Composites Science and Technology 184 (2019) 107865

Contents lists available at ScienceDirect

Composites Science and Technology

journal homepage: http://www.elsevier.com/locate/compscitech

High performance epoxy-based composites for cryogenic use: A approach

based on synergetic strengthening effects of epoxy grafted polyurethane
and MWCNTs-NH2
Liying Jia a, 1, Pengfei Qi a, 1, Ke Shi a, Xin Liu a, Wenli Ma a, Song Lin c, Fei Zhang a,
Xiaolong Jia a, b, *, Qing Cai a, Xiaoping Yang a, b
a
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, PR China
b
Key Laboratory of Carbon Fiber and Functional Polymer, Ministry of Education, Beijing University of Chemical Technology, Beijing, 100029, PR China
c
North China Institute of Aerospace Engineering, Hebei, 065000, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Synergetic strengthening effects of epoxy grafted polyurethane (EP-PU) and aminated MWCNTs (MWCNTs-NH2)
Polymer-matrix composites (PMCs) on mechanical performance of EP-based composites at 77 K were systematically investigated using the tested
Carbon nanotubes results at room temperature (RT) as comparisons. EP-PU was successfully synthesized by controlling the reaction
Mechanical properties
between –OH in EP and –NCO in PU prepolymer, which showed the advantages of relatively low viscosity and
Synergism
outstanding chemical miscibility with EP matrix. The most obvious enhancements were achieved with contents
of 30 wt% EP-PU and 0.2 wt% MWCNTs-NH2 in tensile, flexural, impact and KIC fracture toughness properties of
EP composites as well as flexural properties and interlaminar shear strength (ILSS) of carbon fiber (CF)/EP
composites at both RT and 77 K, which confirmed the synergetic strengthening effects of EP-PU and MWCNTs-
NH2. Specifically, KIC fracture toughness of EP composites and ILSS of CF/EP composites at 77 K were enhanced
by 26.0 and 31.4%, respectively, compared with the corresponding neat composites. The EP-PU component
showed β or γ relaxation behavior at cryogenic condition and existed in form of scattered micro-spheres in cured
EP matrix due to the phase separation. The riveting and bridging of MWCNTs-NH2 around EP-PU micro-spheres
were considered to provide extraordinary synergy on the effective stress diversion and crack propagation inhi­
bition at cryogenic condition through establishing the chemically bonded multi-scale interface.

1. Introduction
Epoxy (EP)-based composites have been increasingly considered as
promising materials in advanced cryogenic technology fields like space
industry and superconducting engineering, due to their advantages of
high specific strength, good thermal characteristics and corrosion
resistance, low shrinkage during cure and ease in processing [1–4].
However, the brittleness was the inherent drawbacks of EP resin, which
greatly limited its performance in meeting the high requirements by the
severe cryogenic environment. Specifically, when EP-based composites
were used as fuel tank structure in space shuttle or satellite to store
cryogenic liquids (liquefied oxygen and liquefied hydrogen), abundant
micro-cracks would be generated in EP matrix by thermal stress induced
during temperature decreasing [5–8]. The accompanying fracture of EP
matrix was more easily to occur as the externally-applied stress excee­
ded its fracture toughness. Such structural damages resulted in the
consequent degradation of mechanical properties in the structures, such
as fiber/matrix interfacial debonding, potholing, and/or delamination,
and final leakage of liquids [9–11]. Therefore, it was significantly
important that the toughness of EP-based composites should maintain
high level even at cryogenic condition.
Among various methods, the incorporation of soft modifiers such as
flexible polyurethane, hyperbranched polyester, rubber particles and
thermoplastic poly(ethersulfone) was a promising path to positively
modify the flexibility of EP composites including fracture toughness and
elongation at cryogenic temperature [12–15]. For instance, it was re­
ported that fracture toughness and thermal contraction of several types
of EP systems at cryogenic temperature were optimized by using

* Corresponding author. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, PR China.
E-mail address: jiaxl@mail.buct.edu.cn (X. Jia).
1
Contributed equally to the work.

https://doi.org/10.1016/j.compscitech.2019.107865
Received 1 April 2019; Received in revised form 15 September 2019; Accepted 8 October 2019
Available online 8 October 2019
0266-3538/© 2019 Elsevier Ltd. All rights reserved.
L. Jia et al.
Fig. 1. (a) FTIR spectra of various materials for the synthesis of EP-PU and GPC results for (b) EP, (c) PUR and (d) EP-PU.
polycarbonate, carboxyl-terminated butadiene acrylonitrile copolymer
or phenoxy [16]. Noticeably, as a result of the solid state or super-high
viscosity of these soft polymer modifiers, the preparation of toughened
EP composites in large quantities and high quality always met compli­
cated process with lots of technical difficulties to achieve the uniform
miscible state. Moreover, the poor chemical compatibility between EP
matrix and these modifiers further limited the achievement in their
miscibility. Most importantly, the strength and modulus of EP compos­
ites were inevitably worsened by incorporating these modifiers [17–20].
Thus, a key challenge for successfully preparing the high performance of
toughened EP composites was to ensure the synchronous enhancement
in their overall properties along with good processability.
Favorably, the further addition of rigid nanofillers into polymer
matrixes after incorporating soft modifiers was a highly efficient way to
realize the further reinforcement and toughening on polymer-based
composites, since the concept had been well documented by many
newly-emerged high-performance composites containing multiscale and
multifunctional fillers in literatures [21–24] and in our previous works
[25–27]. For instance, it was proved in our previous work that the
synchronous enhancements in strength and toughness of carbon fiber
(CF)/EP composites were ascribed to the chemically bonded multi-scale
interface established by MWCNTs-EP/PA self-assembled hybrid parti­
cles, which combined the PA particulate toughening effects on the
microscale and MWNTs-EP pullout and bridging effects on the nanoscale
[26]. Logically, it was predicted that the synchronous modifications on
2
Composites Science and Technology 184 (2019) 107865
strength and toughness of polymer-based composites at cryogenic con­
dition by using both soft polymer modifiers and rigid nanofillers were
feasible. However, recent literature survey clearly suggested that such
modifications were relatively unexplored area of research. For EP resin
containing both soft polymer modifiers and rigid nanofillers, therefore,
the attempt to investigate overall performance at cryogenic condition
was rather necessary. It was vital for the design and fabrication of new
generation high-performance EP-based nanocomposites applied in
cryogenic engineering by elucidating the mechanism of synergetic
reinforcing and toughening.
Thereby, in this study, the soft polymer modifier, EP grafted poly­
urethane (EP-PU), was successfully synthesized by controlling the re­
action between –OH in EP and –NCO in PU prepolymer, which showed
the advantages of relatively low viscosity and outstanding chemical
miscibility with EP matrix. Aminated MWCNTs (MWCNTs-NH2) were
used as the rigid nanofiller, which possessed remarkable reinforcement
capability on EP matrix as well as excellent dispersibility and high
reacting ability in EP matrix as an amine-type curing agent due to the
existence of a reactive –H in amine group, as reported in our previous
work [28,29]. Synergetic strengthening of EP-PU and MWCNTs-NH2 on
cryogenic performance of EP-based composites at 77 K were systemati­
cally investigated using the tested results at room temperature (RT) as
comparisons. The effects of EP-PU content on tensile, flexural, impact
and KIC fracture toughness properties of EP composites as well as flex­
ural properties and interlaminar shear strength (ILSS) of CF/EP
L. Jia et al.
Fig. 2. Effects of EP-PU content on (a) tensile, (b) flexural, (c) impact and (d) KIC fracture toughness properties of EP composites at RT and 77 K.
composites were evaluated at both RT and 77 K. The functioning role of
EP-PU in composites was analyzed on basis of fractured morphology
observation and mechanical-thermal behavior analysis. Then, the effects
of MWCNTs-NH2 content on all-above properties were further examined
at both RT and 77 K after EP-PU at the optimum addition content was
incorporated into composites. The distribution of MWCNTs-NH2 along
with EP-PU in EP composites was observed from fractured morphology.
Finally, the synergetic reinforcing and toughening mechanism of EP-PU
and MWCNTs-NH2 in EP composites at cryogenic condition was
reasonably proposed.
2. Results and discussion
2.1. Analysis of EP-PU
The synthesized EP-PU was characterized by FTIR, NMR and GPC. As
shown in Fig. 1(a), PPG and MDI showed the strong absorption peak of
–OH stretching vibration at 3450 cm 1 and the wide asymmetric ab­
sorption peak of –N¼C¼O stretching vibration at 2271 cm 1 in their
spectra, respectively. After the reaction of PPG and MDI, in the spectrum
of PUR, the absorption peak at 3450 cm 1 was weakened while the peak
at 2271 cm 1 remained still strong. Then, with the continuous reaction
of PUR with EP resin, the characteristic absorption peak of –N¼C¼O at
around 2271 cm 1 completely disappeared, which demonstrated the
successful synthesis of EP-PU. The peaks around 3300 and 1740 cm 1
corresponded to the stretch vibration of -N-H and –C¼O, indicating the
formation of urethane bonds in PUR and EP-PU. As shown in 1H NMR
spectra of EP-PU in Fig. S3, the peak at 7.16 ppm was ascribed to the
proton of benzene rings adjacent to –NH–(C¼O)–O-. The chemical shifts
at 3.97 and 3.67 ppm were attributed to the hydrogen of –NH–(C¼O)–O-
, while the peak at 2.14 ppm was ascribed to the proton of –OH. The
3
Composites Science and Technology 184 (2019) 107865
appearances of chemical shifts at 3.97, 3.67 and 2.14 ppm in 1H NMR
spectrum further confirmed the chemical structure of the final product
EP-PU (Fig. S3). With each step proceeding of the synthesis reaction, the
molecular weights of various products were increased. It could be seen
that the values of number-averaged molecular weights for EP and PUR
were ~430 and ~4400 (Fig. 1(b and c)). The final product of EP-PU
possessed the number-averaged molecular weight of ~4800 with a
narrow distribution (polydispersity index, PDI ¼ 1.19) (Fig. 1(d)), which
almost equaled to the sum of those values for PUR and EP (Fig. 1(b–d)),
which meant the delicated controlling in synthesis reaction of EP-PU.
2.2. Cryogenic performance of EP composites with EP-PU
As seen in Figs. S4(a and b), the phase separation was distinctively
observed for EP/PUR mixture, while EP/EP-PU mixture exhibited ho­
mogeneous state, indicating the outstanding miscibility between EP-PU
and EP as a result of their high chemical affinity due to containing the
similar EP segments in EP-PU molecular structures. As expected, the
synthesized EP-PU showed the relatively low viscosity and reduced the
viscosity of the whole EP matrix (Fig. S4(c)), which would result in good
processability of EP composites. And the viscosity of EP/EP-PU mixture
decreased dramatically with EP-PU content, which was as low as
433 mPa s at 30 wt% EP-PU (Fig. S4(c)). The low viscosity of EP matrix
was always beneficial to accelerating the impregnation between fiber
and matrix and thus enhancing the overall properties of the resulting
composites. The PU molecular segment in EP-PU could have enough
probability to interpenetrate into the molecular chain of EP matrix [30],
forming the typical semi-interpenetrating network (semi-IPN) in the
final micro-structure of the whole system as shown in Step III in Fig. S1
(a). When EP composites were subjected to external stress, more en­
ergies were dissipated during the stress transmission between PU and EP
L. Jia et al. Composites Science and Technology 184 (2019) 107865

Fig. 3. SEM images of fractured surfaces for (a1-a2) neat EP and (b1-b2, c1-c2) EP composites with 30 wt% EP-PU at RT (Left column) and 77 K (Right column) after
tensile test. (c1) and (c2) are the high magnification images of the selected areas in panel (b1) and (b2), respectively.

networks. enhancements in mechanical properties of EP composites at both 77 K

The advantages of outstanding miscibility and low viscosity for EP-
PU evoked our keen interest to review its effects in the resulting com­
posites. Firstly, mechanical testings were carried out to investigate ef­
fects of EP-PU content on tensile, flexural, impact and fracture toughness
properties of EP composites at 77 K (Fig. 2). Obviously, all mechanical
properties of EP composites at both RT and 77 K increased when the
content of EP-PU changed from 0 to 30 wt%, and these values began to
decrease after the component of EP-PU was further added. The
and RT, as shown in Fig. 2, were definitely attributed to the strength­
ening effect of EP-PU component. Naturally, mechanical properties of
EP composites continuously increased with EP-PU content. Specifically,
the enhancements in impact strength and KIC fracture toughness were
more obvious, which were attributed to the flexible PU segment in EP-
PU and the phase separation toughening by EP-PU. SEM images of
fractured surfaces for EP composites indicated that the addition of EP-
PU changed the micro-morphology of composites evidently (Fig. 3).

Fig. 4. (a) Effects of EP-PU content on tan δ of EP at the temperature range of RT - 250 � C and (b) mechanical-thermal behavior of neat EP and EP composites with
30 wt% EP-PU at the temperature range of 140–250 � C. The inset in panel (b) is the high-magnification image of the curves at low temperature range.

4
L. Jia et al. Composites Science and Technology 184 (2019) 107865

Fig. 5. Effects of EP-PU content on (a) flexural properties and (b) ILSS of CF/EP composites at RT and 77 K.

As shown in Fig. 3(b1, b2), EP composites with 30 wt% EP-PU exhibited
rougher micro-structure. The EP-PU component existed in form of
micro-spheres due to the phase separation. A large amount of EP-PU
micro-spheres were scattered uniformly in the cured EP matrix of
composites as observed from the high magnification images (Fig. 3(c1,
c2). In contrast, neat EP exhibited relatively flat morphology in the
fractured surfaces (Fig. 3(a1, a2)). As reported in literature [31] and our
previous works [25,26], such uniformly distributed micro-spheres in EP
matrix would prevent the crack propagation and absorbed more energy
effectively. As labeled by the circles in Fig. 3(c1, c2), the deflection and
termination happened when the crack met the EP-PU micro-spheres. The
fish scale-like uneven surface for fractured EP composites with EP-PU
was the feature of high toughness. While, the flat surface for fractured
EP composites without EP-PU was the typical brittle morphology. There
was no obvious crack termination phenomenon found in such fractured
surfaces (Fig. 3(a1, a2)). Howbeit when EP-PU content was over the
critical value (e.g. 30 wt%), the compatibility of EP-PU and EP matrix
gradually deteriorated, resulting in the decrease of mechanical

Fig. 6. Effects of MWCNTs-NH2 content on (a) tensile, (b) flexural, (c) impact and (d) fracture toughness properties of EP/EP-PU composites at RT and 77 K.

5
L. Jia et al.
Fig. 7. (a) Tensile, (b) flexural, (c) impact and (d) fracture toughness properties of neat EP and EP composites with 30 wt% EP-PU or 0.2 wt% MWCNTs-NH2 or both
30 wt% EP-PU and 0.2 wt% MWCNTs-NH2 at RT and 77 K.
properties.
Moreover, the addition of EP-PU also affected the Tg of EP composites
significantly. As shown in Fig. 4(a), with increasing the content of EP-
PU, the Tg of EP composites was gradually declined. When the EP-PU
content was 30 wt%, the Tg of EP composites decreased to 123 � C. And
compared to neat EP, EP composites with EP-PU showed several extra
peaks in the tanδ curve at the low temperature range from 20 to
140 � C (Fig. 4(b)). This result indicated that the molecular chains in EP
composites with EP-PU had the secondary transformation ability at
cryogenic condition. Noticeably, tensile and flexural properties of EP
composites demonstrated much higher values at 77 K than at RT when
containing the same amount of EP-PU. For instance, when the content of
EP-PU was 30 wt%, the average tensile and flexural strengths at 77 K
were as high as 124 and 265 MPa, respectively, while those values at RT
were only 79 and 162 MPa. The more obvious enhancements in tensile
and flexural properties of EP composites at 77 K than at RT were
attributed to the magnifying of the cohesive energy and interaction force
among molecular chains at cryogenic condition. Since the free volume of
molecular chains of EP-based matrix was greatly reduced after the
shrinkage of crosslinked network micro-structure during cooling pro­
cess, the stacking density of molecular chains of EP-based matrix ob­
tained a big increase. Besides, these enhancements at 77 K by the
addition of EP-PU, especially in impact strength and KIC fracture
toughness, were also definitely attributed to the positive effect of EP-PU
at cryogenic condition. According to literature [32,33], these extra
peaks in low temperature range section of the tanδ curve of polymers
such as polyurethanes were derived from β or γ relaxation behavior of
flexible segments at cryogenic condition (Fig. 4(b)). The flexible seg­
ments such as branched side group and ether bond were originated from
6
Composites Science and Technology 184 (2019) 107865
the PU in EP-PU component, which indicated the movement capability
along with consuming the impact energy in the free space of crosslinked
network micro-structure at cryogenic condition. Therefore, EP-PU mi­
cro-spheres originated from the phase separation still played the
toughening role in EP matrix at cryogenic condition.
Then, the testings on flexural properties and ILSS of CF/EP com­
posites containing various contents of EP-PU were performed (Fig. 5).
Apparently, flexural strength and modulus of CF/EP composites were far
higher than those of EP composites, showing the reinforcing effect of CF.
Similar to the above case, as increasing the content of EP-PU, all these
properties of CF/EP composites were maximum at 30 wt% EP-PU, and
subsequently decreased. The measured values for flexural properties and
ILSS of CF/EP composites were higher at 77 K than at RT at the same
content of EP-PU. And the increment was much bigger in ILSS than in
flexural property values. When the temperature went down, the radial
geometry size of CF was rather stable because the radial shrinkage co­
efficient (or expansion coefficient) was normally close to zero (as small
as ~10 ppm/K) at the wide temperature range as reported in the liter­
atures [34–36]. Nevertheless, the shrinkage of crosslinked network
micro-structure of EP matrix was prominent at cryogenic condition. In
this case, benefiting from the enhancement in the interfacial interaction
between CF and EP matrix via the micro-structure shrinkage of EP ma­
trix at cryogenic condition, the stress transfer from EP matrix to CF
reinforcement was strengthened effectively. Without any doubt, as
shown in Fig. 5(a and b), the measured values for flexural properties and
ILSS of CF/EP composites were higher at 77 K than at RT at the same
content of EP-PU. The similar results were reported in the literatures [6,
37,38]. Since the ILSS directly reflected the intensity in interfacial
interaction of fiber reinforced composites, thus the increment was much
L. Jia et al.
Fig. 8. SEM images of fractured surfaces for EP composites with (a1-a2) 0.1, (b1-b2) 0.2 and (c1-c2) 0.5 wt% MWCNTs-NH2 at RT (Left column) and 77 K (Right
column) after tensile test.
bigger in ILSS than in flexural strength at 77 K as shown in Fig. 5(a and
b).
2.3. Cryogenic performance of EP composites with EP-PU and MWCNTs-
NH2
In this part, the nanofiller of MWCNTs-NH2 was incorporated into EP
composites with 30 wt% EP-PU (Labeled as EP/EP-PU composites). The
mechanical testings were carried out to evaluate the effects of MWCNTs-
NH2 content on the mechanical response of EP/EP-PU composites. As
shown in Fig. 6, all the measured mechanical properties of EP/EP-PU
composites at both RT and 77 K increased up to 0.2 wt% MWCNTs-
NH2, and then decreased with higher MWCNTs-NH2 content. And tensile
and flexural properties of EP/EP-PU composites were also much higher
at 77 K than at RT when containing the same amount of MWCNTs-NH2.
It was also as expected that impact strength and fracture toughness of
EP/EP-PU composites were lower at 77 K than at RT at the same content
of MWCNTs-NH2. For comparison, tensile, flexural, impact and fracture
toughness properties of neat EP and EP composites with 30 wt% EP-PU
or 0.2 wt% MWCNTs-NH2 or both 30 wt% EP-PU and 0.2 wt% MWCNTs-
NH2 at RT and 77 K were summarized in Fig. 7. Noticeably, all these
properties of EP composites with both 30 wt% EP-PU and 0.2 wt%
MWCNTs-NH2 were obviously higher than those of other composites.
Specifically, tensile strength, flexural strength, impact strength and KIC
fracture toughness of EP composites with both 30 wt% EP-PU and 0.2 wt
% MWCNTs-NH2 at 77 K were enhanced by 31.2, 70.2, 100.0 and 26.0%,
7
Composites Science and Technology 184 (2019) 107865
respectively, compared with those of neat EP.
As reported in literatures [8,24], mechanical performance of
polymer-based nanocomposites was closely dependent on the dispersion
state of nanofillers in the matrix. Here, the dispersibility and interfacial
affinity of MWCNTs-NH2 in EP/EP-PU composites were detected using
SEM. As shown in Fig. 8, the fractured surfaces of EP/EP-PU composites
with various contents of MWCNTs-NH2 indicated the rough feature at
both RT and 77 K. Most of MWCNTs-NH2 were dispersed uniformly
along with the scattering EP-PU micro-spheres in the EP matrix. From
the high-magnification images in insets of Fig. 8, it was observed that the
pulled-out MWCNTs-NH2 were adhered to the EP matrix tightly, sur­
rounded by EP-PU micro-spheres in the nearby area. The amount of
sporadic aggregations of MWCNTs-NH2 increased as the addition con­
tent of MWCNTs-NH2 in EP composites increasing.
Subsequently, effects of MWCNTs-NH2 content on mechanical
response of EP/EP-PU composites with CF reinforcement at both RT and
77 K were further investigated. Also similar to the above case, as the
increase of MWCNTs-NH2 content, all these properties of CF/EP/EP-PU
composites reached maximum value at 0.2 wt% MWCNTs-NH2.
Consistent with the results in Fig. 5(a and b), for CF/EP/EP-PU com­
posites, the measured values for flexural properties and ILSS were higher
at 77 K than at RT at the same content of MWCNTs-NH2 (Fig. 9(a and b)).
And the increment was also much bigger in ILSS than in flexural strength
and modulus at both RT and 77 K. Also for comparison, flexural prop­
erties and ILSS of neat CF/EP composites and CF/EP composites with
30 wt% EP-PU or 0.2 wt% MWCNTs-NH2 or both 30 wt% EP-PU and
L. Jia et al. Composites Science and Technology 184 (2019) 107865

Fig. 9. Effects of MWCNTs-NH2 content on (a) flexural properties and (b) ILSS of CF/EP/EP-PU composites at RT and 77 K, and (c) flexural properties and (d) ILSS of
neat CF/EP composites and CF/EP composites with 30 wt% EP-PU or 0.2 wt% MWCNTs-NH2 or both 30 wt% EP-PU and 0.2 wt% MWCNTs-NH2 at RT and 77 K.

Fig. 10. Schematic model of stress transfer in (a1, a2) neat EP, (b1, b2) EP composites with EP-PU and (c1, c2) EP composites with both EP-PU and MWCNTs-NH2 at
RT (Left column) and 77 K (Right column).

8
L. Jia et al.
0.2 wt% MWCNTs-NH2 at RT and 77 K were summarized in Fig. 9(c and
d). Similar to the above case in Fig. 7, all these properties of CF/EP
composites with both 30 wt% EP-PU and 0.2 wt% MWCNTs-NH2 were
obviously higher than those of other composites. Specifically, flexural
strength, flexural modulus and ILSS of CF/EP composites with both
30 wt% EP-PU and 0.2 wt% MWCNTs-NH2 at 77 K were enhanced by
32.6, 38.9, and 31.4%, respectively, compared with those of neat CF/EP
composites.
Actually, MWCNTs-NH2 could act as an amine-type curing agent due
to the existence of a reactive –H in amine group, as reported in our
previous works [28,29]. It was possible that MWCNTs-NH2 were
chemically bonded with EP-PU micro-spheres and EP matrix due to the
crosslinking reaction of amino group and epoxide group. As shown in
Figs. 6 and 9(a, b), all the measured mechanical properties of EP/EP-PU
composites and CF/EP/EP-PU composites at both RT and 77 K achieved
the maximum at 0.2 wt% MWCNTs-NH2, as the dispersibility of
MWCNTs-NH2 in EP matrix was the best at this content value. Quite
similar to the case containing EP-PU, the measured values for flexural
properties and ILSS of CF/EP/EP-PU composites were also higher at 77 K
than at RT at the same content of MWCNTs-NH2, where the increment
was also much bigger in ILSS than in flexural strength. Thus, these above
results were attributed to the enhancement in the interfacial interaction
between MWCNTs-NH2 and EP matrix via the micro-structure shrinkage
of EP matrix at cryogenic condition, which strengthened positive func­
tion of MWCNTs-NH2 on EP matrix and interfacial bonding of
CF/EP/EP-PU composites.
Totally, the continuous enhancements in properties of EP composites
with EP-PU and CF/EP composites with EP-PU after incorporating
MWCNTs-NH2, especially at cryogenic condition, were resulted from the
synergetic effect of MWCNTs-NH2 and EP-PU. As found from compari­
son data in Figs. 7 and 9(c and d), all the measured properties for EP
composites and CF/EP composites with both 30 wt% EP-PU and 0.2 wt%
MWCNTs-NH2 were obviously higher than those of the corresponding
composites with 30 wt% EP-PU or 0.2 wt% MWCNTs-NH2. These results
confirmed the synergetic effect of MWCNTs-NH2 and EP-PU in both EP
composites and CF/EP composites. A synergetic strengthening mecha­
nism of MWCNTs-NH2 and EP-PU on EP composites (or CF/EP com­
posites) is illustrated in Fig. 10. Indeed, fracture toughening behavior
involved intrinsic toughening mechanisms ahead of the crack tip and
extrinsic toughening mechanisms trying to impede it mainly behind the
tip [39]. In the case of neat EP composites, the crosslinked
micro-structure exhibited the typical brittleness with flat and smooth
fractured surface. The formation of dissipation zone ahead of crack tip
was limited and the crack growth to a catastrophic size was unstoppable
(Fig. 10(a1, a2)). For EP composites with EP-PU, the fractured surfaces
at both 77 K and RT exhibited more ductility than brittleness. The
flexible semi-IPN structure of EP/EP-PU system would lead to effective
stress transfer from resin matrix to EP-PU micro-spheres [40]. EP-PU
micro-spheres could even exhibit the toughening function at cryogenic
condition due to the β or γ relaxation behavior of PU segment. The cracks
suffering from stress would be deflected or pinned at the interface area
between EP-PU micro-spheres and EP matrix (Fig. 10(b1, b2)). In
contrast, there were three phases in the micro-region of EP composites
with both EP-PU and MWCNTs-NH2: EP matrix, the scattering EP-PU
micro-spheres and the uniformly distributed MWCNTs-NH2. As shown
in Fig. 8(b1, b2), the pulled-out MWCNTs-NH2 were adhered to EP
matrix tightly, surrounded by EP-PU micro-spheres in the nearby area.
As mentioned above, the chemically bonded multi-scale interface was
formed among EP-PU micro-spheres, MWCNTs-NH2 and EP matrix. The
riveted and bridging MWCNTs-NH2 on the surface of EP-PU micro-­
spheres would result in the effective stress diversion from resin matrix to
EP-PU micro-spheres (Fig. 10(c1, c2)). Therefore, the enhanced stress
transfer could inhibit the propagation of cracks and slow down the
advancing of the crack front effectively, which was attributed to the
chemically bonded multi-scale interface established among EP-PU mi­
cro-spheres, MWCNTs-NH2 and EP matrix. Noticeably, the failure
9
Composites Science and Technology 184 (2019) 107865
feature for EP composites at RT was different from the case at cryogenic
condition at three aspects. Firstly, the failure behavior for EP composites
at 77 K was more inclined to the brittle style failure in comparison with
the case at RT, since the toughness related properties for the whole
system of EP composites was worsened a lot at cryogenic condition. This
phenomenon was strongly proved from the obvious decreasing in impact
strength and KIC fracture toughness of EP composites as shown in Figs. 2
and 7. Secondly, the internal stress at cryogenic condition was greatly
intensified for EP composites due to the shrinkage of crosslinked
network micro-structure during cooling process (eg. the prominent
shrinkage of EP-PU micro-spheres). Thirdly, in comparison with the case
at RT (Fig. 10(a1-c1)), more micro-cracks were generated at the initial
stage and they would propagate quickly to become big macro-cracks at
cryogenic condition accordingly (Fig. 10(a2-c2)).
3. Conclusions
EP-PU was successfully synthesized by controlling the chemical
grafting reaction between –OH in EP and –NCO in PUR. The obtained
EP-PU possessed the advantages of relatively low viscosity and
outstanding chemical miscibility with EP matrix. Benefiting from β or γ
relaxation capability of flexible segments in EP-PU and the semi-IPN
network between EP-PU and EP matrix, the obvious enhancements
were achieved with the addition of EP-PU in tensile, flexural, impact and
KIC fracture toughness properties of EP composites as well as flexural
properties and ILSS of CF/EP composites at 77 K. Moreover, the further
addition of MWCNTs-NH2 continuously enhanced all-above properties
at 77 K, due to their reinforcement capability, excellent dispersibility
and high reacting ability in EP composites. Totally, it was found that the
riveting and bridging of MWCNTs-NH2 on the surface of EP-PU micro-
spheres provided extraordinary synergy on the effective stress diversion
and crack propagation inhibition through establishing the chemically
bonded multi-scale interface, which contributed to synergetic
strengthening effects of EP-PU and MWCNTs-NH2 on EP-based com­
posites at cryogenic condition.
Declaration of competing interest
We declare that we have no financial and personal relationships with
other people or organizations that can inappropriately influence our
work, there is no professional or other personal interest of any nature or
kind in any product, service and/or company that could be construed as
influencing the position presented in, or the review of, the manuscript
entitled.
Acknowledgement
The authors are very pleased to acknowledge financial support from
Beijing Natural Science Foundation (Grant No. 2192044), Fundamental
Research Funds for the Central Universities (Grant No. XK1802-2), Na­
tional Natural Science Foundation of China (Grant No. U1362205,
5157031049, 51373016), Natural Science Foundation of Jiangsu Prov­
ince (Grant No. SBK2014040489) and Beijing Youth Talent Plan (Grant
No. YETP0492).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.compscitech.2019.107865.
References
[1] M.D.R. Batista, L.T. Drzal, Carbon fiber/epoxy matrix composite interphases
modified with cellulose nanocrystals, Compos. Sci. Technol. 164 (2018) 274–281.
[2] V. Eskizeybek, A. Yar, A. Avci, CNT-PAN hybrid nanofibrous mat interleaved
carbon/epoxy laminates with improved Mode I interlaminar fracture toughness,
Compos. Sci. Technol. 157 (2018) 30–39.
L. Jia et al.
[3] Y. He, Q. Chen, Y. Song, Micro-crack behavior of carbon fiber reinforced Fe3O4/
graphene oxide modified epoxy composites for cryogenic application, Compos.
Appl. Sci. Manuf. 108 (2018) 12–22.
[4] M. Li, H. Zhou, Z. Yun, Y. Liao, H. Zhou, Effect of defects on thermal conductivity
of graphene/epoxy nanocomposites, Carbon 130 (2018) 295–303.
[5] S.I.B.S. Abdullah, L. Iannucci, E.S. Greenhalgh, On the translaminar fracture
toughness of vectran/epoxy composite material, Compos. Struct. 202 (2018)
566–577.
[6] J. Yang, G. Yang, G. Xu, Cryogenic mechanical behaviors of MMT/epoxy
nanocomposites, Compos. Sci. Technol. 67 (2007) 2934–2940.
[7] A. Hussein, S. Sarkar, K. Lee, Cryogenic fracture behavior of epoxy reinforced by a
novel graphene oxide/poly(p-phenylenediamine) hybrid, Compos. B Eng. 129
(2017) 133–142.
[8] Y. He, S. Yang, H. Liu, Reinforced carbon fiber laminates with oriented carbon
nanotube epoxy nanocomposites: magnetic field assisted alignment and cryogenic
temperature mechanical properties, J. Colloid Interface Sci. 517 (2018) 40–51.
[9] Y. Liu, C. Qu, Q. Feng, H. Xiao, S. Fu, Enhancement in mode II interlaminar fracture
toughness at cryogenic temperature of glass fiber/epoxy composites through
matrix modification by carbon nanotubes and n-butyl glycidyl ether, J. Nanomater.
(2015) 1–6, 2015.
[10] Y. Zhao, Z. Chen, Y. Liu, H. Xiao, Q. Feng, S. Fu, Simultaneously enhanced
cryogenic tensile strength and fracture toughness of epoxy resins by carboxylic
nitrile-butadiene nano-rubber, Compos. Appl. Sci. Manuf. 55 (2013) 178–187.
[11] J. Yang, Z. Chen, Q. Feng, Cryogenic mechanical behaviors of carbon nanotube
reinforced composites based on modified epoxy by poly(ethersulfone), Compos. B
Eng. 43 (2012) 22–26.
[12] S. Fu, Q. Pan, C. Huang, Y. Guo, A preliminary study on cryogenic mechanical
properties of epoxy blend matrices and SiO2/epoxy nanocomposites, Key Eng.
Mater. 312 (2006) 211–216.
[13] M. Xia, H. Yang, J. Ling, The mechanical behaviors of epoxy-terminated
hyperbranched polyester (E-HBP) as toughener in different epoxy resins, Adv.
Compos. Hybrid Mater. 1 (2018) 310–319.
[14] A. Keller, H. Chong, A.C. Taylor, C. Dransfeld, K. Masania, Core-shell rubber
nanoparticle reinforcement and processing of high toughness fast-curing epoxy
composites, Compos. Sci. Technol. 147 (2017) 78–88.
[15] Sadaki Samitsu, Thermally stable mesoporous poly(ether sulfone) monoliths with
nanofiber network structures, Macromolecules 51 (2018) 151–160.
[16] T. Ueki, S. Nishijima, Y. Izumi, Designing of epoxy resin systems for cryogenic use,
Cryogenics 45 (2005) 141–148.
[17] N. Domun, K.R. Paton, H. Hadavinia, Enhancement of fracture toughness of epoxy
nanocomposites by combining nanotubes and nanosheets as fillers, Materials 10
(2017) 1179.
[18] H. Liu, J. Zhang, X. Gao, G. Huang, Simultaneous reinforcement and toughness
improvement of an epoxy-phenolic network with a hyperbranched polysiloxane
modifier, RSC Adv. 8 (2018) 17606–17615.
[19] A. Reghunadhan, J. Datta, N. Kalarikkal, Toughness augmentation by fibrillation
and yielding in nanostructured blends with recycled polyurethane as a modifier,
Appl. Surf. Sci. 442 (2018) 403–411.
[20] N. Zheng, Y. Huang, H. Liu, Improvement of interlaminar fracture toughness in
carbon fiber/epoxy composites with carbon nanotubes/polysulfone interleaves,
Compos. Sci. Technol. 140 (2017) 8–15.
[21] X. He, J. Shi, L. Wu, P. Jiang, B. Liu, Study on synergistic toughening of
polypropylene with high-density polyethylene and elastomer-olefin block
copolymers under ultrasonic application, Compos. Sci. Technol. 161 (2018)
115–123.
10
Composites Science and Technology 184 (2019) 107865
[22] J. Misasi, Q. Jin, K.M. Knauer, S.E. Morgan, Hybrid POSS-hyperbranched polymer
additives for simultaneous reinforcement and toughness improvements in epoxy
networks, Polymer 117 (2017) 54–63.
[23] S. Chopra, K.A. Deshmukh, A.D. Deshmukh, C.L. Gogte, Prediction, evaluation and
mechanism governing interphase strength in tensile fractured PA-6/MWCNT
nanocomposites, Compos. Appl. Sci. Manuf. 112 (2018) 255–262.
[24] W. Li, D. Xiang, L. Wang, Simultaneous enhancement of electrical conductivity and
interlaminar fracture toughness of carbon fiber/epoxy composites using plasma-
treated conductive thermoplastic film interleaves, RSC Adv. 8 (2018)
26910–26921.
[25] P. Li, D. Liu, B. Zhu, Synchronous effects of multiscale reinforced and toughened
CFRP composites by MWNTs-EP/PSF hybrid nanofibers with preferred orientation,
Compos. Appl. Sci. Manuf. 68 (2018) 72–80.
[26] D. Liu, G. Li, B. Li, Establishment of multi-scale interface in interlayer-toughened
CFRP composites by self-assembled PA-MWNTs-EP, Compos. Sci. Technol. 130
(2016) 53–62.
[27] X. Jia, G. Li, B. Liu, Multiscale reinforcement and interfacial strengthening on
epoxy-based composites by silica nanoparticle-multiwalled carbon nanotube
complex, Compos. Appl. Sci. Manuf. 48 (2013) 101–109.
[28] Q. Zhang, X. Li, S. Liang, A kind of liquid-like MWCNT reinforcements for T1000
carbon fibre filament winding composites, Compos. Sci. Technol. 131 (2016)
89–97.
[29] W. Zhang, X. Deng, G. Sui, X. Yang, Improving interfacial and mechanical
properties of carbon nanotube-sized carbon fiber/epoxy composites, Carbon 145
(2019) 629–639.
[30] R. Cheng, C. Zhang, J. Wang, Preparation and characterization of epoxy resin
composite modified by flexible polyurethane resin, Adv. Mater. Res. 904 (2014)
170–172.
[31] M.R. Ricciardi, I. Papa, A. Langella, T. Langella, V. Lopresto, V. Antonucci,
Mechanical properties of glass fibre composites based on nitrile rubber toughened
modified epoxy resin, Compos. B Eng. 139 (2018) 259–267.
[32] M.F.D. Velasco-Ruiz, I. Quijada-Garrido, R. Benavente, J.M. Barrales-Rienda,
Miscibility studies of erucamide (13-cis-docosenamide)/poly(laurolactam) (nylon
12) (PA-12) blends, Polymer 41 (2000) 5819–5828.
[33] H. Wang, J. Chen, Toughening of epoxy resin by functional-terminated
polyurethanes and/or semicrystalline polymer powders, J. Appl. Polym. Sci. 82
(2001) 2903–2912.
[34] Y. Zhang, F. Xu, C. Zhang, J. Wang, Z. Jia, D. Hui, Y. Qiu, Tensile and interfacial
properties of polyacrylonitrile-based carbon fiber after different cryogenic treated
condition, Compos. B Eng. 99 (2016) 358–365.
[35] G. Korb, J. Korab, G. Groboth, Thermal expansion behaviour of unidirectional
carbon–fibre-reinforced copper-matrix composites, Compos. Appl. Sci. Manuf. 29
(1998) 1563–1567.
[36] C. Pradere, C. Sauder, Transverse and longitudinal coefficient of thermal expansion
of carbon fibers at high temperatures (300-2500K), Carbon 46 (2008) 1874–1884.
[37] Y. He, Q. Li, T. Kuila, N.H. Kim, Micro-crack behavior of carbon fiber reinforced
thermoplastic modified epoxy composites for cryogenic applications, Compos. B
Eng. 44 (2013) 533–539.
[38] K. Lau, T.T. Wong, J. Leng, D. Hui, Property enhancement of polymer-based
composites at cryogenic environment by using tailored carbon nanotubes, Compos.
B Eng. 54 (2013) 41–43.
[39] D. Quan, J.L. Urd� aniz, A. Ivankovic, Enhancing mode-I and mode-II fracture
toughness of epoxy and carbon fibre reinforced epoxy composites using multi-
walled carbon nanotubes, Mater. Des. 143 (2018) 81–92.
[40] S. Ganguly, P.P. Maity, S. Mondal, Polysaccharide and poly(methacrylic acid)
based biodegradable elastomeric biocompatible semi-IPN hydrogel for controlled
drug delivery, Mater. Sci. Eng. C Mater. 92 (2018) 34–51.