Composites: Part B 45 (2013) 232–238

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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

The structure and thermal properties of novel polyurethane/organoclay

nanocomposites obtained by pre-polymerization
Jelena Pavličević a,⇑, Milena Špírková b, Mirjana Jovičić a, Oskar Bera a, Rafał Pore˛ba b,
Jaroslava Budinski-Simendić a
a
University of Novi Sad, Faculty of Technology, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia
b
Institute of Macromolecular Chemistry AS CR, v.v.i., Heyrovského nám. 2, 162 06 Prague, Czech Republic

a r t i c l e i n f o a b s t r a c t

Article history: All aliphatic polycarbonate-based polyurethanes (PC-PUs) and their layered-silicate nanocomposites
Received 25 January 2012 were synthesized by pre-polymerization procedure. Hard domains of materials prepared in the form of
Received in revised form 17 July 2012 films consist of hexamethylene-diisocyanate and 1,4-butane diol (chain extender). Two polycarbonate
Accepted 5 September 2012
diols differing in chain constitution were used as soft segments. The ratio (R) of OH groups belonging
Available online 13 September 2012
to the diol and the chain extender, as well as hard segment content (HS) was kept constant (R = 1 and
HS = 30 wt.%). For nanocomposites preparation, organically modified montmorillonite and bentonite
Keywords:
were used (1 wt.%). FTIR was performed to investigate hydrogen bonding formation and degree of phase
A. Layered structures
A. Polymer–matrix composites (PMCs)
separation. The micro-phase structure of obtained polyurethanes was studied using SAXS. The influence
B. Thermal properties of morphology and phase behavior of prepared elastomers was estimated combining WAXD and DSC.
Thermal properties of PC-PU hybrid materials are found to be influenced by dispersion of nanofillers with
layered structure.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Aliphatic polycarbonate polyurethanes are very promising
melt-processable materials with wide range of applications
belonging to typical thermoplastics with rubber-like behavior at
their service temperature. Thermoplastic polyurethanes (TPUs)
consist of hard and soft segments and the incompatibility of those
two phases causes microphase-separated structure which is a main
reason for their interesting thermal and mechanical performances
[1]. These properties are connected to the high degree of phase
mixing due to the hydrogen bonding between soft segment car-
bonate groups and hard segment urethane groups [2]. In industry,
due to their improved elastic behavior, excellent low temperature
flexibility, chemical and heat resistance, biostability and biocom-
patibility, compared to the traditional polyurethanes (based on
polyether or polyester) [3–5], they have found various usage as
industrial parts, building materials, sports goods, medical equip-
ment, and even artificial tissues [6–10]. Polycarbonate (PC) diols
are mostly prepared by the reaction of alkane diol with dialkylcar-
bonates. The most used polycarboante diols (PCDs) are based on
poly(hexamethylene carbonate) diol, or on PCD copolymers con-
⇑ Corresponding author. Tel.: +381 214853742; fax: +381 21450413.
E-mail addresses: jelenapavlicevic@gmail.com (J. Pavličević), spirkova@imc.
cas.cz (M. Špírková), jovicic.mirjana@gmail.com (M. Jovičić), oskarbera@gmail.com
(O. Bera), poreba@imc.cas.cz (R. Pore˛ba), jarkamer@gmail.com (J. Budinski-Simendić).
taining 3–10 alkane units [11]. Previous studies based on the prep-
aration of polycarbonate-based polyurethanes (PC-PUs) and their
characterization, confirmed that the chemical structure, constitu-
tion of building units and molecular weight of PC diols has domi-
nant influence on mechanical, thermal and morphological
properties of PC-PUs [12,13]. Polyurethane-layered nanocompos-
ites as an important class of mineral-reinforced thermoplastics
have been intensively investigated in the last decades as promising
nano-engineered materials with achieved a significant improved
performances compared to pristine ones [14]. Among the inorganic
materials, layered silicates have attracted great attention in the
field of nanocomposites because of their ability to disperse into
individual layers [15]. By introducing organoclays in polymer ma-
trix, the nanometer-scale silicate layers dispersed in polyurethane
can create large interfacial areas where the hydroxyl groups on the
silicate layers can form hydrogen bonding with either the hard or
the soft segments in polyurethane. The influence of preparation
procedure, organoclay structure, hard segment content (HS) and
nanofiller content on hydrogen bonding, microphase morphology
and thermal properties of polyurethane hybrid materials was stud-
ied by many authors [16–18]. The microstructure, mechanical and
thermal properties of novel polyurethane elastomers (PUs) are
strongly dependent on the synthesis method employed. Our previ-
ous research was focused on the characterization of all-aliphatic
polyurethanes and their nanocomposites prepared by one-step
technique based on polycarbonate diols 4671 or 5651 (differing

1359-8368/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2012.09.018
 J. Pavličević et al. / Composites: Part B 45 (2013) 232–238
in chain constitution) [19,20]. The main difference between the
materials prepared by the pre-polymer and the one-step methods
involves the chain build-up [21]. In the polyurethanes obtained in
two-steps statistically more regular structure of chain sequences is
expected compared to material synthesized using one-step tech-
nique with more random sequences. This paper is focused on the
investigation of the PC-PU systems in the form of films, but
obtained by pre-polymerization. The influence of preparation pro-
cedure, polycarbonate chain constitution and addition of organi-
cally modified montmorillonite and bentonite (1 wt.%) on phase
and thermal behavior of synthesized elastomers was studied. Fou-
rier transform infrared (FT-IR) spectroscopy and X-ray scattering
were applied for the investigation of hydrogen bonding formation
and collecting the information on the nanometer-scale physical
structures of the PC-PUs and their hybrids achieved by the two-
step technique. The morphology of unfilled and filled materials
influenced by microphase-separated state has been studied by
small-angle X-ray scattering (SAXS) and differential scanning calo-
rimetry (DSC) measurements.
2. Experimental
2.1. Materials
Aliphatic polycarbonate macrodiols with molecular mass
around 1000 (PCDL T5651 and T4671), were kindly provided by
Asahi Kasei Chemical Corporation. All characteristics of macrodiols
were given by the supplier. For PCDL T5651: OH value:
111.4 mg KOH/g; water content: 0.0052 wt.%; viscosity at 50 °C:
1619 mPa s. For PCDL T4671: OH value: 109.9 mg KOH/g; water
content 0.0072 wt.%; viscosity at 50 °C: 2388 mPa s. Hexamethyl-
ene-diisocyanate (HDI), 1,4-butane diol (1,4-BD) and the catalyst,
dibutyltin dilaurate (DBTDL), all Fluka, were used. The catalyst
solution was prepared in oil Marcol (20%). As a solvent, tetrahydro-
furan (Sigma Aldrich) was used. Organically modified montmoril-
lonite (CloisiteÒ 15A produced by Southern Clay Products, Inc.)
and organically modified bentonite (Bentonite for organic systems,
BO, Fluka) were used as fillers.
2.2. Polyurethane film preparation
The thermoplastic polyurethane films were prepared by pre-
polymerization technique. During two-step procedure, the ratio of
OH groups belonging to diol and to the chain extender (1,4-butane
diol, BD) was kept constant (R = 1), while isocyanate component
was added in slight excess (NCO/OHtotal = 1.05). In the first step, tet-
rahydrofuran was added to the macrodiol, then DBTDL (catalyst
concentration was 0.05 m/m%) and after that the pertinent excess
of HMDI. The mixture was stirred for 24 h at room temperature.
The viscosity of the system increased due to the NCO encapped
pre-polymer formation. Chain extender was put as the last compo-
nent to the reaction system, mixed and degassed in order to remove
residual bubbles. Finally, such prepared reactive system was spread
on polypropylene sheet using a ruler (slot width 500 lm) and left for
24 h at room temperature in inert atmosphere for reaction of BD
with the pre-polymer, and for gradual solvent evaporation. The
sample preparation was finalized by post curing at 90 °C for 1 h.
For the synthesis of hybrid materials, the procedure was the same,
but in the first step, the filler nanoparticles were left to be dispersed
in the mixture of macrodiol and solvent by brief stirring for 48 h.
2.3. Fourier Transform Infrared Spectroscopy (FTIR)
Measurements were performed at room temperature with a
Thermo Nicolet Nexus 670 FTIR-ATR spectrometer. Single beam
233
spectra of the samples were obtained after averaging 40 scans be-
tween 4000 and 500 cm1 with a resolution of 2 cm1, in a trans-
mittance mode.
2.4. Wide-angle X-ray diffraction (WAXD)
WAXD measurements were conducted with the use of the HZG/
4A powder diffractometer (Seifert GmbH, Germany). The peak
positions were employed to obtain periodicities according to
Bragg’s law, d = k/2sin h, where k is the X-ray wavelength
(kCu Ka = 0.154 nm) and 2h is the scattering angle. The degrees of
crystallinity Cr were calculated with help of integral intensities
diffracted by crystalline C and amorphous A part of structure
according to relation Cr = C/(C + A).
2.5. Small-angle X-ray scattering (SAXS)
SAXS experiments were performed using a three pinhole cam-
era (Molmet/Rigaku) attached to a multilayer aspherical optics
(Osmic Confocal Max-Flux) which simultaneously monochroma-
tizes as well as concentrates the beam of a microfocus X-ray tube
(Bede) operating at 45 kV and 0.66 mA (30 W). The camera was
equipped with a multiwire, gas-filled 2D detector with an active
area diameter of 0.2 m (Gabriel design). It was possible to reach
the interval of 0.043 to 10.5 nm1 of the scattering vector magni-
tude q = (4p/k)sin h, where k = 1.54 Å is the wavelength and 2h is
the scattering angle, since in the high resolution mode, the sample
to detector distances was 2.24 m and in the low resolution mode
0.41 m. Calibration was done using Ag Behenate sample. The peak
positions were employed to obtain characteristic length D accord-
ing to Bragg’s law, D = 2p/q. Scattering intensities were put on
absolute scale using a glassy carbon standard. Typical counting
times were 3600 or 10,000 s.
2.6. Differential Scanning Calorimetry (DSC)
Thermal characterization of thermoplastic unfilled and filled
polyurethane elastomers prepared by pre-polymerization was car-
ried out using differential scanning calorimeter (DSC Q100 TA
Instruments). The instrument was calibrated using an indium stan-
dard. The heating and the cooling rates in the temperature range
from 90 °C to 180 °C were 3 °C/min. The sample masses were
about 5 mg. The measurements were done under the nitrogen
atmosphere, at the purge gas flow rate of 50 cm3/min. In order to
erase the previous thermal history of annealed samples (in vacuum
at 90 °C for 1 h), the glass transition temperature Tg (determined
using the midpoint inflection method) and the heat of fusion were
determined from the data recorded in the second cycle. The melt-
ing temperatures of hard domains Tm were read at endothermic
peak maxima. The temperature of hard segment crystallization,
heat of crystallization and the rubber to glass transition were stud-
ied from the cooling curves.
3. Results and discussion
According to pre-polymerization method used for the synthesis
of segmented PC-PUs (see Section 2), two series of polyurethanes
based on polycarbonate diols and their nanocomposites were pre-
pared, and their codes with the compositions are given in Table 1.
In all samples ratio R (R = [OH]diol/[OH]ext.) was kept constant
(R = 1). In two-step method, the previously synthesized pre-
polymer was allowed to react with butanediol, while in one-shot
method diol, diisocyanate and chain extender were mixed and
allowed to react. Degree of phase separation (DPS) and degree of
234 J. Pavličević et al. / Composites: Part B 45 (2013) 232–238

Table 1 ties of segmented polyurethane materials and connected to their

Codes, composition, degree of phase separation and degree of phase mixing for PC- thermal properties [22].
based PU materials.

Sample code PC diols Nanofiller Degree of phase Degree of phase

(1 wt.%) separation (DPS) mixing (DPM) 3.1. Hydrogen bonding formation and degree of phase separation in
PC-PUs and their nanocomposites
5651/0 5651 – 75.0 25.0
5651/BO 5651 BO 72.5 27.5
5651/15A 5651 15A 69.2 30.8 In order to investigate the microdomain structure of segmented
4671/0 4671 – 68.2 31.8 PC-PUs and their nanocomposites prepared by pre-polymerization,
4671/BO 4671 BO 68.1 31.9
FT-IR spectroscopy was used. There were no detected unreacted
4671/15A 4671 15A 66.0 34.0
isocyanate and alcohol peaks in the spectra indicating that the
most isocyanate and alcohol groups reacted to form the corre-
sponding urethane groups. The description of other bands (beside
phase mixing (DPM) are also given in Table 1. Their calculation is ANH and AC@O groups) found in IR spectra of prepared polyure-
described in details later (see Section 3.1). thanes is given in the previous work [19]. It is well known that
Linear aliphatic polyurethanes contain flexible soft segments ANH and AC@O bands in IR are two typical bands used to investi-
and alternating crystallisable hard segments. The flexible segments gate H-bonds constitution in PUs and their frequencies are usually
are made from pure polycarbonate diols and form the continuous used to analyze the H-bond strength [23]. The hydrogen bonding is
amorphous soft phase with a low glass transition temperature Tg, formed by the ANH groups being as proton donor and the oxygen
giving the material low temperature flexibility. The chain extender in carbonyls of the hard segment and in carbonate of the soft seg-
(1,4-BD) forms hard segments with diisocyanate component HDI, ments as proton acceptors [24]. The enlarged ANH stretching re-
which act as physical crosslinks and reinforce the soft segment ma- gion (between 3200 and 3500 cm1) of pristine PC-PUs and their
trix. The major hydrogen bonds are involved with the urethane nanocomposites is shown in Fig. 1. All –NH band areas were nor-
group with itself (hard–hard segment interaction) and with the malized on the basis of total ANH stretching area.
carbonate group (hard–soft segment mixing). The presence of hard In the infrared region from 3400 to 3500 cm1 there is no ob-
domains in the structure is directly related to the physical proper- served band assigned to free ANH groups. In order to investigate

Fig. 1. Enlarged FTIR spectra of –NH stretching region of PUs and their nanocomposites based on: (a) 5651 diol and (b) 4671 diol.
 J. Pavličević et al. / Composites: Part B 45 (2013) 232–238
Fig. 2. Deconvolution of IR spectra of the ANH stretching region for PC-PUs and their nanocomposites.
in details ANH stretching region of unfilled and filled PC-PUs,
deconvolution of this area was performed to give the best fits using
Gaussian equations (Fig. 2). This method has confirmed the exis-
tence of three peaks with determined band positions and their
areas.
A sharp absorption peak positioned at 3319 cm1 is connected
to H-bonded ANH groups (band II). This band has stronger inten-
sity for almost all PU nanocomposites in regard to pristine ones,
confirming the formation of hydrogen bonding due to the interac-
tion between matrix and reinforced fillers. The only exception is
the sample based on diol 4671 and filled with 15A. But, in case
of 1 wt.% bentonite addition, the positive influence of nanofiller
presence on hydrogen bonding formation in the structure of PUs
based on both diols is achieved. Bands I and III (observed at 3385
and 3273 cm1, respectively) are related to two phonon vibrations
in ANH stretching vibration with strong carbonyl C@O carbonate
groups.
The best choice for studying the effect of an intercalated silicate
layers on the degree of phase separation in polyurethane is to
Fig. 3. Deconvolution of IR-spectrum of the carbonyl group absorbance region for
5651-based PU filled with 1 wt.% of montmorillonite.
235
determine it only from the extent of hydrogen bonding in the hard
segments [25,26]. The formation of hydrogen bonding can be
investigated by determination of position and area of four bands
found by deconvolution of carbonyl region (Fig. 3, as an example).
Three peaks at 1662, 1685 and 1716 cm1 are connected to
H-bonded AC@O, and one at 1745 cm1 is attributed to non
H-bonded (free) AC@O [19]. The degree of phase separation and
the degree of phase mixing of segmented PUs can be calculated
as well using Eqs. (1 and 2) [26]. Values of DPM and DPS are
summarized in Table 1.
Abonded;tot A1662 þ A1685 þ A1716
DPS ¼ ¼ ð1Þ
Atot A1662 þ A1685 þ A1716 þ Afree;1745
DPM ¼ 1  DPS ð2Þ
On the basis of the calculated values for DPS and DPM, it is noticed
that there is no significant change in the phase separation ratio for
all unfilled and filled samples determined to be about 70 ± 5%,
which might be explained by uniform dispersion of silicate layers
in the PU matrix.
3.2. The morphology and the micro-phase structure of PC-PUs and
their nanocomposites
X-ray diffraction in the region of wide was performed to inves-
tigate the degree of crystallinity in the aliphatic PC-PUs and their
nanocomposites prepared by pre-polymerization. Small angle
X-ray scattering was used to obtain information about the micro-
phase structure of unfilled and filled polyurethane elastomers. In
order to determine the influence of preparation procedure on the
structure and degree of crystallinity, these results are compared
to data from the previous research based on PC-PUs, but synthe-
sized using one-step technique [19].
WAXD and SAXS profiles of PC-PUs and their hybrid materials
based on 5651 or 4671 polycarbonate diol are presented in
Fig. 4. Detailed discussion of WAXD and SAXS patterns of PC-PUs
prepared by one step technique is described in our previous work
[19,27]. The degree of crystallinity for all samples, determined by
deconvolution of signals belonging to the amorphous and crystal-
line parts, is given in Table 2.
236 J. Pavličević et al. / Composites: Part B 45 (2013) 232–238

Fig. 4. (a) WAXD patterns of 5651-PUs, (b) WAXD paterns of 4671-PUs, (c) SAXS patterns of 5651-PUs and (d) SAXS patterns of 4671-PUs.

The influence of preparation procedure was found for of 4.6 nm), which can be assigned to a wider range of differently
5651-based series; samples prepared by pre-polymerization have strong intercalated filler domains. Intercalation of 15A particles
higher crystallinity (14–16%) than their analogues prepared by was found in 5651-PU due to shifted lower maximum, located at
one-step synthesis where the degree was in the range from 7% to 2.3° (with the corresponding d = 3.8 nm).
11 %. This might be explained that the solvent presence causes bet- According to SAXS results, both unfilled samples exhibit scatter-
ter ordering in irregular 5651 macrodiol than in 4671 matrix which ing peaks with the similar shape and position due to the same HS
chains show higher regularity compared to 5651 matrix [27]. The content (Fig. 4c and d). The interdomain spacing of HS in 4671- or
dispersion of 1 wt.% of nanoclays (15A and BO) slightly increases 5651-based PC-PUs was calculated from the peak position and the
ordering by 1–2% in 4671-based PUs which can be assigned to values for all polyurethanes and their nanocomposites are given in
the contribution of layered silicates to better organization of nano- Table 2.
composites. The addition of BO nanoparticles causes moderately The average value of maxima interdomain spacing for less reg-
decrease of ordering (overall ordering in matrix) by 1%, while rein- ular 5651-based samples is found to be smaller in comparison with
forcement with 15A slightly increases 5651-polyurethane crystal- the same value of more regular 4671-based elastomers. The addi-
linity. The neat nanofillers exhibit main diffraction maxima at tion of organoclay causes the lower interdomain spacing and
2.8° (for BO) and at 3.0° (for 15A) which correspond to the dis- smaller scattering peaks, indicating that the lamellar patterns in
tances of 3.1 and 2.9 nm, respectively [19]. This ‘‘silicate-layer- the presence of 15A or BO lamellae correspond to higher level of
distance maximum’’ of the PU elastomers based on 5651 or 4671 lamellar ordering. SAXS profiles for all nanocomposites possess
macrodiol and filled with 1 wt.% of 15A, is shifted to lower scatter- two additional peaks. The first is detected between 3.5 and
ing angles, to 2.6° and 2.1°, respectively, with the corresponding 4.0 nm and the second one at ca 2.0 nm. These two peaks corre-
distances of 3.4 and 4.2 nm, indicating the presence of intercalated spond to well order lamellar structure of BO particles intercalated
aggregates with wider silicate plate distance. XRD pattern of by PU matrix with the periodicity of about 3.5 nm.
BO-nanocomposites based on 4671 shows a flat ‘‘silicate-layer- The presence of one scattering peak in SAXS profiles of un-
distance maximum’’ at very small angle at 1.9° (with the distance filled samples and two additional detected in the patterns of
nanocomposites which are connected to organoclays might be
Table 2 the evidence of heterogeneous microstructure with phase sepa-
Codes, degree of crystallinity and position of SAXS maxima for PC-PUs and their ration. This observation is also confirmed by FTIR and DSC
nanocomposites prepared by pre-polymerization. experiments.
Sample code Degree of SAXS max 1 SAXS max 2 SAXS max 3
crystallinity (%) (nm) (nm) (nm)
5651/0 15 13.1 – –
3.3. Thermal properties of PC-PUs and their nanocomposites
5651/BO 14 11.6 4.0 2.0
5651/15A 16 11.6 3.9 2.0 Thermoplastic segmented polyurethane elastomers exhibit usu-
4671/0 11 12.3 – – ally several phase transitions due to the microstructure of hard and
4671/BO 13 12.3 3.7 1.9
soft segments and the strong intermolecular interaction of
4671/15A 12 11.6 3.9 2.0
hydrogen bonding between the hard–hard segments of urethane
 J. Pavličević et al. / Composites: Part B 45 (2013) 232–238 237

and Tg of the original polycarbonate diol (DTg) is necessary to be

Fig. 5. Thermal curves of heat flow versus temperature for segmented polyure-
thanes and their nanocomposites based on 5651 polycarbonate diol.
Fig. 6. Thermal curves of heat flow versus temperature for polyurethanes and their
nanocomposites based on 4671 polycarbonate diol.
linkages [28]. According to DSC results, 5651 and 4671 polycarbon-
ate diols, differing in chain constitution, possess a broad glass tran-
sition region, with determined low glass transition temperatures at
60 °C and 58 °C, respectively. Obtained Tg values of two macro-
diols are in good accordance with the literature data [11].
The influence of 1 wt.% nanofiller addition on thermal behavior
of polyurethane nanocomposites based on different soft segment
(5651 or 4671), is illustrated in Figs. 5 and 6, respectively. Thermal
data obtained from the second heating run and cooling curve of
heat flow versus temperature for all the samples are given in
Table 3.
The broadness of the glass transition range depends on the
amount of hard segments and their separation from the soft seg-
ments (in FTIR experiments DPS is found to be around 70%). The
glass transition temperature of unfilled elastomers was found at
35 °C. The addition of bentonite and montmorillonite slightly
decreased Tg of obtained elastomers by about 3 °C (Table 3).
For detailed investigation of the micro-phase separated struc-
ture, the difference between Tg of the soft segment in the PUs
determined. Higher DTg of the soft segments caused the increasing
miscibility of the two components on account of the molecular
interaction between the soft and hard segments [11]. For both soft
segments, this difference was about 24 °C indicating the presence
of microphase separation in all samples.
The first heating curves of polyurethane elastomers and their
nanocomposites based on 5651 or 4671 matrix showed two endo-
thermic events (first smaller and second bigger) after 60 °C, and,
with nanoclay addition, the temperatures of those peaks were
shifted to higher values by about 10 °C. Seymour and Cooper have
suggested that these endotherms can be assigned to break-up of
short-range ordered hard segment domains and break-up of
long-range ordered hard segment domains [29]. In the second
heating run, only one broad endotherm with the minimum (Tm)
above 100 °C can be observed. It might be explained that by addi-
tional heating, all hard domains became well ordered and, for this
reason, the starting of physical crosslink disruption appears at
higher temperatures.
The temperature of hard segments melting is significantly influ-
enced by nanoparticles dispersion. By addition of 1 wt.% bentonite
and montmorillonite, Tm values of 5651-based polyurethanes were
increased by 9 °C and 11 °C compared to Tm of unfilled sample
based on the same polycarbonate diol (which melting temperature
is 111 °C). The similar positive trend was noticed for 4671-based
samples, where the melting temperature of hard segments for un-
filled elastomer, determined at 109 °C was registered at higher val-
ues, at 117 °C and 124 °C by incorporation of bentonite and
montmorillonite, respectively. This positive influence of nanoclay
addition on thermal properties of segmented thermoplastic poly-
urethanes presents the evidence of the reaction between nanopar-
ticles and hard phase. The enthalpy of HS melting region of studied
polyurethanes based on both soft segments (DHm) was moderately
increased with nanoclay addition; indicating that by filler incorpo-
ration, the ordering degree of hard domains is slightly increased,
which is in accordance with WAXD results. The cooling DSC curves
(recorded also with 3 °C/min) show a retarded solidification above
65 °C assigned to the crystallization of hard segments. By addition
of organically modified bentonite and montmorillonite, the
crystallization temperature (Tc) of samples based on diol 5651 is
increased from 68 °C to 72 °C and 77 °C, respectively, and for elas-
tomers based on diol 4671 from 75 °C to 79 °C and 81 °C. The rub-
ber to glass transition is observed in the same temperature range
like during the heating. The big difference between Tm and Tc is
connected to slow process of the hard domains recrystallization.
4. Conclusions
A series of all aliphatic polycarbonate-based polyurethanes and
their hybrid materials, with 30 wt.% of hard segments, were syn-
thesized using pre-polymerization procedure. Mineral reinforced
nanocomposites were obtained by 1 wt.% addition of organically
modified bentonite and montmorillonite. The formation of hydro-
gen bonding due to the interaction between polyurethane and

Table 3
DSC data for PC-PUs and their nanocomposites based on 5651 or 4671 macrodiol.

Sample code Glass transition Temperature of HS Enthalpy of HS Temperature of HS Enthalpy of

temperature of SS, Tg (°C) melting, Tm, (°C) melting, DHm (J/g) crystallization, Tc (°C) recrystallization, DHc (J/g)
5651/0 35 111 12.8 68 12.1
5651/BO 38 120 13.1 72 17.9
5651/15A 38 122 12.9 77 19.7
4671/0 35 109 17.9 75 22.0
4671/BO 37 117 18.2 79 23.6
4671/15A 38 124 18.8 81 22.9
238 J. Pavličević et al. / Composites: Part B 45 (2013) 232–238
reinforced fillers was confirmed by deconvolution of –NH
stretching and carbonyl group absorbance region of obtained IR
spectra. On the basis of determined degree of phase separation
(70 ± 5%), it was concluded that there was no significant change
in the phase separation ratio for all PC-PUs and their nanocompos-
ites due to achieved uniform dispersion of silicate layers. It is
estimated that degree of crystallinity for all elastomers was in
the range from 11% to 16%. The dispersion of 1 wt.% of nanoclays
(15A and BO) slightly increases ordering of 4671-based polyure-
thane hybrid materials. All experiments (FTIR, SAXS and DSC) have
confirmed the existence of heterogeneous microstructure with
phase separation. The glass transition temperature, the tempera-
ture of hard segments melting and the recrystallization tempera-
ture, obtained from the second DSC curves, were found to be
influenced by dispersion of nanofillers with layered structure.
Acknowledgement
This work was financed by the Ministry of Education and Sci-
ence of the Republic of Serbia for (Project No. III45022). The
authors from Prague wish to acknowledge to the Grant Agency of
the Czech Republic (Czech Science Foundation, Project No. P108/
10/0195). The authors also express their gratitude to Dr. Josef Bal-
dian for WAXD and SAXS experiments made in IMC Prague.
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