Composites: Part A 50 (2013) 65–72

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Creep behavior of polyurethane nanocomposites with carbon nanotubes

Zhen Yao a, Defeng Wu a,⇑, Chong Chen b, Ming Zhang b
a
School of Chemistry & Chemical Engineering, Yangzhou University, Jiangsu 225002, PR China
b
Testing Center, Yangzhou University, Jiangsu 225002, PR China

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

Article history: The polyurethane (PU) nanocomposites containing carbon nanotubes (CNTs) were prepared through
Received 12 January 2013 in situ polymerization for the creep study. The results show that the presence of CNTs leads to a signif-
Received in revised form 21 March 2013 icant improvement of creep resistance of PU. However, this creep resistance does not increase monoto-
Accepted 23 March 2013
nously with increase of CNT contents because it is highly dependent on the dispersion of CNTs. Several
Available online 2 April 2013
theoretical models were then used to establish the relations between CNT dispersion and final creep
and creep–recovery behaviors of nanocomposites. The as-obtained viscoelastic and viscoplastic parame-
Keywords:
ters of PU matrix and structural parameters of CNTs further confirmed the retardation effect by CNTs dur-
A. Polymer–matrix composites (PMCs)
B. Creep
ing creep of the nanocomposite systems. Besides, the time–temperature superposition (TTS) principle
C. Analytical modeling was also employed in this work to make a further evaluation on the creep of PU/CNT nanocomposites
D. Mechanical testing with long-term time scale.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction materials, creep and creep–recovery of the polymer/CNT compos-

As an important engineering material, polyurethane (PU) exhib-
its many attractive properties, such as adjustable mechanical
strength, unique shape-memory ability and superior chemical
resistance, because of its special soft–hard segment structure
[1,2]. In order to further extend its applications, several techniques,
including interpenetrating [3,4], blending [5] and copolymeriza-
tion [6], have been developed to control hierarchical structures
and final properties of the PU material. Besides, hybridation with
nanofiller [7,8] is also an effective strategy to improve the perfor-
mance of PU.
In recent years, the carbon nanotubes (CNTs) have become the
next-generation reinforcements for nano-structured polymeric
composites, owing to its extraordinarily high elastic modulus,
strength, and resilience [9–11]. Hitherto, many CNTs based poly-
mer nanocomposites [12–14] have been successfully prepared
via various methods, also including the PU/CNT nanocomposites
[15–30]. The structure and properties of PU/CNT systems have
hence been extensively studied and the focus of attention are:
(1) the dispersion of CNTs and the microstructure of nanocompos-
ites [15–19]; (2) the thermal and rheological behaviors in the pres-
ence of CNTs [20,21]; (3) the improvement of active shape memory
with addition of CNTs [22–24]; (4) the mechanical properties,
especially the reinforcing effect of CNTs [20,25–30].
As an interesting time dependent behavior and as an important
evaluation standard on the dimensional stability of engineering
⇑ Corresponding author. Tel.: +86 514 87975590x9115; fax: +86 514 87975244.
E-mail address: dfwu@yzu.edu.cn (D. Wu).
ite systems have attracted much attention recently [30–37]. It
has been reported that the presence of CNTs restrains the creep
deformation of matrix polymer significantly, but the improvement
of creep resistance diminishes with the growing stress and in-
creased temperature [34–36]. The recovery property is also highly
improved, especially at high temperature [31,35]. Such improve-
ment is attributed to two possible reasons: (1) the presence of
CNTs leads to the formation of a significant interphase zone with
altered polymer mobility, namely chain immobilization, which re-
sults in the initial reduction of the creep compliance [33–35]; (2)
good CNTs–matrix interfacial bonding further reduces creep
through frustrating chain disentanglement, stretching and frag-
mentation of the macromolecule [33].
The creep study is also very important to the PU/CNT nanocom-
posites. There are merely few reports on the creep of PU/CNT nano-
composites found in the literatures, however. Jia et al. [30]
performed a preliminary study on the creep properties of the ther-
moplastic polyurethane (TPU)/CNT nanocomposites and found that
the presence of CNTs (pure or functionalized) could improve the
creep resistance through their good interfacial adhesion to the
TPU matrix. The interesting results reveal a common creep behav-
ior of the PU/CNT systems, similar with that reported on the other
CNTs based polymeric composites. To deeply understand how the
presence of CNTs affects the time dependent properties of PU,
however, it is necessary to further explore the creep and creep–
recovery behaviors of PU/CNT nanocomposites. Therefore, in this
work, the PU/CNT nanocomposites with different contents of CNTs
were prepared through in situ polymerization for the creep and
creep–recovery studies at different temperatures and load levels.

1359-835X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesa.2013.03.015
66 Z. Yao et al. / Composites: Part A 50 (2013) 65–72
Some constitutive models were then used to establish the relations
between CNT dispersion and creep of nanocomposites. Besides, the
creep with long-term time scale was also explored by time–tem-
perature superposition (TTS), aiming at further evaluating the time
dependent properties of PU/CNT nanocomposites.
2. Experimental
2.1. Materials and treatment
The purified multi-walled carbon nanotubes (CNTs, purity
>95 wt%) with the outside diameter of 10–30 nm and the special
surface area of 250 m2/g were supplied by Chengdu Organic Chem-
istry Institute, Chinese Academy of Science. 2,4-Toluene diisocya-
nate (TDI) (C. P.) was purchased by Shanghai Lingfeng Chemical
Reagent Co., Ltd. Castor oil (CO) with hydroxyl number of 163 mg
KOH/g was purchased from Sinopharm Chemical Reagent. The
other reagents, including 1,4-butanediol (1,4-BDO) (chain exten-
der), xylene (solvent) and dibutyltin dilaurate (DBTDL) (catalyst)
were analytically pure and purchased from Sinopharm Chemical
Reagent. CO and 1,4-BDO were dried under a vacuum before use
and the other reagents were directly used without any treatments.
The equivalent weight per AOH group of CO is 344.83 g and per
ANCO group of TDI is 87.08 g. These two values were used to cal-
culate the NCO/OH ratio for the synthesis of the PU.
2.2. Preparation of PU and PU/CNT composites
A reported two-step bulk polymerization method [38,39] was
employed in this study to synthesize PU with a 2.25:1:1 M ratio
of ANCO (TDI):AOH (CO):AOH (1,4-BDO). Firstly, a weighed
amount of castor oil was placed in around-bottomed flask, heated
to 60 °C, and thoroughly mixed with a predetermined amount of
TDI, in which the ANCO/AOH ratio is 2.25. The reaction system
was then stirred vigorously with mechanical stirring for 60 min
to prepare a urethane pre-polymer. Secondly, a stoichiometric
amount of DBTDL and 1,4-BDO were added to the stirred system
before addition of certain amount of xylene to control the viscosity
of the system. Thirdly, the mixture was degassed under a vacuum
for about 30 min (until bubbling ceased) and then poured into pre-
heated molds (150 mm  120 mm  1 mm glass cavity). Finally,
the system was cured at 120 °C for 6 h.
The PU/CNT nanocomposites were prepared by in situ polymer-
ization. Firstly, the calculated amounts of CNTs were added to CO
(60 °C). Then the mixtures were stirred vigorously with magnetic
stirring for 24 h, followed by 2 h of ultrasonic oscillation to obtain
a stable suspension system. The subsequent steps were the same
as those for the preparation of neat PU. The weight contents of
CNTs were 0.5%, 1%, 2% and 3%.
2.3. Morphological characterization
The dispersion of CNTs in PU matrix was investigated using a S-
4800 field-emission scanning electron microscope (FE-SEM, Hit-
achi, Japan) with a 15 kV accelerating voltage. The sheet samples
were frozen in liquid nitrogen and fractured. The fractured surfaces
were then coated with gold using an SPI sputter coater for en-
hanced conductivity before observation.
2.4. Mechanical property characterizations
The tensile properties of PU and its nanocomposites were deter-
mined by an Instron Mechanical Tester (ASTM D638) at a cross-
head speed of 2 mm/min at 30 °C using the dog-bone shaped
specimens.
2.5. Dynamic mechanical analysis
Dynamic mechanical analysis (DMA) were performed on a DMA
242 C analyzer (NETZSCH Instruments, Germany) with tensile
mode over a temperature range from 100 °C to 200 °C at various
frequencies (1 Hz, 5 Hz and 10 Hz). The heating rate is 3 °C/min.
Three rectangular specimens (30 mm  5 mm  1 mm) were
tested for each composition.
2.6. Creep and creep–recovery measurements
Creep tests were conducted on a DMA Q800 analyzer (TA
Instruments, USA) with tensile mode at various temperature and
stress levels. The applied stress levels (1.5, 2.5, 3.0, 5.0 and
7.0 MPa) were determined by the tensile tests, which are in the lin-
ear viscoelastic region of all samples. The duration of measure-
ments was determined as 10 min and 30 min for the creep and
creep–recovery tests, respectively. The creep/recoverable strain
and compliance were recorded as a function of the time. Three
rectangular specimens (30 mm  5 mm  1 mm) were tested for
each composition. To obtain master curves of creep, time–temper-
ature superposition was employed to deal with the results from
short-term creep tests performed at various temperatures. The
temperature ranged from 30 °C to 90 °C, and then 2.5 MPa creep
stress was applied for 10 min at each temperature level. Before
each measurement, the specimen was equilibrated for 5 min at
each temperature in order to evenly adjust for the correct temper-
ature of the sample.
2.7. The Soxhlet extraction experiments
The Soxhlet extraction is used here to determine the degrees of
crosslinking of PU and its nanocomposites. The sample in the
weight of W1 was extracted with acetone for 48 h using Soxhlet
extractor and then, dried in a vacuum oven to constant weight
(W2). The degree of crosslinking, Cd, can be determined by:
W1
Cd ¼  100% ð1Þ
W2
3. Results and discussion
3.1. Creep and creep–recovery behaviors
Fig. 1 shows the creep compliance–time curves of the neat PU at
various temperatures. As expected, the creep compliance increases
1.0x105
40 oC 50 oC 60 oC
o o
70 C 80 C 90 oC
creep compliance (μm/N2)
8.0x10 4 secondary creep
primary creep
6.0x104
instantaneous deformation
4.0x104
2.0x104
0.0
0 2 4 6 8 10
time (min)
Fig. 1. Creep compliance–time curves for the neat PU at various temperatures
under 2.5 MPa. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)

3.5 25
3.0 7.0 MPa 20
stress (MPa)
15
2.5
10
strain (%)
2.0
5.0 MPa
5 linear region
1.5
3.0 MPa 0 10
0.00 0.05 0.10 0.15
1.0 stain (mm/mm)
0.5 2.5 MPa
1.5 MPa
0.0
0 5 10 15 20 25 30
time (min)
Fig. 2. Creep and creep-recovery strain–time curves for the neat PU under various
stress levels at 30 °C. The stress–strain curves of the neat PU and its nanocompos-
ites with different CNT contents are given in the inset graph. (For interpretation of
the references to color in this figure legend, the reader is referred to the web version
of this article.)
with temperature, and three typical creep stages (instantaneous
deformation, primary and secondary creeps) are clear. At the
experimental stress level, the tertiary creep, i.e. creep rupture,
which would require longer time, does not appear. This is in favor
of the following modeling study. Fig. 2 gives the creep and creep–
recovery strain–time curves of the neat PU at various stress levels.
The inset graph shows the stress–strain curves of the neat PU and
its nanocomposites obtained from tensile tests. Clearly, all the ap-
plied stress levels are in the linear viscoelastic region. Similar with
other polymers [31,34], the creep and creep–recovery of the neat
PU sample present typical viscoelastic–viscoplastic characteristics:
the creep strain increases with the time and applied stress level
monotonously, and the residual strains become noticeable under
high loads even after a long time period exceeding the time of ac-
tive loads.
The PU/CNT nanocomposites show similar viscoelastic–visco-
plastic characteristics on their creep and creep–recovery behaviors,
as can be seen in Fig. 3. It is clear that the creep strain level of nano-
composites is lower than that of the neat PU, indicating that the
creep of PU matrix is restrained by the presence of CNTs. However,
the creep strain level is not reduced monotonously with the in-
crease of CNT contents. As the CNT contents achieve up to
1.0 wt% and above, the nanocomposites show higher creep level
and higher unrecoverable strain than those containing lower con-
tents of CNTs (indicated parts in Fig. 3). Similar results have also
been reported on the other CNTs based polymer nanocomposites
[32].
This CNT content dependence is closely related to the disper-
sion of CNTs. Fig. 4 gives the SEM images of PU/CNT nanocompos-
ites. At the lower content level (0.5 wt%), CNTs are dispersed
randomly in the form of single nanotube or small bundles, present-
ing good dispersion and distribution throughout the PU matrix, as
can be seen in Fig. 4(a and a0 ). The presence of CNTs can impede the
movements of polymer chain segments and restrain the relax-
ations of chain coins as a result [40–42]. Therefore, the creep of
PU matrix, especially viscoelastic and viscoplastic parts, are con-
strained evidently in the presence of well dispersed CNTs.
At the higher content level (3 wt%), however, CNTs are mainly
dispersed as big bundles or even small aggregates, showing poor
distribution in the PU matrix (Fig. 4(b and b0 )). This indicates that
the primary CNT aggregates cannot be fully detached at the higher
contents during pre-mixing and in situ polymerization because of
Z. Yao et al. / Composites: Part A 50 (2013) 65–72 67
0.0 wt%
0.8
0.8 0.5 wt%
0.6
1.0 wt%
strain (%)
2.0 wt%
0.6 0.4
0.0 wt% 3.0 wt%
strain (%)
0.2
0.5 wt%
1.0 wt% 0.4
0.0
2.0 wt%
11 12 13
0.20 0.25 0.30
0.2 time (min)
0.0
35 40 0 5 10 15 20 25 30 35 40
time (min)
Fig. 3. Creep and creep-recovery strain–time curves for the PU/CNT nanocompos-
ites with different CNT contents at 30 °C and 2.5 MPa. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of
this article.)
strong van der Waals interactions among the nano-scaled CNTs
[43,44]. In this case, the CNTs cannot be distributed throughout
the PU matrix and as a result, their constraining effect on the creep
of matrix reduces. This is further confirmed by the DMA results. As
can be seen in Fig. 5, all nanocomposites show modulus and a tran-
sition temperature values higher than the neat PU. This is attrib-
uted to the presence of high-modulus CNTs and their impeding
effect on the chain mobility [45,46]. But with increasing CNT con-
tents, the modulus and transition temperature decrease somewhat,
indicating that the sample with higher CNT contents even has low-
er effective volume filling ratio than the samples with lower CNT
contents. This agrees with the creep and SEM results.
Besides, the presence of CNTs may influence the bulk structure
of PU such as crosslinking structure, which is also highly relevant
to the final creep properties. To a crosslinkable system, the addi-
tion of nanofiller may affect crosslinking process in different ways.
For instance, the presence of filler can enhance the viscosity of
reaction system, changing molecule diffusion ability. Moreover,
the surface group of filler may change or even participate in the
curing reactions. Both will affect the final crosslinking level. Srik-
anth et al. [47] found that in the epoxy/amino functionalized
CNT composites, the presence of CNTs improved the crosslinking
density of epoxy evidently because the surface amino groups of
CNTs participated in the crosslinking reactions of epoxy. Similar re-
sult has also been reported by Dubey et al. [48] on the CNT based
PCR/EPDM blend composites. They found that the radiation could
induce interface crosslinking between matrix polymers and CNT,
resulting in an increased crosslinking density. For the PU/CNT sys-
tem in this work, it is hard to directly describe the effect of CNTs on
the crosslinking structure of PU through chemical approaches or
spectrum analysis because the used CNTs are merely purified but
not surface-functionalized. Hence the Soxhlet extraction method
was employed here to detect the degrees of crosslinking (Cd) of
the PU and its nanocomposites roughly. The results are listed in
Table 1.
It is seen that the values of Cd increase to some extent with CNT
contents, especially at the lower content levels. Further addition of
CNTs leads to a decrease of Cd values. However, considering the er-
ror range, the difference of crosslinking degrees between PU and its
nanocomposites is not evident. This is reasonable because the used
CNTs are merely purified but not surface-functionalized. Therefore,
the presence of CNTs may have little effect on the crosslinking of
PU matrix during reaction and, the final dispersion and distribution
68 Z. Yao et al. / Composites: Part A 50 (2013) 65–72

(a) (a')

(b) (b')
small aggregates

small bundles

Fig. 4. SEM micrographs of PU/CNT nanocomposites with different CNT contents: (a0 and a) 0.5 wt% and (b0 and b) 3.0 wt%. The scale bar for (a and b) and (a0 and b0 ) are 10 lm
and 5 lm, respectively.

4 Table 1
10 The calculated values of crosslinking degree (Cd) of the neat PU
(a) 0.0wt% and its nanocomposites.
0.5wt%
CNT contents (wt%) Cd (%)
1.0wt%
0.0 97.45 ± 0.15
3 3.0wt%
10 0.5 97.65 ± 0.25
log [E' (MPa)]

1.0 98.41 ± 0.30

2.0 97.89 ± 0.26
0.0wt%
0.5wt% 3.0 97.78 ± 0.28
1.0wt%
log [E' (MPa)]

2 3.0wt%
10
of CNTs is dominant on the final creep performance of PU/CNT
nanocomposites.
o
1 temperature ( C)
10 3.2. Theoretical modeling
-100 -50 0 50 100 150 200
o
temperature ( C) In order to further understand how the presence of CNTs affect
the creep process of nanocomposites, several classic creep models
0.30
were used here to describe the relations between CNT contents and
0.0wt% (b) final creep behavior qualitatively. The power law model is one of
0.5wt%
0.25 most commonly used constitutive models, which was developed
1.0wt%
by Findley et al. [49] based on a power law equation:
3.0wt%
0.20 eðtÞ ¼ e0 þ Atn ð2Þ
tan δ

where e(t) is the creep strain at time t, e0 the instantaneous initial

0.15 strain, A the amplitude of transient creep strain and n the time
exponent. The values of e0 can be obtained from creep curves, and
0.10 A and n can be used as the adjusting parameters to apply Eq. (2)
to fit e(t) of the neat PU and its nanocomposites, by which the val-
ues of those parameters can be obtained. The results are listed in
0.05
Table 2. It is seen that the Findley power law model can be well
used to describe the creep of PU/CNT nanocomposites (solid
-100 -50 0 50 100 150 200
o
curves), as shown in Fig. 6.
temperature ( C) Compared with those of the neat PU, the values of A and n of the
Fig. 5. (a) The dynamic storage modulus (E0 ) and (b) loss factor for the neat PU and
nanocomposites decrease more or less. Similar results have also
its nanocomposites under 10 Hz. (For interpretation of the references to color in this been observed on the PA-66/TiO2 [50] and the PCL/SiO2 composite
figure legend, the reader is referred to the web version of this article.) systems [37]. The decrease of A is indicative of reduced creep levels
 Z. Yao et al. / Composites: Part A 50 (2013) 65–72 69

Table 2
Average values of parameters obtained from Findley power law model prediction on
the neat PU and its nanocomposites.

CNT contents (wt%) A n

0.0 0.22 ± 0.03 0.24 ± 0.03
0.5 0.14 ± 0.06 0.17 ± 0.07
1.0 0.13 ± 0.04 0.21 ± 0.07
2.0 0.17 ± 0.05 0.19 ± 0.05
3.0 0.17 ± 0.06 0.17 ± 0.06

0.90
__ Findley power law model prediction

0.75
Fig. 7. Typical strain–time curve in a creep and creep-recovery test for polymer
material.
0.60
strain (%)

Table 3
0.45 Average values of parameters obtained from Burgers model prediction on the neat PU
0.0wt%
and its nanocomposites.
0.5wt%
0.30 1.0wt% CNT contents (wt%) EE (MPa) EVl (GPa) gV1 (GPa s) gVp (GPa s) s (s)
2.0wt% 0.0 514.45 1.59 12.9 7.66 8.13
0.5 668.32 2.19 17.2 14.8 7.85
3.0wt%
0.15 1.0 727.76 2.58 24.6 17.6 9.53
0 2 4 6 8 10 2.0 679.68 2.45 19.6 14.3 8.00
3.0 640.91 2.26 15.9 12.4 7.03
time (min)

Fig. 6. Prediction on the creep (30 °C, 2.5 MPa) of the neat PU and its nanocom-
posites by Findley power law model. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
1.0
__Burgers model prediction
of PU in the presence of CNTs and, the decreased values of n sug-
0.8
gest that the nanocomposites would spend more time than the
neat PU to achieve to identical creep level. Both confirm the imped-
ing effect on creep by the CNTs. Theoretically, the values of A and n 0.6
strain (%)

should depend on the CNT volume fraction monotonously. Consid-

ering error ranges, however, these two parameters are nearly inde-
pendent of CNT contents. One possible reason is that the CNTs
show poor distribution and dispersion at higher content levels,
resulting in irregular variations of their effective filling volume,
as discussed above.
Another model commonly used is the Burgers model, which is a
combination of Maxwell and Kelvin–Voigt elements [51]. Accord-
ing to the Burgers model, the total strain is the sum of three essen-
tially separate parts, as schematically shown in Fig. 7:
eðtÞ ¼ eE þ eV1 þ eVp
where subscripts E, Vl and Vp correspond to the elastic, viscoelastic
and viscoplastic contributions. The time dependence of e(t) is:
  
r r tEV1 r
eðtÞ ¼ þ 1  exp  þ t
EE EV1 gV1 gVp
where EE and EVl are elastic moduli, gV1 and gVp viscosities, r the
applied stress and t the creep time. When the r is applied, the initial
deformation takes place in the spring with the modulus EE. Later
deformation comes from the spring EVl and dashpot gV1, in parallel,
and from the dashpot with the viscosity gVp. The four unknown
physic variables EE, EVl, gV1and gVp can be used as the adjusting
parameters to apply Eq. (4) to fit e(t) of the neat PU and its nano-
composites. The as-obtained values are listed in Table 3.
It is clear that Burgers model prediction results are in good
accordance with the experimental data for the neat PU and its
nanocomposites, as can be seen in Fig. 8. All the viscoelastic and
viscoplastic parameters of the nanocomposites show higher values
0.4
0.0wt%
0.5wt%
0.2 1.0wt%
2.0wt%
3.0wt%
0.0
0 2 4 6 8 10
time (min)
ð3Þ
Fig. 8. Prediction on creep curves (30 °C, 2.5 MPa) of the neat PU and its
nanocomposites by Burger’s model. (For interpretation of the references to color
in this figure legend, the reader is referred to the web version of this article.)
ð4Þ than those of the pure PU. The parameter EE associated to the Max-
well spring establishes instantaneous creep strain which would be
recovered after stress elimination. The result shows that the CNTs
are able to improve the elastic modulus of PU matrix, which agrees
well with the results of DMA shown in Fig. 5. The maximum of EE
for the nanocomposites with 1 wt% CNTs implies highest volume
filling ratio of CNTs in this content level. Further addition of CNTs
leads to decrease of EE rather than increase, again confirming a de-
graded dispersion of CNTs indirectly.
The retardant modulus EVl is related to the stiffness of amor-
phous polymer chains. It shows the same tendency with EE, which
reflects the reinforcement of CNTs on the Kelvin–Voigt unit. gV1 is
related to the viscosity of the Kelvin–Voigt unit and the ratio of
gV1/EV1 is defined as relaxation time s. Minor increase of s also
70 Z. Yao et al. / Composites: Part A 50 (2013) 65–72

1.0 0
10
__Weibull model presiction 0.0wt% 0.0wt%
0.5wt% 0.5wt%
0.8 1.0wt% 1.0wt%
2.0wt% -1
3.0wt%
10

log [strain (%)]

3.0wt%
0.6
strain (%)

0.4
-2
10

0.2

-3
0.0 10
-2 0 2 4 6 8 10 12
10 15 20 25 30 35 40 10 10 10 10 10 10 10 10
time (min) log [t/α T (s)]

Fig. 9. Prediction on creep–recovery curves of the neat PU and its nanocomposites Fig. 10. The master curves for the neat PU and its nanocomposites to a reference
(30 °C, 2.5 MPa) by Weibull distribution function. (For interpretation of the temperature of 40 °C. (For interpretation of the references to color in this figure
references to color in this figure legend, the reader is referred to the web version legend, the reader is referred to the web version of this article.)
of this article.)

recovery, suggesting that the experimental time is not nearly en-

means that the presence of CNTs does not have strong impeding ef- ough for full recovery of those samples after creep.
fect on the PU chain segments movements. But the evidently in-
creased gV1 especially at the content level of 1 wt%, is indicative
3.3. The long-term creep behavior
of strong inhibition on the relaxation of chain coins or local cross-
linking network because their sizes are in same scale with CNT
The time–temperature superposition (TTS) is a convenient way
bundles. These results are hence in accord with the discussion in
to obtain the results with long time scale through shift of the
Section 3.1.
experimental data at various temperatures. The horizontal shift
gVp is related to the unrecoverable creep strain, which is caused factor aT can be calculated according to the Arrhenius equation:
by the permanent deformation. The increased values of gVp indi-  
cate an increased level of permanent deformation for the nano- Q 1 1
log aT ¼  ð6Þ
composites relative to the neat PU. Similar phenomenon has also 2:303R T T r
been observed on the PP/CNT systems [31]. In order to further
where Q is the activation energy and R the universal gas constant. Tr
illustrate the role of CNTs acted during unrecoverable creep defor-
is reference temperature. The as-obtained master curves are shown
mation, the Weibull distribution equation [52] was applied here.
in Fig. 10. The experimental temperatures (30–90 °C) are lower than
On removing the loads, the instantaneous recovery strain er(t) is:
" a transition temperature and the applied stress are in the linear vis-
 b !#
t  t0 r coelastic region of the PU and its nanocomposites. It is clear that the
er ðtÞ ¼ eV1 exp  þ eVp ð5Þ neat PU sample reveals an evident strain platform next to the strain
gr
failure stage after about 109 s of creep at present stress loads, while
where eV1 is the viscoelastic strain recovery determined by the all nanocomposites are still in the secondary creep stage with lower
parameters gr and br over recovery time t. gr characteristic life creep strain level. Beside, the slope of primary stage in master
parameter and br shape parameter. t0 is the time of stress removed. curves, which is indicative of creep rate, reduces evidently in the
eVp is the permanent strain caused by viscous flow effects. The fit-
ting results using Eq. (5) are shown in Fig. 9 and the obtained
parameter values are list in Table 4. 0
0.0wt% slope -0.147
Clearly, the values of viscoelastic strain recovery eV1 decreases
in the presence of CNTs, which is predictable because of inhibiting 0.5wt% slope -0.134
-2 1.0wt% slope -0.143
effect of CNTs. The decrease of characteristic life (gr) values is
indicative of higher recovery rate of nanocomposites than that of 3.0wt% slope -0.122
the neat PU. In other words, the nanocomposites tend towards sta-
shift factor

-4
bility more rapidly during creep–recovery in comparison with the
neat PU. Besides, the values of permanent strain (eVp) through
model prediction are lower than those obtained after 30 min of -6

Table 4 -8
Average values of parameters obtained from Weibull distribution function Burgers
model prediction on the neat PU and its nanocomposites.

CNT contents (wt%) eV1 (%) gr (s) br eVp (%) -10

40 50 60 70 80 90 100
0 0.749 1.237 0.137 0.073 o
0.5 0.553 0.287 0.096 0.009
temperature ( C)
1 0.461 0.067 0.140 0.068
2 0.512 0.162 0.140 0.070 Fig. 11. The shift factor for the neat PU and its nanocomposites as a function of
3 0.508 0.070 0.123 0.081 temperature. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
 Z. Yao et al. / Composites: Part A 50 (2013) 65–72
presence of CNTs, especially at the content of 1 wt%. This confirms
impeding effect of CNTs on the creep of PU in long-term time scale.
For the nanocomposite with 1 wt% CNTs, it may need additional
105–106 s to reach the strain failure stage in comparison with the
neat PU. It is notable that the long-term creep level of the nanocom-
posites with 3 wt% CNTs becomes higher refer to the nanocompos-
ite with 1 wt% CNTs. As discussed above, the degraded dispersion of
CNTs is one of the most important reasons. But there may be some
other possible reasons, such as alteration of bulk structure or other
unknown factors. This is worthy of further study.
Moreover, the shift factors at various temperatures reveal good
linearity for all samples, as can be seen in Fig. 11. This suggests that
Arrhenius equation can be well used to deal with the time–temper-
ature superposition of creep of those samples. Considering linear
deviation, the neat PU and its nanocomposites show almost identi-
cal slopes on their shift factor–temperature curves, which indicates
that all samples have the relaxation active energy (Q) values close
with one another. Similar results have also been observed on the
linear dynamic rheological responses of clay based polymer com-
posite system [53]. This illustrates that the interactions between
polymer chain segments and CNTs is not the root of creep imped-
ing effect, and the formation of mesoscopic structure of CNTs with-
in the crosslinking network of PU, maybe account for such
retardation behavior during creep.
4. Conclusions
The PU/CNT nanocomposites prepared by in situ polymerization
show enhanced creep resistance behavior with decreased creep
strain level in comparison with that of the neat PU. However, the
creep strain level is not reduced monotonously with the increase
of CNT contents, which also highly depends on the dispersion of
CNTs. At identical stress level, the nanocomposite containing
1.0 wt% CNTs shows the lowest creep level. The creep behaviors
of the neat PU and its nanocomposites can be well described by
the Findley model and the Burgers model, and the recovery behav-
iors can be well predicted by the Weibull model. The as-obtained
parameters further confirm the impeding effect on the creep by
the presence of CNTs.
Acknowledgements
This work was supported by the Research Grants from the Na-
tional Natural Science Foundation of China (No. 51173156).
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