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
3SOT
550DF
1 10 10‘ 1 U’
SHEAR RATE (SECI)
T
 = temperature
0 1802
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 
5
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,
(w)
(=>
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
~  lnT/jo I
1 1 e
I dlogjl 1
= _
1 e

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 viscosityshear slope and the
smaller the viscositytemperature 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
7
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.
r)
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
1
 [
1
To
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 viscosityshear 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
follows.
The first and most evident approximation involves and
J log ?) for nonNewtonian 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
n
PI
= , where n is the exponent in the socalled power law expression
R
, , (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
type.
The choice of whether to discuss melt rheology as
applied to injection molding at constant shear stress or
I alog7, 1 I
I .I