Materials Letters 274 (2020) 127999

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Enhanced the mechanical and damping properties of epoxy

nanocomposites by filling with a multi-core solvent-free nanofluids
Yudeng Wang, Dongdong Yao, Fangfang Su, Dechao Wang, Yaping Zheng ⇑
School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710129, People’s Republic of China

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

Article history: To improve the mechanical and damping properties of epoxy, a kind of solvent-free nanofluids, which
Received 12 March 2020 contain a multi-core of graphene oxide (GO) and Fe3O4 nanocrystalline, was designed. Various analysis
Received in revised form 29 April 2020 technologies were employed to characterize the morphology, chemical structure of the nanofluids. It
Accepted 15 May 2020
exhibited liquid-like behavior at room temperature, and good dispersion in solvent and epoxy. The study
Available online 18 May 2020
on the mechanical and damping properties of the nanofluids/epoxy nanocomposite indicated that the
nanofluids can adjust the interface between GO and epoxy matrix, and it enhanced the bending strength,
Keywords:
impact strength and loss factor of epoxy by 18.65%, 41.95% and 24.74% at the 4.5 wt% content,
Nanoparticles
Solvent-free nanofluids
respectively.
Nanocomposites Ó 2020 Elsevier B.V. All rights reserved.
Mechanical properties
Damping properties

1. Introduction Although functionalization of graphene, such as oxidizing and sur-

Damping is an important parameter to measure the energy
absorption and dissipation of materials, and damping properties
have significant effect on the life of materials, which under
mechanical vibration, high-speed shock, and cyclic loading. Rub-
bers and rubber-based composites have been widely used in the
fields of damping and vibration control. However, the poor
mechanical properties and low glass transition temperature (Tg)
of rubbers limit their application in the fields of structural materi-
als [1]. In recent years, some researchers studied the damping
properties of nanocomposites, the results showed that nanomate-
rial reinforced polymer could be applied in structure damping
fields [2,3]. Nanofillers can introduce a large amount of interface
in the matrix, and the slip between the interface of fillers and
matrix can consume energy [4,5].
Researches on carbon nanotubes (CNTs)/epoxy nanocomposites
have proved that the CNTs can simultaneously improve the loss
factor and storage modulus of the epoxy matrix [6–8]. Compared
with CNTs, graphene has excellent mechanical properties, vis-
coelastic damping properties and enormous specific surface area,
which is also an ideal filler for the fabrication of nanocomposite
[9,10]. However, the main difficulties in the application of gra-
phene in structure damping materials relate to the dispersion of
graphene and the interface strength between graphene and matrix.
face modifying, can prevent the aggregation, the strong interface
strength does not contribute to damping properties of the matrix
[11,12]. Fortunately, solvent-free nanofluids, which is synthesized
by nanoparticles and flexible organic chains, could be a candidate
to solve the problems. The flexible organic chains can prevent
the aggregation of nanoparticles and adjust the interface strength
between nanofillers and matrix [13–16].
In the present work, Fe3O4 nanocrystalline were introduced
onto the surface of graphene oxide (GO) to form a multi-core struc-
ture. Subsequently, a multi-core based solvent-free nanofluid
(GCNF) was synthesized by decorating the multi-core with
organosilanes (KH560) as corona and polyether amine (M2070)
as canopy. In the end, effects of GCNF on the mechanical properties
and damping properties of GCNF/epoxy nanocomposite were
studied.
2. Experimental details
2.1. Materials
The materials are discussed in detail in the supporting
information.
2.2. Synthesis of multi-core based solvent-free nanofluid

⇑ Corresponding author. The GO was obtained by a modified Hummers method [17].

E-mail address: zhengyp@nwpu.edu.cn (Y. Zheng). Firstly, 1.345 g FeCl3
4H20 (in 20 mL water) was added to 20 mL

https://doi.org/10.1016/j.matlet.2020.127999
0167-577X/Ó 2020 Elsevier B.V. All rights reserved.
2 Y. Wang et al. / Materials Letters 274 (2020) 127999
GO aqueous solution (5 mg/mL); After 30 min sonication, 0.495 g
FeCl2
6H20 (in 10 mL water) was added to the solution. The solu-
tion was sonicated for another 10 min before ammonia (12 mL)
was slowly added. The above solution was stirred for 30 min at
35 ℃ with sonication to obtain the multi-core structure. Then,
equal molar KH560 was added to 10 wt% M2070 solution in
methanol and the solution was stirred at 45 ℃ for 12 h. Finally,
the multi-core suspension was added dropwisly into the KH560-
M2070 solution and the resulting mixture was stirred for 5 h at
25 ℃ and then dialyzed (MWCO 5.0 K) against deionized water
for 24 h in order to remove excess KH560-M2070.
2.3. Preparation of GCNF/epoxy nanocomposite
The preparation of GCNF/epoxy nanocomposite is discussed in
detail in the supporting information.
2.4. Characterization
Characterization methods of the properties of GCNF, the
mechanical properties and damping properties of GNCF/epoxy
nanocomposite are discussed in detail in the supporting
information.
3. Results and discussion
FTIR spectrum of the GCNF exhibits absorption bands character-
istic of the multi-core structure, corona and canopy (Fig. 1a). The
absorption peak at 560 cm1 (Fe–O) confirms that Fe3O4 nanocrys-
talline has been attached onto GO. The absorption peaks at
2880 cm1 (–CH3), 1107 cm1 (–CH2–O–CH2–) and 950 cm1 (–
Si–O–), which are attributed to the corona (KH560) and canopy
(M2070), show that the solvent-free nanofluids has been success-
Fig. 1. (a) FTIR spectra of GO@Fe3O4, KH560-M2070 and GCNF; (b) TGA curves of GO@Fe3O4, M2070 and GCNF; (c) TEM image of GCNF; (d) Modulus (G’, G”) versus
temperature traces; (e) Modulus (G’, G”) versus frequency trace; (f) Photos of GCNF in ethanol with different weight fraction.
fully synthesized. TGA shows that the GCNF is solvent-free with
a decomposition temperature, which is higher than pure canopy
and multi-core content of 12.81% w/w (Fig. 1b). TEM image
(Fig. 1c) of GCNF reveals the presence of Fe3O4 nanocrystalline,
which is virtually monolayer distributed on the surface of GO,
and the agglomeration of multi-core has been prevented by the
polymeric canopy (see Fig. S1). The storage modulus (G0 ) and the
loss modulus (G00 ) versus the temperature (Fig. 1d) and frequency
(Fig. 1e) trace are characterized by the rotation rheometer. In the
measured temperature and frequency range, the G00 is always
higher than G0 , and it indicates that the GCNF exhibits a typical
liquid-like behavior. Fig. 1f shows the dispersion of GCNF in etha-
nol at different concentration (w/w) after setting for one day. The
photos show that there is no precipitation in all solution, and it
indicates that the GCNF exhibits excellent dispersion stability in
ethanol.
The bending strength, bending modulus and impact strength of
GCNF/epoxy nanocomposites with the addition of 0, 3, 4.5, 6, 7.5,
9 wt% GCNF (by weight of epoxy and cure agent) are shown in
Fig. 2a–c. Compared with the neat epoxy, the 4.5 wt% GCNF
enhanced the bending strength by 18.65%, but decreased the bend-
ing modulus by 11.73%. The increase of bending strength is attrib-
uted to the excellent dispersion of GCNF. The 4.5 wt% and 6 wt%
GCNF enhanced the impact strength of epoxy by 41.95% and
65.53%, respectively. However, with the content rising, the impact
strength begins to decrease. This is because of the GCNF introduced
too much of microcracks in the matrix, which will evolve into
macrocracks, causing the broken of composite. As shown in the
SEM photos of the fracture surface of neat epoxy and the nanocom-
posite filled with 6.0 wt% GCNF (Fig. S3a and b), the fracture sur-
face of nanocomposite is much rougher than the fracture surface
of neat epoxy, it indicates that the nanocomposite generates more
cracks and absorbs more energy when it is damaged by impact.
 Y. Wang et al. / Materials Letters 274 (2020) 127999
Fig. 2. (a) Bending strength of GCNF/epoxy nanocomposites; (b) Bending modulus of GCNF/epoxy nanocomposites; (c) Impact strength of GCNF/epoxy nanocomposites.
The storage modulus, loss modulus and loss factor of GCNF/
epoxy nanocomposites with the addition of 0, 3, 4.5, 6, 7.5, 9 wt%
GCNF are shown in Fig. 3a–c. The storage modulus was reduced
with the GCNF content increasing, the 4.5 wt% and 9 wt% GCNF
reduced the storage modulus of nanocomposite by 9.68% and
14.64% at 25 ℃, respectively. At the meantime, the loss modulus
of the nanocomposites with 4.5 wt% and 9 wt% GCNF increased
by 11.40% and 26.96%, respectively. The canopy of GCNF induced
a soft interface between the multi-core and epoxy matrix, and they
slip easily when the composite is under stress, which result in a
decrease of storage modulus and an increase of loss modulus. As
Fig. 3c shown, the 4.5 wt% and 9 wt% GCNF increase the loss factor
of nanocomposites by 24.74% and 49.32% at 25 ℃, and the loss fac-
tor of nanocomposites with different weight fraction of GCNF are
always higher than the neat epoxy at the temperature range from
25 ℃ to 200 ℃. The Tg of nanocomposites with different GCNF con-
tent are also investigated. As it shown in Tab. S1, GCNF has no neg-
ative influence on Tg until the content rises up to 9 wt%.
4. Conclusion
A solvent-free nanofluids, which was based on the Fe3O4
nanocrystalline decorated GO, was successfully synthesized in this
article. The nanofluids exhibited an excellent dispersion stability
and enhanced the bending strength, impact strength and damping
properties of epoxy resin. The present work provides a useful route
to design a nano filler to simultaneously improve the mechanical
and damping properties of epoxy. However, there are many issues
in this work that deserve further study, such as how does the prop-
erty of canopy (molecular mass, flexible of molecular chain) effects
the mechanical and damping properties of epoxy resin.
Fig. 3. (a) Storage modulus of GCNF/epoxy nanocomposites; (b) Loss modulus of GCNF/epoxy nanocomposites; (c) Loss factor of GCNF/epoxy nanocomposites.
3
CRediT authorship contribution statement
Yudeng Wang: Conceptualization, Methodology, Investigation,
Writing - original draft. Dongdong Yao: Writing - review & editing,
Supervision, Funding acquisition. Fangfang Su: Investigation.
Dechao Wang: Investigation. Yaping Zheng: Writing - review &
editing, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matlet.2020.127999.
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