Feature Article

Segmental Mobility in the Non-crystalline

Regions of Semicrystalline Polymers and its
Implications on Melting

Sanjay Rastogi,* Yefeng Yao, Dirk R. Lippits, Günther W. H. Höhne,

Robert Graf, Hans Wolfgang Spiess, Piet J. Lemstra

Detailed knowledge on chain mobility in polymers is of fundamental interest in order to

understand their mechanical properties. As a specific example, the melting behavior of semi-
crystalline polyethylene can be studied by thermal analysis and NMR spectroscopy. In ultra high
molecular weight polyethylene (UHMW-PE)
crystallised via different routes, i.e., directly
during polymerisation, from solution, or from
the melt, and melted under different protocols,
different melting processes involving detach-
ment of stems from the crystals and cluster
melting can be distinguished. Melting by the
consecutive detachment of chain stems from
the crystal substrate ultimately results in a melt
state where chain dynamics for entanglement
formation are much more restricted.

S. Rastogi
Department of Materials, Loughborough University, Leicester-
shire LE11 3TU, United Kingdom
E-mail: s.rastogi@lboro.ac.uk
S. Rastogi, D. R. Lippits, G. W. H. Höhne, P. J. Lemstra
Department of Chemical Engineering and Chemistry/ The Dutch
Polymer Institute, Eindhoven University of Technology, P.O. Box
513; 5600MB Eindhoven, The Netherlands
E-mail: s.rastogi@tue.nl
S. Rastogi, Y. Yao, R. Graf, H. W. Spiess
Max-Planck-Institute for Polymers, Ackermannweg 10, 55128
Mainz, Germany
Y. Yao
Department of Physics, East China Normal University, North
Zhongshan Road 3663, 200062 Shanghai, P. R. China
Introduction
In semicrystalline polymers, crystalline regions are linked
by non-crystalline domains. Depending on the crystal-
lisation conditions, chain stiffness, and molecular weight, a
chain may traverse between crystals or fold back within the
parent lamella, thus influencing the number of entangle-
ments residing in the non-crystalline regions and their
topology. This, in turn, has pronounced effects on chain
organisation, dynamics and melting, considered here for
a well studied flexible polymer - linear ultra high
molecular weight polyethylene of molar mass greater
than 106 g
mol1 (UHMW-PE).[1,2,3]
The chain topology can be also controlled by crystallizing
the polymer from solution. Below a critical overlap

Macromol. Rapid Commun. 2009, 30, 826–839

826 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200900025
Segmental Mobility in the Non-crystalline Regions of . . .
concentration, the entanglements are reduced to an extent
that the solution cast films can be drawn more than
150 times in the solid state.[4] Recently, we demonstrated
that careful synthesis with a single site catalyst produces PE
where the nascent crystals are highly disentangled. Similar
to solution cast films, the films obtained on compression of
the nascent crystals, below the melting temperature, can be
drawn in the solid state more than 150 times.[3] Distinct
morphological differences between solution crystallised and
nascent crystallised ‘‘disentangled’’ crystals exist. While in
the solution crystallised sample lamellae of 12.5 nm are
regularly stacked on top of each other that allows crystal
thickening,[5] whereas in the nascent sample, the regular
stacking of lamellae is absent. In both cases, the solid-state
drawability is lost once the ‘‘disentangled’’ crystals are melt
crystallised. This loss in drawability is attributed to the
increase in entanglements in the non-crystalline region of
the semicrystalline polymer influencing the chain topology
between the crystalline domains. Synthesis with the highly
active heterogeneous Ziegler-Natta catalyst on the other
hand, yields nascent (entangled) UHMW-PE, which is less
drawable in the solid state (7 times), indicating the influence
of the synthesis conditions on the chain topology in the non-
crystalline region of the semicrystalline polymer.
The melting temperatures of samples crystallised during
polymerisation (nascent) or from a melt of the same
polymer are distinctly different. For example, while the
nascent UHMW-PE, on heating at 10 8C
min1, melts
around 141 8C, close to the reported equilibrium melting
temperature for polyethylene of 141.5 8C, crystals obtained
via the solution route melt already at approximately 136 8C
and the melt crystallised sample at approximately 135 8C.
The high melting temperature for the nascent polymers has
been a subject of debate. Using electron microscopy and
DSC, Engelen[6] et al. conclusively showed that the nascent
crystals contained folded chains and displayed a lamellar
thickness in the region of 12 nm. Thus, the high melting
temperature for nascent polymers was attributed to
successive thickening prior to melting. However, no
experimental evidence of successive thickening was
provided. On the contrary, Kurelec et al. showed that, even
on annealing close to the melting point for several hours,
the lamellar thickness of these nascent crystals does not
exceed 26 nm.[7,8] The melting temperature predicted
from the Gibbs-Thomson equation for polyethylene[9]
(Tm ¼ 414.2–259.7/l) for a lamellar thickness l of 26 nm is
131 8C.[10] Furthermore, the high melting temperature of
141 8C is lost on second heating, where a melting
temperature of only 135 8C was found.[10] A similar
discrepancy was observed between the first and second
heating run of solution crystallised UHMW-PE, where the
lamellae double their initial thickness upon annealing
below the melting temperature to a maximum of 25 nm.[5]
From the Gibbs-Thomson equation we again expect
Macromol. Rapid Commun. 2009, 30, 826–839
ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Tm  131 8C, i.e., 5 8C lower than the experimentally
observed melting point of 136 8C. Furthermore, the high
melting temperature of 136 8C is lost on second heating
where a melting temperature of 131 8C is measured, which
now coincides with the prediction of the Gibbs-Thomson
equation.
The melting aspects involved in nascent, melt- and
solution-crystallised polymers cannot be explained by
established thermodynamic concepts alone. Therefore, in
this article we feature an extended investigation into the
melting behavior of these polymers. We correlate the time,
as well as the temperature, required for melting with the
chain topology in the non-crystalline regions. The intro-
duced kinetic aspect of melting is probed by different
experimental techniques: differential scanning calorimetry
(DSC), temperature modulated differential scanning calori-
metry (TM-DSC), 1H and 13C NMR spectroscopy and
relaxometry. The key observation in our study is that, at
sufficiently low heating rates, disentangled nascent poly-
ethylene melts can be prepared with unusual properties.
The lowest temperature where melting is observed
corresponds to the value predicted by the Gibbs-Thomson
equation. This indicates that topological constraints in the
non-crystalline domains influence the melting of the
crystalline regions in the semicrystalline polymer, an
observation which should hold for melting of polymer
crystals in general.
Experimental Part
Materials
To correlate the melting behavior of UHMW-PE to the chain
topology, four different samples were studied as specified in
Table 1. The two nascent grades differ in synthesis conditions and
catalyst type. The nascent entangled sample is a commercial grade
of Montell (1900CM) synthesised with a heterogeneous Ziegler-
Natta catalyst. The nascent disentangled grade is synthesised at
temperatures below the dissolution temperature of PE using a
homogeneous metallocene catalyst.
The solution crystallised samples were obtained with the
entangled nascent UHMW-PE on crystallisation from solution (for
example 1 wt.-% of UHMW-PE in decalin). Crystals thus obtained
are disentangled and have been investigated in detail before.[5] The
melt crystallised samples were obtained by cooling the entangled
melt at 10 K
min1.
Tensile testing was used to investigate drawability of the
materials in the solid state below the melting point. In the
following, we denote drawable materials (>150 times) as
‘‘disentangled’’ and un-drawable (<7) materials as ‘‘entangled’’.
Experimental Techniques
Differential Scanning Calorimetry (DSC)
DSC was performed using a standard Perkin-Elmer DSC-7. Samples
of 0.7–2.0 mg mass were weighed with a precision balance and
www.mrc-journal.de 827

Table 1. Molecular properties and synthesis temperature conditions of the UHMW-PE samples.
Mw
g
mol1
Nascent, Entangled 4.5  106
6
Nascent, Disentangled 3.6  10
Solution-crystallised 4.5  106
6
Melt-crystallised 4.5  10
encapsulated in standard (crimped) aluminium pans of known
mass. An identical empty pan was used as a reference. Nitrogen was
purged at a rate of 25 ml
min1. The DSC was calibrated using
indium and tin.
Tensile Testing
For draw ratio determination, dumb bell-shaped samples with a
gauge length of 10 mm and a width of 0.5 mm were used. Samples
were drawn in the solid-state at a crosshead speed of 50 mm
min1
at 125 8C. The draw ratio was determined by measuring the
separation of the ink marks prior and after the deformation.
NMR Spectroscopy
1
H NMR experiments were carried out without sample rotation on a
Bruker DMX spectrometer operating at a 1H NMR frequency of
500 MHz and equipped with a special 7 mm probehead that resists
temperatures above 150 8C. The transverse relaxation time T2 was
measured using a two pulse sequence 908-t-1808-t-aq with a
variable t time starting from t ¼ 2 ms. The 908 pulse length was 5 ms
and the repetition time was 3 s, which proved long enough for
quantitative measurements. The relaxation decay was charac-
terised by 60 data points at properly selected echo times. This pulse
sequence was chosen because it offered the possibility to both
qualitatively as well as quantitatively analyse relaxation of the
non-crystalline and crystalline components. Temperature calibra-
tion was carried out by monitoring peak separation in the 1H NMR
spectrum of glycol and the melting-induced 1H NMR line
narrowing of a series of compounds also employed as DSC
reference materials. 1H NMR spin-spin relaxation decays were
obtained from the total integral of the spectra after Fourier
Transformation, phase and baseline correction. The relaxation
decay was analyzed by a non-linear least-square fitting. The
relaxation times were determined by fitting the relaxation data
with a sum of two or three exponentials. From the determined
relaxation times below the melting point, appropriate t-delay
times were chosen for real-time monitoring of the T2 relaxation by
12 data points. In this way it was possible to follow the changes in
the sample with 5 min intervals.
All solid state NMR[12] studies were performed on a Bruker
DSX spectrometer operating at 500 MHz 1H Larmor-frequency.
Advanced NMR recoupling techniques correlating isotropic che-
mical shifts observed under magic angle spinning (MAS) with
motionally averaged 1H-13C heteronuclear dipole-dipole couplings
were used to study the local chain dynamics in the samples. The
measurement of 1H-13C heteronuclear dipole-dipole couplings was
Macromol. Rapid Commun. 2009, 30, 826–839
828 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Rastogi, Y. Yao, G. W. H. Höhne, R. Graf, H. W. Spiess, P. J. Lemstra
Mw =Mn Melting point Draw ratio
on first heating at 120 -C
8 141 8C 7
3.0 141 8C >150
8 136 8C >150
8 135 8C 7
achieved by the rotor encoded REDOR (ReREDOR) technique.[13] For
the ReREDOR experiments, a commercial 2.5 mm MAS double-
resonance probe was used at a spinning frequency of 25 kHz. The
same probe was used to study the chain diffusion between non-
crystalline and crystalline regions based on a 13C exchange type
experiment[12,14] under MAS at 6 kHz. The 908 pulse length in
the 2.5 mm MAS probe was adjusted to 2.5 ms on both channels. The
temperature of the bearing gas was varied for temperature
dependent experiments.
Temperature Modulated Differential Scanning
Calorimetry (TM-DSC)
TM-DSC was performed using a standard Perkin Elmer DSC-7
apparatus modified for temperature modulation.[15] For the TM-
DSC measurements, an underlying heating rate of 0.5 K
min1 was
used, which was low enough to ensure good linearity and stability
during measurements. Time dependent temperature-modulated
measurements were performed in quasi-isothermal mode at
different temperatures (110 8C, 120 8C, 130 8C, 135 8C, 136 8C,
137 8C and 138 8C) at a frequency of 12.5 mHz. The temperature
amplitude TA of 53 mK was kept low enough to ensure a linear
response. Before evaluation, the empty pan run (taking the same
measuring parameters and phase position) was subtracted from
the curve of the sample to reduce surroundings and apparatus
influences. The measured (modulated) heat flow rate signal F(T,t)
consists of two parts: the underlying part Fu(t) and the periodic part
Fper.(T,t). Gliding integration over one period provides the under-
lying part Fu(t) which, when subtracted from the total measured
signal, yields the periodic part Fper.(T,t). The ‘‘apparent’’ heat
capacity is calculated from the periodic part using a mathematical
procedure described in ref. [16].
Results and Discussion
First Melting Point of Nascent UHMW-PE
Figure 1 shows a standard DSC run of entangled and of
disentangled nascent UHMW-PE. Independent of the
synthesis route, no differences in the melting peak, onset
and end temperatures exist, though the polydispersity and
the topological constraints (estimated by differences in the
drawability of the two samples in the solid state[9])
generated during synthesis of the two samples are
DOI: 10.1002/marc.200900025
Segmental Mobility in the Non-crystalline Regions of . . .
Figure 1. DSC curves obtained on heating the nascent entangled
and the nascent disentangled samples at 10 8C
min1. Indepen-
dent of the synthesis route the polymer melts at 140.5 8C, close to
the equilibrium melting point of the linear polyethylene.
different. The observed high melting point of 141 8C of the
nascent powders is 5–6 8C higher than for melt-crystallised
UHMW-PE.[6] On heating at rates of 20 down to 0.1 K
min1,
, a non-linear relationship between the peak temperature
and the heating rate of entangled and disentangled nascent
UHMW-PE polymer is observed. However, plotting the
melting temperature versus the heating rate to power 0.2,
yields a linear relationship (Figure 2). Similar observations
were reported by Toda et al.[18]. However, unlike Toda et al.,
no instrumental corrections are applied to the measure-
ments reported here. The shift in the observed melting
temperature at non-zero heating rates is attributed to
‘‘superheating’’. This superheating is caused (i) by thermal
inertia (the transport of heat from the heater to the sample)
Figure 2. Measured melting peak temperatures for the entangled
and the disentangled nascent ultra high molecular weight poly-
ethylenes (UHMW-PE) at different heating rates (b).
Macromol. Rapid Commun. 2009, 30, 826–839
ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
and (ii) by the time dependence of the melting process. The
‘‘true’’ melting temperature is usually determined by
extrapolation to zero heating rate, yielding Tm ¼ 138.4 8C
and 138.2 8C for the disentangled and entangled samples,
respectively (Figure 2). According to the Gibbs-Thomson
equation, these melting temperatures correspond to a
crystal thickness of approximately 100 nm.[19] The experi-
mental observations, however, show clearly that the
crystals do not thicken to more than 26 nm,[7,8] even when
the sample is left to anneal for several hours at 120 8C.
Similar to the nascent UHMW-PE, the solution-crystal-
lised films of the UHMW-PE also show significantly higher
melting temperatures than expected from their crystal
thickness. For example, lamellar doubled crystals with a
thickness of 25 nm melt at 5 8C above the anticipated
melting point of 131 8C.
Thus, the Tm of solution-crystallised and the nascent
UHMW-PEs differ by more than 5 8C, despite similar crystal
thickness. Likewise, the melting temperatures of the melt-
crystallised and the nascent state of the same polymer
differ by more than 6 8C, though the crystal thickness of the
two samples is similar. Apparently, in addition to the
crystal thickness, other structural and dynamic parameters
influence the melting process. In order to determine
differences in local chain organisation and dynamics on
different time and length scales, solid state NMR was
employed.[12]
Solid State NMR Studies of UHMW-PE
Linear polyethylenes crystallised from solution and from
the melt were investigated by solid-state NMR[12] to
probe the segmental/medium-range chain mobility.[20,21]
Advanced NMR recoupling techniques were used to detect
the motionally averaged 1H-13C heteronuclear dipole-
dipole coupling.[13] The medium-range chain diffusion
between non-crystalline and crystalline regions was
monitored via 13C exchange type experiments[12,14] under
MAS.
Figure 3(a) and 3(b) show 13C CP/MAS spectra of the
solution and melt-crystallised samples, respectively. The
peak at 33 ppm arises from the all-trans conformations in
the crystalline regions.[22] Chain segments in the non-
crystalline regions adopt different conformations leading
to a peak at 31 ppm.[22] Due to differences in the
distribution of chain conformations, the position of the
peak is slightly different in the solution- and melt-
crystallised samples. Moreover, in contrast to the melt-
crystallised sample, the peak width of the non-crystalline
region in the solution-crystallised sample is rather broad
and reaches all the way to the all-trans peak. This is a first
indication of extended trans conformations and reduced
dynamics in the non-crystalline region of such samples.
www.mrc-journal.de 829

Figure 3. The 13C CP/MAS spectra (6 kHz MAS, 2 ms CP contact) of
PEs and ReREDOR35 sideband patterns (25 kHz MAS, 3 rotor
periods recoupling) from the non-crystalline regions, recorded
at T ¼ 320 K. The 13C CP/MAS spectra of (a) solution-crystallised
and (b) melt-crystallised PE show two components, the non-
crystalline signal (31 ppm, red dashed line) and the crystal peak
(33 ppm, green dashed line). The ReREDOR sideband pattern of
non-crystalline, solution-crystallised and of non-crystalline melt-
crystallised PE. The underlying blue pattern are simulations with
a dipole-dipole coupling constant of DIS/2 ¼ 9.1 kHz for the
solution-crystallised sample and 6.3 kHz for the melt-crystallised
sample.
In Figure 3(c) and 3(d), the 1H-13C dipole-dipole sideband
spectra of solution- and melt-crystallised samples are
compared. The profile of the sidebands represents the
strength of the 1H-13C dipolar coupling. The broad profile of
the sidebands of the non-crystalline region in the solution-
crystallised sample compared to that of the melt-crystal-
lised sample is indicative of a stronger residual dipole-
dipole coupling in the former. From the sideband patterns,
the strength of the residual dipole-dipole coupling of the
non-crystalline component was obtained[20] as 9.1 kHz for
the solution-crystallised and only 6.3 kHz for the melt-
crystallised sample. The higher dipole-dipole coupling in
the solution-crystallised sample is attributed to extended
trans conformations and more restricted local chain
dynamics in the non-crystalline region, for details see
ref.[20, 21].
To investigate the influence of local chain organisation
and mobility on the cooperative chain motion between the
crystalline and the non-crystalline regions (chain diffu-
sion), 1D 13C NMR exchange spectra[12,14] have been
recorded. Figure 4(a) shows a series of NMR spectra recorded
at a fixed temperature of 320 K for different waiting
(exchange) times, where the waiting time is the time
needed for the build up of the signal after saturation of the
13
C signal. Due to the large difference in the relaxation times
of the crystalline (>1 500 s at 320 K) and the non-crystalline
regions (0.6 s at 320 K), build up of the signal for the non-
crystalline region will be much faster than the build up of
the signal for the crystalline region. With increasing
Macromol. Rapid Commun. 2009, 30, 826–839
830 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Rastogi, Y. Yao, G. W. H. Höhne, R. Graf, H. W. Spiess, P. J. Lemstra
Figure 4. 13C MAS exchange spectra of the solution-crystallised
sample (SC-PE) and the melt-crystallised sample (MC-PE): (a)
measured at 6 kHz MAS, T ¼ 320 K with different exchange times;
(b) measured at 6 kHz MAS, a fixed exchange time (5 s) and with
different experimental temperatures.
waiting time two peaks are observed in the solution-
crystallised sample. The peak positions match with those of
the non-crystalline and the crystalline regions. The
intensity of the crystalline peak increases rapidly with
the exchange time. Considering the long relaxation times
required for the crystalline component, the build-up of the
crystal peak is attributed to the exchange of chain segments
from the non-crystalline to the crystalline region. Such
exchange, though very weak, is also observed in the melt-
crystallised samples at a much longer exchange time of
400 s.
The exchange process in linear polyethylenes has been
studied earlier by Schmidt-Rohr and Spiess[14] and more
recently on UHMW samples of different morphol-
ogy.[20,21,23] These studies demonstrate that the extended
chain conformations present in the non-crystalline region
of the solution-crystallised sample play a conclusive role in
the cooperative chain motion, despite the restricted local
chain mobility. The higher disorder in the non-crystalline
region of the melt-crystallised sample of the same polymer
suppresses cooperative chain diffusion despite higher local
mobility. This has implications for our understanding of
crystal thickening. For example, the solution-crystallised
sample exhibits enhanced chain mobility along the crystal-
lographic c-axis, which ultimately leads to doubling of
the initial crystal thickness.[5] Contrary to this, crystals in
the melt-crystallised sample of the same material
hardly thicken. Moreover, the higher chain order in the
non-crystalline regions of solution-crystallised samples
together with the high translational chain mobility
explains the observed easy mechanical deformation of
the crystals in the solid state. Last but not least, melting of
the crystals and chain reorganisation of the chains prior to it
DOI: 10.1002/marc.200900025
Segmental Mobility in the Non-crystalline Regions of . . .

involves chain motion on different time and length scales

identified here. Therefore, the NMR findings should be kept
in mind when discussing the melting behavior of the
different samples.

Melting Kinetics in Solution-crystallised UHMW-PE

as Probed by DSC
To get more insight into the melting mechanism, annealing
experiments at temperatures below the ‘‘true’’ melting
point of 138.4 8C (determined from Figure 2) were
performed in the range from 132 8C to 138 8C. After
annealing at the requisite temperature, the sample was
cooled to room temperature and reheated (at 10 K
min1)
to 150 8C. On re-heating, two melting peaks at about 135 8C
Figure 6. Arrhenius plot of the time constants determined from
and 141 8C are observed (Figure 5). The peak at 135 8C is the relaxation time of the annealed sample for the entangled and
ascribed to the melting of that part of the sample which was disentangled nascent UHMW-PEs (see ref. [11]). The activation
molten and re-crystallised during cooling from the energies of the three different processes are realised from the
annealing temperature and the second peak at 141 8C is three different slopes of the curves in the Figure (reproduced
from ref. [11]).
ascribed to the remaining crystal domains still in the initial
nascent state. The ratio between the areas of the two peaks
changes with the annealing time at the given annealing
temperature. As the peak area is proportional to the amount
the heat of fusion) reads:
of the respective crystals, the ratio between the areas is also
a measure for the ratio between the amounts of crystals
which are re-crystallised and those which are in the initial HðT; tÞ ¼ H0 ðTÞet=tðTÞ (1)
nascent state.
From such studies,[11] it is possible to determine the where the time constant (t) can be related to an activation
relaxation times for the different melt processes of the energy (EA) by
different samples. With a Debye (Arrhenius) type time law
for the fusion process in question, the enthalpy change (i.e., t ¼ t 0 eEA =RT (2)

Figure 6 summarizes the relaxation

times at different annealing tempera-
tures. Closed symbols represent the
relaxation times for the nascent disen-
tangled UHMW-PE sample. Open sym-
bols in the Figure represent the relaxation
times for the nascent entangled sample.
For the disentangled sample above
135.5 8C only one single relaxation time
is found, whereas below this temperature
two relaxation times are observed. Con-
trary to that, the entangled polymer
shows only one relaxation time over
the whole temperature range of 133–
138 8C. In fact, altogether three regions
with different slopes are observed indi-
Figure 5. Heating run of the disentangled UHMW-PE, after annealing at 135 8C for cating the involvement of three different
different annealing times. The annealing times are mentioned in the corresponding
activation energies in the two different
figures. The first peak at 133 8C corresponds to melting of the crystals which crystallised
from the melt obtained on annealing. The second peak at 141 8C corresponds to the temperature regions (see Table 2). The
nascent crystals. The high temperature melting peak disappears on annealing the activation energies vary from
sample at 135 8C (reproduced from ref. [11]). 5.0  1.0  103 kJ
mol1 (slope (c)) for

Macromol. Rapid Commun. 2009, 30, 826–839

ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mrc-journal.de 831
 S. Rastogi, Y. Yao, G. W. H. Höhne, R. Graf, H. W. Spiess, P. J. Lemstra

Table 2. Activation energy determined from the Arrhenius plot shown in Figure 6 and Figure 7.

Activation energy Number of CH2 Chain length Lamellae thickness Stems

(T103 kJ
mol1)a) units involved involved prior to melt involved

nm nm

Nascent entangled 4.3  1.0 (c) 1 600  370 202  50 260,0 6–10
2.4  0.2 (b) 900  90 110  10 260,0 4–5
0,0
Nascent disentangled 5.0  1.0 (c) 1 850  370 235  50 26 7–11
2.1  0.2 (b) 780  50 99  7 260,0 4
0,0
0.6  0.05 (a) 220  20 28  2 26 1
Solution-crystallised 4.2  1.0 (c) 1 560  370 197  50 250 6–10
0.7  0.05 (a) 250  20 32  2 250 1

a)
(a),(b),(c) refer to the three slopes determined from the Figure 6 and 7. Activation energies in the Table are determined from slopes in the
Figures.

temperatures above 136 8C via 2.1  0.2  103 kJ
mol1
(slope (b)) to 0.6  0.05  103 kJ
mol1 (slope (a)) for
temperatures below 136 8C, respectively.
The three activation energies suggests to consider three
different melt processes in the disentangled nascent
UHMW-PE, assigned to detachment/removal of chain
stem(s) from the crystal, followed by the diffusion of the
detached chain segment into the melt. From physical
chemistry it is known[24] that the molecular motion in
liquids is an activated process and the viscosity follows an
Arrhenius type law. The detachment of stems from the
crystal can be seen as a dynamic process with activation
energy proportional to the number of CH2-groups involved.
The rate of desorption of molecules from any surface
follows a similar law.[24] Within the frame of this model, the
lowest activation energy (a) can be assigned to a
cooperative detachment of only a couple of chain stems
from the crystal surface and their diffusion into the
surrounding melt. The intermediate activation energy (b)
then refers to the simultaneous detachment of a larger
number of stems from the crystalline substrate and their
diffusion and finally the highest activation energy (c) refers
to the cooperative breakdown of larger parts of the crystal
lattice because of instability in the thermodynamic sense.
The low activation energies determined from the slopes (a)
and (b) suggest the involvement of a ‘‘new melting’’
behavior, whereas the slope (c) refers to the conventional
(thermodynamic) melting at higher temperatures.
More quantitatively, the activation energy (a) can be
assigned to the detachment of a single stem 28 nm (this
has been calculated considering the activation energy
for detachment of one CH2 group and its diffusion into the
melt equal to 2.7 kJ
mol1 and the CC distance in the
orthorhombic lattice along the c-axis equal to 0.127 nm).[25]
The intermediate activation energy (b) then refers to the
simultaneous detachment of 3–4 stems from the crystalline
substrate and their cooperative diffusion and the activation
energy (c) refers to the breakdown of parts of the crystal by
simultaneous randomisation of at least 7–8 stems.
Contrary to the disentangled polymer, the entangled
polymer does not show slope (a), suggesting the absence of
melting through consecutive detachment of single chain
stems from the crystalline substrate. Apparently this
process is not possible in such samples due to the
constraints in the non-crystalline regions. However, the
slopes of (b) and (c) of the entangled and the disentangled
samples are similar, indicating that melting of the
entangled sample occurs in clusters of at least several
chain stems. Such a melting process further confirms the
presence of topological constraints in the nascent
entangled UHMW-PE compared to the disentangled
UHMW-PE.
Figure 7 shows the measured time constants of the
relaxation process for solution cast films at different
temperatures. In the explored temperature region,
similar to Figure 6, two distinct slopes (a) and (c) are
observed. Slope (a) refers to the activation energy of
0.7  0.05  103 kJ
mol1 required for the detachment and
diffusion of one chain stem of approximately 30 nm length,
a value in accordance with the measured crystal thick-
ness.[8] Slope (c) refers to the activation energy of
4.2  1.0  103 kJ
mol1, a value comparable to that of
the respective process in the nascent UHMW-PE. This high
activation energy is again assigned to the breakdown of the
crystal lattice. The absence of the slope (b) in Figure 7
suggests that within the temperature region of 128 to
130.5 8C melting in these solution cast films mainly occurs
by removal of single chain stems from the crystal substrate.
The lowest and the highest activation energies (repre-
sented by slopes (a) and (c)) of the disentangled nascent
sample in Figure 6 and the solution-crystallised sample in
Figure 7 are similar. The crystal thicknesses of the

Macromol. Rapid Commun. 2009, 30, 826–839

832 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200900025
Segmental Mobility in the Non-crystalline Regions of . . .
Figure 7. Arrhenius plot for solution-crystallised UHMW-PE
samples. The different relaxation times at the given annealing
temperatures show two activated processes.
disentangled nascent and the solution-crystallised samples
are comparable, and both samples can be deformed
mechanically in the solid state. This suggests that the
activation energy required for the respective processes,
namely the removal of single chain stems from the surface
followed by their diffusion in the melt (slope (a)), as well as
the breakdown of larger parts of the crystal lattice (slope (c)),
is largely independent of the differences in the crystal-
lisation conditions of the two samples. The melting
processes are distinctly different, however, from the
melting behavior observed for the melt-crystallised sam-
ples, where only one melting process occurs at 135 8C (at a
heating rate of 10 K
min1) without any time dependence
of melting at low heating rates or at annealing tempera-
tures below 135 8C. To follow the processes in the crystal
lattice prior to melting (e.g., reorganisation and pre-
melting) temperature modulated DSC (TM-DSC) measure-
ments on the entangled and disentangled nascent UHMW-
PE were performed and have been described elsewhere.[8]
Reorganisation in Solid State prior to Melting as
Probed by Temperature Modulated DSC (TM-DSC)
From the above described experiments it is evident that
different processes are involved in the melting of crystals.
Temperature-modulated differential scanning calorimetric
(TM-DSC) investigations provide the opportunity to sepa-
rately measure the individual contributions of different
processes to the ‘‘apparent’’ heat capacity. In the quasi-
isothermal operation mode it is possible to study the
contributions of such processes dependent on time.
Detailed information about such processes and the TM-
Macromol. Rapid Commun. 2009, 30, 826–839
ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DSC method can be found in a review article of
Wunderlich.[26]
By use of TM-DSC Höhne et al. recently showed[15] that
the magnitude of the complex apparent heat capacity of the
nascent disentangled UHMW-PE in the pre-melting region
is higher than the heat capacity obtained by conventional
DSC in that region. This indicates that chain reorganisation
occurs in the solid state and contributes to the apparent
heat capacity. The magnitude of the ‘‘excess heat capacity’’
is lower on second heating suggesting that the process is
irreversible and is best observed on first heating of the
nascent sample. Quasi-isothermal TM-DSC experiments
revealed that this apparent heat capacity is time depen-
dent. Evaluation of the relaxation times of the processes
contributing to the apparent heat capacities is possible
under the assumption that the involved relaxation
processes are of Arrhenius type (i.e., the contributions to
the apparent heat capacity follow an exponential decay). It
should be noted, however, that due to the assumptions and
the large uncertainty of the determined relaxation times
the results should be used with care.
Quasi-isothermal TM-DSC measurements on the disen-
tangled nascent UHMW-PE samples are performed at
different temperatures below the melting peak and the
change of the apparent heat capacity in time is plotted in
Figure 8. The respective excess heat capacity function
is fitted with a sum of 2 or 3 exponentials (a1et/t1 þ
a2et/t2þ a3et/t3) and the results of the best fit are plotted
in Figure 9. The approximately linear behavior in this so-
called Arrhenius-plot allows determination of activation
energies for chain reorganisation in the solid state as
30  10, 60  10 and 500  150 kJ
mol1, respectively, for
the three processes found in this sample. Comparing the
two lower activation energies (30  10, 60  10 kJ
mol1)
with the enthalpy change from solid to liquid of one CH2-
group (4.11 kJ
mol1[25]) the corresponding processes are
Figure 8. Apparent heat capacity from four quasi-isothermal TM-
DSC measurements in the melting region of the disentangled
nascent UHMW-PE (frequency 12.5 mHz, period 80s, TA ¼ 53 mK).
www.mrc-journal.de 833

Figure 9. Activation diagram of the three processes determined
from Figure 8. The slope gives the activation energy (solid symbol:
exothermic, open symbols: endothermic). The stars represent the
time constants determined from the slope (a) of the Figure 6.
This is attributed to the melting and diffusion of the stems from
the crystal sides. The activation energy is determined from the
slopes.
likely to involve less than twenty methylene units, a
number lower than the units of a single stem in the crystal.
Thus the two processes observed in TM-DSC cannot be
attributed to real melting, but suggest local dislocations
which enable chain diffusion related to the a-relaxation
which occurs just in this temperature region. These findings
and the low activation energy are also in agreement with
the NMR studies of chain diffusion indicated above and
described in detail elsewhere.[20,21,23]
The third process, observed above 130 8C in the TM-DSC
experiments (unfilled symbols along line (c), in Figure 9) is
linked to irreversible melting. It seems to be one of the
melting processes seen in the conventional DSC studies
mentioned in the section above. Indeed, the data points
obtained from slope (a) of Figure 6 inserted as star
symbols () in Figure 9 coincide with the TM-DSC data,
indicating that the two relaxation processes are of similar
origin. Thus, as above we attribute the third process from
the TM-DSC experiments to the detachment of one chain
stem from the crystal substrate and its diffusion to the melt.
Origin of the High Melting Point of
Nascent and Solution-Crystallised UHMW-PE
If we compare the low activation energies of 30 and
60 kJ
mol1 for the first and second process in the TM-DSC
experiment with the activation energy required for the
detachment of a single chain stem (600 kJ
mol1), it is
concluded that the two processes with low activation
energy are associated with chain diffusion within the
crystals rather than detachment of the chain. The third
process takes place when the disentangled polymer sample
Macromol. Rapid Commun. 2009, 30, 826–839
834 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Rastogi, Y. Yao, G. W. H. Höhne, R. Graf, H. W. Spiess, P. J. Lemstra
is annealed close to the onset melting temperature. In this
case melting proceeds by successive detachment of chain
stems from the crystal substrate and diffusion into the
neighboring melt. The minimum temperature required for
this process is in good agreement with the melting
temperature determined from the Gibbs-Thomson equa-
tion. At higher annealing temperatures (>135.5 8C) another
melting process occurs where larger clusters, exceeding the
size of one stem, are co-operatively involved (for details see
ref. [11]).
The relaxation times required for the successive detach-
ment of chain stems from the crystal substrate and the
diffusion into the surrounding matrix (>150 min) are
considerably longer than the relaxation times for melting in
clusters. Apparently, at standard heating rates, melting
mainly proceeds via the cluster melting involving 7–8 chain
stems. The experiments clearly show that such a cluster
melting of the nascent UHMW-PE leads always to a high
melting temperature of 141 8C, normally ascribed to
extended chain crystals. In the second heating of the
nascent samples (i.e., melt-crystallised), no time dependent
melting on annealing is observed and the melting
temperature is 5 8C lower than the melting temperature
of the nascent polymer during the first run. When combined
with the NMR findings on differences in the mobility of the
non-crystalline regions of the melt and solution/nascent-
crystallised samples,[20,21] these findings suggest that the
above described ‘‘cluster melting’’ (slope (b) in Figure 6) is
absent in the melt-crystallised samples. Therefore, we
conclude that distinction in the melting behaviour and
temperature also reflects topological differences of the
chains in the non-crystalline regions of the semicrystalline
polymers rather than differences in crystal size only.
The dynamics of crystal melting is usually related to the
increasing number of defects in the crystal lattice,
ultimately leading to complete breakdown of the lattice
at a certain concentration of defects.[27] In semicrystalline
polymers, where a chain within the lattice is connected
to chain segments in the non-crystalline regions, the
dynamics of melting requires cooperative motion of the
chain segments both within the lattice and in the non-
crystalline region. Differences in tight or loose chain folds
connecting chains in the non-crystalline and crystalline
regions will therefore have implications in the breakdown
of the crystal lattice. This concept is shown schematically in
Figure 10. In nascent UHMW-PE with adjacent or tight folds,
a greater number of CH2 groups have to move
cooperatively (Figure 10(b), 10(c)), thus melting requires
the number of involved CH2 groups to be higher than
those present in a single chain stem residing within the
crystal lattice. The cooperative melting will involve several
chain stems connected by tight folds, resulting in a higher
melting temperature than that predicted from the Gibbs-
Thomson equation.
DOI: 10.1002/marc.200900025
Segmental Mobility in the Non-crystalline Regions of . . .

from 133.5 8C to 135.5 8C and a fast melting ranging from

136 8C to 141 8C. To probe the structural changes during the
melting processes in the fast and slow melting regions on
the molecular level 1H NMR studies were performed.

Melting in UHMW-PE Probed by 1H NMR

1
H NMR lineshapes and spin-spin (T2) relaxation are
strongly affected by rotational chain motions on time-
scales < 103 s.[12] The more restricted the motion, the
Figure 10. Illustration of the crystal structure of a) melt-crystal- broader is the resonance and the faster the relaxation decay
lised sample having inter crystal molecules and loose loops. b) of the so-called Hahn-echo produced by a 908-t-1808-t pulse
Nascent disentangled sample having tight folds c) Nascent
sequence versus the echo time 2t. Spin-spin relaxation is a
entangled sample having tight folds. The depicted entangle-
ments in the figure are circled. better measure for polymer chain motion than the spectral
line shape, because the latter is also broadened by other
mechanisms, which are eliminated in the Hahn-echo
experiment. 1H NMR T2 relaxometry is therefore a regular
tool to determine entanglement- and crosslink density in
In the melt-crystallised UHMW-PE sample, on the other
rubbers,[29,30,31,32] and polymers melts.[33,34] At T  Tg chain
hand, chain segments in the non-crystalline region are free
mobility at timescales <103 s is controlled by chemical
to adopt a larger number of chain conformations, the stems
crosslinks and physical entanglements with lifetimes
in the crystal are connected by loose folds and are
>103 s. For simplicity of data analysis it is assumed that
dynamically decoupled. Then, melting requires cooperative
polymer motions can be divided into fast and slow
mobility of one chain stem only, corresponding to the
dynamics compared to 103s without a significant inter-
crystal thickness (shown schematically in Figure 10(a)).
mediate fraction. To distinguish between the crystalline
Therefore, the number of repeating units involved in the
and non-crystalline regions of entangled and disentangled
melting process corresponds to the lamella thickness of the
nascent UHMW-PE, the relatively robust and quantitative
crystal, resulting in a melting point of 135 8C, as predicted
Hahn-echo method as a tool is applied.
from the Gibbs-Thomson equation. 1
H NMR Hahn echo decays were monitored at constant
By modifying the Gibbs-Thomson equation, Höhne[17,28]
temperature (Figure 11 and Figure 12). Between the
correlated the number of CH2 units cooperatively involved
experiments at different temperatures, the sample is
in the melting dynamics with the melting temperature. In
heated at a rate of 0.1 K
min1. Below the onset of melting,
this approach the number of CH2 groups of the
the observed Hahn-echo decays of the nascent entangled
respective molecule, incorporated into the crystallite via
UHMW-PE sample are well described in terms of two
tight folds is the essential variable, rather than the crystal
exponential components (Figure 11). The fastest compo-
thickness. The total (molar) enthalpy DmHmol and entropy
nent has a fairly temperature-independent short T2 value
DmSmol of fusion (melting) of chain molecules each
consisting of n repeat units in the crystals is composed of
the respective values of the subunits. Accordingly, in the
modified Gibbs-Thomson equation crystal thickness is
replaced by the number of repeating units n and the total
excess (Gibbs) free energy replaces the surface free energy,
yielding

 
1 1 Dm Ge 1
n
 1
1  1 n
(3)
Tm Tm Dm Hr:u:

In the case of cluster melting of 7–8 stems, with n  1 800

CH2 units, a melting temperature of 139.7 8C is predicted in
agreement with the experimentally determined melting
temperature (138.2 8C) obtained by extrapolation to the
zero heating rate (Figure 2). Figure 6, however, clearly shows Figure 11. T2 relaxation time versus temperature of nascent
two distinct melting regions, i.e., a slow melting ranging entangled UHMW-PE (reproduced from ref. [33]).

Macromol. Rapid Commun. 2009, 30, 826–839

ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mrc-journal.de 835

Figure 12. T2 relaxation time versus temperature of the nascent
disentangled UHMW-PE (reproduced from ref. [33]).
10 ms and disappears above 140 8C and is assigned to the
rigid, crystalline regions. Above 120 8C, the long T2
relaxation time of the non-crystalline fraction increases
strongly with temperature. The steepest increase occurs
around the melting point Tm  140 8C. Apparently, below
Tm, chain motion in the entangled non-crystalline region is
confined by the crystalline domains, see also ref. [35]. The
resulting melt state is described by a single T2 relaxation
time of 1 ms.
Using a similar heating protocol, a third T2 component
shows up in the Hahn-echo decays of the nascent
disentangled sample (Figure 12) about 2–3 times longer
than that of the non-crystalline region. Because of its long T2
value, we attribute the third T2 component to a more mobile
type of non-crystalline region to be distinguished from the
normal non-crystalline region observed for the entangled
and disentangled nascent UHMW-PE. The third T2 mobile
amorphous component arises on slow melting of the
disentangled polyethylene crystals.
Quantitative analysis of the nascent disentangled
sample is shown in Figure 13. The crystalline fraction
(shortest T2 component) of approximately 72% as deter-
mined from the Hahn-echo decay at 120 8C is consistent
with the crystallinity of the sample estimated from DSC. As
the crystallinity decreases with increasing temperature
from 130 8C to 137 8C, the normal non-crystalline fraction
increases (Figure 13). Upon further increasing the tempera-
ture above 137 8C, the highly mobile non-crystalline region
increases simultaneously with the disappearance of the
crystalline region.
To recall, melting at low temperatures (observed with a
heating rate of 0.1 K
min1 from 130 8C to 137 8C) is
associated with the successive detachment and diffusion of
a few chain stems from the crystal surface (Figure 6). The
increase of the normal non-crystalline fraction suggests
Macromol. Rapid Commun. 2009, 30, 826–839
836 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Rastogi, Y. Yao, G. W. H. Höhne, R. Graf, H. W. Spiess, P. J. Lemstra
Figure 13. Changes in the relative fractions of the crystalline,
mobile non-crystalline and normal non-crystalline components
of the disentangled nascent UHMW-PE sample with temperature
as probed from a Hahn echo pulse program (reproduced from
ref. [33]).
that the polymer chain stems that are molten by the
successive detachment are able to entangle with the
surrounding non-crystalline region. Upon increasing
the temperature further with the melting of the remainder
of the disentangled crystalline fraction (approximately
40%), a highly mobile non-crystalline component of the
same fraction evolves. The amount of the highly mobile
non-crystalline fraction as well as the normal non-crystal-
line fraction remains almost constant upon further
increasing the temperature. This suggests a barrier for
the mixing of the two non-crystalline-regions. As the
polyethylene chains are chemically uniform, the presence
of the two non-crystalline fractions with two different
mobilities above 140 8C, originate from the ‘heterogeneous’
distribution of entanglements, which arises on slow
melting of the disentangled crystals.[3]
On fast heating (10 K
min1) the disentangled nascent
sample to its melt state, the T2 relaxation decay determined
at 150 8C is faster than that of the slowly heated sample
(0.1 8C
min1) at the same temperature (see Figure 14(a)).
In the fast heated sample, the mobile non-crystalline
component is absent and the T2-relaxation can be described
with a single relaxation time. The T2-relaxation at 150 8C
determined for the entangled nascent sample, shown in
Figure 14(b), is independent of heating rate. Using the
different T2 relaxation time as a filter, thereby suppressing
the less-mobile fractions of the melt, we observe significant
differences in the peak width of the NMR spectrum of the
two melt states arising with different heating rates from
the initially disentangled nascent sample. The narrower
peak of the slowly heated melt indicates a higher local
mobility in part of the sample. In fact, an increase in T2 filter
DOI: 10.1002/marc.200900025
Segmental Mobility in the Non-crystalline Regions of . . .
Figure 14. NMR line shapes and T2 relaxation curves of fast (10 K
min1, filled squares)
and slow (0.1 8C
min1, unfilled square) heated UHMW-PE melts of the initially
entangled and disentangled nascent samples. Experiments were performed at 150 8C.
The dynamic heterogeneity of the slow heated disentangled nascent sample can be
monitored as well via variation of the line width in the T2-filtered spectra. (10 ms is the free movement of the chain ends in the
applied T2 relaxation filter time). Reproduced from ref. [33].
time leads to suppression of the rigid fractions of the sample
and decreasing peak width in the slow heated disentangled
melts, strengthening the idea of heterogeneity in the local
mobility.[3]
These dynamic NMR results suggest that upon fast
melting, associated to melting in clusters of 7–8 polymer
chain stems, the chains are homogenously distributed in
the melt, resulting in a homogenous distribution of
entanglements. If the disentangled nascent UHMW-PE is
given more time to melt (slow heating), the crystals are
molten first from the sides (chain ends) before complete
breakdown of the crystal lattice occurs. The resulting
melt state contains a heterogeneous distribution of
chain entanglements. The resulting melt state exhibits
interesting rheological phenomena as summarised in
ref.[3,37]
Macromol. Rapid Commun. 2009, 30, 826–839
ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Melt Mechanism
Combining the findings from DSC and
1
H NMR a scheme for the melt mechan-
ism involved in melting of the disen-
tangled nascent UHMW-PE was devel-
oped. Figure 15(a) depicts slow melting of
the disentangled nascent crystals. The
adjacently re-entrant chains melt by
consecutive detachment of a chain seg-
ment (stem) equal to the lamella crystal
thickness from the crystal lattice (AA’and
BB’in Figure 15(a)). The initially disen-
tangled molten chains will form entan-
glements by reptation (circles) leading to
a shorter T2 relaxation time. Upon melt-
ing the whole crystal at higher tempera-
tures, the section AB in Figure 15(a), will
transform from a disentangled crystal to
a disentangled non-crystalline region (as
was shown in the NMR experiments). As
a result of the absence of physical
entanglements, the disentangled com-
ponent of the non-crystalline fraction
can be described by a high T2 value
referring to the overall higher local
mobility. Thus, depending on the heating
rate, chain dynamics in the resultant
melt state of the disentangled nascent
crystals can be altered. Detailed study on
the influence of heating rate on chain
dynamics is reported elsewhere.[3,36]
Contrary to the slow melting, a com-
plete collapse of the crystal lattice occurs
upon fast melting. This causes an instant
melt, resulting in a homogenous distri-
bution of entanglements (Figure 15(b)).
Finally, in the nascent entangled samples, physical
entanglements present in the non-crystalline region of the
semicrystalline polymer restrict the consecutive detach-
ment of chains. Therefore the low activation energy
component (slope (a) in Figure 6) is absent. Thus on
melting, independent of the heating rate, entanglements
present in the non-crystalline region become homoge-
neously distributed along the main chain (Figure 15(c)).
A theory on the evolution of the heterogeneous melt state
arising on the controlled melting of the disentangled
crystals is proposed by McLeish.[36] The influence of the
mobile disentangled domains on crystallisation kinetics is
addressed in ref. [37] Molar mass dependence on build-up of
the modulus on melting of the disentangled samples as a
function of time is addressed in ref. [38] Details of the work
can be found in a PhD thesis.[39]
www.mrc-journal.de 837
 S. Rastogi, Y. Yao, G. W. H. Höhne, R. Graf, H. W. Spiess, P. J. Lemstra

scale. Melting in the low temperature

region (130–135 8C) occurs by cooperative
detachment of chain stems from the
surface involving a time-dependent pro-
cess, whereas melting in the high tem-
perature region (136–141 8C) leads to a
breakdown of larger parts of the lattice.
Therefore the normal extrapolation of the
observed Tm to zero heating rate of
Figure 2 needs modification at low
heating rates, as shown in Figure 16.
Recently, similar to the disentangled
nascent polyethylenes Toda et al. have
also attributed the melting kinetics in the
single crystals of linear polyethylenes to
an entropic barrier.[18]
The high melting temperature of nas-
Figure 15. Depicting melting process of the disentangled nascent crystals during slow
heating. (a) On annealing below 137 8C, with the consecutive detachment of chain stems
cent and solution-crystallised UHMW-PE
from the crystal substrate and their diffusion in the melt, normal entangled non- compared to that of melt-crystallised
crystalline region is formed. On heating above 137 8C, the remainder of the crystal melts UHMW-PE is ascribed to the differences
invoking the mobile non-crystalline region. The two non-crystalline regions, mobile and in the chain topology. Depending on the
normal, do not mix even above the melting temperature. This leads to the origin of a nature of chain folds in the crystal, loose
melt having differences in the local mobility of the two non-crystalline components.
Entanglements are encircled. (b) Depicting the melting process of the disentangled
or tight, the number of CH2 units that
nascent crystals during fast heating. (c) Depicting the melting process of the entangled require cooperative motion for melting
nascent crystals. On melting, entanglements initially present in the non-crystalline differs. Melt-crystallised samples with
region get homogeneously distributed. Reproduced from ref. [3]. loose folds melt at the temperature
predicted by the Gibbs-Thomson equa-
tion, i.e., the number of CH2 units that
require cooperative motion to adopt a random coil
corresponds to the crystal thickness. In nascent and
solution-crystallised samples, however, having tight folds,
the number of CH2 units required for cooperative melt
dynamics is much larger than calculated from the crystal
thickness. Therefore, the melting point of the samples shifts
to higher temperatures than in the melt-crystallised
samples.
1
H NMR shows the influence of the different melting
processes on the local mobility of the non-crystalline
regions and in the melt. The chain ends of the disentangled
nascent sample, which detach from the crystal sides prior to
melting (T < 135 8C) form entangled non-crystalline
Figure 16. The measured melting peak temperatures for the domains. Melting of the remainder of the crystal occurs
entangled and the disentangled nascent UHMW-PE at different
at a higher temperature, leading to a melt with mobile
heating rates. The non-linear abscissa allows extrapolation to
zero heating rate0. However, the extrapolation fails at the lower disentangled and normal entangled non-crystalline
heating rates. domains. With the help of 1H NMR, a remarkable distinction
in the distribution of the topological constraints in the melt
can be probed. The disentangled melt state is consistent
Conclusion with the lower plateau modulus determined by rheological
studies.[3]
From the series of experiments reported above it is evident
that melting of nascent-, solution-crystallised and melt-
crystallised UHMW-PE samples shows profound differ- Acknowledgements: Financial assistance from the Dutch Polymer
ences. The number of CH2-groups that are involved in a melt Institute and DSM Research (The Netherlands) is gratefully
process depends on the temperature as well as on the time acknowledged.

Macromol. Rapid Commun. 2009, 30, 826–839

838 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200900025
Segmental Mobility in the Non-crystalline Regions of . . .
Received: January 13, 2009; Revised: March 23, 2009; Accepted:
March 24, 2009; DOI: 10.1002/marc.200900025
Keywords: differential scanning calorimetry (DSC); lamellar;
melting point; NMR; polyethylene (PE)
[1] P. Smith, H. D. Chanzy, B. P. Rotzinger, Polym. Commun. 1985,
26, 258.
[2] B. P. Rotzinger, H. D. Chanzy, P. Smith, Polymer 1989, 30, 1814.
[3] S. Rastogi, D. R. Lippits, G. W. M. Peters, R. Graf, Y. Yao, H. W.
Spiess, Nature Mat. 2005, 4, 635.
[4] P. J. Lemstra, C. W. M. Bastiaansen, S. Rastogi, ‘‘Structure
Formation in Polymeric Fibers’’, Chapter 5, D. R. Salem, Ed.,
Hanser, Munich 2000.
[5] S. Rastogi, A. B. Spoelstra, J. G. P. Goossens, P. J. Lemstra,
Macromolecules 1997, 30, 7880.
[6] Y. M. T. Tervoort-Engelen, P. J. Lemstra, Polym. Commun. 1991,
32, 343.
[7] S. Rastogi, L. Kurelec, D. R. Lippits, J. Cuijpers, M. Wimmer, P. J.
Lemstra, Biomacromolecules 2005, 6, 942.
[8] L. Corbeij-Kurelec, ‘‘Chain mobility in polymer systems’’, Chap-
ter 3, Ph.D. thesis, Eindhoven University of Technology 2001;
http://alexandria.tue.nl/extra2/200113706.pdf
[9] B. Wunderlich, G. Czornyj, Macromolecules 1977, 10, 906.
[10] The authors are aware that depending on the experimental
methods used, different numerical Gibbs-Thomson
equations exist (see: T. Y. Cho, B. Heck, G. Strobl, Colloid
Polym. Sci. 2004, 282, 825). A difference arises because of
different surface free energy values resulting in a somewhat
different melting temperature of 136 8C for a crystal thick-
ness of 25 nm. However, such discrepancies in the calculated
melting temperatures have no implications on our exper-
imental findings.
[11] D. R. Lippits, S. Rastogi, G. W. M. Höhne, Phys Rev Lett. 2006, 96,
218303.
[12] K. Schmidt-Rohr, H. W. Spiess, ‘‘Multidimensional solid-state
NMR and polymer’’, Academic Press Ltd, San Diego, USA 1994.
[13] K. Saalwächter, I. Schnell, Solid State Nucl. Magn. Reson. 2002,
22, 154.
[14] K. Schmidt-Rohr, H. W. Spiess, Macromolecules 1991, 24, 5288.
[15] G. W. H. Höhne, L. Kurelec, S. Rastogi, P. J. Lemstra, Thermo-
chim. Acta 2003, 396, 97.
[16] G. W. H. Höhne, Thermochim. Acta 1997, 304/305, 209.
[17] G. W. H. Höhne, Polymer 2002, 43, 4689.
Macromol. Rapid Commun. 2009, 30, 826–839
ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[18] A. Toda, M. Hikosaka, K. Yamada, Polymer 2002, 43, 1667.
[19] From T. Y. Cho, B. Heck, G. Strobl, Colloid Polym Sci. 2004, 282,
825, the calculated crystal thickness for the melting tempera-
ture of 138.4 8C is 47 nm; this is also larger than the measured
thickness.
[20] Y. F. Yao, R. Graf, H. W. Spiess, D. R. Lippits, S. Rastogi, Phys.
Rev. E 2007, 76(6), 060801.
[21] Y. F. Yao, R. Graf, H. W. Spiess, S. Rastogi, Macromolecules
2008, 41, 2514.
[22] D. L. Vanderhart, J. Magn. Resonan. 1981, 44, 117.
[23] Y. F. Yao, R. Graf, H. W. Spiess, S. Rastogi, Macromol. Rapid
Commun. 2009, 30, in press.
[24] P. W. Atkins, ‘‘Physical Chemistry’’, 5th Edition, Chapter 24.6, 27.4,
28.12, Oxford University Press, 1995.
[25] Considering 1/3rd lesser neighbor interactions on the surface
than in bulk, the detachment energy and its diffusion into
the melt is likely to be 2.7 kJ
mol1 since the melting
enthalpy of the bulk is 4.11 kJ
mol CH1 2 , a value obtained
from the ATHAS data bank (http://athas.prz.rzeszow.pl/).
[26] B. Wunderlich, Prog. Polym. Sci. 2002, 391, 51.
[27] G. Strobl, ‘‘The Physics of Polymers’’, 2nd edition, Springer-
Verlag, Berlin 1997.
[28] G. W. H. Höhne, Thermochim. Acta 2003, 403, 25.
[29] C. G. Fry, A. C. Lind, Macromolecules 1988, 21, 1292.
[30] M. E. L. Wouters, V. M. Litvinov, F. L. Binsbergen, J. G. P.
Goossens, M. van Duin, H. G. Dikland, Macromolecules
2003, 36, 1147.
[31] D. L. Tillier, J. Meuldijk, P. C. M. M. Magusin, A. M. van Herk,
C. E. Koning, J. Polym. Sci. A, 2005, 43, 3600.
[32] R. A. Orza, P. C. M. M. Magusin, V. M. Litvinov, M. van Duin,
M. A. Michels, Macromol. Symp. 2005, 230, 144.
[33] T. Cosgrove, M. J. Turner, P. C. Griffiths, J. Hollingshurst, M. J.
Shenton, J. A. Semlyen, Polymer 1996, 37, 1535.
[34] A. Guillermo, J. P. Cohen Addad, D. Bytchenkoff, J. Chem. Phys.
2000, 113, 5098.
[35] H. W. Spiess, Colloid Polym. Sci. 1983, 261, 193.
[36] T. C. B. McLeish, Soft Matter 2007, 3, 83.
[37] D. R. Lippits, S. Rastogi, S. Talebi, C. Bailly, Macromolecules
2006, 39, 8882.
[38] D. R. Lippits, S. Rastogi, G. W. M. Höhne, B. Mezari, P. C. M. M.
Magusin, Macromolecules 2007, 40, 1004.
[39] D. R. Lippits, ‘‘Heterogeneity in polymer melts by controlled
melting of polymer crystals’’, PhD Thesis, Eindhoven Univer-
sity of Technology, March 6th 2007.
www.mrc-journal.de 839