Polymer 60 (2015) 107e114

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Origin of toughness in b-polypropylene: The effect of molecular

mobility in the amorphous phase
!, Ji"r Hodan, Jiri Brus*, Ji"r Kotek
Olvia Policianova
Institute of Macromolecular Chemistry, AS CR, v.v.i., Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 3 December 2014
Received in revised form
16 January 2015
Accepted 19 January 2015
Available online 24 January 2015

This study aims to explore the origin of toughness in b-phase isotactic polypropylene (i-PP). Samples of
commercial-grade i-PP, both neat and nucleated with a specic b-nucleating agent (N,N0 -dicyclohexylnaphthalene-2,6-dicarboxamide), were subjected to a combination of structure-sensitive methods and
fracture mechanical testing. In addition to common structural characterisation methods, solid-state NMR
data were collected to obtain information about the dynamics of the polymer segments as well as the
structure. In particular, temperate-induced transformation between the free and constrained amorphous
phase was monitored by variable-temperature 13C MAS NMR, whereas T1r(1H) relaxation was used to
estimate correlations times of segmental motions. Lower thermodynamic stability of rigid amorphous
fraction was found in the b-crystalline systems. In contrast helical chains in crystalline and constrained
amorphous phase were found to be more restrained in the a-crystalline system. Overall, the results
indicate larger restrictions in chain mobility in the amorphous phase of the a-polymorphic PP system
than in that of the b-crystalline ones.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Isotactic polypropylene
b-modication
Toughness

1. Introduction
Isotactic polypropylene (i-PP) is known for its extensive polymorphism, which is attributed to the packing variation of polymer
chains adopting the same, threefold 31-helical conformation [1,2].
Six different crystal phases have been identied to date. Among
them the monoclinic (a), trigonal (b) and orthorhombic (g) phases
occupy a privileged position. The toughness of the b-modication
has been demonstrated to be considerably higher than that of the
a-modication. Thus far, no generally accepted structural mechanism that explains the observed effect of the b-modication on the
toughness of i-PP has been proposed. The rst published model
suggested that a stress-induced transformation from a less dense
(trigonal b-modication) to a more dense (monoclinic a-modication) crystalline structure at the root of a growing crack results in
crack blunting and toughness enhancement [3]. However, the
phase transformation in PP is associated with a volume decrease, in
contrast to the volume increase in zirconia ceramics. Therefore, the
greater toughness of the b-modication appears to be an inherent
property of the b-modication itself. Indeed, a majority of structural explanations ascribe the toughness enhancement to a specic

* Corresponding author. Tel.: 420 296 809 350.

E-mail address: brus@imc.cas.cz (J. Brus).
http://dx.doi.org/10.1016/j.polymer.2015.01.047
0032-3861/ 2015 Elsevier Ltd. All rights reserved.

arrangement of the material structure. Several authors have suggested that greater toughness reects a distinct spherulitic
morphology: an organisation of b-phase lamellae in a bundled
structure [4e6]. In contrast, the authors of previous studies [7e9]
have proposed that the particular arrangement of the crystalline
phase and a greater number of tie molecules in the amorphous
phase may contribute to the greater toughness of the b-phase. The
micromechanical processes initiated by the amorphous material
have been conrmed to dominate in the initial stages of deformation [10]. Recently, Luo et al. showed [11e13] that toughening in bPP arises from improvements in the chain mobility of the amorphous portion of the material and not from changes in the crystalline morphology. However, the chain mobility was revealed
indirectly through the dynamic mechanical analysis spectra. The
studies of the mechanism affecting the toughness in PP systems
have not produced clear answers; therefore, we decided to devote
our effort to further investigating the questions concerning the
diversity in PP toughness.
For probing the structure and mobility of i-PP chains with
atomic-level resolution, solid-state NMR spectroscopy (ss-NMR) is
one of the most efcient experimental methods. This is particularly
because the different crystal modications of i-PP have considerable impact on NMR resonance frequencies. In the thermodynamically stable monoclinic a-form, the 31-left- and right-handed

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O. Policianova

helices are enmeshed in the pairs [14]. The upward and downward
orientations of methyl groups allow the stems to adopt either ordered or disordered packing structures. Complete upward or
complete downward orientation of the methyl groups is a typical
feature of the ordered a2-phase; these orientations allow for a
compact arrangement of helical molecules and generate two nonequivalent packing environments for each carbon site. Consequently, the resulting 13C CP/MAS NMR spectrum shows wellresolved splitting (2:1) of the corresponding resonances (CH2, CH
and CH3). On the contrary, the a1-phase formed by rapid crystallisation from melting displays the statistical disorder of the up- and
down-orientations, leading to a more open structure [14]. Because
the pairs of helices are separated to a greater extent, the environment of the carbon sites is less distinct and the resonance splitting
is considerably reduced. The asymmetrically broadened single lines
are observed in the 13C CP/MAS NMR spectra instead of doublets.
Left- and right-handed 31-helices of the less thermodynamically
stable b-form are arranged in groups with the same handedness
[14]. This arrangement, however, does not allow close-packing.
Consequently, the inter-chain interactions are weakened, resulting in the absence of any resolvable splitting in the 13C CP/MAS
NMR spectra. Other polymorphic forms, such as the g- and dphases and the recently prepared -phase, are rather exotic structural modications of i-PP that represent singularities in polymer
crystallography [15e17]. Although the presence of these exotic
forms can be neglected in ordinary i-PP samples, a straightforward
interpretation of ss-NMR spectra is complicated by the existence of
two distinct amorphous phases. In addition to the amorphous
phase containing molecules with a random-coil (r.c.) conformation,
another non-crystalline component adopting the 31-helical
conformation has been identied [18,19]. Generally mobile amorphous fraction (MOF) and rigid amorphous fraction (RAF) are being
distinguished [20]. At room temperature, these non-crystalline
components give broad and largely overlapping signals. With
increasing temperature, however, a more vigorous molecular motion is activated in the r.c. amorphous phase, and new well-resolved
CH2 and CH resonance lines appear in the high-frequency region
[21]. Therefore, ss-NMR experiments at elevated temperatures are
important for understanding the molecular origin of the physicochemical and mechanical properties of i-PP systems.
The aim of this work was to elucidate the effect of molecular
mobility in the amorphous phase on the toughness in a- and bisotactic PP and to investigate the material characteristics in greater
depth. Three samples from our previous research [22e24] were
used for this study: a-PP and two b-nucleated samples that differ in
the concentration of the nucleating agent. Two concentrations of
the nucleator were chosen: 0.03 and 0.1 wt%. The rst concentration represents the critical nucleator concentration, which is
necessary to obtain a signicant percent of crystalline b-modication. Further increasing the nucleator concentration only slightly
increases the percentage of the b-modication [22]. Detailed
structural and dynamic surveys were performed using highresolution solid-state NMR (ss-NMR) spectroscopy in combination
with Wide-angle X-ray scattering (WAXS).
2. Experimental
2.1. Materials and specimens
Isotactic polypropylene homopolymer Mosten 52.412 (Chemopetrol, Czech Republic) was used as a starting material
throughout this study. To obtain a material rich in the b-phase, the
polymer was modied with a selective b-nucleator NJ-Star
NU-100
(RIKA,
UK),
N,N0 -dicyclohexylnaphthalene-2,6dicarboxamide. On the basis of our previous studies [22e24],

two concentrations of the nucleator were chosen: 0.03 and 0.1 wt

%. The nucleator was premixed with a PP powder and compounded with neat PP pellets using a co-rotating twin-screw
extruder. For the toughness assessment, bars (length L, 80 mm;
width W, 10 mm; thickness B, 4 mm) were cut from 4 mm-thick
compression-moulded sheets. The b-nucleated materials were
labelled as PPB03 and PPB1 according to the nucleator concentration. The starting material was labelled as PP.
2.2. Toughness assessment
An instrumented CEAST impactor (a Charpy impact tester with a
work capacity of 7.5 J) was used for the measurements. The
experimental parameters were as follows: notch depth, a 2 mm
(a/W 0.2); support span, s 40 mm (s/W 4); and pendulum
hammer speed, vH 1.5 m/s. The tests were repeated under
identical conditions 10 times. An average value of the J-integral
according to Sumpter and Turner and the standard deviation were
calculated from individual test results. The experimental procedure
is described in more detail elsewhere [25].
2.3. Wide-angle X-ray scattering
WAXS was performed in transmission mode. A HZG
(Pr
azisionmechanik Freiberg, Germany) powder diffractometer
equipped with a Cu-Ka radiation source and a b-lter monochromator was used for the measurements. The relative amount
of b-modication in the crystalline phase was characterised by
the ratio K. Its value was assessed from the intensities of the
crystalline reections of a- and b-modications using the relation
proposed in the literature [26]. The total integral intensities I and
the integral intensities diffracted by the crystalline part Icr were
used to determine the crystallinity Xc according to the equation
Xc Icr/I.
2.4. Solid-state NMR (ss-NMR)
ss-NMR experiments were performed using a Bruker Avance
500 WB/US NMR (Karlsruhe, Germany, 2003; B0 11.7 T) in 4mm ZrO2 rotors at MAS frequencies ranging from 4 to 11 kHz. The
13
C cross-polarisation (CP) MAS NMR spectra were measured
with a B1(13C) eld nutation frequency of 62.5 kHz, a contact time
of 2 ms and a recycle delay of 5 s. To record quantitative data, the
single-pulse 13C MAS NMR spectra were measured with a repetition delay of 180 s. To record the T1-ltered domain-selective
spectra of the mobile components, the repetition delay time
was shortened to 4 s. The 13C-detected T1(1H) relaxation times
were measured using a saturation-recovery experiment in which
the initial train of 1H saturation pulses was followed by a variable
delay (0.1e180 s). For the measurement of the 13C-detected
T1r(1H) relaxation times, an initial 1H(90# ) pulse was followed by
a variable 1H spin-lock pulse of 0.1e25 ms. The intensity of the 1H
spin-locking eld was 58 kHz. To suppress the 1H spin diffusion
during the variable pulse, complementary experiments with LeeGoldburg spin-locking were recorded [27]. In this case, the 1H
carrier resonance was offset by 44 kHz. The site-specic measurements of one-bond 1He13C dipolar couplings [28] under the
Lee-Goldburg condition were achieved by 2D separated-localelds experiments, T1-ltered-PISEMAS [29,30] and PILGRIM
[31]. Variable-temperature experiments were performed in the
temperature range from 295 to 355 K. Frictional heating of the
sample was compensated for, and the sample temperature was
calibrated using the 207Pb chemical shift in Pb(NO3)2 [32].

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O. Policianova
Table 1
The effect of nucleating agent concentration (NC) on the fraction of the b-crystallites
within the crystalline phase (K), the overall crystallinity (Xc) and the fracture
toughness (JId).
Sample

NC (wt.%)

K ($)

Xc ($)

JId (N/mm)

PP
PPB03
PPB1

0
0.03
0.1

0.10
0.89
0.89

0.40
0.43
0.45

3.5 0.3
10.2 2.6
7.5 1.6

3. Results and discussion

3.1. Toughness and WAXS analyses
As evident from the results in Table 1, the addition of 0.03 wt% of
the nucleating agent led to a marked increase in the b-modication
content from 10% (non-nucleated polymer) to 89%. For the highest
nucleator concentration (0.10 wt%), the value of K remained identical. At the same time, the overall crystallinity, Xc, increased slowly
and steadily from 40 to 45% as the nucleating-agent content was
increased from 0 to 0.10 wt%. These facts thus conrm that the
samples were prepared in such a way that crystalline phase of
isotactic PP is dominated either by a-polymorphic form (90%) or bpolymorphic form (90%). Therefore we believe that possible crosseffects i.e., inuence of the rigid amorphous phase originating from
the a-crystallites on the toughness of i-PP dominated by the bpolymorphic form and vice versa are negligible.
The toughness, as expressed by a critical value of the J-integral,
increased from 3.5 N/mm for the unmodied material to 10 N/mm
for the critically nucleated concentration; in the case of higher
nucleator content, it decreased to 7.5 N/mm. This maximum indicates an optimum structural arrangement for the development of
plastic deformation. To understand the molecular origin of this
behaviour, a set of variable-temperature solid-state NMR experiments was performed.
3.2. Line-shape analyses of solid-state

13

C and 1H NMR spectra

We rst acquired room-temperature cross-polarisation 13C CP/

MAS NMR spectra (Fig. 1) in which three lines corresponding to the
CH2 (44 ppm), CH (26 ppm) and CH3 (22 ppm) groups were
detected. Asymmetric lines at 44 and 22 ppm from the PP sample
clearly reected the presence of a large fraction of the a2-polymorphic form of i-PP, whereas the symmetric lines observed for the
PPB1 and PPB03 systems conrmed that the b-phase prevailed. In
all of the samples, no signs of the a1-polymorphic form were
observed. At elevated temperatures (far above Tg z 0e10 # C),
segmental motions in the amorphous phase were released and
separate signals corresponding to the free r.c. amorphous phase
appeared in the high-frequency regions (Fig. 1). As a result, the
linewidths and relative signal intensities of these signals could be
analysed.

Fig. 1. 13C CP/MAS NMR spectra of the prepared samples PP, PPB1 and PPB03 measured
at 305 and 355 K.

As shown in Table 2, the free r.c. amorphous phase in the a2polymorphic system is reected by slightly broader 13C CP/MAS
NMR signals compared to those of the b-polymorphic samples. If
the line-narrowing observed above Tg is assumed to be associated
with released segmental motions, then the observed differences
could indicate greater chain mobility. Moreover, the relative intensities of the corresponding signals indicate that greater amounts
of the free r.c. amorphous fractions in the b-polymorphic systems
are released at elevated temperatures.
Given that cross-polarisation efciency strongly depends on
segmental mobility, we also recorded the single-pulse 13C MAS
NMR spectra. The spectra provided more accurate quantitative data
with the use of a long repetition delay between the consecutive
transients (180 s); this approach allowed for the estimation of the
relative amounts of the r.c. amorphous components. As demonstrated in Table 3, the general trends in the signal linewidths and
intensities in the 13C CP/MAS NMR spectra were also observed in
the 13C MAS NMR spectra, even though the absolute intensities of
the r.c. amorphous components were higher. However, even with a
repetition delay tenfold longer than the T1(13C) relaxation times of
the CH and CH2 groups, the amounts of r.c. amorphous components
(29, 35 and 35%) were still considerably lower than the expected
values calculated on the basis of the WAXS measurements of the
sample crystallinity (60, 55 and 57% for PP, PPB1 and PPB03,
respectively; Table 1). The missing fraction of the amorphous phase
can be attributed to the conned non-crystalline component, and
the amount of this conned amorphous phase appears to be greater
in the a2-polymorphic samples than in the b-polymorphic samples.
Because the measured differences in the CH and CH2 linewidths
are very small, particular attention was devoted to the analysis of

Table 2
The linewidths Dn and relative intensities Irel of the CH2 and CH signals relating to the amorphous and crystalline phases obtained by deconvolution of the 13C CP/MAS NMR
spectra measured at 355 K.
Sample

CH2

CH
31-Helical crystalline and
amorphous (44 ppm)

r.c. amorphous
(46 ppm)

PP
PPB1
PPB03
a

r.c. amorphous (28 ppm)

31-Helical crystalline
and amorphous (26 ppm)

Dn, Hz

Irel, %

Dn, Hz

Irel, %

Dn, Hz

Irel, %

Dn, Hz

Irel, %

110
99
108

18
22
23

110, 120a
129
129

82
78
77

115
98
107

23
27
27

53
52
53

77
73
73

Two lines representing the doublet of the a2-polymorphic form of i-PP were used to simulate the CH2 signal.

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Table 3
The linewidths Dn and relative intensities Irel of the CH2 and CH signals related to the amorphous and crystalline phases obtained by deconvolution of the 13C MAS NMR spectra
measured at 355 K.
Sample

CH2

CH

r.c. amorphous (46 ppm)

PP
PPB1
PPB03
a

31-Helical crystalline
and amorphous (44 ppm)

r.c. amorphous (28 ppm)

31-Helical crystalline
and amorphous (26 ppm)

Dn, Hz

Irel, %

Dn, Hz

Irel, %

Dn, Hz

Irel, %

Dn, Hz

Irel, %

100
92
95

29
34
35

110, 120a
140
150

71
66
65

95
90
90

29
36
36

57
58
60

71
64
64

Two lines representing the doublet of a2-polymorphic form of i-PP were applied to simulate the CH2 signal.

the methyl signals that produced a clear representation of the

three-component behaviour of the prepared i-PP systems (Fig. 2).
For the correct signal assignment, we performed variabletemperature measurements of 13C CP/MAS NMR spectra in the
temperature range of 295e355 K; in which interconversion between the constrained non-crystalline component, mostly 31-helical, and the free r.c. amorphous phase occurs. To quantitatively
follow the conversion of the constrained non-crystalline component, the methyl signals were decomposed into three Gauss/Lorentz lines.
As demonstrated in Fig. 3, the low-frequency broad component
resonating at 21.4 ppm (signal A) exhibited a weak thermally
induced decrease in intensity from approximately 55 to 45%. A
much steeper reduction in the signal intensity was observed for the
broad high-frequency component at 22.4 ppm (signal C), whereas a
strong increase in the signal intensity was observed for the narrow
component resonating at 21.9 ppm (signal B). The changes
observed during cooling of the heated samples were reversible
within the experimental error of our measurements (3%). Additionally, the low-frequency broad signal was nearly unaffected by
temperature variation and was attributed to the crystalline phases
of i-PP. In contrast, the thermally labile 13C NMR resonances at 21.9
and 22.4 ppm were assigned to the free r.c. amorphous phase and
the constrained non-crystalline component, respectively. The slight
signal intensity increase for the crystalline phase (compared to the
total crystallinity determined by WAXS (Table 1)) indicated that
another component may have contributed to the signal. This fraction likely corresponds to the disordered X-ray amorphous phase,
which correlates structurally to the crystalline phase. Therefore, the
presence of nanosized protocrystalline domains is possible (some
attempts to verify the presence of such a phase are discussed later
in the analyses of the T1r(1H) relaxation data).

In addition to the signal assignment, the temperature dependencies presented in Fig. 3 were used to compare the thermodynamic stability of the conned amorphous phases of i-PP samples.
Visual inspection indicated that the constrained non-crystalline
fraction is considerably less stable in b-crystalline systems and
consequently its conversion into the free r.c. amorphous phase is
more extensive. This conversion was quantied for each sample
using a linear approximation. Whereas in the case of the a2-polymorphic system the conned non-crystalline component converted
into the free highly mobile r.c. amorphous phase at the extent of
0.28%.K$1, the transformation reached much higher extent in the bcrystalline systems PPB1 and PPB03 (0.52 and 0.62%.K$1, respectively). These ndings indicate that some barriers restrain the
release of polymer chain motions in the a-polymorphic system.
The variable-temperature 1H MAS NMR spectra were recorded
to further understand the internal dynamics of the prepared i-PP
systems and to verify the aforementioned differences. The aim of
these experiments was to estimate the critical temperature at
which the release of the high-amplitude cooperative motions induces splitting of the originally broad 1H MAS NMR signals. As
demonstrated in Fig. 4, the critical temperature in all samples was
reached slightly below 350 K. At this temperature, thermally activated processes considerably enhanced the spectral resolution and
the CH2 and CH resonances of the most mobile polymer segments
in the free amorphous phase were clearly observed. In the 1H NMR
spectra of the PPB1 and PPB03 samples, the CH signal at approximately 1.1 ppm was discernible; however, the signal splitting
observed for the a2-polymorphic PP system was less pronounced.
These results provide further evidence that larger restrictions in
chain mobility exist in the amorphous phase of the a-polymorphic
PP system than in the PPB1 and PPB03 systems predominated by
the b-polymorphic form.

Fig. 2. Methyl regions of the 13C MAS NMR spectra of the prepared PP and PPB03 samples measured with a long repetition delay (180 s) at 355 K. The recorded methyl signals were
deconvoluted into three lines.

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O. Policianova

3.3. Spin-lattice relaxation times

Fig. 3. Temperature dependence of the relative intensities of the spectral components

(A), (B) and (C) identied in methyl regions of the 13C MAS NMR spectra of i-PP
systems.

Molecular motions covering a wide range of time-scales have

long been considered to affect the physicochemical properties of
polymer systems. High-amplitude motions have been observed in
amorphous fractions at temperatures above the Tg as well as in the
glassy state and crystalline domains. NMR spectroscopy is a
powerful tool for studying segmental dynamics. In general, two
distinct types of motions are recognised via nuclear-spin relaxation: i) high-frequency motions (librations, rotations and jumps of
small groups with frequencies in the hundreds of MHz) that are
examined by the measurement of T1 relaxation times at the laboratory reference frame; and ii) low-frequency motions (approximately tens of kHz) involving movements of larger molecular
segments that are examined by T1r relaxation experiments at the
rotating frame.
In semicrystalline i-PP, three distinct types of motion are expected: i) fast three-site jumps of methyl groups; ii) slow three-fold
jump rotations of the whole polymer chain about the 31-helical
chain axis; and iii) fast gauche-trans-gauche-cis conformational
ips. To probe these motions quantitatively, we measured the
rotating-frame spin-lattice relaxation times T1r(13C) and T1r(1H)
and the spin-lattice relaxation times T1(13C) and T1(1H). All these
measurements were conducted at laboratory and elevated temperatures (300 and 355 K, respectively). The determined T1(13C),
T1r(13C) and T1(1H) relaxation times did not show any considerable
differences among the prepared systems. However, distinctly
different relaxation behaviours were observed for 1H spins at the
rotating frame.
The obtained 1H spin relaxation dependencies indicated much
faster T1r(1H) relaxation for the b-polymorphic PPB1 and PPB03
systems, whereas the relaxation was considerably slowed in the a2polymorphic PP sample (Fig. 5a). When analysing data from the
T1r(1H) relaxation experiments, however, one must take into account variations in segmental dynamics as well as possible differences in the distribution of crystalline and amorphous domains in
the investigated samples. Previously, i-PP has been demonstrated
to be a nanoheterogeneous system with a minimum crystal thickness of approximately 10e20 nm. In this case, rapid 1H-spin
diffusion (i.e., relayed 1H magnetisation exchange) can partially
equilibrate relaxation behaviour; the T1r(1H) relaxation times are
essentially distorted. To test the extent of 1H spin diffusion in the
analysed systems, we performed complementary T1r(1H) relaxation experiments employing the Lee-Goldburg spin-locking eld.
With this method, the 1He1H spin-diffusion processes was
considerably suppressed. The obtained relaxation dependencies
demonstrated in Fig. 5b revealed trends almost identical to those
observed using the standard procedure. The efciency of 1H spindiffusion was motionally suppressed, probably because of the
high mobility of polymer chains in the i-PP; this suppression
allowed us to monitor the true relaxation times for individual
amorphous and crystalline components without interference.
To extract the T1r(1H) relaxation times and the corresponding
relative amounts of individual spectral components, the signalintensity decays I(t)recorded for CH groups (Fig. 5a) were tted
to single- or double-exponential functions according to the
following relation:

$T t

It Ia e
Fig. 4. 1H MAS NMR spectra of the prepared samples PP (upper black trace), PPB1
(middle blue trace) and PPB03 (bottom red trace) measured at 350 K. (For interpretation of the references to colour in this gure legend, the reader is referred to the web
version of this article.)

1a

$T t

Ib e

1b

where Ia and Ib are extrapolated intensities of individual components at zero time t and T1a and T1b are the corresponding T1r(1H)
relaxation times. To determine corresponding correlation times we
applied an expression:

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O. Policianova

Fig. 6. 2D 1He13C PILGRIM NMR spectra of the a-polymorphic PP sample. The rigidlimit value nCH,rig 13.4 kHz corresponding to the dipolar coupling constant
DCH,rig 23.1 kHz (CeH distance 1.09 A) was applied to calculate the order parameter
S nCH/nCH,rig. The relation between the dipolar coupling
constants and the splitting of
p
dipolar proles is given by DnCH sin 54:7DCH;rig = 2.

Fig. 5. T1r(1H) relaxation decay of 1H magnetisation of CH groups in the samples PP

(upper black trace), PPB1 (middle blue trace) and PPB03 (bottom red trace) measured
at 355 K. The upper graph represents relaxation data measured using a standard 1H
spin-lock eld (a). The bottom graph corresponds to the relaxation data obtained using
at the Lee-Goldburg 1H spin locking (b). (For interpretation of the references to colour
in this gure legend, the reader is referred to the web version of this article.)

1
1
1
d2 Jue 2J2ue 6JuH 6J2uH ( d2CH 2Jue
T1r 10 HH
30
3Juc 3JuH Juc $ uH 6Juc uH (
where uC and uH represent the 13C and 1H Larmor frequencies,
respectively; ue/2p 58 kHz is the effective eld for relaxation;
dHH 44 kHz and dCH 23 kHz are the estimated rigid-limit protoneproton and protonecarbon dipolar coupling strengths,
respectively; and J(ui) represents the spectral density functions
[33]. If a single-motion mechanism is assumed to describe the
segmental reorientation, then the spectral density function is given
by:

Jui 1 $ S

phase indicating order parameter ca. 0.20. However, these zerofrequency signals must be interpreted very cautiously because
they can originate from other contributions such as long-range
1
He13C dipolar interactions or incompletely refocused homonuclear 1He1H dipolar couplings [34].
To determine the correct part of the logarithmic T1r(1H)-tc plot,
i.e., to assign segmental dynamics to a slow- or fast-motion regime
(Fig. 7), the relaxation experiments were measured at two temperatures (335 and 355 K).
For all samples, the intensity of the weak CH signal corresponding to the free r.c. amorphous phase (28 ppm) exhibited
single-exponential decay with T1r(1H) values 5 1 ms. With
decreasing temperatures, the relaxation times decreased to
2 1 ms, indicating the fast-motion regime of the corresponding
polymer segments. The correlation time describing reorientation of
polymer segments in the free r.c. amorphous phase at 355 K was
approximately 0.5 ms and increased to 1.1e2.0 ms at 335 K. In
contrast, the intensities of the main CH signals (26 ppm) followed
the double-exponential functions. The intensities revealed the
presence of the slow-relaxing component with T1r(1H) values between 18 and 35 ms and the presence of a rapidly relaxing
component in which T1r(1H) spanned a much narrower range,
3 1 ms. As summarised in Tables 4 and 5, the corresponding
relaxation times increased at lower temperatures, conrming the
slow-motion regime of the corresponding polymer segments.

tc
1 u2i t2c

where S is the generalised order parameter of the motion and tc is

the correlation time. To roughly estimate the order parameters for
the reorientation of CH groups in different components of the
prepared PP systems, we measured a set of high-temperature 2D
1
He13C separated-local-elds experiments. The 1He13C dipolar
spectra were extracted from these data for each resolved carbon
structure unit (Fig. 6). The order parameter was estimated from the
splitting and/or half-width of the dipolar spectra (nCH, kHz) as the
ratio S nCH/13.4 kHz. While the order parameter found for the
polymer chains in r.c. mobile amorphous fractions is ca. 0.15, the
order parameter of crystalline i-PP chains is considerably higher to
be ca. 0.82. The small splitting observed at 44 and 26 ppm can be
attributed to the dipolar coupling for the constrained amorphous

Fig. 7. The spin-lattice relaxation rates in the rotating frame, R1(1H), as a function of
the rotational correlation time, tc.

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O. Policianova

Table 4
The rotating-frame spin-lattice relaxation times (T1r(1H)), relative intensities of individual components (I), and the corresponding correlation times (tc), calculated from the
relaxation decays of the CH groups in the PP, PPB1, and PPB03 samples at 355 K.
Sample

PP
PPB1
PPB03

Free amorphous phase (28 ppm)

Slowly relaxing component (26 ppm)

Rapidly relaxing component (26 ppm)

T1r(1H) ms

I%

tc ms

T1r(1H) ms

I%

tc ms

T1r(1H) ms

I%

tc ms

4.4
4.8
5.1

0.10
0.12
0.18

0.5
0.4
0.4

35
18
22

0.80
0.40
0.35

77
40
48

3.6
3.8
4.0

0.10
0.60
0.65

7.1
7.6
8.1

Typical correlation times for the slow-relaxing polymer chains

were between approximately 80 and 40 ms (355 K), depending on
the original crystal structure, whereas the correlation times of
rapidly relaxing polymer chains were approximately 7e8 ms for all
of the investigated systems.
We observed signicant differences in the T1r(1H) values of the
slow-relaxing component as well as in their relative intensities
when comparing the relaxation behaviours of the investigated
samples. In the case of the a2-polymorphic PP sample, the slowrelaxing component was predominant, with 80% relative intensity
and a T1r(1H) value of 35 ms; the relaxation was considerably faster
in both b-polymorphic samples, with T1r(1H) reaching approximately 20 ms and the relative intensities remaining below 45%.
These ndings indicate that slowly and rapidly relaxing components cannot be simply separated and do not strictly correlate to
the crystalline and constrained amorphous components, respectively. We rather speculate that the slow-relaxing component corresponds to the crystalline fraction and to the strongly constrained
31-helical non-crystalline polymer chains, whereas the rapidly
relaxing component reects partially released PP chains that still
adopt the 31-helical conformation. With high probability thus the
major dynamical differences between the a2-and b-crystalline
systems are located in the interfacial area between crystalline
phase and strongly conned non-crystalline PP chains. Much
stronger intermolecular interactions seem to exist in the interfacial
area in the a2-crystalline systems, whereas in the b-crystalline
systems the arrangement of PP chains on the interface is more
disentangled. The detail structural analysis of the interfacial area is
currently in progress with applying 1He1H spin-diffusion
experiments.
4. Conclusions
A range of variable-temperature (VT) ss-NMR experiments were
used to investigate the molecular origin of enhanced toughness in
b-polymorphic variants of i-PP. Elevated temperatures amplied
spectroscopic differences between various phases of i-PP, thereby
allowing exploration of the segmental dynamics of polymer chains
in detail via line-shape analyses of ss-NMR spectra and 13C-detected T1r(1H) relaxation experiments.
Three distinctly different populations of i-PP were identied.
The free amorphous phase with the r.c. conformation was identied
by the high-frequency signals in 13C MAS NMR spectra recorded at
elevated temperatures; the constrained non-crystalline component
and crystalline phase, both with 31-helical conformations, were

also clearly resolved. Moreover, analyses of VT 13C MAS NMR

spectra and 13C-detected T1r(1H) relaxation experiments indicated
the presence of two subpopulations in the constrained noncrystalline phase.
Analyses of the lineshapes in 13C CP/MAS, 13C MAS and 1H MAS
NMR spectra revealed considerable barriers restraining the release
of polymer chain motions in the amorphous phase at elevated
temperatures in a2-polymorphic PP. Moreover, the presence of
these barriers signicantly increases the thermodynamic stability
of the constrained amorphous phase in the a2-polymorphic i-PP. In
this way, the extent of temperature-induced conversion of this rigid
amorphous fraction into the free (mobile) amorphous phase is
considerably reduced. This extent is approximately two times
smaller in a2-polymorphic PP than in the b-crystalline systems.
Furthermore, detailed analyses of 13C-detected T1r(1H) relaxation data revealed that these barriers considerably reduced polymer chain dynamics in the crystalline phase and in the strongly
constrained 31-helical amorphous phase. Typical correlation times
of segmental motions in these domains reached almost 60 ms in a2polymorphic PP; in the b-crystalline systems, these correlation
times were approximately 30 ms at 355 K. Moreover, in the a2polymorphic PP, the strongly constrained non-crystalline component composed considerably a substantially greater percentage of
the sample than in the b-polymorphic samples. In the b-polymorphic samples, a majority of non-crystalline polymer chains
were located in much more mobile domains and the characteristic
correlation time was approximately 6 ms at 355 K. The existence of a
strongly constrained (rigid) non-crystalline component that is
closely related to the a2-polymorphic form was proposed. To test
the existence of this component, the motional amplitudes are
currently being investigated using a set of variable-temperature 1H
spin-diffusion experiments combined with measurements of
1
He13C dipolar proles.
In a summary, the investigated polymorphic variants of i-PP
systems differ considerably with respect to phase compositions and
segmental dynamics of polymer chains in the crystalline phase as
well as in the non-crystalline components. The amorphous phase of
the a-polymorphic PP system exhibits larger restrictions in chain
mobility in comparison to the amorphous phases in the PPB1 and
PPB03 systems, which are predominated by the b-polymorphic
form. We conclude that these differences in segmental dynamics
correlate to the differences in toughness of i-PP. The results from
the ss-NMR experiments indicate that segmental dynamics in the
amorphous phase are, at least partially, responsible for the mechanical properties of i-PP.

Table 5
The rotating frame spin-lattice relaxation times (T1r(1H)), relative intensities of individual components (I), and the corresponding correlation times (tc), calculated from the
relaxation decays of CH groups in PP, PPB1 and PPB03 samples at 335 K.
Sample

PP
PPB1
PPB03

Free amorphous phase (28 ppm)

Slowly relaxing component (26 ppm)

Rapidly relaxing component (26 ppm)

T1r(1H) ms

I%

tc ms

T1r(1H) ms

I%

tc ms

T1r(1H) ms

I%

tc ms

2.0
2.4
2.2

0.05
0.07
0.07

2.0
1.1
1.3

42
23
28

0.86
0.45
0.40

92
50
60

6.6
6.4
5.5

0.10
0.55
0.60

14.1
13.6
11.7

114

! et al. / Polymer 60 (2015) 107e114

O. Policianova

Conict of interest
The authors declare no competing nancial interest.
Acknowledgement
The work was supported by the Czech Science Foundation
(project 13-29009S).
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