International Journal of Biological Macromolecules 158 (2020) 1259–1267

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Preparation of lignin containing cellulose nanofibers and its application

in PVA nanocomposite films
Mingyan Yang a,b,⁎, Xiao Zhang a, Shuyi Guan a, Yan Dou a,b, Xiaofeng Gao a
a
School of Water and Environment, Chang'an University, Xi'an 710054, China
b
Shaanxi Key Laboratory of Exploration and Comprehensive Utilization of Mineral Resources, Xi'an 710054, China

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

Article history: Lignin containing cellulose nanofibers (LCNFs) were successfully prepared from wheat straw using an acid
Received 19 February 2020 hydrotrope of p-toluene sulfonic acid (p-TsOH) combined with ultrasonication. p-TsOH pretreatment was ap-
Received in revised form 19 April 2020 plied below 80 °C to selectively remove hemicellulose and lignin and generate purified cellulose fibers containing
Accepted 6 May 2020
approximately 15% lignin. Subsequently, high-intensity ultrasonication was used for b6 min to effectively defi-
Available online 11 May 2020
brillate the p-TsOH-pretreated cellulose fibers to nanoscale fibers. AFM and TEM analyses showed that the diam-
Keywords:
eter distribution of the resultant nanofibers decreased with the increase in ultrasonic intensity. The FTIR and XRD
p-Toluene sulfonic acid results indicated that the molecular structures and cellulose crystallinity were not changed during the ultrasonic
Ultrasonication process. An amount of 5 wt% of the obtained LCNFs was introduced into a polyvinyl alcohol (PVA) matrix. The
Lignin containing cellulose nanofibers (LCNFs) resulting nanocomposite products exhibited improved thermal performance and surface properties compared
with the pure PVA matrix. The mechanical properties, including the tensile stress and Young's modulus, were en-
hanced significantly, although the elongation at the break was slightly decreased. PVA composites with the addi-
tion of LCNFs are expected to be used in a variety of fields, such as biodegradable plastics, pharmaceutical carrier,
filtration media and packaging materials.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction reinforcement and oxygen-barrier layers in composites, packaging ma-

The valorization of naturally abundant lignocellulosic resources, in-
cluding agricultural residues, woods, energy crops and other industrial
resources, can help solve environmental problems caused by the exces-
sive use of fossil resources [1]. Cellulose is the most important and abun-
dant natural biopolymer resources, and it can be deconstructed,
resulting in different types of nanocellulose, such as cellulose
nanocrystals (CNCs), cellulose nanowhiskers (CNWs), microfibrillated
cellulose, microfibrile aggregates and cellulose nanofibers (CNFs) [2,3].
Among these nanocelluloses, CNFs, which contain bundles of long, flex-
ible and entangled fibers with a diameter in the range of 4–20 nm and a
length in micrometers, have been drawing great attention in recent
years due to their unique structures and properties. In addition to biode-
gradability and biocompatibility, CNFs present markedly improved
properties, such as crystallinity, mechanical resistance, flexibility and
barrier properties, due to their large specific surface area and surface ac-
tivity [4,5]. As a result, CNFs have been considered as a promising basic
building block for various applications, such as for additive
⁎ Corresponding author at: School of Water and Environment, Chang'an University,
Xi'an 710054, China.
E-mail address: yangmingyan67@163.com (M. Yang).
terials, cosmetics, pharmaceuticals and biomedical devices [6–9].
CNFs are conventionally produced using mechanical delamination
from microcrystalline cellulose, bleached chemical (lignin free) pulps
or cotton litter. However, the process increases the product cost and
limits its commercial utilization [1,10,11]. In addition, the CNFs from
bleached pulps or with lower lignin content below 5% are highly hydro-
philic, leading to poor interaction and compatibility between CNFs and
non-polar media, which are challenges that need to be addressed in
some applications [12]. The direct conversion of cellulose into nanofi-
bers from low-cost lignocellulosic biomass can generate a new kind of
nanocellulose material: lignin containing cellulose nanofibrils (LCNFs)
[13]. The amount of lignin in the LCNFs depends on the degree of
delignification of the biomass. Having the advantages of a higher yield,
lower cost and less environmental impact, LCNFs have been demon-
strated to be a promising alternative to high-purity nanocellulose
[14,15]. The residue lignin in the LCNFs is beneficial to improving the
properties of LCNFs, including the reduction of the hydrophilicity and
polarity and the enhancement of thermal stability [16,17]. In addition,
lignin-based nanomaterial can be used as a delivery system or excipient
formulation to enhance drug delivery or improve drug properties
[18–20]. This application opens the possibility of using lignin-
containing nanomaterials for high-value applications in the pharmaceu-
tical industry. The major obstruction in separating cellulose from the

https://doi.org/10.1016/j.ijbiomac.2020.05.044
0141-8130/© 2020 Elsevier B.V. All rights reserved.
1260 M. Yang et al. / International Journal of Biological Macromolecules 158 (2020) 1259–1267

complex polymeric matrix containing hemicellulose and lignin is the re-
calcitrance of the hierarchal structure of the plant wall [21]. A mechan-
ical process combined with chemical pretreatment is believed to be a
promising technology for resolving the recalcitrance problem of the
raw material. However, the existing chemical pretreatment process in-
volving strong concentrated acids, alkaline, (TEMPO)-mediated oxida-
tion and reducing agents is still limited by several factors, including
low solution recovery, negative environmental impacts and high inef-
fective cost [11].
Recently, a recyclable acid hydrotrope was shown to be a promising
technology for biomass fractionation. Aqueous p-toluenesulfonic acid is
capable of achieving high delignification efficiency in an aqueous solu-
tion at low temperature, resulting in cellulose-rich water insoluble
solid (WIS) and spent liquor (SL) mainly composed of xylan and dis-
solved lignin [22,23]. The resultant WIS can be used for ethanol fermen-
tation [24] or other high value-added production processes, including
nanocellulosic materials based on a mechanical process, such as super
mass colloider (SMC) [10] and microfluidizer [23]. In addition, p-TsOH
can be reused or recovered by crystallization technology [22–24].
Wheat is one of the most common crops in China at N120 million tons
of production annually. Wheat residues account for 15.7% of all the post-
harvest crop residues, and they are traditionally buried in soil or burnt
in the field, which not only leads to the waste of biomass sources but
also negatively impacts the environment [25]. As a renewable, inexpen-
sive and underutilized resource, agricultural residues used for the pro-
duction of high value-added products, such as nanomaterial, can
introduce a new alternative resource and reduce the use of forest re-
sources worldwide [26].
The p-TsOH pretreatment combined with ultrasonication to prepare
LCNFs has not been reported previously. In addition, the role of LCNFs in
improving the overall performance of biobased nanocomposite de-
pends on various factors, such as the biomass source, fractionation pro-
cess and extraction methods. In this study, p-TsOH pretreatment was
used in combination with ultrasonication to prepare LCNFs from
wheat straw. Field Emission Scanning Electron Microscope (FE-SEM),
atomic force microscopy (AFM) and transmission electron microscopy
(TEM) were used to analyze the morphological and structural charac-
teristics of the resultant LCNFs. The changes of the functional groups
and crystallization degree during the processing procedures were stud-
ied by Fourier transform infrared (FTIR) spectroscopy and X-ray diffrac-
tion (XRD). The LCNFs were applied to PVA to prepare a bio-
nanocomposite film. The thermal stability, mechanical performance
and surface hydrophobicity of the resulting films were explored. This
work will provide a novel, feasible, and environmentally friendly pro-
cessing technology to produce lignin containing cellulose nanomaterials
for a variety of applications.
2. Material and methods
2.1. Material
Wheat straw collected from Chang'an County (Shaanxi Province,
China) was cut into small pieces and milled into powder. The powder
sieved through a 20 mesh was collected for further use.
generator (GH-IID/GH-1000Y, China) at a concentration of 1 wt%.
The ultrasonic process was performed in an ice bath to avoid excess
heat. Three samples were prepared by sonicating for 6 min at an out-
put power of 800, 1200 or 1600 W, and they were labeled as LCNFs-
800, LCNFs-1200 and LCNFs-1600, respectively. The suspensions of
0.3 wt% of the raw material, purified WIS, and cellulose nanofibers
after ultrasonication were allowed to rest for 0 and 30 min. The sta-
bility of the suspensions was studied through visual examination ac-
cording to other previous reports [27,28].
2.3. Chemical composition
The raw material and purified WIS were analyzed to determine their
chemical composition according to the procedures reported by the Na-
tional Renewable Energy Laboratory (NREL) as previously described
[29].
2.4. Characterization of LCNFs
2.4.1. FE-SEM observation
The LCNFs samples were freeze dried using a freeze drier (Eyela
FDU-2110, Japan), coated with gold and analyzed via FE-SEM (Hitachi
su8020, Japan).
2.4.2. AFM analysis
A mica substrate was prepared by depositing a drop of the LCNFs
suspension at approximately 0.01 wt% and drying for 24 h at room tem-
perature. The LCNFs image was obtained using AFM (Bruker, dimension
Icon) according to a previous study [20]. Gwyddion software (Depart-
ment of Nanometrology, Czech Metrology Institute, Czech Republic,
64-bit) was used to analyze the AFM images.
2.4.3. TEM
Samples were prepared by depositing a drop of the LCNFs suspen-
sion at approximately 0.01 wt% on Cu grids and drying at room temper-
ature. Then, the samples were staining with 2% phosphotungstic acid for
2–3 min and observed via TEM (Tecnai G2 F20, Japan). The diameter
and the size distribution of the LCNFs were analyzed using Nano Mea-
surer version 1.2.5 software (Department of Chemistry, Fudan Univer-
sity, China).
2.4.4. FTIR analysis
The FTIR spectra of the raw wheat straw, purified WIS and freeze-
dried LCNFs were performed using a FTIR instrument (Magna 560, Nico-
let, Thermo Electron Corp., USA). Spectra were recorded in the range of
400–4000 cm−1 with a resolution of 4 cm−1.
2.4.5. XRD analysis
The X-ray diffraction pattern spectra of the raw wheat straw, puri-
fied WIS and freeze-dried LCNFs samples were measured using an X-
ray diffractometer (XRD, D8 Advance, Bruker) at a scan speed of 4°/
min. The crystallinity index (CrI) was calculated using the Segal method
(Eq. (1)).

2.2. Preparation of lignin containing cellulose nanofibrils (LCNFs)  

Iam
CrI ð%Þ ¼ 1−  100 ð1Þ
The production process of LCNFs consists of chemical pretreat- I 200
ment followed by an ultrasonic process. First, 10 g of the dry wheat
straw powder was mixed with 70 wt% p-TsOH solution at 80 °C for
10 min, and it had a liquor to mass ratio of 10:1. The reaction was Table 1
stopped by adding 133.3 mL DI water. The hydrolysate solution Chemical composition changes after p-TsOH fractionation.
was separated by filtration under vacuum. The obtained spent liquor
Solid yield (%) Glucan (%) Hemicellulose (%) Lignin (%)
(SL) was used for the recovery of acid and dissolved lignin. The ob-
tained water insoluble solids (WIS) were rinsed with DI water to Wheat straw 100 34.10 ± 0.28 24.96 ± 0.14 23.04 ± 0.21
WIS 47.55 ± 1.41 64.38 ± 0.18 12.87 ± 0.46 14.86 ± 0.44
neutral pH and subjected to ultrasonic processing in an ultrasonic
 M. Yang et al. / International Journal of Biological Macromolecules 158 (2020) 1259–1267 1261

Fig. 1. Dispersion states of 0.3 wt% suspensions of raw material (A), WIS (B), LCNFs-800 (C), LCNFs-1200 W (D), and LCNFs-1600 (E) at different times.

where I200 represents both crystalline and amorphous region material
and Iam represents amorphous material.
2.5. Preparation of LCNFs/PVA nanocomposite films
The solvent cast process was used to prepare nanocomposite films.
The obtained LCNFs were mixed with a 5 wt% PVA solution by stirring
and then sonicated for 60 min to improve the dispersion of the
nanofillers in the matrix. Each mixture was degassed, poured onto a
polished glass plate and dried at 60 °C for approximately 6 h in an
oven. A pure PVA film (without LCNFs) was prepared as a control
using the above procedures. The resulting films were stored in a desic-
cator before testing.
2.5.1. Thermal stability analysis
The thermal stability of the LCNFs/PVA films obtained with different
ultrasonic output powers were tested in a thermogravimetric analyzer
(TGA Q50; TA Instruments-Waters LLC, USA) from 35 to 600 °C at a
heating rate of 10 °C/min under nitrogen flow. The weight-loss rate, ini-
tial degradation temperature (Tonset) and maximum thermal degrada-
tion temperature (Tmax) were obtained from the TGA and derivative
thermogravimetric (DTG) curves.
2.5.2. Tensile properties
The tensile properties, including the tensile strength (TS), tensile
modulus (TM), and elongation at break (EB%), of the studied films
were tested using a WDW-200 Universal Testing Machine (China) at a

Fig. 2. SEM images of the LCNFs obtained from wheat straw (A) LCNFs-800 (B) LCNFs-1200 and (C) LCNFs-1600.
1262 M. Yang et al. / International Journal of Biological Macromolecules 158 (2020) 1259–1267
crosshead speed of 5 mm/min according to the standard of ASTM D1708
[30].
2.5.3. Static water contact angles (WCAs)
The WCAs of the nanocomposite film samples were tested using a
contact angle analyzer (XG-CAMB, China). Images of the droplets were
recorded at different times after the drop touched the film surface.
3. Result and discussions
3.1. Preparation and characterization of LCNFs
The wheat straw was fractionated into two parts by the p-TsOH pre-
treatment: cellulose-rich WIS and spent liquor (SL), which mainly
contained xylose and dissolved lignin. Table 1 shows the composition
changes after the p-TsOH pretreatment. The cellulose content in the
WIS increased from 34% to 64%, with a recovery of approximately 90%.
Correspondingly, the hemicellulose and lignin content decreased to
12.87% and 14.86%, respectively. The results indicated that the p-TsOH
pretreatment can selectively remove lignin and hemicellulose from
the biomass under mild condition and produce more purified
cellulose-rich WIS containing no N15% lignin content. Previous studies
suggested that lignin content above 13% had a significant effect on im-
proving the properties of the resultant LCNFs [31,32]. The obtained
WIS were fibrillated via an ultrasonic treatment for 6 min with an out-
put power of 800, 1200 and 1600 W. The dispersion properties of the fi-
bers in water were substantially changed after the ultrasonic process. As
shown in Fig. 1, the raw material and WIS fibers were precipitated
completely at the bottom of the glass bottle, while all ultrasonic samples
presented a good dispersion property in water. After 30 min of rest,
Fig. 3. Effects of the ultrasonic intensity on the morphologies and height distribution of the resulting LCNFs measured by AFM (First row-LCNFs 800; Middle row-LCNFs 1200; third row-
LCNFs 1600. Left two panels, scale bar = 10 μm; and right two panels, scale bar = 2 μm).
LCNFs-800 had a small portion of sediment, suggesting that
unfibrillated and partially fibrillated fibers still remained, while the fi-
bers in samples LCNFs-1200 and LCNFs-1600 were nearly dispersed in
water, indicating that increasing the intensity of ultrasonication can
promote the fibrillation process of the fibers.
3.2. FE-SEM of LCNFs
The FE-SEM morphologies of the LCNFs obtained from different in-
tensities of ultrasonic treatment are shown in Fig. 2 (A, B, C). Well-
delaminated nanocellulose fibers were observed in all three different ul-
trasonic treatments samples. Some dispersed globular shaped patches,
which are likely to be lignin nanoparticle (LNPs), were visible in all
three samples.
3.3. AFM analysis
The nanoscale topography and the height distribution of the LCNFs
studied using AFM are plotted in Fig. 3. Long, flexible and filament-like
nanosized fibers and dispersed spherical nanoparticles were observed
in all three samples. The average AFM height of the three different sam-
ples shown in Fig. 3 indicated that a higher intensity of ultrasonication
can decrease the height of the fibers and thus promote the degree of
nanofibrillation of the cellulose fibers. This result was consistent with
the visual observations. In addition, one particular area in Fig. 3A1 re-
corded the depolymerizing process from micron-sized cellulose
branches to individual nanofibers with the impact of 800 W
ultrasonication. Small globular-shaped particles, which are likely lignin
nanoparticles (LNPs), were dispersed around the crosslinked nanofi-
bers. This fibril network and globular-shaped particles were similar
 M. Yang et al. / International Journal of Biological Macromolecules 158 (2020) 1259–1267 1263

Fig. 4. Effects of ultrasonic intensity on the morphologies and diameter distributions of the resulting LCNFs measured by TEM (left panel-LCNFs 800; middle panel-LCNFs 1200; right panel-
LCNFs 1600).

with the SEM result. Similar results for LCNFs derived from various
sources were reported by several authors, such as Rojo et al. [15], Nair
and Yan [16], Herrera et al. [17] and Ewulonu et al. [33].
3.4. TEM
The morphology and diameter distribution of the prepared LCNFs
were further studied by TEM. As shown in Fig. 4, the long nanofibers
are interconnected like a ‘cobweb’, and a similar result is observed in
the AFM images. Some strands agglomerated to each other to form a
large width. These agglomerations have been reported in the prepara-
tion of nanofibers from different materials by previous studies
[33–35]. The TEM diameter distribution plots showed that N58% of the
LCNFs-800 samples had a diameter of no N20 nm and exhibited a
wide range of diameter sizes. The diameter ranges of the nanofibers be-
came more uniform and narrow as the ultrasonic intensity increased,
with 84.66% of the LCNFs-1200 and 93.33% of the LCNFs-1600 showing
a diameter range of no N20 nm. The average diameters of the resultant
nanofibers of LCNFs-800, LCNFs-1200 and LCNFs-1600 samples were
20.01, 13.32 and 10.12 nm, respectively. All these results indicated
that increasing the output power of the ultrasonic treatment can posi-
tively facilitate the degree of nanofibrillation and obtain more uniform
and slender nanofibers. In addition, lignin nanoparticles observed in
the TEM image (Fig. 5) exhibited a spherical shape with the size range
of 20–50 nm, suggesting that the lignin nanoparticles were synthesized
during the ultrasonic process as well [33].
3.5. FTIR analysis
FTIR spectroscopy was performed to compare the changes of the
chemical structure before and after each treatment. As depicted in
Fig. 6, the absorbance peaks at 3350, 2900, 1160, 1110, 1034 and
897 cm−1 represent the typical features of cellulose appeared in all
spectra [3,36]. The peaks at approximately 1737 cm−1 and 1252 cm−1
in raw fiber represent ester and ether linkages formed between lignin
and hemicellulose, and they nearly disappeared in the WIS and LCNFs
samples, indicating that most of the hemicellulose and lignin were re-
moved from the biomass after chemical pretreatment [24]. The removal

Fig. 5. TEM morphology of the lignin nanoparticles prepared by ultrasonic treatment.

1264 M. Yang et al. / International Journal of Biological Macromolecules 158 (2020) 1259–1267

1.4
100 PVA
raw material LCNFs 800/PVA 1.2
80 LCNFs 1200/PVA
LCNFs 1600/PVA 1.0

DTG (mg/min)
Weight loss (%)
60
WIS 0.8
40
0.6
LNCFs 800 20
0.4
0
LCNFs 1200 0.2
-20
1503 1737 LCNFs 1600 0.0
897 2900 100 200 300 400 500
1252 3350
1160 1450 Temperature (℃)
1034 1110

1000 1500 2000 2500 3000 3500 4000 Fig. 8. Thermal stability of pure PVA and LCNFs/PVA nanocomposites.
-1
Wavenumber (cm )
both amorphous and crystalline cellulose. This result is in agreement
Fig. 6. FTIR spectra of the raw material, WIS and LCNFs with different ultrasonic
with previous reports [2,37].
treatments.
3.7. Thermal stability of the LCNFs/PVA nanocomposites

of lignin in the WIS and LCNFs samples can also be verified by eliminat-
ing of the peaks at 1450 cm−1 and 1503 cm−1, which was attributed to
the aromatic skeletal vibration of lignin. There was no difference be-
tween the spectra of the WIS and LCNFs obtained from the different ul-
trasonic treatment, suggesting that the ultrasonic treatment did not
destroy the molecular structure of cellulose.
3.6. XRD analysis
X-ray diffraction was carried out to compare the crystalline behavior
of the treated and untreated cellulose fibers. X-ray diffractograms are
presented in Fig. 7. All samples exhibited similar diffractograms with
main characteristic peaks at 2θ angles of approximately 16° and 22°
and 34°, which represent typical peaks of cellulose I structure reflections
[36]. The results suggested that the inherent crystal structure of cellu-
lose was not changed during the chemical and ultrasonic processes.
The CrI of the WIS was 49%, which represented an increase of 8.9% com-
pared with the raw material due to the reduction of hemicellulose and
lignin. No significant difference was observed between the WIS and
LCNFs, implying that the ultrasonic effect was non-selective in removing
Sample
Wheat straw
WIS
Intensity / a.u.
The thermal properties and degradation behavior are crucial in bio-
nanocomposite processing. According to the TGA and DTG curves
shown in Fig. 8, three degradation stages were observed for all tested
samples. The first minor weight loss was observed below 100 °C due
to evaporation of water or degradation of low molecular weight com-
pounds. The second major weight loss occurred in the temperature
range from 200 to 400 °C because of the decomposition of the side
chains of PVA. The Tonset and Tmax of the second degradation process
(Table 2) for the LNCFs/PVA films were higher than those for pure
PVA. With the addition of LCNFs, the Tonset and Tmax increased from
201.1 °C/234.2 °C for pure PVA to 209.2 °C/246.8 °C for LCNFs-1600.
The results indicated that the incorporation of LCNFs had a positive ef-
fect on the thermal stability of the nanocomposites. The improved ther-
mal stability of the LCNFs nanocomposites may have resulted from the
residual lignin content (approximately 15%) in the LCNFs, which are ex-
pected to present a thermal barrier due to the stable aromatic units and
the covalent linkages between the cellulose and lignin [38,39]. In addi-
tion, higher cellulose crystallinity of LCNFs is another factor that contrib-
utes to thermal stability of the composites [40]. Compared to LCNFs-
1200 and LCNFs-1600, LCNFs-800 presented slower weight loss from
50 to 300 °C, indicating that the size of the fibers might affect the ther-
mal stability of the LCNFs. The mass loss started much sooner for more
Crystallinity uniform nanocellulose due to the higher surface area when compared
(%) to the larger-sized fibers [16]. The third weight loss at 360 to 500 °C re-
45 sulted from the decomposition of the PVA backbone.
49

LCNFs 800 50 3.8. Tensile properties

LCNFs 1200 50
LCNFs 1600 52 The mechanical properties of the nanocomposites are shown in
Fig. 9. All composite samples with LCNFs nanofillers exhibited excellent
mechanical properties compared to pure PVA. The tensile stress and
Young's modulus with a 5 wt% addition of LCNFs-1600/PVA were

Table 2
Degradation temperatures of main peaks and residues at 500 °C for PVA and LCNFs/PVA
nanocomposite films.

10 20 30 40 50 Sample Tonset (°C) Tmax (°C) Residues @ 500 °C (%)

2 Theta (degrees) PVA 201.1 234.2 12.4

LCNFs 800/PVA 209.1 244.1 12.9
LCNFs 1200/PVA 206.5 246.8 16.9
Fig. 7. X-ray diffraction patterns of the raw material, WIS and LCNFs with different
LCNFs 1600/PVA 209.2 246.8 22.8
ultrasonic treatment.
 M. Yang et al. / International Journal of Biological Macromolecules 158 (2020) 1259–1267 1265

Fig. 9. Mechanical properties of pure PVA and LCNFs/PVA nanocomposites.

76 MPa and 4.3 GPa, respectively, which were 1.75 and 3.3 times higher were expected [41]. The effect can result from the percolated network
than those of pure PVA film, indicating that LCNFs can be used as an ex- formed by strong intermolecular binding, including hydrogen bonds
cellent reinforcement agent to improve the mechanical performance of and mechanical interlocking between nanocellulose, which affect the
bio-based nanocomposites. In contrast, the elongation at break (EB%) stiffness and strength of composites [42,43].
decreased slightly with the presence of LCNFs. Generally, when the
nanocellulose was incorporated with the polymer matrix, increased 3.9. Surface hydrophobicity
tensile strength and Young's modulus as well as reduced elasticity
The water contact angle (WCA) of the pure PVA and PVA nanocom-
posites over a time course is shown in Fig. 10. The WCA of the pure PVA
50 films at 0 s was 43° and decreased to 21° after 80 s. Compared with the
PVA pure PVA film, the hydrophobicity of the LCNFs/PVA nanocomposite
LCNFs 800/PVA films over a time course of 80 s was improved due to the hydrophobicity
45 LCNFs 1200/PVA of residual lignin in the LCNFs. This result was consistent with previous
LCNFs 1600/PVA research [15]. Among the samples with different ultrasonic treatments,
40 the WCA deceased with the increase of ultrasonic intensity. According
to the AFM and TEM analyses, more uniform nanofibers with lower di-
WCA

35 ameters were obtained with the increase of ultrasonic intensity and re-
sulted in reduced surface roughness of the film, which contributed to
30 the lower contact angle [44].

4. Conclusion
25
LCNFs can lower the cost of production and reduce the polarity and
20 hydrophilicity of the nanocellulose, which represent factors that restrict
the large-scale utilization of polymer biocomposites. This study demon-
0 20 40 60 80 strated an easy, feasible, and environmentally friendly processing tech-
Time (s) nology to produce lignin containing cellulose nanomaterials (LCNFs)
from agricultural residue using a recyclable hydrotropic agent followed
Fig. 10. WCAs of pure PVA and LCNFs/PVA nanocomposites. by high intensity ultrasonication. Aqueous hydrotrope p-TsOH
1266 M. Yang et al. / International Journal of Biological Macromolecules 158 (2020) 1259–1267
pretreatment was effective at removing hemicellulose and lignin below
80 °C and resulted in cellulose-rich fibers with 15% lignin content. The
AFM and TEM analyses showed that the extent of nanofibrillation of
the obtained cellulose fibers was improved significantly as the intensity
of ultrasonication increased. The presence of these LCNFs in the PVA
composites films resulted in significant improvements in both tensile
strength and Young's modulus and slight decreases in elongation at
break. The thermal resistance and surface properties of the resultant
nanocomposites were improved as well. Thus, LCNFs are expected to
be a suitable candidate for various types of applications, including as ad-
ditives to composites and biomedical devices.
Credit author statement
Mingyan Yang conceived the overall project and finalized the manu-
script writing; Xiao Zhang performed the experiments and data analy-
sis; Shuyi Guan and Xiaofeng Gao performed the experiments; Yan
Dou supported the experiment and data analysis.
Acknowledgments
This work was supported by the Natural Science Foundation of
Shaanxi Province [grant numbers 2015SF263, 2018JQ4042].
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