JPOL 3406

Polymer 40 (1999) 3433–3441

Effect of water absorption in polymers at low and high temperatures

G. Baschek a, G. Hartwig a,*, F. Zahradnik b
a
Forschungszentrum Karlsruhe, Institut für Materialforschung II, PO Box 3640, D-76021 Karlsruhe, Germany
b
Universität Erlangen, WW V, Martensstr. 7, D-91058 Erlangen, Germany
Received 26 January 1998; received in revised form 4 June 1998; accepted 21 July 1998

Abstract

Water is absorbed by most polymers, but a change of properties is induced only in specific types of polymers. Water is considered to be
present in the free volume and active only when attached to polymer chains by hydrogen bonds. The materials considered are PEI, PEEK,
PES, PC, PA 12, and PA 6. The changes in damping spectra, moduli, and thermal expansion due to the moisture absorption have been
investigated in the broad temperature range of 4.2–320 K. It is surprising that properties are changed by water in a different or opposite ways
at low and high temperatures. Even at very low temperatures, absorbed water influences the mechanical performance in an unexpected way.
The results at low temperatures might be a tool for a better understanding of the features of the hydrogen bonded water, which itself could be
a sensor for analysing molecular mobilities. The interpretation of results is generally not yet clear and some cryogenic results are in
contradiction to well established correlations for dry polymers. Ideas for solving these problems are given in the conclusions of this
study. 䉷 1999 Elsevier Science Ltd. All rights reserved.

Keywords: Polymers; Water absorption; Cryogenic properties

1. Introduction water acts as a spacer between chains. However, cryogenic

measurements and the behaviour of thermal expansion
It is well known that moisture induces property changes makes the spacer model doubtful.
in polymers. At RT and above, water is considered to act as a Fewer measurements have been performed at low tem-
softening agent (spacer between chains). At cryogenic tem- peratures and nearly none at very low temperatures. In the
peratures, however, the contrary is true: wet specimens are temperature range between 160 and 200 K, for all polymers
stiffer than dry ones. Most polymers absorb more or less considered, a strong damping peak (‘water peak’) is induced
water, but not all of them exhibit a change in properties. or superimposed upon existing ones by water absorption.
i.r.- and MRS-analyses by several authors [1,2] indicated The temperature–frequency position of the ‘water peak’
that only water connected to macromolecules by hydrogen depends on the type of polar groups to which water is
bonds causes property changes. Polymer chains with strong bonded. The nature of the ‘water peak’ has been a topic of
polar groups are able to bind water by hydrogen bridges. many theoretical and experimental investigations [9,10]. A
Some examples are the ketone group (C ¼ O) or the sulphone consistent solution is not yet available. Most interpretations
group (O ¼ S ¼ O) and nitrogen. There are, however, restric- concentrate on two lines.
tions. Oxygen on both sides of a ketone group is considered to
hinder the formation of hydrogen bonds [2]. An example is 1.1. Side group motion of hydrogen bonded water
PC which contains ketone groups framed by oxygen.
The phenomenon of moisture absorption has been studied The ‘water peak’ is caused by the mobility of water which
by several authors in polymers [3,4] and polymer-based acts as a side group [11]. Some authors conducted test series
composites [5] mainly at room temperature and above. In of experiments on PEEK; absorbing water or alcoholic
that temperature range, absorbed water reduces moduli and groups of increasing length resulted in the correlated damp-
the main glass transition temperature [6] enlarges fracture ing peaks being shifted to higher temperatures [9]. The cal-
strain and impact strength [7,8] (softening or plasticizing culated activation energy of approx. 60 kJ/mol is rather high
effect). These features may be explained by assuming that for side group motions. At similar configurations (e.g.
PEMA, PPMA, PS) even longer side groups, which are
* Corresponding author. Tel.: +49-7247-823789; Fax: +49-7247-823039. covalently bonded, are correlated to an activation energy
0032-3861/99/$ - see front matter 䉷 1999 Elsevier Science Ltd. All rights reserved.
PII: S0 03 2 -3 8 61 ( 98 ) 00 5 60 - 6
3434 G. Baschek et al. / Polymer 40 (1999) 3433–3441

of approx. 10 kJ/mol, and damping peaks occur at approx. These bonds occur in general between hydrogen and the
30 K at 10 Hz [12]. For PEEK, another suggestion is a col- electronegative elements nitrogen, oxygen, and fluorine,
lective motion of the ketone group (with water) and both termed proton acceptors, where the electron density of the
aromatic rings, which are linked. hydrogen atom will decrease by interaction with unbonded
electron pairs of these proton acceptors. Typical hydrogen
1.2. Bonded water as a spacer which enhances preformed bond strengths between low-molecular weight molecules in
mobilities of chain segments general are between 1 and 50 kJ/mol.
This paper covers investigations of four aromatic poly-
The range of activation energies of ‘water peaks’ is simi- ethers and two polyamides. Only aromatic polymers are
lar to that found for collective motions (e.g. crankshaft). It considered below. Besides aromatic rings and ether bridges
ranges from 40 to 70 kJ/mol and the damping peaks occur in these polymers contain polar groups, like imide (-CO-NH-
the range of 150–200 K, and at 10 Hz [13]. The idea of CO-) moieties in poly(ether imide), sulfone (-SO 2-) groups
providing space for collective segment motions by water in poly(ether sulfone), ketone (-CO-) groups in poly(ether
could be realistic from the energetic point of view. How- ether ketone), and carbonate (-O-CO-O-) groups in polycar-
ever, results on thermal expansion contradict this idea. bonate. These characteristic polar groups contain nitrogen
When crankshaft motions start, thermal expansion should and/or oxygen as potential proton acceptors to form hydro-
be increased because more free volume is formed. But this gen complexes.
has not been observed. There is no clear evidence in favour Water molecules close to polar groups should be able to
of any of the present explanations. form hydrogen-bonded complexes with nitrogen and oxy-
The investigations presented in this paper cover a very gen. As indicated above, this interaction between hydrogen
broad temperature range from 4.2 to approx. 320 K. In par- in water molecules and the corresponding proton acceptor
ticular, results at very low temperatures exhibit unexpected results in a shorter distance and higher bond strength than in
features which might help to better understand molecular physisorption.
motions when water is bonded. Furthermore, not only the In contrast to physisorption and hydrogen bonding, che-
damping behaviour has been studied but also the moduli and misorption is the result of much stronger bonding forces,
thermal expansion over the hole temperature range. Damp- comparable with those leading to the formation of chemical
ing spectra, moduli and thermal expansion of polymers are compounds, i.e. the formation of covalent bonds. The ener-
compared in the dry and nearly water-saturated conditions. gies of chemisorption are of the order of 40– 400 kJ/mol.
It is surprising that property changes are very different at
low and high temperatures. For example, at low and very
low temperatures the Young’s and shear moduli are 3. Materials
increased and the damping spectra are drastically changed
by the incorporation of water. It is also surprising that, at Test polymers were selected according to their content of
very low temperatures, the damping behaviour is changed in strong polar groups and their ability to absorb water. The
the opposite way. Peaks existing for dry polymers between PEI, PEEK, PES, PA 12, and PA 6 polymers contain strong
30 and 100 K are suppressed in the wet state. It will be polar groups which favour the bonding of water molecules
pointed out that there are some discrepancies concerning by hydrogen bridges. PC also contains strong polar groups
the influence of water on the modulus and on thermal expan- (C ¼ O), but there are oxygen atoms on both sides which
sion, especially at cryogenic temperatures. It is surprising suppress the ability to bind water molecules. The aromatic
that all polymers investigated exhibit nearly the same ther- polymers considered exhibit damping peaks or shoulders at
mal expansion in the dry and wet states. A damping peak is very low temperatures (30–80 K), which are a special topic
usually considered an indicator for the onset of molecular of these investigations. They are assumed to occur by intra-
mobilities, which increase the free volume and thus thermal chain rotation of rings which are in the right chemical posi-
expansion. It is surprising that thermal expansion is nearly tion to establish potential barriers. Polyamides are known
uncorrelated to the ‘water peak’. In fact, a tendency towards for their high water absorption capability.
the opposite behaviour has been observed. Some polymers
(e.g. PA12) exhibit a small decrease of thermal expansion 3.1. Conditioning of specimens
above the ‘water peak’ in the wet state. Studying moisture in
polymers could be a tool for better understanding the fea- Water absorption depends on temperature, time, thick-
tures of the free volume (see also ref. [10]). ness of specimen, and the amorphous content in a polymer.
The latter is not well known for semi-crystalline polymers
(PA 12, PA 6, PEEK) used for this investigation. Their
2. Hydrogen bridges and bonding of water maximum water content thus is not a well defined quantity.
It is intended to study the property changes only qualita-
This kind of weak bonds result from the ability of the tively when more and more water is absorbed. For this
hydrogen atom to act as a link between two other atoms. purpose it is sufficient to end at a nearly saturated state.
 G. Baschek et al. / Polymer 40 (1999) 3433–3441 3435

Table 1
Conditioning parameters

Material Morphology or Initial a Water content after the

degree of crystallinity max. water content experiment
[wt.%] [wt.%]

Polyetherimide (PEI) amorphous 1.1 0.8

Polyetheretherketone semi-crystalline 0.4 —
(PEEK)
Polyethersulphone amorphous 1.7 1.1
(PES)
Polycarbonate (PC) amorphous 0.3 —
Polyamide (PA 12) semi-crystalline 0.8 0.7
Polyamide (PA 6) semi-crystalline 10.5 9.5
a
The initial max. water content is nearly that of the saturated state and published by the producers.

The maximum thickness of specimens was 3 mm; most vibrations. Young’s modulus was determined in a tensile-
specimens had a thickness of 1 mm. Immersion in water test machine by stress–strain diagrams. For measuring
for more than 6 days at ambient temperatures was sufficient thermal expansion, an inductive dilatometer was applied.
to establish a nearly saturated state. Dry specimens were For low-temperature measurements down to 4.2 K, the
conditioned under vacuum in an oven for 24 h at 100⬚C. equipment was modified for cryogenic use. More details
The relative water content, W, was determined as the per- of the cryogenic measuring devices are given in ref. [15].
centage increase in weight, m, at different times, t. The accuracy of these devices was better than 3%.
mwet (t) ¹ mdry
W ¼ 100
mdry
4. Results
The saturated water contents of test specimens are compiled
in Table 1. There is a broad range of W. The highest value in The measurements comprise a very wide temperature
this series applies to PA 6 (ca. 10 wt.%), the lowest to PC range between 4.2 and 320 K. As already mentioned, the
(0.3 wt.%). It should be mentioned that the different water influence of water absorption is different, even opposite, at
contents of polymers are not reflected directly in the extent high, low, and very low temperatures. For easier under-
of property changes; even a low water content might induce standing of the complex situation, schematic diagrams of
a large effect. the damping spectra (loss factor, tan d) and the shear moduli
All measurements were performed on dry and nearly (G) of dry and wet specimens over the whole temperature
saturated specimens. Tests in the intermediate state are range are shown in Fig. 1. They reflect the typical response
added for some polymers. After conditioning, the samples to water absorption. The figures apply to the aromatic-based
were immediately installed in the measuring devices. The polymers which exhibit damping peaks at very low tempera-
water content unavoidably changes over the time of mea- tures; this is not the case for polyamides. The general ten-
surement. A change by ¹0.3 wt.% was detected after dencies of property changes by water absorption are these.
cryogenic measurements for polymers which contained
more than 1 wt.% at the beginning. Some values are listed
in Table 1. The spatial distribution in the specimens is prob-
ably not homogeneous and will be changed somewhat dur-
ing the time of the experiments. It is not the goal of this
study to find a quantitative correlation of water absorption
and property changes. It has been verified by i.r.-spectro-
scopy that water is incorporated only in the bonded state and
not as a free deposit in holes or microcracks [14]. The spec-
trum of free water is clearly different from that in the
bonded state (small amount of free water was detected for
PES).

3.2. Apparatus

Damping spectra and shear moduli were measured in a

torsion pendulum at approx. 10 Hz. The loss factor, tan d,
can be determined from the logarithmic decrement, and the Fig. 1. Schematic presentation of loss factor and shear modulus for dry and
shear modulus from the frequency of the free torsional wet specimens.
3436 G. Baschek et al. / Polymer 40 (1999) 3433–3441

4.1. Damping spectra (loss factor, tan d) The experimental results on the loss factor, tan d, the
shear modulus, G, and the coefficient of thermal expansion,
• Reduction of the main glass transition temperatures a, are presented in Figs. 2–8. They display properties of
without change in the damping peak height. polymers in the dry and nearly water-saturated state. An
• Formation of a ‘water peak’ or enhanced damping beha- intermediate state is added in some figures.
viour in the range 1600–200 K. It can be seen from Fig. 2 that the results on PEI reflect
• Suppression of peaks at very low temperatures (for aro- directly the features summarized in the schematic diagrams.
matic polymers). Below the ‘water peak’, the shear modulus, G wet, is
increased, the damping peak at very low temperatures is
suppressed by water absorption, and nearly no influence
4.2. Moduli
on the thermal expansion has been observed below 320 K.
It should be mentioned that the ‘water peak’ is increased by
• Reduction of shear (and Young’s) moduli especially in
more water absorption, but the temperature position is
the vicinity of the main glass transition (softening
almost unchanged. A similar behaviour has been observed
effect).
for PEEK, but to a lesser degree as less water (0.4 wt.%) is
• Increase in the moduli especially below the temperature
absorbed, and PEEK is semi-crystalline. As seen from Fig.
of the ‘water peak’ (stiffening effect).
3, a ‘water peak’ at 170 K is superimposed upon a small
• No water influence on moduli in the temperature range
existing one at 190 K, while a peak (or shoulder) below
between the ‘water peak’ and the main glass transition
100 K is suppressed in the wet state. In the temperature
temperature (neutral range).
range 180 to at least 320 K water does not influence the
Another result is that the thermal expansion well below modulus. Thermal expansion again is not influenced in the
the main glass transitions is nearly unaffected by water. whole temperature range considered.

Fig. 2. Loss factor, shear modulus, and thermal expansion of dry and wet Fig. 3. Loss factor, shear modulus, and thermal expansion of dry and wet
PEI. PEEK.
 G. Baschek et al. / Polymer 40 (1999) 3433–3441 3437

Table 2
Young’s modulus of dry and wet specimens

T PES PA 12

E dry E wet E dry E wet E wet

(1.4 wt.% H 2O) (0.4 wt.% H 2O) (1.0 wt.% H 2O)

77 K 4580 MPa 5660 MPa 6650 MPa 6700 MPa 6700 MPa
293 K 2830 MPa 2700 MPa 2050 MPa 1830 MPa 1290 MPa

The influence of water on PES is similar, but again less polymers, the results on PC are given in Fig. 5. For the reasons
pronounced on the damping behaviour, although PES is mentioned above there is indeed no influence of water.
amorphous and much more water ( ⬇ 1.7 wt.%) is incorpo- The situation is somewhat different for polyamides,
rated. One reason might be that water is attached to a dif- which are non-aromatic and have a low main glass transition
ferent polar group (sulphone group). As is seen from Fig. 4, temperature. No damping peaks exist at very low tempera-
the existing damping peak at 175 K is increased only tures and no influence of water has been observed below
slightly while the shear modulus is increased remarkably 140 K at low water concentrations. For PA 12, as seen in
below 170 K. This is also true of the Young’s modulus. In Fig. 6, water absorption causes an existing peak at T ⬇
Table 2, some results on the Young’s modulus, E, are given. 140 K (probably crankshaft motion) to be reduced slightly
A slight reduction of E wet has been observed at RT. How- at one end and a small ‘water peak’ at 200 K to be induced.
ever, the shear modulus is almost uninfluenced by water A small increase in modulus due to water has only been
between 180 and at least 320 K. In the series of aromatic observed in the small temperature region of the ‘water

Fig. 4. Loss factor, shear modulus, and thermal expansion of dry and wet Fig. 5. Loss factor, shear modulus, and thermal expansion of dry and wet
PES. PC.
3438 G. Baschek et al. / Polymer 40 (1999) 3433–3441

peak’ down to the existing peak at 140 K. Below that tem- existing for dry specimens at 140 K are totally suppressed.
perature no modulus increase has been observed. A modulus The shear modulus, G wet, is increased generally below
decrease by water (softening effect), however, starts above 250 K (even below the suppressed peak), but drastically
280 K. Probably this is already the influence of the main decreased above 250 K. This feature is surprising. There is
glass transition whose tail can be seen from the damping a stiffening effect below 250 K directly followed by a
spectra above 300 K. In Table 2, the Young’s modulus of softening effect above 250 K. Furthermore, the strong
PA 12 is plotted for the dry, intermediate, and nearly water- damping peak ‘caused’ by water at 250 K induces a drastic
saturated state. The coefficient of thermal expansion is increase in thermal expansion. This is what is expected
changed slightly by water absorption, but surprisingly in from a damping peak, but never has been observed for
the opposite direction than expected. Wet PA 12 shows a ‘water peaks’. As will be demonstrated by Fig. 9, the
lower expansion coefficient. peak at 250 K and 10 Hz is not a ‘water peak’. It is the
Even more surprising are the results on PA 6. It absorbs a main glass transition peak of the amorphous phase of PA 6
tremendous amount of water (about 10 wt.%) and proper- which is shifted to such a low temperature by water
ties are influenced greatly by water. As a first step, the absorption. The indication is obvious. First, the loss factor
effect of a low water content (0.7 wt.%) is considered in is high (tan d ⬇ 10 ¹1) and secondly, the peak is shifted
Fig. 7. The situation is similar to that found for PA 12. A successively to lower temperatures by more water being
‘water peak’ is superimposed to an existing small one at absorbed. The peak height is relatively constant. At a main
approx. 210 K. However, PA 6 is capable of more water glass transition, thermal expansion is increased and the
absorption. At a higher water content ( ⬇ 10 wt.%), the modulus is decreased as expected. From Fig. 9 it can be
situation has changed drastically, as is seen from Fig. 8. A seen that already at some 4 wt.% of water a new category
large damping peak occurs at approx. 250 K for water- of property changes starts. An increase in absorbed water
saturated specimens, and the ‘water peak’ and a peak produces only minor changes.

Fig. 6. Loss factor, shear modulus, and thermal expansion of dry and wet Fig. 7. Loss factor, shear modulus, and thermal expansion of dry and wet
PA 12. PA 6 (0.7 wt.%).
 G. Baschek et al. / Polymer 40 (1999) 3433–3441 3439

5. Discussion • Neighbouring peaks at lower temperatures, however, are

suppressed or narrowed by water absorption.
5.1. Damping • Even a ‘water peak’ is reduced when the main glass
transition is shifted to its neighbourhood.
For secondary glass transitions of amorphous polymers
This means that the ‘water peak’ does not suppress damp-
the statistical process of place changes in a double poten-
ing peaks of the same temperature range. It suppresses only
tial is assumed to cause damping. Two neighbouring
the next peak at lower temperatures (i.e. a peak character-
potential minima are separated by a potential barrier
ized by a lower activation energy). For the different poly-
whose height controls the temperature position of a damp-
mers considered, the ‘suppressed’ peaks originate from
ing peak at a given activation frequency. It is not clear
mobilities of chemically different groups. It can be con-
whether or not a ‘water peak’ follows the same principle
cluded therefore that the process of suppression is a univer-
of molecular dynamics. There are, however, several gen-
sal one.
eral tendencies of how water absorption influences the
damping spectra:
5.2. Moduli
• The main glass transition is shifted to lower tempera-
tures. The peak height remains relatively unchanged. The moduli of polymers are controlled by:
• A ‘water peak’ is formed whose height is increased by
• binding forces (mainly Van-der-Waals forces),
more water being attached; the temperature position,
• unfreezing of molecular mobilities (dispersion steps).
however, is nearly unchanged. The peak height is not
proportional to the water content. The former is responsible for the elastic behaviour, the
• A ‘water peak’ can be superimposed upon an existing latter for viscoelasticity. At very low temperatures, the
peak at a similar temperature position. polymer chains are stiff and the moduli are controlled
mainly by the Van-der-Waals forces (force constant). At
glass transition, mobilities of segments unfreeze and the
chains become flexible, which results in a modulus
decrease (dispersion step). The dispersion or modulus
step is roughly proportional to the maximum loss factor
of the relevant peak. The exact value is given by the Kra-
mer Konig’s relation which correlates the modulus step to
the area of the damping peak integrated over the inverse
temperature.

Fig. 8. Loss factor, shear modulus, and thermal expansion of dry and water- Fig. 9. Shift of main glass transition temperatures by increased water
saturated PA 6 (10 wt.%). absorption in PA 6 (0.7–10 wt.%)
3440 G. Baschek et al. / Polymer 40 (1999) 3433–3441

For a rough estimate a ‘water peak’ can be characterized 5.3. Thermal expansion
by Dtan d w ¼ (tan d wet ¹ tan d dry). Without going into
quantitative details, the results are these: Several parameters control thermal expansion of poly-
mers:
• A modulus step occurs in the temperature range of the
‘water peak’ • modes of vibration,
• No correlation exists between the height of the ‘water • glass transitions.
peak’ and the magnitude of the modulus step:
At very low temperatures interchain vibrations dominate;
For PES, even a small (superimposed) ‘water peak’ above 80 K intrachain vibrations are activated. The latter
causes a relative large modulus step and vice versa are rather insensitive to temperature, but depend on the
for PEI and PEEK. mode of vibration: longitudinal vibrations yield a low posi-
PA 12 and PA 6 (with 0.7 wt.% H 2O) is in between. tive expansion coefficient, while transverse (or rotational)
ones produce a small negative one [16].
There are general tendencies found for the influence of
The vibration-based expansion is similar for most amor-
water on moduli:
phous and semi-crystalline polymers, respectively. Major
• Nearly all polymers considered exhibit a higher modulus changes occur as a result of the influence of glass transitions,
below the ‘water peak’ (stiffening effect). This could be where more free volume is generated by unfreezing of mole-
explained by water attached as a side group to the poly- cular mobilities. A damping peak is an indicator of the onset
mer chains. Below the temperature of the ‘water peak’ it of unfreezing. The main increase arises at the temperature of
gets frozen and makes a polymer stiffer. the main glass transitions and, to a lesser degree, by secondary
• In the broad temperature range within the ‘water peak’ ones [16]. It is surprising, however, that the ‘water peak’ is
and main glass transition there is no influence of water nearly uncorrelated to thermal expansion. Obviously, the free
on the modulus (neutral range). This makes the explana- volume is not changed. In fact, the opposite tendency has been
tion with a ‘water side group’ less powerful. Even in the observed. If thermal expansion is at all changed by water, it is
unfrozen state water should act as a spacer. not increased but decreased slightly. For example, the thermal
• In the vicinity of the main glass transition temperature expansion coefficient of PA 12 is decreased by approx. 10% in
water strongly reduces the modulus (softening effect). If the wet state (Fig. 6). Thus, the specific volume is decreased
water acts as a spacer, why is its effect only strong at the slightly by water. This is in contradiction to common expecta-
main glass transition? Is there a conglomeration of tions. A large increase of thermal expansion occurs, however,
water? in the vicinity of the main glass transition when shifted to
• For PA 12 and PA 6 (with ⬇ 0.7 wt.% H 2O) there is a much lower temperatures by attachment of water as is
modulus increase only in the small range between the shown for PA 6 (Fig. 8).
‘water peak’ (T ⬇ 200 K) and the existing peak (T ⬇
140 K), which is narrowed by water. Below this peak
there is no influence of water at all. 6. Conclusions
• PA 6 with a high water content (4–10 wt.%) exhibits a
modulus increase in the temperature range between Wanted: The process which kills all damping peaks at
absolute zero and the (shifted) main glass transition tem- very low temperatures and, in a secret way, establishes
perature, where a strong modulus decrease follows. The ‘water peaks’ without passing any information to thermal
modulus increase also exists below the existing peak at expansion. Protected by main glass transitions shifted to low
140 K, which is suppressed by a high water concentra- temperatures by water, the process is even able to kill a ‘water
tion. It seems that different mechanisms prevail when peak’. This has been proven for PA 6. Several results indicate
water is connected to PA 6 at low and high concentra- that the process changes mechanical properties, probably by
tions. attaching water to its victims by hydrogen bonds. Several
traces have been found by i.r.-spectroscopy. It cannot be
A final remark should make clear that obvious errors (e.g. excluded that water agglomeration is involved. The process
swelling of the specimens or desorption of water) in the appears as a stiffening effect below the ‘water peaks’ and as a
measuring procedure are not the reason for these strange softening agent in the range of the main glass transitions. In
findings. The values of damping and moduli were corre- between, it is not active for whatever reason. Readers are asked
lated to the cross-section of specimens in the wet and dry to save no water in discovering and imprisoning the process.
states, respectively. Measurements were started directly
after conditioning. Cross-checks were performed at RT
before and after the experiments; the values of the loss Acknowledgements
factor and the modulus were nearly the same. The loss of
water during the experiments was relatively small (see The authors wish to thank S. Knaak for tensile measure-
Table 1). ments and G. Hofmann for i.r.-spectroscopy.
 G. Baschek et al. / Polymer 40 (1999) 3433–3441 3441

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