENGlNEERlNG AND SCIENCE, MIDDECEMBER 1992, VOl. 32, NO. 23
Temperature D e p e n d e n c e of P o l y o l e j h Melt Rheology
nation of E q s A. 1 and A . 3 gives:
POLYMER ENGlNEERlNG AND SCIENCE, MIDDECEMBER 7992, VOl. 32, NO. 23 1791