Composites Part A 123 (2019) 149–157

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

Functional & enhanced graphene/polyamide 6 composite fiber constructed T

by a facile and universal method☆
Yunhai Zhang, Yue Lu, XiaoJie Yan, WenSheng Gao, HuQiang Chen, Qinjia Chen, YongXiao Bai
⁎

Institute of Material Science and Engineering, Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Key Laboratory of Special Function
Materials and Structure Design of Ministry of Education, Lanzhou University, Lanzhou 730000, China

ARTICLE INFO ABSTRACT

Keywords: Demand for multifunctional and high-strength fiber has substantially increased in textile industry, biomedical,
FGO and biotechnological applications. In this study, an efficient and environment-friendly method was developed for
PA6 functionalizing graphene through weak interaction and the construction of polyamide 6 composite functional
Multifunctional composite fiber fiber. With a loading of 0.5 wt% functionalized graphene oxide, the tensile strength reached 4.21 cN/dtex, and
Anti-UV
the tensile modulus reached 33.86 cN/dtex, indicating 31.6% and 33.6% enhancement, respectively. Moreover,
Antibacterial property
the UV protection factor increased to more than 471, and the antibacterial property also increased to a certain
level (antibacterial efficacy (AE)% > 94%) with a low addition (0.9 wt%) of functionalized graphene oxide,
indicating that the fabric can effectively prevent the encroachment of bacteria. These functionalization and
composite preparation methods provide a convenient and scalable route to prepare graphene-based nano-
composite fiber with high strength and multifunctional properties. It has promising practical application in
textile, biomedical, and biotechnological fields.

1. Introduction butadiene styrene (ABS), respectively. All these shortcomings of PA6

Graphene is a single-atom-thick and two-dimensional carbon allo-
trope consisting of a sheet of hexagonally arrayed sp2-bonded carbon.
Graphene has attracted tremendous interest because of their special
structure and prominent physical properties, e.g., high mechanical
strength and elasticity [1,2], superior thermal conductivity [3,4], and
high thermal stability [2,5-8]. Therefore, all these special character-
istics of graphene sheets make it an important candidate for applica-
tions in high-performance polymer composites [9-13]. Graphene can
improve the performance of a matrix and introduce the inherent per-
formance of graphene into composites, such as enhancing the me-
chanical and thermal properties [12,14] and antibacterial activity
[15,16]. However, there are some problems between pristine graphene
and polymer matrix [15,17], such as poor compatibility, weak inter-
actions, and difficulty in scattering, thus reducing the composite per-
formance directly [4,18]. Therefore, it is essential to modify the surface
of graphene.
PA6 is a widely produced and consumed engineering thermoplastics
and widely used in engineering plastic films and fibers [19,20]. How-
ever, the drawbacks of PA6 are poor thermal stability and mediocre
mechanical performance compared to phenolic resin and acrylonitrile
matrix have caused a huge obstacle to its practical application and
development [21]. Therefore, it is essential to develop a high-return,
scalable production method for the preparation of high-quality gra-
phene sheet and multifunctional & high-strength composites.
To date, several methods have been reported to modify graphene,
but the experimental conditions are tedious [22], demanding [8], re-
quire a lot of organic solvents [1,22], or need a long time to synthesize
[23,24], severely affecting the environment and low efficiency. Besides,
to develop high-performance nanocomposites, Zhang et al. [24] pre-
pared TiO2/PA6 nanocomposites by melt spinning and increased its
conductivity, but could not achieve high mechanical properties due to
poor compatibility and dispersibility of TiO2 in matrix. Wang et al.
prepared sulfonated graphene/nylon 6 composites using an in-situ
polymerization methodology and enhanced its mechanical properties
[25]; however, a large amount of organic solvent and low efficiency
limit its scalable production in industry.
To solve these problems, in this work, graphene oxide (GO) was
used as a precursor to fabricate functionalized graphene oxide (FGO)
using a highly efficient and environment-friendly route through weak
interaction. Using melt spinning, a versatile environmental-friendly
process, graphene/polyamide 6 (PA6) nanocomposite fiber was

☆
This article for the celebration of the 110th anniversary of Lanzhou University.
⁎
Corresponding author.
E-mail address: baiyx@lzu.edu.cn (Y. Bai).

https://doi.org/10.1016/j.compositesa.2019.05.008
Received 11 December 2018; Received in revised form 21 March 2019; Accepted 8 May 2019
Available online 09 May 2019
1359-835X/ © 2019 Published by Elsevier Ltd.
Y. Zhang, et al.
prepared. In this work, phenyl-quaternary ammonium salt was selected
as the modifier and water as the solvent at normal temperature, and a
one-step method was used to produce high-quality modified graphene
in batches, satisfying the requirements of environment-friendly char-
acteristic and high efficiency [19,26]. The grafting process of FGO costs
several minutes, and the subsequent washing steps and drying process
are more facile because of the excellent hydrophobicity of FGO. After
incorporating with PA6 by melt spinning, the FGO/PA6 nanocomposite
fiber exhibited an obvious increase in comprehensive properties, such
as high strength, large modulus, and good anti-UV and antibacterial
properties owing to the uniform dispersion and strong interfacial in-
teraction between FGO and PA6. This methodology provides a rapid
and facile route to prepare FGO and FGO/composites with high per-
formance and functional properties in a large scale.
2. Experimental section
2.1. Materials
Flake graphite powder (325 mesh) purchased from Sinopharm
Chemical Reagent Co., Ltd.; Benzalkonium chloride (BAC) purchased
from the company of Chengdou HuaXia Reagent Company. The nylon 6
granules (Taiwan Libaolon Co., Ltd.), concentrated sulphuric acid
(H2SO4, 98%), hydrochloric acid (HCl, 37.5%), phosphorus pentoxide
(P2O5), potassium permanganate (KMnO4), H2O2 were used without
any further purification and treatment.
2.2. Preparation of GO and functionalized graphene oxide (FGO)
GO was prepared using the modified Hummers’ method [27]. De-
tails of the method are described in SI Appendix (SI Preparation and
Methods). The prepared GO (2.5 g) was dispersed in deionized water
(DI water) (500 mL) and then ultrasonicated for 30 min in an ultrasonic
bath. Then, the suspension was heated to 50 °C under mechanical agi-
tation. A certain amount of BAC was suspended in DI water (100 mL)
and ultrasonicated for 10 min. Then, the solution was added to the
prepared GO suspension and stirred for 10 min. BAC and GO underwent
self-assembly in this process. The flowchart is shown in Scheme 1.
Then, the product was cleaned with DI water for several times until
pH = 7 and no bubble appeared. Finally, the cleaning solution was
tested with silver nitrate until no precipitation occurred. The product
was recorded as FGO. The solubility of FGO is shown in Fig. S1.
Scheme 1. The preparation flowchart of BAC modifying graphene oxide. (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
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Composites Part A 123 (2019) 149–157
2.3. Fabrication of FGO/PA6 master batch and nanocomposite fiber
A Lab Tech co-rotating twin-screw extruder with an L/D of 32–40
and screw diameter of 21.7 mm (SHJ-20, Nanjing Giant Machinery Co.,
Ltd.) was used to prepare the master batch of graphene/PA6 composite.
A typical preparation procedure is as follows: First, 5 g of FGO was
mixed with 1000 g of neat PA6 in a high-speed mixer for 5 min.
Then, the premixed samples were oven dried at 100 °C for 24 h and
added to a twin-screw extruder at a barrel temperature of
240–245–248–250–248–245 °C.
Different loadings of FGO such as 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt
%, and 0.9 wt% of FGO were used. Dried PA6 granules (100 °C; 24 h in a
vacuum oven) were mechanically premixed with the FGO for 5 min and
then extruded and granulated. A dried master batch was obtained with
the same drying process, and the composite master batch was melt-spun
at a barrel temperature of 250–255–260–265–265 °C using an FDY
spinning machine (H25, WuXi Lanhua Co., Ltd.). The filament was
heated to 100 °C for thermal stretch, and the stretch multiple is 3.5
times.
2.4. Characterization
X-ray diffraction (XRD) patterns were recorded by a Rigaku D/Max-
2400 diffractometer using Cu Kα radiation. Raman spectra of the GO,
FGO were obtained with a Horiba Jobin Yvon LABRAM-HR800 with a
wavelength range of 0–4000 cm−1. The Fourier transform infrared
spectra (FT-IR) of the samples were recorded using a Nicolet NEXUS
670 FT-IR spectrophotometer, and the sample and KBr were pressed to
form a tablet. The transmission electron microscopy (TEM) images were
taken from Hitachi H-600 microscope. Thermogravimetric analysis
(TGA) for the samples was performed on Perkin–Elmer Diamond
thermal analyzer from room temperature to 600 °C, using a heating rate
of 10 °C/min with N2 as the sample purge gas. The surface chemical
composition of the samples was evaluated based on X-ray photoelectron
spectroscopic (XPS) measurement. The XPS spectra were obtained with
a Kratos AXIS ULTRA DLD at room temperature. The fracture surface of
the composites analyzed Scanning Electron Microscopy (SEM; Hitachi
S-4800). Tensile testing was performed using an Instron machine, ac-
cording to GB/T14344-2008, the gauge length was 100 mm with the
tensile speed of 100 mm/min.
The anti-UV properties were evaluate according to the Australia/
New Zealand standard AC/NZS 439:1996, with detailed methods are
Y. Zhang, et al.
Fig. 1. The AFM image of GO (a) and FGO (b). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)
described in SI Appendix (SI methods), and the flame retardant prop-
erties was investigated using GOVMARK MCC-2 Micro Combustion
Calorimeter (USA) and Oxygen limiter, with detail measuring para-
meter can be find in SI Appendix (Flame retardant performance).
3. Results and discussion
3.1. Characterization of GO and FGO sheets
The atomic force microscopy (AFM) image of graphene is shown in
Fig. 1. Fig. 1a shows that most individual GO sheets have an average
height of about 0.5–1.0 nm. Fig. 1b shows the AFM image of FGO, there
are many white dots uniformly grafted on the GO surface. Besides,
transmission electron microscopy (TEM) was also used. The results are
shown in Fig. 2. The morphology of FGO was found to be more crum-
pled; a large number of black nanoparticles are observed on the surface
Fig. 2. The TEM image of GO (a and b) and FGO (c and d).
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Composites Part A 123 (2019) 149–157
of FGO nanosheets in the magnified images. More importantly, after
washing the FGO several times with DI water until pH = 7 and the
absence of chloride in washing liquid as detected using AgNO3, these
nanoparticles still remained on the surface of FGO. This phenomenon
agrees well with the surface morphology as shown in the AFM images,
indicating that the BAC was successfully grafted on the active groups of
GO.
FTIR spectroscopy was performed to characterize the structure of
investigated materials. Fig. 3 shows the FTIR spectra of FGO, GO, and
BAC. For GO, a wide and concentrated peak was observed at 3420 cm−1
and 1054 cm−1; it can be assigned to OeH and CeO stretching bands,
which may originate from water molecules assimilated inside [4,28].
Besides, peaks at 1729, 1634, 1396, and 1094 cm−1 belong to C]O,
C]C, CeOH, and CeOeC vibration frequencies respectively, in-
dicating the presence of various oxygen-containing functional groups in
GO [4,29–31]. In the FTIR spectrum of FGO, narrow and shrill peaks at
Y. Zhang, et al.
Fig. 3. FTIR spectra of BAC, graphene oxide, and FGO. (For interpretation of
the references to color in this figure legend, the reader is referred to the web
version of this article.)
2922, 2851, 1459, and 1383 cm−1 can be assigned to eCH3, eCH2e,
and eNeCH3 stretching vibrations [4,32]. Moreover, a peak at
1729 cm−1 can be ascribed to C]O, indicating the presence of oxygen-
containing functional groups in GO [30,33]. Compared with the spec-
trum of neat BAC, new bands appeared in the spectrum of FGO at
1118 cm−1; they were assigned to CeO vibration frequencies, coin-
ciding with the peaks of GO at 1052 cm−1 stretching vibration shift for
FGO. This can be ascribed to the N-H stretching of amine groups [34].
Fig. 4. The XPS spectra of GO (a–c) and FGO (d–f). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)
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To further prove the successful preparation of FGO, XPS was used to
analyze the samples. Before the modification, as shown in Fig. 4a, ni-
trogen in the air can be absorbed by the sample because of a high
surface energy of GO, resulting the presence of nitrogen in the XPS
spectrum. The atomic concentration of nitrogen is less than 0.82%.
After the modification, the atomic concentration of nitrogen was ap-
proximately 2%. Fig. 4b shows a high-resolution C1s spectrum of GO-
BAC. The C1s peak can be separated into four typical components at
284.5, 286.9, 287.3, and 289.8 eV. Compared with unmodified GO, a
new CeN characteristic peak was observed. The other characteristic
peaks corresponds to C]C, CeO, C]O, and HOeC]O. This is similar
to a previous report [35]. By comparing the mass content of HOeC]O
from the C1s spectrum of GO and FGO, it was found that a mass of BAC
was grafted into GO. This is supported by the XRD (Fig. S2a), Raman
spectra (Fig. S2b), AFM, and TEM results. As shown in Fig. 4(e, f), the
binding energy position of O element of typical components did not
obviously change after modification, indicating that the grafted BAC
did not form a new chemical bond with the oxygen atoms on graphene.
In addition, the N1s spectrum of FGO shows that the carbon and ni-
trogen atoms form a CeN bond only, without characteristic peaks for
double and triple bonds, i.e., the structure of BAC is not destroyed
during modification and grafting on GO surfaces through π–π interac-
tions [35]. The conjugated structure of quaternary ammonium salt can
be directly affiliated to the GO carboxyl groups by electrostatic inter-
actions.
3.2. Morphology and property of PA6 fiber
3.2.1. Morphology of PA6 and FGO/PA6 fiber
Fig. 5 shows the morphology and fractured surfaces of neat PA6 and
FGO/PA6 nanocomposites. Fig. 5a shows the neat PA6 surface mor-
phology, and its fracture surface is shown in Fig. 5b, exhibiting obvious
Y. Zhang, et al. Composites Part A 123 (2019) 149–157

Fig. 5. The SEM images of neat PA6 and FGO/PA6 composites fiber: (a and b) neat PA6; (c–f) 0.5% and 0.9% FGO/PA6 composites. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

ductile fracture owing to its favorable toughness. The fracture samples
were prepared under liquid nitrogen. Fig. 5(c, d) shows that when the
fiber is broken, the modified graphene is not pulled out, but tightly
wrapped by the matrix. This phenomenon shows that the BAC modified
graphene can be nicely combined with the PA6 matrix. This can be
attributed to the newly introduced amino group on graphene, forming
more hydrogen bonds with PA6 matrix. A large number of hydrogen
bonds makes the two linkages tighter and improves the interfacial
compatibility between them [36]. As shown in Fig. 5(e, f), with the FGO
loading at 0.9%, the graphene dispersed in matrix tends to aggregate
and unevenly distributed. This result indicates that with a larger
addition of FGO, graphene aggregation has a higher probability,
leading to stress concentration and significantly reducing the perfor-
mance of composites.
3.2.2. Mechanical properties
The mechanical performances of prepared FGO/PA6 nanocompo-
sites fibers are shown in Fig. 6 and Table S1. Neat PA6 fibers are also
shown for reference. It can be observed that the addition of FGO to the
PA6 matrix significantly affects the mechanical behavior of composite
fibers. The tensile strength of fibers increased as the FGO content was
increased to 0.5 wt% and reached a maximum value at 4.21 cN/dtex,

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Y. Zhang, et al. Composites Part A 123 (2019) 149–157

Fig. 6. Strain–stress curves of FGO/PA6 fibers with different FGO contents (a) and tensile modulus (b). (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

Fig. 7. The tensile strength/strain (a) and tenacity (b) of FGO/PA6 fiber with different FGO loading. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

with an enhancement of 31.6% compared to neat PA6 fibers. However, at higher loading concentrations in composites, as observed in a pre-
the tensile strength starts to decrease as the content exceeds 0.5 wt%. vious study of polymer/CNT nanocomposites [42].
Delightfully, when the loading content was increased to 0.9 wt%, the
strength of composite fiber was still maintained at 3.94 cN/dtex, with
3.2.3. Anti-UV property
an increase of 23.1% compared to neat PA6 fibers. In addition, the
Flexible fabric with extraordinary anti-UV prosperities is considered
tensile modulus, according to the variation tendency of strength, first
as a feasible personal protection to protect human body against UV
increased with the increase in FGO content from 0.1 wt% to 0.5 wt%
radiation [43]. In this study, the UV transmittance of composite fiber
and then decreased with further increase in FGO amount from 0.5 wt%
was evaluated as shown in Fig. 8. With the scanned wavelength ranging
to 0.9 wt%. When the FGO loading was 0.5 wt%, the tensile modulus of
from 250 nm to 420 nm, the spectra of samples are shown in Fig. 8a.
composite fiber reached its maximum value of 33.86 cN/dtex, with an
Considering the wavelength at 400 nm as an example, the UV trans-
increase of 33.6% compared to neat PA6. This is because the introduced
mittance of neat PA6 fiber, which is at the level of 5% in Fig. 8b, de-
FGO in the matrix was randomly oriented [37,38]. Therefore, when the
creased by almost 3.5 times with a low loading of 0.1 wt% FGO, and
loading content exceeds 0.5 wt%, the FGO would show obvious ag-
decreased by approximately 20 times with the addition of 0.9 wt% FGO
gregation, decreasing the strength and modulus because of the accu-
after 10 times laundering. Furthermore, it can be observed that after 10
mulation of stress concentration. However, this random orientation
times laundering, the UV transmittance of composite fibers shows a
indicates that the external tensile loads can be successfully transmitted
slightly increase but no more than 6%, indicating that the loaded FGO
to the graphene sheet across the FGO-PA6 interface [39,40]. The tensile
was uniformly coated on the FGO/PA6 composite fabric and can ef-
elongation of composite fiber decreased as the content of FGO in-
fectively block UV rays from penetrating the fabric. Therefore, the
creased, and at the same time, the tenacity showed a similar variation
prepared composite fiber garment can have long-time wearability and
tendency (Fig. 7). This can be ascribed to a large aspect ratio of FGO
maintain excellent laundering durability. Besides, as shown in Fig. 8c
and stronger interfacial interaction between the two, restricting the
and d, the UV protection factor (UPF) values, UVA and UVB, were also
movement of polymer chains. Thus, the tensile elongation and tenacity
evaluated. To our delight, the UPF value reached over 470, indicating
decreased. Besides, when FGO was added to the PA6 matrix, the crys-
that the composite fiber has great anti-UV property, and the UVA/UVB
tallinity degree of polymer was affected [41], further reducing tenacity.
value was lower than 0.3. Thus, the result shows that FGO/PA6 com-
It can be generally concluded that the improvement rate is more
posite fiber can block UV rays in the range of 290–420 nm.
noticeable with a low FGO content (≤0.5%), but the increase in
modulus and strength will decrease after a higher loading of FGO. This
phenomenon is closely related to the fact that FGO is prone to aggregate 3.2.4. Antibacterial capacities
The antibacterial activity of FGO/PA6 composite fiber was

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Y. Zhang, et al.
Fig. 8. The UV transmittance spectrum of FGO fabrics (a) and UV transmittance values at 400 nm (b), and UPF value was set in (c) and (d). (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 9. Antibacterial efficacy tests on S. aureus and E. coli in direct contact with
FGO/PA6 nanocomposite fiber. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
evaluated using viable cell counting method against Gram-positive S.
aureus and Gram-negative E. coli. Fabric with prominent antibacterial
activity is considered as a feasible personal protection to protect human
beings against illness [43]. The ability of FGO/PA6 composite fiber in
inhibiting the growth of tested bacteria is shown in Fig. 9. The anti-
bacterial efficiencies (AE%) of FGO/PA6 composite fiber against S.
aureus and E. coli are 97.7% and 94.3%, respectively, with the FGO
loading at 0.9 wt%, indicating that the FGO nanosheets are responsible
for the antibacterial activity of composite fibers [16,44]. The FT-IR,
XPS, XRD, and AFM results show that the BAC was successfully grafted
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Composites Part A 123 (2019) 149–157
on GO. Besides, after the modification, the products were washed until
pH = 7, and the chloride content in washing liquid was tested, in-
dicating that there is no residual GO or BAC. By comparing the anti-
bacterial results (Figs. 9 and S4) of neat and composites fibers, it can be
concluded that GO-BAC can obviously improve the antibacterial prop-
erties of composite fibers.
3.2.5. Thermal stability and flame retardant properties
TGA, an important tool to evaluate the thermal stability of carbon-
based materials [45], was used to investigate the neat PA6 and FGO/
PA6 composites fiber. The results are shown in Fig. 10. After the ad-
dition of FGO, the thermal stability of FGO/PA6 nanocomposites was
superior to neat PA6. This is because the nanofillers act as a barrier and
restrict the rotation of PA6 molecular chain and slow down the de-
gradation rate of composites. However, when the FGO loading content
exceeded a certain value, the filler may aggravate matrix degradation
[45,46]. Table 1 shows that in comparison to neat PA6, the T5% of FGO/
PA6 composites increased by 12.4 °C at 360.9 °C corresponding to the
filler loading at 0.5%, indicating that the introduction of FGO improved
the thermal stability of PA6. As shown in Fig. 10b and Table 1, the
temperature of maximum decomposition rate of neat PA6 occurred
earlier than that of FGO/PA6 composites. This is probably because the
well-dispersed two-dimensional materials can prevent and hinder the
removal of volatile degradation products, similar to MoS2-based na-
nocomposites [47]. Moreover, the results of flame retardant perfor-
mance evaluation (SI Flame retardant performance and Fig. S3, Table
S2) show that the HRR and THR of 0.9 wt% FGO/PA6 nanocomposites
decreased from 631.7 to 542.5 W/g and 36.3 to 27.6 kJ/g, respectively.
At the same time, the limit oxygen index (LOI) of 0.9 wt% FGO/PA6
nanocomposites was close to 26%, and the LOI of neat PA6 was only
20.2% (Fig. S3, Table S3), indicating that the composites satisfy the
Y. Zhang, et al. Composites Part A 123 (2019) 149–157

Fig. 10. TGA curves and DTG for the neatPA6 and FGO/PA6 fiber. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)

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