Research Article

Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX pubs.acs.org/journal/ascecg

Water Hyacinth: A Sustainable Lignin-Poor Cellulose Source for the

Production of Cellulose Nanofibers
Supachok Tanpichai,*,†,‡,§ Subir Kumar Biswas,† Suteera Witayakran,⊥ and Hiroyuki Yano*,†
†
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
‡
Learning Institute, King Mongkut’s University of Technology Thonburi, 126 Pracha Uthit Road, Bangkok 10140, Thailand
§
Cellulose and Bio-based Nanomaterials Research Group, King Mongkut’s University of Technology Thonburi, 126 Pracha Uthit
Road, Bangkok 10140, Thailand
⊥
Kasetsart Agricultural and Agro-Industrial Product Improvement Institute, Kasetsart University, 50 Paholyothin Road, Bangkok
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10900, Thailand
*
S Supporting Information

ABSTRACT: The extraction of cellulose nanofibers (CNFs) from a

lignocellulosic source containing less lignin would be an effective
way to avoid repetitious and energy-consuming chemical treatments.
In the present study, we used water hyacinth (Eichhornia
crassipes)a fast-growing, rapidly reproducing, sustainable, and
inexpensive raw material with a low lignin content (4.1%)to
successfully prepare CNFs with diameters of 10−30 nm and lengths
of several μm. We used three different chemical approaches:
chemical-free, alkaline, and combined sodium chlorite and alkaline
treatments. The results indicate that the alkaline treatment alone
was sufficient to eliminate most of the lignin and hemicellulose from
water hyacinth, providing CNFs with morphological, crystallinity,
and thermal characteristics similar to those of CNFs prepared using combined sodium chlorite and alkaline treatment. Also,
mechanical properties and thermal expansion of the nanopapers prepared from these chemically treated CNFs were
comparable. Water hyacinth has potential as a sustainable cellulose source for the large-scale production of CNFs for advanced
applications in tropical and subtropical countries in comparison with wood or other lignocellulosic sources due to a lower
requirement for chemical treatments. Moreover, water hyacinth has other positive aspects such as its rapid breeding rate,
availability, and economical price.
KEYWORDS: Cellulose nanofibers, Chemical treatment, Nanopaper, Mechanical properties, Thermal properties, Transparency

■ INTRODUCTION
Water hyacinth, Eichhornia crassipes, is a tropical monocotyled-
onous aquatic species of the Pontederiaceae family (pick-
erelweeds) that is native to the Amazon region of Brazil and
Ecuador.1−3 It is a perennial plant that floats on water with thick
leaves and purple flowers. The water hyacinth reproduces either
by seeds or stolons. Vegetative propagation is the most common
form of reproduction; it can double its population in 6−18 days
and, in high-nutrient areas, in as little as 5 days. Within a month,
the number of water hyacinth plants can increase exponentially
from 1 to 1000 offspring.4 The yield of water hyacinth varies
within the range of 60−150 tons per hectare.2,5 It is now
widespread in the wetlands of tropical and subtropical countries
such as India, the U.S.A., Australia, and Thailand.1−3,6−9 Owing
to its rapid rate of reproduction, large colonies of water hyacinth
form dense impermeable mats, clogging water bodies. This leads
to environmental problems with fish populations, irrigation,
biodiversity, water quality, and water transportation.1,2,4,7,10,11
The overall water hyacinth population floating on rivers in
Thailand in January 2016 was reported to be 5.6 million tons.9
Each year, the Thai government spends a large amount of money
in an attempt to solve this problem, and the water hyacinth
population has become a national issue. After it is gathered from
areas of open water, water hyacinth typically ends up in landfill
or is used as a fertilizer or animal food.4,8 Small and medium-
sized enterprises extract fibers from water hyacinth for textile
and paper applications. There have been several investigations
into the possibility of using water hyacinth for the production of
ethanol and biogas.7,8
Water hyacinth is fast-growing, inexpensive, plentiful, and
sustainable with a high rate of reproduction; furthermore, it
contains less lignin and high cellulose contents.8,10,11 The lignin
content of water hyacinth is lower than 10 wt %,12−14 whereas
that of wood is 25−35 wt % and that of agricultural residues,
such as rice straw and sugar cane bagasse, is approximately 18 wt
%.8,15−17 Fast-growing plants have a lower lignin content than
Received: July 19, 2019
Revised: September 23, 2019

© XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.9b04095

ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
wood or other slow-growing plants.8,18,19 Lignina complex
three-dimensional polymer that acts as an adhesive to bind
microfibrils and cross-link wall componentsis essential for
support, for upright growth in air, and for resisting gravity.8,20 As
in other aquatic plants, water hyacinth requires less lignin to
stiffen its body, and the less availability of lignin in its cell walls is
the main characteristic of its evolution from a terrestrial to an
aquatic existence.20,21 It is worth mentioning that the ancestors
of the aquatic family Pontederiaceae (water hyacinth) were
terrestrial before adaptation to life in an aquatic environment.22
Recently, cellulose nanofibers (CNFs) have received a great
deal of attention in a wide variety of applications such as
reinforcement in nanocomposites, biomaterials, paper, pack-
aging, electronic devices, and filtration membranes.23−27 This is
owing to their unique properties such as low density, low
thermal expansion, superior mechanical properties, biodegrad-
ability, biocompatibility, and a large surface-to-volume
ratio.16,28−31 Commonly, a series of chemical treatments is a
prerequisite for the removal of lignin and hemicellulose from
lignocellulosic materials before disintegration.15,32,33 For
example, the well-known combination of acidified sodium
chlorite (NaClO2) and alkaline has long been used to treat
lignocellulosic materials such as wood,15 rice straw,15 potatoes,15
kenaf,33 and agricultural residues.32 With its long processing
time and high chemical and energy consumption, this chemical
purification process is very expensive.34 Moreover, an environ-
mentally friendly enzymatic approach has been introduced to
facilitate nanofibrillation associated with the reduction of the
energy consumption caused by mechanical treatment such as
homogenization or grinding.35−37 But, this process requires an
additional time-consuming step for the CNF preparation.
Therefore, fibers with a limited lignin content would eliminate
or reduce the need for such procedures and would provide a
promising alternative source for the preparation of CNFs to
wood or plant-extracted cellulose sources, which contain a
higher lignin content.15,16
In the present study, we selected the water hyacinthwhich
has a fast rate of growth, low lignin content, and a high rate of
reproduction and is sustainable and inexpensiveas a raw
material. To devise a greener approach using fewer chemicals,
we investigated three different chemical methods for preparing
CNFs: no treatment, treatment with alkaline, and a NaClO2 and
alkaline treatment combination. The characteristics of these
prepared CNFs were investigated using scanning electron
microscopy (SEM), chemical analysis, Fourier-transform infra-
red (FTIR) spectroscopy, X-ray diffraction (XRD), and
thermogravimetric analysis (TGA). We also produced nano-
papers from the CNFs and determined their transparency,
wettability, mechanical properties, and thermal expansion.
Although previous studies have reported the isolation of
CNFs or cellulose nanocrystals from water hyacinth using a
combination of alkaline treatment and bleaching,10,13,38,39 as
well as the use of water hyacinth-extracted CNFs and cellulose
nanocrystals to reinforce polymer matrixes,40−42 none has taken
advantage of the lower lignin content of water hyacinth to
prepare CNFs without the delignification step or with fewer
chemical treatments for a greener approach. The use of water
hyacinth would definitely be beneficial because it would reduce
the production time, chemical cost, and solvent disposal expense
of CNF fabrication compared with similar considerations
involved in the use of wood or other lignocellulose sources
with a high lignin content.
B DOI: 10.1021/acssuschemeng.9b04095
Research Article
■ MATERIALS AND METHODS
Materials. We bought water hyacinth fibers from a local market in
Thailand. Potassium hydroxide (KOH), acetic acid, and sodium
chlorite (NaClO2) were purchased from Wako Pure Chemical
Industries, Japan. All chemicals were used without any further
purification.
Preparation of Cellulose Nanofibers. The preparation of CNFs
from water hyacinth is illustrated in Figure 1. We isolated the CNFs
Figure 1. Preparation of the cellulose nanofibers isolated from water
hyacinth fibers.
with the aid of alkaline treatment or a combination of NaClO2 and
alkaline treatments, and compared them to CNFs prepared using a
chemical-free treatment. Before beginning the chemical treatment, we
soaked the water hyacinth fibers in distilled water for 2 h at 90 °C to
remove water-soluble extractives such as carbohydrates.
The acidified NaClO2 treatment was carried out according to a
method described by Abe and Yano,15 with modifications. Briefly, 25 g
of the water hyacinth fibers were initially soaked in 1 L of distilled water
at 80 °C, and 10 g of NaClO2 and 1 mL of acetic acid were added to the
fiber suspension. NaClO2 and acetic acid were introduced into the
suspension every hour for 4 times. The treated fibers were filtered and
thoroughly rinsed with distilled water. The treated cellulose fibers were
subsequently soaked in a 4 wt % KOH solution at 90 °C for 2 h, and this
step was conducted twice. After chemical treatment, fibrillation was
initialized by a Vita-mix blender (ABSOLUTE 3; Osaka Chemical Co.,
Ltd., Japan) at a speed of 37000 rpm for 2 min, and the slurry was then
passed twice through a grinder (MKCA6−2; Masuko Sangyo Co., Ltd.,
Japan) at 1500 rpm with a clearance gauge of −2.5 from the zero
position (corresponding to 0.25 mm shift). The CNFs prepared using
these treatments were designated as “S”.
Alkaline-treated CNFs (referred to as “A”) were prepared as follows.
The cellulose fibers were soaked in a KOH solution (4 wt %) at 90 °C
for 2 h, and this treatment was repeated twice. The treated fibers were
primarily fibrillated with a Vita-mix blender and then treated in a
grinder under the same conditions described above. The CNFs
prepared without chemical treatment (referred to as “U”) were
disintegrated by means of the blender and grinder. All the CNF
suspensions were kept at 4 °C before use.
Formation of Cellulose Nanofiber Nanopapers. We prepared a
nanofiber suspension with a fiber content of 0.1% and vacuum-filtered
250 g of the suspension on a glass filter funnel using a polytetrafluoro-
ethylene membrane filter with 0.1 μm pores to obtain a wet cellulose
sheet. The wet sheet was placed between metal wire nets and filter
papers and dried at 110 °C for 30 min at a pressure of 0.1 MPa to
produce a CNF nanopaper with a thickness of ∼40 μm and a diameter
of ∼7.5 cm.
Chemical Component Analysis. The cellulose, hemicellulose,
and lignin contents of the untreated and chemically treated water
hyacinth fibers were determined according to the method proposed by
the Technical Association of the Pulp and Paper Industry (TAPPI).5
The comparison of chemical components of water hyacinth and other
plants is presented in the Supporting Information.
Yield. The yield of the water hyacinth fibers after the chemical
treatment was calculated using the following equation
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ACS Sustainable Chemistry & Engineering Research Article

ij dried weight of the chemically treated fibers yz

Yield (%) = jjj
j
k dried weight of the raw fibers
zz × 100
zz
{
■ RESULTS AND DISCUSSION
Chemical Components. The water hyacinth used in the
(1) present study mainly comprised 57% cellulose, 25.6% hemi-
cellulose, and 4.1% lignin. We found that the contents of
Field-Emission Scanning Electron Microscopy. The morphol- cellulose and hemicellulose were higher than those previously
ogy of the raw water hyacinth fibers and CNFs was investigated using a reported owing to variations in the environment atmosphere
field-emission scanning electron microscope (JSM-7800F; JEOL, Ltd., such as water temperature, climate and density of water hyacinth
Japan) with an acceleration voltage of 1.5 kV and a working distance of
10 mm. All the samples were sputter-coated with platinum to avoid
in that area, maturity, and method of the chemical
charging by the ion sputter coater (JEC-3000FC; JEOL, Ltd., Japan) determination, whereas there was good agreement with previous
before investigation. We used the ImageJ program to determine the studies regarding the low amount of lignin.12−14 Owing to its
widths of the CNFs. flexibility and rapid rate of growth, water hyacinth has less lignin
Fourier-Transform Infrared Spectroscopy (FTIR). FTIR meas- and more cellulose than agricultural crops such as pineapple
urements of the CNF samples were obtained using a spectrometer leaves, bagasse, and switchgrass.12−14,45−49,17,50 Table S1 of the
(Nicolet IR200; Thermo Fisher Scientific Co., Ltd., U.S.A.) in Supporting Information compares the chemical components of
attenuated total reflectance (ATR) mode. The dried samples were water hyacinth with those of plants reported in previous studies.
scanned at wavenumbers in the range 400−4000 cm−1 and measured at Therefore, cellulose-rich water hyacinth with a low lignin
4 cm−1 resolution with 64 repeated scans. The background was content has potential as an alternative to wood and agricultural
recorded at the beginning of the measurement.
residues as a source of cellulose for CNF production.
X-ray Diffraction (XRD). We obtained the XRD profiles using an X-
ray diffractometer (D8 DISCOVERY; Bruker AXS, Germany)
The contents of cellulose, hemicellulose, and lignin of the
equipped with a Goebel mirror. The sample was mounted in a sample untreated and chemically treated water hyacinth fibers are
holder and scanned with Cu Kα radiation at a wavelength of 0.154 nm, presented in Figure 2. As is usual after chemical treatment, there
with the equipment operated at 40 kV and 40 mA. The scattered light
was detected in the 2θ range between 5 and 50°, and the sample was
scanned at a speed of 0.8 s per step and an angle step increment of 0.02°.
The degree of crystallinity (CI) was calculated, according to Segal’s
method,43 from the XRD profiles using the following equation:

ij I − IAM yz
CI (%) = jjj 200 zz × 100
j I200 zz
k { (2)

where I200 is the maximum intensity of the crystalline peak located at 2θ

between 22 and 23°, and the minimum intensity of the amorphous
region at 2θ between 18 and 19°.44
Thermogravimetric Analysis. We investigated the thermal
properties of the prepared CNFs using a Q50 thermogravimetric
analyzer (TA Instruments, U.S.A.). Approximately 5 mg of each dried
sample was placed on a platinum pan, stabilized at 110 °C for 10 min to
remove moisture, and analyzed from 110 to 600 °C at a heating rate of
10 °C min−1 under nitrogen supplied at a flow rate of 100 mL min−1.
UV−vis Spectroscopy. The regular transmittances of the CNF
nanopapers were measured using a UV−vis spectrophotometer (U-
4100; Hitachi High-Tech Corp., Japan) with a 60 mm diameter
integrating sphere. Each sample was placed close to the entrance port of
the integrating sphere and scanned at wavelengths from 200 to 800 nm.
Contact Angle Measurement. To determine the surface
hydrophilicity of the nanopapers, the contact angle was measured by
a sessile drop method using a static optical contact angle meter
(SL150E; USA KINO Industry Co., Ltd., U.S.A.) equipped with a
camera. A 1 μL water droplet was placed on a surface of the dried CNF
nanopaper with a microsyringe at 23 ± 2 °C.
Mechanical Testing. We determined the tensile properties of the
CNF nanopapers using an Instron 3365 Universal Testing Machine
(Instron Corp., U.S.A.) equipped with a load cell of 5 kN. The 5 mm
wide samples were tested at a cross-head speed of 1 mm min−1 and a
gauge length of 20 mm. Prior to testing, we kept the specimens in a
controlled room at 23 ± 2 °C and a relative humidity of 50 ± 2% for 24
h. The Young’s modulus was calculated from the slope of the initial
linear region of the stress-strain curve. At least five samples were tested
to obtain averages and standard deviations for the tensile strength,
Young’s modulus, and strain at break of each material.
Thermal Expansion. We used a thermomechanical analyzer
(TMA/SS6100; Seiko Instruments, Japan) to determine the coefficient
of thermal expansion (CTE) values of the CNF nanopapers in tensile
mode over the temperature range 20−150 °C at a heating rate of 5 °C
min−1 and a preload force of 29.4 mN under a nitrogen atmosphere.
The CTE values were calculated between 20 and 150 °C.
C DOI: 10.1021/acssuschemeng.9b04095
Figure 2. Chemical constituents of untreated and chemically treated
water hyacinth.
is an increase in the proportion of cellulose and a reduction in
the proportions of lignin and hemicellulose in the treated fibers.
Surprisingly, following treatment with alkaline only (treatment
A), the cellulose content increased to 89.5%, and the contents of
hemicellulose and lignin were markedly reduced to 5.3 and 0.4%,
respectively. This large reduction in the contents of hemi-
cellulose and lignin may have been due to the porous structure of
the water hyacinth fibers, which facilitated the ingress of the
alkaline solution. During the alkaline treatment, the fibers
swelled, causing the solubilization of both hemicellulose and
lignin and cleavage of the α-ether linkages and ester bonds
between the lignin and hemicellulose.51 A longer treatment time
and a higher alkaline concentration resulted in the elimination of
more lignin. In the present study, we observed a delignification
efficiency of 91.1% following the treatment with 4% alkaline for
120 min. After the fibers were treated with the combination of
acidified NaClO2 and alkaline (treatment S), the contents of
cellulose, hemicellulose, and lignin were 85.0, 11.7, and 0.2%,
respectively. In comparison with the A fibers, the S fibers had a
lower content of cellulose and a higher content of hemicellulose.
The increase of the hemicellulose content in the S sample could
be attributed to the degradation of cellulose caused by the
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Figure 3. Scanning electron microscopy (SEM) images of a cross-section of the water hyacinth fiber (a) and cellulose nanofibers (CNFs) extracted
from water hyacinth (b) without chemical treatment, (c) by alkaline treatment, and (d) by treatment with a combination of sodium chlorite (NaClO2)
and alkaline. Arrows indicate the fiber aggregations.

Figure 4. (a) Fourier-transform infrared (FTIR) spectra, (b) X-ray diffraction (XRD) patterns, (c) thermogravimetric (TG) curves, and (d) derivative
thermogravimetric (DTG) curves of the cellulose nanofibers (CNFs) following the various chemical treatments.

D DOI: 10.1021/acssuschemeng.9b04095
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reduction in the molecular weight and degree of polymerization,
resulting from the harsh NaClO2 and alkaline treatment. The
reduction in the degree of polymerization of cellulose caused by
acid hydrolysis and oxidative cleavage of the cellulose chains
during the acidified NaClO2 treatment has already been
reported.52−54 Effect of the NaClO2 delignification on the
degree of polymerization of cellulose has been studied by
Hubbell et al.54 The degree of polymerization of cellulose
decreased to 303 and 294 when the lignin content in the
cellulose samples were 1 and 0%, respectively, while untreated
cellulose had a degree of the polymerization of 309. Similarly,
there was a significant reduction in the degree of polymerization
of cellulose (from 1500 to 410) when the filter paper was treated
with acidified NaClO2 for 6 h.53 Moreover, when the NaClO2-
delignified bamboo powders (degree of polymerization of 754
and molecular weight of 12 × 105) were treated with alkaline
treatment at room temperature for 15 h, the result was
reductions in the degree of polymerization to 556 and molecular
weight to 0.9 × 105.55 This might be the cause of the higher
content of hemicellulose after treatment with NaClO2 and
alkaline treatments in this study.
In contrast to a study by Nobuta et al.,33 treatment with
alkaline alone slightly reduced the hemicellulose and lignin
contents of kenaf bast fibers owing to their high lignin content.
The combined acidified NaClO2 and alkaline treatment is still
required to cleave and dissolve lignin and hemicellulose in high-
lignin content fibers and residues, whereas the alkaline treatment
is sufficient to purify cellulose fibers with a limited lignin content
extracted from the water hyacinth.
Owing to the removal of lignin and hemicellulose and the
partial degradation of cellulose, the fiber yield from the material
treated with a combination of NaClO2 and alkaline (S) was
42.2% whereas the mild alkaline treatment yielded a higher fiber
content of 50.6%, and the yield from untreated hyacinth fibers
was 83.1%.
Morphology. A cross-section of a water hyacinth fiber is
presented in Figure 3a. Unlike flax or wood, which contain a
central luminal cavity surrounded by a cell wall,56 water hyacinth
fibers consist of porous subfibers that are similar to celery
fibers.57 The large air cavities inside the fibers allow the water
hyacinth to float on water.7,11,58 The morphologies of CNFs
produced using different chemical treatments are compared in
Figure 3b−d. The field emission scanning electron microscope
(FE-SEM) images reveal the successful defibrillation of CNFs
produced from water hyacinth with or without chemical
treatment. Free-chemical treated CNFs (U) with diameters of
23.7 ± 5.1 nm were successfully fibrillated from the water
hyacinth fibers, but groups of fiber aggregates were easily
observed. The thicker widths of the U nanofibers and fiber
aggregates could be attributed to the less disintegration caused
by the presence of lignin. With the aid of the alkaline treatment,
the widths of the A nanofibers decreased slightly to 22.1 ± 5.2
nm, and no fiber aggregation could be found for this sample,
implying full disintegration. In the meantime, CNFs (S) with the
widths of 18.4 ± 4.7 nm were disintegrated after the
combination of NaClO2 and alkaline treatment. This indicates
that only the alkaline treatment is sufficient to isolate nanofibers
from water hyacinth with the aid of the grinding treatment. The
nanofibers prepared from the water hyacinth in the present work
are comparable to those extracted from other plants such as
banana,59 oil palm,60 wood,61 bamboo,61 and flax61 in terms of
the width and length. It has been reported that the diameter
distribution of the CNFs depends on the cellulose source.15
E DOI: 10.1021/acssuschemeng.9b04095
Research Article
Chemical Structures. The chemical structures of the CNFs
prepared by the various chemical procedures are compared in
Figure 4a. After chemical treatment, the CNFs (A and S) had
similar FTIR spectra because they had similar contents of
cellulose, hemicellulose, and lignin. The absorption bands at
3,334 cm−1, attributable to the hydroxyl groups of cellulose,62
and at 1,060 cm−1, attributable to C−O stretching of the
cellulose structure,10 were more intense in the chemically
treated CNFs (A and S) than in the U nanofibers. Furthermore,
the A and S nanofibers, which contained less hemicellulose and
lignin, produced hemicellulose- and lignin-related peaks with the
weaker intensity, e.g., the 1,640 cm−1 peak, attributable to the
carbonyl groups of hemicelluloses,16,63 and the 1,240 cm−1
peak,64,65 attributable to ester, ether, or phenol compounds.
Peaks attributable to lignin in the A and S samples, such as 1,740
cm−1, assigned to either the acetyl and uronic ester groups of
hemicelluloses or the ester linkage of the carboxylic groups of
lignin,10,16,61 and those at 1,512 and 858 cm−1, corresponding to
C=C and C−C stretching in the aromatic rings of the lignin
structure,6,16,61disappeared. These changes and the disappear-
ance of the bands confirmed the removal of hemicellulose and
lignin, and the incremental increase in the proportion of
cellulose in the chemically treated CNFs, which agreed well with
the chemical component results.
Crystallinity and Thermal Stabilities. We carried out
XRD measurements to investigate the effects of chemical
treatment on the crystalline structures of the nanofibers, because
cellulose contains amorphous and crystalline regions. Figure 4b
shows the XRD patterns of the nanofibers prepared using the
various procedures. We found similar diffraction patterns at
16.5, 22.5, and 34.5° corresponding to the (110), (200), and
(400) planes (the figures in parentheses represent the Miller
indices) for all three CNF samples, indicating typical cellulose I
structure.33,59 This suggests that the crystalline structure of the
fibers could not be affected by the chemical treatments used in
the present study. A structural transition from cellulose I to
cellulose II arises when a high-concentration alkaline solution
(20 wt %) is used to treat the fibers.66 At this level of alkaline
concentration, swollen fibers with less rigid interfibrillar
structures are formed, allowing the development of different
types of intra- and interhydrogen bonding. The degree of
crystallinity of the U CNFs was 67.7%, according to Segal’s
method.43 Following chemical treatment, the degree of
crystallinity of the CNFs increased (76.8% for A and 78.8%
for S). This increase was unquestionably due to the removal of
hemicellulose and lignin. Similar increases in the degree of
crystallinity after a series of chemical treatments have also been
reported for other cellulosic materials such as wood, bamboo,
rice straw, and flax.61 Furthermore, mechanical treatments, such
as grinding15,16 and high-intensity sonication,59 have a smaller
effect on the cellulose structure but do improve its crystallinity.
It is worth noting that although the S nanofibers contained a
lower concentration of cellulose than the A sample, the
combined sodium chlorite and alkaline treatment could destroy
the amorphous region in cellulose, increasing the crystalline
region in cellulose.37 The dissolution of amorphous cellulose
could be found when cellulose was alkaline-treated for 60 min,
increasing the crystallinity of the cellulose sample.67 Similar
increase of crystallinity has been found when the bamboo fibers
were treated with the alkaline solution with a concentration of 4
wt %.68
We investigated the thermal stability of the CNFs produced
by various chemical treatments using thermogravimetric analysis
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Figure 5. (a) UV/visible transmittances of the cellulose nanofiber (CNF) nanopapers and (b) water contact angles of the nanopapers.
(TGA), and the thermogravimetric (TG) and derivative
thermogravimetric (DTG) curves of these CNF samples are
shown in Figure 4c,d. A single thermal decomposition stage was
observed for the CNFs prepared by chemical treatments (A and
S) whereas the U CNF had several thermal decomposition
stages, implying multiple components in the nanofibers. The
initial decomposition of hemicelluloses begins in the range 220−
315 °C, and cellulose subsequently decomposes at 315−400 °C
owing to the decarboxylation, depolymerization, and decom-
position of glyosidic linkages.69,70 At temperatures higher than
400 °C, cellulose is almost pyrolyzed with a small amount of
solid residues.69
The lower thermal stability of hemicellulose is caused by its
structure of the random amorphous saccharides with rich of
branches (xylose, mannose, glucose, galactose, etc.), which is
easily converted to volatiles (CO, CO2, and hydrogen carbon) at
low temperature. Cellulose is a linear polysaccharide polymer
with a high order of arrangement and higher molecular weight,
making it more stable than hemicellulose at high temper-
ature.69,71 Furthermore, lignin decomposes in a wider temper-
ature range than hemicelluloses and cellulose (200−600 °C)72
because its structure comprises various functional oxygen groups
with different thermal stabilities, such as aromatic carbons,
phenolics, and hydroxyphenolics.73,74 Thermal decomposition
of lignin can be separated into two major states. The initial
decomposition of lignin is found between 120 and 300 °C,
resulting in the fragmentation in the phenyl propane side chains
at the end positions which forms formic acid, formaldehyde,
water, carbon dioxide, and sulfur dioxide.73 A small component
of lignin is likely degraded in this state.71,75 The main thermal
decomposition occurs between 300 and 480 °C with more than
50% of the mass loss. The fragmentation and cleavage of the
major chain linkages between monomeric phenol units in the
lignin structure yield methanol, carbon dioxide, carbon
monoxide, water, methane, and two phenolic compounds
(guaiacol and a 2-methoxy-4-akyl-substituted phenol).73,74,76
The difference of these two decomposition stages of lignin has
been found to be dependent on the lignin sources.77 Zhang et
al.75 studied the relationship between the activation energy and
the thermal decomposition reaction of CNFs with various
contents of lignin and found that higher energy was required to
thermally degrade CNFs which contained a higher content of
lignin.
The thermal stability of the CNFs increased following
chemical treatment. This increase was caused by the removal
F DOI: 10.1021/acssuschemeng.9b04095
Research Article
of hemicellulose and lignin.78,79 The onset degradation
temperature of U was 298.5 °C, which was lower than that of
the A and S CNFs. The lower thermal stability of the U CNFs
was attributed to the presence of hemicellulose with the low
thermal degradation temperature.78 The A and S CNFs began to
degrade at 313.7 and 312.6 °C, respectively. The similar thermal
stabilities of the A and S CNFs suggest that alkaline treatment is
sufficient to remove most lignin and hemicellulose from a
cellulose source in comparison with the use of the NaClO2 and
alkaline treatment. In addition, the higher residue content of the
U nanofibers at 600 °C was attributed to the formation of a
complex between cellulose and lignin and to the aromatic
structure of the lignin complexes in the fibers.69,74 A greater
content of solid residues has been reported following lignin
pyrolysis at 900 °C.69 Similarly, a lower thermal decomposition
temperature and higher amounts of carbonized residues have
been reported for raw banana fibers in comparison with
bleached and acid-treated banana fibers.80
Transparency and Wettability. The total light trans-
mittances of the CNF nanopapers in the wavelength range 200−
800 nm are presented in Figure 5a. The U sample was brownish,
and the nanopapers became colorless following treatment with
acidified NaClO2 and alkaline, owing to the elimination of lignin
by the reactions of chlorine and the chlorite ions from
NaClO2.33 The S nanopaper had the highest light transmittance
(49.8% at 600 nm) whereas the A and U nanopapers had
transmittances of 33.6 and 16.7% at the same wavelength,
respectively. The high intensity of the brownish color observed
in the U nanopapers was proportional to the availability of lignin,
which contains chromophore groups such as phenolic units,
ketones, and other chromophores that absorb light81,82 while the
lower light transmittance of the U samples was due to the high
lignin content, larger width CNF distribution, and fiber
aggregates. Furthermore, the lower light transmittance of the
U samples can be attributed to less formation of hydrogen
bonding between fibrils within the paper (small gaps formed
between fibrils) interfered by lignin. The higher light trans-
mittance obtained from the S samples over the A samples could
be attributed to the smaller widths of the S nanofibers and lesser
lignin content. A higher content of hemicellulose in the S CNFs
might be another key to provide a higher value of the light
transmittance. Hemicellulose has been reported to prevent the
coalescence of microfibrils (hornification) by physically
hindering the direct contact between microfibils.83 The
cohesion forces between microfibrils could be also deducted
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
Figure 6. (a) Stress−strain curves and (b) thermal expansion curves of the cellulose nanofiber (CNF) nanopapers.
by the moisture absorption of hemicellulose during rewet-
ting.83,84
Moreover, the U nanopapers completely absorbed UV light
(200−380 nm) while around 7 and 35% of the UV light could
pass through the A and S nanopaper samples. The difference of
the transmittance between the A and S nanopapers could be
attributed to the lignin content. Although the lignin content in
the A and S samples was different by only 0.2 wt %, this
difference might be enough to block more light and exhibit the
lower light transmittance of the A nanopapers. This might be
because during the nanopaper preparation, the nanopaper was
pressed at 110 °C for 30 min, and this process condition could
be possibly enough for lignin as a binder to soften and fill cavities
between nanofibers.71,85 This random filling of lignin in pores
between nanopapers had an influence on transmittance,
wettability, mechanical properties, and thermal expansion of
the prepared nanopapers. Recent studies have shown that the
light transmittance of CNF nanopapers decreases as the lignin
content increases.82 It is worth mentioning that the U samples
exhibited a dip in transmittance at ∼670 nm (the red region)
whereas the other materials showed no such abnormal behavior.
This might have been due to the presence of chromophores in
the lignin that are particularly light absorbent in that region.
Therefore, the lignocellulosic CNF nanopapers would be useful
for UV protection. Moreover, surface light scattering plays an
important role in the transparency of nanopapers.86
The wettability values of the CNF nanopapers, evaluated by
measuring the water droplet angles on their surfaces, are
compared in Figure 5b. The U nanopapers had a higher contact
angle of >90°, suggesting that a greater proportion of lignin in
the CNFs makes the nanopaper less wettable. The A (60.2°) and
S (48.1°) nanopapers, which contained less lignin, were more
hydrophilic. Similar results have been reported for CNF
nanopapers with different lignin contents.81,85 CNF nanopapers
with a higher lignin content exhibited lower total water
absorption capacity and less wettability. This was due to the
higher hydrophobicity of lignin in comparison with cellulose and
hemicellulose, resulting in the reduction of the accessibility of
water molecules to interact with hydroxyls groups of cellulose
and hemicellulose.81,82,85 Surface free energy has been found to
play a key role to control the interfacial properties such as
absorption and wettability.81,82,85 The total surface free energy
has been dominated by the disperse component in the
nanopapers which depends on the percentage and presence of
free hydroxyl groups on the surface. With increasing a higher
lignin content, a value of the disperse component became lower
G DOI: 10.1021/acssuschemeng.9b04095
Research Article
owing to the reduced amount of the hydroxyl groups from
cellulose. Therefore, the reduction of the surface energy of the
fibrils could be caused by the appearance of lignin due to the
larger percentage of C−C and C−H bonds and the lower
composition of O to C in lignin compared with cellulose.85
Mechanical Properties and Thermal Expansion. The
density and mechanical properties of the prepared nanopapers
are summarized in Table S2 of the Supporting Information, and
the stress−strain curves of the CNF nanopapers are shown in
Figure 6a. The densities of the U, A, and S nanopapers were not
significantly different with values close to ∼1.3 g cm−3. The
filling of voids between nanofibrils with lignin during the process
of hot-pressing and compression has been not related to the
densities of the nanopapers.85 The U nanopapers had the lowest
tensile strength (40.6 MPa) and Young’s modulus (4.3 GPa).
These low values arose because lignin prevented the formation
of hydrogen bonds between the CNF fibrils and the fiber
aggregates; the mechanical properties of nanopapers are
dominated by the properties of the fibers and by the bonding
strength.82,87 With the removal of lignin, the values of the
mechanical properties of the CNF nanopapers (strength, strain,
and Young’s modulus) increased significantly. The S nanopapers
had a tensile strength of 73.3 MPa and a Young’s modulus of 6.3
GPa whereas the A nanopapers had a tensile strength of 66.6
MPa and a Young’s modulus of 5.6 GPa. The slightly higher
mechanical properties of the S nanopapers might be ascribed to
the smaller-width nanofibers and stronger interactions between
the individual CNF fibrils, but the presence of a small amount of
lignin (0.4%) within the A nanopapers may have caused fibril
slippage during tensile deformation, leading to a higher strain,
and slightly lower values for strength and modulus. Also, the
higher strength and modulus of the S nanopapers over the A
nanopapers might also be due to the higher content of
hemicellulose. Hemicellulose has been found to adhere
nanofibers and prevent hornification in the dried state, yielding
improvement in the stiffness and strength of the nanopapers.83
However, other works have revealed large differences in the
mechanical properties of nanopapers formed from CNFs
produced by alkaline treatment and a combined acidified
NaClO2 and alkaline treatment.33,88 For example, in one study,
the alkaline-treated CNF nanopapers had a tensile strength of
12.8 MPa and a modulus of 1.7 GPa, and the tensile strength and
modulus increased to 68.2 MPa and 7.0 GPa, respectively, when
the fibers were treated with an alkaline and bleaching solution.88
Large improvements in the mechanical properties have also
been reported for nanopapers made from kenaf CNFs treated
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
with an alkaline solution and by bleaching, compared with those
formed from alkaline-treated CNFs. The similar mechanical
behaviors of the A and S nanopapers may be attributed to the
low lignin content of water hyacinth (4.1%), compared with
27.5% for parica88 and 18.8% for kenaf.33 Therefore, the lignin
content of cellulosic raw materials could play an important role
in CNF fibrillation and may also affect the mechanical properties
of nanopapers.
In general, materials tend to expand when the temperature
increases. Therefore, the thermal stability of materials at high
temperatures is important, especially with regard to composite
and electronic applications. The coefficient of thermal expansion
(CTE) of each nanopaper material is reported in Table S2, and
the thermal expansion behavior of each nanopaper is presented
in Figure 6b. The CTE values of the nanopapers made from the
U, A, and S nanofibers were 15.6, 13.0, and 12.7 × 10−6 K −1,
respectively. A reduced CTE was related to the crystallinity of
chemically treated CNFs and the lignin content of the fibers,
because lignin interferes with the formation of hydrogen bonds
between fibrils.33 All prepared CNF nanopapers exhibit
significantly limited expansion at higher temperature compared
with engineering plastics such as polyethylene terephthalate,
polyether sulfones, polycarbonates, and nanopapers of CNFs
extracted from kenaf and chitin.27,33,89
Water hyacinth has a critical advantage over other
lignocellulosic sources, which require tedious and time-
consuming treatment procedures for the preparation of CNFs
with characteristics similar to those extracted from wood or
other lignocellulosic sources. The preparation of CNFs from
lignin-poor water hyacinth would accelerate the production of
CNFs by the omission of some of the chemical treatment steps
used for hemicellulose and lignin elimination. This would
decrease the cost of CNF preparation because it would reduce
the need for expensive chemicals and shorten the processing
time, while retaining the performance of the CNFs (i.e., close to
that of fully chemically treated CNFs). Moreover, there were no
significant differences in the mechanical properties and thermal
expansion behavior of nanopapers formed from CNFs prepared
by the two different chemical approaches. Therefore, these
findings could facilitate the use of CNFs extracted from the
water hyacinth in a wide range of applications such as
composites, electronics, packaging, and membrane applications
in the near future.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.9b04095.
Comparison of the chemical components of water
hyacinth with those of aquatic weeds and agricultural
crops, summary of the mechanical properties and
coefficients of thermal expansion of the cellulose
nanofiber (CNF) nanopapers (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: supachok.tan@kmutt.ac.th.
*E-mail: yano@rish.kyoto-u.ac.jp.
ORCID
Supachok Tanpichai: 0000-0002-6316-3080
Subir Kumar Biswas: 0000-0002-9538-4726
H DOI: 10.1021/acssuschemeng.9b04095
Research Article
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors are grateful for the financial support provided by
King Mongkut’s University of Technology Thonburi in the form
of the KMUTT 55th Anniversary Commemorative Fund and
Skill Development Grant (to Supachok Tanpichai) and by the
Ministry of Education, Culture, Sports, Science, and Technol-
ogy, Japan, for the Monbukagakusho Scholarship (No. 143492;
to Subir Kumar Biswas).
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