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2 VOL. 6 , NO. 1
MELT FLOW INDEX. I
~~~~ ~
FIGURE 2
Effect of Diston
height on melt flow
7.2 - index for samples
with different
pretreatments as
taken from
Han~on.~
6.4 -
.
s
0
. .--
0
? 5.6 - .
-
0
'"
--
0
c
E
0
-
-5
I
Lr
4.8 NORMAL
EXTRUDATE
RUN
I
4.0
80 70 60 so 40 30 20 10 CI
PISTON HEIGHT ( m m )
from Figure 2, which shows a significant rise in the formed extensive experiments for using the melt flow
pressure drops in the barrel depending on the piston index test for molten polypropylene. Despite this time-
height above the die end for a shear sensitive polymer dependent deformation behavior, there is no correc-
like polypropylene. A number of ~ o r k e r s ' ~have
'~ tion recommended for entrance and exit abnormali-
discussed the time dependence of polymer flow in a ties. This would also be difficult to specify as the
capillary viscometer with a very short die such as in corrections would be expected to vary from polymer
the melt flow indexer. The manifestations of this time to polymer.
dependence is the gradual rise in the output rate at a Another source of error in the melt flow indexer is
fixed temperature and applied pressure, from an initial the load required to shear the film of polymer between
to a higher, steady-state value. A simple calculation the plunger and the barrel or reservoir as was first
in the case of the melt flow indexer13 shows that noted by Marker et al. l6 This could also tend to result
in an increase in the effective applied stress and in
the output rate as noted by Skinner13as well as Rudin
and Schreiber. l 2 SkinnerI3emphasizes the importance
of designing a proper barrel for use with short cap-
where subscripts b and c represent the barrel and cap- illaries in order to minimize the error due to friction.
illary and P, L, and r are the pressure drop, length, If the reservoir is too small, then it can contribute
and radius. significantly to the overall pressure drop. If it is large,
Substituting the appropriate values shows that the the plunger friction would be considerable. Marshall
capillary pressure drop will increase from 78 to 100% and Riley,I7 however, do not agree with S k i ~ e ras '~
of the applied pressure as the melt flow indexer goes regards the effect of large barrel diameters. They argue
from completely filled to empty. Thus, a 50% increase that at constant pressure and piston speed, the friction
in the output rate is possible, as has been shown for force increases in proportion to the circumfefence of
polyethylene by Skinner.l 3 With polypropylene, the the piston, whereas the pressure force increases with
position is shown to be worse by Charley," who per- the area of the piston. Therefore, the friction force
ADVANCES IN POLYMER TECHNOLOGY 3
MELT FLOW INDEX. I
4 VOL. 6,NO. 1
MELT FLOW INDEX. I
the zero shear viscosity, the viscosity vs. shear rate of application. The different grades result due to con-
relationship, the elasticity vs. shear rate relationship, trolled manipulations in the reaction conditions and
the die swell, the elongationalviscosity, the activation reactants during the polymer synthesis stage leading
energy for viscous flow, etc., could all be determined to polymers with different molecular weights, differ-
through only the MFI. Further, the stability of the ent molecular weight distribution, and different levels
polymer during processing, its reprocessibility, die of branching. It will be shown in the following how
design, mold filling behavior during injection mold- MFI could be correlated directly or indirectly with
ing, etc., could be adjudged merely through MFI. each of the relevant parameters so that it could act as
Similarly, the physical, mechanical, thermal, as well a rather beneficial control parameter.
as the certain optical properties could be related very
well with the MFI of the raw material. With all these
enhanced abilities to predict a variety of properties,
2.1. Effect of Reaction Conditions on MFI
MFI has certainly been upgraded in its value. It is
with the objective of bringing about this awareness During the polymer synthesis stage, the polymer
that this article is being written. The possible existing manufacturer can optimize his reaction conditions to
correlations between MFI and various other important get a particular grade of choice through the use of
parameters encountered in polymer manufacture, MFI. For example, the reaction temperature, as well
polymer processing, and end-product properties eval- as the catalyst activation temperature can be seen to
uation will be discussed in detail. vary significantly with MFI as shown in Figures 3 and
4 taken from Hogan et al.19 for polyethylene. It can
be seen that seemingly small temperature gains are
2. MFI USE IN POLYMER MANUFACTURE quite significant in terms of achieving higher polymer
MFI. Similarly, increase in activation temperature
The possibility of manufacturing polymers differing sharply increases the MFI increase potential to the
from one another in density and MFI enables the man- point where the catalyst undergoes a sharp decline in
ufacturers to prepare grades suitable for specific fields pore volume because of sintering.
FIGURE 3
Effect of reaction
temperature on
polymer melt flow
index as taken from
Hogan et al.lg
R E A C T I O N T E M P E R A T U R E ,.C
FIGURE 4
Effect of catalyst
activation a
temperature on
melt flow index as
taken from Hogan
et aI.l9
- 6
N
c
.-
E
2
\
54
-
c
LL
I
0
5 00 60 0 roo aoo 900 1000
CATALYST ACTIVATION TEMPERATURE ( * C
FIGURE 5
Variation of weight-
average molecular
weight of linear and
.
branched LOW DENSITY
polyethylenes vs.
logarithm of melt
flow index as taken
from Dark.20
.
.
.\
\
\
\
\
\
\
\
\
I I
0.0 1-0 4 0
log M F I ( g m / l O r n i n r )
6 VOL. 6,NO. 1
MELT FLOW INDEX. I
2.2. Effect of Weight-Average Molecular Weight Even though the above expressions represent the best
and Branching on MFI fit of Gw,as given in Figure 5, the data for branched
polyethylene cannot be in order as it indicates a higher
A relationship between MFI and weight-average
MFI for a higher Gw,which is incorrect. The data
molecular weight of linear and branched polyethylene
for the branched polyethylenes as collected by Darkzo
was explored by Dark.” It was found that two families
covered a broad range of branching, reactor config-
of curves resulted: one for branched and other for the
uration, and telogen level. To eliminate the effect of
linear polyethylenes. Thus, the following relation-
these variables, data was taken from a single autoclave
ships were given by Dark”:
configuration, where AT was held constant so that,
but for Ew, all other variables were nearly constant.
Branched: Only the pressure drop across the autoclave was var-
ied, and the effect of-the changes in pressure was
log (MFI),, = (0.454 x 10-5)Mw - 0.12713 (2) reflected in MFI and M, values as shown in Figure
6. It can thus be concluded that, with branched pol-
Linear: yethylene, consideration must be given to long chain
branching, nonrandom termination, and reactor pro-
- log (MFI), file, whereas for linear polyethylene a simple expres-
= (0.6723 x 10-5)Mw - 0.49359 (3) sion like that given by EQ. (3) would suffice.
FIGURE 6
Variation of weight-
average molecular
weight of branched
polyethylene vs.
logarithm of melt
flow index when
changes in the
autoclave pressure
are made during
the polymerization
(taken from Darkm).
I I 1 I \I
-0.4 0.0 0.4 0.8 1.2 4.6
LOO ( M F I )
FIGURE 7
Variation of weight-
average molecular
weight of low-
density
polyethylenes
versus melt flow
index for autoclave
and tubular grades
of resin: (0)A
series; (0)B series;
(A) C series; (0) T
series (taken from
Rokudai and
Okada2').
MFI
~ _ _ _ _ _ ~
FIGURE 8
Relationship
between melt flow
index and weight Rokudai and Okada" made a detailed study of a
average molecular number of low-density polyethylenes in order to de-
weight using a - velop relationships between MFI, density, and mo-
corredion factor g:
(o,O, A) autoclave lecular parameters. Figure 7 shows the variation of
grades; (0)tubular weight average molecular weight with MFI.It is seen
grades (taken from that the curves are different for the different series.
Rokudai and
Okada*'). A, B, and C series are different in density, but they
are all from the autoclave reactor whereas the T series,
which has a density intermediate between B and C
series is exclusively from the tubular reactor. Thus,
T series differs radically in the level of branching from
the A, B, and C series. It was found that in order to
get a relationship between MFI and weight-average
molecular weight, Rokudai and Okada" had to use
the parameter 2,which is defined as the ratio of root-
mean square radii of the branched and linear polymers
with same molecular weight. Thus, the relationships
for the autoclave and tubular grades of polyethylene
as obtained by Rokudai and Okada*' are as follows
and shown in Figure 8.
8 VOL. 6,NO.1
MELT FLOW INDEX. 1
flGURE 9
Relationship
between long chain
branching
frequency and melt
flow index (symbols
same as in Figures
7 and 8) (taken
*0 from Rokudai and
t Okada2').
W
3
0
u
t'
0
5
X
0
t
4
a
m
z4
X
0 1
Q
2
s.
x
as shown in Figure 9. The curves obtained had a where (MFI)Iis the melt flow index for linear samples
scatter for the tubular resin which was no better than in g/10 min obtained under a load of 5 kg at 250°C.
that in Figure 7 for Gwversus MFI. They thus de- For branched samples with different trifunctional unit
veloped a summation series to predict MFl from weight content, it can be seen that the MFI is different for
average molecular weight and long chain branching the same molecular weight and the relationship be-
frequency as follows. tween MFI and Gwalso changes.
Using weight-average degree of branching defined
n as B,, Pilati et a1.22modified the equation suggested
log MFI = aij(log Mw)' (log z)' (6) by Bates,23namely,
ij=o
FIGURE 10
Comparison of the
observed melt flow
index with that
predicted from Eq.
(6) (symbols same
as in Figures 7 and
8) (taken from
Rokudai and
Okada”).
FIGURE 11
Experimental
values of melt flow
index at 250°C with Ob) = (1 + 0.25Bw)0.7b for Bw< 100 (8)
a 5-kg load (rlJ
condition vs. weight
average molecular
weight for in terms of MFI knowing the inverse relationship be-
unbranched tween viscosity and melt flow index as given by Eq.
samples of
poly(buty1ene
- (18). They thus made a plot of (MFII)/(MFIb) vs.
terephthalate) ( 0 )
and branched
LA
5 +
(1 0.2%) and obtained a straight line for branched
m samples of PBTP as shown in Figure 12.
samples with 0
different J The relationship between MFI and weight average
trifunctional unit molecular weight can be effectively used to check the
content (A, 0 , m, A) structural arrangement of teleblock polymers such as
(taken from Pilati et
aLZ2). butadienehtyrene as shown in Figure 13 taken from
Haws.24 By evaluating MFI and the corresponding
molecular weight, it would be easy to adjudge whether
the polymerized species is linear, trichain, or tetra-
chain. At equal molecular weight, viscosity is lower
for tetrachain (or trichain) radial polymers than for
Log Mw
- linear polymers; or at equal viscosity level, one can
use a radial tetrachain polymer of higher molecular
weight.
10 VOL. 6, NO. 1
MELT FLOW INDEX. I
I I . a . . I t .
0.0 0 -5 1.0
Log ( 1 + 0 * 2 5 e '~)
FIGURE 13
Variation of melt
flow index with
weight-average
molecular weight
for teleblock
polymers 70130
butadienelstyrene
(taken from
Hawsz4).
4 O(
T E T RACHAIN
\
3Ot
\
1 O(
TRICHAIN
LINEAR
FIGURE 14
Variation of melt
flow index with
number-average
molecular weight
for narrow
distribution high
pressure
polyethylenes
(taken from
Mortimer et aLZ5).
2.3. Effect of Number-Average Molecular which gives the m,, with a standad deviation of z t 2200.
Weight on MFI The standard deviation of mints about this line is close
Basically MFI is known to relate better with weight- to the standard deviation of the osmotic M,,measure-
average molecular weight; however, Mortimer et al.” ment. The particular advantage in determining M,, by
found excellent correlations between number-average the above equation is that it is faster than the con-
molecular weight M, and MFI as can be seen from ventional method. In fact, Mortimer et aLZ5used it
Figure 14. The curve shown in Figure 14 is described on a routine basis for over two years in order to es-
by the following equation: timate M,,for narrow-distribution batch-type poly-
mers. During this period, there was no change de-
- tected in the correlation. The line given by Mortimer
M, = 37000 - 8610 log MFI (9) et aLZ5differs from that of Sperati et a1.,26 especially
at higher molecular weight. The reason for this a p
parent discrepancy is not very clear. Though it is
known that MFI is related to aw rather tha&n,27-29
- correlation given by Eq. (9) holds because
the above
-
TABLE V Mw/M, was constant for the samples of Mortimer et
Comparison between M,,Obtained through MFI and GPC al.25
(Source: Ref. 30) For branched polyethylene, using the following re-
lationship between ii?, and MFI, Tomis3’ has shown
Polyethylene
-
Bralen FA7-15 Bralen FB1-28 Bralen RB 03-23
that the value of mn is not too different from that
-
M, by GPC 30,000 35 ,000 50,000 obtained by GPC measurements, as can be seen from
M. by MFl 26,440 35,340 40,670 Table V:
12 VOL. 6,NO. 1
MELT FLOW INDEX. I
M F I , Gm / 1 0 m i n s
where MF15 and MF11.2represent the MFI values at [q] = 0.966 - 0.189 log M R (13)
5- and 1.2-kg loads, respectively.
With a view to investigate the effect of branching
parameters on solution viscosity, Pilati et al.34 ex-
tended their melt viscosity work22 and studied the
2.5. Effect of Solution Viscosity on MFI effect of branching parameters on intrinsic viscosity.
There is a close relationship between solution vis- Interestingly, the plot made by them of log[q] vs.
cosity and MFI, as has been pointed out by a number log(MFI) shows a near straight line as can be seen
of w ~ r k e r s . ~Gar~ia-Borras~~
~”~~~ states that when- from Figure 17, which is the same for branched and
ever solution viscosity was required, an initial cali- linear samples. Pilati et al.34suggest that this behavior
bration plot was prepared between solution viscosity is probably because the effect of branching on melt
and MFI with results within 5% error as shown viscosity gets partly balanced by a decrease in intrinsic
in Figure 15. Accuracy of such a plot was found to viscosity.
be so good that plotting only three or four data Combs and Nation3’ studied 52 polyesters having
points spaced by a few centipoise each has been various molecular structures and developed relation-
recommended.32 ships between MFI, glass transition tempemhms, melt
FIGURE 16
Variation of melt
flow index with
intrinsic viscosity for
narrow distribution
high pressure
polyethylenes
(taken from
Mortimer et al.25).
10'
m
.-C
E
0
--
7
E
0
e
loo
o L I N E A R SAMPLES
lb 9 \
0.6 0.6 1.0 1.2 1-4
[%I
FIGURE 17
Experimental
values of melt flow temperatures, and the inherent viscosities. A regres-
I
index vs. intrinsic 0
viscosity for sion analysis was used for determining the constants
A of the following models investigated:
unbranched (0)and
branched samples 1.5 A 0
of PBTP (A, 0,
A) (taken from ln(MFI) = A + B(Tg - 273)/(T - 273)
Pilati et a P ) .
1.0 + c In {d (14)
t! ln(MFI) = A + BTJT + C ln{q} (15)
5
," 0 . 5
-I
-
mol-
TMT 'A
8
ln(MFI) = A + B/T + C/Tg + D ln{q} (16)
t o -
mol DMT
Be ln(MFI) = A + B(T - Tg)/(C + T - Tg)
+ D ln{4 (17)
14 VOL. 6,NO. 1
MELT FLOW INDEX. I
would be preferred. Equation (16) is the analytical viscosity. He showed that for polyethylenes the fol-
form implied by the graphical procedures used to re- lowing relationship held:
late corrected MFI with T, by Gray et al.36Equation
(17) is a generalized form of the Williams, Landel, log MFI = const - log qo (18)
and Ferry (WLF) equation, which has been success-
fully used to describe the rheological properties of Busse,40on the other hand, gave the relationship be-
amorphous polymers within 100°C of their T, values. tween MFI and inherent viscosity, from which he
Any of the equations could be used to predict the MFI derived the inverse correlation between MFI and zero
of an unknown polyester if its T, and {q}are known. shear viscosity as follows:
The measurements of Tg and {q} require c 0 . 3 g of
material, whereas an MFI measurement requires at
least 5 g. Combs and Nation35suggest that the equa-
tions given above could be used for predicting the
MFI values of other polymers. However, this needs Recently, Dutta4’ showed that for most thermoplastic
to be checked. Nevertheless, the method is useful for polymer melts (possessing a low shear Newtonian vis-
oxygen- and moisture-sensitive polymers whose MFI cosity plateau), a reasonably good estimate of zero-
determination might involve a certain degree of error. shear viscosity can be obtained from the knowledge
of MFI through the following equation:
0.0495Wp
3. MFI USE IN POLYMER PRODUCT qo =
MFI
FABRICATION
where qo is in poise, W is the MFI test load value
(g), p is the density of the polymer (g/cm3), and MFI
3.1. Rheological Considerations
is in g/10 min.
During polymer product fabrication, the only flow Dutta4’ provided a comparison between experi-
parameter that the processor has ready access to is the mental and calculated zero-shear viscosities from Eq.
MFI. However, MFI is a single point viscosity mea- (20) for 35 different polymer grades covering several
surement at relatively low shear rate and temperature. polymeric species of widely varying melt indices.
Since the values of temperature and shear rate em- However, the given plot of qo (calculated) vs. qo
ployed in an MFI test differ substantially from those (measured) on log-log scales of 3 X 3 cycles masks
encountered in actual large scale processes, MFI does a lot of error in the estimate. MFI is rather insensitive
not correlate directly with processing behavior, as has to changes in molecular weight distribution, as can
been shown by Smith3’ as well as Shida et al.38 As be seen from Figure 18 given by Hanson.’ However,
far as processing is concerned, both high and low MWD has profound effects in low shear viscosity
shear viscosities of the material are critical. Low shear behavior. Thus, MFI cannot truly predict zero-shear
properties are important in applications where melt viscosity even within acceptable accuracy in such cases,
strength, sagging are critical such as in blow molding and hence the method of Dutta4’ could involve errors
and coating. On the other hand, high shear properties of even greater than 50%. Hence the prediction of
are relevant to applications where melt instability, zero-shear viscosity from MFI must be done with ut-
melt fracture, and heat generation are important. MFI most caution.
has often been considered as an empirically defined
parameter which does not indicate any fundamental
3.1.2. From MFI to Rheogram
polymer property. However, there have been recent
attempts to seek correlations of MFI with basic rheo- It is often said that “MFI gives a dot when actually
logical parameters and thus predict processing behav- what is needed is a plot” for polymer processors. The
ior through this simple parameter. All such attempts rheological data needed for constructing a plot can be
are reviewed in the following. obtained only from sophisticated scientific instruments
such as the Weissenberg Rheogoniometer, the Rheo-
metrics Mechanical Spectrometer, the Instron Capil-
3.1 .I. Zero-Shear Viscosity-MFI Relationship
lary Rheometer, etc. These, however, are beyond the
B ~ e n i was
g ~ ~the first to indicate that there existed financial as well as technical capabilitiesof most poly-
an inverse relationship between MFI and zero shear mer processors. Recently, a method has been pro-
FIGURE 18
Effect of molecular
weight distribution
(MWD) on the
shear sensitivity of
melt viscosity
showing how the f
MFI test load z
condition of 2.16 kg
would give results
leading to incorrect
conclusions (taken
from Hansons). >
I-
z
w
IY
a
a
a
posed by Shenoy et al.42for estimating the rheogram from the resin manufacturer or determined from the
of a polymeric material from the knowledge of its melt flow apparatus.
MFI at the appropriate temperature and load condi- 0 If the loading condition of the obtained MFI does
tion. Their method involves the generation of unified not correspond to that in the unified curve, then a
curves by coalescing rheograms of various grades of new MFI value ought to be calculated42using the
-
a resin at various temperatures using a plot of q MFI following equation:
and .;Y/MFI.Based on mechanistic considerations, it
has been shown that the curves are unique for each
generic type of polymer, as can be seen from Figure
19 for polypropylene. Unified curves have been pro-
vided for a large number of homopolymer types such where n is the slope of the master curve in the
as polyolefins and ~ t y r e n i c s ? ~cellulosics,a
.~~ vi- straight portion covering the MFI range and Ll
nyls?’ engineering thermoplastics,46and some spe- and LZ are two test load conditions.
ciality polymer^.^' The technique has been shown to 0 If the temperature at which the q vs. 9 curve is
be effectively applicable to filled polymers ,48*49 poly- desired is different from that at which MFI value
mer blends,’O and copolymers.’’ is determined, then one of the following two equa-
The viscosity versus shear rate behavior for any tions ought to be used:
grade of a polymer at any temperature can be obtained
from the master curves given in refs. 42-51 by fol- Modijied WLF type equation42:
lowing the procedure as given below:
- -
mT2 - 8.86(T2 - T,)
0 Initially, obtain the MFI value of the particular
log MFIT, +
101.6 (T2 - T,)
grade of the polymer under consideration using - 8.86(Tl - T,)
(22)
standard test load and temperam conditions, either 101.6 + (T, - T,)
16 VOL. 6 , NO. 1
MELT FLOW INDEX. I
FIGURE 19
Unified curve for
lo6 polypropylene at
2.16 kg test load
condition for MFI
using viscosity vs.
shear rate data for
11 grades and six
different
temperatures (taken
frhShenoy et
10’ al.@).
18 VOL. 6,NO. 1
MELT FLOW INDEX. I
-
However, when plot of (q * MFI)/(Mz/Mw)'.7vs. (Mzl Mn Mw Mn
- -
M,)'~7(~/MFI)was made, a unique curve resulted as
shown in Figure 22, which took care of the differences
in the width of the molecular weight distribution. Shenoy
-
Mz+l =
M,
-
Q0.567
&
-
Mn
-
Q2.31 (28)
- --
and SainP appropriately modified the rheological model
suggested earlieP3 to fit the upgraded curve in Figure
- M,
Mz
+ , -
Q2.06 Mz,Mz+l
- =- Q4.06
Mi M,2
22. Thus, the following modified form of the Carreau
model is to be used in place of Eq.(24) when polymer
grades with widely different MWD are coalesced.
TABLE IX
Shear Rate Ranges Encountered in Polymer
Processing Operations
[ . (&)I2}-" (27)
Process
Compression molding
Typical Shear Rates (s-I)
1-10
Calendering 10 -102
Molecular weight distribution is often e-ressed as Extrusion 102-103
-- Injection molding 103-104
-
one of the following ratios, namely, M,lM,, MJM,,
M,, '/GZ,etc. An approximate interrelationship be-
tween the various expressions has been given by Van
FIGURE 20
Coalesced shear
viscosity curve for
broad and regular
molecular weight
distribution
polypropylene at
2.16-kg test load
condition for MFI
(taken from Shenoy
and SainP).
FIGURE 21
Coalesced shear
viscosity curve for
narrow molecular
weight distribution
polypropylene at
2.16-kg test load
condition for MFI
(taken from Shenoy
and Saini-).
~~
20 VOL. 6,NO.1
MELT FLOW INDEX. I
FIGURE 22
Coalesced shear
viscosity curve for
broad, regular, and
narrow molecular
weight distribution
polypropylene at
2.16-kg test load
condition for MFI;
(-) predictions of
Eq. (27) (taken
from Shenoy and
Saini-).
FIGURE 23
Coalesced normal
stress difference 10’
curve for broad and
regular molecular
weight distribution
polypropylene at
2.16-kg test load
condition for MFI
(taken from Shenoy
and Saini5’). lo4
c
z
to3
lo2
16’ 10-2 100
( ~ I M F I i2
FIGURE 24
Coalesced normal
stress difference
curve for narrow
molecular weight
distribution
polypropylene at
2.16-kg test load
condition for MFI
(taken from Shenoy
and Saini5’).
22 VOL. 6,NO. 1
MELT FLOW INDEX. I
FIGURE 25
Coalesced normal
stress difference
curve for broad,
regular, and narrow
molecular weight
distribution of
N, - OYNES/cm2
polypropylene at
2.16-kg test load
condition for MFI
'i0 (taken from Shenoy
and Saini5').
3
io
~ ieo-c A B C D E F G n
The above method, however, becomes effective only 3.1.6. Die Swell from MFI
if there is already available data of elasticity of a
Another form in which elasticity of a polymer melt
particular polymer. There is, however, very limited
manifests itself is by die swell-that is, by an increase
elastic data on various polymers. Since viscosity func-
in the diameter of the polymeric extrudate upon emer-
tion has been studied much more extensively in com-
gence from the die. NakajimaWhas shown how die
parison to normal stress functions, there have been
swell could be predicted through the knowledge of
attempts in the past by Abdel-Kalik et al.,59 Bird et
MFI. The salient features of his approach are as fol-
al. ,60 and Wagner6',62to find methods for the predic-
lows. He used a material function, namely, the time
tion of the normal stress difference from the viscosity
constant A defined as
function. Using the method of Wagner,6"62 Shenoy
and Saini63have given a simplified approach to the
prediction of primary normal stress differences in
A = y/j (30)
polymer melts. Thus Where i, is the shear rate in the capillary rheometer
and y is the strain which is related to die swell as
2N follows:
$1 * (MFI)' = (qo . MF1)- (A MFI)2 (j/MFI)
m
[l + (A * MFI)2 * (j/MFI)2]-"C"
(29) where S, is the die swell defined as the ratio of the
extrudate diameter to the die diameter after the extru-
where the parameters qo . MFI, A MFI, and N are date completes recovery. If the time constant A is
determined from the viscosity equation (24). m is the known, then S, can be calculated. For the linear poly-
adjustable parameter whose value lies between 0.13 ethylene samples analyzed with MFI values of 0.4-9,
and 0.2 given the upper and lower limit of the pre- NakajimaW found that the time constant varied in-
dicted normal stress difference curve. versely as the power of shear rate as
FIGURE 26
Correlation between
the degree of 1.6
swelling of the melt
and the MFI for
polystyrene (---)
and high impact -I
polystyrene (-) J J
J W
containing different
plasticizers: (0)
W
z f
butyl ester; ( 0 ) LL
0
naphthanic LL
0 W
compressor oil; (A) W 1.6 w
mixture of paraffins; W a
(0)medicinal
a a
paraffin oil; (m)
initial polymer
Q
W
0
W
Q
Q
-
(taken from Nikiton 9
et
1.4
2 4 ei
MFI , gm / 10 min
24 VOL. 6,NO.1
MELT FLOW INDEX. I
1.5
istics of the polymers used; samples 1-5 were obtained
in a tubular reactor under specific reaction conditions,
while samples 6-14 were produced in an autoclave
1.4
divided into conveniently arranged multiple reaction
chambers. The main aim of the study of Romanini et
al.67 was to get a correlation between the rheological
parameters and the molecular structure of polyethyl- 1.1
3 4 5 6 7 e
ene. The ratio Pa/MFI in Figure 30 may be associated MFt , gm/ 1 0 n i n
with the balance between the elastic and viscous com-
ponent of the material. The molecular weight being
FIGURE 28
Correlation between
the melt flow index
--I M F I R = 14.1 [[n195/[q50] +20.9
recovery and ratio
of intrinsic
viscosities at Z wt
% of 95 and 50
from the distribution
curves (taken from
Guillet et aI.=).
20 ~
FIGURE 29
Correlation between
the critical shear
rate at which
roughness on
extruded sample
first occurs vs. the
melt flow index
recovery (taken
from Guillet et
aLm).
1 Tubular 0.9176 2.14 13 280 5.4 3.1.7. Melt Strength from MFI
2 Tubular 0.9172 1.57 18 360 5.7
3 Tubular 0.9176 0.24 130 550 5.7 When a polymer is extruded from the orifice of the
4 Modified tubular 0.9205 3.12 8.5 120 4.9 melt flow indexer, the diameter of the extrudate changes
5 Modified tubular 0.9234 2.13 12 135 4.1 due to the stress applied to the melt by the weight of
6 Vessel 0.9128 84.0 0.16 210 6.6 the material that has preceded it. By measuring the
7 Vessel 0.9144 22.4 0.95 340 8.8
8 Vessel 0.9156 6.58 4 420 9.6
change in diameter of the extruded cord over the first
9 Vessel 0.9176 1.19 18 690 9.4 1/2 in. of length, a melt viscosity at extremely low
10 Modified vessel 0.9198 1.75 10 140 4.5 shear rates is calculated and termed as the melt strength
11 Modified vessel 0.9204 1.69 16 185 5.5 (MS) since it indicates how well the melt can support
12 Modified vessel 0.9211 0.25 110 275 4.7 its own weight. Guillet et a1.% suggested the following
13 Modified vessel 0.9207 0.24 130 330 5.8
14 Modified vessel 0.9217 0.24 80 600 6.6
equation to calculate the melt strength based on their
15 Linear 0.9780 15.1 0.78 52 3.0 experience:
polyethylene
16 Linear 0.9500 0.98 22 110 5.3 MS = 3.54 x 105~126/MFI (36)
polyethylene
17 Linear 0.9445 0.21 160 140 8.0
polyethylene
where A1 is the length of the cord (in.) for a 50%
18 Linear 0.9440 0.04 1200 220 9.1 decrease in diameter and r, is the radius (in.) of the
polyethylene cord as it first emerges from the die (measured by
extrapolation of measurements at 1/16, 1/4, and 1/2
in.).
26 VOL. 6, NO. 1
MELT FLOW INDEX. I
flGURE 30
Dependence of the
swelling ratiolmelt
flow index
parameter on the
molecular weight
for different
annealed
polyethylene
samples; symbols
are as given in
Table X (taken from
Romanini et aLs7).
The above equation suggested by Guillet et a1.% A number of other assumptions were made during the
was later corrected by Combs et a1.68 as a mistake derivation of Eq. (37) which are not truly correct and
was noted in the conversion of the units used in the accurate.@It was found that the above equation showed
equation. The actual data reported by Guillet et a1.% a 37-fold difference in the melt viscosities of poly-
were correct, but the equation was different by a factor ethylenes having similar melt indexes. The reason for
41.62 or (2.54)4. The correct equation, therefore, re- this is simply because MFI is insensitive to molecular
lating to MS and MFI is as follows: weight distribution and hence a normalizing factor of
the kind used by Shenoy and would be required
for more accurate predictions.
1.492 x 107(~1)*6
MS = (37) Figure 3 1 shows a plot of melt strength determined
MFI at 180°C vs. MFI for a number of polyethylene sam-
ples described in Table X as studied by Romanini et
It was assumed that the melt strength expressed above al.67It can be seen that long-chain branching causes
was equivalent to the melt viscosity at low shear rates. an increase in melt strength.
FIGURE 31
Correlation between
melt strength and lo’
melt flow index for
different annealed
polyethylene
samples; symbols
are as given in
Table X (taken from
Romanini et aL8’).
M F I(gm/10 mine )
3.1.8. Breakage Stretch Ratio and Elongational curve is shown in Figure 33 for high density polyeth-
Viscosityfrom MFl ylene as taken from Shenoy and Saini.69The elon-
gational viscosity vs. extension rate behavior for any
The breakage stretch ratio (BSR) and the elonga-
grade of a polymer at any temperature can be obtained
tional viscosity give a measure of the stretchability of
from the generated master curves by using a procedure
the polymer. The behavior of the polymer in extension
similar to that described in Sec. 3.1.2.
is important in certain processing operations like fiber
spinning and film blowing.
3.1.9. Flow Activation Energy from MFl
Basically, breakage stretch ratio is the ability of the
polymer extruded from a die to withstand breakage An understanding of the mechanism of polymer melt
when stretched at a particular rate on drawing roll flow processes in relation to the nature and composi-
system. Figure 32 shows a plot of breakage stretch tion of the material can be elucidated by a study of the
ratio determined at 180°C vs. MFI for the polyeth- temperature dependency of melt viscosity. The tem-
ylenes specified in Table X as studied by Romanini perature sensitivity of the melt viscosity has a pro-
et al.67It can be seen that long chain branching causes found effect on the choice of processing conditions as
a decrease in BSR for the same MFI. The same be- well as on the quality of the end product. An increase
havior was observed earlier by Bussem during the in temperature sets up thermal motion of the molecules
study of melt strength and elasticity and their rela- resulting in their displacements based upon the avail-
tionship to the mechanical structures of the polymers. able free motion and the overcoming of forces of inter-
The ratio of the tensile stress to the extensional rate molecular interactions. There are two commonly used
is basically defined as the elongationalviscosity. Shenoy expressions to evaluate the temperaturedependency of
and S a i d 9 conducted a reanalysis of the theoretical the viscosity--one based on free-volume concepts,
treatment for extensional flows and evolved a method namely, the equation proposed by Williams, Landel,
for the unification of existing extensional viscosity vs. and Ferry’’ and the second of the Arrhenius type based
extension rate data using plots of qE * MFI vs. (El on the absolute theory of rate processes as derived by
MFI)*. It has been shown that the plots are unique Eyring.’l Both give a measure of the flow activation
for each generic type of polymer. A typical coalesced energy but need the evaluation of the zero-shear vis-
28 VOL. 6,NO. 1
MELT FLOW INDEX. I
FIGURE 32
Correlation between
breakage stretch
ratio and melt flow
index for different
annealed
polyethylene
samples; symbols
are as given in
Table X (taken from
Romanini et aLs7).
cosity which is known to be a difficult rheological pa- energy for viscous flow E. Equation (23) suggested
rameter for experimental determination. by them for this evaluation has been shown5' to give
Recently, Saini and Shenoy5' have proposed the a standard and meaningful value of E as the MFI
concept of using MFI at two different temperatures measurement is done at constant shear stress. For
within the range of interest to evaluate the activation polymer melts, it is beneficial to use the activation
FIGURE 33
Coalesced
elongational
viscosity curve for
high density
polyethylene at
2.16-kg test load
condition for MFI
(taken from Shenoy
and Saini").
30 VOL. 6, NO. 1
MELT FLOW INDEX. I
FIGURE 35
Effect of molding
temperature on the MOLDING PRESSURE = 1000 PSI
flow distance in -A RESIN
spiral cavity mold
for different melt
___ STANDARD RESIN
flow index A resin r
and standard resin
at molding pressure 45 '
30'
25
~
M o L D I N G TEMPERATURE,OF
with a higher MFI the injection energy decreases and known the importance of operating under minimum
the pressure in the filled mold increases since the pressure drop conditions during cavity filling in order
pressure drop in the nozzle and gates becomes lower. to minimize frozen-in stresses and minimum clamping
e ~ ~a plot of WEvs. the
It was found by K n a ~ p that forces to prevent mold opening. A detailed theoretical
reciprocal of MFI gave a linear correlation with some calculation of the effect of the cooled mold on the
deviation for the lowest MFI. In contrast to MFI, pressure vs. flow rate curve is essential to be known
which is measured under constant shear stress con- for calculating the minimum pressure requirements.
ditions, WEis caused by a viscosity at constant shear Even for the simplest geometry, this would require
gradient; yet the linear relationship between WEand high technical sophistication and expensive compu-
MFI-' is surprisingly good. tational and experimental facilities which are beyond
The injection molder and the mold designer have the means of any processor. Saini and S h e n ~ have
y~~
derived an expression for the minimum pressure gra-
dient for cavity filling which can be estimated merely
from MFI. Their final expresion can be written as
FIGURE 36
Effect of molding MOLDING TEMPERATURE 400.F
pressure on the -A RESIN
flow distance in
spiral cavity mold v)
W --- STANDARD R E S I N POminX' +4n K7F"
- (38)
for different melt
flow index A resin 52 55- MFI = 12 C3% " = An)(MFI)"
+
1-n
0
2 30-
0
0
0
and x is the original cavity thiwess, & is the radius
-1 25- 0
a 0 of the circular disc cavity, and C is the proportionality
a 0
I' I I
h 20
v) 1000 1250 1500
constant given as
MOLD1NG PRESSURE, PS I
32 VOL. 6,NO. 1
MELT FLOW INDEX. I
FIGURE 37
Relationship
between the
Mooney value and
melt flow index of
rubber mixes (taken
from Kandyrin et
a ~75).
.
a being the heat diffusion coefficient of the melt, 8 constants and, for a given circular type mold, R,, and
being the mold temperature, T being the melt tem- x are fixed. Hence the minimum pressure for cavity
perature, and To being the freeze-off temperature. filling can be estimated through only the knowledge
The values of K and n to be used in Eq. (38) and of the MFI at the melt temperature T of mold filling.
(39) are given in Table VIII along with the applica- The MFI determined at the ASTM test temperature’
bility range of shear rate which can be seen to be of would thus have to be converted to the MFI value at
practical significance to the injection molder. the required temperatures. This could be done through
For a given polymer type, An), c, K, and n are either of the two equations (22) and (23).
FIGURE 38
Variation of
injection energy
with melt flow index
for polypropylene
(taken from
Knappem).
More centrally gated, flat, and symmetrical moldings For circular disc:
would show higher values of B and lower clamping
force. For engineering design, one could choose the Fcdh&fFI)o.156 -hie 0.312
~3.156 = 4.6 x 1 0 6 ( ~ ) (46)
exefession (19) which would give the lower estimate
of B. Thus, in the present case, a value of B = 4.0
for n = 0.33, B = 3.5 for n = 0.44 and B = 3.0 For $at strips:
for n = 0.50 may be used as rough estimates.
0.312
The simplistic approach given above is not a pan- FfSb(MFI)O.” = 1.07 X 1 0 6 ( ~ )
w ~ 2 156
. (47)
acea but would certainly be a useful handy tool to the
plastic processor to get quick order of magnitude es-
In compression molding operations, the typical
timates of the design parameters.
squeezing rate and the initial separation would be such
as to give values of ( - hl”/b) between 0.01 and 0.1
(cm * s)-l/’. Figure 39 shows the variation of the left-
3.2.2. Compression Molding hand sides of Eqs. (46) and (47) with the ( - h1’2/ho)
factor in this range. It is now evident that knowing
Compression molding is one of the most common
the geometrical factors of the mold, one can easily
methods for producing articles from thermosetting
determine the compaction force merely from the
plastics. It is rarely used as a production process for
knowledge of the MFI at the appropriate temperature
thermoplastic materials due to the long cycle times
and load conditions determined through the method
required for cooling and reheating the press. However,
discussed in Sec. 3.1.2.
there are some specialized materials like ultra high
molecular weight polyethylenes (UHMWPE) which
are preferentially compression molded rather than in-
3.2.3. Calendering
jection molded to form the product. In fact, more than
50% of UHMWPE is processed via compression The term “calendering” as applied to thermoplastic
molding. Shenoy and Saini79have suggested a sim- materials refers to the shaping of the material into
plified approach for determining the compaction force sheet or film by feeding it through a pair of corotating
F from MFI. The given expressions for circular disc heated rolls. This process is commonly used for the
molds and flat strips are as follows: manufacture of various poly(viny1 chloride) (PVC)
products such as leather cloth, shrink films for pack-
For circular discs: aging, resilient flooring tiles, etc. The various critical
2 r K (2, n+
Fed=--
(n + 3)
K23 -
- ’>’ ( -”>
(MFI)” h?+’
(44)
parameters during PVC calendering are the pressure
distribution on the rollers, the torque exerted by each
roll, the power input into each roll, and the average
34 VOL. 6, NO. 1
MELT FLOW INDEX. 1
FIGURE 39
Unified curve
showing the
variation of the
compaction force
with the rate of
plate separation
(taken from Shenoy
and Sainin).
temperature rise due to viscous dissipation. A method where Qo is the flow rate of the melt through the
to estimate these through the appropriate value of MFI calender.
has been suggested by Ray and Shenoy.80 Note that C, is a constant for a given resin and, C2
The expression derived is as follows: for given process parameters and that A* = 0.503 for
PVC formulations. Thus, numerical integration of Eq.
(48) gave the pressure distribution vs. the dimension-
less distance as given in Figure 40. The same cal-
culation was performed using the condition of hydro-
dynamic slip at the roll surface, also resulting in a
unique plot as given in Figure 41. Merely through the
where value of MFI, the pressure distribution could thus be
calculated. The predictions of this simple approach
2 n + l n were found to give more realistic values than those
Cl = K ( 7) (49) obtained by Vlachopoulos and Hrymak," who used
complete rheological information of viscosity vs. shear
rate. A comparison of the two sets of predictions along
with the experimental data used by Vlachopoulos and
Hrymak" given in Figures 42 and 43 show that the
where P is the pressure developed between the rolls, present simple approach fits better.
U the velocity at the roll surface, Ho half the distance The expression for the torque exerted by each roll
between the rolls, & the radius of the roll, K and n (r)and the power input (+p) as given by Ray and
are power-law parameters as in Eq. (26), and A*, x* ShenoyX0are as follows:
dimensionless parameters defined below. Thus
r(MFl)n =
FIGURE 40
Plot of P(MFI)O.=
vs. dimensionless
distance X* -
Master curve for
the theory without
slip (taken from 9.10' KPo
Ray and Shenoys0).
I I I I
-4 -3 -2 -t
X.
FIGURE 41
Master curve as in
Figure 35 for the
theory with the
effect of slip taken 6 i$0' K Po
into account (taken
trwn Ray and
Shenop).
X*
36 VOL. 6,NO. 1 I
MELT FLOW INDEX. I
FIGURE 42
Comparison of
predictions made in
Ref. 80, those
9 I loa KPa made in Ref. 81,
and an
T s t82.C
experimental curve
E
from Ref. 81 for the
- - _ _V L A C H O P O U L O S - H R Y Y A K (771
theory without slip.
-R A Y - S H E N O Y 176)
EXPERIYENTAL DATA ( 7 7 ) /-\
r
\
6
----
-4 -3
,
-2
1
-I
\,
0 0.0
FIGURE 43
Comparison as in
Figure 42, for the
theory with slip.
X*
(54)
APHJMFI)"
2Ld = flf2 (Z)" (55)
whereh2 is the constant lateral taper factor given by
the ratio of the width W2 at the end of the channel to
the width WI at the start of the channel and SH is the
where f , is the function of the geometric parameters
shape factor given by the ratio of the entrance width
based on the shape of the die, f2 is a function of the
WI to the constant height H of the channel.
fluid properties, namely, K and n as given by Eq.
(26), Ld is the length of the die, and H, is a charac- Case 4: Rectangular Channel with a Constant Ver-
teristic geometric parameter specific to each geometric tical Taper along with a Constant Lateral Taper.
shape. The expressions for f l and f2 are given below
for each specific die shape.
H, = HI (65)
Case 1: Rectangular Channel without Taper
fI = " I - + n(l - A21
(57)
+-1 2n2 (A,
- 2n (1
- A:")(l
- AT)(l
- A,)
- XI)
K 4 n + 2 "
4n+2
f2 = K(--) f2 = 2n (7)
where A l is the constant vertical taper factor given by
where tWH is the shape factor given by the ratio of the ratio of the height H2 at the end of the channel to
the width W to the height H of the channel. Thus 5 the height HI at the start of the channel, A2 is the
---f1 represents a square while 5 -+ = represents a constant lateral taper factor given by the ratio of the
wide slit. width W2 at the end of the channel to the width WI
38 VOL. 6 , NO. 1
MELT FLOW INDEX. I
at the start of the channel and 6 is the shape factor where R is the radius of the circle whose cross-sec-
given by the ratio of the entrance width WI to the tional area is equal to the cross-sectional area of the
entrance height H, of the channel. polygon-
Case 5: Rectangular Channel with a Taper Such Case 9: Constant Taper Polygonal Channel with
That the Cross-SectionalShape Factor is Constant. N1Sides.
f 1 = (
( m + 1
)
&&’ + 1 AY(l - A,)
1-A:”
(69)
:(
f l = -tan- [ ’ ”]
l1),,’ - (81)
A? (1 - AR)
K 4n+2
f2 = G ( Y ) K 3n+1
f2 = 3n (7)
where A1 is the taper factor given by the ratio of the
height H2 at the end of the channel to the height HI where R I is the radius of the circle whose cross-sec-
at the start of the channel and twHis the shape factor tional area is equal to the cross-sectional area of the
which is constant such that the tapering channel has entrance of the polygon, R2 is the radius of the circle
a constant cross-sectional rectangular shape. whose cross-sectional area is equal to the cross-sec-
tional area of the exit of the polygon, and AR is equal
Case 6: Cylindrical Channel. to RZ/Ri.
The values of f2 can be generated by using the
H, = R appropriate values of K and n from Table VIII. Know-
fl = 1 ing the geometry of the die, f l values in all cases
considered can be easily calculated. From Q. ( 5 3 ,
f2 = K(--)n
3n +1 (73)
a relationship between APHC/2Land Q/H3 can thus
be generated through only the MFI using an appro-
priate value of f l calculated from the geometry of the
where R is the radius of the channel. die, an appropriate value of f2 based on the generic
type of polymer and the corresponding value of n from
Case 7: Truncated Right Cone Table VIII.
Figure 44 shows a plot of APH/2L vs. Q/H3 for
H, = R1 (74) polypropylene melt flow through a rectangular die.
The data points correspond to the experimental values
(75) of White and H ~ a n gwhile ~ ~ the solid lines are pre-
dictions of Shenoy and Saini.82For comparison, the
dashed line is shown giving the predictions of
based on the rheological data as given by White and
H ~ a n g It. ~can
~ be seen that the prediction merely
where AR is the constant taper factor given by the ratio through MFI is as effective as the other cumbersome
of the exit radius R2 to the entrance radius R1. approach through the knowledge of the entire flow
curve.
Case 8: Untapered Polygonal Channel with N1
Sides. 3.2.5. Viscous Heat Dissipation
During all polymer processing operations, viscous
H, = R (77) heat is dissipated due to the friction between the highly
viscous melt and the various parts of the processing
f, =
(:]
-tan-
N:JM equipment that it comes in contact with. The viscous
heat dissipated leads to a temperature rise, resulting
f2 = K 3( n y+ 1) in an offset of the setting of the extruder temperature
(79) profile with respect to throughput rate or screw speed.
FIGURE 44
Pressure drop vs.
flow rate through a
rectangular die for
polypropylene
(taken from Shenoy
and Saini=).
04 i 10 too 1000
o/ H'
FIGURE 45
Unified curve for
viscous dissipation
factor vs. shear rate
for polypropylene at
2.1 6-kg test load
condition (taken
from Shenoy and
Sainia5).
40 VOL. 6,NO. 1
MELT FLOW INDEX. I
(83)
MFI MFI
The values of a Iand PI for each of the polymer types compounding method and conditions. Most often the
considered are given in Table XIII. Equation (83) can component grade selection and choice of compound-
be readily used for estimating the viscous heat vs. ing process parameters are arbitrary. It is the general
shear rate behavior at any temperature of interest only practice to finalize the appropriate grades of the com-
through the knowledge of the appropriate MFI by ponents and the compounding conditions based on the
following the steps as outlined in Sec. 3.1.2. end property evaluations. This becomes more a trial
and error procedure. Single phase blends would gen-
erally provide synergistic property advantages, and
3.2.6. Blending and Filling
this cannot be achieved even in thermodynamically
During recent years, multicomponent polymeric miscible polymers if they are mechanically incom-
systems have attained great importance due to the patible due to large differences in the melt viscosities
possibility of obtaining compounds with novel phys- at conditions of compounding. Shenoys6 has sug-
ical properties and optimum cost performance bene- gested a simplistic approach of getting quantitative
fits. From a macrostructural viewpoint, polyblends estimation of compounding conditions or grade se-
and composites would fall under the category of mul- lection of blend components through MFI.
ticomponent systems consisting .of a polymeric con- The temperature of compounding of the blends in
tinuous phase or matrix and of a dispersed phase. The order to achieve maximum mechanical compatibility
dispersed phase could either be another polymer (as as suggested by Shenoyg6is as follows:
in the case of polyblends) or fillers such as calcium
carbonate, talc, etc., or reinforcing agents such as Tc
glass fibers, mica, etc. (as in the case of composites). -
- EPZ - E P ~
All PVC formulationswould also fall into the category R In ( M ~ ~ PTZNFIPI,TI
Z, + E P ~ -ZE P ~ ~ I )
of multicomponent systems due to the presence of a (84)
number of additives such as plasticizers, fillers, sta-
bilizers, lubricants, etc., which go into such forrnu- where MFIpl,TIand MFIPZ,TZ represent the MFI values
lations. The final properties of the products depend to of the two component polymers, EPI and Em their
a large extent en how well the dispersion level of one respective activation energies, and TI and Tzrespec-
phase into the other is. tive temperatures of MFI measurement.
In the case of polyblends, the critical steps involved The compounding temperature graphically repre-
are (a) selection of the component polymers, their sents the point of intersection of the two curves shown
appropriate grades and their composition based on in Figure 46(a), for polymers PI and Pz. If the grade
property requirements, and (b) the proper choice of selection of the two component polymers has been
FIGURE 46
Four possible ways
in which curves of
melt flow index vs.
reciprocal
temperature on a
semilogarithmic plot
would exist for two
given component -
b.
polymers (taken 5
from Shenofs).
i/T
(C)
done a priori, then the compounding temperature as where MFIe,=, is the melt flow index value of either
determined from the intersection of the two curves is component, i.e., of the blend at the temperature of
fixed. The value of T, as determined through Eq. (84) compounding T,. K, and K2 as well as n, and n2
may not always be relevant for the selected grades. correspond to the parameters of Eq. (26) and given
For example, the cases, as shown in Figures 46(b), in Table VIII for the two component polymers. The
46(c), and 46(d) clearly indicate that the blending above shear rate condition is determined by the in-
temperature as determined by the point of intersection tersection point of the two curves as shown in Figure
could be too low (even below the melting tempera- 47. These are based on the master curves of Shenoy
ture), too high (even above the degradation temper- and Saini.” Note that in Eq. (85) when nl = n2 the
ature), or none at all if the activation energy of the curves do not intersect and hence no shear rate con-
two components are equal. Such values may not be dition can be specified for achieving mechanical com-
relevant for use but are certainly an indication of the patibility. When K and n values for the component
incompatibility of the component polymers. polymers are nearly the same, then the blending shear
Shenoysbhas also indicated the method for deter- rate truly does not matter as the two components are
mining the shear rate level in the compounding op- undoubtedly compatible provided that they have the
eration in order to achieve mechanical compatibility same MFI value at the blending temperature. Shenoy86
conditions. The equation for this determination is as has discussed a number of case studies to illustrate
follows: the above-postulated method of determining the com-
pounding conditions (temperature and shear rate) and,
alternatively, to select the appropriate grades of the
component polymers if the compounding process pa-
rameters are fixed a priori.
42 VOL. 6,NO. 1
MELT FLOW INDEX. I
FIGURE 47
Four possible ways
in which curves of
shear stress vs.
shear rate
normalized by MFI
on a log-log plot
would exist for two
given component
polymers (taken
from Shenoy86).
44 VOL. 6, NO.1
MELT FLOW INDEX. I
FIGURE 52
Variation of (MFlo
1.0 - MFI)IMFlowith
irradiation dose for
nine types of high
pressure
0.8 polyethylenes
(taken from
HarpePg).
5lOE-O
0.6
610 M - A
500M-JC
700E- A
0.4 900M- V
5 5 0 E- 8
7 7 0 M- 0
0.2 9 9 0 M- 8
0
0 2 4 6 e 10
DOSE IN M R A D
FIGURE 53
Variation in melt
flow index with
number of
reprocessing cycles POLYPROPY L E N € -
UNITS
FIGURE 54
Shear viscosity
master curve for
reprocessed
polypropylene at
2.16-kg test load
condition (taken
from Shenoy et
a195).
46 VOL. 6, NO. 1
MELT FLOW INDEX. I
FIGURE 55
Effect of extrusion
temperature on the
film melt flow index
for polypropylene of
9 different melt
stability (taken from
Evansg7).
E X T R U S I O N TEMP
FIGURE 56
Effect of galvinoxyl
on the melt flow
index of
20
polypropylene in an
open mixer;
I)
numbers on the
;. i 6 curves are
concentration (1O4
2 mol/l Oog) with
'E
12 temperature in
0
parenthesis (taken
from Bagheri et
t : * aI.%).
t
4
0
0 10 IS 20
PROCESSINQ T I M E ,rninr
~~ ~
FIGURE 57
Shear viscosity rate
for polypropylene I1
plotted as q .
,.-
0
MFl/aT as a
+ -
x t 90%. 0- 2 1O F , 0 2 30.c-
function of
In(+ * aT/MFI); 10 - A- 250*C,W -270% 280%
0
+ - 2 90%, A - 3OO%,O - 3 10%
(taken from
Zavadsky et aI.=). - &+o
<-
c An
9- A t
* M0
0
-s
c
c 8 -
:3 . *A x *
A
xnLv*
all
7 - OVd(
X X
I I I I 1 I
-2 -1 0 1 2 3 4 5
It is known that polypropylene has a great tendency the amount of rise in the melt flow index, which in-
to decompose during melting and at elevated temper- creases at more elevated extrusion temperatures. Ex-
ature. Hence all commercially available polypropyl- amples of the increase of the melt flow index in cor-
ene grades contain thermostabilizers. Even then it is relation with the extrusion temperature for various
advisable to maintain the processing temperature in isotatic polypropylene grades stabilized to a different
the metering zone as low as possible in order to min- degree are given in Figure 55 taken from Evans.97
imize losses in the mechanical properties of the end Bagheri et al.98 studied the melt stabilization of
product due to thermal decomposition of the polymer. polypropylene by galvinoxyl at three different tem-
The extent of degradation can be easily checked by peratures (170, 190 and 200°C) for various periods of
FIGURE 58
Effect of
temperature and
residence time
during extrusion of
-
polypropylene on
the melt flow index 80 -
(taken from
Zavadsky et aI.=). -
m
-
2 60-
0
\
-
--a -
40
L
I -
20 -
I 1 I 1 I I
0
240 260 280 3 00
T, 'c
48 VOL. 6,NO. 1
MELT FLOW INDEX. I
mixing under three sets of conditions: (a) open to the where E is the activation energy, R the universal gas
atmosphere, (b) mixer closed, and (c) mixer closed constant, To the absolute reference temperature, and
after purging with nitrogen. In each case, the effect T the absolute temperature of measurement.
of galvinoxyl on the melt stability of PP was tracked It was, however, found that the data for tempera-
by observing the changes in the MFI with processing tures lower than 280°C lie on a single curve, whereas
time as shown in Figure 56 for the open mixer. It was the data for temperatures 280°C and higher did not.
observed that, in the presence of oxygen, the additive This was due to the degradation of the polymer.
was less effective. There was no real induction period Nevertheless, a master curve incorporating even the
and the additive was less effective at 200°C than at degraded polymer data could be got by using a mod-
190°C. Whereas, in the open mixer, oxidation was ified shift factor a, defined as the ratio of the tem-
effectively inhibited for up to 10 min, it was observed perature shift factor aT and the melt flow index MFI
that, in a closed mixer for the same concentration of as shown in Figure 57. The dependence of the melt
galvinoxyl and the same temperature, the PP was sta- index upon the temperature & and the residence time
bilized for 20 min of processing time. The end of the t, as shown in Figures 58 and 59 was determined in
MFI induction period actually corresponds to the com- the form
mencement of an irreversible removal of hydrogal-
vinoxyl from the system.
Zavadsky et al.99studied the melt viscosity of pol-
ypropylene and its dependence upon temperature, shear,
time of shear, and molecular weight. A master curve
of viscosity vs. shear rate in the form q/aTas a function The relationship was found to fit experimental data
of aT+ was attempted for all temperatures with a tem- rather well as can be seen from Figure 59.
perature shift factor aT defined as Most of the flow curves were fitted by a power-law
model of the following type by Zavadsky et al.* so
FIGURE 59
Effect of
temperature and
residence time
during the extrusion
of polypropylene on
the melt flow index;
(x) experimental
data (taken from
Zavadsky et aLW).
0
tc
FIGURE 60
Effect of shear rate
and melt flow index
on the parameter k
of the power-law
model given in Eq. 0.009 -
(89)(taken from
Zavadsky et aLW). ->-
-e 0~008-
0.007 -
0.006 -
I I I 1 I I I
0 40 20 30 40 50 60
YFI (pn/lOnins)
FIGURE 61
Effect of shear rate
and melt flow index
on the parameter n
of the power-law
model given in Eq. t = 1 s-1
(89)(taken from
Zavadsky et a1.9.
I I I I I
10 20 30 40 50
MFI ( p m / f O m l n s )
FIGURE 62
Effect of shear rate
and melt flow index 30000
on the parameter
mo of the power-law
model given in Eq.
(89)(taken from
\ 1 = 290.C
0 I 1 1 I I ,
~ ~ _ _ _ _
50 VOL. 6, NO. 1
MELT FLOW INDEX. 1
FIGURE 63
Effect of shear rate
and melt flow index
on the apparent
viscosity of
1600 - polypropylene
(taken from
Zavadsky et at.=.
(400 -
t : 290.C
(200 -
to00 -
-t
-
8 600 -
l
e
600 -
400 -
200 -
300 C'
01 I 1 I I I
0 10 20 30 40 50 60
HFI ( g n 1 1 0 n i n r )
q = m,, exp( - kt,,J .;u"-' (89) where k is the rate in terms of percent scissions per
unit time t, MFI, is the MFI at time t, M a is the
The variation of k, n, m,,, and q with MFI for various initial value, E is a constant which includes the mon-
levels of shear rate y' are given in Figures 60-63. omer molecular weight, the polydispersity of the poly-
The influence of the shear rate and the melt flow index mer, and the value of the intercept at the R, axis of
upon the parameters k and n is distinct but diminishes the log MFI vs. log RW curve, and m is the slope of
with increasing values of both quantities. There is a this curve.
strong influence of melt flow index on the parameter A plot of MF1°.25vs. hydrolysis time was used to
Q, but the effect of shear rate on it is rather negli- calculate the reaction rates as shown in Figure 64 for
gible. 30% glass-reinforced PBT while a plot of MF1°.23vs.
The hydrolytic stability of glass fiber reinforced hydrolysis time as shown in Figure 65 was used for
poly(buty1ene terephthalate), poly(ethy1ene tereph- 30% glass-reinforced PET. The value of the exponent
thalate), and polycarbonate was studied by Kelleher is the value of the slope of the curve in accordance
et al. following the changes in the melt flow index with the mathematical treatment given by Pryde et
during the process of hydrolytic degradation. Their a1.'02 It can be seen that the reaction rates decrease
entire approach was similar to that used earlier for with decreasing temperature in both cases while PET
unreinforced poly(buty1ene terephthalate)"' and po- hydrolyzed at a faster rate than PBT. A possible ex-
lycarbonate.lo2Since MFI is related to the degree of planation for this behavior is that, for a given &,
polymerization, the following relationship was PET has more ester groups than PBT. Though MFI
developed102to study the rate of hydrolysis: was found to be considerably sensitive to hydrolytic
degradation, the same was not the case for tensile
properties. It was found"' that, for unfilled PBT, there
1 1
kt = E(- MFI" --)MFIE (90)
was a fundamental correlation between MFI and elon-
gation so that the final MFI could be equated to a
FIGURE 64
Variation of melt
flow index with
I
hydrolysis time for
J
30% glass-fiber-
reinforced
poly(butylene 3.5
terephthalate)
pellets at 95%
relative humidity
(taken from
Kelleher et al.lW).
0
Q
I k . 1.30~10-'*/. LINKAGEIhr
2.2 1 I I
0 5 10 15
TI ME ( HR x iOY
flGURE 65
Variation of melt
flow index with
hydrolysis time for 8 5 *C
i
30% glass-fiber- value of elongation which was considered a failure
reinforced km I.3X10-3 LINKAGES/hr point. So also it was found that the tensile strength
poly(ethy1ene
terephthalate) at of unfilled PET almost changes linearly with MFI.
95% relative However, no such adequate correlation was seen to
humidity (taken exist for the reinforced system. This is because MFI
from Kelleher et
a1.lW). is not sensitive to the resin-filler bond and cannot
predict strength properties due to the uncertainties at
the interface. Consequently, MFI cannot be used to
define a failure criterion for filled system; instead, to
predict serviceability of filled polymers, one must rely
primarily on actual mechanical property data.
Generally rheological experiments require a stabil-
ity test, which makes sure that the rheological prop-
erties do not change during a rheological test. The
duration of most rheological tests is much longer than
the average residence time in processing equipments
and hence thermal stability tests do assume consid-
erable importance. Winter'03 has presented the results
of the thermal stability tests on LDPE samples at 190°C
by measuring the MFI (19OoC/2.16 kg) at different
residence times. The thermal stability at 190°C seemed
I
1.0 2.0
1
to be good for the two LDPE samples up to 200 min,
TIME . ~ xr while for larger residence times the melt flow index
decreased rapidly, as can be seen from Figure 66.
Thus, MFI can be considered to be a sufficiently sen-
52 VOL. 6, NO. 1
MELT FLOW INDEX. I
FIGURE 66
Stability test:
variation of the melt
flow index at 190°C
and 2.16-kg test
load conditions with
the residence time
of the polymer in
the apparatus
(taken from
Winter").
sitive material function when monitoring material chanical properties such as tensile strength at yield,
changes with time. tensile strength, and elongation at break, the dielectric
Prolonged storage of polymeric materials may lead constant and the electrical strength changed very little
to deterioration in properties as a result of aging. This over a storage period of 13 years of unstabilized and
point was investigated for polyethylenes by Neverov stabilized LDPE. However, the most marked change
and Vasil'eva.'04 It was observed by them that me- during storage of the polymer occurred in the MFI of
FIGURE 67
Relative variation in
the melt flow index
for nonstabilized
low density
polyethylene (curve
1) and stabilized
polymer (curve 2)
- with time of storage
IA (taken from
I Neverov and
\ Vasil'evalW).
w
;0 4 -
L
0.6 I I
0 6 T I M E , Y E A R S 12 1e
~~
the material. It can be seen from Figure 67 that for H, = characteristic geometric parameter specific to
the unstabilized material there was a monotomic, prac- geometric shape (cm) in Eqs. (55). (56), (59),
tically linear change in MFI with time even up to a (62). (65). (71L (74). (77). and (80)
k = rate in terms of percent scissions per unit time t in
storage period of 17 years. For the stabilized material, Eq. (90)
only a slight reduction in MFI is observed during the K = consistency index of the power-law model (glcm
early stages of storage, followed by a slight increase, s*-") in Eqs. (26), (4% (4% (481, (49L (50A (53,
and then a decrease after 6-7 vears. Changes " of this (58L (61), (W, (67), (70), (73), (76), (79), and
type in MFI can be attributed to the process of oxi- (82)
K I , KZ = consistency index for polymers 1 and 2 (g/cm s2-"),
dative crosslinking. respectively, in Eq. (85)
= length of extrudedthread at fifty decrease in
diameter (in.) in Eqs. (36) and (37)
= length of plate (cm) in Eqs. (45) and (47).
= test load at condition I (kg) in Eq. (21)
NOMENCLATURE = test load at condition 2 (kg) in Eq. (21)
= length of barrel (cm) in Eq. ( 1 )
heat diffusion coefficient of the melt (cm2/s) in Eq. = length of capillary (cm) in eq. (1)
(40). = length of die (cm) in Eq. (55)
coefficient in Eq. (6), values given in Table V = damping constant in Eq. (29)
constant in Eqs. (14)-(17) = model parameters in Eq. (89)
constant in Eq. (34) = number average molecular weight in Eqs. (9), (lo),
effective projected area of the molding in Eq. (41) and (28)
constant in Eqs. (14)-(17) = viscosity average molecular weight in Eq. (19)
constant in Eq. (35) = weight average molecular weight in Eqs. (2)-(6).
numerical function dependent on n for different (1 I), ( 2 3 , and (28)
geometries appearing in Eqs. (41)-(43). = average molecular weight in Eqs. (27) and (28)
weight average degree of branching in Eq. (8) = (z + I)-average molecular weight in Eq. (28)
constant appearing in Eqs. (14)-(17) = melt flow index (g/10 min) in Eqs. (6), (9), (lo),
proportionality constant in Eqs. (48). (53), and (12)-(l9), (24)-(27), (29), (34)-(38), (44)-(48),
(54). defined in Eq. (49) (53)-(55), (83). and (88)
proportionality constant in Eqs. (48). (53). and = melt flow index at time t = 0 (g110 min) in Eq.
(54). defined in Eq. (50) (90)
proportionality constant in Eq. (381, defined in Eq. = melt flow index at 1.2 kg load condition (g/IO min)
(40) in Eq. ( I I )
constant appearing in Eqs. (15)-(17) = melt flow index at 5 kg load condition (g/10 min)
activation energy for viscous flow (KcaVmol K) in Eq. (11)
appearing in Eqs. (23) and (87) = melt flow index for autoclave reactor polymer (g/IO
activation energy for viscous flow of polymer 1 min) in Eq. (4)
(kcal/mol K) in Eq. (84) = melt flow index of branched polyethylene (g/lO
activation energy for visous flow of polymer 2 min) appearing in Eq. (2)
(kcal/mol K) in Eq. (84) = melt flow index at compounding temperature for
function of geometric parameters based on the polymer blend (g/IO min) in Eq. (85)
shape of die as given in Eqs. (53, (57), (60).(63), = melt flow index of linear plyethylene (g/10 min) in
(66), (69h (72). (7% and (78) Eqs. (3) and (7)
function of fluid properties as given in Eqs. (56). = melt flow index at load condition I (g/lO min) in
(58), (61), (6% (671, (70). (73). (76), and (79) Eq. (21)
compaction force required for squeezing operation = melt flow index at load condition 2 (g/10 min) in
of circular disc component (dyn) defined in Eqs. Eq. (21)
(44) and (46). = melt flow index at temperature condition 1 for
compaction force required for squeezing operation polymer 1 (g/IO min) in Eq. (44)
of flat strip component (dyn) defined in Eqs. (45) = melt flow index at temperature condition 2 for
and (47) polymer 2 (dl0 min) in Eq. (44)
minimum clamping force to prevent mold opening = melt flow index at time t (g/lO min) in Eq. (90)
as given by Eq. (41) = melt flow index at temperature condition I (g110
ratio of root mean square radii of branched and min) in Eqs. (22) and (23)
linear polymers in Eq. (6) = melt flow index at temperature condition 2 (g/lO
initial gap between plates (cm) appearing in Eqs. min) in Eqs. (22) and (23)
(44)-(47) = melt flow index for tubular reactor polymer (g/10
rate of plate separation with time (cm/s) in Eqs. min) in Eq. (5)
(44)-(47) = melt flow index recovery defined as the percentage
half distance between calendering rolls (cm) in increase in diameter of extrudate over that of the
Eqs. (50), (53), and (54). orifice
VOL. 6,NO. 1
MELT FLOW INDEX. I
5. ASTM D1238, “Flow Rates of Thermoplastics by Extrusion Plas- 53. A. V. Shenoy and D. R. Saini, Rheol. Arra. 23, 368-317 (1984).
timeter.” Philadelphia, 1979. 54. F. 1. Borzenski, Plasr. Compounding, 25-28 (SeptJOct. 1978).
6. DIN 53735, “Determination of the Melt Flow Index of Thermo- 55. A. V. Shenoy and D. R. Saini, J . Appl. Polym. Sri., 29, 1581-1593
plastics,” 1977. (1984).
7. R. V. Charley. Br. Plasr., 34, 476-481 (l%l). 56. D. W. Van Krevelan. D. J. Goedhar, and P. I. Hofiijzer, Polymer,
8. A. Rudin and H. P. Schreiber, Sor. Plasr. Eng., 20. 533-539 (1964). 18, 750-751 (1977).
9. D. E. Hanson, Plast. T h y , ~ ~ ( N o v .7-9
) . (1973). 57. A. V. Shenoy and D. R. Saini. Rheol. Arra, 23, 608-616 (1984).
10. H. P. Schreiber and A. Rudin, J . Appl. Polym. Sri.. 3, 122-124 58. K. Oda, I. L. White. and E. S. Clark. Polym. Eng. Sri., 18,25-28
(1960). ( 1978).
1 I . H. P. Schreiber, J . Appl. Polym. Sri.. 4, 3 8 4 (1960). 59. S. 1. Abdel-Khalik, 0. Hassager, and R. B . Bird, Polym. Eng. Sci..
12. A. Rudin and H. P. Schreiber, J . Polym. Sri., 44,261-264 (1960). 14, 859-862 (1974).
13. S. 1. Skinner, J . Appl. Polym. Sri., 5, 55 (1961). 60. R. B. Bird, 0. Hassager, and S. 1. Abdel-Khalik, AIChE J . , 20,
14. H. P. Schreiber and A. Rudin, J . Appl. Polym. Sri.. 6, 545-546 1041-1966 (1974).
(1962). 61. M. H. Wagner. Rheol. Arta. I S , 136-142 (1976).
15. R. V. Charley, J . Appl. Polym. Sci., 6, 519 (1%2). 62. M. H. Wagner, Rheol. Acta. 16, 43-50 (1977).
16. L. Marker, R. Early, and S. L. Aggarwal. J. Polym. Sci.. 38, 63. A. V. Shenoy and D. R. Saini, Chem. Eng. Commun.. UI, 1-27
381-392 (1959). (1984).
17. D. 1. Marshall and D. W. Riley, J . Appl. Polym. Sci.. 6, 546548 64. N. Nakajima, Rheol. Acra. 13, 538-541 (1974).
(1%2). 65. Yu. V. Nikiton. E. A. Belova, and P. B. Chudinov, Inr. POlym.
18. H. Krassig, 1. Lenz, and H. F. Mark, Fiber Technology. Marcel Sri. Terhnol., 10, T59-T60 (1983).
Dekker. New York and Basel, 1984. 66. J. E. Guillet, R. L. Combs, D. F. Slonaker, D. E. Weemes, and
19. J. P. Hogan, D. D. Nowood. and C. A. Ayres, J . Appl. Polym. H. W. Coover, Jr., J . Appl. Polym. Sri., 8, 757-765 (1965).
Sri., Appl. Polym. Symp.. 36, 49-60 (1981). 67. D. Romanini, A. Savadori, and G. Gianotti, Rheol. Polym., 21,
20. W. A. Dark, Determination of Polyethylene Melt Index from GPC 1092-1101 (1980).
Data, Chromalographic Science Series. Vol. 19. Liquid Chromatography of 68. R. L. Combs, D. F. Slonaker, and H. W. Coover, Jr., J. Appl.
Polymers and Related Marerials I l l . Jack Cazes, Ed., Marcel Dekker, New Polym. Sci., 11, 747-750 (1%7).
York, 1981. 69. A. V. Shenoy and D. R. Saini, Angew. Makrol. Chem. 137,77-81
21. M. Rokudai and T. Okada, J . Sor. Rheol. Jpn., 8, 15&160 (1980). (1985).
22. F. Pilati, A. Munari, and P. Manaresi, Marer. Chem., 7 , 661-674 70. M. L. Williams, R. F. Landel, and J. D. Ferry, J . Am. Chem. Soc.,
(1982). 77, 3701-3707 (1955).
23. T. W. Bates, Eur. Polym. J . , 8, 19-34 (1972). 71. H. Eyring, J . Chem. Phys., 4, 283-291 (1936).
24. J. R. Haws, in New Industrial Polymers, R. D. Deanin, Ed., ACS 72. R. L. Combs, D. F. Slonaker, and H. W. Coover, Jr., S P E M E C
Symposium Series 4 Am. Chem. Soc.,Washington, DC, 1972, pp. 1-14. Tech. Paper. 13, 104-109 (1967).
25. G. A. Monimer, G . W. Daues, and W. F. Hammer, J . Appl. Polym. 73. C. Cipriani and C. A. Trishman. Jr., J . Appl. Polym. Sci.. Appl.
Sri., 8, 839-847 (1964). Polym. Symp., 36, 101-112 (1981).
26. C. A. Sperati, W. A. Franta, and H. W. Starkweather, J . Am. Chem. 74. L. Griffiths, Mod. Plasr. 34, 12 (Aug. 1957).
Soc., 75,6127-6133 (1953). 75. L. B. Kandyrin, V. S. Al’tzitser, B. N. Anfimov, and V. N. Ku-
27. W. F. Busse and R. Longworth, J . Polym. Sri., 58,49-69 (1%2). leznev, Int. Polym. Sri. Technol.. 4, T53-T55 (1977).
28. H. P. Schrieberand E. B. Bagley, J . Polym. Sri.. 58,2948(1%2). 76. W. Knappe, Rheol. Arla. 21, 478480 (1982).
29. W. T. F’eticolas and J. M. Watkins, J. Am. Chem. Soc.,79,50835088 77. D. R. Saini and A. V. Shenoy, Plasr. Rubber Pror. Appl.. 3, 175-180
(1957). (1983).
30. F. Tomis, Inr. Polym. Sri. Terhnol.. 7 , T90-T92 (1980). 78. I. T. Barrie. Plast. Polym., 38, 47-5 1 ( I 970).
31. I. E. Shekhtmeister, S. S. Mnatsakanov, V. V. Nesterov, and B. 79. A. V. Shenoy and D. R. Saini, Plasr. Rubber Pror. Appl.. 5 , (1985).
G. Belen’kii, Inr. Pofym. Sri. Terhnol.. 5, T47-T48 (1978). 80. A. Ray and A. V. Shenoy, J . Appl. Pohm. Sri., 30, 1-18 (1985).
32. T. Garcia-Borras, Plastics Terhnol., 89-95 (June 1977). 81. 1. Vlachopoulos and A. N. Hrymak, Polym. Eng. Sri.. 20,725-731
33. L. D. Moore, J . Polym. Sri., 36, 155-172 (1959). (1980).
34. F. Pilati, A. Munari, and P. Manaresi, Mater. Chem. 7 , 649-660 82. A. V. Shenoy and D. R. Saini, Polym. Plasr. Terhnol., Eng., 23,
(1982). 169-183. (1984).
35. R. L. Combs and R. G . Nation, J . Polym. Sci., 30,407-414 (1970). 83. I. L. White and D. Huang, Polym. Eng. Sri.. 21,1101-1 107 (1981).
36. T. F. Gray, Jr., R. L. Combs, D. F. Slonaker. and W. C. Wooten, 84. R. S. Lenk, J . Appl. Polym. Sci., 22, 1775-1779 (1978).
11.. Technical Papers, SPE Meeting, Detroit, MI, May 1%7, Vol. 13, pp. 85. A. V. Shenoy and D. R. Saini, Polym. Plasr. Tech. Eng.. 23,3748
370-372. (1984).
37. D. J. Smith, TAPPI. 60, 131-133 (1977). 86. A. V. Shenoy, Polym. Plasr. Terhnol. Eng.. 24, 2 7 4 1 (1985).
38. M. Shida, R. N. Shroff, and L. V. Cancio, Polym. Eng. Sci., 17, 87. A. V. Shenoy and D. R. Saini, Colloid Polym. Sci.. 261, 846854
169-774 (1977). (1983).
39. H. V. Boenig, Polyolefins. Elsevier, Amsterdam, 1966, Chapt. 8. 88. D.G . Brady, J . Appl. Polvm. Sci., Appl. Polym. Symp., 36,231-239
p. 262. ( I98 I ).
40. W. F. Busse, 1. Polym. Sci., A-2, 5, 1249-1259 (1967). 89. B. G. Harper, J. Appl. Polym. Sci.. 5,601-605 (1961).
41. A. Dutta. Rheol. Arra.. 23., 565-569 (1984).
. . 90. B. G. Harper, J . Appl. Polym. Sci., 2, 363-366 (1959).
42. A. V. Shenoy, S. Chattopadhyay, and V. M. Nadkami, Rheol. Acra, 91. F. Mitterhofer. Polvm. Enn. Sri.. 20. 692-695 (1980).
22, 90-101 (1983). 92. M. Rokadai, S. Mihara, &d T. Fujiki, J . Appl. Polym. Sri.. 2s; ,
43. D. R. SainiandA. V. Shenoy, Eur. Polym. J . , 19,811-816(1983). 3289-3294 (1979).
44. A. V. Shenoy, D. R. Saini, and V. M. Nadkami, J . Appl. Polym. 93. G. R. Rideal and 1. C. Padget, J . Polym. Sri. Symp. 57, 1-15
Sci., 27, 4399-4408 (1982). (1976).
45. A. V. Shenoy, D. R. Saini, and V. M. Nadkami, J . Vinyl Terhnol.. 94. 1. Cuspor and T. Toth, Inr. Polym. Sri. Terhnol., 7, T16T19
5, 192-197 (1983). ( 1980).
46. A. V. Shenoy, D. R. Saini, and V. M. Nadkarni, Rheol. Arra, 22, 95. A. V. Shenoy, D. R. Saini, and V. M. Nadkami, Polymer, 24,
209-222 (1983). 722-728 (1983).
47. D. R. SaiN and A. V. Shenoy, J. Elastomers P h t . 17, 189-217 96. A. V. Shenoy and D. R. Saini, Polym. Degrad. Stab.. 11,297-307
(1985). (1985).
48: A. V. Shenoy, D. R. Sahi, and V. M.Nadlrami, 1. Mater. Sci., 97. M. E. Evans, ‘The Influence of Additives on Processing and Prop
18,2149-2155 (1983). enies of Polypropylene Film Fibers”, Conf. Textiles from Film 11. Man-
49. A. V. Shenoy. D. R. Saini, and V. M. Nadkami, Polym. Compos.. Chester, July 6-7, 1971.
4, 53-63 (1983). 98. R. Bagheri, K. B. Chakraborty, and G. Scott, Polym. Degrad.
50. A. V. Shenoy, D. R. Saini, and V. M. Nadkami, Int. J . Polym. Srabil., 5, 145-160 (1983).
Muter.. 10, 213-235 (1984). 99. E. Zavadsky, J. Kamis, and V. Pechoc, Rheol. Arta, 21, 470-474
51. A. V. Shenoy and D. R. Saini, Br. Polym. J., 17,314-322 (1985). ( 1982).
52. D. R. Saini and A. V. Shenoy, 1. Macromol. Sci., 822, 4 3 7 4 9 100. P. G. Kelleher, R. P. Wentz, M. Y. Hellman, a n d E . H. Gilben,
(1983). Polym. Eng. Sci.. 23, 537-542 (1983).
56 VOL. 6,NO.1
MELT FLOW INDEX. I
101. P. G. Kelleher, R. P. Wentz, and D. R. Falcone, Polym. Eng. Sci.. 103. H. H. Winter, Pure Appl. Chem., 55,943-976 (1983).
22, 260-264 (1982). 104. A. N. Neverov and N. P. Vasil'eva, fnr. Polym. Sci. Technol.. 11,
102. C. A. Pryde, P. G . Kelleher, M. Y. Hellman, and R. P. Wentz, T85-85 (1984).
Polym. Eng. Sci., 22, 370-375 (1982).
APPENDIX
TABLE AIa
Standard Testing Conditions of Temperature and Load as per
ASTM 1238
Load Approximate
Piston + Pressure
Temp Weight Shear Stress
Condition ("C) (kg) (kg/cm2) (psi) (dynkm2 X i t 5 )
TABLE AIb
Testing Conditions for Commonly Used Resins as per ASTM
1238
Resin Condition
Acetals E, M
Acrylics H,1
Acrylonitrile-butadiene- G
styrene
Cellulose esters
Nylon
Polychlorotrifluoroethylene
Polyethylene
Polycarbonate
Polypropylene
Polystyrene
Polyterephthalate
Vinyl acetal
TABLE AIc
Test Temperature Summary
~~~~~
125
150
190
200
230
235
250
265
275
300
TABLE AId
Test Load Summary
Load (kg) Condition
0.325
1 ,000
1.050
1.200
2.160
3.800
5.000
10.000
12.500
21.600
TABLE AIe
ASTM Specifications for Piston and Die Dimensions
Piston Die
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