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of Plastics PART 1 --Theoretical Development

Based on F. E. Weir, Shell Development Company, Emeryville, California

Melt Rheology

he general character of the flow behavior of thermo- can be done is to rely on a single point test such as the
Tpas 1 tic melts has been known for some time. It is
known, for example, that the viscosity is usually a de-
melt index as an approximation to anticipated molding
behavior, though it is generally recognized that this is
creasing function of shear stress or shear rate and that riot an entirely satisfactory approach.
it varies considerably with the temperature. It seems clear that the field would be improved if
In recent years many sophisticated devices have been there existed some theory, simple enough to apply yet
suggested ( 2 ) for the measurement of melt viscosities comprehensive enough to be an improvement over older
iu fundamental units as a function of shear rate and practice, whereby the melt viscosity information such as
temperature. The importance of this information to the sliear rate and temperature sensitivity could be ap-
development of practical plastics processing has been plied. Such a scheme is presented in the body of this
widely recogniied. article in the hope that it might be useful in interpreting
Although the more involved measurements have melt viscosity data in such a way as to better predict
added to our knowledge of viscosity, it has been diffi- injection moldability.
cult to apply them to practical processing technology in Figure 1 shows the melt viscosity of a thermoplastic
such a way as to make the best use of the available material, in this case a polypropylene, as a function of
information. For want of better theories it has been often shear rate at several temperatures. Evidently the vis-
necessary to fall back onto simpler, more empirical tests cosity can take on all values within the limits shown.
of the conventional type in our attempts to describe An injection molding machine forces a material at
processability of thermoplastics. high temperature through a complex series of colder
An example of a processing field where it has proven cavities where the rate of shear varies as time and posi-
difficult to apply basic information is injection molding. tion. During the filling process, the temperature is re-
Everyone familiar with the practice realizes the com- duced. In an injection molding shot, the viscosity at a
plexity of the injection molding process. The shear rate given point in the melt might follow a course something
and the temperature vary in an extremely complex like that shown in Figure 2. In this diagram the viscosity
fashion during the filling of an injection mold. Obvi- goes from its value at essentially zero shear rate to some
ously, the variations in plastic melt viscosity arc at least high shear rate as the plunger forces it into the mold and
equally difficult to deal with. It would be difficult to then travels up, through the diagram to lower shear
take a graph of melt viscosity as a function of shear rate rates and lower temperatures as the flow proceeds more
and temperature, determined in the laboratory, and slowly, ending at a low temperature and zero shear rate.
from this determine what the injection molding be- During mold filling, the viscosity suffers a rapid de-
havior of a material might be. Without a theory relating crease due to shear, followed by a rise due to decreas-
the viscosity responses to moldability, practically all that ing temperature and shear rate. Evidently, the average


value of the viscosity during this process depends on how
steep the viscosity-shear rate curves are and how far
apart are the different curves at different temperatures.
Intuitively, it is evident that the steeper the slope of
the viscosity-shear rate curve, the lower the viscosity
attained during the molding process, and the closer to-
gether the curves (determined at different tempera-
tures), the lower the viscosity remains during fill-out. If
it were known how to define an “average” shear rate and
temperature condition for a given molding process (per-
haps the star in Figure 2 ) , a one-point viscosity deter-
mination could be made, thereby producing a number
truly representative of moldability .
Unfortunately, there seems to be no way of defining
“average” conditions of molding, particularly since any
specific average would vary from mold to mold and
machine to machine. Any theory attempting to predict SHEAR RATE (SEC’1
moldability from viscosity behavior, in order to be suc-
Figure 1. Relation between melt viscosity and shear rate for
cessful, must be more general and must somehow avoid a typical polypropylene.
the necessity for defining “average” conditions of shear
and temperature.
However, let us consider the “average” viscosity \ STATlC
during a molding cycle for a moment. It is seen from
Figure 1 that the viscosity-shear rate-temperature rela-
tion can be approximated, at least at higher shear rates,
by a set of parallel straight lines as shown in Figure 3.
Over a wide range of shear rates and temperatures, a
graph such as Figure 3 is a reasonable approximation to
the true viscosity behavior. If this is the case, an ex-
pression for the average viscosity realized during mold
filling is given as follows,



1 10 10‘ 1 U’

- Figure 2. A course followed by the viscosity of a volume ele-

where: 9 = “average” viscosity ment of melt during flow into a cold mold.
7. = viscosity measured at y = y o , T = T,
(reference y and T)
y = shear rate
= “average” shear rate

- = temperature
0 180-2
0 200T
T = “average” temperature A 230.C
j . = reference shear rate 104 -
To= reference temperature
Is :
Equation 1 relates the viscosity, measured at essentially
zero shear rate and some reference temperature, To,to
aP -
the “average” viscosity realized during the molding of a 10‘ -
material in a given machine and mold. The form of the
expressions selected is that which most nearly yields -
linear plots and therefore constant derivatives,
a 1% ri , and . Cross derivatives are
10’ I I ,lil,,l I ,,,,,,,I , ~/,,,,,I , , , I , , ,
- 10 10‘ 10’

eliminated by the assumption that the viscosity response SHEAR FATE (SEC-‘1

surface as a function of y and T is planar, i.e., parallel

lines and constant activation energy. Performing the in-


dicated integrations we obtain an expression for the the expansion of the exponentials in power series, taking
“average” fluidity (US),during a molding cycle as, only the first and second terms;

~ - lnT/jo I
1 1 e
I dlogjl 1
--= _
1 e

where II
indicates absolute value. This expression tells
us that the higher the average shear rate and the higher
the average temperature the higher will be the 5uidity (3)
or ease of flow during the molding cycle. Further, as was
pointed out earlier as intuitively evident, this expression
shows that the greater the viscosity-shear slope and the
smaller the viscosity-temperature slope, the higher the Evidently, such an approximation only applies in cases
average fluidity during the molding cycle. where the shear and temperature variations are so minor
as to make the present approach unnecessary.
The expression (Equation 2 ) cannot be used as it
stands to compute the average fluidity during a molding Another possible approach is simple substitution of
the arguments of the exponentials (multiplied by a
cycle because it involves and T which are not known. constant) for the exponentials themselves. It can be
If we knew these we could simply make a single viscosity shown that a straight line terminating at the origin can
measurement under these conditions and would be
spared the necessity of computing
- at all.
be forced through the points of an exponential such
that the resulting error is no greater than about 15%
for values of the arguments lying between 0.5 and 2.
- -
tion (2) if y = -j and T = To,l = - ‘1 ex - kx (0.5 < x < 2.0) (4)
7) 70 At values of (x) greater than 2 the error becomes very
More can be seen from Equation 2. It shows that great.
the average fluidity during molding is given by the An examination of the probable magnitude of the tem-
product of two terms. h e is the fluidity at some stated perature variable reveals that the substitution is prob-
level of shear rate (or shear stress) and temperature,
much like a conventional melt flow or melt index. The ably reasonable, i.e., d log r)/a log l / T
- [
is -]
second term gives the interactions of the more involved
melt flow properties with the intricacies of the molding very likely between 0.5 and 2. However in the case of
process. Note that the viscosity-shear dependence of the shear variable, d log q / a log In ;/yo, the approxima-
the polymer melt viscosity is mixed in the exponent tion fails badly unless ,; the “average” or controlling
with the average shear rate occurring in the molding shear rate, is smaller than is generally believed. This
machine, mold, etc. Likewise, the temperature depend- problem is discussed later.
ence of the polymer melt viscosity is mixed with the When these approximations are made, one obtains,
average temperature caused by details of the operation,
machine, etc. If these could be separated into one term I 1 - 1 1
involving only polymer characteristics and another
containing only machine characteristics, a polymer char-
acterization parameter might result which would be of
considerable use in predicting injection moldability.
At this point it must be decided that the two types
of quantity are hopelessly mixed and cannot be sepa-
rated or one must resort to certain mathematical approxi-
mations which may or may not be valid, or may be valid
only in certain cases. Empirical testing can serve to
decide the validity of such approximations in the event
the latter course is followed. In order to attempt to
derive a polymer characterization parameter of value (7)
in predicting moldability, the approximation approach
The first and most evident approximation involves and

J log ?) for non-Newtonian viscosity, E is the activation energy for viscous flow
* It will be noted that = In - 11 and that ___
ai / ~
and R is the gas law constant. Thus, a simplified expression for a s T T
= -, where n is the exponent in the so-called power law expression


ln y / y .
M(j,T) =K

and the desired separation has been accomplished. There

now exists an approximate expression, Equation 6, such
that the average fluidity during the mold filling opera-
tion is given by the product of two terms, one a term
depending only on polymer flow properties, aSTV, and a
second, M,;( T), depending only on machine conditions.
a S T v should rank different materials with respect to mold-
ability if the approximations hold well enough.
If the approximations used in the derivation of Equa-
tion 6 are sufficiently valid, aSTV(STV standing for 0 I I I I I I I

shear-temperature-viscosity) should be a better charac-

terization parameter than a single point flow test (such
as the melt index) since it includes the response of the
polymer to changing shear rate and to changing tem-
perature. The empirical tests to which Equation 6 has
been subjected and the degree to which it correlates
with performance will be given in Part 11.
and the slopes determined. These were averaged over
Melt viscosities were determined for a number of the three or four temperatures at which the data were
polypropylene samples in order to acquire data for test- determined. This yielded a log ?l/a log y.
ing the ideas stated above. Polypropylene happened to 3 ) From the viscosity-shear rate plots the viscosities at
be the predominant material studied but the application 10 sec-' were taken at the various temperatures. These
of the theory should by no means be confined to this were plotted as log viscosity vs. 1/T (where T is the
m.ateria1. Pertinent data concerning the properties and temperature in degrees Kelvin). These data generally
melt viscosity behavior of these materials will be found yielded an excellent straight line.
in Part 11. 4) From the viscosity-temperature plot, the slope was
The instrument used was a capillary melt viscometer taken to give (a log ?/a 1 / T ) . The viscosity-shear slope
of Shell design which is to be the subject of a future as determined in ( 2 ) above was divided by the viscosity-
publication. ( a ) Appropriate corrections for entrance temperature slope to give a rheological ratio,
effects were made but the Rabinowitsch correction to
absolute or "true" viscosity or shear rate was ignored
for present purposes.
Treatment of Data 5 ) At various temperatures of interest to molding, i.e.,
Each polymer studied yielded a set of melt viscosity 400, 450, 500, 550"F, the viscosities at 10 sec-' were
curves such as that shown in Figure 1. In order to pur- obtained from the viscosity-temperature plot.
sue treatment given in the theoretical section, two de- 6) The rheological ratio determined in (4) above was
rivatives or slopes had to be determined as did a viscos- divided by the viscosity at the temperature of interest
ity at a reference temperature and shear rate. The to vield.
reference shear rate was chosen as 10 sec-I and the
reference temperature was taken as a variable in the
calculation of aSTV, making this quantity a function of (The quantity is multiplied by TO8 to give numbers be-
temperature. The temperature of an appropriate aSTvfor tween 1 and 10.)
a given molding process would be the temperature of 7 ) aSTVwas plotted vs. temperature as shown in Figure
the mass of material in the molding cylinder. 4 for a number of different materials.
The calculation of an aSTyproceeded through the fol-
lowing steps: Discussion
Since the purpose of this work is to find the effect of
1) Melt viscosity data were obtained using the capillary melt flow characteristics on molding, the rheological
melt viscometer and plotted as log viscosity vs. log shear aspect is most emphasized in preference to the engi-
rate. Shear rates ranged between essentially zero to one neering considerations. This is at variance with certain
hundred sec-I or slightly greater. Temperatures were other studies ( 3 , 4) which have appeared recently and
generally 180, 200, 230 and on occasion 245°C. which have used a somewhat different approach.
2) On the viscosity-shear rate plots, the best straight
For those who think in molecular terms it will be ob-
lines were drawn through the points in the linear region 1
served that in the expression aSTv,the first term, -, is a
a S . Davison and D. E. Meier-unpublished results. 7"


reflection of the average molecular weight of the mate- of a constant shear rate operation to warrant treating
rial, probably close to the weight average. The rheo- the data in this manner. Qualitatively, the same result
logical ratio, on the other hand, should come about regardless of which data treatment
method is used.
Data for this treatment were obtained at rates of shear
somewhat below those generally thought of in connec-
depends largely on the molecular weight distribution. tion with injection molding. This seems completely rea-
Thus, a S T V goes beyond most single point rheological sonable for the following reasons: 1) Shear rates vary
tcsts which reflect only some sort of average molecular l’rom extremely high to extremely low during a molding
weight and it includes effects due to the distribution of cycle, making it difficult to say which range is the more
molecular weights. This’seems to be one of the first important; 2 ) The low shear rate period of the molding
attempts to systematically take distribution into ac- cycle must occur near the end of the mold filling and
1 packing operations, which seems to be where the flow
count. If the term - can be looked upon as essentially properties become most critical; 3 ) The treatment in-
% volves slopes of lines which are known to remain essen-
equivalent to the melt flow or index as conventionally
tially linear over wide ranges of shear rate; and 4) The
determined, the rheological ratio can be considered a
difficulty of obtaining reliable data at extremely high
second order correction term reflecting the distribution,
showing up the more subtle variations in flow. rates of shear (because of rapid temperature rise) is
This treatment, being an extremely simple one, has such as to make many such data suspect.
been kept deliberately so. An attempt has been made to
retain the simplest approach possible which would still
be an improvement in the understanding of how flow A method for the treatment of basic rheological data
properties affect injection molding. In this treatment klas been suggested whereby insight into the reasons for
no mention is made of melt compressibdity, melt elas- variable “moldability” of polymers can be gained. This
ticity, specific heats, thermal conductivities or the host method involves the determination of the melt viscosity
of other properties which can be shown to affect mold- over a range of temperatures and shear rates, extracting
ing. The result of these omissions is that while an asTV from these data numbers related to the viscosity-shear
may faithfully reflect the moldability of a resin of a rate dependence, the viscosity-temperature dependence
given chemical type, i.e., polypropylene, polystyrene, and the absolute level of the viscosity. These are com-
nyIon, etc., a given wSTv will not mean the same thing bined in such a way as to give a quantity, aSTv, related
for one type as for another. Evidently, the difference in in a direct manner to the average fluidity achieved dur-
set-up characteristics between amorphous and semi- ing a molding operation. (The latter is subject to the
crystalline polymers, one with a heat of fusion and the approximations in the derivation.)
other without, is enough to change the scales of values aSTV is made up of the product of the absolute level
of the reciprocal viscosity, measured under some stand-

, , (a)
considerably. The asTvconcept is only valid when dis-
cussion is confined to a material of a given chemical
ard set of conditions (t> and a rheological ratio
The choice of whether to discuss melt rheology as
applied to injection molding at constant shear stress or
I alog7, 1 I
I .I

. The first is a measure of the

at constant shear rate is a difficult one to make. Cer-
tainly the injection molding machine is neither a con- lbvel 2 the molecular weight average while the second
stant shear stress nor constant shear rate device. In die is dependent on the molecular weight distribution and
controlled flow it may resemble more a constant shear perhaps other polymer variables.
rate operation and in machine controlled flow, constant It has been pointed out that the use of this quantity
shear stress. Certainly, never is it clearly one or the must be confined to the case where one is discussing
other, Still, the rheological data must be stated at one different samples of polymer of the same chemical type.
or the other condition. Constant shear rate has been
selected in this case largely because in observing the Literature References
temperature sensitivity of many polymers in injection 1. Eirich, F. R., “Rheology” 2, 431.
molding it was observed that molecular weight and 2. Ibid., 3, 18.
molecular weight distribution make significant changes 3. Ballman, R. L., and Toor, H. L., Modem Plastics,
in the apparent temperature-moldability relationship. Sept. 1959, 105, Oct. 1959, 115.
Since the viscosity-temperature sensitivity of high poly- 4. Skinner, S. J., and Taylor, W., Transactions and J.,
mer melts is well known to be relatively insensitive to Plastics Institute 28, 78, 237 (1960).
molecular weight if stated at constant shear stress, it 5. Bernhardt, E. C., “Processing of Thermoplastic Mate-
was decided that the process must have enough aspects rials,’’ 308.