Materials Letters 309 (2022) 131401

Contents lists available at ScienceDirect

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

Effect of graphene size on the mechanical and damping properties of

polyether amine modified r-GO and ZnO multi-nanoparticles filled epoxy
Yudeng Wang , Dongdong Yao , 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

Keywords: To prepare structural damping epoxy nanocomposites, three kinds of organic–inorganic hybrids containing r-
Nanoparticles GO@ZnO nanoparticles with different graphene sizes and polyether amine were synthesized. The mechanical
Organic-inorganic hybrids and damping properties of the epoxy nanocomposites containing 2 wt% of the hybrids were investigated. It is
Nanocomposites
found that the filler size has a significant effect on the mechanical and damping properties of nanocomposites.
Mechanical properties
Damping properties
The nanocomposite containing the smallest size hybrid had the highest bending strength and impact strength,
which improved by 3.9 % and 59.7 % respectively. The nanocomposite containing the biggest size hybrid had the
highest bending modulus, which improved by 28.8 %. The medium size hybrid had little effect on the mechanical
properties of nanocomposite, it is more effective in improving the damping properties, and the loss factor of
nanocomposite is increased by at least 38.4% at the glass stage.

1. Introduction properties and damping properties of OIH/epoxy nanocomposites were

studied.
Adding nanofillers into epoxy is a promising method for preparing
structural damping materials [1,2]. The nanofillers with a large specific 2. Experimental details
surface area can introduce a large number of interfaces in the epoxy
matrix, and the vibration energy can be consumed in the relative sliding 2.1. Materials
process of the matrix and the fillers [3]. Graphene, a two-dimensional
nanomaterial with a huge specific surface area, is an ideal filler to Graphite powder (Diameter ~ 5 μm, ~ 40 μm and ~ 100 μm) was
fabricate structural damping materials. Recent researches have shown purchased from Xiamen Knano-tech Port Co. Ltd. Other materials are
that the slip between graphene itself can dissipate the vibration energy discussed in detail in the Supporting information.
[4,5]. However, the unique conjugated structure of graphene leads to a
strong interfacial interaction between graphene and the epoxy matrix,
2.2. Synthesis of the organic–inorganic hybrids
which can improve the mechanical properties of the nanocomposites,
but not the damping properties [6–8]. In the previous work, a kind of
The GO was obtained by a modified Hummers method [10]. The r-
organic–inorganic hybrid was applied to fabricate the structural
GO@ZnO nanoparticles were prepared by hydrothermal reaction as
damping epoxy nanocomposites, the nanocomposites exhibit higher
reported in the previous study [11]. In a typical synthesis of the OIH, 1 g
bending strength, impact strength and loss factor than pure epoxy resins
M1000 and 0.24 g KH560 were added into 20 mL methanol, and the
[9]. However, the modulus of nanocomposites containing the hybrid is
solution was stirred at 50 ℃ for 12 h to obtain the oligomer KH560-
significantly reduced, which is a problem that must be solved.
M1000. Then 0.1 g r-GO@ZnO multi-nanoparticle was added to 20
In the present study, three kinds of r-GO@ZnO nanoparticles with
mL methanol. After stirring 0.5 h, the r-GO@ZnO suspension was added
different graphene sizes were synthesized by hydrothermal reaction.
into the KH560-M1000 solution, and the resulting mixture was stirred
Subsequently, the organic–inorganic hybrid (OIH) was synthesized by
for 12 h at 25 ℃. The final suspension was dialyzed (MWCO 5.0 K)
decorating r-GO@ZnO with organosilanes (KH560) and polyether amine
against deionized water for 24 h to remove excess KH560-M1000, and
(M1000). In the end, the effects of graphene size on the mechanical
then dried at 60 ℃ for 48 h to obtain the OIH. The OIH prepared from

* Corresponding author.
E-mail address: zhengyp@nwpu.edu.cn (Y. Zheng).

https://doi.org/10.1016/j.matlet.2021.131401
Received 20 August 2021; Received in revised form 1 November 2021; Accepted 27 November 2021
Available online 2 December 2021
0167-577X/© 2021 Elsevier B.V. All rights reserved.
Y. Wang et al. Materials Letters 309 (2022) 131401

Fig. 1. TEM images of (a) 5-OIH, (b) 40-OIH and (c) 100-OIH.

Fig. 2. (a) FTIR spectra of GO, r-GO@ZnO and 5-OIH; (b) TGA curves of 5-OIH, 40-OIH and 100- OIH; (c) DSC curves of M1000, 5-OIH, 40-OIH and 100-OIH.

graphite with diameters of 5 μm, 40 μm and 100 μm were named 5-OIH,
40-OIH and 100-OIH respectively.
2.3. Preparation of OIH/epoxy nanocomposite
The preparation of OIH/epoxy nanocomposite is discussed in detail
in the Supporting information.
2.4. Characterization
Characterization methods are discussed in detail in the Supporting
information.
3. Results and discussion
Fig. 1a, 1b and 1c were the TEM images of 5-OIH, 40-OIH and 100-
OIH respectively. It can be seen that the ZnO particles are evenly
distributed on the graphene. The high magnification TEM image, energy
dispersive X-ray spectroscopy analysis (Fig. S1) and the XRD pattern
(Fig. S2) of r-GO@ZnO prove that it contains ZnO crystal. Besides, the
TEM images show that the modification of the multi-nanoparticles did
not destroy their original structure, the ZnO nanoparticles are still
covered on the surface of graphene.
Fig. 2a shows the FTIR spectra of GO, r-GO@ZnO and 5-OIH. In the
FTIR spectra of r-GO@ZnO, the peaks of functional groups in GO (C = O
at 1735 cm− 1 and C-O at 1045 cm− 1) are reduced or even disappeared,
indicating that GO was reduced during the solvothermal reaction [12].
Besides, a new absorption peak at 1570 cm− 1 which is attributed to the
skeletal vibration of graphene sheets, can be observed in the spectra of r-
GO@ZnO [13]. The Raman spectroscopy of the HCl treated r-GO@ZnO
(Fig. S3) also proved the GO had been reduced. The FTIR spectra of 5-
OIH shows the characteristic absorption peaks at 1107 cm− 1 (–CH2-O-
CH2) and 2880 cm− 1 (C–H), which indicates that the polyether amine
was successfully grafted on the r-GO@ZnO. The FTIR spectra of 40-OIH
and 100-OIH (Fig. S4a and 4b) show that they have the same absorption
peak as 5-OIH, which proves that they have the same chemical
composition. The TGA curves of 5-OIH, 40-OIH and 100-OIH are shown
in Fig. 2b, the residual content of them is 10.79 %, 10.53 % and 12.42 %
respectively. There are two steps in the TGA curve of all the samples, the
first one (240 ℃ ~ 420 ℃) is attributed to the decomposition of M1000
and the second one (420 ℃ ~ 575 ℃) is caused by the decomposition of
r-GO. Fig. 2c shows DSC curves of pure M1000, 5-OIH, 40-OIH and 100-
OIH. Endothermic and exothermic peaks appear in curves, which are
caused by the melting and crystallization of M1000. The OIH containing
large-sized r-GO has a lower melting temperature and crystallization
temperature.

Fig. 3. The (a) Bending strength, (b) bending modulus and (c) impact strength of nanocomposites containing different OIHs.

2
Y. Wang et al.
Fig. 4. The (a) storage modulus, (b) loss modulus and (c) (d) loss factor of pure epoxy and the nanocomposites filled with 5-OIH, 40-OIH and 100-OIH.
The mechanical tests of nanocomposites with different 5-OIH con­
tents (Fig. S5) show that the nanocomposite filled with 2 wt% 5-OIH has
the best mechanical properties. Therefore, in all nanocomposites, the
weight fraction of OIH is fixed at 2 wt% to ensure that the interface
introduced in the matrix is the same. The mechanical properties of
nanocomposites containing different OIHs at a content of 2 wt% were
studied, and the results are showed in Fig. 3. The bending strength of
nanocomposite containing 2 wt% 5-OIH increased about 3.9 %, its
impact strength increased 59.7 % while its bending modulus decreased
about 8.4 %. The nanocomposite containing 2 wt% 40-OIH had the same
bending strength as pure epoxy, its bending modulus increased about
5.2 % and its impact strength decreased about 6.4 %. The bending
strength of nanocomposite containing 2 wt% 100-OIH decreased about
2.4 %, its bending modulus increased about 28.8 % and its impact
strength decreased about 6.6 %. The differences in the mechanical
properties of nanocomposites are attributed to the r-GO size and the
weak interface strength between the fillers and the matrix [9]. The large-
sized fillers will generate greater internal stress [14]. Besides, the fillers
cannot play a reinforcing role because of weak interface strength, so the
bending strength and impact strength of nanocomposites containing 40-
OIH and 100-OIH are lower than pure epoxy.
The storage modulus (E′ ), loss modulus (E′′ ) and loss factor of
nanocomposites containing different OIHs were tested by DMA. As
shown in Fig. 4a, the storage modulus of nanocomposites increases with
the increase of the r-GO size, and the nanocomposite containing 100-
OIH has the highest storage modulus at the glass stage. Besides, the
temperature at the inflection point of the storage modulus of all nano­
composites was reduced, which is attributed to the slip between the
matrix and the fillers [15]. As shown in Fig. 4b, pure epoxy has the
lowest loss modulus at the glass stage, and nanocomposites containing
large-sized fillers have a higher loss modulus. This is because the stress
between the large-sized fillers and the matrix is greater when the matrix
is deformed, which promotes relative slippage between the fillers and
the matrix. As shown in Fig. 4c and 4d, the nanocomposite containing
3
Materials Letters 309 (2022) 131401
40-OIH has the highest loss factor in the glass stage, and the loss factor
can be increased by at least 38.4 % (at 61.4 ℃).
4. Conclusion
A series of organic–inorganic hybrids containing r-GO@ZnO nano­
particles with different r-GO sizes and polyether amine were synthesized
in this work. The size of OIH has a significant effect on the properties of
the nanocomposites. The small size OIH improves the mechanical
strength of the matrix but reduces its modulus. The large size OIH in­
creases the modulus of the matrix while slightly reducing the mechan­
ical strength, and the nanocomposites containing medium size OIH
exhibited better damping properties.
CRediT authorship contribution statement
Yudeng Wang: Conceptualization, Methodology, Investigation,
Writing – original draft. Dongdong Yao: Writing – review & editing,
Supervision, Funding acquisition. Yaping Zheng: Writing – review &
editing, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
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.2021.131401.
Y. Wang et al. Materials Letters 309 (2022) 131401

References [8] Y. Gogotsi, Carbon 61 (2013) 650–651.

[9] Y.D. Wang, D.D. Yao, F.F. Su, D.C. Wang, Y.P. Zheng, Mater. Lett. 274 (2020),
127999.
[1] R. Chandra, S.P. Singh, K. Gupta, Compos. Struct. 46 (1) (1999) 41–51.
[10] J. Chen, B. Yao, C. Li, G. Shi, Carbon 64 (2013) 225–229.
[2] M. Rafiee, F. Nitzsche, M.R. Labrosse, J. Compos. Mater. 53 (15) (2019)
[11] Q. Zhang, C. Tian, A. Wu, T. Tan, L. Sun, L. Wang, H. Fu, J. Mater. Chem. 22 (23)
2105–2118.
(2012) 11778–11784.
[3] J. Suhr, N.A. Koratkar, J. Mater. Sci. 43 (13) (2008) 4370–4382.
[12] C. Yang, Z. Liu, C. Chen, K. Shi, L. Zhang, X.J. Ju, W. Wang, R. Xie, L.Y. Chu, ACS
[4] D. Lahiri, S. Das, W. Choi, A. Agarwal, ACS Nano 6 (2012) 3992–4000.
Appl. Mater. Interfaces 9 (18) (2017) 15758–15767.
[5] Y. Su, H. Wei, R. Gao, Y. Zhi, J. Zhang, Z. Zhong, Y. Zhang, Carbon 50 (2012)
[13] H. Zhang, X. Lv, Y. Li, Y. Wang, J. Li, ACS Nano 4 (1) (2010) 380–386.
2804–2809.
[14] G. Valérie, L. Yves, E.M. Jan-Anders, Macromol. Mater. Eng. 297 (2) (2012)
[6] M. Rafiee, F. Nitzsche, J. Laliberte, J. Thibault, M.R. Labrosse, Polym. Compos. 40
155–166.
(S2) (2019) E1732–E1745.
[15] A. Montazeri, Mater. Des. 45 (2013) 510–517.
[7] M. Rafiee, F. Nitzsche, M.R. Labrosse, Polym. Compos. 40 (10) (2019) 3914–3922.