Polymer Degradation and Stability 28 (1990) 67-75

Influence of Injection Rate and Melt Temperature on

Polypropylene during Injection Moulding without
Packing*

J. Billiani & E. F l e i s c h m a n n

Institut fiir Chemische und Physikalische Technologie der Kunststoffe,

Montanuniversitfit Leoben, Franz-Josef-Strage 18, 8700 Leoben, Austria

(Received 11 May 1989; accepted 27 May 1989)

ABSTRACT

The molecular degradation of isotactic polypropylene, which occurs during

injection moulding without packing, has been studied. Particular attention
was given to the effects of injection rate and melt temperature on the
molecular weight distribution of the polypropylene. Selected layers of the
plates produced were analyzed to determine changes in the molecular weight
averages by gel permeation chromatography. Molecular weight distributions
were obtained for surface layer and core. Serious degradation ( - 3 0 % in
weight average) is caused mainly by high melt temperatures. The effect of
high shear rates and high shear stresses was found to be less. The result of
thermal and mechanical measurements are correlated with the polymer
degradation especially as measured by changes in the weight average
molecular weight.

INTRODUCTION

There have been few publications on the subject of the thermomechanical

degradation of polypropylene during injection moulding using the
conditions typically encountered in industrial processing, x'2 Generally,
correlations between polymer degradation and mechanical properties are
reported. Other publications have been concerned with degradation
phenomena due to repeated injection moulding 3 and repeated extrusion, 4- 6
or with environmental degradation. 6'7
* Dedicated to Professor J. Schurz on the occasion of his 65th birthday.
67
Polymer Degradation and Stability 0141-3910/90/$03"50 © 1990 Elsevier SciencePublishers
Ltd, England. Printed in Great Britain
68 J. Billiani, E. Fleischmann

In this investigation, results are presented on degradation during injection

moulding without packing, using industrial processing conditions. In this
processing method, especially high injection rates and injection pressures are
used. Thus, significant degradation effects are to be expected. These are
investigated in various layers of moulded plates by means of gel permeation
chromatography (GPC), differential scanning calorimetry (DSC) and tensile
impact tests.

EXPERIMENTAL

Materials and sample preparation

The material used was a commercial isotactic polypropylene, DAPLEN

KS 10 (melt flow index (230°C/21.19N) = 8.0 g/10 min, M w = 290 000 g/mol,
M w / M , = 5.7) produced by Petrochemie Danubia, Austria. Rectangular
plates (230 × 70 x 2 m m 3) with film gate were moulded without packing
using an injection moulding machine, model ES 250 manufactured by
ENGEL, Austria. The flow front velocities, the injection pressures, and the
processing temperatures used to prepare the plates are detailed in Table 1.
Furthermore, calculations were made to estimate the magnitude of wall
shear stress, Zw, and shear rate, 7, in the cavity. The values of Zw and
calculated at the end of the filling phase are given in Table 1. By the use of a
three-plates tool the mould cavity was mechanically sealed in the gate. In
principle, the skin-core structure characteristic of injection moulded
polypropylene articles consists of two layers; namely, a highly oriented
surface layer, and a typically spherulitic core. a Using a polarizing
microscope (Leitz, West Germany) the thicknesses of both these layers were

TABLE 1
Injection Moulding Conditions for the Plates of PP-KS 10 (TM Melt
Temperature, TW Wall Temperature, VF Flow Front Velocity, Pim.x
Maximum Pressure in the Cavity; 7m.x Maximum Shear Rate, rw Wall Shear
Stress, cf Text)

Sample no. TM/TW VF P/max Ymax ~'w

[°C/°C] [mm/s] [bar] [l/s] IN/mini

1 100 1 559 400 198000

2 200/20 800 1 627 3 800 197 000
3 2 200 1 478 11 900 209 000
4 100 1 544 400 112 000
5 280/50 800 1 464 3 500 123 000
6 2200 1472 9400 141000
 Influence of injection rate and melt temperature on polypropylene 69

determined at a distance of 100mm from the gate. Microtome sections

(25 mg) of both the layers were removed from the plates at a distance of
100 mm from the gate, and these specimens were used for GPC- and DSC-
measurements.

Gel permeationchromatography(GPC)

Molecular weight distribution and molecular weight averages were

determined using a high-temperature GPC system consisting of solvent
delivery pump (Model 560, Waters Associates, USA), sample injector and
column oven (Knauer, FRG) and an IR detector (DuPont Company, USA).
Three columns connected in series--GMH6--HT 30cm (Toyo Soda,
Japan), PS40000 and PS4 25 cm (Merck, FRG)--were employed with 1,2,4-
Trichlorobenzene (TCB) at 135°C as the mobile phase. The flow rate was
0.59ml/min. Polymer concentration was measured by IR using the
absorption of the CH 2 - groups at 3.41/~m.
The system was calibrated with a series of narrow polystyrene standards
(Polymer Laboratories Inc., USA) in the range M = 1250 to 7.7 x 107 g/mol
and a broad polyethylene standard (NBS 1475 HDPE, 9 National Bureau of
Standards, USA) using the integral calibration method.l° Calibration data
were converted to polypropylene by universal calibration using the
following Mark-Houwink constants, K = 1.9 x 10-4dl/g, 1.9 x 10-4dl/g,
and a = 0"690, 0.725 for polystyrene ~ and polypropylene 12, respectively.
It may be difficult to obtain molecular disperse solutions of polyolefins.
The thermal stability of these solutions and the reproducibility of data
remain a subject of research. 13'a4 Polypropylene solutions were heated
under nitrogen at 170°C for 90min and stirred occasionally. The
preparation of polystyrene calibration samples involved dissolution at
ambient temperature overnight in TCB and short heating periods (10 min,
140°C) in a nitrogen atmosphere. Sample concentrations were in the range
0.2~.4mg/ml and 0.5mg/ml of stabilizer (Irganox 1010, Ciba-Geigy,
Switzerland) was added to the solvent before dissolution of the sample to
prevent oxidation. The stabilizer peak was used as an internal standard for
flow rate monitoring. The sample solutions (loop volume = 0.305 ml) were
injected without filtration.
During the sample run on the GPC system, the analog data from the
concentration detector and the system pressure were digitized and collected
by means of a personal computer equipped with a commercially available
analog/digital converter device of 5/~V resolution (model DASCON,
Metrabyte, USA). Software for acquisition and processing of GPC data was
developed in our laboratory. Due to the broad distribution of the
polypropylene samples no axial dispersion correction was applied to the
70 J. Billiani, E. Fleischmann

chromatograms. 15 A critical examination and further development of the

G P C interpretation used are in progress. ~6

Differential Scanning Calorimetry (DSC)

A DSCo7 apparatus (Perkin Elmer, USA) was used to determine the melting
point. Samples (3-5 mg) were sealed in a standard aluminium pan and
analyzed in a nitrogen atmosphere at 10 K/min scanning rate. Temperature
and heat of fusion calibrations were carried out by using indium and zinc as
references. The peak temperatures were taken as the melting temperatures Tm.

Mechanical measurements

A degradation effect is especially expressed in the impact load properties.

For this reason tensile impact tests according to DIN 53448 were carried out
at ambient temperature. The specimens were taken from the plates in the
direction of flow at a distance of 100 m m from the gate.

Results and Discussion

The investigation of small changes in the molecular weight distribution

(MWD) of polymers requires careful interpretation of the GPC results. In
some cases shear degradation has been reported to occur within the
chromatographic columns. 17 - 19 Therefore, the raw material was chromato-
graphed several times to establish the precision of the GPC separation
system. Variations of flow rate were derived from the retention volume of
the stabilizer peak and proved a standard deviation of _+0.12%. In most
cases, in-column degradation is correlated with a perceptible pressure rise
during the passage of the polymer solution through the columns. 19 In our
measurements, no pressure rise was observed during the GPC runs.
The individual chromatograms were normalized with respect to the area
and averaged (Fig. 1). The area of the standard deviation curve was found to
be less than 6% of the whole chromatogram area. This averaged
chromatogram was used to calculate the molecular weight distribution of
the raw material. The average molecular weights were determined as weight
average M w = 323 000 g/mol and number average Mn = 46 000 g/mol. The
standard deviation from eight runs was _+4% for Mw and -+8% for Mn.
The results for the surface zone and core zone are given in Table 2. For
samples 1-3 (melt temperature 200°C) the variation of the flow front velocity
from 100 mm/s to 2200 mm/s yields practically the same average molecular
weights, for both the core zone and the surface layer. It may be noted,
 Influence o f injection rate and melt temperature on polypropylene 71

40.0

i i

20.0
>

iO.O

0.0 '
14.0 18.0 tB.O 20.0 22.0
Volume [roll

Fig. 1. Reproducibility of G P C measurements by averaging eight independent runs. ( )

averaged normalized chromatogram, (. . . . . ) standard deviation, (. . . . . ) standard
deviation/chromatogram height (relative error).

however, that the weight average decreases significantly compared with the
raw material.
At the melt temperature of 280°C (samples 4-6) the weight average
decreases rapidly with rising flow front velocity whereas no significant
changes in the number average molecular weight and the melting point are
noted. Again it is observed that there are no differences in the results for the
inner and surface zones.
TABLE 2
Influence of the Processing Conditions on Mw, M., and Tm of
Surface Layer (a) and Core Zone (b)

Sample no. M w[g/mol] M. [g/mol] T,, [° C]

× 10 -3 × 10 -3

a b a b a b

1 287 290 37 42 164 163

2 283 282 37 34 164 163
3 289 270 36 40 164 164
4 270 263 45 43 164 164
5 257 260 39 39 164 164
6 242 240 40 40 163 163
 72 J. Billiani, E. Fleischmann

70.0

mlo-~

60.0

50.0

40.0
z

• 30.0

20.0

t0.0

0.0
3.0 4.0 5.0 5.0 7.0
log 14
(a)

50.0

wt°'s ~ i

25.0

• • • • • . . . . . . . .

g
o o
: ~--.~''~..----- ....
"-, .......
" . . ./~..

e-i

-25°( " ' ..... " " ' ' " " ' ..... " " " " ~ ~ " - - - ' ~

-50.¢ i i I i i i i I i i i

3.0 4.0 5.0 6.0 7.0

log 14
(b)
Fig. 2. (a) Molecular weight distribution of the raw material ( ), sample 3 (----), and
sample 6 (----). (b) Differences in the molecular weight distribution between the raw material
and samples 3 ( - - - - ) and 6 ( ) compared with the error band (.... ).
 Influence of injection rate and melt temperature on polypropylene 73

At a constant flow front velocity, the rise of the melt temperature from
200°C to 280°C leads to a significant decrease in the weight average. On the
other hand, the influence of the flow front velocity on Mw is exhibited only at
the high melt temperature. Hence the temperature seems to have a greater
effect on degradation processes than the flow front velocity. 6 Obviously, the
two effects cannot be differentiated from each other. Comparison of the
results concerning the core and the surface layer indicates that a separate
discussion on each is not necessary. Therefore the results for the surface
layer and core are averaged for the purposes of the following discussion.
From the results for various processing conditions (cf Table 1), a
significant change in the molecular weight distribution of the specimens was
observed. Figure 2(a) shows the effect of processing on the distribution
function of the virgin granulate. The high molecular weight tail of the
distribution is reduced in all cases. To quantify the changes, the reference
distribution of the virgin granulate was subtracted from the average
distributions of the individual specimens (Fig. 2(b)). In the range of M = 5 x
105 to M = 5 x 106 a weight loss of 2"5-4"5% was observed. The lost mass
appears in the medium molecular weight range of the distribution. Whereas
the extent of the degradation process is rather low in this case in comparison
to other approaches, the effects are significant in comparison with the
precision of the measurement. The changes of the M W D behave as predicted
from a midpoint scission mechanism of degradation.
Tensile impact strength tests were carried out to obtain correlations
between degradation and mechanical properties. Table 3 shows the impact
strengths compared with averaged values of weight average, number
average and melting point. These values are also given for the virgin
granulate.

TABLE 3
The Effect of Processing Parameters on Weight Average and Number Average
Molecular Weight, Melting Point T,, and Tensile Impact Strength az, (DIN
53448, Five Samples for Each Measurement; the Scattering is + 11%)

Sample no. Mw [g/mol] M. [g/moll T,. az.

X 10 -3 × 10 -3 ['~C] [kpcm/cm z]

granulate 323 46 163.5 --

1 288.5 39'5 163.5 271
2 282.5 35'5 163.5 --
3 279-5 38 164 196
4 266'5 44 164 177
5 258.5 39 163.5 --
6 241 40 163 149
74 J. Billiani, E. Fleischmann

The impact strength decreases with decreasing Mw. But it must be taken
into consideration that different processing conditions cause different
layered structures and, consequently, different mechanical behavior. Thus
molecular orientation usually increases impact strength if the impacting
force is parallel to the chain orientation. 2° The orientation decreases as melt
temperature and/or flow front velocity increase. 21 The samples involved in
this work have already been the subject of optical and morphological
investigations.22 The effects of polymer structure and degradation on the
impact strength cannot be clearly differentiated.
The melting points show no changes due to degradation. So it can be
assumed that the temperature ranges in which crystallization occurs are not
shifted by the decrease in Mw.2

CONCLUSIONS

In this study, various layers of polypropylene plates injection moulded

without packing were investigated for the first time by GPC measurements.
The experiments were performed on plates moulded with very high injection
rates and pressures of about 1500 bar. As expected, the degradation effect
due to processing is significantly expressed by the weight average molecular
weight. However, the number average molecular weight does not change
within the precision of the measurements. Thus injection moulding without
packing causes narrowing of the molecular weight distribution. Whereas the
shear rates for samples 3 and 6 are of the same order, only sample 6 is
significantly degraded. Hence degradation is caused by oxidative chain
scission processes due to the high melt temperatures.
The impact strength strongly decreases both with increasing melt
temperature and flow front velocity. The surface layer and the spherulitic
core cannot be differentiated with respect to molecular weight distribution
and melting temperature. Therefore it seems likely that the degradation
processes take place in the sprue and plasticizing system.

ACKNOWLEDGEMENTS

The authors are very much indebted to the Austrian 'Fonds zur F6rderung
der wissenschaftlichen Forschung' for sponsoring this work in the course of
a national research program on injection moulded articles (projects S 3305
and S 3307). Thanks are due to Maschinenfabrik Engel KG for assistance in
the preparation of the plates and to PCD Ges.m.b.H. for supplying the test
material. Last, but not least, the cooperation of M. Sabernik is very much
appreciated.
 Influence of injection rate and melt temperature on polypropylene 75

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