EFFECT OF OVERDRYING HYGROSCOPIC RESINS AND A TECHNOLOGICAL
SOLUTION FOR ITS PREVENTION.
Suhas Kulkarni
David Hart
Molding International and Engineering,
42136 Avenida Alvarado
Temecula, CA 92590
Abstract
Hygroscopic resins are dried before processing. Most
polymers are blended with low molecular weight
additives as heat stabilizers, processing aids and/or other
specialty additives. If the resin is dried for an extended
period of time, these additives tend to break down causing
deterioration properties. Moisture can play an important
role in the melt rheology. Experiments were done to study
this effect with the help of thermal analysis and
evaluation of physical properties. A technological
solution to prevent overdrying is presented.
Introduction
Additives are added to polymers to enhance their
properties for specific applications and/or to reduce their
cost. In volume, fillers such as glass and minerals are the
most widely used additives. Other additives include
plasticizers, lubricants, flame retardants, heat stabilizers,
colorants, blowing agents and biocides. Most of these are
added to the polymers in small percentages and are low
molecular weight compounds or oligomers. Details of
their chemical compositions and their specific
applications can be found in literature (1). The resin
supplied to the processor is a blend of the base polymer
and the additives. Most resins, especially those from
condensation polymers absorb moisture in between the
time they are manufactured and processed. Nylons,
acetals and polyesters are examples of such resins. The
presence of moisture during the processing of these
resins, as in injection molding or extrusion, can cause the
polymer to degrade resulting in the loss of properties.
Other effects are surface defects such as splay and voids
in the end product. Processing difficulties such as gassing
and foaming of the melt as in the case of nylons is
encountered. Therefore, the resin must be dried before it
is processed. Since the water molecules form a chemical
bond with the polymer, depending on the type of base
polymer, the resin is subjected to varying drying times
and temperatures. The resin manufacturer supplies this
data. Typical drying times are three to four hours.
It is typical in the molding industry to first load the resin
into the dryer and then complete the mold change. This
ensures that the resin is being dried during the setup
operation and no time is being wasted. If for some reason,
736 / ANTEC 2003
the mold was not setup in time, or the first shots from the
mold were not acceptable and mold had to be pulled out for
maintenance, the resin that is in the dryer is now being
subjected to the drying temperature for additional time.
During the authors’ experience as molders we have found
that subjecting the resin to long drying times led to
unacceptable parts. This was particularly seen with a
polyester resin where parts would become brittle and would
easily break with application of small forces. Parts that
normally looked black would look gray. In other cases,
discoloring would often occur with increasing drying times.
A natural or white resin would turn yellow. This was seen in
case of acetals and polyphenylene oxides. It was therefore
clear that there is a definite effect of excessive drying on the
end product. The above problems are also encountered if the
residence time of the resin inside the dryer during normal
operation is long. This can happen with large dryers fitted
on to small size machines. A solution to this problem is to
incorporate a electronic control mechanism in the drying
system that would automatically dry the resin for the
required amount of time and shut the dryer off if the
molding machine was not operational. If the molding
machine was operational then resin had to be loaded
continuously into the dryer and the dryer would be left
turned on. A level sensor would accurately control the level
of the plastic in the dryer so that the residence time in the
hopper equaled to the recommended drying time for the
particular resin.
Experimental:
Materials:
30% glass filled Poly (butylene terepthalate) (PBT)
15 % glass filled Nylon 66
Equipment:
JSW Molding Machine 32 mm screw, 74 gram shot size
Injection Mold supplied by MIE
Tup Impact Tester fabricated by MIE
Flexural Strength
Thermogravimetric Analyzer: Perkin Elmer TGA-7
Capillary Rheometer: Dynisco LCR-6000
 Procedures:
Drying of the resins: 10 kg of each resin was dried in a
dryer at their recommended drying temperatures. The
PBT was dried at 136 deg C and the Nylon was dried at
98 deg C. The dryer was equipped with a digital readout
and this was constantly monitored to check for any
failures in the equipment. The dew point was checked
with the help of the dew point meter. Resin samples for
the thermal analysis and rheological studies were
collected from the dryer at intervals of 4, 12, 24, 36, 48
hours. Each sample was stored in an airtight glass
container till the analysis was done.
Molding of the test specimens: Parts molded from an
existing production mold were used as test specimens.
Both resins were molded from the same mold. 50 kg of
the resin was loaded into the dryer and parts were then
molded at intervals of 4, 12, 24, 36, and 48 hours. The
drying and processing conditions were set at the
manufacturer’s recommended settings. The samples were
then stored in the Quality Lab at 23 deg C and 50 % RH.
Thermal Analysis: Thermogravimetric Analysis
(TGA) was performed at 10 deg C per minute in the
presence of Nitrogen. The temperature range was 30 deg
C to 760 deg C.
Capillary Rheometry - Shear Sweep: Shear Sweep
study for the PBT was performed from 102 sec-1 to 7000
sec-1 at 260 deg C. Shear Sweep study for the Nylon was
performed from 102 sec-1 to 7000 sec-1 at 277 deg C.
Capillary Rheometry - Thermal Degradation:
Thermal degradation study for the PBT was done at a
shear rate of 500 sec-1 at 260 deg C. The data was
collected at intervals of 3 minutes for 33 minutes.
Thermal degradation study for the Nylon was done at a
shear rate of 500 sec-1 at 277 deg C. The data was
collected at intervals of 3 minutes for 33 minutes.
Flexural Test: A fixture was fabricated at MIE for this
test. The specimen was clamped such that the force
would be applied in the center of the specimen simulating
a three point loading system. The equipment was limited
to display only the load at which failure would occur. The
data did not provide strain values at break nor did it
provide percentage strain at a given load or vice versa.
Drop Impact Test: A Drop Impact Tester was
fabricated. It consisted of a hollow tube clamped upright
on a sturdy base. Holes at intervals of 12.7 mm (0.5
inches) were drilled into the side of the tube to notice the
actual height of the tup before impact. The total weight of
the tup was 370 grams. The geometry of the tup where it
would impact the part had a radius for point contact. The
fixture used to clamp the parts for the flexural testing
mentioned above was also used for this impact test. The
part was clamped and then placed underneath the tube.
Care was taken to make sure that the part was clamped
consistently in the same spot and that the fixture was
placed in the same place for every test. This was done
with the help of mechanical stops. Impact testing was done
based on ASTM procedure D5628. A mark on the tup
indicated its height in the tube and the drop height and the
result were recorded. The mean failure energies and their
standard deviations were calculated as per the same ASTM
procedure. 30 parts were tested for each sample of resin.
Identification of Samples: The resins were identified as
follows. PBT-n and Nylon-n where n was the number of
hours the resin was dried. For example, PBT-4 was resin
dried for 4 hours and Nylon-48 was resin dried for 48 hours.
Results and Discussion:
PBT: The resin and the molded parts were tested with the
procedures mentioned above. During the molding process it
was seen that as the drying time increased, flash on the parts
increased indicating a drop in the viscosity of the melt.
However, there was no significant change in the actual
values, such as fill time, cushion value, screw recovery time
and so on. Considering the diameter of the screw (32 mm),
the observed increase in flash would not have reflected in
changes in cushion values.
TGA data is shown in Fig 1. The final residue left
behind was about 33% of the initial weight. Since the resin
was a 30 % glass filled material, most of this residue must
have been the glass. t1/2 is defined as the temperature at
which 50% of the weight loss occurs. Considering the
percentage of the residue remaining, 50% of the weight loss
occurs at around 420 deg C for PBT-4, 410 deg C for PBT-
12 and at around 475 deg C for the PBT-48. This indicates
that for the lower drying times, a weight loss occurred at
lower temperatures suggesting there must be a component in
the resin that decomposed at lower temperature leading to
an earlier loss in weight. This additive was decomposed
during the lengthy drying process and so the PBT–48 had a
t1/2 that was almost 55 deg C higher that PBT-4. Looking
closely at the numerical data and recharting it to closely
analyze the initial weight loss in the PBT, it can be seen that
the slope of the curve is higher for the PBT-4 indicating
sudden weight loss similar to those seen in low molecular
weight compounds and oligomers. After the initial
differences in the slopes of the curves, the lines then seem to
run parallel to each other suggesting the decomposition of
the base resin.
The Capillary Rheometry - Shear Sweep data is
shown in Fig 2. The data did not show any difference in the
rheology of the melt. This could suggest that the additive
that was lost during the drying process was not a processing
aid to lower viscosity for ease of processing. No other
conclusions could be made.
Capillary Rheometry - Thermal Degradation data is
shown in Fig. 3. The data showed a difference between the
two resins only at residence times of 9 minutes and above.
The PBT-48 showed a lower viscosity compared to the
PBT-4. This could have been because of the degradation of
the base resin lowering its molecular weight and thereby
ANTEC 2003 / 737
lowering its viscosity. This could be an indication that the
component lost during the excessive drying process could
have been a heat stabilizer. It is also interesting to note
that the viscosity curve almost flattens out past 9 minutes,
possibly suggesting that the polymer is completely
degraded and that it is the glass fibers now being carried
by the degraded resin and contributing to the viscosity.
PBT parts molded from this resin and with excessive
residence times have known to ‘crumble’ when a small
amount of forces was applied.
Flexural Testing of the parts did not show any
noticeable difference in the force required to break the
sample. The average breaking force was around 45 kg.
Since the equipment was limited to showing load values,
it was difficult to observe any other pertinent information
such as deflection at break or load at 5% strain. However
it was noticed that the break was an increasingly brittle
failure with increasing drying times.
Drop Impact Testing of the parts demonstrated a
clear difference between PBT-4 and PBT-48. This data is
shown in Fig. 7. As can be seen, the mean failure energy
reduced with the increase in drying time. The parts tend to
become more brittle. This could be either because of the
loss of an additive such as an impact modifier and/or it
could be because of the degradation of the resin. There
was a sharp drop in the mean failure energy between 12
and 36 hours of drying time. Before and after these times
the curve stayed relatively flat. Looking at this data,
drying times should be limited to 12 hours to retain the
material properties.
Preliminary data from tensile testing, not
mentioned in this study, has shown that parts molded
from over dried resin seem to have brittle failures. The
failure occurred at the weld line on the part as compared
to yielding in another section of the part molded from the
resin dried for 4 hours.
Nylon: In case of the Nylon, the studies were conducted
only at drying times of 4 hours and 48 hours. The resin
and the molded parts were tested with the procedures
mentioned above.
TGA data is shown in Fig 4. The resin was a
15% glass filled resin. The residue left behind was
approximately 17%. We can again be certain that most of
it was the glass that was left behind. The t1/2 values for
both the Nylon-4 and the Nylon-48 seemed to be around
470 deg C. The weight loss also started around the same
time and imitated each other. We can therefore infer that
there was no significant difference between the TGA
curves for the regularly dried and the overdried resin.
There was no noticeable loss of any additive.
The Capillary Rheometry - Shear Sweep data is
shown in Fig 5. It is interesting to note that the viscosity
for the Nylon-48 was higher than that for Nylon-4.
Khanna, et al (2) have noticed a similar increase in the
viscosity of nylons with increase in drying temperature
738 / ANTEC 2003
and time held constant. Similar studies by Pezzin and
Gechele (3) showed that the melt viscosity increased with
time for lower moisture contents. Khanna hypothesizes that
the increase in the viscosity could be because of the
following two reasons. (i) The moisture in the nylon acts as
a plasticizer for the melt, reducing its viscosity. With higher
drying temperatures, loss of moisture leads to increase in
viscosity. (ii) The melt equilibrium is represented by a
characteristic equilibrium constant, Kcond. If excess H2O is
added to the melt in equilibrium, the reaction will go in the
direction of the reactants, (i.e. degradation) while the
reverse (i.e. polycondensation) should occur if H2O is
removed from the equilibrium melt. In the present study, the
drying temperature was held constant (98 deg C) and the
drying time was varied. Considering the theories put forth
by Khanna, and the similar results obtained here, the net
result of the increase in drying time must be the same as the
increase in drying temperature. The loss of moisture
between drying times of 4 hours and 48 hours must have
contributed to the increase in viscosity of the melt. The
evidence of this was also seen during the molding of the
parts. A feature that was 48 mm long with an average height
of 3.5 mm and width of 6mm was almost completely filled
(99%) during the injection phase of the molding cycle when
molding with Nylon-4. When Nylon-48 was used, this
feature was only filled to 30 mm, which was only about
62% of the original flow length. Photographs of this are
shown in Fig. 8.
Capillary Rheometry - Thermal Degradation data is
shown in Fig. 6. The two resins do not seem to differ in
viscosity at and above the 12 minute residence time. At the
6 minute residence time, the Nylon-48 has a higher viscosity
compared to the Nyon-4. The same reasoning as in the
above section can be applied here. Once past the 6 minute
interval, the resin probably begins to degrade and the final
viscosity of the two resins match each other.
Flexural Testing of the parts did not show any
noticeable difference in the force required to break the
sample. The average breaking force was around 50 kg.
Since the equipment was limited to showing load values, it
was difficult to observe any other pertinent information such
as deflection at break or load at 5% strain.
Drop Impact Testing of the parts demonstrated no
significant difference between the Nylon-4 and the Nylon-
48. The average Mean Failure Energy for the two samples
was 0.774 Joules. Long drying times did not seem to effect
the Drop Impact Strength of the resin. The results are
included in Fig. 7.
Solution for Overdrying:
A programmable controller (patent pending) that
would control the drying process of the resin was
developed. The logic behind the controller is presented in
the flow chart below. Initially the controller would set the
drying time and temperature. Based on shot weight of the
 mold, a resin level sensor would be set such that the
residence time of the resin in the hopper exceeds the
recommended drying time by an hour to two hours. Once
the set drying time has elapsed, the controller looks for a
signal from the machine indicating that the machine is
operational and molding parts. Such a signal can be
picked up from screw rotation or mold open close. If the
controller receives this signal it will maintain the dryer
temperature. If it does not receive the signal, indicating
that the machine is not operational, the controller will
start to drop the drying temperature by a preset value, for
example 50 deg. If in a preset time, for example 15
minutes, the controller does not get the machine operation
signal, it will further drop the temperature down by
another step. It will do so till it reaches a temperature of
100 deg. At this time, dry air will be circulating in the
hopper and keep the resin dry. As soon as the machine is
ready for operation and the controller gets this signal, the
temperature of the hopper will begin to rise to the desired
drying temperature in preset steps of temperature and
Set Level Sensor
Set Drying Temperature = T
Set Drying Time = H
Set Run Time = 0
NO
Continue Drying
Is run time≥ H
YES
Start Molding
Continue Molding
Has the machine
operational in last 10 min?
NO
Drop Dryer Temperature by 50 deg
NO Is Hopper Temperature = 100 deg
YES
Maintain Hopper Temperature to 100
Flow Chart for the logic behind controller. (Patent Pending)
1000
App. Shear Viscosity (Pa-sec)
time. During normal operation if the molding operation is
interrupted, then the controller will follow the same logic
described above and begins to drop the dryer temperature.
Such a control mechanism will ensure that the resin will
never see excessive drying times and prevent it from
overdrying.
Conclusions:
It is evident from the above discussion that it is
important to control the drying process of the resin.
Overdrying can result is a loss of physical properties as seen
in case of the PBT. The impact strength reduced with
increasing drying times. There was no significant change in
the flexural properties or the rheology of the PBT. Thermal
analysis showed that PBT-48 had t1/2 value that was almost
55 deg C higher than that of PBT-4 the In case of the Nylon,
there was no change in the impact strength and flexural
strength. Thermal analysis data was almost identical.
However, there was a change in the rheology of the resin.
Since the rheology changes, and the viscosity is higher for
longer drying times, it is almost certain that there could be
an impact on the weld line strength of parts. Other
properties affected by flow, such as surface finish,
polymer/filler ratio could also be impacted by long drying
times. Secondary operations such as ultrasonic welding and
joining require a certain amount of polymer to be present on
the surface to have successful bonding. These processes
could be impacted. Therefore in case of Nylons, presence of
moisture below a certain weight content is important. There
are other properties and resins not studied here that can be
affected. It will be important and beneficial to understand
the impact of long drying times on these resins.
The solution presented will eliminate the over
YES drying problem maintaining the resin properties and
characteristics. It will also provide potential energy savings.
References:
1. J.A.Brydson, Plastics Materials, Butterworth
HeinemannLtd, Oxford.
2. Y.P.Khanna, et al, Polymer Engineering and Science,
Vol. 36 (13), p1745, (July 15, 1996)
3. G. Pezzin and G.B. Gechele, J. Appl. Polymer Sci., Vol
8, p 2195, (1964)
110
PBT-4
100
PBT-4 PBT-12
90
PBT-48 PBT-48

80
70
Weight %

60
50
100
40
30
20
10
0
10 0 100 200 300 400 500 600 700 800
100 1000 10000
Temperature deg C
Apparent Shear Rate (1/sec)
Fig. 2: Capillary Shear Data at 260 deg C for PBT Fig. 1: TGA Curves for PBT

ANTEC 2003 / 739

 110
NYLON-4
100
NYLON-48
1000 90
PBT-4
80
PBT-48
App. Shear Viscosity (Pa-sec)

70

Weight %
100
60

50
40

30
10
20

10

0
1
0 100 200 300 400 500 600 700 800
0 5 10 15 20 25 30 35 Temperature deg C
Time (mins)
Fig. 3: Thermal Degradation Data for PBT at 260 deg C,500 per sec Fig. 4: TGA Curves for Nylon

1000 1000
NYLON-4 NYLON-4
App. Shear Viscosity (Pa-sec)

NYLON-48 NYLON-48
App. Shear Viscosity (Pa-sec)

100

100

10

1
10
100 1000 10000 0 5 10 15 20 25 30 35
Apparent Shear Rate (1/sec) Time (mins)
Fig. 5:Capillary Shear Data at 277 deg C for Nylon Fig. 6: Thermal Degradation Data for NYLON at 277 deg C, 500 per sec

1.10
PBT
Mean Failure Energy (Joules)

1.05
NYLON
1.00

0.95

0.90

0.85

0.80
1 .1 0

1 .0 5

1 . 00

0. 9 5

0.75 0 .9 0

0. 8 5

0 .8 0

0 4 8 12 16 20 24 28 32 36 40 44 48 52 0. 7 5

Drying Time (Hours)

Fig. 7: Mean Failure Engergy vs Drying Time Fig. 8: Parts molded with identical processes from different resins.

740 / ANTEC 2003