European Polymer Journal 116 (2019) 488–496

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Microcellular polyetherimide/carbon nanotube composite foam: Structure, T

property and highly reinforcing mechanism
⁎
Xuejie Sun, Lin Ye, Xiaowen Zhao
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu 610065, China

A R T I C LE I N FO A B S T R A C T

Keywords: Microcellular polyetherimide (PEI)/carbon nanotube (CNT) composite foams were prepared via water vapor-
Polyetherimide (PEI) foam induced phase separation (WVIPS) process. The hydroxylated multi-wall nanotubes (MWNTs-OH) were applied,
Hydroxylated multi-wall nanotubes (MWNTs- and strong interfacial interaction formed with PEI molecules by high grafting ratio. Much PEI resin adhered to
OH) MWNTs-OH surface, resulting in an obvious increase of MWNTs-OH diameter and formation of coating structure.
Interfacial interaction
For the composite foams, the homogenous spherical-like cell structure can be observed. With increasing MWNTs-
Thermal property
Mechanical property
OH content, the tensile strength of the composite foam first increased, and then decreased, reaching maximum at
Reinforcing mechanism 4 wt% MWNTs-OH, a roughly 53% increase as a result of reinforcing effect of MWNTs-OH on matrix. Meanwhile,
the storage modulus of the composite foam was much higher than that of pure PEI foam over the temperature
range tested and still maintained above 610 MPa at 200 °C, suggesting a remarkable improvement of thermal
mechanical stability. MWNTs-OH distributed uniformly in the matrix, and under stress it was pulled out with
surface completely wrapped by PEI resin, confirming that the failure mode was the deformation and destruction
of non-interface resin. By incorporation of MWNTs-OH, the thermal decomposition temperature, char yield and
LOI values of the composite foam increased, while the UL-94 tests were classed as a V-0 rating.

1. Introduction
Polyetherimide (PEI) with aryl imide heterocycle structure, is a kind
of amorphous engineering thermoplastic with extremely high rigidity
and superior thermo-oxidative stability, which possesses excellent me-
chanical properties even at elevated temperature due to its high glass
transition temperature (Tg ∼ 217 °C) [1–4]. In addition, the presence of
ether groups in molecular chain endows PEI with improving fluidity
characteristics and processability. Therefore, PEI based foams show
promising application prospect in the fields of aerospace, transporta-
tion, medical equipment, machinery manufacturing, etc.
Carbon nanotubes (CNTs) are comprised of coaxial tubules of gra-
phitic sheets with the carbon atom hexagons arranged in a helical
fashion around the tube axis [5–7]. It possess high aspect ratio and
surface area, excellent electrical, thermal and mechanical properties
[8–12], showing broad applications in nano-electronics, sensors and
field emission as well as high performance nanocomposites [13–15].
The incorporation of small amount of CNTs to PEI matrix can achieve
remarkable enhancement in mechanical and electrical properties
[16,17]. Liu et al. [18] prepared PEI/CNT nano-composite films using
in situ polymerization approach. It was found that the glass transition
temperature of PEI increased by about 10 °C with addition of 1 wt%
CNTs. Meanwhile, the storage modulus increased from 2.10 GPa to
5.17 GPa and the tensile strength increased from 77.5 MPa to 95.0 MPa
for PEI/1wt%CNTs nanocomposite film compared to pure PEI film.
Isayev et al. [19] prepared PEI/CNTs composites via ultrasound assisted
twin screw extrusion. It was found that the volume resistivity decreased
by almost 7 orders of magnitude at 10 wt% CNTs loading compared to
pure PEI, while the tensile strength increased from 115 MPa to
123 MPa. Abbasi et al. [20] prepared PEI/CNTs composite foam using
water vapor induced phase separation (WVIPS). It was observed that
the cellular structure of the PEI/CNTs foams changed from homo-
geneous closed-cell (0.1 wt% CNTs) to porous inter-connected (2 wt%
CNTs) and the average cell size varied between 17.7 μm and 55.3 μm.
The electrical conductivity increased to 9.2 · 10−3 S/m at 2 wt% CNTs
content. Although plenty of researches have been dedicated to various
PEI/CNTs composites [21–23], research on the structure, thermal and
mechanical properties of PEI/CNTs composite foams were rarely re-
ported. In the composite system, due to the lack of functional groups on
CNTs surface, the weak interfacial interaction forms between CNTs and
PEI matrix, leading to the aggregation of CNTs as a result of intrinsic
van der Waals force, and thus it is difficult to achieve uniform disper-
sion in the composite. However, most researchers directly applied CNTs
in PEI foams, resulting in an unobvious improvement of mechanical

⁎
Corresponding author.
E-mail address: zhaoxiaowenscu@126.com (X. Zhao).

https://doi.org/10.1016/j.eurpolymj.2019.04.047
Received 6 March 2019; Received in revised form 23 April 2019; Accepted 25 April 2019
Available online 26 April 2019
0014-3057/ © 2019 Elsevier Ltd. All rights reserved.
X. Sun, et al. European Polymer Journal 116 (2019) 488–496

Fig. 1. FTIR spectra of PEI, MWNTs, MWNTs-OH, g-MWNTs and g-MWNTs-OH.

Table 1
The grafting ratio of PEI onto MWNTs and MWNTs-OH surface.
Samples MWNTs g-MWNTs MWNTs-OH g-MWNTs-OH

W(%) 92.82 76 88.26 61

D(%) – 22 44

2.2. Preparation of PEI/MWNTs-OH composite foam

The preparation process of the PEI/MWNTs-OH composite foam was

carried out as follows: firstly, MWNTs-OH (0.5–5 wt% based on PEI)
was dispersed in NMP (33.2 g) via ultrasonication for 1 h. Afterwards,
PEI (8.3 g) was dissolved into MWNTs-OH suspension by stirring con-
stantly for 4 h at 75 °C, and then the homogeneous solution was poured
onto a flat glass plate and put into the chamber with high humidity at
23 °C for 4 days. Finally, the sample was taken out and put into water to
remove excessive solvent, and dried in the oven at 140 °C.
Fig. 2. TGA curves of MWNTs, MWNTs-OH, g-MWNTs and g-MWNTs-OH.

properties, while few literatures can be available on enhancing inter-
facial interactions for the PEI/CNT composite foams.
In this work, the hydroxylated multi-wall nanotubes (MWNTs-OH)
were chosen to composite with PEI in N-methyl pyrrolidone (NMP)
solution, and PEI/MWNTs-OH composite foams were prepared via
water vapor-induced phase separation (WVIPS) process. The interfacial
bonding of the composite system was expected to be enhanced via the
interaction between the hydroxyl groups of MWNTs-OH and functional
groups (end anhydride carbonyl and amino group) on PEI molecular
chain [24], and highly reinforcing effect would be achieved for the
foam. The effect of MWNTs-OH on the dispersion structure, cellular
structure and thermal mechanical stability of the composite foams was
studied, and the reinforcing mechanism was explored.
2. Experimental
2.3. Characterization
2.3.1. FT-IR analysis
The structure analysis of PEI and MWNTs samples were conducted
with a Nicolet-560 Fourier-transform infrared spectrometer (FT-IR)
(USA). The scanning rate and resolution were 20 min−1 and 4 cm−1,
respectively.
2.3.2. TGA analysis
The TA2950 thermobalance from TA Co. (USA) was used to in-
vestigate the grafting ratio of MWNTs samples and the thermal stability
of PEI composite foam samples under nitrogen atmosphere. The flow
rate was 50 ml/min, and the heating rate was 10 °C/min.
2.3.3. Foam density
The density ρ (g/cm3) of PEI composite foam samples was measured
according to ASTM D792 and calculated as follows:

2.1. Materials ρ = m/v (1)

3
where m is the mass (g), and v is the volume of foam samples (cm ).
PEI (Ultem 1000), a transparent and amber colored material, was
purchased from Saudi Basic Industry Corporation (Sittard, The
2.3.4. SEM analysis
Netherlands), which has a density of 1.28 g/cm3 and a glass transition
The morphologies of PEI composite foam samples were observed
temperature of 217 °C. MWNTs-OH was supplied by the Chengdu
with a JEOL JSM-5900LV SEM (Japan) at an operating voltage of 15 kV.
Organic Chemicals Co. Ltd., Chinese Academy of Science (Chengdu,
The specimens were freeze-fractured in liquid nitrogen and coated with
China). NMP was obtained from Kemiou Chemical Reagent Co. Ltd.
gold.
(Tianjin, China).

2.3.5. TEM analysis

The micro-morphologies and structures of MWNTs samples and PEI

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X. Sun, et al.
Fig. 3. TEM images of MWNTs, MWNTs-OH, g-MWNTs and g-MWNTs-OH.
composite samples were observed on JEOL JEM 100CX II TEM equip-
ment (Japan), and the acceleration voltage of 200 kV was applied.
2.3.6. Tensile performance
According to ISO1926:2009, the tensile performance of PEI com-
posite foam samples was determined by a 5567 universal material
testing machine from Instron Co. (U.S.A). The tensile speed was 5 mm/
min. The sample was dumb-bell type with size of
150 mm × 25 mm × 1 mm and cut by fixed size cutters. Five samples of
each type were tested.
The strain (ε ) was obtained by measurement of the sample length
after deformation and calculated with the following formula:
ε = (L − L0)/ L0 × 100% (2)
where L0 was the original length of sample; L was the length of sample
after deformation.
2.3.7. DMA analysis
The DMA measurement of PEI composite foam samples was con-
ducted with a TA Instrument Q800 DMA (U.S.A). A stretching mode
was applied, the heating rate was 3 °C/min, and the frequency applied
was 1 Hz with a strain of 0.02%.
3. Results and discussion
The PEI/MWNTs-OH composite foam was fabricated through water
vapor-induced phase separation (WVIPS) process. First, a homogenous
PEI/MWNTs-OH solution in NMP was obtained by ultrasonication and
vigorous stirring. After being exposed to air, the water vapor, as
blowing agent, diffused into the solution, and was divided into small
droplets. Then the cell nucleation occurred, and after removing residual
NMP and water, the PEI/MWNTs-OH composite foam was obtained.
3.1. Interfacial interaction of PEI/MWNTs-OH composite foam
In order to study the interfacial interaction between PEI and
MWNTs or MWNTs-OH, a homogenous solution was prepared by dis-
solving a proper amount of PEI composite filled with MWNTs or
MWNTs-OH in NMP, then centrifugated and washed repeatedly with
NMP to remove free PEI, and the obtained grafted MWNTs and MWNTs-
OH samples were denoted as g-MWNTs and g-MWNTs-OH, respectively.
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European Polymer Journal 116 (2019) 488–496
The structure of PEI, MWNTs, MWNTs-OH, g-MWNTs and g-
MWNTs-OH were analyzed by FTIR analysis, as shown in Fig. 1. For
MWNTs, the absorption peak at 3436 cm−1 was assigned to eOH
stretching vibration, the band at 1634 cm−1 was related to eOH
bending vibration or C]C skeletal ring vibration [25,26]. For MWNTs-
OH, the characteristic peaks resembled that of MWNTs. However, the
increase in the relative intensity of the peak at 3437.12 cm−1 for
MWNTs-OH indicated more eOH groups on its surface. Besides, the
characteristic peaks at 1560.2 cm−1 and 1173.55 cm−1 were found,
assigned to skeletal vibration and CeO stretching vibration, respec-
tively. For PEI, the characteristic peak at 1780.48 cm−1 was related to
anhydride carbonyl group (C]O) at the molecular chain end.
For the samples of g-MWNTs and g-MWNTs-OH, it can be seen that
the FTIR spectra was similar to that of pure PEI. For g-MWNTs, the band
at 1776.3 cm−1 corresponding to anhydride carbonyl group (C]O) of
PEI was observed, which revealed that the chemical structure of PEI
molecule had no obvious change [27]. And the slight blue-shift of eOH
groups suggested the weakening of hydrogen bonding interactions be-
tween g-MWNTs. However, for g-MWNTs-OH, the characteristic peak
related to anhydride carbonyl group (C]O) disappeared, which in-
dicated that the covalent bonding formed between two phases by re-
action between anhydride carbonyl group (C]O) of PEI and eOH
groups on MWNTs-OH surface. Furthermore, the further blue-shift of
eOH groups indicated that hydrogen bonding interactions of MWNTs-
OH were destroyed due to the grafted PEI molecules on MWNTs-OH
surface.
TGA was used to quantify the grafting ratio of PEI molecules onto
MWNTs and MWNTs-OH surface, as shown in Fig. 2. For MWNTs and
MWNTs-OH, the weight loss in the range of 30–800 °C was 7.18% and
11.74%, respectively, resulting from the removal of water and the de-
composition of oxygen groups like hydroxyl held on MWNTs and
MWNTs-OH surface, leaving residual carbon. For g-MWNTs and g-
MWNTs-OH, the obvious weight loss in the range of 500–800 °C was
observed, which was assigned to the decomposition of the grafted PEI
molecular chains on MWNTs surface. Compared with MWNTs and
MWNTs-OH, the thermal weight loss for g-MWNTs increased by
16.82%, and a further weight loss of 10.44% for g- MWNTs-OH was
observed.
According to above analysis, the grafting ratio (D) of PEI molecules
on the unit mass of MWNTs or MWNTs-OH (per gram) can be calculated
with following equation:
X. Sun, et al.
Fig. 4. SEM images and corresponding cell size distribution (a) and the average cell diameter and apparent density (b) of PEI/MWNTs-OH composite foam with
varying MWNTs-OH content.
M1 = M0 × Wg − MWNTs − (M0 − M1) × WMWNTs
that is,
M1 = (Wg − MWNTs − WMWNTs )/(1 − WMWNTs ) × M0
D = M1/(M0 − M1) × 100%
where Wg-MWNTs and WMWNTs were the weight loss ratio of g-MWNTs
and MWNTs, respectively. M0 was the weight of g-MWNTs and M1 was
the weight of the grafted PEI molecules on MWNTs surface. For g-
MWNTs-OH, the same method was applied to estimate the grafting ratio
of PEI molecules. M0 and M1 were the weight of g-MWNTs-OH and the
grafted PEI molecules on MWNTs-OH surface, respectively.
As shown in Table 1, the grafting ratio of g- MWNTs-OH reached
44%, twice as much as that of g-MWNTs, which suggested that more
PEI molecules were grafted onto MWNTs-OH surface. The result
European Polymer Journal 116 (2019) 488–496
(3) coincided with FTIR and Raman analysis.
The effect of functional groups on the surface morphology of
MWNTs has been evaluated by employing TEM analysis technique, and
the diameter and the coating structure of MWNTs samples were pre-
(4)
sented in Fig. 3. Under low magnification of TEM images, for g-MWNTs,
(5) the surface was smooth and no obvious PEI resin can be observed on it.
For g-MWNTs-OH, the surface became fuzzy and rough, and obvious
PEI resin adhered on it. Under high magnification of TEM images, it can
be observed that MWNTs-OH was wrapped by PEI resin, and the
average diameter of g-MWNTs and g-MWNTs-OH both increased com-
pared with MWNTs and MWNTs-OH. For g-MWNTs-OH, the increased
diameter was ∼7.2 nm, larger than that of g-MWNTs, which increased
diameter was ∼1.1 nm, confirming that there was a stronger interfacial
interaction and improved compatibility between PEI and MWNTs-OH.
Therefore, more PEI resin adhered to MWNTs-OH surface, resulting in
the formation of coating structure.
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X. Sun, et al.
Fig. 5. (a) Stress-strain curves of PEI/MWNTs-OH composite foam with varying MWNTs-OH content; (b) Tensile properties of PEI/MWNTs-OH composite foam as a
function of MWNTs-OH content.
Fig. 6. Storage modulus curves (a), Tanδ curves (b) and Tg (c) of PEI/MWNTs-OH composite foam with varying MWNTs-OH content.
3.2. Effect of MWNTs-OH content on the cell structure of PEI/MWNTs-OH
composite foam
The typical SEM images of the fracture surface, the corresponding
cell size distribution, the average cell diameter and density of PEI/
MWNTs-OH composite foam as a function of MWNTs-OH content were
illustrated in Fig. 4. As shown in Fig. 4(a), for all samples of PEI/
MWNTs-OH composite foam, homogenous spherical-like cell structure
and a small amount of open cell structure as well as narrow cell size
distribution can be observed. At low MWNTs-OH content (0–1%), the
perfect cell structure with thin cell walls formed during phase separa-
tion can be observed. With increasing MWNTs-OH content (> 1%), it
was found that the cell size decreased and the cell walls thickened with
lots of carbon nanotubes aggregates enriched in it.
As shown in Fig. 4(b), the cell size of pure PEI foam was 4.9 μm.
With the increase of MWNTs-OH content, the cell size increased first,
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European Polymer Journal 116 (2019) 488–496
reaching maximum of 5.6 μm at 1% MWNTs-OH, and then decreased,
while the apparent density of composite foam showed the steady in-
creasing tendency. This phenomenon may be related to foam formation
process and increasing viscosity of the composite system. During water
vapor-induced phase separation (WVIPS) process, the nuclei grew up
with the entry of water and coalescence of bubbles between each other
[28,29]. At low MWNTs-OH content (0–1%), the composite foam
formed via removing the water in cells, which made MWNTs-OH en-
riched in the cell walls and molecular entanglement enhanced, resulting
in the strengthening of cell walls and holding of more water, leading to
larger cell structure. Meanwhile, the viscosity of composite system in-
creased with increasing MWNTs-OH content, resulting in slow increase
in foam density. At high MWNTs-OH content (2–5%), the increasing
viscosity of the composite system became dominant and cell coales-
cence was hindered [18], while the cell wall thickened due to MWNTs-
OH aggregates enriched in it and foam density increased significantly.
X. Sun, et al.
Fig. 7. Comparison of mechanical properties between PEI/4wt%MWNTs-OH
and PEI/4wt%MWNTs composite foam.
3.3. Effect of MWNTs-OH content on the thermal mechanical stability of
PEI/MWNTs-OH composite foam and reinforcing mechanism
Fig. 5(a) shows the stress-strain curves of pure PEI foam and PEI/
MWNTs-OH composite foam with varying MWNTs-OH content. It can
be seen that the stress-strain curves showed an untypical yield point
and strain hardening behavior, exhibiting the characteristic of ductile
fracture. The tensile properties of PEI/MWNTs-OH composite foam as a
function of MWNTs-OH content were illustrated in Fig. 5(b). It can be
observed that with the increase of MWNTs-OH content, the tensile
Fig. 8. (a) TEM images of PEI/MWNTs and PEI/MWNTs-OH composite; (b) SEM image of tensile fracture surface of PEI/MWNTs-OH composite.
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European Polymer Journal 116 (2019) 488–496
strength and Young’s modulus of the composite foam both increased
first, and then decreased, reaching a maximum at 4% MWNTs-OH
content. The incorporation of 4% MWNTs-OH caused a roughly 53%
increase in tensile strength, from 15.5 MPa of pure PEI foam to
23.69 MPa as a result of the reinforcing effect of MWNTs-OH on PEI
matrix. The Young’s modulus showed the same tendency with tensile
strength.
The dynamical mechanical properties and the glass transition tem-
perature (Tg) of PEI foam with different content of MWNTs-OH were
presented in Fig. 6. As can be seen from Fig. 6(a), below Tg, the storage
modulus of all tested samples decreased with increasing temperature,
and when the temperature reached Tg, it decreased sharply owing to the
free movement of PEI molecular segments in high elastic state. By ad-
dition of MWNTs-OH, the storage modulus increased first, reaching
maximum (960 MPa) at 4% MWNTs-OH, and then decreased. More-
over, all storage modulus values of the composite foam were higher
than that of pure PEI foam over the temperature range tested. Sur-
prisingly, the composite foam still maintained the storage modulus
above 610 MPa at 200 °C in the range of 4-5 wt% MWNTs-OH content,
which suggested a remarkable improvement of thermal mechanical
stability due to the reinforcing effect of MWNTs-OH.
The tanδ curves for pure PEI foam and PEI/MWNTs-OH composite
foam were illustrated in Fig. 6(b). The curves for all tested samples
showed one relaxation peak around 235 °C, corresponding to Tg of
foams (Fig. 6(c)). With the increase of MWNTs-OH content, the peak
intensity (tanδmax) shifted to low values, which was related to the in-
creasing rigidity of composite foam as a result of the strong interaction
between MWNTs-OH and PEI matrix. As shown in Fig. 6(c), no obvious
variation tendency of Tg was observed with the addition of MWNTs-OH.
The comparison of mechanical properties of PEI foam filled with
X. Sun, et al.
Fig. 9. The steric repulsion of MWNTs-OH by grafting with PEI macromolecular chains.
Fig. 10. The diagrammatic sketch of crack propagation path in PEI/MWNTs-
OH composite foam.
MWNT-OH and MWNT respectively was shown in Fig. 7. It can be seen
that compared with PEI/4wt%MWNTs foam, the sample of PEI/4wt%
MWNTs-OH foam showed much higher mechanical strength and mod-
ulus, resulting from superior reinforcing effect MWNTs-OH on PEI
foam.
Fig. 8(a) shows the TEM images of PEI composite filled with MWNTs
and MWNTs-OH respectively. It can be seen that obvious agglomerate
of MWNTs existed in PEI/MWNTs composite. However, no agglomerate
was observed for PEI/MWNTs-OH composite, and MWNTs-OH dis-
tributed uniformly in the matrix as a result of the increasing steric
hindrance effect by grafting with PEI molecules, which prevented its
Fig. 11. TGA curves of PEI/MWNTs-OH composite foam with varying MWNTs-OH content.
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European Polymer Journal 116 (2019) 488–496
agglomeration tendency and decreased stress concentration under load,
as shown in Fig. 9.
SEM analysis was used to characterize the tensile fracture surface of
PEI/MWNTs-OH composite. As shown in Fig. 8(b), MWNTs-OH was
pulled out with surface completely wrapped by PEI resin. The interface
was fuzzy and rough, and presented a coating structure, indicating
strong interfacial bonding formed between two phases, through which
the load-transfer ability was enhanced. Thus, more stress was shared by
MWNTs-OH. The failure mode was the deformation and destruction of
non-interface resin under load.
The main cause of the damage to pure PEI foam lies in the bending
and torsional deformation of cell walls, leading to instability and
fracture. For PEI/MWNTs-OH composite foam, addition of MWNTs-OH
changed the failure mode of cell walls. The initial micro crevice of
composite foam can be produced when subjected to external stress, and
then expanded into crack. With further crack propagation, the path
would be hindered by MWNTs-OH. Then, the cracks continued to
propagate along the weak point of cell wall away from MWNTs-OH,
which extended the propagation path and dissipated more energy
during fracture process, as shown in Fig. 10. Consequently, the me-
chanical strength of PEI foam was improved.
3.4. Effect of MWNTs-OH content on the thermal stability and flame
retardancy of PEI/MWNTs-OH composite foam
TGA analysis of PEI/MWNTs-OH composite foam was conducted
under nitrogen atmosphere, as shown in Fig. 11. The thermal de-
gradation characteristic temperatures, maximum thermal degradation
rate (Vmax) and char yield of PEI foam filled with varying MWNTs-OH
content were listed in Table 2. The initial decomposition temperature is
X. Sun, et al. European Polymer Journal 116 (2019) 488–496

Table 2
TGA results for PEI/MWNTs-OH composite foam with varying MWNTs-OH content under N2 atmosphere.
Sample T5% (°C) T20% (°C) T40% (°C) Vmax (%/min) Char yield (%)

PEI 508.33 543.7 599.16 10.45 48.78

PEI/0.5wt%MWNTs-OH 502.57 546.34 612.72 8.823 51.35
PEI/1wt%MWNTs-OH 511.63 544.7 617.80 9.531 52.27
PEI/2wt%MWNTs-OH 503.33 543.4 613.95 8.065 50.94
PEI/3wt%MWNTs-OH 508.03 544.7 619.0 9.072 51.98
PEI/4wt%MWNTs-OH 511.62 545.5 628.54 8.65 55.31
PEI/5wt%MWNTs-OH 509.77 542.24 641.28 9.197 55.68

Table 3 in the matrix and was pulled out with surface completely wrapped by
The UL-94 classification and LOI values of PEI/MWNTs-OH composite foam PEI resin during stretching process, which confirmed that the failure
with varying MWNTs-OH content. mode was the deformation and destruction of non-interface resin under
Sample UL-94 t1/t2(s) Vertical burning test rating LOI (%) stress. For PEI/MWNTs-OH composite foam, the difference of the
thermal degradation temperature significantly increased with in-
PEI 3.7/0.3 V-0 32 creasing weight loss, while the UL-94 tests were classed as V-0 rating
PEI/0.5wt%MWNTs-OH 3.06/0.1 V-0 35.7
and the LOI values can reach 42%. Such PEI/MWNTs-OH composite
PEI/1wt%MWNTs-OH 3.0/0.2 V-0 37.7
PEI/2wt%MWNTs-OH 1.8/0.2 V-0 39 foam shows promising application potentials in harsh conditions like
PEI/3wt%MWNTs-OH 1.27/0.1 V-0 40.4 high temperature in the field of aerospace, machinery manufacturing,
PEI/4wt%MWNTs-OH 1.48/0.1 V-0 41 etc.
PEI/5wt%MWNTs-OH 0.91/0 V-0 42

Acknowledgements

defined as the temperatures of the samples with the weight loss of 5%

(T5%). T20% and T40% are the temperatures of the samples with the
weight loss of 20% and 40%, respectively. For all tested samples, it was
observed that TG curves had an inverse “S” shape, indicating one-step
decomposition process due to the cleavage of phenyl–phthalimide
bonds [30]. As listed in Table 2, for comparison, the increase in initial
degradation temperature was not significant for the composite foam,
the likely possibility for which may be due to the high thermal con-
ductivity of MWNTs-OH caused a greater flow of heat throughout
composite foam [30,31]. However, the difference of the thermal de-
gradation temperature significantly increased with increasing weight
loss. A noticeable increase in decomposition temperature was observed
when the weight loss was 40%, which increased from 599.16 °C of pure
PEI foam to 641.28 °C. Compared with pure PEI foam, Vmax of PEI/
MWNTs-OH composite foam decreased and the char yield increased.
To evaluated flame retardancy, PEI/MWNTs-OH composite foam
was measured by the limiting oxygen index (LOI) as well as vertical
burning UL-94 test and the related results were presented in Table 3. It
can be noted that, the UL-94 tests were classed as a V-0 rating for pure
PEI foam and all PEI/MWNTs composite foam. The LOI values in-
creased gradually from 32% of pure PEI foam to 42% with the increase
of MWNTs-OH content.
4. Conclusions
Through WVIPS process, PEI/MWNTs-OH composite foam was
successfully fabricated. PEI was grafted onto MWNTs-OH surface
through strong interfacial interaction. Compared with g-MWNTs, the
grafting ratio and average tube diameter for g-MWNTs-OH increased
significantly, and the obvious coating structure formed For the com-
posite foam samples, homogenous spherical-like cell structure and a
small amount of open cell structure can be observed. With increasing
MWNTs-OH content, the cell size increased first, reaching maximum at
1% MWNTs-OH, and then decreased, while the apparent density of
composite foam showed the steady increasing tendency. Compared
with pure PEI foam, incorporation of MWNTs-OH caused a roughly 53%
increase in tensile strength, from 15.5 MPa of pure PEI foam to
23.69 MPa, and the storage modulus of composite foam increased from
380 MPa to 960 MPa, which kept high storage modulus even at high
temperature, reaching above 610 MPa at 200 °C due to the reinforcing
effect of MWNTs-OH on PEI matrix. MWNTs-OH distributed uniformly
This work was supported by Joint Fund of National Natural Science
Foundation of China and China Academy of Engineering Physics, China
(NSAF) (No. U1530144), and Science and Technology Project of
Sichuan Province, China (2019YFG0240).
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
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