Thermochimica Acta 672 (2019) 150–156

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Determination of moisture gradients in polyamide 6 using StepScan DSC T

A. Sambale , M. Kurkowski, M. Stommel
⁎

TU Dortmund University, Chair of Plastics Technology, Leonard-Euler Str. 5, D - 44227, Dortmund, Germany

ARTICLE INFO ABSTRACT

Keywords: Polyamides are known to absorb and desorb water to establish an equilibrium with their environment. Water
Polyamide uptake by diffusion leads to a drastic reduction in the strength and stiffness of the material, which is referred as
Water-induced plasticizing effect the water-induced plasticizing effect. This effect leads to a shift of the glass transition region towards lower
StepScan DSC temperatures what can be determined by differential scanning calorimetry (DSC). However, a determination of
the glass transition temperature Tg is not accurate in samples with inhomogeneous moisture distribution before
an equilibrium is reached by diffusion and Tg is superimposed by water-specific effects. It is shown that the glass
transition can be measured by StepScan DSC even with inhomogeneous moisture distribution within the sample.
In addition, a method is developed and validated which uses the low thermal conductivity and the shift of Tg to
detect a water-saturated sample boundary layer in inhomogeneously conditioned PA 6 samples.

1. Introduction
Polyamide 6 (PA 6) is a linear polycondensate which is one of the
most important engineering thermoplastics due to its high strength and
stiffness as well as good chemical resistance. As a versatile technical
material, PA 6 undergoes constant change due to the humidity of the
environmental air. Water can be absorbed from the ambient air because
of the hygroscopic properties of the material and it can be released at
low surrounding humidities. This is caused by the chemical structure of
the material: The polar amide groups in the molecular chains attract
polar liquids such as water, which form hydrogen bonds between the
amide groups and which cause the material to swell due to the in-
creased space required by the water molecules [1–4]. This diffusion of
water molecules into the material is mainly dependent on temperature
and time. The exchange of water with the environment causes unsteady
conditions and locally varying moisture concentrations in the material
until PA 6 reaches an equilibrium with its environment [4–6].
The water absorbed by the material reduces the glass transition
temperature Tg . This fact significantly influences the mechanical prop-
erties of PA 6 and is of considerable technical importance: The water
molecules bound between the molecular chains facilitate the sliding of
the chains at mechanical load by increasing the free volume in the chain
gaps [3; 4]. As the water content increases, stiffness and strength de-
crease, while toughness increases. In literature the so-called water-in-
duced plasticizing effect is mentioned, which has been mechanically
characterized by different methods [7–15]. In addition, the thermo-
mechanical properties are influenced by the presence of water, which
manifests itself in the shift of the glass transition temperature Tg with
increasing moisture content to lower temperatures. This can be de-
termined both by thermomechanical measurements using DTMA and by
thermal analysis using DSC [4,11,16–19]. The glass transition tem-
perature of PA 6 shifts from about 60 °C for dry material to about
−25 °C for material that is completely saturated with water [9]. The
glass transition temperature Tg describes the temperature range at
which energy-elastic material behavior changes to entropy-elastic ma-
terial behavior in the amorphous part of the plastic by enabling a co-
operative chain segment mobility [20]. The determination of the glass
transition range is defined in DIN EN ISO 11357-1 and described with
the aid of the initial temperature (Ti, g ), half-step height (T 1 2 , g ) and the
final temperature (Tf , g ) of the glass transition [21,22].
Thermal analysis of the glass transition can be performed using
differential scanning calorimetry (DSC). The value of Tg with dynamic
DSC measurements at constant heating rate depends on the heating rate
[23]. Tg shifts with increasing heating rate to higher temperatures. The
heating rate dependence is particularly pronounced with plastics
compared to metals, since the temperature within the sample is in-
homogeneous due to the lower thermal conductivity of the plastic. In
addition, Tg can be superimposed by other effects such as water loss or
relaxation [20].
In literature, the determination of Tg is usually based on a homo-
geneous moisture content and thus on samples that are in equilibrium
with the ambient air. However, this condition cannot be assumed in
practical application [14]. During their use, technical components are
usually exposed to considerable variations in environmental

⁎
Corresponding author.
E-mail address: anna.sambale@tu-dortmund.de (A. Sambale).

https://doi.org/10.1016/j.tca.2018.12.011
Received 24 July 2018; Received in revised form 9 December 2018; Accepted 11 December 2018
Available online 12 December 2018
0040-6031/ © 2018 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
A. Sambale et al.
temperatures and moistures. The temporally changing moisture con-
tents in the environment lead to unsteady conditions in the material
due to desorption and thus to locally different moisture contents, which
cause a formation of boundary layers with significant moisture gra-
dients [17,24–26]. This suggests that the water-induced plasticizing
effect also leads to the development of significantly different thermo-
mechanical properties locally. Therefore, the aim of this work is to
determine the glass transition temperature of PA 6 samples with
homogeneous and inhomogeneous moisture distribution, which is the
basis for the development of a method for determining a moisture
gradient from the sample boundary layer.
2. Materials and methods
2.1. Sample preparation
An unreinforced PA 6 (Durethan B 31 SK, Lanxess AG, Germany) is
used for the experiments. Cube-shaped specimens (2 mm edge length)
with a mass of 10 ± 1 mg are taken from the center of injection-
molded specimens (80 mm x 4 mm x 2 mm). Until the samples are ex-
tracted, the specimens are stored in drying granules. After extraction,
the samples are dried for 20 h in an oven (Heraeus Holding GmbH,
Germany) at 60 °C and then annealed at 150 °C for 2 h. This ensures that
all samples are dry and in the same (aging) state and that any post-
crystallization is finished at the beginning of the test. After annealing,
the samples are dried for 96 h in a vacuum cell in the oven at 20 mBar
and 60 °C until they reach a constant weight. Immediately after vacuum
drying, the dry mass of the samples is determined. The samples are then
stored at 23 °C in an airtight aluminium bag, which is additionally
vacuum-sealed in a plastic bag. This ensures that the absorption of
humidity does not distort the initial state of the samples before con-
ditioning.
2.2. Sample conditioning
Immediately before the tests, the dry samples are conditioned to a
defined state at 70 ± 1 °C in an Emmi 40 water bath (EMAG AG,
Germany) and then weighed. The integral mass fraction of the absorbed
water c is determined according to DIN EN ISO 62 using the initial
weight m 0 of the sample after vacuum drying and the weight of the
sample after water absorption m1 with the following formula [27]:
m1 m0
c= 100 [%]
m0 (1)
The integral moisture content can be adjusted by means of storage
time in a water bath. This sample conditioning results in a moisture
gradient which is formed between the saturated boundary layer and the
dry sample core. Samples with inhomogeneous moisture distribution
are thermally analyzed immediately after conditioning. If these samples
are removed from the water bath after a defined time and diffusion of
the water out of the sample is inhibited, a homogeneous moisture dis-
tribution within the sample is attained. For this purpose, the samples
are stored for 14 days at 23 °C in a medium-proof aluminium bag which
is vacuum-sealed in a plastic bag. After removal from storage, the
sample mass m1 is determined again immediately before the measure-
ment and the moisture content c of the sample is calculated from this
mass. The completely saturated samples are conditioned in a water bath
at 23 °C to a constant weight.
2.3. Analysis methods
2.3.1. Development of a method to determine moisture gradients
The StepScan DSC method is a special form of differential scanning
calorimetry whose measuring principle is described in literature
[28,29]. In a StepScan DSC measurement the sample is heated step by
step and after each temperature step the temperature is kept constant
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until the sample is in thermodynamic equilibrium. The method uses two
criteria which determine the reaching of the thermodynamic equili-
brium via the change of the heat flow or determine the maximum time
of the isothermal step. When one of the two criteria is reached, the next
temperature step is initiated. With StepScan DSC it is also possible to
separate fast, thermodynamic effects such as the glass transition from
slow, kinetic effects such as water loss through desorption, relaxation or
crystallization [29]. The specific heat capacity cp and the value of an
isokinetic Baseline (IsoK) are determined for each temperature step. A
baseline correction is performed using an empty pan to ensure accurate
determination of cp and IsoK. Each IsoK value is defined by the end
point of the corresponding isothermal step where the sample is in the
thermodynamical equilibrium. Kinetic effects such as relaxation, crys-
tallization or water loss can be detected on the resulting IsoK tem-
perature diagram. To calculate the cp values, the start and end points of
the measurement are aligned with the empty pan-baseline for each
temperature step and the resulting difference area is determined. This
area indicates the amount of heat required for the respective tem-
perature increase. By dividing the sample mass and the temperature
step height, cp is determined for the corresponding temperature step.
The glass transition temperature can be determined on the cp -curve
calculated in this method. [28,29]
If the heat flow is integrated over the entire temperature step in the
time domain, this integral determines the required heat flow for heating
the entire sample. If not the entire temperature step, but the integral
curve is determined within one temperature step, the required heat
quantity can thus be calculated depending on the heat penetration
depth (see Fig. 1). In the following, the values for the time intervals of
the integral curve are named time steps and the evaluation method for a
performed StepScan DSC is referred to as Time-Step Evaluation.
The Time Step Evaluation method is based on a StepScan DSC
measurement consisting of a high heating rate at the beginning of each
temperature step and a temperature holding phase afterwards until a
thermodynamical equilibrium is reached. A high heating rate leads to a
fast temperature change of the measuring cell of the DSC and therefore
to a fast reaching of the target temperature of the temperature step. Due
to the comparatively low thermal conductivity of the plastic compared
to the metal material of the measuring cell, a maximum temperature
difference between the plastic and the measuring cell is reached at the
beginning of the temperature step. The heat flow penetrating into the
sample at the beginning of the measurement is therefore maximized.
When penetrating the boundary layer of the sample, the heat flow
signal is thus maximum. Therefore, the high heating rate optimizes the
quality of the measurement for penetration into the sample boundary
layer. Preliminary tests with heating rates of 1 K min , 60 K min , 120 K min
and 250 K min have shown that 250 K min delivers best results concerning
Fig. 1. Schematic representation of the evaluation method for one temperature
step.
A. Sambale et al.
the measuring of a sample boundary layer. The resolution of the sample
boundary layer can be optimized by taking advantage of the low
thermal conductivity of the plastic by low temperature step heights. In
preliminary tests, a step height of 1 K step proved to be a good ratio be-
tween resolution and required measuring time.
The validation of the Time Step Evaluation method is carried out
with the help of the water absorption of PA 6. It is known from the
literature that the glass transition temperature decreases with in-
creasing moisture content. A boundary layer with a higher moisture
content should therefore have a lower Tg than the dry core of a sample.
2.3.2. Thermogravimetric analysis
The aim of this test is to investigate a possible mass change by re-
drying the samples during the DSC measurements. For this purpose, the
mass loss of samples with homogeneous and inhomogeneous moisture
distribution based on the measurement parameters of DSC measure-
ment series 1 is investigated. The samples are isothermally kept at 30 °C
for 3 min directly after conditioning and then heated to 100 °C at
20 K min in a TGA 4000 (PerkinElmer Inc., USA). The measurement is
performed in a nitrogen atmosphere (20 ml min ). A baseline without
sample is subtracted for the evaluation.
2.3.3. DSC analysis
All DSC measurements are performed with a DSC 8500 with
Intracooler 2 (PerkinElmer Inc., USA). The purge gas is nitrogen with a
flow rate of 20 ml min . Samples are examined in aluminum pans without
lids (Standard Alum Pan, PerkinElmer Inc., USA). Before each measure-
ment series, a baseline without sample is measured and subtracted from
the measurement in the evaluation. Two series of measurements are
carried out on samples with homogeneous and inhomogeneous
moisture distribution:
2.3.3.1. Measurement series 1 (conventional method). The aim of these
measurements is the conventional determination of Tg in samples with
homogeneous and inhomogeneous moisture distribution and variation
of the overall moisture content. The conditioned samples are deposited
in the DSC measuring cell at 30 °C and immediately cooled down to
-50 °C. After reaching the temperature, the samples are kept isothermal
for 3 min to ensure a homogeneous sample temperature. The samples
are then heated to 100 °C at 20 K min and then maintained at this
temperature for 1 min. Tg is determined using the half-step height
method [22].
2.3.3.2. Measurement series 2 (StepScan DSC method). The aim of these
measurements is to determine Tg in samples with homogeneous and
inhomogeneous moisture distribution while varying the overall
moisture content using the StepScan DSC method in order to compare
these with conventionally measured Tg values. In addition, a boundary
layer examination is to be carried out using the developed Time Step
Evaluation method. The conditioned samples are deposited in the DSC
at 30 °C and immediately cooled down to -50 °C. After a three-minute
isothermal holding phase, the StepScan DSC measurement starts. The
sample is heated to 100 °C in 1 K step at a heating rate of 250 K min . The
criterion is set to ± 0.001 mW. The maximum time is 2 min step . The time
is chosen so that the criterion always initiates the next step. The sample
is then isothermally held at 100 °C for 1 min. Tg is evaluated using the
half-step height method on the calculated cp -curve. In addition, Tg is
determined at different time steps in the temperature step using the
developed method. For this examination, the starting points of each
step of the empty pan baseline and sample measurement are aligned
and the baseline is then subtracted from the measurement. The
calculated data are displayed as time steps of the integral curve and
divided at any time by the sample mass and temperature step height to
determine the heat capacity for each temperature step. It should be
noted that the calculated values do not represent the specific cp value
until the thermodynamic equilibrium is reached. In earlier time steps, cp
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Thermochimica Acta 672 (2019) 150–156
Fig. 2. TGA investigations on homogeneous and inhomogeneous samples with
different moisture contents.
is reduced because not all the heat required is used for the calculation,
but the entire sample mass. However, since the weight is divided by a
constant value, a glass transition temperature range can still be
determined using the cp -curves.
3. Results & discussion
Fig. 2 shows the results of the thermogravimetric analysis mea-
surements (TGA) carried out on homogeneous and inhomogeneous
moisture distributions in samples at different moisture contents. The
TGA measurements show that a dry sample shows no weight loss in the
range of 30 to 100 °C. In the case of dry samples, water loss is therefore
not expected to affect the DSC measurements over the measurement
period. Comparing the homogeneous and the inhomogeneous samples
with respectively 1.9% moisture content, the sample with homogeneous
moisture distribution loses significantly less water (0.09%) than the
sample with inhomogeneous moisture distribution. This in-
homogeneous sample exhibits a mass loss of 0.40% to 100 °C, which is
about four times the water loss of the homogeneous sample. This can be
explained by the maximum saturated boundary layer, which gives a
greater difference in water concentration of the boundary layer to the
measuring atmosphere compared to a sample with homogeneous
moisture distribution. In addition, less water is released into the mea-
suring atmosphere by the homogeneous samples, as the water takes
longer to reach the sample surface from the bulk material due to dif-
fusion processes. The course of the water loss of the sample with 5.6%
moisture content is qualitatively similar to that of the inhomogeneous
sample with 1.9% moisture content, but shows a higher overall loss of
moisture. This can be explained by a higher amount of water in the
boundary layer. In the following DSC measurements, a superposition of
water effects from approx. 60 °C for homogeneous samples and from
approx. 30 °C for inhomogeneous samples is to be expected.
Fig. 3 shows measurement curves of conventional DSC measure-
ments of representative samples with homogeneous moisture distribu-
tion and different total moisture contents. Dry samples have a glass
transition temperature of 49.53 ± 0.38 °C. With increasing moisture
content, a reduction of the glass transition temperature to
-21.29 ± 0.45 °C can be observed for fully saturated samples. These
values can also be found in literature [9,30,31]. It can be seen that the
glass transition can be superimposed by various effects like water loss,
annealing effects and relaxation [20]. All homogeneous samples show
an overlay of evaporating water from approx. 60 °C, which is confirmed
by the TGA measurements carried out. Furthermore, all samples exhibit
an endothermic annealing peak at approx. 60 °C, which can no longer
be detected after subsequent melting of the sample and new measure-
ment cycle. These effects mean that an exact determination of the glass
A. Sambale et al.
Fig. 3. Conventional DSC measurements on samples with homogeneous
moisture distribution.
transition temperature is only possible to a limited extent due to su-
perposition.
The measurements on samples with inhomogeneous moisture dis-
tribution, shown in Fig. 4, differ from the measurements on samples
with homogeneous moisture distribution. From approx. 30 °C the slope
of the measurement curves changes. This endothermic effect can be
explained by the water loss measured in the TGA, since the maximum
saturated boundary layer releases water to the environment at this
temperature. The glass transition is determined for samples with 1%
moisture content to -10.07 ± 0.49 °C and is reduced to
-14.57 ± 0.58 °C for samples with 6% moisture content. The step
height of the glass transition increases with increasing moisture con-
tent. A comparison with Fig. 3 shows that the detected displacement of
Tg is significantly reduced compared to the homogeneous samples.
Samples with similar moisture content but homogeneous moisture
distribution have significantly higher glass transition temperatures for
samples with low moisture content.
Fig. 5 shows the calculated cp curve of the StepScan DSC measure-
ments performed on selected samples with homogeneous and in-
homogeneous moisture distributions. As seen in the conventional
measurements, a shift in the glass transition temperature with in-
creasing moisture content towards lower temperatures can be observed.
An evaluation of the glass transition temperature is more accurate with
the StepScan DSC method than an evaluation with the conventional
Fig. 4. Conventional DSC-Measurement on samples with inhomogeneous
moisture distribution.
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Fig. 5. StepScan DSC measurements on samples with homogeneous and in-
homogeneous moisture distribution.
method, since the glass transition temperature is separated from su-
perimposed effects like evaporating water. Fig. 5 shows that the mea-
sured glass transition temperatures on samples with inhomogeneous
moisture distribution correlate with the glass transition temperatures of
samples with homogeneous moisture distribution.
Fig. 6 shows the course of the glass transition temperature as a
function of the moisture content of the sample. The results of the
StepScan DSC measurements correlate with the results of conventional
tests with homogeneous moisture distribution. However, the results of
StepScan DSC measurements of samples with maximum water satura-
tion deviate significantly from conventional measurements. In addition,
a significant deviation of the conventional measurements with in-
homogeneous moisture distribution can be seen in comparison to the
other results. The measured Tg shift is comparable with values pub-
lished in literature [9; 17; 30].
In the following, the developed Time-Step Evaluation method for
the determination of Tg from samples with inhomogeneous moisture
distribution using StepScan DSC are applied. There are no qualitative
differences in the measured heat flow curve for the temperature steps
and different sample types.
Fig. 7 shows an example of the temperature increase from −16 °C to
-15 °C of the StepScan DSC measurement on a sample with 1.3%
moisture content. The starting point of the empty pan baseline is
aligned with the starting point of the measurement data. It can be seen
Fig. 6. Shift of the glass transition temperature as a function of the present
moisture content.
A. Sambale et al.
Fig. 7. Example of one StepScan DSC measuring step from −16 °C to −15 °C
with 1.3% moisture content.
that the measured sample temperature (red curve) reaches a constant
value after 9 s. From about 2.6 s to 43 s the measured heat flow of the
sample deviates from the baseline. An evaluation of the heat flow into
the sample is meaningful only in this time range, since previous time
steps represent only the heating of the measuring cell.
Fig. 8 shows the time steps from 1 s to 10 s that represent the in-
tegral curves of the sample heat on a sample with inhomogeneous
moisture distribution at a moisture content of 3.5% for all temperature
steps performed. It can be seen that the heat capacity initially assumes a
constant value for the first three time steps over each temperature step.
This can be explained by the fact that the measuring cell is heated up to
this point in time and there is no heat conduction into the sample
(compare Fig. 7). In the time range of 4 s to 6 s Tg appears in a clear
step-shaped form. The analysis of Tg is no longer possible after 7 s using
the half-step height method (T 1 2 , g ), which is the reason why the eva-
luation is carried out using the final temperature of the glass transition
area (Tf , g ). Tf , g shifts over the time steps from 15 °C at 4 s to 50 °C at
10 s.
Fig. 9 displays the developed Time Step Evaluation for all tem-
perature steps of the StepScan DSC measurement of a sample with 1.3%
integral moisture content with an inhomogeneous distribution (left
side) in comparison with a sample with 1.6% integral moisture content
with homogeneous moisture distribution (right side). The time steps
above 10 s that are displayed in on the left side for a sample with in-
homogeneous moisture distribution exhibit no further shifts of Tf , g ,
whereby at higher time steps a clearly step-shaped Tg appears again.
Fig. 8. Time Step Evaluation for all temperature steps of the StepScan DSC
measurement of a sample with 3.5% integral moisture content with in-
homogeneous distribution.
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The last time step corresponds to the specific heat capacity curve de-
termined with the StepScan DSC method (see Fig. 5). Due to the use of
integral curves, the boundary layer effects detected at the beginning of
the measurement become less and less with increasing time steps. The
time-limited conditioning in a water bath during sample preparation
generates significant moisture gradients through the diffusion of the
water into the material, so that a maximum saturated sample boundary
layer with a dry sample core is conditioned. As a result of the limited
heat conduction of the material, the characteristics of wet PA 6 in the
boundary layer are measured at the beginning of each temperature step.
Over the time course of each temperature step, the heat penetrates
deeper and further into the material and a superposition of boundary
layer and core material is measured. The glass transition temperature
determined from the specific heat capacity is thus composed of a wet
boundary layer and dry core material, which means that a shift to
higher temperatures is to be expected compared to the wet boundary
layer. The measured displacement of the glass transition over the eva-
luation of the time steps is therefore due to the inhomogeneous
moisture distribution due to the applied sample conditioning.
Fig. 9 (right side) also shows the evaluation method used on an
exemplary sample with a homogeneous moisture distribution of 1.6% at
different time steps to compare the homogeneous and the in-
homogeneous moisture distribution for samples with approximately the
same integral moisture content. The step height of Tg increases at higher
time steps. As a result, Tg becomes more and more apparent. In the
calculated final time step, the glass transition curve is similar to the
specific heat capacity curve taken from the DSC-software in Fig. 5. It
can be seen that the glass transition does not shift over the evaluated
time steps for samples with homogeneous moisture distribution. All
samples examined with different defined moisture contents and
homogeneous moisture distribution show glass transition temperatures
corresponding to the moisture content, but no shift of Tg over the time
steps. The determined glass transition corresponds to that of the stan-
dard StepScan DSC evaluation for all time steps.
For inhomogeneous samples, there is no Tg shift to higher tem-
peratures visible within the respective time step. So it can be excluded
that the Tg shift results from a re-drying of the sample during the
measurement. The effect of re-drying results in a reduction of the
moisture content in the boundary layer and a loss of mass, that would
increase the heat capacity at elevated temperatures.
Fig. 10 shows the shift of the averaged values of the glass transition
temperature with indication of the standard error over the time steps
for three samples with comparable moisture contents (see also Fig. 6).
Small time steps represent the moisture content of the boundary layer
and higher time steps represent the superposition of the sample core
and boundary layer.
Due to this superposition, an exact determination of the local
moisture content with the developed Time Step Evaluation method for
inhomogeneous samples is only possible for a boundary layer. Samples
with homogeneous moisture distribution show no Tg shift over time
steps and Tf , g correlates with the present moisture content. In samples
with inhomogeneous moisture distribution, a reduction of the glass
transition temperature towards the boundary layer can be observed.
These samples can therefore be clearly separated from the samples with
homogeneous moisture distribution. After 10 s, the heat in both gra-
dient samples has penetrated so deeply into the sample that only the
dry core is measured. From this time step the Tf , g of the dry polyamide
is determined. The slope of the Tg shift allows a qualitative statement
about the moisture gradient within the sample. A lower slope of the Tg
gradient stands for a sharp moisture gradient. The determined Tf , g at the
maximum time step correlates with the integral overall moisture con-
tent, here for the dry material. For example, it is also possible to make a
statement for samples with a higher moisture content and different
boundary layers, e.g. a sample with a homogeneous moisture dis-
tribution of 1% and an additionally applied wet or dry boundary layer.
A. Sambale et al.
Fig. 9. Time Step Evaluation for all temperature steps of the StepScan DSC measurement of a sample with 1.3% integral moisture content with inhomogeneous
distribution (left side) in comparison with a sample with 1.6% integral moisture content with homogeneous distribution (right side).
Fig. 10. Determination of the end point of the glass transition area over the
time steps of the StepScan DSC measurement for the visualization of a local
moisture distribution within a sample.
4. Conclusion
The glass transition temperatures of PA 6 with different moisture
contents are determined on samples with homogeneous and in-
homogeneous moisture distribution. A shift of the glass transition
temperatures to lower temperatures can be observed with increasing
moisture content of the homogeneous samples. The determination of
glass transition temperatures is often difficult with conventional mea-
surements, as effects such as relaxation, annealing effects, crystal-
lization or moisture loss are superimposed during the measurement. For
samples with inhomogeneous moisture distribution, the determination
of the glass transition with conventional methods is not useful, as this is
usually at the value of completely saturated PA 6 despite the different
moisture contents. Using the StepScan DSC method, glass transition
temperatures of samples with inhomogeneous moisture distribution can
also be determined. The StepScan DSC method is also useful for samples
with homogeneous moisture distribution, since the glass transition is
not superimposed by competing effects. A dependence of the heating
rate on the conventionally measured glass transition temperatures
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Thermochimica Acta 672 (2019) 150–156
cannot be determined. Some of the samples with inhomogeneous
moisture distribution have a significantly wider glass transition range.
This is due to the fact that due to the inhomogeneous moisture dis-
tribution these samples do not show a clear Tg , but a local shift of the
glass transition temperature. In this paper, the Time Step Evaluation
method for detecting this local displacement was developed and vali-
dated using the water uptake of PA 6. By evaluating the time steps of a
StepScan DSC temperature step it is shown that these samples show a
reduction of the glass transition temperature to the boundary layer.
Samples with homogeneous moisture distribution show no displace-
ment of Tg over time steps and can therefore be clearly distinguished
from samples with inhomogeneous moisture distribution. In addition, a
qualitative statement about the degree of inhomogeneity of the
moisture distribution within the sample is possible.
Acknowledgements
This research was supported by the German National Science
Foundation (DFG).
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