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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
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
108
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],
109
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
13
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
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.
110
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
PP
PPB1
PPB03
a
31-Helical crystalline
and amorphous (44 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.
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.
111
$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:
112
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.
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
Fig. 7. The spin-lattice relaxation rates in the rotating frame, R1(1H), as a function of
the rotational correlation time, tc.
113
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
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
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
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
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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