Carbohydrate Polymers 183 (2018) 62–69

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Review Article

Preparation and characterization of tree-like cellulose nanofiber membranes T

via the electrospinning method
⁎
Kai Zhanga,1, Zongjie Lia,1, Weimin Kanga,b, , Nanping Denga, Jing Yanb, Jingge Jua,b, Yong Liub,
⁎
Bowen Chenga,
a
State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic University, Tianjin 300387, China
b
School of Textiles, Tianjin Polytechnic University, Tianjin 300387, China

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

Keywords: A novel tree-like cellulose nanofiber membrane was controllably fabricated via the electrospinning method by
Cellulose adding certain amount of tetra butyl ammonium chloride (TBAC) into the cellulose acetate solution followed by
Electrospinning a deacetylation treatment process. The morphological structure, material structure and air filtration performance
Tree-like nanofiber of both the cellulose and the cellulose acetate tree-like nanofiber membranes were characterized. Water contact
Deacetylation
angles, mechanical properties, and air filtration properties were also evaluated. The air filtration efficiency of
cellulose acetate tree-like nanofiber membrane can reached 99.58%, and the eventually cellulose tree-like
membrane still maintain 98.37%. The eventual cellulose tree-like nanofiber membranes exhibited small pore
size, excellent hydrophilicity, good solvent resistance and preferable mechanical property. The small average
pore size caused by the tree-like structure and the strong resistance to organic solvent can make it a potential
candidate for the membrane separation.

1. Introduction
Nature creatures have been endowed with fascinating structures,
which exhibit numerous excellent functions (Wu, Wang, Zhao, & Jiang,
2013). With intensive understanding of the objects in nature, many
structures have been found to have unique properties attracting lots of
attention.
Electrospinning is an effective method for preparing nanofibers. In
recent years, many micro/nanofibers with bionic structures have been
fabricated by the combination of the electrospinning and bionic tech-
nologies, such as lotus-leaf fibers (Jin, Kim, Jung, & Kim, 2013), spider-
like fibers (Pant et al., 2013), peapod-like fibers (Yang et al., 2011),
porous fibers (Wu et al., 2012), tubular fibers (Jia et al., 2007), neck-
lace-like fibers and tree-like nanofibers (Li, Kang, Zhao, Hu, Ju et al.,
2016; Li, Kang, Zhao, Hu, Wei et al., 2016; Li, Xu, Fan, Kang, & Cheng,
2016).
Tree-like nanofibers, as its name implies, are composed of trunk
fibers and branch fibers, the thick trunk fibers act as a skeleton support
which can improve the mechanical property, and the thin branch fibers
act as connection props which can increase the surface area to volume
ratios and decrease the pore size (Li, Kang, Zhao, Hu, Ju et al., 2016; Li,
Kang, Zhao, Hu, Wei et al., 2016; Li, Xu et al., 2016). Inspired by the
special structures of tree trunks and branches, some research groups
have successfully prepared hierarchical tree-like nanofibers with un-
ique structures, enhanced specific surface areas and internal cavities. Li
reported the formation of ZnO tree-like fibers obtained from PVP, zinc
acetate and methyl alcohol via electrospinning and calcinations process
(Li & Li, 2014). Bai et al. developed tree-like TiO2 nanofiber (NF)/ZnO
nanorod (NR) materials by the combination of the electrospinning of
TiO2-NFs and the hydrothermal growth of ZnO-NRs (Bai, Liu, & Sun,
2011). The above mentioned materials have enhanced application
performance, however, fabricated by multi-step methods which is
complicated in actual production. Our research group firstly reported
the formation of PVDF tree-like nanofibers by one-step electrospinning
of solutions added organic branched salt (TBAC) (Li, Kang, Zhao, Hu, Ju
et al., 2016; Li, Kang, Zhao, Hu, Wei et al., 2016; Li, Xu et al., 2016).
After that, Zhao et al. reported the formation of tree-like PA6 nanofibers
by the same method (Zhao et al., 2017). Due to the unique advantage,
the tree-like nanofiber membranes exhibited excellent performance in
air filter, liquid filter (Li, Kang, Zhao, Hu, Ju et al., 2016; Li, Kang,
Zhao, Hu, Wei et al., 2016; Li, Xu et al., 2016), oil and water separation
(Cheng et al., 2017), catalysis (Zhao et al., 2017) and antibiosis (Kang
et al., 2016), etc.
Recently, increasing attentions have been paid to nature polymers

⁎
Corresponding authors at: State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic University, Tianjin 300387, China.
E-mail addresses: kweimin@126.com (W. Kang), bowen15@tjpu.edu.cn (B. Cheng).
1
First author, contributed to this work equally.

https://doi.org/10.1016/j.carbpol.2017.11.032
Received 11 August 2017; Received in revised form 8 November 2017; Accepted 8 November 2017
Available online 11 November 2017
0144-8617/ © 2017 Elsevier Ltd. All rights reserved.
K. Zhang et al.
because of their sustainability, eco-efficiency, and renewability, such as
cellulose, lignin, starch, protein, peptide, etc. (Ma, Gao, Gong, Ji, &
Shen, 2002). These nature polymer shave become important precursor
materials for the electrospining preparation and been successfully used
in a range of applications. Nonetheless, up to now, there has been no
research reported about the preparation of tree-like nanofibers from
any natural biopolymers.
As one of the most abundant renewable polymer resource, cellulose
has caused extensive concern due to the good chemical resistance,
thermal stability and biodegrade ability, etc. (Frey 2008; Jin et al.,
2017; Li, Wang, Li, Cheng, & Adhikari, 2014). However, on account of
the slight solubility in lots of solvents, cellulose is difficult to form
nanofibers or fibrous membranes until some effective solvents were
found. The loycell process of cellulose fiber was established by spinning
its direct solutions in solvents such as N-methyl-morpholine-N-oxide/
water (NMMO/H2O), lithium chloride/N,N-dimethylacetamide (LiCl/
DMAc) and so on (Ang and Zhang (2007); Ahn et al., 2012; Lu & Zang,
2007; Zhuang et al., 2012). But it is still hard to obtain nanofibers by
the electrospinning because the cellulose/NMMO hydrate solutions are
required to be processed at elevated temperatures in the range of
80–130 °C due to the high melting temperature of NMMO hydrate. And
the resulted cellulose nanofibers are relatively less uniform and have to
be carefully washed with distilled water in order to completely remove
the residual NMMO (Kulpinski, 2010). Comparing to cellulose, cellulose
acetate (CA) has good solubleness that it can be dissolved in many kinds
of common organic solvents, such as acetic acid, acetone, DMAc, etc.
(Konwarh, Karak, & Misra, 2013; Omollo, Zhang, Mwasiagi, & Ncube,
2014; Wu , Qin & Li, 2013 ; Zhou, Shao, Jian-Xin, Cui, & Gao, 2010).
Most importantly, the cellulose acetate can be used to prepared cellu-
lose by a simple deacetylation treatment which has been adopted by
many scholars to broaden its application (Ahmed et al., 2017; Khatri
et al., 2017; Murphy, 1991; Vallejos, Peresin, & Rojas, 2012).
In this study, we firstly report a facile process to prepare large-scale
cellulose tree-like nanofiber membrane by the deacetylation of elec-
trospun CA tree-like nanofiber membranes. The tree-like cellulose na-
nofiber membranes possess the general properties and functions of
conventional electrospinning nanofiber membranes, as well as the fas-
cinating feature characters, such as extremely small pore size, excellent
mechanical properties, which can be used as promising materials for a
variety of potential applications in separation field. More significantly,
the cellulose tree-like membrane is non-toxic and may have potential
applications in the field of tissue engineering (Nasrinasrabadi et al.,
2014; Rodríguez, Gatenholm, & Renneckar, 2012).
2. Experimental
2.1. Materials
Cellulose acetate (CA) (acetyl content 38–40%,Tianjin Baishi
Chemical Co.) was used as the precursor material, acetic acid
(purity > 99%, Tianjin Fengchuan Chemical Reagent Co.) was used as
the solvent and tetra butyl ammonium chloride (TBAC) (Tianjin Fine
Chemical Industry Research Institute) was used as the additive. Sodium
hydroxide (NaOH), N,N-dimethylformamide (DMF), N,N-dimethylace-
tamide (DMAc), acetone and ethanol (EtOH) were purchased from
Tianjin Kermel Chemical Reagent Co., Ltd for post-processing. All of the
materials were used as received without further purification.
2.2. Preparation of cellulose acetate nanofibers
Spinning solutions were prepared by dissolving TBAC (0.05, 0.10
and 0.15 mol/L) and CA (9 wt%) in acetate acid with vigorous stirring
until CA was dissolved completely. The prepared CA solution was
placed in a 10 mL pipette and extruded at the speed of 1.0 mL/h by a
syringe pump, and a high voltage (30 kV–40 kV)was applied between
the spinning needle and ground collector with the distance of 15 cm.
63
Carbohydrate Polymers 183 (2018) 62–69
The roller collector was covered with aluminum foil. The experiment
was carried out at approximately room temperature of 24 °C and re-
lative humidity (RH) of 30%–50%. The obtained common CA nanofiber
membrane and CA tree-like nanofiber membrane was abbreviated to C-
CA membrane and T-CA membrane, respectively.
2.3. Deacetylation of cellulose acetate nanofibers
The CA nanofibers were deacetylated in a 0.5 mol/L NaOH ethanol
solution at 25 °C for 24 h. Then the sample was washed with alcohol
and dried in an oven at 60 °C for 6 h. NaOH molecules could penetrate
into the nanofibers which could be deacetylated homogeneously both
on the surfaces and inside (Dixit, Tewari, & Obendorf, 2010; Khatri,
Wei, Kim, & Kim, 2012; Liu & Hsieh, 2002). The eventually deacety-
lated common CA nanofiber membrane and deacetylated CA tree-like
nanofiber membrane were abbreviated to be D-C-CA membrane and D-
T-CA membrane.
2.4. Characterization
Morphological structures of the cellulose and CA nanofiber mem-
branes were observed using a HITACHI S-4800 Field emission scanning
electron microscope(FE-SEM)at an accelerating voltage of 10 kV after
coated with gold particles. The diameters of the fibers were measured
using an image analyzer (IPPwin32, Soft Imaging System) based on 100
fibers. The conductivities of spinning solutions were measured with a
digital conductivity meter (DDS-307A). To achieve that, the conductive
electrode was soaked into the solution completely at room temperature,
and then the stabilized readings were recorded. The mechanical prop-
erties were measured with a monofilament tensile testing machine (YG
005E) under a tensile speed of 10 mm/min with the samples size of
5 mm × 40 mm. The water contact angles (WCA) of the samples were
analyzed by a JYSP-180 contact angle tester equipped with a high-re-
solution TV camera. The transformation of the crystalline structure of
samples was confirmed with the X-ray diffraction (XRD) spectrum using
an AXS D8 Discover machine. The diffraction angle 2θ was recorded
from 10° to 45°. Fourier-transform infrared spectrometer (Nicolet iS50)
and X-ray photoelectron spectroscopy (K-alpha) were also adopted to
characterize the material. The air filtration efficiency and filtration
resistance of membranes with different surface density coated on non-
woven were substrates tested by an air filtration tester (TIS8130) with
0.3 μm NaCl aerosol and 32 L/min air flux. To test the filtration per-
formance, the membranes with different basis weights were obtained
by controlling the electrospinning time.
3. Result and discussion
3.1. Morphological structure of nanofiber membranes
The tree-like structure as a new discovery in nanofibers had been
vastly study by our group. According to the previous study of our group,
the formation of nanofibers with tree-like structure was attributed to
the splitting of the jet during the electrospinning process due to the
addition of TBAC. TBAC was used as a kind of organic branching salt
easily dissolved in CA solution and significantly increased the electrical
conductivity of the solution. When the charge density at the bending
segments was above a certain threshold value, the electric forces
overcame the surface tension, enhancing the splitting of the jet (Fig. 1)
(Li, Kang, Zhao, Hu, Ju et al., 2016; Li, Kang, Zhao, Hu, Wei et al.,
2016; Li, Xu et al., 2016). The electrospinning voltage and the con-
centration of TBAC are two important factors, and the change of mor-
phology was investigated by controlling the influencing factors.
Fig. 2(a) shows the effect of TBAC content on the conductivity of so-
lutions and Fig. 2(b) shows that the SEM images of CA nanofibers with
various parameters.
It was clear that the solution conductivity was 0.42 μs/cm without
K. Zhang et al. Carbohydrate Polymers 183 (2018) 62–69

Fig. 1. Schematic diagram for the preparation of

tree-like cellulose nanofibers.

Fig. 2. (a) The image of the relationship between the

conductivity and the concentration of TBAC in 9 wt
% CA solution, (b) SEM images of CA membrane
with different TBAC concentrations and electrospin-
ning voltages: (b1) 0.05 mol/L 30 kV, (b2) 0.05 mol/
L 35 kV, (b3) 0.05 mol/L 40 kV, (b4)0.1 mol/L 30 kV,
(b5) 0.1 mol/L 35 kV, (b6) 0.1 mol/L 40 kV, (b7)
0.15 mol/L 30 kV, (b8) 0.15 mol/L 35 kV, (b9)
0.15 mol/L 40 kV.

64
K. Zhang et al.
addition of TBAC, and the solution conductivity increased to 225 μs/cm
when the TBAC concentration was 0.15 mol/L, as shown in Fig. 2(a).
Therefore, the solution conductivity could be controlled by the addition
of TBAC. However, there was almost no tree-like structure at a low
concentration (0.05 mol/L) of TBAC even the voltage increased from
30 kV to 40 kV, as shown in Fig. 2(b1–b3). With increasing the con-
centration of TBAC, the uniformity and content of tree-like branches
increased (Fig. 2(b1, b4, b7)). The larger area density of the tree-like
branches could result from the greatly increased conductivity owing to
the increasing amount of TBAC, and then the increased charge density
promoted the splitting of the jet, forming the thinner branches. How-
ever, the spinning process was unstable for the solution at high elec-
trical conductivity when the concentration of TBAC was higher than
0.1 mol/L, indicating that TBAC content played an important role in
determining the morphological structure of T-CA nanofibers. Another
influencing element was the electrospinning voltage. Taking
Fig. 2(b4–b6) as an example, the tree-like structure of nanofibers was
extremely scarce when the voltage was 30 kV, and the dense and uni-
form tree-like nanofibers were obtained at 35 kV. Subsequently
Fig. 2(b6) showed that the content of tree-like structure was reduced
with the voltage increasing to 40 kV. It resulted from the fact that the
augment of voltage enhanced the electric field force and then promoted
the jet splitting at the beginning.
Through the contrast analysis of SEM images, the nanofiber mem-
branes obtained from voltage of 35 kV and TBAC concentration of
0.1 mol/L exhibited the optimal morphological structure and was se-
lected as the sample to be deacetylated. The diameters of trunk and
branch fibers were measured with the software of IPP, respectively.
Fig. 3 exhibits the diameter distribution of C-CA membrane and T-CA
membrane before and after the deacetylation. It was found that C-CA
and D-C-CA membrane have uniform nanofibers with diameter of
80 nm–200 nm and the diameter have a slight increase after deacety-
lation. For the T-CA nanofiber membrane, the diameter of trunk fibers
ranged from 100 nm to 500 nm and the diameter of branch fibers
ranged from 20 nm to 100 nm. Most of the branch fibers distributed in
the range of 30–50 nm while the fiber diameter became thicker after
Fig. 3. SEM images and the diameter distribution of (a) C-CA membrane, (a1) the diameter distribution of C-CA membrane, (b) T-CA membrane, (b1) the diameter distribution of T-CA
membrane branch fibers, (b2) the diameter distribution of T-CA membrane trunk fibers, (c) D-C-CA membrane, (c1) the diameter distribution of D-C-CA membrane, (d) D-T-CA membrane,
(d1) the diameter distribution of D-T-CA membrane branch fibers, (d2) the diameter distribution of D-T-CA membrane trunk fibers.
65
Carbohydrate Polymers 183 (2018) 62–69
the NaOH ethanol solution treatment. Both of them showed a slight
swollen morphology after deacetylation Han , Ji , Min , Kang & Park,
2008. This phenomenon may be because the cellulose molecular is non-
axial re-orientated after deacetylation. What’s more, cellulose nanofi-
bers possess more hydroxyl which can bond more solvent molecular.
3.2. Structure of nanofiber membranes
The XPS spectrums of C-CA, D-C-CA, T-CA and D-T-CA nanofiber
membranes is shown in Fig. 4. The Fig. 4(a) shows the C and O elements
content of the four samples. Especially, the T-CA nanofiber membrane
obtain N and Cl was result of addition of TBAC. What’s more, the
spectra of sample indicated three profile peaks assigned to CeC
(285.1 eV), CeO (286.4 eV) and OeC]O (288.7 eV) in Fig. 4(b) and
(d). These three molecular bonds were feature structure of cellulose
acetate. In Fig. 4(c) and (e), the spectra of deacetylated CA membrane
contained two obvious peaks at 285.1 eV and 286.4 eV respectively,
where as the peak at 288.7 eV was almost disappeared, which were
attributed to the decomposition of ester groups and formation of hy-
droxyl group with NaOH/Ethanol solution treatment (Son, Youk, Lee, &
Park, 2010). It proved that the cellulose acetate membranes have
converted to cellulose membranes.
Fig. 5 shows the FT-IR spectrums of the D-T-CA membrane, T-CA
membrane, D-C-CA nanofiber membrane and C-CA nanofiber mem-
brane. The infrared spectra of C-CA nanofiber membranes display the
characteristic peaks of CA at 1216 cm−1 (CeOeC), 1375 cm−1
(CeCH3), 1735 cm−1 (C]O) and an extremely weak hydroxyl ab-
sorption peak at 3497 cm−1 (OeH). The FT-IR curve of T-CA nanofiber
membrane occurred a more obvious absorption peak at 3479 cm−1
attributed to the addition of TBAC. This broad peak was likely to from
the residue water in the membranes caused by the hygroscopic nature
of TBAC (Li, Kang, Zhao, Hu, Ju et al., 2016; Li, Kang, Zhao, Hu, Wei
et al., 2016; Li, Xu et al., 2016). After the deacetylation, the char-
acteristic adsorption peaks of acetate group at 1735 cm−1 (C]O),
1369 cm−1 (CeCH3) and 1216 cm−1 (CeOeC) disappeared, on the
contrary, the absorption peak at 3362 cm−1 (OeH) have an obvious
K. Zhang et al. Carbohydrate Polymers 183 (2018) 62–69

Fig. 4. XPS spectrums of the tree-like CA nanofiber membrane and the deacetylated CA tree-like nanofiber membrane: (a) full spectra of T-CA membrane and D-T-CA membrane, (b) C 1s
spectrum of C-CA membrane, (c) C 1s spectrum of D-C-CA membrane, (d) C 1s spectrum of T-CA membrane, (e) C 1s spectrum of D-T-CA membrane.

increase in both D-C-CA and D-T-CA nanofiber membranes (Son, Ji, Lee,
& Park, 2004). The above results proved that cellulose acetate mem-
branes have been converted to cellulose membranes eventually.
Fig. 6 shows XRD pattern of C-CA materials, T-CA membrane and D-
T-CA membrane. It is well known that cellulose acetate is acetylated
from cellulose, and its crystalline structure is weakened to some extent
(Jianxin, Tang, & Wang, 2008). As shown in Fig. 6, X-Ray diffraction
patterns revealed that the C-CA materials presented non-orientation
character while the tree-like CA membrane and the deacetylated
membrane had obvious peaks at 2θ = 25.2° and 2θ = 25.9°. What’s
more, a new peak at 20.2° present and the peak at 25.9° were enhanced
for the deacetylated CA membrane. The variation of crystal structure

Fig. 5. (a) Fourier infrared spectras of C-CA membrane, D-C-CA mem-

brane, T-CA membrane and D-T-CA membrane. (b) Schematic diagram for
the deacetylation process.

66
K. Zhang et al.
Fig. 6. XRD pattern of C-CA membrane, D-C-CA membrane, T-CA membrane and D-T-CA
membrane.
resulted from the recrystallization of CA molecules, which the OH−
made hydrogen bond broken and rebuilt, and molecule chain occurred
arrangement after alkaline immersion (He, Tang, & Wang, 2008).
3.3. Characteristics of different nanofiber membranes
The pore sizes of different nanofiber membranes were measured.
Comparing to that of the common nanofiber membrane, the pore size of
nanofiber membrane with tree-like structure was smaller. As shown in
Fig. 7(a), the pore size of C-CA and D-C-CA membrane was 3.6 μm and
3.3 μm, respectively, while the pore size of T-CA and D-T-CA membrane
was 0.69 μm and 0.65 μm. It proved that the tree-like structure can
significantly reduce the pore size of nanofiber membranes. The slight
67
Carbohydrate Polymers 183 (2018) 62–69
reduce of pore size after deacetylation due to the slight swollen of na-
nofibers.
The value of the contact angle presents the basic information about
the hydrophilicity of membrane surfaces. The contact angle of the C-CA
membrane, the T-CA membrane and the deacetylated nanofiber mem-
brane were given in Fig. 8. The contact angles of C-CA and D-C-CA
membranes (Fig. 8(b1, b2)) were 74° and 11°, respectively. However,
the T-CA membrane (Fig. 7(b3)) had a hydrophilic contact angle of 62°
and the D-T-CA membranes (Fig. 7(b4)) demonstrated extreme hydro-
philicity with a measured contact angle of 0°. Due to the high hygro-
scopicity of TBAC, the T-CA membrane was more hydrophilic than C-
CA nanofiber membrane. As to the cellulose nanofiber membrane, it
was result from the conversion of ester into hydroxyl after deacetylation
which led to the enhancement of hydrophilicity (Liu & Hsieh, 2002).
Fig. 7(c) illustrated the stress-strain curves of C-CA nanofiber
membrane and T-CA nanofiber membrane before and after deacetyla-
tion. All the samples were hot-pressed at 60 °C and 120 MPa for three
minutes. For the measurement of mechanical properties, the C-CA
membrane possessed a tensile strength of 1.9 MPa and an elongation at
break of 0.94% while the tensile strength and elongation at break were
1.83 MPa and 1.69% respectively for the deacetylated membrane. The
tensile strength and elongation of tree-like CA membrane increase to
6.5 MPa and 2.3% while D-T-CA membrane increase to 3.9 MPa and
3.1%. Interestingly, the membrane with tree-like structure have a dis-
tinctly change in tensile strength and elongation at break. The increase
of mechanical properties may due to the appearance of tree-like
structure. The trunk fibers provide skeleton supports and branch fibers
can acted as connection props (Li, Kang, Zhao, Hu, Ju et al., 2016; Li,
Kang, Zhao, Hu, Wei et al., 2016; Li, Xu et al., 2016). On the other hand,
the difference in mechanical property between CA and deacetylated CA
membrane is because that the alkali penetrated into the macro-
molecules destroyed the structure of macromolecules. The hydrogen
bonds were destroyed and recombined in the new position and mac-
romolecules occurred re-crystallization. But the arrangement of
Fig. 7. (a) Pore size distributions of different nano-
fiber membranes. (b) Images of the water contact
angle with different nanofiber membrane: (b1) C-CA
membrane, (b2) D-C-CA membrane, (b3) T-CA
membrane and (b4) D-T-CA membrane. (c) tensile-
strain curve of different nanofiber membranes. (d)
Optical images of T-CA and D-T-CA membrane
soaked in DMF, DMAc and acetone respectively.
K. Zhang et al.
macromolecules is not definitely along the axial direction of the fibers
result in the increase of elongation at break (Zhang, Wang, & Wang,
2008).
The solvents (Acetone, DMF and DMAc) resistance of the D-T-CA
and the T-CA membrane was shown in Fig. 7(d). It was obvious that T-
CA nanofiber membrane occurred shrink and dissolution while D-T-CA
nanofiber membrane almost had no change. It implied that the per-
formance of D-T-CA nanofiber membrane was stable for the separation
of organic solvent.
3.4. The air filtration performance
For the air filtration performance, the thin nanofiber membranes
were electrospun on nonwoven substrates. The filtration efficiency and
pressure drop of nonwoven substrates were 18.8% and 4.6 Pa, respec-
tively which was negligible. Fig. 8 compared the filtration efficiency
and pressure drop of common CA nanofiber membrane and tree-like CA
nanofiber membrane with different weights. The filtration efficiency of
tree-like CA membrane and common CA membrane was 95.59%/
50.5%, 98.11%/70.5% and 99.58%/88.9% with the basis weight was
0.27 g/m2, 0.54 g/m2 and 0.81 g/m2, respectively. And the pressure
drop was 47.9 Pa/15 Pa, 102.8 Pa/32.7 Pa and 110.8 Pa/48.7 Pa, re-
spectively. In related literature, Wang report the air filtration perfor-
mance of PEO and PVA nanofiber membranes for air filtration was
800 Pa/92.8% and 1100 Pa/97.6%, respectively, with the thickness
was 350 μm and 400 μm (Wang, Zheng, & Sun, 2008). Vitchuli report
that they electrospun nylon 6 fiber mats were deposited on woven 50/
50 nylon/cotton fabric for air filtration. The efficiency can reach 99.5%
and the pressure drop was about 500 Pa (Vitchuli et al., 2010). Feng
report the PAN nanofiber membrane for air filtration by electrospun.
When the membrane thickness increased from 18 μm to 35 μm, the
filtration performance for DOP aerosol particle sized 0.33 μm was
121.93 Pa/81.78% and 591.75 Pa/99.24%, respectively (Feng, Wang,
Wang, & Congju, 2017). It is obvious that T-CA membrane had a higher
efficiency than C-CA membrane under the same condition. It resulted
from that the tree-like structure owned smaller pore size which could
prevent more particles. On the other hand, dense branch fibers could
capture more tiny particles. At the same time, the T-CA membrane also
had a higher resistance than C-CA membrane, which was caused by the
smaller pore size of the T-CA membrane. While the tree-like and C-CA
membranes obtained after deacetylation possessed filtration efficiencies
of 90.8%/52.8%, 96.7%/70.2% and 98.37%/90.3%.The press drops-
were46.9 Pa/21 Pa, 106.1 Pa/43 Pa and 115 Pa/63.2 Pa, respectively.
The filtration efficiency of D-T-CA membrane had a slight reduce be-
cause tree-like structure was damaged to some extent. Reversely, the C-
CA nanofiber membrane had an increase of filtration efficiency and
press drop after deacetylation. It resulted from the increase of the pore
size. Then the quaintly factor was introduced to evaluate the perfor-
mance of different membranes.
The equal of quaintly factor was defined as
68
Carbohydrate Polymers 183 (2018) 62–69
Fig. 8. Filtration efficiency and pressure
drop of different nanofiber membranes with
different basis weight.
ln(1 − η)
QF = −
ΔP
(Where the η and ΔP are the filtration efficiency and press drop)
(Nicosia et al., 2016). The QF of the T-CA membrane and C-CA nano-
fiber membrane were 0.065/0.046, 0.039/0.035 and 0.049/0.042 with
the basis weight was 0.27 g/m2, 0.54 g/m2 and 0.81 g/m2, respectively,
while the QF of the membrane after deacetylation were 0.050/0.035,
0.032/0.028 and 0.038/0.037. It means that tree-like nanofiber mem-
brane possessed better filtration performance.
4. Conclusions
In summary, the continuous uniform tree-like cellulose nanofiber
membranes can be obtained via deacetylation of CA tree-like nanofiber
membranes. Firstly, large-scale CA tree-like nanofiber membranes were
controllably fabricated by the electrospinning. Optimal parameters for
preparing CA/TBAC (0.1 mol/L) tree-like nanofiber membranes were
voltage of 35 kV, tip to collector distance of 15 cm, spinning rate of
1.0 mL/h. Advantages of the tree-like structure and natural materials
were combined through this method. The eventual cellulose tree-like
nanofiber membrane had excellent hydrophilicity, preferable mechan-
ical properties, good solvent resistance and high air filtration efficiency.
Especially, the air filtration efficiency can reach to 98.37% and the
pressure drop was 115 Pa when the basis weight was 0.81 g/cm2. It is
obvious better than common cellulose nanofiber membranes. What’s
more, the decreased fiber diameter and average pore size caused by the
tree-like structure make it as a potential candidate for various future
applications, including separation, tissue engineering, sensors, and
catalysis, etc.
Acknowledgments
The author would like to thank the National Natural Science
Foundation of China (51673148), the Science and Technology Plans of
Tianjin (16JCTPJC45600, 16PTSYJC00110, 15PTSYJC00230) and
Innovative Research Team in University of Ministry of Education of
China (IRT13084) for their financial support.
References
Ahmed, F., Ayoub, A. A., Jatoi, A. W., Khatri, M., Memon, N., Khatri, Z., et al. (2017).
Ultrasonic-assisted deacetylation of cellulose acetate nanofibers: A rapid method to
produce cellulose nanofibers. Ultrasonics Sonochemistry, 36, 319.
Ahn, Y., Hu, D. H., Hong, J. H., Lee, S. H., Kim, H. J., & Kim, H. (2012). Effect of co-
solvent on the spinnability and properties of electrospun cellulose nanofiber.
Carbohydrate Polymers, 89(2), 340–345.
Ang, L., & Zhang, L. (2007). Advance in solvents of cellulose. Acta Polymerica Sinica,
007(10), 937–944.
Bai, H., Liu, Z., & Sun, D. D. (2011). Hierarchical ZnO/Cu “corn-like” materials with high
photodegradation and antibacterial capability under visible light. Physical Chemistry
Chemical Physics Pccp, 13(13), 6205–6210.
Cheng, B., Li, Z., Li, Q., Ju, J., Kang, W., & Naebe, M. (2017). Development of smart poly
K. Zhang et al.
(vinylidene fluoride)-graft-poly(acrylic acid) tree-like nanofiber membrane for ph-
responsive oil/water separation. Journal of Membrane Science, 534, 1–8.
Dixit, V., Tewari, J., & Obendorf, S. K. (2010). Fungal growth inhibition of regenerated
cellulose nanofibrous membranes containing Quillaja saponin. Archives of
Environmental Contamination & Toxicology, 59(3), 417.
Feng, X., Wang, B., Wang, J., & Congju, L. I. (2017). Preparation and properties of
polyacrylonitrile nanofiber membranes used for air filtering by electrospinning.
Journal of Textile Research, 4, 6–11.
Frey, M. W. (2008). Electrospinning cellulose and cellulose derivatives. Polymer Reviews,
48, 378–391.
Han, S. O., Ji, H. Y., Min, K. D., Kang, Y. O., & Park, W. H. (2008). Electrospinning of
cellulose acetate nanofibers using a mixed solvent of acetic acid/water: Effects of
solvent composition on the fiber diameter. Materials Letters, 62(4–5), 759–762.
He, J., Tang, Y., & Wang, S. Y. (2008). Alkaline treatment of diacetate fibers and sub-
sequent cellulase degradation. Journal of Applied Polymer Science, 107(4), 2466–2474.
Jia, C. J., Sun, L. D., Yan, Z. G., Pang, Y. C., You, L. P., & Yan, C. H. (2007). Iron oxide
tube-in-tube nanostructures. Journal of Physical Chemistry C, 111(35), 13022–13027.
Jianxin, H. E., Tang, Y., & Wang, S. (2008). Crystalline structure and thermal property of
cellulose acetate. Journal of Textile Research, 29(10), 12–16.
Jin, I. L., Kim, S. I., Jung, Y., & Kim, S. H. (2013). Fabrication and medical applications of
lotus-leaf-like structured super hydrophobic surfaces. Polymer Korea, 37(4), 411–419.
Jin, T., Xiong, J., Jiao, C., Zhang, D., Hong, L., & Chen, Y. (2017). Cellulose/polymer/
silica composite cotton fiber based on a hyperbranch-mesostructure system as ver-
satile adsorbent for water treatment. Carbohydrate Polymers, 166, 271–280.
Kang, W., Ju, J., Zhao, H., Li, Z., Ma, X., & Cheng, B. (2016). Characterization and an-
tibacterial properties of Ag-nps doped nylon 6 tree-like nanofiber membrane pre-
pared by one-step electrospinning. Fibers & Polymers, 17(12), 2006–2013.
Khatri, Z., Wei, K., Kim, B. S., & Kim, I. S. (2012). Effect of deacetylation on wicking
behavior of co-electrospun cellulose acetate/polyvinyl alcohol nanofibers blend.
Carbohydrate Polymers, 87(3), 2183–2188.
Khatri, M., Ahmed, F., Shaikh, I., Phan, D. N., Khan, Q., Khatri, Z., et al. (2017). Dyeing
and characterization of regenerated cellulose nanofibers with vat dyes. Carbohydrate
Polymers, 174, 443–449.
Konwarh, R., Karak, N., & Misra, M. (2013). Electrospun cellulose acetate nanofibers: The
present status and gamut of biotechnological applications. Biotechnology Advances,
31(4), 421.
Kulpinski, P. (2010). Cellulose nanofibers prepared by the n-methylmorpholine-n-oxide
method. Journal of Applied Polymer Science, 98(4), 1855–1859.
Li, J. N., & Li, J. F. (2014). Preparation of dendritic zinc oxide by electrospinning and its
photocatalytic application. Academic conference of Chinese Chemical Society (In
Chinese).
Li, M., Wang, L. J., Li, D., Cheng, Y. L., & Adhikari, B. (2014). Preparation and char-
acterization of cellulose nanofibers from de-pectinated sugar beet pulp. Carbohydrate
Polymers, 102(3), 136–143.
Li, Z., Kang, W., Zhao, H., Hu, M., Ju, J., Deng, N., et al. (2016). Fabrication of poly-
vinylidene fluoride tree-like nanofiber web for ultra high performance air filtration.
RSC Advances, 6(94).
Li, Z., Kang, W., Zhao, H., Hu, M., Wei, N., Qiu, J., et al. (2016). A novel poly-
vinylidenefluoride tree-like nanofiber membrane for microfiltration. Nanomaterials,
6(8), 152.
Li, Z., Xu, Y., Fan, L., Kang, W., & Cheng, B. (2016). Fabrication of polyvinylidene fluoride
tree-like nanofiber via one-step electrospinning. Materials & Design, 92, 95–101.
Liu, H., & Hsieh, Y. L. (2002). Ultrafine fibrous cellulose membranes from electrospinning
of cellulose acetate. Journal of Polymer Science Part B Polymer Physics, 40(18),
2119–2129.
Ma, Z., Gao, C., Gong, Y., Ji, J., & Shen, J. (2002). Immobilization of natural macro-
molecules on poly-l-lactic acid membrane surface in order to improve its
69
Carbohydrate Polymers 183 (2018) 62–69
cytocompatibility. Journal of Biomedical Materials Research, 63(6), 838–847.
Murphy, A. P. (1991). Accelerated deacetylation of cellulose acetate by metal salts with
aqueous chlorine. Research Journal of the Water Pollution Control Federation, 63(2),
177–180.
Nasrinasrabadi, B., Mehrasa, M., Rafienia, M., Bonakdar, S., Behzad, T., & Gavanji, S.
(2014). Porous starch/cellulose nanofibers composite prepared by salt leaching
technique for tissue engineering. Carbohydrate Polymers, 108(20), 232–238.
Nicosia, A., Keppler, T., Müller, F. A., Vazquez, B., Ravegnani, F., Monticelli, P., et al.
(2016). Cellulose acetate nanofiberelectrospun on nylon substrate as novel composite
matrix for efficient, heat-resistant, air filters. Chemical Engineering Science, 153,
284–294.
Omollo, E., Zhang, C., Mwasiagi, J. I., & Ncube, S. (2014). Electrospinning cellulose
acetate nanofibers and a study of their possible use in high-efficiency filtration.
Journal of Industrial Textiles, 45(5).
Pant, H. R., Pant, B., Pokharel, P., Han, J. K., Tijing, L. D., Chan, H. P., et al. (2013).
Photocatalytic TiO2–RGO/nylon-6 spider-wave-like nano-nets via electrospinning
and hydrothermal treatment. Journal of Membrane Science, 429(4), 225–234.
Rodríguez, K., Gatenholm, P., & Renneckar, S. (2012). Electrospinning cellulosic nano-
fibers for biomedical applications: Structure and in vitro biocompatibility. Cellulose,
19(5), 1583–1598.
Son, W. K., Ji, H. Y., Lee, T. S., & Park, W. H. (2004). Electrospinning of ultrafine cellulose
acetate fibers: Studies of a new solvent system and deacetylation of ultrafine cellulose
acetate fibers. Journal of Polymer Science Part B Polymer Physics, 42(1), 5–11.
Son, W. K., Youk, J. H., Lee, T. S., & Park, W. H. (2010). Preparation of antimicrobial
ultrafine cellulose acetate fibers with silver nanoparticles. Macromolecular Rapid
Communications, 25(18), 1632–1637.
Vallejos, M. E., Peresin, M. S., & Rojas, O. J. (2012). All-cellulose composite fibers ob-
tained by electrospinning dispersions of cellulose acetate and cellulose nanocrystals.
Journal of Polymers & the Environment, 20(4), 1075–1083.
Vitchuli, N., Shi, Q., Nowak, J., Mccord, M., Bourham, M., & Zhang, X. (2010).
Electrospun ultrathin nylon fibers for protective applications. Journal of Applied
Polymer Science, 116(4), 2181–2187.
Wang, H., Zheng, G., & Sun, D. H. (2008). Electrospun nanofibrous membrane for air
filtration. Nanotechnology, 2007. Ieee-Nano 2007. IEEE Conference on (pp. 1244–
1247).
Wu, J., Wang, N., Wang, L., Dong, H., Zhao, Y., & Jiang, L. (2012). Electrospun porous
structure fibrous film with high oil adsorption capacity. ACS Applied Materials &
Interfaces, 4(6), 3207–3212.
Wu, S., Qin, X., & Li, M. (2013). The structure and properties of cellulose acetate mate-
rials: A comparative study on electrospun membranes and casted membranes. Journal
of Industrial Textiles, 44(1), 85–98.
Wu, J., Wang, N., Zhao, Y., & Jiang, L. (2013). Electrospinning of multilevel structured
functional micro-/nanofibers and their applications, Vol. 1, Ministry of Industry and the
seven schools of young scholars forum7290–7305.
Yang, Y., Liu, L., Güder, F., Berger, A., Scholz, R., Albrecht, O., et al. (2011). Regulated
oxidation of nickel in multisegmented nickel-platinum nanowires: an entry to wavy
nanopeapods. Angewandte Chemie, 50(46), 10855–10858.
Zhang, H. J., Wang, D. W., & Wang, S. Y. (2008). Alkali degradation performance of
diacetate cellulose. Cellulose Science and Technology, 16(1), 45–49 (In Chinese).
Zhao, H., Kang, W., Ma, X., Deng, N., Li, Z., & Cheng, B. (2017). Fabrication and catalytic
behavior of hierarchically-structured nylon 6 nanofiber membrane decorated with
silver nanoparticles. Chinese Journal of Catalysis, 38(1), 73–82.
Zhou, W. T., Shao, Q. J., Jian-Xin, H. E., Cui, S. Z., & Gao, W. D. (2010). Effect of solvents
on spinnability of electrospun cellulose acetate nanofiber. Journal of Cellulose Science
& Technology, 2, 22–26.
Zhuang, X., Yang, X., Shi, L., Cheng, B., Guan, K., & Kang, W. (2012). Solution blowing of
submicron-scale cellulose fibers. Carbohydrate Polymers, 90(2), 982.