Melt Flow Index: More

Than Just A Quality

Control Rheological
Parameter. Part I
A . V . Shenoy
Department of Materials Science and Engineering
University of Florida
Gainesville, Florida 32611 , USA
D . R . Saini
Polymer Science and Engineering Group
Chemical Engineering Division
National Chemical Laboratory
Pune 41 1 008, India

1. INTRODUCTION polyolefins, caution is necessary in selecting the ap-

The Melt Flow Index test originated in the labo-
ratories of ICI, in the early stages of development of
polyethylene, and was mainly used in the past for
characterization and specifications of polyethylenes.
It was specified as a standard rheological quality con-
trol test in the ISO, BS, and ASTM. However, each
of the standard tests had a number of variants. For
example, in the Method 105C of BS 2782 (1970),’
three variants are described corresponding to IS0 R292
(1967).*These two standards specifically refer to only
“The Determination of Melt Flow Index of Polyeth-
ylene and Polyethylene Compounds.” Later, its use
was extended to other thermoplastics. The IS0 R1133
( 1969)3 and later BS method 720A ( 1979)4used the
same principle of test bur carried a broader variation
of test procedures to cover a number of different ther-
moplastics. The ASTM D1238 (1979y and DIN 53735
(1977)6differ from I S 0 R1133 in respect of the num-
ber of different loading conditions that are allowed.
When using the test method for polymers other than
propriate conditions. I S 0 R1133, ASTM D1238, and
DIN 53735 do not always agree on the suggested
procedures. For example, IS0 R1133 and ASTM D1238
mention a temperature of 200°C and a piston loading
of 5 kg for determining the melt flow index value of
ABS, whereas DIN 53735 offers two alternatives of
200°C with a loading of 2 1 kg or 220°C with a loading
of 10 kg.
The basic principle employed in the melt flow index
test by any of the standards is that of determining the
rate of flow of molten polymer through a closely de-
fined extrusion plastometer whose important parts are
shown in Figure 1. The cylinder is of hardened steel
and is fitted with heaters, lagged, and controlled for
operation at the required temperaturewith an accuracy
of 20.5”C. The piston is made of steel and the di-
ameter of its head is 0.075 ? 0.015 m less than
that of the internal diameter of the cylinder, which is
9.5 mm. The die (or “jet”) has an internal diameter
of 2.095 k 0.005 mm or 1.180 m k 0.005 mm
(depending on the procedure used) and is made of

Advances in Polymer Technology, Vol6, No. 1 , 1-58 (1986)

0 1986 by John Wiley & Sons, Inc. CCC 073O-6679/86/01OOO1-58$04.oO
 MELT FLOW INDEX. I

hardened steel. All surfaces of the apparatus which

FIGURE 1
Schematic diagram come into contact with the molten polymer are highly
of the melt flow polished.
index apparatus Melt flow index (MFI) is basically defined as the
showing a cross-
sectional view of weight of the polymer (g) extruded in 10 min through
the important parts. a capillary of specific diameter and length by pressure
applied through dead weight under prescribed tem-
perature conditions. ASTM D1238 specifies the de-
tails of the test conditions as summarized in Appendix
A for commonly used polymers. The test conditions
PISTON
include temperatures between 125 and 300°C and dif-
-BARREL ferent applied dead loads from 0.325 to 21.6 kg giving
pressures from 0.46 to 30.4 kg/cm2. The specifications
have been selected in such a way as to give MFI values
between 0.15 and 25 for reliable results. ASTM D1238
INSUL AT 10N
gives the accuracy of the MFI value obtainable from
a single measurement as carried out by different op-
RE MOVABLE erators at different locations to be in the range of
2 9-2 15% depending upon the magnitude of the MFI.
Variability in the MFI value and proper interpretation
of test data have been the subject of discussion in the
~ , ~ I, taken from H a n ~ o nlists
p a ~ t .Table , ~ the possible
sources of errors resulting in the variability of MFI
tests.
Precise measurement of M H calls for very strict
control of all possible variables, and the test, though
simple, must be performed with considerable care.
The first and foremost care that should be taken is to
ensure that the cylinder, piston, and jet are scrupu-
lously clean, by treatment with hot solvents and wip-
TABLE I ing with lint-free nonabrasive cloths. The cylinder
should be maintained at the test temperature for 15
Sources of Variability in MFI and the Magnitude of Their
Effects (Source: Ref. 9) min and then charged with test sample weighing be-
tween 4 and 8 g within a period not exceeding 1 min.
Factor Error in Extreme Circumstances The unloaded piston should be inserted and then the
necessary weight is to be added only after 4-6 min.
1. Poor packing during charging + 150% or higher When the molten polymer begins to extrude out, the
(resulting in possible oxidative
degradation) rate of extrusion is to be measured by cutting off
2. Dirty barrel + 100% (very variable) extrudate at suitable intervals as specified in the stan-
3. Partially blocked die - 100% (very variable) dards. Several such “cutoffs” should be taken up to
4. Piston height 30 min maximum after insertion of the sample. The
(a) In excess of standard 50 mm - 50%
- 15%
first cutoff, as well as any containing bubbles, should
(b) Within standard 50 mm
5. Delays between charging and + 10% be discarded; the remainder, at least three, are to be
packing (leading to possible weighed to the nearest 0.001 g and the average mass
oxidative degradation) is to be calculated. The maximum and minimum val-
6. Extended test time (leading to + 5% (more if the polymer ues of the individual weighings must be within spec-
possible oxidative degradation) is poorly stabilized)
+ 10% for 0.5 mm ified values of the average; otherwise the results are
I. Worn die
wear in diam. to be discarded, and a further test should be performed
8. Worn piston + 10% for 0.13 mm wear on fresh portion of the sample.
9. Test temperature 2 1% for ? 1°C It is rather imperative that all the cutoffs are taken
10. Variations in load Pro rata when the piston head is between 50 and 20 mm above
the upper end of the die as marked by the scribed
lines on the piston. The importance of this can be seen

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

SOUEEZED OUT UNDER HIGH LOAD FROM 3 0 m m t o S S m m

L
A HIGH LOAD FROM 9 0 m m to 25 mm

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
pressure drops in the barrel depending on the piston
height above the die end for a shear sensitive polymer
like polypropylene. A number of ~ o r k e r s ' ~have
'~
discussed the time dependence of polymer flow in a
capillary viscometer with a very short die such as in
the melt flow indexer. The manifestations of this time
dependence is the gradual rise in the output rate at a
fixed temperature and applied pressure, from an initial
to a higher, steady-state value. A simple calculation
in the case of the melt flow indexer13 shows that
where subscripts b and c represent the barrel and cap-
illary and P, L, and r are the pressure drop, length,
and radius.
Substituting the appropriate values shows that the
capillary pressure drop will increase from 78 to 100%
of the applied pressure as the melt flow indexer goes
from completely filled to empty. Thus, a 50% increase
in the output rate is possible, as has been shown for
polyethylene by Skinner.l 3 With polypropylene, the
position is shown to be worse by Charley," who per-
ADVANCES IN POLYMER TECHNOLOGY
formed extensive experiments for using the melt flow
index test for molten polypropylene. Despite this time-
dependent deformation behavior, there is no correc-
tion recommended for entrance and exit abnormali-
ties. This would also be difficult to specify as the
corrections would be expected to vary from polymer
to polymer.
Another source of error in the melt flow indexer is
the load required to shear the film of polymer between
the plunger and the barrel or reservoir as was first
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-
illaries in order to minimize the error due to friction.
If the reservoir is too small, then it can contribute
significantly to the overall pressure drop. If it is large,
the plunger friction would be considerable. Marshall
and Riley,I7 however, do not agree with S k i ~ e ras '~
regards the effect of large barrel diameters. They argue
that at constant pressure and piston speed, the friction
force increases in proportion to the circumfefence of
the piston, whereas the pressure force increases with
the area of the piston. Therefore, the friction force
3
 MELT FLOW INDEX. I

indexer such that dry nitrogen purging is possible dur-

ing measurements on polyesters and nylons which are
TABLE I1 known to degrade with moisture. For a highly filled
End Use Indication Through MFI for Various Grades of High system, there would be a tendency of Bingham plastic
Density Polyethylene (Source: Ref. 18) (yield stress) behavior, and hence the proper choice
of load condition would be essential for reliable re-
MFI (190”C/5 kg) Processing Method Typical Applications sults. Filled systems like PVC would also create some
Profile, preformed
difficulty due to migration of the fillers towards the
0.05-0.15 Compression molding
extrusion blocks capillary center, thereby giving erroneous results. There
0.1-1.3 extrusion Pipes, round bars is a limitation on particle size and shape of the filler
0.1-0.4 Blown film extrusion Films due to the standard diameter of the capillary and must
0.4-0.7 Extrusion blow molding Fuel oil tanks be borne in mind when generating filled polymer sys-
1.3-3 Extrusion blow molding Hollow bodies (i.e.,
bottle)
tem data. In such cases, too, a modified MFI apparatus
3-13 Extrusion blow molding Toys, household may be used by changing the capillary diameter to
Injection molding articles suit the needs.
Screw caps Despite the fact that MFI is an empirically defined
13-25 Injection molding Beer cases parameter with certain limitations as described above,
25 Injection molding Mass-produced articles
for household uses,
it is still one of the most popular parameters in the
non deposit goods plastics industry for distinguishing various grades of
polymers. Polymer manufacturers have used it rou-
tinely to specify the most suitable end use of a par-
ticular grade of the polymer (see, for example, Tables
II and 111taken from Krassig et a1.18) It is worth noting
must decrease in importance, not only because of the that the test conditions of MFI in each of the tables
ratio of circumference to area but also because re- is different; hence a similar value of MFI for two
quired piston speeds are lowered. The smaller barrel different polymers may not indicate the suitability of
may cause significant piston friction, but is still pre- the material for the same type of application. Krassig
ferred to shorter heat-up time. One possible method et al.I8 have discussed the general experience in the
to reduce the frictional error is by use of a piston ring choice of raw material for high-density polyethylene
as suggested by Marshall and Riley.I7 and isotactic polypropylene in the manufacture of film
Care should be taken when taking MFI data on tubes and of film fibers. A high MFI polypropylene
moisture sensitive polymers as well as filled polymeric is preferred in the manufacture of flexible film prod-
systems. It might be advisable to modify the melt flow ucts with high fibrillation tendency. However, when
fibrillation tendency is a disadvantage, as in the case
of film tapes for sacks or fabrics for packaging pur-
poses, it is preferable to use a polypropylene grade
with lower melt-flow index. In fact, MFI values greater
TABLE III than 2-3 g/10 min would tend to disturb the weaving
End Use Indication Through MFI for Various Grades performance due to fibrillation. In the case of strap-
of Polypropylene (Source: Ref. 18) pings where maximum strength is required, the choice
of grade should be of even lower MFI value, ranging
MFI (230°C/5 kg) End Use Application
from 0.3 to 0.5 g/10 min. For high density polyeth-
2 Compression moldings, pipes ylene, due to its inherent low fibrillation tendency and
1-5 Extrusion blow moldings lower intermolecular cohesion, it is most beneficial
5-15 Biaxially oriented films for film tape production and hence a lower MFI is the
5-15 Film tapes preferred choice.
5-15 Monofilaments
5-20 General injection moldings Over the years, it has been found that MFI corre-
30 High-speed injection moldings lates well with a number of other useful parameters.
30-40 Flat films For example, during polymer manufacture, it has been
40-80 Staple fibers observed that the reaction temperature, the catalyst
60 Spun-bonded fabrics activation temperature, the molecular weight build-
up, etc. could all be correlated with MFI. Similarly,
the rheological characteristics of the polymer such as

4 VOL. 6,NO. 1

the zero shear viscosity, the viscosity vs. shear rate
relationship, the elasticity vs. shear rate relationship,
the die swell, the elongationalviscosity, the activation
energy for viscous flow, etc., could all be determined
through only the MFI. Further, the stability of the
polymer during processing, its reprocessibility, die
design, mold filling behavior during injection mold-
ing, etc., could be adjudged merely through MFI.
Similarly, the physical, mechanical, thermal, as well
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,
MFI has certainly been upgraded in its value. It is
with the objective of bringing about this awareness
that this article is being written. The possible existing
correlations between MFI and various other important
parameters encountered in polymer manufacture,
polymer processing, and end-product properties eval-
uation will be discussed in detail.
2. MFI USE IN POLYMER MANUFACTURE
The possibility of manufacturing polymers differing
from one another in density and MFI enables the man-
ufacturers to prepare grades suitable for specific fields
R E A C T I O N T E M P E R A T U R E ,.C
ADVANCES IN POLYMER TECHNOLOGY
MELT FLOW INDEX. I
of application. The different grades result due to con-
trolled manipulations in the reaction conditions and
reactants during the polymer synthesis stage leading
to polymers with different molecular weights, differ-
ent molecular weight distribution, and different levels
of branching. It will be shown in the following how
MFI could be correlated directly or indirectly with
each of the relevant parameters so that it could act as
a rather beneficial control parameter.
2.1. Effect of Reaction Conditions on MFI
During the polymer synthesis stage, the polymer
manufacturer can optimize his reaction conditions to
get a particular grade of choice through the use of
MFI. For example, the reaction temperature, as well
as the catalyst activation temperature can be seen to
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
quite significant in terms of achieving higher polymer
MFI. Similarly, increase in activation temperature
sharply increases the MFI increase potential to the
point where the catalyst undergoes a sharp decline in
pore volume because of sintering.
FIGURE 3
Effect of reaction
temperature on
polymer melt flow
index as taken from
Hogan et al.lg
5
 MELT FLOW INDEX. I

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
and Branching on MFI
A relationship between MFI and weight-average
molecular weight of linear and branched polyethylene
was explored by Dark.” It was found that two families
of curves resulted: one for branched and other for the
linear polyethylenes. Thus, the following relation-
ships were given by Dark”:
Branched:
log (MFI),, = (0.454 x 10-5)Mw - 0.12713
Linear:
- log (MFI),
= (0.6723 x 10-5)Mw - 0.49359
Even though the above expressions represent the best
fit of Gw,as given in Figure 5, the data for branched
polyethylene cannot be in order as it indicates a higher
MFI for a higher Gw,which is incorrect. The data
for the branched polyethylenes as collected by Darkzo
covered a broad range of branching, reactor config-
uration, and telogen level. To eliminate the effect of
these variables, data was taken from a single autoclave
configuration, where AT was held constant so that,
but for Ew, all other variables were nearly constant.
Only the pressure drop across the autoclave was var-
ied, and the effect of-the changes in pressure was
(2) reflected in MFI and M, values as shown in Figure
6. It can thus be concluded that, with branched pol-
yethylene, consideration must be given to long chain
branching, nonrandom termination, and reactor pro-
file, whereas for linear polyethylene a simple expres-
(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).

AREA O F P M A S E CMAN9E UNSTABLE R E A C T O R

I I 1 I \I
-0.4 0.0 0.4 0.8 1.2 4.6
LOO ( M F I )

ADVANCES IN POLYMER TECHNOLOGY 7

 MELT FLOW INDEX. 1

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.

MFI,,, = 3.15 x 1oZ5(sMw)-5.41 (4)

.- MFItUbu= 1.06 x loz8(s iE?,>-"." (5)
to3 1o4
-- I 05
g MY)
x,
Rokudai and O W 2 ' also defined a parameter which
represented the long-chain branching frequency and
attempted to get the correlation between it and MFI

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
scatter for the tubular resin which was no better than
that in Figure 7 for Gwversus MFI. They thus de-
veloped a summation series to predict MFl from weight
average molecular weight and long chain branching
frequency as follows.
n as B,, Pilati et a1.22modified the equation suggested
log MFI = aij(log Mw)' (log z)'
ij=o
where (MFI)Iis the melt flow index for linear samples
in g/10 min obtained under a load of 5 kg at 250°C.
For branched samples with different trifunctional unit
content, it can be seen that the MFI is different for
the same molecular weight and the relationship be-
tween MFI and Gwalso changes.
Using weight-average degree of branching defined
(6) by Bates,23namely,

where the values of the coefficient aij are given in

Table IV. A comparison of the predictions of Eq. (6)
with actual determined values of MFI shows excellent TABLE IV
agreement, as can be seen from Figure 10. Coefficientsin Eq. (6) for tubular resins (Source: Ref. 21)
The relationship between MFI and branching pa-
aij i=O i = l i = 2
rameters was also studied by Pilati et a1.22Figure l l
shows a plot of MFI vs. Gwon log-log scales. It is j = O -0.3757 X 10' -0.3643 x 10' -0.5287 X 10'
seen that only for unbranched samples an equation of j = 1 -0.1731 X 10' -0.4464 x 101 -0.2370 X 10''
the following form can be fitted: j = 2 -0.1933 X 10' -0.1579 X 10' -0.1982 X 10"

log (MFI), = 16.9 - 3.5 log M, (7)

ADVANCES IN POLYMER TECHNOLOGY 9
 MELT FLOW INDEX. I

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”).

lo-’ 100 10’ lo2

M F I observed

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

mol TMT FIGURE 12

I mol D M T Plots of modified
B
B - 0.005 Bate's Eq. (8): log
(MFI1lMFlb) vc
0
0 - 0.0075 log (1 + 0.25 B,J
0 - 0.010 for branched
-1 - 0 - 0.015 samples of
poly(butylene
terephthalate)
-2 - (symbols same as
in Figure 11) taken
0
-3 - from Pilati et al. ").

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

60@00 too,ooo 140,000

MOLECULAR WEIGHT

ADVANCES IN POLYMER TECHNOLOGY 11

 MELT FLOW INDEX. I

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:

(M,)’”= 188 - 30 log MFI (10)

12 VOL. 6,NO. 1
 MELT FLOW INDEX. I

It is seen that, in particular for polyethylene grade FB FIGURE 15

1-28, the value an by GPC and by MFI agree very Plot of solution
well. For the other two values, the Mncalculated from 34
o P S P L A N T PRODUCT viscosityvs. melt
flow index at 392“F,
Eq. (10) is slightly lower. The grades- -FA 7-15 and A OTHERS
5-kg load with
RB 03-23 have almost identical MJMw values and results within 5% or
contain some very high molecular weight fraction of t better as taken
v) from Garcia-
the order of 10. This particular fraction is missing in 0
0 31 Borras.*
FB 1-28 and hence behaves differently in the rheo- v)

logical sense. Had Eq. (10) closely predicted an for

FA 7-15 as well as RB 03-23, it would have failed
to predict the same for FB 1-28. This is because any
relationship between MFI and Hnwould hold only
when the molecular weight distribution is not different
between the grades of the particular polymer. 1-0 1-5 2.0 2.1 3.0 3.5

M F I , Gm / 1 0 m i n s

2.4. Effect of Molecular Weight

Distribution on MFI
Shekhtmeister et al.31have suggested a method of
determining the MWD h m MFI using the values of MFI
evaluated under not less than two different load condi-
tions. The selection of the right loads is of prime impor-
tance so that the determined MFIs are different to a
maximum extent and yet should be within the measur-
able limits for a reliable correlation with MWD.
Shekhtmeister et al. ,31 based on extensive data analy-
sis, recommend the following combinations of loads:
region I, 5/1.2; 11, 21.6/5; 111, 21.6/0.325. Region I
corresponds practically to all injection molding grades
and some extrusion grades of HDPE._They - expressed the
interrelationship between MFI and MJM, as follows:
+ 3.21[CH3] (11)
Figure 16 shows yet another correlation between
[q] and MFI and is given for polyethylenes by the
equation
[q] = 1.064 - 0.183 log MFI (12)
It can be seen that the above correlation suggested
by Mortimer et aL2’ is consistent with the data of
Moore.33The samples of Moore33did not contain high
molecular weight tail. It was observed by Mortimer
et al.25 that variations in short-chain branching had
no observable effect on this correlation. However,
experimental points for samples containing long-chain
branching lie to the left of the MFI-[q] line for linear
polymer in Figure 16. The relationship for long-chain
branched samples were fitted by a straight line given
as

where MF15 and MF11.2represent the MFI values at
5- and 1.2-kg loads, respectively.
2.5. Effect of Solution Viscosity on MFI
There is a close relationship between solution vis-
cosity and MFI, as has been pointed out by a number
of w ~ r k e r s . ~Gar~ia-Borras~~
~”~~~ states that when-
ever solution viscosity was required, an initial cali-
bration plot was prepared between solution viscosity
and MFI with results within 5% error as shown
in Figure 15. Accuracy of such a plot was found to
be so good that plotting only three or four data
points spaced by a few centipoise each has been
recommended.32
[q] = 0.966 - 0.189 log M R (13)
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
effect of branching parameters on intrinsic viscosity.
Interestingly, the plot made by them of log[q] vs.
log(MFI) shows a near straight line as can be seen
from Figure 17, which is the same for branched and
linear samples. Pilati et al.34suggest that this behavior
is probably because the effect of branching on melt
viscosity gets partly balanced by a decrease in intrinsic
viscosity.
Combs and Nation3’ studied 52 polyesters having
various molecular structures and developed relation-
ships between MFI, glass transition tempemhms, melt

ADVANCES IN POLYMER TECHNOLOGY 13

 MELT FLOW INDEX. I

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)

The values of the constants for each of the above

equations are given in Combs and Nation.35Equations
-0.4 -0.2 0.0 (14) and (15) are the simplest models that adequately
fitted the data. They differ only in that T, and T are
expressed in "C for Eq. (14) whereas they are in K
for Eq. (15). Equation (16) has a more theoretical
backing because it is of the Arrhenius form and hence

14 VOL. 6,NO. 1

would be preferred. Equation (16) is the analytical
form implied by the graphical procedures used to re-
late corrected MFI with T, by Gray et al.36Equation
(17) is a generalized form of the Williams, Landel,
and Ferry (WLF) equation, which has been success-
fully used to describe the rheological properties of
amorphous polymers within 100°C of their T, values.
Any of the equations could be used to predict the MFI
of an unknown polyester if its T, and {q}are known.
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
to be checked. Nevertheless, the method is useful for
oxygen- and moisture-sensitive polymers whose MFI
determination might involve a certain degree of error.
3. MFI USE IN POLYMER PRODUCT
FABRICATION
3.1. Rheological Considerations
During polymer product fabrication, the only flow
parameter that the processor has ready access to is the
MFI. However, MFI is a single point viscosity mea-
surement at relatively low shear rate and temperature.
Since the values of temperature and shear rate em-
ployed in an MFI test differ substantially from those
encountered in actual large scale processes, MFI does
not correlate directly with processing behavior, as has
been shown by Smith3’ as well as Shida et al.38 As
far as processing is concerned, both high and low
shear viscosities of the material are critical. Low shear
properties are important in applications where melt
strength, sagging are critical such as in blow molding
and coating. On the other hand, high shear properties
are relevant to applications where melt instability,
melt fracture, and heat generation are important. MFI
has often been considered as an empirically defined
parameter which does not indicate any fundamental
polymer property. However, there have been recent
attempts to seek correlations of MFI with basic rheo-
logical parameters and thus predict processing behav-
ior through this simple parameter. All such attempts
are reviewed in the following.
3.1 .I. Zero-Shear Viscosity-MFI Relationship
B ~ e n i was
g ~ ~the first to indicate that there existed
an inverse relationship between MFI and zero shear
ADVANCES IN POLYMER TECHNOLOGY
MELT FLOW INDEX. I
viscosity. He showed that for polyethylenes the fol-
lowing relationship held:
log MFI = const - log qo (18)
Busse,40on the other hand, gave the relationship be-
tween MFI and inherent viscosity, from which he
derived the inverse correlation between MFI and zero
shear viscosity as follows:
Recently, Dutta4’ showed that for most thermoplastic
polymer melts (possessing a low shear Newtonian vis-
cosity plateau), a reasonably good estimate of zero-
shear viscosity can be obtained from the knowledge
of MFI through the following equation:
0.0495Wp
qo =
MFI
where qo is in poise, W is the MFI test load value
(g), p is the density of the polymer (g/cm3), and MFI
is in g/10 min.
Dutta4’ provided a comparison between experi-
mental and calculated zero-shear viscosities from Eq.
(20) for 35 different polymer grades covering several
polymeric species of widely varying melt indices.
However, the given plot of qo (calculated) vs. qo
(measured) on log-log scales of 3 X 3 cycles masks
a lot of error in the estimate. MFI is rather insensitive
to changes in molecular weight distribution, as can
be seen from Figure 18 given by Hanson.’ However,
MWD has profound effects in low shear viscosity
behavior. Thus, MFI cannot truly predict zero-shear
viscosity even within acceptable accuracy in such cases,
and hence the method of Dutta4’ could involve errors
of even greater than 50%. Hence the prediction of
zero-shear viscosity from MFI must be done with ut-
most caution.
3.1.2. From MFI to Rheogram
It is often said that “MFI gives a dot when actually
what is needed is a plot” for polymer processors. The
rheological data needed for constructing a plot can be
obtained only from sophisticated scientific instruments
such as the Weissenberg Rheogoniometer, the Rheo-
metrics Mechanical Spectrometer, the Instron Capil-
lary Rheometer, etc. These, however, are beyond the
financial as well as technical capabilitiesof most poly-
mer processors. Recently, a method has been pro-
15
 MELT FLOW INDEX. I

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

APPARENT SHEAR STRESS (Nni‘)

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.@).

Modified Arrhenius type equariod2: T, + 100, the temperature dependency of MFI is

decisively affected by overcoming of the forces
-
MFIT, = exp[-(-E l - 5!)] (23)
of intermolecular interactions, in which case the
MRT, R T2 Arrhenius type equation (23) would give better
predictions.

where TI is the ASTM recommended test tem-

0 The plot of q vs. .;Y under the required conditions
perature (K), T2 is the temperature at which MFI
can now be readily obtained by substituting the
is required (K), T, is the standard reference tem-
correct value of MFI in the unified curve.
perature ( = T, + 50) (K), T, is the glass transi-
tion temperature (K), R is the gas constant, and
E is the activation energy for viscous flow. The
choice of equation for determiningthe temperature
3.1.3. Rheological Models for Unified
dependence of MFI is mainly governed by whether
Viscosity-MFI Curves
T < T, + 100 or T > T, + 100. At tempera-
tures relatively nearer to T,, free volume and its In order to simplify the final step in generating the re-
changes with temperature play a dominant role. quired viscosity vs. shear rate curve from MFI by the
Hence, the WLF type equation (22) could provide above procedure, Shenoy and Saini53fitted appropriate
better estimates. At temperatures greater than rheological models such as those given below:

ADVANCES IN POLYMER TECHNOLOGY 17

 MELT FLOW INDEX. I

Modijied Carreau Model:

TABLE VI q * MFI = q o * MFI [I

Rheological Parameters of the Modified Carreau Model [Eq. + -
(A MFI)2 * (i(/MFI)2]-N (24)
(24)Jfor Polymers of Different Generic Type (Source: Ref. 53)
Modijed Ellis model:
Applicability
Range of Shear
Polymer Type qo.MFl A.MFI N Rate (s-') 7 * MFI = qo * MFI/[l + (25)
Low density 3 x I05 25.3 0.17 0.1-1 Modijed Ostwald-de Waele power-law model:
polyethylenes
High density 2.1 X 105 24.0 0.15 0.1-1
polyethylenes q * MFI = K[i(/MFI]"-' (26)
Polypropylenes 1.2 x I05 4.6 0.125 0.1-1
Cellulose esters 8.5 X 104 0.72 0.06 1-10 where qo * MFI is the modified zero-shear viscosity
Cellulose ethers 8.5 X 10" 5.0 0.18 1-10 function, q MFI the modified non-Newtonian vis-
Acrylics 2.1 x 105 2.4 0.16 1-10 cosity function, +/MFI the modified shear rate func-
Nylons 9.5 x 104 11.6 0.03 0.1-1
Poly(ethy1ene 8 X 104 0.3 0.1 4-50
tion, and A * MFI the modified time constant. K is
terephthalate)s the consistency index. N, a,and n are dimensionless
Polycarbonates 4.2 X 104 0.19 0.11 540 parameters associated with power-law behavior, T is
-
the shear stress given by the product of q MFI and
+/MFI, and T ~is /that~ special value of the shear stress
for which q * MFI = (qo* MFI)/2. Tables VI-VIII
list the model constants for each of the polymers in-
vestigated based on the modified Carreau model, the
modified Ellis model, and the modified Ostwald4e
Waele model, respectively. The range of applicability
of each of the models has also been shown in the
tables. The Carreau and Ellis models fit the low to
medium shear rate region. In most industrial polymer
TABLE VII processing operations, the shear rate ranges of interest
Rheological Parameters of the Modified Ellis Model [Eq. (25)] (see, for example, Table IX) fall within the domain
for Polymers of Different Generic Type (Source: Ref. 53) of the Ostwald-de Waele power-law model and hence
would find much wider use. The advantage of fitting
Applicability
such rheological models to the unified curves lies in
Range of Shear
Stress (dyd the fact that calculations involving entrance length
Polymer Type q o . MFI 71/2 a cm2) estimates, heat transfer, die design, mold design, etc.,
are greatly simplified, as will be shown in the later
Low density 3 x 105 6 x 104 2.14 3 x 103-106 sections.
polyethylenes
High density 2.1 X 105 3.67 X 104 1.85 104-106
polyethylenes 3.1.4. Upgrading the MFI to Rheogram Approach
Polypropylenes 1.2 x 105 1.54 x 104 2.89 6 x I@-106
4 x 106 8 x 104 2.53 4 x 104-106
in the Low Shear Region
Polystyrenes
Cellulose esters 8.5 x 104 1.27 x 106 2.13 105-4 x 106 During the generation of the unified curves, the
Cellulose ethers 8.5 x 104 3.82 x 105 2.63 105-106
Acrylics 2.1 x 105 4.09 x 105 2.23 105-107
coalescence was governed entirely by the shape of the
Nylons 9.5 X 104 1.18 X 106 2.24 104-107 original viscosity vs. shear rate curves. Similar shaped
Poly(ethy1ene 8 x 10" 3 x 106 2.28 105-107 curves, undoubtedly, coalesced better. As the shape
terephthalate)s of the curves is known to vary with regard to molecular
Polycarbonates 4.2 x 104 2.73 x lo6 1.82 4 x 105-10' parameters like long chain branching and molecular
Poly(viny1 1.2 x 106 1.32 x 105 2.75 105-107
chloride)s
weight distribution, the coalesced curves which are
formed by normalizing viscosity and shear rate via
MFI have this limitation present in them. MFI is itself
insensitive to subtle changes in molecular parameters

18 VOL. 6,NO. 1
 MELT FLOW INDEX. I

as has been shown by Smith37 and B ~ r z e n s k i ias~ ~

well as Shida et aL3*The effects of the differences in
molecular weight distribution are seen in the low shear TABLE VIII
rate and very high shear rate region as can be seen Rheological Parameters of the Modified Ostwald4eWade
from Figure 18. However, since the width of shear Power-Law Model [Eq.(26)] for Polymers of Difterent
rates of interest for most polymer processing opera- Generic Type (Source: Ref. 53)
tions lie within the medium range as can be seen from
Applicability ASTM Test
Table IX, the unified curves of Shenoy et al.42-51for K (gkm Range of Shear Load Condition
the viscosity function would, nevertheless, be handy Polymer Type n S*-") Rate (s-') Used 0%)
tools for the processors.
However, from a fundamental viewpoint, it is es- High density 0.54 9.0 X 10' 4-1000 2.16
polyethylenes
sential to relieve the MFI to rheogram technique of
Low density 0.46 1.3 X lv 4-1000 2.16
this inherent limitation so that even ambitious corre- polyethylenes
lations of estimating zero-shear viscosity from MFI Polypropy lenes 0.34 1.4 X lo5 4-1000 2.16
such as those attempted by B ~ e n i g Busse,40
,~~ and Polystyrenes 0.39 3.5 x 105 0.4-1000 5.00
Dutta4' could become more meaningful. An attempt Styrene acrylonitriles 0.33 3.0 x lo5 3-2000 3.80
Cellulose esters 0.47 3.2 X lo5 10-1000 2.16
at upgrading the MFI to rheogram technique in the
Cellulose ethers 0.38 1.1 x 105 3-100 2.16
low shear region was done by Shenoy -and- S a i t ~ iIt. ~ ~ Acrylics 0.44 3.2 X l@ 100-1000 3.80
was suggested that a correction factor (M,/Mw)'.7should Nylons 0.44 2.8 X 10s 50-1000 2.16
be used when coalescing low shear viscosity data for Poly(ethy1ene 0.43 5.0 X 104 50-1000 2.16
polymer grades with widely different molecular weight terephthalate)s
Polycarbonates 0.52 1.5 X lo5 40-1000 1.20
distributions. Eight different polypropylene samples
Poly(viny1ch1oride)s 0.36 4.6 X lv 2-2000 20.00
were found to give two distinct unified curves when
plotted as q . MFI vs. jdMF1 as shown in Figures 20
and 2 1. The molecular characteristics of the samples
were such that B, C, E, and F had broad and regular
molecular weight distribution and coalesced on one
&eveIan et a1.56based on the of data for a
curve (Figure 20), while A, D, G, and H formed
number of polymers.
another group with narrow molecular weight distri-
bution and coalesced separately as another curve (Fig- - - -
ure 21) which did not superimposen &e earlier one. Mw = -
Q, M
2 -40.75, -- -
Mz - a1.75

-
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

ADVANCES IN POLYMER TECHNOLOGY 19

 MELT FLOW INDEX. 1

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

Any of the -above
- expressions could thus be used in
place of (M,/Mw)1.7in the unified curve after proper
conversion.
As a natural consequence of this upgrading tech-
nique for low shear unified viscosity curve, it is ev-
- -with
ident that zero-shear viscosity can be predicted
-
greater accuracy consideringthat (qo MFI)/(MJvI,)~~~
is fairly constant for a generic type of polymer. This
method would be more effective than those discussed
3.1.5. Normal Stress Difference from MFI
The elasticity of polymer melts is manifested through
two material functions, namely, the primary normal-
stress coefficient JI1and the secondary normal stress
coefficient J12. The secondary normal-stress coeffi-
cient is not as well characterized as the primary nor-
mal-stress coefficient due to its small magnitude. Even
so, the primary normal stress measurements are dif-
ficult. They require very expensive rotational viscom-
eters which have high operating and maintenance costs
and also have an effective upper limit of shear rate
not greater than 10 s-' when in actual processing op-
ADVANCES IN POLYMER TECHNOLOGY
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-).
erations shear rates are several orders of magnitude
higher. Under such constraints, it is attractive to seek
for a method to at least estimate the primary normal
stress difference with reasonable accuracy limits based
on a simple parameter like MFI. Such an attempt was
successfully done by Shenoy and Based on
mechanistic arguments similar to those forwarded ear-
lier for the viscosity case,42Shenoy and SainP7 showed
+
that it should be possible to coalesce Jrl vs. curves
of polymer grades with different MFI by plotting
JI1 * (MFI)2vs. (+/MFI)*or, alternatively, by plotting
NI vs. (+/MFI)2as shown in Figures 23 and 24. Since
the primary normal-stress difference is known to ex-
hibit a stronger dependence on molecular weight dis-
tribution than viscosity,56 the correction term (GJ
-
Mw)3.5was needed to yield a unique curve in the case
of polymer grades with varied molecular weight dis-
tributions as shown in Figure 25. The steps for gen-
erating the original normal-stress difference from the
unified curves knowing the MFIs are similar to those
described earlier in the case of viscosity. The method
can give a quick engineering estimate of elasticity
even with limited rheological information such as only
the MFI.
21
 MELT FLOW INDEX. I

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

GRADE PP-H-N PP-H-R-B PP-H-B-R PP-M-N PP-M-R PP-M-B PP-L-N PP-L-R-N

~ ieo-c A B C D E F G n

10-2 lo-' 100 10' 102

The above method, however, becomes effective only
if there is already available data of elasticity of a
particular polymer. There is, however, very limited
elastic data on various polymers. Since viscosity func-
tion has been studied much more extensively in com-
parison to normal stress functions, there have been
attempts in the past by Abdel-Kalik et al.,59 Bird et
al. ,60 and Wagner6',62to find methods for the predic-
tion of the normal stress difference from the viscosity
function. Using the method of Wagner,6"62 Shenoy
and Saini63have given a simplified approach to the
prediction of primary normal stress differences in
polymer melts. Thus
2N
$1 * (MFI)' = (qo . MF1)- (A
m
[l + (A * MFI)2 * (j/MFI)2]-"C"
where the parameters qo . MFI, A MFI, and N are
determined from the viscosity equation (24). m is the
adjustable parameter whose value lies between 0.13
and 0.2 given the upper and lower limit of the pre-
dicted normal stress difference curve.
3.1.6. Die Swell from MFI
Another form in which elasticity of a polymer melt
manifests itself is by die swell-that is, by an increase
in the diameter of the polymeric extrudate upon emer-
gence from the die. NakajimaWhas shown how die
swell could be predicted through the knowledge of
MFI. The salient features of his approach are as fol-
lows. He used a material function, namely, the time
constant A defined as
A = y/j (30)
Where i, is the shear rate in the capillary rheometer
and y is the strain which is related to die swell as
follows:
MFI)2 (j/MFI)
(29) where S, is the die swell defined as the ratio of the
extrudate diameter to the die diameter after the extru-
date completes recovery. If the time constant A is
known, then S, can be calculated. For the linear poly-
ethylene samples analyzed with MFI values of 0.4-9,
NakajimaW found that the time constant varied in-
versely as the power of shear rate as

ADVANCES IN POLYMER TECHNOLOGY 23

 MELT FLOW INDEX. I

The introduction of plasticizers, naphthenic oil,

For convenience, in order to eliminate the propor-
tionality factor, Eq. (32) was written as
where A50 is the value of A at + = 50 s-'. Further,
A50 and p were expressed as
The values of A, q, B, and r were determined from
the time constant vs. shear rate curves.@
Using Eqs. (30)-(35), the die swell could be cal-
culated for a given sample of known MFI. The values
of die swell thus calculated for over 100 observed data
showed a variation from the actual within &3.5% at
50% confidence level. However, the above cannot be
taken as a general method to correlate MFI with die
swell. It is known that die swell is sensitive to mo-
lecular parameters such as molecular weight distri-
bution, branching, etc. whereas MFI is not. Hence,
the present method needs to be extended to incorporate
these parameters on the lines done by Shenoy and
S a i r ~for
i ~ upgrading
~ the melt flow index to rheogram
approach in the low shear region.
paraffin oil as well as paraffin wax into polystyrene
and high-impact polystyrene is known to reduce its
effective viscosity while improve its elastic properties
as assessed from the degree of swelling, p. Actually,
the reduction in viscosity that occurs upon plastici-
zation would lead to the easier movements of con-
glomerates of chains and consequently, to an accel-
eration of the process of transition of PS macromolecules
and the polystyrene matrix of HIPS to forced high-
elastic state.65The display of higher elasticity by the
polymer according to the rate of movement of the
macromolecules is confirmed by the existence of a
correlation between p and MFI which is invariant in
relation to the plasticizers despite different plasticizing
capacity as shown in Figure 26. During mechano-
chemical mixing of HIPS containing 5 and 9% po-
lybutadiene rubber with a thermoplastic rubber taken
in a quantity of 5, 10, and 15%, a similar relationship
between p and MFI is observed as can be seen from
Figure 27 for reasons akin to those mentioned above.
Melt flow index recovery (MFIR) is the term given
to a percentage increase in the diameter of the extru-
date over the diameter of the orifice, i.e., 100 (d-d,,)/
$, where $ is the orifice diameter. In order to un-
derstand the effect of MWD and branching on the
rheological parameters of polyethylene melts, Guillet
et a1.66 correlated MFIR with the ratio [q195/[q]50as
shown in Figure 28, where [q]95and [qI5,, are the

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

intrinsic viscosities at Z wt % of 95 and 50 from the

FIGURE 27
distribution curves. It is clear that the MFIR decreases Correlation between
as the distribution broadens because the ratio [q]& 2.0 the degree of
[qls0 is truly proportional to the breadth of the mo- swelling of the melt
and MFI for high
lecular weight distribution and is particularly sensitive impact polystyrene
to the high end of the distribution. Guillet et al.66also 1.9 containing 5% (-)
found that there was a strong relation between critical and 9%(---) rubber
and 5% (o), 18%
shear rate at which roughness on extruded sample first (o), and 15% (A)of
occurs and melt recovery as shown in Figure 29. It 1.8 thermoplastic
shows the regression line obtained by analysis of crit- J
J
ical shear rate measurements on 38 samples of PE. w
Romanini et al.,67 too, studied the dependence of L 1 ~ 7
the swelling ratio Pa (after annealing of PE samples) L
0
to the MFI (taken under identical conditions of load w
and temperature) with changes in the molecular weight w
as shown in Figure 30. The numbers in Figure 30
g 1.6
w
correspond to the sample numbers given in Table X,
which outlines the main chemicophysical character-
.
0

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 ~

ADVANCES IN POLYMER TECHNOLOGY 25

 MELT FLOW INDEX. I

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).

TABLE X the same, long chain branching causes a shift of this

Specifications of the Polyethylenes (Source: Ref. 67) ratio toward lower values, corresponding to a decrease
qo x
in the recoverable elastic deformation and/or to an
Sample Synthesis Density, 23°C MFl 180°C increase in the product flowability.
No. Process (g/cc) (g/lOmin) (Pas) M, X lW3 MJM.

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.%
was later corrected by Combs et a1.68 as a mistake
was noted in the conversion of the units used in the
equation. The actual data reported by Guillet et a1.%
were correct, but the equation was different by a factor
41.62 or (2.54)4. The correct equation, therefore, re-
lating to MS and MFI is as follows:
1.492 x 107(~1)*6
MS = (37)
MFI
It was assumed that the melt strength expressed above
was equivalent to the melt viscosity at low shear rates.
A number of other assumptions were made during the
derivation of Eq. (37) which are not truly correct and
accurate.@It was found that the above equation showed
a 37-fold difference in the melt viscosities of poly-
ethylenes having similar melt indexes. The reason for
this is simply because MFI is insensitive to molecular
weight distribution and hence a normalizing factor of
the kind used by Shenoy and would be required
for more accurate predictions.
Figure 3 1 shows a plot of melt strength determined
at 180°C vs. MFI for a number of polyethylene sam-
ples described in Table X as studied by Romanini et
al.67It can be seen that long-chain branching causes
an increase in melt strength.

ADVANCES IN POLYMER TECHNOLOGY 27

 MELT FLOW INDEX. 1
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’).
I Ci2 16’
M F I(gm/10 mine )
3.1.8. Breakage Stretch Ratio and Elongational
Viscosityfrom MFl
The breakage stretch ratio (BSR) and the elonga-
tional viscosity give a measure of the stretchability of
the polymer. The behavior of the polymer in extension
is important in certain processing operations like fiber
spinning and film blowing.
Basically, breakage stretch ratio is the ability of the
polymer extruded from a die to withstand breakage
when stretched at a particular rate on drawing roll
system. Figure 32 shows a plot of breakage stretch
ratio determined at 180°C vs. MFI for the polyeth-
ylenes specified in Table X as studied by Romanini
et al.67It can be seen that long chain branching causes
a decrease in BSR for the same MFI. The same be-
havior was observed earlier by Bussem during the
study of melt strength and elasticity and their rela-
tionship to the mechanical structures of the polymers.
The ratio of the tensile stress to the extensional rate
is basically defined as the elongationalviscosity. Shenoy
and S a i d 9 conducted a reanalysis of the theoretical
treatment for extensional flows and evolved a method
for the unification of existing extensional viscosity vs.
extension rate data using plots of qE * MFI vs. (El
MFI)*. It has been shown that the plots are unique
for each generic type of polymer. A typical coalesced
28
10” 1 o2
curve is shown in Figure 33 for high density polyeth-
ylene as taken from Shenoy and Saini.69The elon-
gational viscosity vs. extension rate behavior for any
grade of a polymer at any temperature can be obtained
from the generated master curves by using a procedure
similar to that described in Sec. 3.1.2.
3.1.9. Flow Activation Energy from MFl
An understanding of the mechanism of polymer melt
flow processes in relation to the nature and composi-
tion of the material can be elucidated by a study of the
temperature dependency of melt viscosity. The tem-
perature sensitivity of the melt viscosity has a pro-
found effect on the choice of processing conditions as
well as on the quality of the end product. An increase
in temperature sets up thermal motion of the molecules
resulting in their displacements based upon the avail-
able free motion and the overcoming of forces of inter-
molecular interactions. There are two commonly used
expressions to evaluate the temperaturedependency of
the viscosity--one based on free-volume concepts,
namely, the equation proposed by Williams, Landel,
and Ferry’’ and the second of the Arrhenius type based
on the absolute theory of rate processes as derived by
Eyring.’l Both give a measure of the flow activation
energy but need the evaluation of the zero-shear vis-
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-
rameter for experimental determination.
Recently, Saini and Shenoy5' have proposed the
concept of using MFI at two different temperatures
within the range of interest to evaluate the activation
energy for viscous flow E. Equation (23) suggested
by them for this evaluation has been shown5' to give
a standard and meaningful value of E as the MFI
measurement is done at constant shear stress. For
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").

10-2 16' 100 10' loz 10'

( 6/UFI)2

ADVANCES IN POLYMER TECHNOLOGY 29

 MELT FLOW INDEX. I

3. the pressure distribution, torque, and power input

to each roller during calendering
TABLE XI 4. the pressure losses through dies of complex cross
Flow Activation Energies at a Constant Shear Stress Based on section during extrusion
Melt Flow Index for a Number of Common Polymers (Source: 5 . the viscous heat dissipation during various pro-
Ref. 52) cessing operations
Temperature ASTM Test
Range of Load
A detailed understanding of the rheological behav-
Validity Conditions Used ior of the polymer melt becomes necessary for the
Polymer Type E (kcaYmol) ("C) (kg) polymer processor in order to estimate any of the
above parameters. The awareness of the importance
High density polyethylenes 6.83 175-220 2.16
of rheology during a processing operation has devel-
Low density polyethylenes 7.25 175-205 2.16
Polypropylenes 9.87 200-250 2.16 oped only during the last decade or so. Earlier the
Polystyrenes 25.5 210-250 5.00 works of rheologists and the practicing polymer pro-
Styrene acrylonitriles 30.7 200-250 3.80 cessor were truly compartmentalized. Polymer melt
Cellulose esters 34.2 190-230 2.16 rheologists came up with highly theoretical analysis
Cellulose ethers 23.2 170-230 2.16
based on complicated equations and computer pro-
Acrylics 38.5 170-260 3.80
Nylons 18.6 230-300 2.16 grams while the practical processor resorted to simple
Poly(ethy1ene terephtha1ate)s 20.1 265-285 2.16 rules of thumb based on experience to get answers to
Polycarbonates 21.9 250-290 1.20 processing problems. Actually, what is desirable is to
develop methods which are an acceptable compromise
between the complex mathematical approaches and
the simple thumb-rule. With this objective in mind,
all approaches which follow such a line, of course,
energy at a fixed shear stress rather than at a fixed will be reviewed. It will be shown that a number of
shear rate due to the constancy of the value over a parameters useful in polymer processing could be es-
very large range of shear stresses ( 104-106 dyn/cm2). timated within reasonable accuracy limits merely
In actual practice, MFI measurement is determined through the knowledge of the MFI of the material.
under constant shear stress conditions lying between MFI is, undoubtedly, a good indicator of the proces-
3 X 104 and 2 x lo6 dyn/cm2 as shown in Appendix sibility of the material as has been discussed earlier
A and, therefore, becomes a simple yet very effective (see, for example, Tables I1 and 111). A high MFI is
method for determination of activation energy. The desired for injection molding whereas a low MFI is
activation energies calculated by this technique for preferred for blow molding. For four major processes,
some common polymers are given in Table XI. the desired rheological properties for proper process-
ing are given in Table XI1 taken from Combs et al.,72
wherein MFI can be seen to be a quite an adequate
3.2. Processing Aspects pointer.
Various plastic products are formed by processing
polymers by one of the available techniques such as 3.2.1. Injection Molding
injection molding, compression molding, blow mold-
Injection molding is one of the most widely used
ing, profile extrusion, and sheet extrusion followed
processes for the fabrication of thermoplastic mate-
by stamping or thermoforming. In all these processes,
rials. It is, in essence, an operation which involves the
the molten polymer is subjected to a wide range of
high pressure squeezing of a polymeric melt through
temperatures and shear rates (see, for example, Table
a very small hole (gate) into a cold cavity and then
IX). It is absolutely essential for process optimization
packing of additional material into the cavity to allow
and product quality to get an idea about certain aspects
for shrinkage as the material cools. Cipriani and
during processing, such as, for example:
T r i ~ c h m a nhave
~ ~ shown how the injection molding
1. the minimum pressure drop during cavity-filling behavior of a polymer can be assessed via MFI dur-
as well as the minimum clamping force to prevent ing the product development and improvement stages.
mold opening during injection molding In their efforts to develop a new class of polypropyl-
2. the compaction force during compression molding ene resins, they compared the behavior of a standard

30 VOL. 6, NO. 1
 MELT FLOW INDEX. I

resin with that of the developed A resin with a broader

weight distribution. It was observed that A resin had
greater melt fluidity than the standard polymers at shear TABLE XI1
rates found in a commercial injection molding oper- Rheological Properties Desired for Polymer Processes (Source:
ation as is brought out by the spiral melt flow data Ref. 72)
given in Figures 34-36. Spiral flow length is a good
Operation Desired Property
indicator of the ease of mold filling, and it was de-
vised as a quick and simple test by ICI to assess the Film extrusion Low melt index, high melt strength, high
mold-filling properties of materials.74From Figure 34 critical shear
it is evident that under the same melt processing con- Extrusion coating Low energy of activation for viscous flow,
high melt index, high melt strength, high
ditions, the A resin flows easier than the standard resin.
critical shear rate
For example, a 10 MFI A resin processes similarly to Injection molding High melt index, high degree of non-
a 14 MFI standard resin, other conditions being equal. Newtonian character, high energy of
It would, therefore, be possible to mold the A resin activation for viscous flow
at a 3 M “ F lower temperature (Figure 35) or, for the Blow molding Low melt index, low energy of activation
for viscous flow, high melt strength
same temperature, under corresponding pressure
(Figure 36) than the standard material of the same MFI.
The broader molecular weight distribution of the A
resin truly accounted for the difference in the rheo-
logical behavior of the two groups of polypropylene.
Kandyrin et al.75 found an interesting correlation creases, the molding of the material becomes more
between Mooney value and MFI of rubber mixes which difficult. Some of the difficulties can be overcome by
would help in monitoring injection molding opera- injection pressure and enlarging the diameter of the
tions. The MFI was determined at 130°C under 21.6- gates. However, this would often lead to degradation
kg load condition with a capillary of diameter equal of the polymers, sink-marks, and distortions of the
to 0.2 cm and length equal to 1 cm. The values of product. With a view to look for a good control pa-
MFI obtained by them were in the range of 0.08-75 rameter for maintaining the quality of molding,
g/10 min. It was observed that the relationship was K n a ~ p studied
e ~ ~ the relationship between the energy
of a power law type such that Mooney value = T((1/ for injection into mold WE vs. the melt flow index
MFI)n, where the value of n corresponded to the nor- for polypropylene. From Figure 38 it is evident that
mal Ostwaldde Waele power-law index in the shear
stress shear rate relation. Thus a plot of Mooney value
ML vs. log(l/MFI) resulted in a straight line as shown
in Figure 37 within limits of 3 decades of MFI values. FIGURE 34
Effect of melt flow
It follows that the MFI characterizes the viscosity of index on the flow
rubbers and mixes with greater accuracy than the Moo- distance in spiral
ney values. Thus the MFI value may be used for cavity mold for A
resin and standard
estimating the processing behavior of mixes and the resin at molding
viscosity properties of mixes in working out formu- temperature of
lations, and also to effect operational monitoring of 400°F and pressure
of 1500 psi (taken
the injection molding properties of the mixes under from Cipriani and
production conditions so long as the shear stresses do Tri~hman’~).
not exceed 2 X lo6 dyn/cm2. Beyond this value of
shear stress, the value n alters considerably and hence
400 OF
it might become necessary to determine MFI of the
E M O L D I N G P R E S S U R E : I500 P S I
mixes under different load conditions. a
J 251,’’

In injection molding, controlled quality molding is E

dependent on process conditions like temperatures, g
-02
1 2 3 4 5 10 20
pressures, and cycle times as well as on the rheological
properties of the molding compound. Higher MFI MFI ,G M / lOMlN
polymers are easily molded with a conventional ram-
type injection molding machine. As the MFI de-

ADVANCES IN POLYMER TECHNOLOGY 31

 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 '

of loo0 psi (taken

from Cipriani and 40.
Trishman'?
35

30'
25
~

400 450 500

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)"
+

and standard resin

-
at molding
temperature of where
400°F (taken from
Cipriani and I? 0
0

Tri~hman'~). 40 MFI= 2 23n+ 1

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
being the mold temperature, T being the melt tem-
perature, and To being the freeze-off temperature.
The values of K and n to be used in Eq. (38) and
(39) are given in Table VIII along with the applica-
bility range of shear rate which can be seen to be of
practical significance to the injection molder.
For a given polymer type, An), c, K, and n are
constants and, for a given circular type mold, R,, and
x are fixed. Hence the minimum pressure for cavity
filling can be estimated through only the knowledge
of the MFI at the melt temperature T of mold filling.
The MFI determined at the ASTM test temperature’
would thus have to be converted to the MFI value at
the required temperatures. This could be done through
either of the two equations (22) and (23).

FIGURE 38
Variation of
injection energy
with melt flow index
for polypropylene
(taken from
Knappem).

ADVANCES IN POLYMER TECHNOLOGY 33

MELT FLOW INDEX. I

The minimum clamping force Fmincan now be es- For$at strips:

timated using the following equation:

where Fcdand Ffs are the compaction forces required

where is the effective projected area of the molding to conduct the squeezing operation, ho is the initial
given as ITR’ and B is a numerical function dependent gap between the plates, - h is the rate at which the
on n as shown by Barrie7*for circular, square, and gap is changing with time, k d is the radius, w the
rectangular moldings as width, and L the length of the plate; K and n are
power-law constants for the modified Ostwald4e Waele
- n + 2 model as given by Eq. (26).
B=- (for circular panel with (42)
n For UHMWPE, the values of K and n are constant
center injection) and equal to 1.66 X lo6 g/cm s2-” and 0.156, re-
n + l spectively, as obtained by Shenoy and Saini.79Thus,
-- (for long thin (43)
n specifically for UHMWPE, Eqs. (44)and (45) can be
panel with center injection) written as:

More centrally gated, flat, and symmetrical moldings
would show higher values of B and lower clamping
force. For engineering design, one could choose the
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 n = 0.50 may be used as rough estimates.
The simplistic approach given above is not a pan-
acea but would certainly be a useful handy tool to the
plastic processor to get quick order of magnitude es-
timates of the design parameters.
3.2.2. Compression Molding
Compression molding is one of the most common
methods for producing articles from thermosetting
plastics. It is rarely used as a production process for
thermoplastic materials due to the long cycle times
required for cooling and reheating the press. However,
there are some specialized materials like ultra high
molecular weight polyethylenes (UHMWPE) which
are preferentially compression molded rather than in-
jection molded to form the product. In fact, more than
50% of UHMWPE is processed via compression
molding. Shenoy and Saini79have suggested a sim-
plified approach for determining the compaction force
F from MFI. The given expressions for circular disc
molds and flat strips are as follows:
For circular discs:
For circular disc:
Fcdh&fFI)o.156 -hie 0.312
~3.156 = 4.6 x 1 0 6 ( ~ ) (46)
For $at strips:
0.312
FfSb(MFI)O.” = 1.07 X 1 0 6 ( ~ )
w ~ 2 156
. (47)
In compression molding operations, the typical
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-
hand sides of Eqs. (46) and (47) with the ( - h1’2/ho)
factor in this range. It is now evident that knowing
the geometrical factors of the mold, one can easily
determine the compaction force merely from the
knowledge of the MFI at the appropriate temperature
and load conditions determined through the method
discussed in Sec. 3.1.2.
3.2.3. Calendering
The term “calendering” as applied to thermoplastic
materials refers to the shaping of the material into
sheet or film by feeding it through a pair of corotating
heated rolls. This process is commonly used for the
manufacture of various poly(viny1 chloride) (PVC)
products such as leather cloth, shrink films for pack-
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

temperature rise due to viscous dissipation. A method
to estimate these through the appropriate value of MFI
has been suggested by Ray and Shenoy.80
The expression derived is as follows:
where
2 n + l n
Cl = K ( 7) (49)
where P is the pressure developed between the rolls,
U the velocity at the roll surface, Ho half the distance
between the rolls, & the radius of the roll, K and n
are power-law parameters as in Eq. (26), and A*, x*
dimensionless parameters defined below. Thus
ADVANCES IN POLYMER TECHNOLOGY
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).
where Qo is the flow rate of the melt through the
calender.
Note that C, is a constant for a given resin and, C2
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
value of MFI, the pressure distribution could thus be
calculated. The predictions of this simple approach
were found to give more realistic values than those
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
present simple approach fits better.
The expression for the torque exerted by each roll
(r)and the power input (+p) as given by Ray and
ShenoyX0are as follows:
r(MFl)n =
35
 MELT FLOW INDEX. I

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*

ADVANCES IN POLYMER TECHNOLOGY 37

MELT FLOW INDEX. I

(bp(MF1)" = Case 2: Rectangular Channel of Constant Width

and a Vertical Taper.
A* lA*2 _x*Zln-I (A*2 - x*2)
dx*
(1 + X*2)2n H, = HI (59)

(54)

Again, the predictions of torque and power input can K 4 n + 2 "

be made merely from the knowledge of MFI. f2 = 2n (7)
where A t is the constant vertical taper factor given by
3.2.4. Extrusion the ratio of the height H2 at the end of the channel to
With the growing importance of plastics, more and the height HI at the start of the channel and twis the
more industrial processes involve extrusion of poly- shape factor given by the ratio of the constant width
mer melts through dies of complex cross section to W to the entrance height H I of the channel.
the product. The shape Of these dies and
Caw 3: Recentangular Channel of Constant
the pressure losses through them are important factors
Height H and a Constant Lateral Taper.
in preventing flow defects and controlling the quality
of the end product. A method for the predictions of
pressure losses through dies of complex cross section H, = H (62)
based on a simple approach using MFI has been given
by Shenoy and Saini.82 The general expression pro-
posed by them is as follows:

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

H, = H (56) E" AF(1 - A (1 - At)

(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
given by the ratio of the entrance width WI to the
entrance height H, of the channel.
Case 5: Rectangular Channel with a Taper Such
That the Cross-SectionalShape Factor is Constant.
where R is the radius of the circle whose cross-sec-
tional area is equal to the cross-sectional area of the
polygon-
Case 9: Constant Taper Polygonal Channel with
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.

ADVANCES IN POLYMER TECHNOLOGY 39

 MELT FLOW INDEX. I

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

For all high output rate operations, it is essential to

know the viscous heat generated in order to appro-
priately design the conventional extruder screw so as TABLE XI11
to minimize the temperature increase in the process Values of a1and Needed in Eq. (83) (Source: Ref. 85)
of plastication and to optimize the extruder temper-
Polymer Type PI Q, [g/cm s2-" (U10 minY1
ature profile with respect to throughput rate or screw
speed. Viscous heat estimation is also critical when Low density polyethylenes 1.46 1.3 X l@
processing heat-sensitive polymers so as to maintain High density polyethylenes 1.54 9 x 104
the melt temperature well below degradation point. Linear low density 1.78 8 X 10''
Shenoy and Sainis5 have established that plots of polyethylenes
Polypropylenes 1.34 1.4 X I@
+/MFI vs. +&IF1 result in unique curves for each Polystyrenes 1.39 3.5 x l@
generic type of polymer. One such typical curve for Cellulose esters 1.47 3.2 X l@
polypropylene is shown in Figure 45. It was also shown Cellulose ethers 1.38 1.1 x l@
by Shenoy and Sainis5that within the ranges of +/MFI Acrylics 1.44 3.2 X l@
Nylons 1.44 2.8 X I@
considered by them, each of the unique plots could
Polyesters I .43 5 x 104
be fitted by a straight line following the relationship Polycarbonates 1.52 1.5 X l@
as given below:

(83)
MFI MFI

The values of a Iand PI for each of the polymer types
considered are given in Table XIII. Equation (83) can
be readily used for estimating the viscous heat vs.
shear rate behavior at any temperature of interest only
through the knowledge of the appropriate MFI by
following the steps as outlined in Sec. 3.1.2.
3.2.6. Blending and Filling
During recent years, multicomponent polymeric
systems have attained great importance due to the
possibility of obtaining compounds with novel phys-
ical properties and optimum cost performance bene-
fits. From a macrostructural viewpoint, polyblends
and composites would fall under the category of mul-
ticomponent systems consisting .of a polymeric con-
tinuous phase or matrix and of a dispersed phase. The
dispersed phase could either be another polymer (as
in the case of polyblends) or fillers such as calcium
carbonate, talc, etc., or reinforcing agents such as
glass fibers, mica, etc. (as in the case of composites).
All PVC formulationswould also fall into the category
of multicomponent systems due to the presence of a
number of additives such as plasticizers, fillers, sta-
bilizers, lubricants, etc., which go into such forrnu-
lations. The final properties of the products depend to
a large extent en how well the dispersion level of one
phase into the other is.
In the case of polyblends, the critical steps involved
are (a) selection of the component polymers, their
appropriate grades and their composition based on
property requirements, and (b) the proper choice of
compounding method and conditions. Most often the
component grade selection and choice of compound-
ing process parameters are arbitrary. It is the general
practice to finalize the appropriate grades of the com-
ponents and the compounding conditions based on the
end property evaluations. This becomes more a trial
and error procedure. Single phase blends would gen-
erally provide synergistic property advantages, and
this cannot be achieved even in thermodynamically
miscible polymers if they are mechanically incom-
patible due to large differences in the melt viscosities
at conditions of compounding. Shenoys6 has sug-
gested a simplistic approach of getting quantitative
estimation of compounding conditions or grade se-
lection of blend components through MFI.
The temperature of compounding of the blends in
order to achieve maximum mechanical compatibility
as suggested by Shenoyg6is as follows:
Tc
-
- EPZ - E P ~
R In ( M ~ ~ PTZNFIPI,TI
Z, + E P ~ -ZE P ~ ~ I )
(84)
where MFIpl,TIand MFIPZ,TZ represent the MFI values
of the two component polymers, EPI and Em their
respective activation energies, and TI and Tzrespec-
tive temperatures of MFI measurement.
The compounding temperature graphically repre-
sents the point of intersection of the two curves shown
in Figure 46(a), for polymers PI and Pz. If the grade
selection of the two component polymers has been

ADVANCES IN POLYMER TECHNOLOGY 41

 MELT FLOW INDEX. I

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
determined from the intersection of the two curves is
fixed. The value of T, as determined through Eq. (84)
may not always be relevant for the selected grades.
For example, the cases, as shown in Figures 46(b),
46(c), and 46(d) clearly indicate that the blending
temperature as determined by the point of intersection
could be too low (even below the melting tempera-
ture), too high (even above the degradation temper-
ature), or none at all if the activation energy of the
two components are equal. Such values may not be
relevant for use but are certainly an indication of the
incompatibility of the component polymers.
Shenoysbhas also indicated the method for deter-
mining the shear rate level in the compounding op-
eration in order to achieve mechanical compatibility
conditions. The equation for this determination is as
follows:
where MFIe,=, is the melt flow index value of either
component, i.e., of the blend at the temperature of
compounding T,. K, and K2 as well as n, and n2
correspond to the parameters of Eq. (26) and given
in Table VIII for the two component polymers. The
above shear rate condition is determined by the in-
tersection point of the two curves as shown in Figure
47. These are based on the master curves of Shenoy
and Saini.” Note that in Eq. (85) when nl = n2 the
curves do not intersect and hence no shear rate con-
dition can be specified for achieving mechanical com-
patibility. When K and n values for the component
polymers are nearly the same, then the blending shear
rate truly does not matter as the two components are
undoubtedly compatible provided that they have the
same MFI value at the blending temperature. Shenoy86
has discussed a number of case studies to illustrate
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).

In the case of multicomponent systems, it is essen-

FIGURE 48
tial to know the changes in the melt flow behavior of Melt flow index
the continuous phase with increasing concentration of variation with blend
the dispersed phase for process design, optimization, composition for
polystyrene/poly(methyl
and trouble-shooting. Shenoy and SainiE7have de- methacrylate) blend
veloped a method of predicting the MFI of the blend at 220°C and 5-kg
or composite at any composition based on the altered test load condition
for MFI: &FI =
free volume model. They have shown that a plot of MFI(T,O)IMFI(T,+)
l/log[MFI(T,O)/MFI(T,+)] vs. l/+ is linear, where (taken from Shenoy
MFI(T,O) is the melt flow index of one phase while and Sainia3.
MFI(T,+) is the melt flow index of the multicom-
+
ponent system at temperature T containing volume
fraction of the second phase. It is imperative to choose
MFI(T,O) > MFI(T,+) as discussed by Shenoy and
In the case of filled systems, this condition
is naturally satisfied when the polymeric matrix is
taken as the reference medium. For polyblends, a 01 I I I 1 J
0 I 2 3 4 5
deliberate choice of the reference medium would have -
1
to be made so that the MFI value of the reference 0 0

medium is greater than that of the multiphase system.

Shenoy and Sainis7 have shown the applicability of
their method to a wide class of polyblinds and b l y -

ADVANCES IN POLYMER TECHNOLOGY 43

 MELT FLOW INDEX. Z

3.2.7. Curing and Crosslinking

FIGURE 49
Melt flow index Certain polymers have the ability to undergo “change”
variation with tiller $1 I I I I I
upon heating or irradiation resulting in enhanced prop-
composition for PP - COCO~
polypropylene/ erties. Two of the common polymers, wherein this
calcium carbonate !l 200-c
“change” phenomenon often referred to as curing or
composite at 200°C
and 2.16-kg test
crosslinking has been drawn to advantage, &e poly-
load condition of 4 phenylene sulfide and polyethylene. Brady88conven-
MFI: &FI = MFI iently monitored the progress of the curing reaction
(T,O)IMFI(T,+)
(taken from Shenoy
and Saini*’). 1;- I
2
3
of PPS by following changes in the MFI. As curing
proceeds, the molecular weight increases and so does
the melt viscosity, as evidenced by a decrease in MFI
from an initial high value as shown in Figure 50. MFI
truly acts like a fingerprint of the degree of cure be-
cause higher the degree of cure, the lower is the value
of MFI.
The effect of electron irradiation on MFI of poly-
0 2 4 6 8 10 12 ethylene was investigated by H a r ~ e r . ’ ~It. was
~ ob-
-
1 served that for a number of different types of poly-
9 ethylene, MFI changed uniformly with radiation dose
as shown in Figure 51 and that this change could be
represented by the following equation:

mer composites. Two typical curves obtained by them D = - a + bx - -x2

b 2.303
+- log -
1
(86)
are shown in Figures 48 and 49 for polyblends and k 2k k 1-x
filled systems, respectively. It is evident that the MFI
of the multicomponent system can now be estimated where D is the radiation dose in Mrad, k, a, and b
from the curves at the composition of choice. Once are constants and x = (MFI, - MFI)/M& represents
this value is known, the entire viscosity vs. shear rate the degree of change in the melt flow index. M& is
curve can be determined by the method of Shenoy et the initial melt flow index and MFI is the melt flow
a1.49.50
index at dose D.
Though only a single equation as defined above
fitted all types of polyethylene samples, the shape of
these curves were affected by the properties of the
FIGURE 50 polyethylene such that the initial s i p - of the curve
Curing rate of of (MFI, - MFI)/MFIo vs. dose as shown in Figure
polyphenylene
sulfide as 52 is proportional to either the molecular weight or
monitored through ; ; the crystallinity of the high pressure polyethylene.
melt flow index .-c Due to the approximate inverse relationship of the
(taken from E
Brady8B). z
\
molecular weight and crystallinity, a firm conclusion
as regards the controlling factor was not reached.
-
b
s 1 7 5.C
LL
z 3.2.8. Degradation and Stability
During processing of polymers through extrusion,
injection molding, blow molding, and other conver-
sion processes, the material is exposed to thermal,
0 150 oxidative as well as shear degradation, causing mo-
lecular scission and hence a reduction in molecular
TLME, HR weight. The decrease in molecular weight is generally
characterized through changes in MFI of the poly-
mer.91-94Figure 53 shows ;he changes in MFI that

44 VOL. 6, NO.1
 MELT FLOW INDEX. I

occur due to repeated extrusions of the material. Pro-

FIGURE 51
cessing conditions for the virgin and recycled material Typical curve of
would be different in accordance with changes in the melt flow index vs.
melt rheology. Curves like those in Figure 53 are, dose of irradiation
for high pressure
undoubtedly, indicative of the changes in molecular polyethylene (taken
structure; however, what is required is the entire flow from HarpeP).
curve depicting the variation of melt viscosity with
shear rate and temperature in order to assess the pro-
cessibility. This has been provided by Shenoy et al.95
wherein the approach proposed by them for virgin
polymers4’ has been extended to recycled material.
Figure 54 shows the unified curve developed by them
for polypropylene from which the entire rheogram of
the recycled material can be got knowing its MFI. It
can be seen that Figure 54 superimposes rather well
on Figure 19. Thus, all the curves proposed by Shenoy
et al.42-51for virgin polymers can be used to get es-
timates of the flow curve for the recycled material and
DOSE IN YRAD
thus provide guidelines for reprocessing.
As all polymer melts are viscoelastic in nature, it
is essential to understand the elastic response besides
viscous response of these materials to deformation
during reprocessing. The extent of degradation in the as proposed earlie?’ for coalescing the curves of dif-
elasticity of the material during various stages of pro- ferent grades of polymers. It is understandable that
cessing can be characterized in terms of the normal polymer samples with different processing histories
stress difference versus shear rate curve. Shenoy and essentially represent polymer grades with different melt
Saini% have shown that an estimate of the variation flow indices. Hence, though Shenoy and Saini%have
of normal stress difference with shear rate for de- validated their approach through limited data, the curves
graded polymer can be got simply through the use of of Shenoy and Saini51*63 giving unified normal stress
MFI. The method involves the generation of unique difference vs. shear rate plots for virgin materials could
curves by plotting N1 vs. (j4MFI)’ along similar lines be used for reprocessed materials as well.

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

ADVANCES IN POLYMER TECHNOLOGY 45

 MELT FLOW INDEX. I

FIGURE 53
Variation in melt
flow index with
number of
reprocessing cycles POLYPROPY L E N € -
UNITS

for polypropylene MFI - qmrI10min at 190.C ond 2.16kg lood

(taken from Cuspor
and TothW).

NUMBER OF PROCESSING CYCLES

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

~~ ~

ADVANCES IN POLYMER TECHNOLOGY 47

 MELT FLOW INDEX. 1

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
to decompose during melting and at elevated temper-
ature. Hence all commercially available polypropyl-
ene grades contain thermostabilizers. Even then it is
advisable to maintain the processing temperature in
the metering zone as low as possible in order to min-
imize losses in the mechanical properties of the end
product due to thermal decomposition of the polymer.
The extent of degradation can be easily checked by
the amount of rise in the melt flow index, which in-
creases at more elevated extrusion temperatures. Ex-
amples of the increase of the melt flow index in cor-
relation with the extrusion temperature for various
isotatic polypropylene grades stabilized to a different
degree are given in Figure 55 taken from Evans.97
Bagheri et al.98 studied the melt stabilization of
polypropylene by galvinoxyl at three different tem-
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

mixing under three sets of conditions: (a) open to the
atmosphere, (b) mixer closed, and (c) mixer closed
after purging with nitrogen. In each case, the effect
of galvinoxyl on the melt stability of PP was tracked
by observing the changes in the MFI with processing
time as shown in Figure 56 for the open mixer. It was
observed that, in the presence of oxygen, the additive
was less effective. There was no real induction period
and the additive was less effective at 200°C than at
190°C. Whereas, in the open mixer, oxidation was
effectively inhibited for up to 10 min, it was observed
that, in a closed mixer for the same concentration of
galvinoxyl and the same temperature, the PP was sta-
bilized for 20 min of processing time. The end of the
MFI induction period actually corresponds to the com-
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
of aT+ was attempted for all temperatures with a tem-
perature shift factor aT defined as
aT = exp[a(+ - k)] (87)
tc
ADVANCES IN POLYMER TECHNOLOGY
MELT FLOW INDEX. I
where E is the activation energy, R the universal gas
constant, To the absolute reference temperature, and
T the absolute temperature of measurement.
It was, however, found that the data for tempera-
tures lower than 280°C lie on a single curve, whereas
the data for temperatures 280°C and higher did not.
This was due to the degradation of the polymer.
Nevertheless, a master curve incorporating even the
degraded polymer data could be got by using a mod-
ified shift factor a, defined as the ratio of the tem-
perature shift factor aT and the melt flow index MFI
as shown in Figure 57. The dependence of the melt
index upon the temperature & and the residence time
t, as shown in Figures 58 and 59 was determined in
the form
The relationship was found to fit experimental data
rather well as can be seen from Figure 59.
Most of the flow curves were fitted by a power-law
model of the following type by Zavadsky et al.* so
as to be suitable for calculations of transport problems
of polymer melts in pipes and extruders
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
49
 MELT FLOW INDEX. I

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

Zavadsky et aI.=). 20000

c
In

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)
The variation of k, n, m,,, and q with MFI for various
levels of shear rate y' are given in Figures 60-63.
The influence of the shear rate and the melt flow index
upon the parameters k and n is distinct but diminishes
with increasing values of both quantities. There is a
strong influence of melt flow index on the parameter
Q, but the effect of shear rate on it is rather negli-
gible.
The hydrolytic stability of glass fiber reinforced
poly(buty1ene terephthalate), poly(ethy1ene tereph-
thalate), and polycarbonate was studied by Kelleher
et al. following the changes in the melt flow index
during the process of hydrolytic degradation. Their
entire approach was similar to that used earlier for
unreinforced poly(buty1ene terephthalate)"' and po-
lycarbonate.lo2Since MFI is related to the degree of
polymerization, the following relationship was
developed102to study the rate of hydrolysis:
1 1
kt = E(- MFI" --)MFIE (90)
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
initial value, E is a constant which includes the mon-
omer molecular weight, the polydispersity of the poly-
mer, and the value of the intercept at the R, axis of
the log MFI vs. log RW curve, and m is the slope of
this curve.
A plot of MF1°.25vs. hydrolysis time was used to
calculate the reaction rates as shown in Figure 64 for
30% glass-reinforced PBT while a plot of MF1°.23vs.
hydrolysis time as shown in Figure 65 was used for
30% glass-reinforced PET. The value of the exponent
is the value of the slope of the curve in accordance
with the mathematical treatment given by Pryde et
a1.'02 It can be seen that the reaction rates decrease
with decreasing temperature in both cases while PET
hydrolyzed at a faster rate than PBT. A possible ex-
planation for this behavior is that, for a given &,
PET has more ester groups than PBT. Though MFI
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
was a fundamental correlation between MFI and elon-
gation so that the final MFI could be equated to a

ADVANCES IN POLYMER TECHNOLOGY 51

 MELT FLOW INDEX. I

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

2-5 /7xIO-'% LINKAGE/hr

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").

.." 10.0 100.0 3.0

R E S I D E N C E TIME

sitive material function when monitoring material
changes with time.
Prolonged storage of polymeric materials may lead
to deterioration in properties as a result of aging. This
point was investigated for polyethylenes by Neverov
and Vasil'eva.'04 It was observed by them that me-
chanical properties such as tensile strength at yield,
tensile strength, and elongation at break, the dielectric
constant and the electrical strength changed very little
over a storage period of 13 years of unstabilized and
stabilized LDPE. However, the most marked change
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

~~

ADVANCES IN POLYMER TECHNOLOGY 53

MELT FLOW INDEX. I
the material. It can be seen from Figure 67 that for
the unstabilized material there was a monotomic, prac-
tically linear change in MFI with time even up to a
storage period of 17 years. For the stabilized material,
only a slight reduction in MFI is observed during the
early stages of storage, followed by a slight increase,
and then a decrease after 6-7 vears. Changes " of this
type in MFI can be attributed to the process of oxi-
dative crosslinking.
NOMENCLATURE
heat diffusion coefficient of the melt (cm2/s) in Eq.
(40).
coefficient in Eq. (6), values given in Table V
constant in Eqs. (14)-(17)
constant in Eq. (34)
effective projected area of the molding in Eq. (41)
constant in Eqs. (14)-(17)
constant in Eq. (35)
numerical function dependent on n for different
geometries appearing in Eqs. (41)-(43).
weight average degree of branching in Eq. (8)
constant appearing in Eqs. (14)-(17)
proportionality constant in Eqs. (48). (53), and
(54). defined in Eq. (49)
proportionality constant in Eqs. (48). (53). and
(54). defined in Eq. (50)
proportionality constant in Eq. (381, defined in Eq.
(40)
constant appearing in Eqs. (15)-(17)
activation energy for viscous flow (KcaVmol K)
appearing in Eqs. (23) and (87)
activation energy for viscous flow of polymer 1
(kcal/mol K) in Eq. (84)
activation energy for visous flow of polymer 2
(kcal/mol K) in Eq. (84)
function of geometric parameters based on the
shape of die as given in Eqs. (53, (57), (60).(63),
(66), (69h (72). (7% and (78)
function of fluid properties as given in Eqs. (56).
(58), (61), (6% (671, (70). (73). (76), and (79)
compaction force required for squeezing operation
of circular disc component (dyn) defined in Eqs.
(44) and (46).
compaction force required for squeezing operation
of flat strip component (dyn) defined in Eqs. (45)
and (47)
minimum clamping force to prevent mold opening
as given by Eq. (41)
ratio of root mean square radii of branched and
linear polymers in Eq. (6)
initial gap between plates (cm) appearing in Eqs.
(44)-(47)
rate of plate separation with time (cm/s) in Eqs.
(44)-(47)
half distance between calendering rolls (cm) in
Eqs. (50), (53), and (54).
H, = characteristic geometric parameter specific to
geometric shape (cm) in Eqs. (55). (56), (59),
(62). (65). (71L (74). (77). and (80)
k = rate in terms of percent scissions per unit time t in
Eq. (90)
K = consistency index of the power-law model (glcm
s*-") in Eqs. (26), (4% (4% (481, (49L (50A (53,
(58L (61), (W, (67), (70), (73), (76), (79), and
(82)
K I , KZ = consistency index for polymers 1 and 2 (g/cm s2-"),
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)
= test load at condition 2 (kg) in Eq. (21)
= length of barrel (cm) in Eq. ( 1 )
= length of capillary (cm) in eq. (1)
= length of die (cm) in Eq. (55)
= damping constant in Eq. (29)
= model parameters in Eq. (89)
= number average molecular weight in Eqs. (9), (lo),
and (28)
= viscosity average molecular weight in Eq. (19)
= weight average molecular weight in Eqs. (2)-(6).
(1 I), ( 2 3 , and (28)
= average molecular weight in Eqs. (27) and (28)
= (z + I)-average molecular weight in Eq. (28)
= melt flow index (g/10 min) in Eqs. (6), (9), (lo),
(12)-(l9), (24)-(27), (29), (34)-(38), (44)-(48),
(53)-(55), (83). and (88)
= melt flow index at time t = 0 (g110 min) in Eq.
(90)
= melt flow index at 1.2 kg load condition (g/IO min)
in Eq. ( I I )
= melt flow index at 5 kg load condition (g/10 min)
in Eq. (11)
= melt flow index for autoclave reactor polymer (g/IO
min) in Eq. (4)
= melt flow index of branched polyethylene (g/lO
min) appearing in Eq. (2)
= melt flow index at compounding temperature for
polymer blend (g/IO min) in Eq. (85)
= melt flow index of linear plyethylene (g/10 min) in
Eqs. (3) and (7)
= melt flow index at load condition I (g/lO min) in
Eq. (21)
= melt flow index at load condition 2 (g/10 min) in
Eq. (21)
= melt flow index at temperature condition 1 for
polymer 1 (g/IO min) in Eq. (44)
= melt flow index at temperature condition 2 for
polymer 2 (dl0 min) in Eq. (44)
= melt flow index at time t (g/lO min) in Eq. (90)
= melt flow index at temperature condition I (g110
min) in Eqs. (22) and (23)
= melt flow index at temperature condition 2 (g/lO
min) in Eqs. (22) and (23)
= melt flow index for tubular reactor polymer (g/10
min) in Eq. (5)
= melt flow index recovery defined as the percentage
increase in diameter of extrudate over that of the
orifice
VOL. 6,NO. 1

= melt strength (P) in Eqs. (36) and (37)
= molecular weight distribution
= power-law index in Eqs. ( I ) , (26). (38), (39),
(42)-(45), (48), (49). (53)-(55), (57), (58), (60).
(61). (63). (W, (W, (67). (6% (70). (73), (75h
(761, and (78)
= power-law index for polymer 1 in Eq. (85)
= power-law index for polymer 2 in Eq. (85)
= Carreau model parameter in Eqs. (24), (27). and
(29)
= number of sides of polygonal channel in Eqs. (78)
and (81).
= power-index in Eq. (33), defined in Eq. (35)
= pressure developed between calender rolls (dyd
cm') in Eq. (48)
= minimum pressure for mold filling (dynlcm') in
Eq. (38)
= pressure drop in barrel (dydcm') in Eq. (1)
= pressure drop in capillary (dydcm') in Eq. (1)
= pressure loss through the die (dydcm') in Eq. (55)
= power-index in Eq. (34)
= flow rate of polymer melt through the die (cm3/s)
in Eq. ( 5 5 )
= flow rate of polymer melt through the calender
(cm'ls) in Eq. (52)
= correlating factor for various molecular weight
distribution expression as given in Eq. (28)
= power-index in Eq. (35)
= radius of the extruded cord emerging from the die
(in.) in Eqs. (36) and (37)
= radius of the barrel (cm) in Eq. ( I )
= radius of the capillary (cm) in Eq. ( I )
= gas constant ( = 1.9874 kcal/mol) in Eqs. (23) and
(87)
= radius of calender rolls (cm) in Eqs. (50) and (53)
= radius of circular disc mold cavity (cm) in Eq. (38)
= radius of circular disc plate (cm) in Eqs. (44)and
(46)
= die swell ratio of extradate diameter to die diameter
in Eq. (31)
= hydrolysis time (min) in Eq. (90)
= residence time (sec) in Eq. (88)
= melt temperature ("C) in Eq. (88)
= polymer melt temperature in Eqs. (14)-(17) and
(40)
= freeze-off temperature in mold (K) in Eq. (40)
= ASTM test temperature (K) in Eqs. (22) and (23)
= temperature of interest (K) in Eqs. (22) and (23)
= compounding temperature (K) in Eq. (84)
= glass transition temperature of polymer (K) in Eqs.
(W-(
17)
= standard reference temperature (K) equal to
T, + 50 in Eq. (22)
= velocity at calender roll surface (cm/s) in Eqs. (50)
and (54)
= width of plate (cm) in Eqs. (45) and (47)
= test load (g) in Eq. (20)
= energy for injection into mold cavity (ergs) in
Figure 38
= original cavity thickness (cm) in Eq. (38)
= dimensionless parameter in Eqs. (48) and
(52)-(54), defined in Eq. (51)
= initial value of x* in Eqs. (53) and (54)
ADVANCES IN POLYMER TECHNOLOGY
MELT FLOW INDEX. I
Greek Symbols
= Ellis model parameter in Eq. (25)
= proportionality constant in Eq. (83)
= proportionality constant in Eq. (90)
= degree of swelling in Figures 26 and 27
= power-index in Eq. (83)
= swelling ratio after annealing in Figure 30
= strain related to die swell in Eq. (30)
= shear rate (s-I) in Eqs. (30). (24), (26), (29), and
(89)
= compounding shear rate (s-I) in Q . (85)
= torque exerted on each calender roll (dyn cm) in
Eq. (53)
= elongational strain rate (sd)
= apparent viscosity (P) in Eqs. (24)-(26) and (89)
= viscosity of branched polymer (P)in Eq. (8)
= zero shear viscosity (P) in Eqs. (18)-(20), (24),
(25), and (29)
= viscosity of linear polymer (P)in Eq. (8)
= elongational viscosity (P)in Figure 33
= inherent viscosity (P)in Eqs. (14)-(17) and (19)
= intrinsic viscosity (P) in Eqs. (12), (13). and (19)
= intrinsic viscosity at 50 wt % of the distribution
curves in Figure 28
= intrinsic viscosity at 95 wt % of the distribution
curves in Figure 28
= mold temperature (K) in Eq. (40)
= time constant (s) in Eqs. (24), (28). and (30)
= vertical taper factor in Eqs. (60).(66),and (69)
= lateral taper factor in Eqs. (63) and (66)
= value of time constant (s) at shear rate = 50 s-' in
Eqs. (33) and (34)
= long chain branching frequency in Eq. (6)
= dimensionless parameters in Eqs. (48) and
(52)-(54)
= taper factor in Eqs. (75) and (81)
= shape factors in Eqs. (57), (60).(63), (66).and
(69)
= polymer melt density (glcc) in Eq. (20)
= shear stress (dyn/cm2) in Eq. (25)
= special value of shear stress (dydcm') when
apparent viscosity is half the zero shear viscosity
given in Eq. (25)
= viscous heat dissipation (dyn/cm2 s) in Eq. (83)
= power input to calender roll (ergs) in Eq. (54)
= primary normal stress difference coefficient (dyn s2/
cm2) in Eq. (29)
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55
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VOL. 6,NO.1
 MELT FLOW INDEX. I

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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 )

A 125 0.325 0.46 6.50 0.3

B 125 2.160 3.04 43.25 1.97
C 150 2.160 3.04 43.25 1.97
D 190 0.325 0.46 6.50 0.3
E 190 2.160 3.04 43.25 1.97
F 190 21 .m 30.40 432.50 19.7
G 200 5.000 7.03 100.00 4.6
H 230 1.200 1.69 24.00 1.1
I 230 3.800 5.34 76.00 3.5
J 265 12.500 17.58 250.00 11.4
K 275 0.325 0.46 6.50 0.3
L 230 2. I 6 0 3.04 43.25 1.97
M 190 1.050 1.48 21 .OO 0.96
N 190 10.000 14.06 200.00 9.13
0 300 1.200 1.69 24.00 1.1
P 190 5.000 7.03 100.00 4.6
Q 235 1 ,000 1.41 20.05 0.91
R 235 2.160 3.04 43.25 1.97
S 235 5.00 7.03 100.00 4.6
T 250 2.160 3.04 43.25 1.97

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

ADVANCES IN POLYMER TECHNOLOGY 57

MELT FLOW INDEX. I

TABLE AIc
Test Temperature Summary
~~~~~

Test Temperature ("C) Condition

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

Diameter (0.3730 f 0.0003 in. (0.0825 f 0.0002 in.

= 9.474 f 0.007 mm) = 2.095 2 0.005 mm)
Length (0.250 f 0.005 in. (0.315 f 0.0008 in.
= 6.35 f 0.13 mm) = 8.00 f 0.02 mm)

58 VOL. 6,NO. 1