Liuyang Zuo,

Feng Zhang,
Fabrication of Electrical Conductivity
Bing Gao,
Baoqi Zuo*
and Reinforced Electrospun Silk Nanofibers
with MWNTs
DOI: 10.5604/12303666.1237223
Department of Soochow University, Abstract
National Engineering Laboratory for Modern Silk, Electrospinning is an effective technique for fabricating submicron to nanoscale fibers
Ren ai road 199, Suzhou, China from synthetic polymer as well as natural proteins. In this study, multiwalled carbon
* E-mail: [email protected] nanotubes (MWNTs) were embedded via electrospinning by adding MWNTs into the
spinning dope, and found to be well aligned along the fiber axis in the silk fibroin nanofi-
bers. The morphology and microstructure of the electrospun nanofibers were characte-
rised using a field emission scanning electron microscope (FESEM) and Transmission
electron microscopy (TEM). X-ray diffraction (XRD) and TG-DTA were used to study
the crystal structure of the silk/MWNTs composite nanofibres, carried out to alter the
strength, toughness and electrical conductivity of silk nanofibers by adding a small
amount of MWNTs. The electrospun random silk mats with 1% MWNTs had a Young’s
modulus, ultimate tensile strength and strain of 107.46 ± 9.15MPa, 9.94 ± 1.2MPa
and 9.25 ± 1.5%, respectively, and electrical conductivity increased to 1.2×10-4S/cm.
The silk/MWNTs composite nanofibres could potentially be applied in nerve repair materials
owing to their excellent mechanical properties and electrical conductivity.

Key words: silk, MWNTs, electrospinning, reinforce electrical conductivity.

Introduction polypropylene [9], polyamide [10], poly- philosophical, economic and other as-
acrylonitrile [11] and so on. Wei K [12] pects, as key links between science and
Bombyx mori silk, a protein-based pol- introduced a small amount of MWNTs economy.
ymer with unique structural and me- in electrospun silk fibers, and clearly in-
chanical properties, has been used as creased the strength. Viviana Lovat [13]
textile materials for a long time [1-6]. demonstrated the possibility of using
Materials and experiment
Degummed bombyx mori silk, which carbon nanotubes (CNTs) as potential Bombyx mori silk were kindly supplied
only consists of silk fibroin, can be repro- devices able to improve neural signal by Gains cocoon silk co., LTD, China.
cessed in various forms, such as porous transfer while supporting dendrite elon- All reagents were purchased from Sigma
film, electrospinning silk nanofibers and gation and cell adhesion. The electrical Aldrich, unless otherwise mentioned, and
gel. Electrospinning is a simple meth- conductivity of polymers, however, rang- all concentrations were weight to weight
od for producing nanofibers from both es from 10−14 to 10−17 S/cm. Polymeric (w/w).
natural [7] and synthetic polymers, with materials are composed of carbon fillers
diameters ranging from 2 nm to several to improve their electrical conductivity, MWNTs (JEIO Co., Korea) used in this
micrometers. Electrospun random silk such as carbon fibers, carbon black and paper were 1 μm in length and 15~20 nm
mats, with their good biocompatibility, synthetic graphite [14]. Several schol- in diameter, synthesised by the thermal
high specific surface area and high poros- ars have focused on fabricating polymer chemical vapour deposition (CVD) meth-
ity, are ideal candidates for biomedical composite nanofibres using MWNTs as od, and their purity was 97%. They were
applications, including tissue-engineered a filler. J.S. Jeong [15] produced conduc- treated with 3 M HNO3 and then flushed
scaffolds, wound dressings and drug de- tive MWNTs/nylon composites and im- in 5 M HCl to obtain pure MWNTs. A re-
livery [2-6]. However, the mechanical proved their electrical conductivity. quired amount of purified MWNTs was
properties of electrospun silk fibers are dispersed in formic acid containing sodi-
lacking in comparison with natural silk In this study, we fabricated silk/MWNTs um dodecysulphate (SDS), whose ratio
fiber because regenerated silk fibroin composite nanofibres using the electros- of weight between the SDS and MWNTs
changes some of the structure during pinning technique. The effect of MWNTs was 1:1. An ultrasonic generator (Kyun-
reprocessing. Introducing a reinforced on the morphology, crystal structure, gill Ultrasonic, Korea) with a nomi-
agent to electrospun silk fibers is a good mechanical properties and electrical con- nal frequency of 28 kHz and power of
way to alter the mechanical performance. ductivity of electrospun silk nanofibres 600 W was used for treatment for 2 h.
were investigated. The silk/MWNTs
Carbon nanotubes (CNTs) as typical composite nanofibres can be potentially Bombyx mori silk was degummed twice
reinforcing agents have attracted con- applied in nerve repair materials owing with 0.05% Na2CO3 (w%) solution at
siderable attention on account of their to their excellent mechanical properties 100 °C for 1 h, and rinsed thoroughly
unique mechanical and electrical prop- and electrical conductivity. As a develop- in warm distilled water to remove the
erties since Dr. Iijima invented them in ing country Serbia is in a constant race glue-like sericin. A new method of dis-
1991 [8]. Introducing a little amount of with the world economy in all spheres solving silk was adopted in this paper.
MWNTs in the form of small bundles or of industries, not to mention the textile Degummed silk was first dissolved in
individual nanotubes can dramatically industry. The poor financial situatment 98% formic acid with 4% CaCl2 for 1 h to
improve the mechanical strength, such as and evaluation of social, psychological, obtain an 8% silk fibroin solution. Then

40 Zuo L, Zhang F, Gao B, Zuo B. Fabrication of Electrical Conductivity and Reinforced Electrospun Silk Nanofibers with MWNTs.
FIBRES & TEXTILES in Eastern Europe 2017; 25, 3(123): 40-44. DOI: 10.5604/12303666.1237223
the solution obtained was cast onto a pol-
a) b)
ystyrene plate and the solvent evaporated
at room temperature [14].

Here, MWNTs were dispersed in a re-

quired amount of formic acid by ultra-
sound for 2 h to obtain a stable dispersed
MWNT solution. Then a spinning dope
was prepared by dissolving the regener-
ated silk film in the MWNT solution and
mechanically stirring for 2 h to obtain an
8% spinning dope with several amounts
of MWNTs. The blended solution was
transferred to a 10 ml syringe with an
18-G needle. The flow rate was 0.6 ml/h,
c) d)
and the voltage was gradually increased
to 18 kV. Random nanofibres got depos-
ited on the collection plate. The distance
between the transmitting and receiving
electrodes was 15 cm and the experiment
was carried out in the conditions of 30%
relative humidity and 20 °C temperature.

Result and discussion

Images of electrospun fibers were ob-
tained using a field emission scanning
electron microscope (FESEM S-4200,
Hitachi, Japan). SEM images of the silk/
MWNT composites with different con- e) f)
centrations of MWNTs are shown in
Figure 1.a-1.d, demonstrating that na-
noscale fibers can be fabricated by add-
ing a small amount of MWNTs, and that
the nanofibers spun are oriented ran-
domly, whose average diameter is about
85 nm. The diameter was measured with
Image-Pro Plus 6.0 software. Pictures
of the MWNTs are shown in Figure 1.e
and 1.f. The diameter of the MWNTs
is about 20 nm, with some tangled up.
The diameters of nanofibres show no
obvious change and there is little entan-
glement between the nanofibres with an
increase in MWNT content. With an in-
crease in the MWNT content, it is easy Figure 1. SEM images of the MWNTs/silk composites with several amounts of MWNTs in
for MWNTs to get tangled in the spin- the spinning solution: a) with 0.5% MWNTs, b) with 1.0% MWNTs, c) with 1.5% MWNTs,
d) with 2.0% MWNTs, e) and (f) MWNTs.
ning dope, and in consequence the ap-
pearance of nanofibres is slightly coarse
in Figure 1.d, compared with others. Table 1. Diameters of MWNTs/silk nanofiber.
For the spinning dope, an increase in the
Fibers with MWNTs, w% Average diameter, nm
apparent viscosity increases the surface
0.5 86
tension of the solution, which is also
1.0 105
a conceivable reason for the result (Fig-
1.5 105
ure 2, see page 42).
2.0 80

Transmission electron microscopy

(TEM) was performed using a Philips of MWNTs/silk spun nanofibers contain- to be well dispersed within the individual
CM 200 unit, operated at an acceleration ing 0.5, 1.0, 1.5 and 2.0 wt.% MWNTs, nanofibers after the electrospinning pro-
voltage of 120 kV. TEM was used to in- respectively. The TEM images showed cess. Some entangled MWNTs appear in
vestigate the internal structural details of that MWNTs were embedded and well Figure 3.d, since a fluid blocked the out-
the MWNTs/silk composites [18]. Fig- aligned along the fiber axis. Furthermore, let spinneret as a result of the high con-
ure 3 (see page 42) shows TEM images it should be noted that the MWNTs appear centration of MWNTs in the fluid.

FIBRES & TEXTILES in Eastern Europe 2017, Vol. 25, 3(123) 41

 30 25.8

25
31.7
Apparent viscosity, Pa·s

44.3
20

Intensity
e
15
d
10
20.2 c
23.3
5 b
a
0

0 1 2 10 20 30 40
Content of MWNTs, wt% 2θ, °

Figure 2. Relationship between the apparent viscosity of the spinning Figure 4. XRD patterns of MWNT – reinforced and as-spun silk
dope and content of MWNTs. nanofibers: a) electrospun silk nanofibers, b) 0.5% MWNT reinforced
nanofibers, c) 1.0% MWNT reinforced nanofibers, d) 1.5% MWNT
reinforced nanofibers, and e) 2.0% MWNT reinforced nanofibers.

An X-ray diffraction (XRD, PAN analyti- known that the secondary structures of silk and pure electrospun silk nanofiber. All
cal X’ Pert Pro M PD System, The Nether- proteins have the characteristics of silk I, samples show a characteristic peak at
lands,is a useful tool for the investigation silk II and random coil structures [19]. 20.2° and 23.3°, indicating a β-sheet
of the secondary structure of proteins, and structure. We noticed that the electrospun
it has already given important insights into Figure 4 shows the X-ray diffractograms fibers showed a very weak peak at 25.8°
the structure of native silk filaments of of five samples reinforced with nanofibers (silk I), getting stronger with an increase
both spiders and silkworms [18]. As it is of 0.5%, 1.0%, 1.5% and 2.0% MWNTs in MWNT content. Indeed a series of new
peaks appeared simultaneously in the
samples containing MWNTs at 31.7°and
a) b) 44.3° which belonged to the MWNTs, in-
dicating that some molecular bonds may
connect silk and MWNTs. However, the
similar shape of the four curves indicated
that increasing the MWNT content had
a limited influence on the structure of the
electrospun silk fibers.

The thermal performance of the compos-

ites was examined by means of a TG-
DTA (PE-S II) (PE company of America).
There are five DTG curves plotted in Fig-
ure 5. The thermal decomposition behav-
iour of MWNT-reinforced silk nanofibers
c) d) was changed compared to as-spun silk
nanofibers, although their two decompo-
sition peaks occurred in the range of 200-
400 °C. A prominent decomposition peak
of as-spun regenerated silk nanofibers ap-
peared at 298.5 °C corresponding to the
thermal decomposition of the silk II struc-
ture [12]. There was a considerably weak
decomposition peak at 219.7 °C attributed
to electrospun silk nanofibers with a main-
ly random coil and silk I conformations.
While the decomposition temperature of
MWNT reinforced nanofibers variedirreg-
ularly in the process of initial decompo-
sition and extended to higher temperature
Fig.3Figure
TEM3.images
TEM images of the
of the MWNTs/silk composites
MWNTs/silk compositeswithwith
several amounts
several of MWNTs
amount in
of MWNTs
the spinning solution: a) with 0.5% MWNTs, b) with 1.0% MWNTs, c) with 1.5% MWNTs,
in as the MWNT content increased
gradually
d) with 2.0% MWNTs. in the second decomposition process.
spinning solution. a) with 0.5% MWNTs, b) with1.0% MWNTs, c) with 1.5%
42 FIBRES & TEXTILES in Eastern Europe 2017, Vol. 25, 3(123)

MWNTs, d) with2.0% MWNTs.

 a
10 c
219.97 °C 298.5 °C
b 8

c b
dm/dt (a.u)

6
d a
d

Stress, MPa
4
e
2 e

308.96 °C
0
0 100 200 300 400 500 600 10 20
Temperature, °C Strain, %

Figure 5. DTG curves of MWNT reinforced and as-spun silk Figure 6. Stress-strain curves of electrospun random silk mats:
nanofibers: a) electrospun silk nanofibers, b) 0.5% MWNT reinforced a) without MWNTs and b), c), d), e) with 0.5%, 1%, 1.5%, 2%
nanofibers, c) 1.0% MWNT reinforced nanofibers, d) 1.5% MWNT MWNTs, respectively.
reinforced nanofibers, and e) 2.0% MWNT reinforced nanofibers.

The nanofibers with 2.0% MWNTs had The thickness of the sample was meas- which decreased with MWNTs incorpo-
a main decomposition peak at 308.96 °C, ured through an electronic screw microm- rated [10]. The random silk mats showed
which indicated that the thermal stability eter gauge (accuracy of 0.01 mm) and the an elongation at break of 19.26 ± 1.2%,
increased compared to as-spun nanofibers. average thickness from 10 different posi- while with 1.0% MWNTs, it decreased
Interestingly the peak of 2.0% MWNT tions of each sample was measured. to 9.25 ± 1.5%, also declining with an
reinforced nanofibers at about 224 °C increase in MWNT content. In addition,
was more obvious compared with that Figure 6 shows the stress-strain curves both the tensile strength and elongation at
at 308.96 °C, which indicated that more for MWNT reinforced silk fibers and break of the 2.0% MWNT/silk composite
entangled aggregates in the nanofibers as-spun silk fibers. It can be evidently were significantly decreased, which was
resulted in molecular chains being placed seen that there are different mechanical thought to be due to the aggregation of
much more irregularly. performances between the as-spun silk MWNTs. Accordingly it was conclud-
fibers and MWNT reinforced fibers from ed that the addition of a little amount of
The results obtained above clearly present the figure. Detailed data are summarised MWNTs enhanced the mechanical prop-
that introducing MWCNTs into silk fi- in Table 2. Both the tensile strength and erties of MWNT/silk nanofiber.
broin fibers had no significant effect on the Young’s modulus were significantly in-
structure of the composite fibers compared creased by introducing different contents MWNTs were introduced into electro-
to silk fibroin fibers. Generally CNTs have of MWNTs, except for nanofibers with 2% spun silk fibers to improve the mechan-
been used as a reinforcing agent, which MWNTs. Incorporating 1.0% MWNTs ical properties as well as the electrical
result in high performance polymer nano- into silk nanofibres, The Young’s mod- conductivity of the composite. To meas-
composite fibers, as mentioned in previ- ulus and tensile strength of the compos- ure the electrical conductivity, we used
ous studies [20].To confirm the influence ite increased from 32.5 ± 4.27 MPa to a ZC-90G high insulation resistance
of the incorporation of MWNTs into silk 107.46 ± 9.15 MPa and increased from meter purchased from the Shanghai Yu-
nanofibers, the mechanical properties of 6.26 ± 0.8 MPa to 9.94 ± 1.2 MPa, respec- anzhong electronic instrument factory
the composites were investigated. For tively. The increased mechanical perfor- (China). The samples were fixed on the
random a mat, strips measuring 4×0.5 mance of 1.0% MWNT/silk composite equipment and the two probes of the
cm were glued on a paper frame and were thought to result from the good dis- machine were lowered onto the sam-
then mounted on a universal test machine persion and alignment of MWNTs along ples. The length, width and thickness
(Model no. 3365, Instron, USA) and the the fiber axis within silk nanofibers (Fig- of the sample were noted. The distance
average tensile properties from five sam- ure 3). The elongation at break, howev- between the probes (probe space) was 2
ples were measured [21]. The displace- er, indicated the flexibility of materials, cm. The known amount of resistance was
ment was converted to strain by dividing
it by the gauge length. The load on the Table 2. Mechanical properties of electrospun random silk mats and silk/MWNT mats.
strips was converted to Newtons. The ten-
sile stress in MPa was calculated using the Fibers with MWNTs, Young’s modulus, Tensile strength, MPa Elongation at break,
following Equation (1): w% MPa %
0 32.50±4.27 6.26±0.8 19.26±1.2

Tensile stress (MPa) =

F
WT
— (1) 0.5
1.0
58.53±1.97
107.46±9.15
7.20±0.6
9.94±1.2
12.30±0.8
9.25±1.5

F – force, N; W – width, mm; 1.5 91.75±10.56 6.12±0.9 6.67±0.6

T – thickness, mm. 2.0 85.94±15.51 4.28±0.4 4.98±0.9

FIBRES & TEXTILES in Eastern Europe 2017, Vol. 25, 3(123) 43

Table 3. Electrical conductivity of the electrospun random silk mats and silk/MWNT carbon nanotube/polypropylene nano-
composite mats. composites through homogeneous dis-
persion with the aid of surfactants. Jour-
Fibers with MWNTs, w% Electrical conductivity of nanofibers, s/cm nal of Applied Polymer Science J 2012;
0 5.04×10-14 124(2): 1117-1127.
0.5 8.66×10-6 11. Coleman JN, Khan U, Blau WJ, et al.
1.0 1.20×10-4 Small but strong: a review of the me-
1.5 8.61×10-8
chanical properties of carbon nanotube–
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—
L carbon nanotubes incorporated bombyx
σ (s/cm) = (2) mori silk nanofibers by electrospinning.
RWT Journal of Polymer Research J 2011;
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44 FIBRES & TEXTILES in Eastern Europe 2017, Vol. 25, 3(123)