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Rheological characterization of PET resins using a multimode Phan-Thien-

Tanner constitutive relation

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DOI: 10.1007/BF00368134

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,|.heolActa 36:568-578(1997)
O Steinkopff Yerlag 1997

Sawas G. Hatzikiriakos Rheological of polyethylene

characterization
Glenn Heffner
Dimitris Vlassopoulos resinsusinga multimode
terephthalate
KostasChristodoulou
relation
constitutive
Phan-Iien-Tanner

Abstract Linear viscoelastic,shear, position.The rheologicaldataob-

Received:22 Apil 1991
Accepted:30 June 1997
Prof. S.G. Hatzikiriakos(t=)
Departmentof ChemicalEngineering
University of British Columbia
VancouverBC V6T lTA,Canada
G. Heffner
Central Researchand Development
DuPontC.
Wilmington, Delaware(19880-03l0), USA
D. Vlassopoulos. K. Christodoulou
Foundationfor Researchand Tixhnology
Institute of Electronic Structureand Laser
Hellas, Heraklion
Crete. Greece
and extensionalrheologicalcharac-
terizationof linear and branched
Poly(EthyleneTerephthalate)resins
(PET) was carried out by meansof
both a parallel-plateand capillary
rheometers.Before loading into the
rheometers,the polymer Pellets
were thoroughly dried at well-char-
actenzedconditions long enough to
obtain consistentand reproducible
results.Continuing polymer degrad-
ation and poly-condensationreac-
tions in the relativelyopen environ-
ment of the parallel-platerheometer
were accountedfor by correcting
the data using material-timesuper-
tained were used to fit by nonlinear
optimization, the linear relaxation
spectrumand nonlinearparameters
of a multi-mode Phan-Thienand
Thnner(PTT) constitutiverelation.
It was found that this model can
representrheological data for PET
resins very well and as a result may
be usedin relevant processingflow
simulations,i.e. film casting.
Key words Polyethylene
terephthalate- Phan-ThienThnner
model - material time correction-
mutating materials

flows such as small-amplitude oscillatory shear flow

lntroduction
between parallel plates and finite-rate flow through ca-
pillaries. Seriousdifficulties are encounteredin rheolog-
Two of the main applicationsof polyethylene-terephtha- ical testing of condensationpolymers like PET, how-
late (PET) resins are film casting and extrusion coating ever: 1) the rheological properties are greatly affected
of sheet material. Efforts to increaseproduction speed by moisture (White and Yamane, 1985; Jabarin and
or reduce film thicknessby going to higher draw ratio Lofgren, 1986); therefore, the material must be care-
(take-up roll speed/dieexit melt speed) are limited by fully dried before testing. 2) The open environment
edge neck-in and bead formation, but mainly by pro- (nitrogen, vacuum, or dry-air) of the parallel-platerhe-
cess instabilities that give rise to spontaneousthickness ometer facilitates rapid withdrawal of reaction bypro-
and width oscillations (draw resonance,edge wave) ducts and shifts poly-condensationand/or degradation
(Pakulaand Fischer,1981). reactions to high conversions (Dealy and Wissbrun,
Computational fluid mechanics modeling can help 1990). Therefore, a procedureis needed to reduce the
predict such instabilities and extend the parameterrange data to zero-time,i.e. the moment of loading before any
of stable and defect-free operation (so-called "process structuralchangestook place.
operability window"). A predictive model requires a In this paper linear viscoelastic,shear,and exten-
constitutive relation that adequatelydescribesthe rheo- sional rheological characteization of three industrial
logical responseof the melt at the shear and extension PET resins were carried out at drying conditions that
rates of the process. Such a relation is usually deter- were iteratively determinedto obtain consistentand re-
mined by testing the material in simple rheometric producible data. The data were then used to fit by non-
 S.G Hatzikiriakoset al. 569
PET rheologyusinga PTT constitutivemodel

linear optimization,the linear relaxationspectrumand 106

additionalnonlinearparametersof a multi-modeconsti-
tutive relation proposed by Phan-Thien and Thnner 105
(Phan-Thienand Tanner, 1977). The fitted relation will @

be used in the future in a finite-element model of the I ''oo

isothermalfilm casting processin the casting span in *
order to detect the operability window of the processas (u 103
,< - - ^aa
(L oo"
a function of the molecular structure of the PET resin E!iio oo oo oo4^!io ooooooooooo
b 10'
l o"
used. o
o

Materials
Three PolyethyleneTerephthalate(PET) resins of differ-
ent molecular weight and structurewere studied.One of
the resins had a linear structure,commerciallyknown
as HoechstCelaneseT-89 (a bottle resin).Here, it is de-
noted as PET:I. From the other two, PET-Z also has a
linear structure although a smaller molecular weight
(deducedfrom viscosity comparison)comparedto PET:
1; finally, PET:3 is a branched polymer. PET:I and
PET:3 have a melting point in the range of 240-250"C
determinedfrom Differential ScanningCalorimeteranal-
ysis (DSC) while PET:2 has a higher one falling in the
range from 255-265"C.
Basedon the DSC results,the rheologicalmeasure-
ments were safely conducted in the range of 260-
300"C for PET:I and PET-3, and 27U300"C for PET-
2. Above 300 "C, the polymers degraderelatively fast
and it was impossibleto get reliable measurements.
Rheolo$cal
measurements
Two types of rheological measurementswere carried
out: i) linear viscoelastic measurements(mainly fre-
quency sweep experimentsfrom 0.1-500rad/s) on a
Rheometric Scientific SR-200 (stress-controlledrhe-
ometer). We used the parallel plate geometry using dis-
posable plates with diameters25 mm and 40 mm. The
linear measurementswere used to fit the viscoelastic
spectra with a small number (typically 3-4) of modes.
They were also used to study the time-dependentstruc-
tural changesof the resins and to reduce the data to
zero time by applying material-timesuperposition;ii) a
capillary rheometeroperatedat constant rate was used
by meansof which the shearand extensionalviscosities
at high rates were determined. The latter were deter-
mined using the Cogswell'sanalysis(Cogswell, 1912).
The dynamic viscosity data were compared with the
shear ones in order to check the applicability of the
Cox-Merz rule (Dealy and Wissbrun,1990).
Among various drying procedurestested,two gave
consistentand reproducibleresults: vacuum drying at
160'C for at least6_10h or vacuumdrvins at 130"C
o
g 10' o
o
o
o
100 oo PET-'I
o oc
T=260
10-1
10r 100 101 1G 103
ro (radls)
Fig. I The effect of drying (160'C for 7 h) on the rheologicalprop-
erties of PET-I at 260"C. Closed symbols refer to dried pellets and
open to notdried. Notdrying decreasesthe propertiesby almost one
order of magnitude
for 18-24 h. It was also found that compressionmold-
ing of the polymer disk samplesfor the parallel-plate
viscometric measurementsresultedin irreversible struc-
tural changesof the material that were manifestedas in-
consistentrheological data regardlessof drying proce-
dure. For all resultspresentedbelow, the polymers were
always loaded into the rheometersin the form of dried
pellets. Care was taken to avoid any formation of bub-
bles during loading.
Figure I illustrates the effect of drying on the rheo-
logical properties of PET:I at 260'C. It can be seen
that no drying of pellets (open symbols) decreasesthe
rheological properties by almost one order of magni-
tude. This is consistently found at other temperatures
(higher) for PET-I as well as for the other two poly-
mers testedin this work.
The effect of pre-forming the sampleby compression
molding before loading onto the rheometeron the rheo-
logical propertiesof PET was also studied.It was found
that such a procedureto measurethe rheologicalproper-
ties results in a dramatic decreaseof the measureddy-
namic moduli, loss and storagemoduli, G" afid G', as
well as of the complex viscosity,r7*. It seemsthat un-
dried pellets under compressionmolding undergo a sig-
nificant irreversible structural change. No matter how
thorough drying follows, the measuredproperties re-
main relatively low compared to those measured on
thoroughly dried pellets before being loaded directly
into the rheometer(no pre-forming of sample).
Figure2 illustratesthe effect of polymer exposureto
high temperaturein an open environment (under nitro-
gen) on the rheologicalpropertiesof PET-2.In particu-
lar, Fig.2 plots four consecutivefrequencysweepson
570 Acta,Vol. 36, No.5 (1997)
Rheologica
@ SteinkopffVerlag1997
105
104
^v,
o
a- tos
* rate of chanseof the material structure.
-<
(I'
102
g 2-
-O10t
3 to o
:-
o presentexperiment,the property of interestare either of
1o-t
10-2
1 10 100 1000
or(rad/s)
Fig. 2 Four consecutivefrequencysweepsfor PET-Zat 270 "C indi-
cating continuing structuralchange in the material. The sample was
dried at 130'C for 24 h
the parallel plate rheometer (SR-200) at 270"C for
PET-2. It can be seenthat the dynamic and storageloss
moduli G', G" change continuouslv and the complex
viscositydefined?s ry*- \/(G"2 + G'z)l@. follows ac-
cordingly. Evidently, at this high temperature,continu-
ing polymer degradationreactionsproceed fast even in
the presenceof nitrogen (Dealy and Wissbrun, 1990).
To infer the rheological propertiesof the material at the
time of loading, i.e. before any structural change took
place, the principles of "time resolved rheometry"
(Mours and Winter, 1994, 1995; Winter, 1996) should
be used. Such a sound theory however, does not exist
at the moment for mutating materials (Winter, 1996).
Instead, a material-time correction technique was used
similar to the time-temperaturesuperposition.This is
discussedin detail in the next section.
Materlal-time
correction
First, it is assumedthat the data in Fig.2 labeled as
"Run#l" refer to the case where the material has not
undergoneany structural change.This is becausethese
data were obtained first immediately after loading the
sample onto the rheometer.Obviously this is not quite
correct since significant time has elapsedfrom the mo-
ment obtaining the data point at the highest frequency
to the moment of obtaining the data point at the smal-
lest frequency (about 30 min). A more consistent and
accurateprocedureis discussedbelow. For the purpose
of data analysisobtained in the presentstudy it is suffi-
cient to assume that for the first data set the overall
structuralchangeis not significant and that this data set
is the referencecurye for all subsequentones.
The differencesbetween the subsequentflow curves
from the referencecurve # I reflect some overall change
in the structure of the mutating material. Mours and
Winter (1994) define these structural changesin terms
of a mutation time, which is a characteristictime of the
- (l)
'L n IU
where )"*u is the mutation time, and g the property of
interest used to express the structural change. In the
the dynamic moduli (G' or G") or the complexviscosi-
ty, rl*. An overall averagestructural change that takes
place over the duration of the experiment can now be
expressedas
I
fdt
cu: I -;- (2)
J Lnu
0
where ay is the material-timeshift factor, representing
the overall structural change over the duration of the
experiment,t. An averagingof a14 oyar severalfrequen-
cies can also be performed to obtain more accurate
results.Thus, for eachsubsequent run (run#2,3 etc. in
Fig.Z) an overall structural change can be calculated
through the shift factor ay. If a sufficient number of
frequency sweep runs are available (in the presentcase
there are 4) one may calculate this shift factor as a
function of time and subsequentlydepending on the
data used one may apply the appropriatecorrection.For
this particular experiment the correspondingshift fac-
tors for Run "2" to Run "4" are0.9, 0.81 and 0.7 that is
about ll%o change for each run. It is noted that in the
experiment plotted in Fig. 2 each run lasts for about
ll2h. To determine these shift factors. the calculations
were based on G". As seen the data for G' do not de-
fine quite smooth curves due to the small torque mea-
sured during this experiment.Needlessto say, the same
shift factors apply to the complex viscosity,ry*.
A master curve was obtained at each temperaturef
by scaling frequency by a shift factor Ilaya, and com-
plex viscosity by ava to superposethe data of Fig.Z.
The new material-time corrected data are plotted in
Fig. 3. For the polymers studied in this work, this sim-
ple procedure resulted in almost perfect superposition
of the data. As may be seenin Fig. 3 a mastercurve is
obtained and overall the superpositionis excellent, i.e.
the data of the all runs superposevery well with those
of the frrst run by using a single shift factor a2a.As dis-
cussedbefore, this shift factor representssome overall
average structural change undergone by the material
over the durationof the individualrun.
To justify the use and explain the physical signifi-
cance of the shift factor ava,we may refer to the struc-
 S.G Hatzikiriakoset al.
PET rheologyusinga PTT constitutivemodel

105 polymer; see Bird et al., 1987).Thereforethe material-

time correction should be applied in both directions
G 104 (verticaland horizontal)of an 4* vs a,rplot. This proce-
(It
(L dure may be applicable only when structural changes
-= 10' proceedrelatively slow, and the factor a1,ais a good in-
* dicator of some overall averagestructural change over
€ 102 the whole duration of each run (complete frequency
(5 sweep).When structuralchangesproceedrelatively fast,
I tot n* one may use a more sophisticated, although time-
(, consuming method developedby Mours andi Winter
G- 100 Run#1 (r99q.
g Run#2
(, 10-1 Run#3
Run#4
10-2 Linearviscoelasticity
10 100 1000
oro" (rad/s) Figure 4 plots several frequency sweep runs at several
temperaturesfor PET-l using the RheometricsScientific
Fig. 3 Material-time correction accounting for structural changes SR-200 rheometer.In particular, the PET pellets were
superposesthe data plofted in Fig. 2 very well. The material-time dried under vacuum at 160'C for 7 h and immediately
shift factors used to superposethe data are 0 9, 0.81 and 0.7 for data
labeled"run 2", "run 3", and "run 4" respectively
were loaded into the rheometer. Three frequency
sweepswere carriedout at 260'C and consequentlythe
temperaturewas set at 270"C. When equilibrium was
established another three frequency sweep runs were
PET-1 carried out. The sameprocedurewas used for the other
10 5
two temperaturesof 282" and 295"C. Thus, a single
o
C;
9 1 tr
* ,4
4ry
sample was used for all frequency sweeps plotted in
Fig.4. As previouslydiscussed,it can be seenthat the
dynamic and storageloss moduli G', G" changecon-
tinuously and the complex viscosity,ry*,follows accord-
o ingly. Evidently, continuing polymer degradation and
I to3 poly-condensationreactionstake place within the poly-
,{. mer at all temperatureswith the former to be more
(!
I 10, dominant reactions. To infer the rheological properties
o of the material at the time of loading, the procedureil-
- 1=26906
-- T=z7ooc lustrated and discussed in the previous section was
T=282oC used.
10 1
T=295oC The various shift factors necessaryto superposethe
1 10 100 1000
data representan averagechangeof the structureof the
material with time. The results using this material-time
or (radls) superpositionare plotted in Fig. 5. As can be seen,sin-
Fig. 4 Consecutivefrequencysweepsfor PET-I at severaltempera- gle master curves were obtained at each temperatures
tures indicating continuing structuralchangein the material. The pel- for all material functions, namely G', G" and ry*. [t is
lets were dried under vacuum at 160'C for 7 h noted that the data at 260"C represent the material
function at the time of loading (before any structural
changestake place), but not for the others. For exam-
tural changesthat take place with time during the ex- ple, to obtain the experimentalresults at 2lO'C, three
periment.As seen in Fig.2 the materialchangeswith frequency sweepsat 260"C were carried out previously
time and is reasonableto assumethat its overall molec- and during this time the structural change was signifi-
ular weight decreasesdue to the combined effect of cant (about 3-8Vo at each run). To correct the data at
poly-condensationand degradation(more dominant) re- 270"C to refer to time zero (before structural changes
actions despite the presenceof nitrogen. This overall take place), one has to use a cumulative shift factor
decreaseof molecular weight has an effect on the vis- over all runs proceeded(see next paragraph).At this
cosity and dynamic moduli (evidentin Fig. 2) but also point the material-time correction was only used to
on the relaxation times of the material. The latter scale superposethe data at each temperatureindividually by
with MW3'a (where MW is the molecular weight of the neglectingall changesundergoneby the material be-
512 RheologicaActa, Vol. 36, No. 5 (1997)
O Steinkopff Yerlag 1997

dataof run "i" to the dataof run "r-1", then the materi-
10 5 PEr-1 al time correction, Gtr4,to infer the data of run "i" to
-1:frj the time before any structural changes take place,
o
o should be equal to fll:r ay,p. Thesecumulativemate-
g 104 rial-time shift factors are labeledin Fig. 6 as "relative to
/.'.7,,1..'"2'
*
fi first run". It can be seen that for longer times (more
than l0 runs or so) the shift factors tend to level off,
G' 103
o_ implying that an equilibrium may be reachedat longer
times.Thesefactorswill be usedlater to apply the data
(,
correctionsfor the data at 270". 282' and 295"C
-6
o-
1n'2 plottedin Fig. 5.
- 1=26q oC
- - . T = 2 7 0o b
f=282oC
10 1 T=295oC
rheometry
Capillary
1 10 100 1000
o/o" (rad/s) As discussedabove,PET resinsdegradein the presence
of moisture at high temperatures.Therefore,for the cap-
Fig. 5 Material-time correction accounting for structural changes illary experiments all polymer pellets were dried for
superposeswell the data plotted in Fig.4 at eachtemperature
18 h at 130'C under partial vacuum with a slow nitro-
gen bleed. Note that a different drying procedure was
1.0 used for linear viscoelasticmeasurements(vacuum dry-
x ing at 160'C for 6-10h) mainly due to the different
L
otor cool'
a
locationswhere parallel-plateand capillary experiments
6 0.e o were carried out. However, both proceduresresulted in
G
IL consistent data as will be demonstratedbelow. The
o
o moisture content of the dried pellets was determinedby
'F 08
o Karl-Fischertitration to be <0.00IVo. After drying, the
(l)
L polymer pellets were handledin a dry nitrogen environ-
o
O vt ment up until the time at which they were loaded into
d, the capillary rheometerfor testing.
E o
'l= The shear viscosity was measuredusing a Kayeness
O
.o o6
PET-1 Galaxy V capillary rheometeroutfitted with a pressure
L o transducer port. Dynisco pressure transducersof 100
o o Relative to previous run o o
(u o Relative to firstrun and 20 bar were employed to measureresultantpressure
05 of flow through a capillary die, I mm in diameter and
0 1 2 3 4 5 6 7 8 I 1 0 1 1 1213 30 mm long (L/D=30). Bagley and Rabinowitchcorrec-
Numberof Run tions have been applied to the shear viscosity data
which are presentedbelow (Dealy and Wissbrun,1990).
Fig. 6 Material-time shift factors indicating structuralchangesfrom
run to run. Theseare consequentlyused to calculatethe overall mate- The "entrance pressure" (Bagley correction) is the
rial-time conection factors to infer the rheological data at zero time pressuredrop associatedwith the flow of the polymer
i.e. before structuralchangestake place in the convergingentry to the capillary die as well as at
the exit (but mainly it is the former). Two methods of
calculating the entrance pressurewere used: first, the
fore. This was done for two reasons:i) to demonstrate pressuredrop versus flow rate relationship was mea-
that the material-timecorrection applies at all tempera- sured by using several dies having the same diameter
tures equally well, and ii) to demonstratethe necessity but varying lengths (different L/D ratios). These data
to apply additional correctionsfor the data at the var- were plotted on a Bagley plot (pressuredrop versus
ious temperatures(exceptat 260 "C). capillary length for severalvaluesof flow rate or appar-
Figure 6 plots the material-time shift factors as a ent shear rate) and consequentlywere extrapolatedto
function of the number of run for the data plotted in obtain the pressureat zero L/D. By this method, one ef-
Fig.4. The material-timeshift factors labeledas "rela- fectively subtractsout the viscous pressuredrop (corre-
tive to previous run" were calculatedby superposing sponding to fully developedflow) from the total pres-
the data of a certainrun to the dataof the previousrun. sure. The second method used was to measuredirectly
It can be seenthat there is an about 2-8Vo changefrom the pressuredrop by using an orifice die [-rD<l).
run to run. If a74,;is the shift factor to superposethe Laun and Schuch(1989) have shown that the pressure
 S.G. Hatzikiriakos et al 573
PET rheology using a PTT constitutive modcl

60 Table I Entrancepressuredetermination
for PET:-3at 288'C
PET-3
T=288oc Shearrate Extrapolationof [-/D to zero Orifice pressures
50 ShearRate(s'1) ( s - ') in MPa
. / Pent (MPa) a (MPa-') Entranceangle
200
r 500
P+o ^
v
1000 90' 1 8 0"
2000
= . 5000 5000 3.87 I Txlor 3.1l 3. 14
930 2000 | .79 l.9xl0 1;72 t . 7I
an t.27 1.02 1. 04
a 1000 3.1xl0-2
500 t.t4 6 5x10-2 0.63 0.62
#ro 200 0.61 1 . 1x l 0 - ' 0.3 0 3l

10
Entrance pressures were also measured using an
orifice die having a l-mm diameterand a length of
10 15 20 25 30 35 0.7 mm. An entranceangle of 90 or 180 degreescould
L/D be employeddependingupon the die orientation.A 5-
Fig. 7 Calculation of the Bagley correction by fitting secondorder
MPa transducer was used to directly measure the
polynomials to pressureversusl,/D capillary data for PET-3 at 288'C entrancepressure.The values are given in Thble I and
can be comparedwith thoseobtainedby using quadra-
tic extrapolation.At high shearrates, the values are in
drop measuredusing such orifice dies is the same as reasonable agreement. The poorer agreement at low
that obtained by extrapolationto zero L/D. Both meth- rates can be anributed to the lower signal-to-noiseratio,
ods actually measure the total pressure drop, AP"n6r, and sensitivity of the calculatedentrancepressureto the
which is the sum of the pressuredrop associatedwith fit of the data used for extrapolation.Consequently,we
the entrance,LP"n, and the pressuredrop associated conclude that direct pressure measurementsusing the
with the exit of the capillary, AP"*. However, the exit orifice die (L/D=0.7) provides a more accuratedetermi-
pressureis typically <l}Vo of the entrancepressure nation of entrance pressure. Subsequentextensional
(Laun, 1983),so that its contributionhere is considered data are obtained from measurementsusing the orifice
to be negligible. die with an entranceangle of 90 degrees.
We measuredthe entrancepressuredrop of all PET We usedthe formulasdevelopedby Cogswell(1972)
resins by using capillary dies having l-mm diameter to calculate the average extension rate, b, and exten-
and LID ratios of 10, 16, 20 and 30. Representative sional viscosity,17,(i), as a function of entrancepres-
results are plotted in Fig. 7 for PET:3 at 288'C. These sure,shearviscosity,and the local power law exponent,
data are extrapolatedto zero LlD by using a quadratic n:
interpolationin order to determinethe entrancepressure
at each shearrate (seeLaun and Schuch, 1989).The en- 4i2 rt 9 (n + t121/P.n12
trance pressureof PET-3 is only a small fraction of the , rln (b) :
3 (n + l) /P."t 32rt yz
total pressure measured,although it increasesslightly
with shearrate. Accurate data are required to determine (3)
the entrance pressure by this method. It is apparent
from the data that the pressureis not a linear function where the local power law exponent, n, is determined
of LlD, but actually slightly curved. This is due to the locally from a shear stress vs apparent shear rate log-
fact that polymer melt viscosity increaseswith increas- log plot.
ing pressure.The dependenceof the viscosity on pres-
sure can be modeled by an Arrhenius equation as,
4 :40 exp (aP), where 4s is the viscosity at atmo- Rheolo$cal characterization
spheric pressure,ry is the viscosity at pressureP, and a
is the coefficient for the pressuredependenceof vis- Figure 8 comparesat various temperaturesthe complex
cosity. This coefficient can be easily calculatedfrom the viscosity of the molten PET-I obtained from the con-
coefficients of a quadratic fit of the data (Table1) at stant stressrheometer(before applicationof the material
288 "C. The values thus obtained are of the order of time) with the correspondingshear viscosity obtained
2xl0-2 MPa-r, which is a typical value for many poly- from the capillary rheometer. From the entire set of
mer melts (Dealy and Wissbrun,1990).At lower shear curves it can be seen that the viscosity does not in
rates,the poorer precisionof the data (lower signal-to- general decreasemonotonically with temperature.Evi-
noise)gives an erroneouslyhigh pressuredependence. dently, there is a mismatch between parallel-plate and
5'74 Rh e o logi caA cta, V ol . 36, N o. 5 (1997)
O Steinkopff Yerlag 1997

10 4 1ff
- oC,ParallelPlate
pET-1 260
-- 2 7 0 "C 10s
^^^ 0a
zoz v
- 295 0C
. 0C, aly
277 Capillary o-
.
i- to'
2920C
. 0C
288
o

I ''o'
Y 0C
o 293
: -----J . \--
103 r.-g..- O \
v . l- ! (9 1ot
*_ : v -:-
\
a

\l 100

10-1
10-1 100 101 102 103
oo, (radls)
1G
1 00 101 102 103 104 Fig.10 Thedynamic moduli,G' andG",of PET-Iat 260"Candits
fit withthreeMaxwellian
relaxation
modes
o, Gad/s)or i (sr)
Fig. 8 Comparisonof complex viscosity of PET-I from SR-200 (no-
material-time coffection) with capillary viscosity revealing inconsis-
tencies due to structural changes taking place in the SR-200 rhe- material-time correctionsare obtained from Fig. 6 as a
ometer(nitrogenenvironment) function of the number of run and listed in the legend
of Fig. 9. Thus, the material-time-correctionfactors, o,14,
were deterrninedsolely on the basis of dynamic experi-
104
PET-1 - 260
oC,
Parallel Plate ments and not to force an agreementbetween dynamic
oc,
- - 270 ar-{.83 and capillary data. The material-time corrected results
2a2oC, dn=o.69 are plotted in Fig.9 and evidently now the viscosity
oC,
- - 295 cr=o 59 (dynamic or shear)is a monotonic function of tempera-
. oc,
277 capillary
| 2820C
ture. Time-materialcorrectionswere applied only to the
o
(I' ^ 288
0C complex viscosity data as the relatively close environ-
oC
o-
__
_ _*--;1-- v 293 ment of the capillary rheometerprobably precludedany
I 10' ll>
l .- structural changes from advancing to a noticeable ex-
tent.
* \ Figure 10 plots the material-timecorrectedand time-
I
temperaturesuperimposeddynamic moduli, G' afid G",
I
as functions of frequency for the PET:-I resin. The data
were measured at various temperatures(260", 270",
282" and 295"C) with Tr"1=/60'C. Material-timecor-
rectionswere applied before applying the time-tempera-
1G
1 00 101 1G 103 104
ture superposition.Evidently, the data superposevery
well on a single master curve. The continuouslines re-
present the fit of three Maxwell modes calculated by
Fig.e compari,.",o"lll:::'#:''*. or*-roo using a nonlinearoptimizationtechnique(seebelow).
", with capillary viscosity data revealing,,u,*
material-timecorrection) con- Figure 11 depicts the complex, shear,and extensional
srstency viscosity of the PET:I polymer as a function of fre-
quency, shear and extensionalrate, respectively.Again,
all data are referencedto 260 "C. The extensional vis-
capillary data. For example the shear viscosity at cosity was calculatedby meansof Cogswell'sanalysis
293'C is about the same as the dynamic viscosity at (1972) from entrancepressuredata as discussedin a
282"C (11'C temperaturedifference)and much higher previoussection.It can be seenthat not only does the
than the dynamic viscosity at 295"C (only ZoC tem- complex viscosity agree well with shearviscosity (ap-
peraturedifference). plicability of the Cox-Merz rule), but also that all the
Once the aforementioned material-time correction extensionalviscosity data fall on a mastercurve. The
was applied to the dynamic viscosity data obtained relatively wider spreadof the extensionalviscosity at
from the Rheometrics Scientific SR-200 rheometer. low extensionrates (less than 10/s) is due to relatively
however, any mismatch disappeared.The appropriate large experimentalerror involved in these measure-
 S.G. Hatzikiriakos et al. 575
PET rheology using a PTT constitutive model

10s
a PET-1
, a T=260oc

6 104
(U
o

ti
10' I

y'oo a PET-I,To=$316 i
i
PET-1,AH/R=5761K
* PET-2,To=$zll(
F 102 o
I

ParallelPlate
r Capillary '/. . 7 PET-2,AH/R=8090K
- PTl-model
,, o PET-3,To=$lt 6
PET-3.AH/R=5600
K
0.3
10 1
10r 100 101 102 103 104 0.0017 0.0018 0. 0019
1rf
<oar,(radls) or tcr, (s-t) or ia, (s-t)
Fig. 12 The shift factorsfor all polymerscalculatedfrom both capil-
Fig. 11 The complex, shear and extensionalviscosity functions of lary and parallel-platerheometerdata
PET-I at 260"C along with the predictionsof a three-modePhan-
Thien Tannerconstitutive relation, The data superposesvery well by
applying the time-temperaturesuperposition principle and comply
with the Cox-Merz rule PET-2 has a melting point at least 10 degreeshigher.
This is an indication that significant differencesexist in
the particular molecular structureof thesepolymers. Fi-
nally, it is noted that the high slope for PET-I is biased
ments. The continuouslines in Fig. 11 representthe
point in Fig. 12 (higher temperature).
predictionsof a three-modePhan-Thien-Tanner differen- from the first
Elimination of this point from the regression analysis
tial viscoelasticconstitutiverelation (seebelow) for the
gives a much lower slope.
rheologicalpropertiesof this polymer.
Also derived from this analysisis the flow activation
energy by plotting the shift factor a7 versus IIT and
assuming the validity of the Arrhenius relation, Constitutive modeling
Gr : exp ILH I R 0 lr - | /ro)l- The results are
plottedin Fig. 12. For the resin PET-I (a linear PET), it The data were fitted with the model proposedby Phan-
was found that A,H/R: 5781K (for a referencetem- Thien and Tanner (1977). This model is based on net-
perature,Z6 equal to 533 K) which is a value reason- work theory of concentrated polymer solutions and
able for a linear polymer (see Wang and Porter, 1995). melts. The version of the multi-mode PTT model with
It can be seenfrom Fig.l2 that all points (shift factors an exponentialrelaxation
from shearand dynamicviscosity)define a singlecurve
indicating the consistency of the data obtained from
.1 --\-..
'
(4)
/-'t
thesetwo experiments.In addition,it can also be seen I

that an Arrhenius equation for the shift factor is ade-

quate in describing the calculateddata. The same con- .*
( 4 ,,r ,) ,, + Aiti * 7 i( i( r .' ,*' , r ) :rr,r;
clusions apply for the other two resins PET-Z and PET:
3. However, it is noted that the flow activation energy
for PET-2 (another linear PET) (another linear PET)
was found to be relatively higher than PET:I, that is was chosen becausethe exponential term results in a
A,HIR=8090 K comparedto 5781 found for PET-I. In maximum in the steady-stateextensional viscosity in
addition, LH lR for the branchedpolymer was found to accord with experimental data on polymer melts. In
be only 5600K which is consideredto be small for a Eq. (5), the pairs Ui, rtij are the relaxationspectrumof
branched polymer. However, no conclusionscan be the polymer, and jr is the rate-of-deformationtensor.In
drawn at this point before more details are known about addition to the usual linear viscoelasticconstants,this
the molecular structureof these resins. For example, model involves two nonlinearparametersper mode, €t
although PET:-I and PET-Z are referred to as linear and (r. Of them, e; characterizesthe rate of destruction
polymersand PET-3 as branched,DSC analysisshows of polymer segmentsin the network model and (; the
that PET-1and PET-3have similar melting points while rate of "slip" (non-affine)deformation (Vlassopoulos
576 RheologicaActa, Vol. 36, No. 5 (1997)
@ SteinkopffVerlag1997

Table 2 Values of the parameter in the Phan-Thien constitutive rela- 105

tion for PET- I

104
2i (s) ri; (Pa.s) G
I 0.6297 95.25 4.02e-3 0.0 103
2 0.02s94 841.00 t.2 3 to 0.0 o
(L
3 0.233e-2 799.60 0.3633 0.0
| 'to,
(Il rnl
o_ lu'
Thble 3 Valuesof the parameterin the Phan-Thienconstitutiverela- G' ^F:
tion for PET-2 100

2i (s) 4i (Pa.s) 10r PET-2

O.ll4e- 2 296.6 0.400 0.00 T= 27ooC
0 227e-1 41.40 0 .10 0 0.983e-2 10-2
0.500 r.072 0.l5e-3 0.00 0.1 't000
coa, (radls)

Fig. L3 The dynamic moduli, G' and G", of PET:-2at 270'C and its
Table 4 Valuesof the parameterin the Phan-Thienconstitutiverela- fit with three Maxwellian relaxationmodes
tion for PET-3

105
,i; (s) ry;(Pa.s)
PET-2
I O.l846e-2 352.0 0.1811 0.0000 T=27ooC
2 O.2275e-l 675.8 0 .1 5 6 9 0.1917
3 02206 757.6 1.3500 0.7852 G 104
4 r.500 t29.0 O.5O6e-2 0.884e-2 o
o-
F

d
ta
to'
and Hatzikiriakos, 1995). The caret in (5) denotesthe
upper-convectedobjective stressrate x
i
*
s1G
t:* * v.vti - (, ,,+r,.i) (6 ) o
.
Parallel Plate
Capittary
- PTTModel

Fining data with the PTT model is usually straightfor- 101

ward, since the term involving (; is most important in 1on to 104
shear flows, and the parameterei is most important in '.t*,,.".1.t,,o*,,J"*r,.,,
shear-freeflows. The linear spectrum Ui,ry,| are fitted
separatelyusing linear oscillatory shear measurements Fig. 14 The complex, shear and extensionalviscosity functions of
and then the nonlinear parameters(;, e; using capillary PEil-2 at 270"C along with the predictions of a three-modePhan-
Thien TannerConstitutiverelation. The data superposesvery well by
measurements.For the best fit of the linear spectrum applying the timetemperature superposition principle and comply
with a given number of modes both tr;, ry, should be with the Cox-Merz rule
treated as unknown parameters(Baumgaerteland Win-
ter, 1989). In our experience,however,such a proce-
dure, although it does produce the best fit to the linear The continuouslines in Figs. 10 and 11 representthe
data, missesthe correct location of the maximum of the model predictions. It can be seen that, in general, this
extensional viscosity curve, becauseit underestimates model adequatelyrepresentsthe rheological behavior of
the maximum relaxation time. In this work all of the PET:I. The oscillationsappearin the predictionscan be
parameters were fitted simultaneously and they are easily eliminated if more modes are used. However, the
listed in Table2 for PET-I, Table3 for PET-2 and Ta- objective here is to fit the data with the minimum num-
ble 4 for PET-3. The fact that four modes are neededto ber of relaxationmodes since the particular model is in-
describethe relaxation of PET:-3with an averagerelaxa- tendedto be used in a stability analysisof the film cast-
tion time much higher than those of the other resins in- ing process,which are computationallydemandingsim-
dicatesthe branchedstructureof this resin. ulations (Christodoulouet al., 1997).
 S.G. Hatzikiriakoset al. 517
PET rheology using a PTT constitutivemodel

1 06 1n,5

t'tr | -J PET-3
1d T=260oC
t:. T=2600C
q 104
1V G
(u (L
o-
l- to3 G ?

a
E r^a
^ l u"
f1d F

1 01
1 00
G'
10-1
0. 01 0.1 10 1 00
roa, (radls)
Fig. 15 The dynamic moduli, G' and G", of PET-3 at 260'C and its
fit with four Maxwellian relaxationmodes
Figure 13 plots the dynamic moduli of PET:2 while
the continuous line representsthe model predictionsby
using the parameterslisted in Table3. Figure 14 plots
the complex, shear and extensional viscosity of the
PET-Z as a function of frequency,shearand extensional
rate respectively.All data are reducedto 270'C. It can
be seenthat not only the complex viscosity agreeswith
shear viscosity, but also the extensionalviscosity data
fall on a mastercurve, giving further evidenceof the ap-
plicability of the Cox-Merz rule (agreementof dynamic
viscosity data with correspondingshear).The continuous
lines in Fig. 14 representthe predictionsof a three-mode
Phan-Thien-Tannerdifferential viscoelastic constitutive
relation (seebelow) for the rheologicalpropertiesof this
polymer.The correspondingresultsfor PET:3 are plotted
in Figs. 16 and 17. In all casesit is demonstratedthat a
multi-mode (three modes) PTT model can representthe
rheologicalbehaviorof PET resinsquite well and hence-
forth sucha model can be usedeffrciently in processsim-
ulation such as film castins.
*i
* 1rl2
o ParallelPlate
. Capittary
- PTT Model
1000 101
10r 100 101 102 103 104
ocr, (rad/s),'icr' ict, (s-1)
Fig. 16 The complex, shear and extensionalviscosity frrnctions of
PET-3 at 260"C along with the predictions of a four-mode Phan-
Thien Thnner constitutive relation. The data superposesvery well by
applying the time-temperaturesuperposition principle and comply
with the Cox-Merz rule
Conclusions
A rheological characterizationof a number of PET re-
sins was carried out by using parallel-plate and capil-
lary rheometry.To obtain consistentresults a material-
time correction was applied to the data which accounts
for structural changestaking place during experimenta-
tion. The complete shearand elongation data were used
to fit, by nonlinear optimization, the linear relaxation
spectrum and nonlinear parameters of a multi-mode
Phan-Thien-Thnnerconstitutive relation. The fitted P-IT
relation was found to representthe rheological behavior
of PET resins well and thereforecan be efhciently used
(only 3-4 modesneeded)in processsimulations.
Acknowledgements This work was supportedby a grant provided
by DuPont (Circleville, Ohio).

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