Carbohydrate Polymers 234 (2020) 115942

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

Preparation and characterization of high yield cellulose nanocrystals (CNC) T

derived from ball mill pretreatment and maleic acid hydrolysis
Frederikus Tunjung Setaa,c, Xingye Ana,*, Liqin Liua, Hao Zhanga, Jian Yanga, Wei Zhanga,
Shuangxi Nieb, Shuangquan Yaob, Haibing Caod, Qingliang Xud, Yifan Bua, Hongbin Liua,*
a
Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology, No. 29, 13th Street, TEDA, Tianjin, 300457, PR China
b
Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control, College of Light Industry and Food Engineering, Guangxi University, Nanning, 530004, PR
China
c
Center for Pulp and Paper, Ministry of Industry of Indonesia, Jalan Raya Dayeuhkolot No. 132, Bandung, 40258, Indonesia
d
Zhejiang JingXing Paper Joint Stock Co., Ltd., No. 1, Jingxing Industry Zone, Jingxing First Road, Caoqiao Street, Pinghu, Zhejiang Province, 314214, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The target of the study is to improve the yield and the colloidal stability of cellulose nano-crystals (CNC) that is
Cellulose nano-crystals (CNC) obtained through maleic acid hydrolysis. Herein, a facile/ green approach to prepare CNC with high yield and
Ball mill pretreatment colloidal stability from bamboo fibers is presented. Ball mill pretreatment can break down and open up the
Maleic acid hydrolysis structure of bamboo fibers, thus exposing more hydroxyl groups on the surface of pulp fibers and increasing the
Yield
access of acid molecules into pulp fibers. The maleic acid molecules can easily hydrolyze cellulose, thus releasing
Colloidal stability
more crystalline parts; maleic acid anhydride can react with hydroxyl groups to generate more −COOH groups
on CNC. The yield of resultant CNC was 10.55–24.50 %, which was much higher than 2.80 % of the control. The
study put forward a facile approach to prepare CNC with high yield and colloidal stability, and paves a possible
way for industrialization of CNC production.

1. Introduction hardwood (Moon et al., 2011) will have 140−150 nm on length,

Cellulose is one of the most important bio-based materials that have
attracted massive usability in recent decades because of their excellent
low toxicity, biocompatibility, and biodegradability for numerous uti-
lizations (Bian et al., 2017). Cellulose can be harvested from various
sources, such as bamboo. As one of the most desirable non-wood raw
material for papermaking process, bamboo can be a kind of potential
bioresource to alleviate the current shortage of wood-based pulp due to
its combination of advantages, such as being rich in cellulose, fast
growth and regrowth, easy propagation, and large-area planting in
many countries (Bystriakova & Kapos, 2006; Huang et al., 2016; Lu
et al., 2018; Nayak & Mishra, 2016).
Cellulose nanocrystals (CNC) can be isolated from many biomass
resources, such as wood (Abushammala et al., 2015; Du et al., 2017;
Isogai & Zhou, 2019), bagasse (Mandal & Chakrabarty, 2011; Sofla
et al., 2016), cotton (Elazzouzi-Hafraoui et al., 2008), waste office
paper (Yeganeh et al., 2017), kenaf (Sulaiman et al., 2015), algae
(Sinha et al., 2015), and bamboo (Brito et al., 2012; Hong et al., 2016;
Yu et al., 2012). The physicochemical properties of the CNC are re-
garded to be determined by its source, for example, CNC from
4−5 nm in width, 43–65 % on crystallinity; from softwood will have
100−150 nm on length, 10−20 nm in width, 78–82 % on crystallinity;
and cotton 70−300 nm on length, 5−11 nm in width, 74–91 % on
crystallinity (Li et al., 2011). CNC has attracted more and more atten-
tion in recent years in various applications, such as food industry,
paper-making area, catalyst area, etc. (An et al., 2017; Yang, 2017),
thanks to its excellent inherent advantages, such as large specific area,
perfect mechanical properties, etc. (George & Sabapathi, 2015).
The basic method to extract CNC from pulp fibers is to remove the
amorphous regions of cellulose thus releasing the crystalline parts, i.e.
CNC particles. Several methods have been developed to isolate CNC,
such as acid hydrolysis (for example sulfuric acid (H2SO4) (Mahmud
et al., 2019; Pirich et al., 2019; Trachea et al., 2017; Yang, 2017) and
hydrochloric acid (HCl) (Cheng et al., 2017; Trachea et al., 2017),
mechanical method (Amin et al., 2015; Zhang et al., 2015; Zhao et al.,
2016), enzymatic hydrolysis (Chen et al., 2012; Xua et al., 2013), ionic
liquid treatment (Tan et al., 2015), subcritical water hydrolysis
(Cantero et al., 2015; Novo et al., 2015; Meillisa et al., 2015), oxidation
method (Sun et al., 2015), and the combined processes (Lu et al., 2016;
Lu et al., 2013; Rohaizu & Wanrosli, 2017; Tang et al., 2015). The acid

⁎
Corresponding authors.
E-mail addresses: anxingye@126.com, anxingye@tust.edu.cn (X. An), hongbin@tust.edu.cn (H. Liu).

https://doi.org/10.1016/j.carbpol.2020.115942
Received 14 December 2019; Received in revised form 31 January 2020; Accepted 31 January 2020
Available online 03 February 2020
0144-8617/ © 2020 Elsevier Ltd. All rights reserved.
F.T. Seta, et al.
hydrolysis is the most commonly used to produce CNC (Moon et al.,
2011; Song et al., 2018) due to its high efficiency for CNC preparation.
The main function of acid catalysis during CNC preparation is to re-
move the amorphous structure of cellulose and produce nano-crystals
by its ability to release hydronium ions for hydrolytic cleavage of gly-
cosidic bonds in cellulose molecular chains within amorphous regions
along the cellulose fibrils (Ng et al., 2015).
However, the main shortcomings of the CNC resulted by acid hy-
drolysis are those: 1) it has low thermal stability and is difficult to be
functionalized due to the presence of sulfate groups (for sulfuric acid-
induced CNC); 2) it has tendency to be aggregated due to the bare
surface charge density (for hydrochloric acid-induced CNC) (Yu et al.,
2013). Furthermore, the potential excessive degradation of cellulose,
large amounts of effluent released from the neutralization stage process
and corrosion hazards of high concentration of strong acid to the
equipment and environment (Chen et al., 2016) are the other draw-
backs of this method.
Solid acid, such as maleic acid, can be utilized to hydrolyze cellulose
to produce CNC (Bian et al., 2017; Espinosa et al., 2013; Lu et al., 2016;
Yeganeh et al., 2017), considering the advantages of maleic acid: 1)
highly safe storage; 2) low transportation cost; 3) environmentally
friendliness and harmless to equipment; 4) maleic acid solution has a
higher boiling point (it can achieve effective acid hydrolysis at tem-
peratures around 100 °C without boiling); 5) possible surface mod-
ification with −COOH during maleic acid hydrolysis. Some studies
have been published to utilize maleic acid as the catalyst to isolate CNC
from cellulose resource, for example, Bian et al. (2017), Chen et al.
(2016), Wang et al. (2017)have successfully produced CNC by using
maleic acid as the catalyst, but all of these experiments showed low
CNC yield (< 10 %), considering the weak acid nature of maleic acid.
Also, the low surface charge density (−COOH) of CNC induced by
maleic acid hydrolysis would cause serious colloidal aggregation during
the storage of CNC colloids. Furthermore, the firm structure of bamboo
pulp fibers that will be applied in this study for CNC preparation would
retard maleic acid molecules penetrating into the fiber structure for
effective cellulose hydrolysis.
Mechanical treatment (i.e., microfluidization, ultrasonication, high-
pressure homogenization, and ball milling) is another alternative
method and has been widely used for the production of cellulose in
nano-size particles. The mechanical method can be used either in
combination or a single method. The advantages of ball mill treatment
are green, simple, high efficiency, no introduction of other groups, etc.,
which has attracted numerous studies on it. Song et al. (2018) used ball
mill treatment as a pretreatment method for oxalic acid hydrolysis. The
resulted products have a relatively high yield of 59 % and the maximum
degradation temperature of 332 ℃. Phanthong et al. (2016) also used
ball mill pretreatment method before sulfuric acid hydrolysis, and they
found that the crystallinity and crystal size of ball-milled cellulose de-
creased with the increase of ball milling time, and the mild acid hy-
drolysis of the ball-milled cellulose resulted in the increasing of crys-
tallinity and thermal stability of CNC at the high-temperature range but
without any changes in chemical structure. Direct production of CNC by
ball mill treatment has also been investigated. Amin et al. (2015) suc-
cessfully prepared CNC with a high aspect ratio and high thermal sta-
bility via High Energy Ball Mill (HEBM) treatment. However, the single
mechanical ball milling without other pre or post treatment would in-
duce CNC products with low crystallinity and high energy consumption
as well (Phanthong et al., 2016; Trachea et al., 2017).
In this work, ball mill pretreatment will be utilized before the
maleic acid hydrolysis of bamboo pulp fibers to enhance the yield and
colloidal stability of CNC. The hypotheses for the study are that: 1) ball
mill pretreatment can break down and open up the structure of bamboo
fibers, thus increasing the accessibility of maleic acid molecules into
amorphous domains and exposing more hydroxyl groups on the surface
of pulp fibers; 2) The maleic acid molecules in the following acid hy-
drolysis can easily react with β-1,4-glucosidic linkages in amorphous
2
Carbohydrate Polymers 234 (2020) 115942
Table 1
Chemical composition of bamboo pulp.
Sample α-cellulose Hemicellulose Lignin Ash
(%) (%) (%) (%)
Bamboo bleached 79.34 ± 2.1 15.10 ± 1.3 0.08 ± 0.003 1.1 ± 0.03
pulp
domains of fibers, releasing more crystalline parts (i.e. CNC) from pulp
fibers (a higher CNC yield); and 3) in addition, the maleic acid anhy-
dride can easily react with the exposed hydroxyl groups to generate
more −COOH groups on the surface of CNC, thus improving the CNC
colloidal stability. SEM, AFM, XRD, FTIR were carried out to char-
acterize the morphology of bamboo fibers and CNC, the crystallinity
and surface functional groups of the CNC, respectively. The yields,
particle size distribution, zeta potential, and colloidal stability analyses
of CNC were also investigated.
2. Materials and methods
2.1. Materials
Bleached bamboo pulp board (air-dried) from native one-year-old
Moso bamboo was obtained from Yibin Paper Co. Ltd., in Sichuan
Province, China. The moisture content of this pulp was 8.56 %. The
chemical composition of bamboo pulp in this experiment was shown in
Table 1 and determined according to the standards provided by Tech-
nical Association of Pulp and Paper Industry (TAPPI). The lignin, α-
cellulose, hemicellulose, and ash contents of the bamboo pulp were
determined according to TAPPI standard methods T222 os-74, T203
cm-99, T223cm-01, and T413 om-93 respectively. The procedures
could also be found in previous studies (Cordeiro et al., 2004; Espino
et al., 2014; Sheltami et al., 2012; Ververis et al., 2004). The sum-
marized chemical analyzed result can be seen in Table 1. Each of the
measurement was calculated from the average of three parallel runs.
Maleic acid was purchased from Nine-Dinn Chemistry (Shanghai) Co.
Ltd. The purity of maleic acid is 99.0 %. Sodium hydroxide was pur-
chased from Tianjin Yongda Chemical Reagent Co. Ltd. Deionized (DI)
water was utilized in the experiment. All other chemicals were of
analytical grade and used without further purification.
2.2. Ball mill pre-treatment
The dried pulp samples were soaked in DI water overnight and
disintegrated using IKA T18 Ultra-turrax homogenizer for about
10 min. The bamboo pulps were separated and diluted into distilled
water for desired concentration (wt %) and the total suspension weight
is 300 g. The prepared pulp suspensions were pretreated in the ball mill
(CSN0.3 from Chile (Shanghai) Mechanical Technology Co., Ltd.), in
which the small balls are made from zirconia with 0.5 mm in diameter
and total ball weight is 350 g. The ball mill processes were carried out
by varying the milling time, speed, and pulp consistency, which have
been listed in Table 2. The Centrifugation process (20 min at
10,000 rpm) was carried out after ball mill pre-treatment followed by
freeze-drying process to obtain the dried treated fiber samples. The
abbreviations of pulp fiber samples after ball mill pretreatment and the
conditions of ball mill pre-treatment are summarized in Table 2.
2.3. Maleic acid hydrolysis process
Maleic acid hydrolysis of bamboo pulp fibers was conducted using
liquor to pulp weight ratio of 100:1 in a maleic acid solution of 75 wt %
concentration at 110 °C for 3 h. The suspensions were constantly mixed
using a mechanical stirrer during the hydrolysis process. Silicone bath
DF-101S from Kenu was used in the hydrolysis process as the heater
F.T. Seta, et al. Carbohydrate Polymers 234 (2020) 115942

Table 2 2.6. Particle size, zeta potential, surface charge, and carboxyl group content
The Abbreviations of Bamboo Fiber Samples after Ball Mill Pretreatment and measurement
the Conditions of Ball Mill Pre-treatment.
Sample Name Condition All the CNC samples were diluted into 0.5 wt % and dispersed under
ultrasonic treatment (Scientz SB-5200DTD) for 20 min before particle
Consistency Speed Time size and zeta potential measurement with DI water as the dispersant, at
(wt %) (rpm) (h)
room temperature (25 °C). Dilute aqueous CNC suspensions were used
BM1 1 1500 1 to measure the particle size by monitoring the scattered light intensity
BM2 1 1500 2 at an angle 90°. The Zeta potential was calculated by measuring the
BM3 1 1500 3 electrophoretic mobility of the suspension and converting the mobility
BM4 1 1500 4
into potential value.
BM5 1 1500 5
BM6 1 1,750 2
Charge densities of the CNC samples were measured using a Mütek
BM7 1 2000 2 PCD 04 Particle Charge Detector based on the colloidal titration
BM8 0.5 1500 2 method. In the colloidal titration, CNC colloids were titrated with
BM9 1.5 1500 2 standard cationic polyelectrolyte [poly (diallyl dimethyl ammonium
chloride) (poly-DADMAC)] (concentration = 0.001 N).
Note: BM stands for Ball Milling.
To measure the carboxyl group content of CNC, 10 g of CNC sus-
pension containing 0.1 wt % of CNC was mixed with 10 mL of 1 mol/mL
source. The reactions were quenched by adding 150 mL of DI water to
NaOH solution and stirred for 30 min at room temperature. The mixture
the suspensions at the end of each reaction. The suspension was washed
then titrated with 1 mol/mL HCl solution. The carboxylic acid content
and centrifuged at 10,000 rpm for 20 min to discard the supernatant
was calculated using the following equation.
and remove the excess acid. The precipitate was then mixed with 30 %
sodium hydroxide solution and distilled water to a total concentration (10·C (NaOH )) − (V ·C (HCl))
COOH Content = (mmol/g CNC)
of 1 wt % and dialyzed in the distilled water for a week or until the pH W
of the dialysis water no longer changed. The dialyzed sample was
Where C was the concentration of NaOH (mol/L) and HCl (mol/L), V
subjected to an ultrasonication at 60 % power for 4 min (4 s on and 8 s
was the volume of HCl required to reach the end of the titration (mL),
off).
and w was the weight of the dry sample (g). The final results were
The resultant cellulose slurry after maleic acid hydrolysis and fol-
calculated from the average of three parallel runs of measurements for
lowing purification process was further centrifuged at 2000 rpm,
error analysis.
3000 rpm for 5 min, and 10,000 rpm for 10 min to separate the small
particles from the cellulose slurry to obtain the supernatant (containing
CNC particles) and precipitation phases (bigger cellulose parts, non- 2.7. Thermogravimetry analyses (TGA)
CNC particles). The dried nanocrystal products were finally obtained by
freeze-drying the supernatant phase. Herein, the prepared CNC samples Thermal stability of bamboo pulp fibers and CNC samples were
derived from bamboo pulp fibers without ball mill pretreatment were tested by Thermogravimetric analysis (TGA) analysis, using a Discovery
noted as CNCB, while CNC samples from ball mill pretreated bamboo SDT650 TGA with temperatures from ambient temperature to 600 °C
pulp fibers were named as CNCBMx, in which x is referred to the sample under a nitrogen steam with a flow rate 20 ml/min and a heating rate of
number of ball mill pretreatment shown in Table 2. 10 °C/min. Approximately 5 mg of sample was used for the TGA test.

2.8. Fourier transform infrared spectroscopy (FTIR) analyses

2.4. CNC yield measurement
CNC Yields were measured by the gravimetric analysis method. The
weight of the final dried CNC sample was designated as M2 and the dry
weight of the initially dried bamboo pulp was determined as M1. The
final yield was calculated from the average of three parallel runs of
measurements for error analysis. The yield of CNC sample was given as
follows:
Each sample was weighed 1 mg approximately, followed by milling
together with 100–200 mg of dried potassium bromide (KBr) powder in
an agate mortar. The mixture powder then pressed by a hydraulic press
at a pressure of 10 MPa for 1 min until a homogeneous thin film was
obtained. The as-prepared thin film was recorded its spectra on an
FTIR-650 (Tianjin Gangdong Science and Technology Development Co.
Ltd.). The spectra were recorded in the range of 4000–650 cm−1.

M2 2.9. Crystallinity analyses

yield (%) = × 100%
M1
To determine the crystallinity index (CrI) of bamboo pulp fibers and
CNC samples, a common method developed by Segal and coworkers
(Park et al., 2010; Segal et al., 1959) was applied. The proposed method
2.5. Scanning electron microscope (SEM) and atomic force microscope
was for empirical measurements to allow the rapid comparison of cel-
(AFM) analyses
lulose samples. CrI was calculated from the ratio of the height of the
002 peaks (I002) and the height of the minimum (IAM). Where I002 is
For the SEM observation of bamboo pulp fibers, pre-weighed sam-
the maximum intensity of the (002) lattice diffraction peak and IAM is
ples were put on a desiccator for overnight at a room temperature. The
the intensity scattered by the amorphous part of the sample. The dif-
samples then mounted on a conductive carbon tape and coated with
fraction peak for plane (002) is located at a diffraction angle of around
gold before the scanning process. The SEM pictures were captured using
2θ = 22.0° and the intensity scattered by the amorphous part was
Oxford instrument with 10 kV beam.
measured as the lowest intensity at a diffraction angle of around
Atomic force microscopy (AFM) observations of CNC samples were
2θ = 18.0°. The crystallinity index (CrI) was determined by using Se-
performed on Multimode Bruker equipment with tapping mode. The
gal's method as stated below:
sample used for AFM imaging was produced by placing a few drops of
CNC with 0.005 % solution (wt %) onto a 1 × 1 cm square of freshly I 002 − I AM
CrI (%) = × 100 %
cleaved mica, then air-dried overnight. I 002

3
F.T. Seta, et al.
Fig. 1. Schematic of CNC preparation via combining ball mill pretreatment and followed by maleic acid hydrolysis for high CNC yield and colloidal stability.
3. Results and discussions
3.1. Schematic of CNC preparation via ball mill pretreatment and following
maleic acid hydrolysis process
Fig. 1 illustrates the schematic of CNC preparation via maleic acid
hydrolysis process facilitated by ball mill pretreatment, in which, the
bamboo pulp fibers are pretreated in ball mill equipment at modified
conditions, therefore, the straight and intact bamboo pulp fibers be-
came shorter and crinkle after going through small balls and suffering
high shear force treatment between balls. The inherent firm structure of
bamboo fibers can be then destroyed and opened up, thus more hy-
droxyl groups will expose on the surface of bamboo fibers. Further-
more, maleic acid molecules can be more accessible into the damaged/
loose fiber structure during the following maleic acid hydrolysis.
As shown in Fig. 1, we proposed a reaction mechanism for the hy-
drolysis of ball-milled bamboo pulp by maleic acid. There are three
functions of the maleic acid during the hydrolysis process: 1) maleic
acid molecules react with β-1,4-glucosidic linkages/hydrogen bonds
between anhydroglucose units in cellulose chains and release cellulose
with small and uniform particle size; 2) maleic acid can hydrolyze the
disordered regions of ball-milled bamboo pulp to release the crystalline
region of the cellulose; and 3) maleic acid can catalyze the esterification
process of hydroxyl groups on the exposed cellulose chains with rich
maleic anhydride anionic groups, thus resulting in good colloidal sta-
bility of the final CNC in aqueous solution.
The hydrolysis mechanism of hemicellulose was similar to cellulose.
Because of the amorphous and heterogeneous structure and lower de-
gree of polymerization of hemicellulose compared with cellulose,
maleic acid molecules will break down hemicellulose easier and faster
to form shorter chained oligomers, thus most of hydrolyzed hemi-
cellulose will be removed during the washing-centrifugation process
and very small amount of hemicellulose will still be remained and
counted as a CNC yield (Hilpmann et al., 2016; Rosli et al., 2013).
Herein, it can be hypothesized that the maleic acid hydrolysis can be
facilitated by the ball mill pretreatment for CNC preparation with
higher CNC yield and colloidal stability. The strong shear and friction
forces from the balls also weaken the inter hydrogen bonds between
fibers (Lin et al., 2019; Piras et al., 2019). In this case, maleic acid
4
Carbohydrate Polymers 234 (2020) 115942
hydrolysis can be more prone to proceed and more beneficial to CNC
preparation. The hypotheses of this study are based on:
1) Ball mill mechanical treatment can open up/ loosen the firm
structure of bamboo fibers, and expose more accessible hydroxyl
groups on it.
2) More maleic acid molecules can be penetrated into the structure of
bamboo fibers, and react with exposed hydroxyl groups to generate
more carboxyl groups on CNC surface.
3) Maleic acid molecules can be more easily to react with β-1,4-glu-
cosidic linkages/ hydrogen bonds between anhydroglucose units in
cellulose chains and release more CNC particles with small and
uniform particle size.
4) CNC derived from the combined method has a higher yield and
colloidal stability compared with the control sample without ball
mill pretreatment.
3.2. Analyses of yields of CNC samples
The yields of CNC samples isolated from different conditions are
shown in Fig. 2. It can be clearly noted that the yield of CNCB with
desirable particle size (has been separated and classified by the given
centrifugation process) that is derived from maleic acid hydrolysis of
bamboo pulp fibers without ball mill pretreatment is only about
2.8 ± 0.36 %, which is comparably low due to the weak acid property
and the poor accessibility of acid molecules into fiber structure (Bian
et al., 2017; Chen et al., 2016; Wang et al., 2017).
It can also be found from Fig. 2 that CNC yields increased from
2.8 ± 0.36–24.50 ± 2.09 % when the milling time increased to 5 h at
1 wt% pulp consistency and 1,500 rpm, which indicated that ball mill
pretreatment can effectively facilitate the following maleic acid hy-
drolysis and enhance the yield of CNC and that the ball milling duration
played a vital role in the process. It may be ascribed to the fact that the
high shears force of ball mill pretreatment can break up the firm
structure of bamboo pulp fibers (Fig. 3), thus increasing the accessi-
bility of maleic acid molecules. Lin et al. (2019) also applied ball mill
pretreatment to open up the structure of microcrystalline cellulose to
make carboxymethyl cellulose, and found that ball mill pretreatment
can help improve the properties of final product and increase the yield
F.T. Seta, et al.
Fig. 2. The yields of CNC samples derived from different conditions.
as well.
In addition, it can also be concluded that the ball milling speed also
facilitated the following acid hydrolysis for higher CNC yield, which
indicated that high ball milling speed would induce high shear force,
thus helping open up the firm fiber structure and improving the ac-
cessibility of maleic acid molecules into bamboo fiber structure.
Interestingly, the higher consistency of bamboo pulp (from 0.5 to 1.5 wt
%) during ball milling pretreatment would lead to a lower CNC yield
(from 18.02 ± 0.75–11.72 ± 0.39 %), which may be due to the
reason that small zirconia balls would have a more sufficient contact
with bamboo pulp fibers when it is in lower pulp concentration. The
excessive and non-uniform high shear force would be induced between
zirconia balls and bamboo pulp fibers when it is in high pulp con-
sistency, thus resulting in low milling efficiency of ball mill
Fig. 3. AFM images of (a): CNC samples hydrolyzed from bamboo pulp fibers without ball mill pretreatment (CNCB, 0.005 wt%); (b) (c) and (d): CNC samples
(0.005 wt%) hydrolyzed from bamboo pulp fibers with different ball mill pretreatment conditions (CNCBM1, CNCBM5 and CNCBM8).
5
Carbohydrate Polymers 234 (2020) 115942
pretreatment. It can also be evidenced from the literature, in which
showed that ball mill treatment can effectively cause the morphology
changes of a majority of substrate (Ogi et al., 2017).
3.3. Analyses of AFM images of CNC samples
AFM images of CNC samples are shown in Fig. 3. It indicated that
CNC derived from bamboo pulp fibers without ball mill pretreatment
(CNCB, Fig. 3(a)) showed a more aggregated CNC dispersion and vague
CNC outline, compared with that of (c) CNCBM5 and (d) CNCBM8
samples. In addition, particle size of CNCB sample was in a wide dis-
tribution, which means maleic acid hydrolysis without ball mill pre-
treatment just produced uneven CNC particle size. It can be hypothe-
sized that once the ball mill pretreatment was utilized before maleic
acid hydrolysis, the treated bamboo pulp with opened up fiber would
let more maleic acid molecules access into its broken and loose struc-
ture and isolate more CNC particles with carboxyl groups, compared the
AFM images of Fig. 3(b)–(a). It was also indicated that CNCBM5 had a
desirable CNC particle size with a width of ca. 15 nm and length of ca.
150 nm, and uniform distribution, which demonstrated that ball milling
pretreatment can effectively facilitate the following maleic acid hy-
drolysis for CNC preparation with high yield and colloidal stability. If
we reduce the mill duration from 5 to 2 h and the pulp concentration
from 1 to 0.5 wt % (as shown in Table 2), CNC colloid with high yield
and uniform particle size/distribution can also be obtained (CNCBM8)
compared with those of CNCBM5. Similar conclusions can also be
identified from the yields and photographs analyses of CNC samples.
3.4. Analyses of SEM images of bamboo pulp fibers
The morphological structure changes of bamboo pulp fibers after
ball mill pre-treatment are shown in Fig. 4. It was illustrated that
bamboo pulp fibers without ball mill pre-treatment have a smooth
surface and stiff structure (Fig. 4(a), (b)), thus would impede the ac-
cessibility of maleic acid molecules into fiber structure, which would
lead to an insufficient hydrolysis and less CNC releasing (Figs. 2 and 5).
Hence, ball mill mechanical treatment can effectively destroy/ open up
F.T. Seta, et al. Carbohydrate Polymers 234 (2020) 115942

Fig. 4. SEM images of (a) pristine bamboo pulp fibers; (b) enlarged image from (a); (c) ball mill treated fibers (BM2, 1 wt %, 1500 rpm, 2 h); (d) ball mill treated fibers
(BM6, 1 wt %, 1750 rpm, 2 h); (e) ball mill treated fibers (BM7, 1 wt %, 2000 rpm, 2 h); and (f) ball mill treated fibers (BM9, 1.5 wt %, 1500 rpm, 2 h).

the firm structure of bamboo fibers (Fig. 4(c)–(f)), thus increasing the and (f) that high fiber concentration would increase the friction and
accessibility of maleic acid molecules and exposing more hydroxyl shear force between fibers, thus improving the ball milling pretreat-
groups on the surface of bamboo fibers. It has been reported that the ment and further destroying the fiber structure (Gotor et al., 2013).
morphology changes on the fibers and the decrease of fiber size after
ball milling can facilitate the fiber swelling in aqueous solvent
3.5. Analyses of particle size, zeta potential, surface charge, and carboxyl
(Nuruddin et al., 2016). In addition, bamboo fibers were crushed and
content group of CNC samples
milled into smaller parts, with a decrease in length and width, in-
dicating that the milling pretreatment can also break the cellulose
The CNC colloidal stability was determined by Zeta potential, par-
crystallites along the direction perpendicular to the crystallite axis
ticle charge density measurement, and sedimentation test. The average
(Zheng et al., 2018).
length and Zeta potential of CNC samples derived from various ball mill
It can also be concluded that the ball milling duration, speed and
pretreatment and maleic acid hydrolysis are listed in Fig. 5(a). CNC
pulp consistency play a vital role in the morphology in bamboo struc-
sample without ball milling process (CNCB) showed the highest nega-
ture, as shown in Figs. 4(c)–(f) and S1. After 2 h of ball milling, bamboo
tive value (-8.66 ± 0.27 mV), while CNCBM5 sample had a lowest Zeta
fibers began to have a distinct morphology change compared to the
potential of -36.58 ± 0.77 mV after 5 h of ball mill pretreatment.
control. The longer milling duration and higher speed of ball mill
Herrera et al. (2018) also reported that cellulose nanocrystals would
pretreatment would produce a higher mechanical shear force and in-
aggregate together if its zeta potential within the range of -30 to 30 mV.
duce a decreased particle size and reduced crystallinity of bamboo fi-
In addition, the lengths of CNC particles shown in Fig. 5(a) were well
bers, which can be supported by the previous reports (Lin et al., 2019;
consistent with those of Fig. 3. Hence, it can be seen that ball mill
Piras et al., 2019). Interestingly, after 5 h of ball milling (Fig. S1(f)),
pretreatment can effectively improve the Zeta potential of CNC colloids,
fiber size was decreased into micro scale and the re-aggregation phe-
along with the decreased particle size of CNC samples, compared to the
nomenon of tiny fibers happened. The results were possibly caused by
results of CNCB, CNCBM1, CNCBM2, and CNCBM3 etc. samples, in-
the activation/ interactions of fiber surfaces generated by milling pro-
dicating that ball milling duration have a positive effect on the Zeta
cess (Ogi et al., 2017; Zheng et al., 2018). It was found from Fig. 4(c)
potential and particle size of CNC samples.

6
F.T. Seta, et al.
It should be noted that CNCBM5 sample has a highest yield and
lowest zeta potential as well as desirable and uniform particle size,
compared with other CNC samples. Besides milling duration, milling
speed and pulp concentration also has a vital effect on the final prop-
erties of CNC. If the pulp concentration for milling process was in-
creased from 1 to 1.5 wt %, the yield of CNCBM9 decreased accordingly
(Fig. 2), along with the increased particle size and decreased zeta po-
tential, which may be ascribed to the fact that: high pulp concentration
can induce high shear force and inhomogeneous milling treatment be-
tween pulp fibers and zirconia beads.
Fig. 5(b) shows the carboxyl group contents and surface charge
densities of several typical CNC samples, i.e., CNCB, CNCBM2, CNCBM5,
and CNCBM7. It can be clearly noted that ball milling process can sig-
nificantly increase the surface charge density of CNC samples, and that
carboxyl groups from esterification reaction induced by maleic acid
hydrolysis mainly contributed to the charge density (Hoeng et al.,
2015). Higher charge density would lead to a higher CNC colloidal
stability, as shown in Fig. 5(c) and (d). The photograph of CNCBM4 (B,
0.1 wt %) and CNCBM7 (C, 0.1 wt %) colloid samples showed perfect
high colloidal stability after standing 5 days, while the photograph of
CNCB sample (A, 0.1 wt %) displayed aggregation phenomenon, which
was ascribed to the low surface charge density.
3.6. TGA analyses of bamboo fibers and CNC samples
The TGA spectra of raw bamboo pulp, ball-milled bamboo pulp and
CNC samples are shown in Fig. 6. It was noted that all samples illu-
strated same thermal degradation trend and had an initial amount of
weight loss at the temperature below 100 °C with a mass loss about 10
% because of the evaporation of absorbed water on the surfaces of
sample (Santos et al., 2013; Tan et al., 2015). DTG curves showed that
all samples have a one-step pyrolysis process, which was in good ac-
cordance with the work done by Yu and his coworkers (Yu et al., 2013).
The weight loss of the pulp fiber was ascribed to the cellulose
7
Carbohydrate Polymers 234 (2020) 115942
Fig. 5. (a) The particle size and zeta
potential results of CNC samples; (b)
the carboxyl group content and surface
charge density of CNCB, CNCBM2,
CNCBM5 and CNCBM7; (c) the photo-
graph of CNCB (A, 0.1 wt %), CNCBM4
(B, 0.1 wt %) and CNCBM7 (C, 0.1 wt
%) colloid samples and (d) the photo-
graph of corresponding CNC colloid
samples after standing 5 days.
degradation of depolymerization, dehydration, or decomposition of
glycosyl units followed by the formation of charred residue (Song et al.,
2018).
Decomposition curves of raw bamboo pulp had a higher tempera-
ture range of 288−382 °C and weight loss of almost 90 % than that of
ball-milled bamboo (BM7) (272−367 °C, weight loss of 70 %). While
CNC samples from ball-milled bamboo pulp (CNCBM7) had a lower
decomposition temperature range of 200−365 °C and a lower weight
loss of 65 % than that of CNCB sample (219−366 °C, weight loss of 80
%). The lower onset decomposition temperature of BM and CNCBM7
sample might due to the breakdown of some crystalline regions (can be
seen in XRD result) during the ball milling process (Nuruddin et al.,
2016). In addition, it was found from Fig. 6(b) that the derivative
weight loss (%/°C) of CNCBM7 sample had a lower level but a higher
amount of char residue, compared to other three samples, indicating
that CNC sample derived from ball milling process and maleic acid
hydrolysis had a higher thermal stability, which is consistent with the
previous literature (Phanthong et al., 2016; Sofla et al., 2016).
3.7. FTIR analyses of bamboo fibers and CNC samples
FTIR spectra of the pristine bamboo pulp, ball-milled bamboo pulp,
and CNC samples (CNCB and CNCBM3) are shown in Fig. 7. All spectra
possessed the same absorption peaks at around 3400, 2900, 1420,
1330, 1045 cm−1, which are associated with the native cellulose type I
(An et al., 2016; Phanthong et al., 2016). It can be clearly seen that BM3
sample has a same FTIR spectra with raw bamboo pulp when compared
with Figure (a) and (b), indicating that the ball milling process cannot
change the chemical structure/ composition of cellulose fibers. The
absorbance peaks observed in the 1,045–1,160 cm−1 range were at-
tributed to CeO stretching and C–H rocking vibrations of the pyranose
ring skeleton. The peaks observed in the range of 1420 cm−1 and
1330 cm−1 in all spectra were attributed to the symmetric bending of
CH2 and the bending vibrations of the C–H and CeO groups of the
F.T. Seta, et al.
Fig. 6. (a) TGA and (b) DTG curves of (1) bamboo pulp fibers, (2) CNC sample derived from maleic acid hydrolysis without ball mill pretreatment (CNCB), (3) ball
milled bamboo pulp fibers (BM7), and (4) CNC sample from the combined method (CNCBM7), respectively.
Fig. 7. FTIR spectra of (a) raw bamboo pulp, (b) ball milled bamboo pulp
(BM3), (c) CNC from raw bamboo pulp (CNCB), and (d) CNC from ball milled
bamboo pulp (CNCBM3).
aromatic rings in polysaccharides. The absorbance peaks in the
3400 cm−1 and 1640 cm−1 regions are attributed to the stretching and
bending vibrations, respectively, of the OH groups of cellulose. The
peak at 2900 cm−1 is corresponded to C–H stretching.
It can be noted that the CNCB and CNCBM3 samples demonstrated
two new peaks at around 1730 cm−1 and 1580 cm-1 as shown in Figure
(c) and (d), which were regarded as ester carbonyl groups (C]O) and
alkenes functional group (C]C), respectively, indicating that maleic
acid hydrolysis process has successfully endowed ester carbonyl groups
and alkenes functional groups on the surface of CNC (Chen et al., 2016).
It was also observed that CNCBM3 has a stronger absorbance of car-
boxyl group than CNC sample without ball mill pre-treatment, in-
dicating that ball mill pretreatment can facilitate the following maleic
acid for higher −COOH content, which is responsible for the higher
CNC colloidal stability shown in Fig. 5.
3.8. Crystallinity analyses of bamboo pulp fibers and CNC samples
The crystallinity of raw bamboo pulp, ball-milled bamboo pulp, and
the resulted CNC was measured and determined by X-ray diffraction
(XRD), which is shown in Fig. 8. The XRD patterns of Fig. 1(a) bamboo
pulp fiber, 1(b) ball milled pulp fiber and 1(c) contained three
8
Carbohydrate Polymers 234 (2020) 115942
characteristic peaks at 2θ = 14.8° (101), 16.4° (10Ī) and 22.5° (002),
which are attributed to cellulose I, indicating that ball milling process
cannot change the characteristic XRD peaks of cellulose. Comparing
with the crystallinity of bamboo pulp, BM5 and BM8 inserted in
Fig. 8(1), the crystallinity of the all ball-milled bamboo pulp decreased
with the increase of milling time and the rotation speed of ball mill,
which can be ascribed to the fact that ball milling process can destroy/
decrease the crystalline structure of bamboo fibers (Feng et al., 2004).
As shown in Fig. 8(2), it is noted that maleic acid hydrolysis for CNC
preparation can lead to improved crystallinity because of the removal
of the amorphous regions of cellulose (Kang et al., 2018), and that CNC
samples from ball milled bamboo pulp fibers (CNCBM5 and CNCBM8)
can have a higher crystallinity, thanks to the high accessibility of maleic
acid molecules into cellulose fiber and high hydrolysis efficiency fa-
cilitated by ball mill pretreatment.
4. Conclusions
In this study, ball mill pretreatment was utilized on the bamboo
pulp fibers before maleic acid hydrolysis to prepare cellulose nano-
crystals (CNC) with higher yield and colloidal stability. Here, ball mill
pre-treatment can break down and open up the firm structure of
bamboo pulp fibers, thus facilitating the following maleic acid hydro-
lysis. It was found that ball mill pretreatment combined with maleic
acid hydrolysis can effectively isolate CNC products from bleached
bamboo pulp with a higher yield (10.55 %–24.50 %) than that of the
CNC sample without ball mill pretreatment (2.80 ± 0.36 %). The ball
mill pretreated cellulose fibers showed a smaller size which can pro-
mote the following acid hydrolysis to obtain the desirable rod-shape
CNC particles with a length of 105.6–223.8 nm. The photographs, FTIR,
charge density, zeta potential, and carboxyl group content analyses
showed that ball mill pre-treatment can facilitate the following maleic
acid hydrolysis of bamboo pulp fibers for CNC preparation. The study
designs a facile and green approach to prepare CNC from bamboo fibers
by maleic acid hydrolysis with high yield and colloidal stability of CNC
and paves a possible way for industrialization of CNC production.
CRediT authorship contribution statement
Frederikus Tunjung Seta: Data curation, Methodology, Software,
Visualization, Writing - original draft. Xingye An: Conceptualization,
Methodology, Software, Supervision, Validation, Writing - review &
editing. Liqin Liu: Software, Data curation. Hao Zhang: Software, Data
curation. Jian Yang: Software, Data curation. Wei Zhang: Resources,
Software, Data curation. Shuangxi Nie: Software, Data curation,
Writing - review & editing. Shuangquan Yao: Software, Data curation.
F.T. Seta, et al.
Fig. 8. (1) XRD spectra of (a) raw materials; (b) ball milled pulp (BM5, 1 wt %, 1500 rpm, 5 h); (c) ball milled pulp (BM8, 0.5 wt %, 1500 rpm, 2 h); (2) XRD spectra of
(a) CNC from raw materials (CNCB); (b) CNC from BM5 (CNCBM5); (c) CNC from BM8 (CNCBM8).
Haibing Cao: Software, Data curation. Qingliang Xu: Software, Data
curation. Yifan Bu: Software, Data curation. Hongbin Liu: Project
administration, Supervision.
Acknowledgments
The authors would like to acknowledge the financial support from
the National Key Research and Development Plan (Grant
2017YFB0307902), the Natural Science Foundation of Tianjin (Grant:
19JCQNJC05400), the State Scholarship Fund for Post-Doctoral Fellow
(PDF) from China Scholarship Council (CSC), the National Natural
Science Foundation of China (Grant: 31670589), the basic scientific
research operation foundation of Tianjin University of Science and
Technology (Grant: 000040186), the research fund of Tianjin Key
Laboratory of Pulp & Paper, China (Grant: 201806), the research fund
of Zhejiang JingXing Paper Joint Stock Co., Ltd (Grant: 21843), and the
Opening Project of Guangxi Key Laboratory of Clean Pulp &
Papermaking and Pollution Control, Nanning 530004, P. R. China
(Grant: KF201815-4).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.carbpol.2020.115942.
References
Abushammala, H., Krossing, I., & Laborie, M.-P. (2015). Ionic liquid-mediated technology
to produce cellulose nanocrystals directly from wood. Carbohydrate Polymers, 134,
609–616.
Amin, K. N. M., Annamalai, P. K., Morrow, I. C., & Martin, D. (2015). Production of
cellulose nanocrystals via a scalable mechanical method. Royal Society of Chemistry,
5(70), 57133–57140.
An, X., Wen, Y., Cheng, D., Zhu, X., & Ni, Y. (2016). Preparation of cellulose nano-crystals
through a sequential process of cellulase pretreatment and acid hydrolysis. Cellulose,
23(4), 2409–2420.
An, X., Long, Y., & Ni, Y. (2017). Cellulose nanocrystal/hexadecyltrimethylammonium
bromide/ silver nanoparticle composite as a catalyst for reduction of 4-nitrophenol.
Carbohydrate Polymers, 156, 253–258.
Bian, H., Chen, L., Dai, H., & Zhu, J. Y. (2017). Effect of fiber drying on properties of
lignin containing cellulose nanocrystals and nanofibrils produced through maleic
acid hydrolysis. Cellulose, 24(10), 4205–4216. https://doi.org/10.1007/s10570-017-
1430-7.
Brito, B. S. L., Pereira, F. V., Putaux, J.-L., & Jean, B. (2012). Preparation, morphology
and structure of cellulose nanocrystals from bamboo fibers. Cellulose, 19(5),
1527–1536. https://doi.org/10.1007/s10570-012-9738-9.
Bystriakova, N., & Kapos, V. (2006). Bamboo diversity: The need for a red list review.
Biodiversity, 6(4), 12–16.
Cantero, D. A., Bermejo, M. D., & Cocero, M. J. (2015). Governing chemistry of cellulose
hydrolysis in supercritical water. ChemSusChem, 8(6), 1026–1033. https://doi.org/
9
Carbohydrate Polymers 234 (2020) 115942
10.1002/cssc.201403385.
Chen, L., Zhu, J. Y., Baez, C., Kitin, P., & Elder, T. (2016). Highly thermal-stable and
functional cellulose nanocrystals and nanofibrils produced using fully recyclable
organic acids. Green Chemistry, 18(13), 3835–3843. https://doi.org/10.1039/
c6gc00687f.
Chen, X., Deng, X., Shen, W., & Jiang, L. (2012). Controlled enzymolysis preparation of
nanocrystalline cellulose from pretreated cotton fibers. BioResources, 7(3),
4237–4248.
Cheng, M., Qin, Z., Chen, Y., Hu, S., Ren, Z., & Zhu, M. (2017). Efficient extraction of
cellulose nanocrystals through hydrochloric acid hydrolysis catalyzed by inorganic
chlorides under hydrothermal conditions. ACS Sustainable Chemistry & Engineering,
5(6), 4656–4664. https://doi.org/10.1021/acssuschemeng.6b03194.
Cordeiro, N., Belgacem, M. N., Torres, I. C., & Moura, J. C. V. P. (2004). Chemical
composition and pulping of banana pseudo-stems. Industrial Crops and Products,
19(2), 147–154.
Du, L., Wang, J., Zhang, Y., Qi, C., Wolcott, M. P., & Yu, Z. (2017). A co-production of
sugars, lignosulfonates, cellulose, and cellulose nanocrystals from ball-milled woods.
Bioresource Technology, 238, 254–262. https://doi.org/10.1016/j.biortech.2017.03.
097.
Elazzouzi-Hafraoui, S., Nishiyama, Y., Putaux, J.-L., Heux, L., Dubreuil, F., & Rochas, C.
(2008). The shape and size distribution of crystalline nanoparticles prepared by acid
hydrolysis of native cellulose. Biomacromolecules, 9, 57–65. https://doi.org/10.1021/
bm700769p.
Espino, E., Cakir, M., Domenek, S., Román-Gutiérrez, A. D., Belgacem, & Bras, N. J.
(2014). Isolation and characterization of cellulose nanocrystals from industrial by-
products of Agave tequilana and barley. Industrial Crops and Products, 62(2014),
552–559.
Espinosa, S. C., Kuhnt, T., Foster, E. J., & Weder, C. (2013). Isolation of thermally stable
cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromolecules, 14(4),
1223–1230. https://doi.org/10.1021/bm400219u.
Feng, Y. T., Han, K., & Owen, D. R. J. (2004). Discrete element simulation of the dynamics
of high energy planetary ball milling processes. Materials Science and Engineering,
815–819. https://doi.org/10.1016/j.msea.2003.10.162.
George, J., & Sabapathi, S. N. (2015). Cellulose nanocrystals: Synthesis, functional
properties, and applications. Nanotechnology, Science and Applications, 8, 45–854.
https://doi.org/10.2147/NSA.S64386.
Gotor, F. J., Achimovicova, M., Real, C., & Balaz, P. (2013). Influence of the milling
parameters on the mechanical work intensity in planetary mills. Powder Technology,
233, 1–7. https://doi.org/10.1016/j.powtec.2012.08.031.
Herrera, M., Thitiwutthisakul, K., Yang, X., Rujitanaroj, P., Rojas, R., & Berglund, L.
(2018). Preparation and evaluation of high-lignin content cellulose nanofibrils from
eucalyptus pulp. Cellulose, 25(5), 3121–3133.
Hilpmann, G., Becher, N., Pahner, F.-A., Kusema, B., Mäki-Arvela, P., Lange, R., Murzin,
D. Y., & Salmi, T. (2016). Acid hydrolysis of xylan. Catalysis Today, 259(2), 376–380.
Hoeng, F., Denneulin, A., Neuman, C., & Bras, J. (2015). Charge density modification of
carboxylated cellulose nanocrystals for stable silver nanoparticles suspension pre-
paration. Journal of Nanoparticle Research. https://doi.org/10.1007/s11051-015-
3044-z.
Hong, B., Chen, F., & Xue, G. (2016). Preparation and characterization of cellulose na-
nocrystals from bamboo pulp. Cellulose Chemistry and Technology, 50(2), 225–231.
Huang, Y., Fei, B., Wei, P., & Zhao, C. (2016). Mechanical properties of bamboo fiber cell
walls during the culm development by nanoindentation. Industrial Crops and Products,
92, 102–108.
Isogai, A., & Zhou, Y. (2019). Diverse nanocelluloses prepared from TEMPO-oxidized
wood cellulose fibers: Nanonetworks, nanofibers, and nanocrystals. Current Opinion in
Solid State & Materials Science. https://doi.org/10.1016/j.cossms.2019.01.001.
Kang, X., Kuga, S., Wang, C., Zhao, Y., Wu, M., & Huang, Y. (2018). Green preparation of
cellulose nanocrystal and its application. ACS Sustainable Chemistry & Engineering,
F.T. Seta, et al.
6(3), 2954–2960. https://doi.org/10.1021/acssuschemeng.7b02363.
Li, W., Wang, R., & Liu, S. (2011). Nanocrystalline cellulose prepared from softwood kraft
pulp via ultrasonic-assisted acid hydrolysis. BioResources, 6(4), 4271–4281. https://
doi.org/10.15376/biores.6.4.4271-4281.
Lin, X., Guo, X., Xu, C., & Wu, M. (2019). Carboxymethyl cellulose assisted mechanical
preparation of cellulose nanocrystals with high yield. Cellulose, 26, 5227–5236.
Lu, H.-F., Cai, C.-J., Zeng, X.-S., Campbell, D. E., Fan, S.-H., & Liu, G.-L. (2018). Bamboo
vs. crops: An integrated emergy and economic evaluation of using bamboo to replace
crops in south Sichuan Province, China. Journal of Cleaner Production, 177, 464–473.
Lu, Q., Cai, Z., Lin, F., Tang, L., Wang, S., & Huang, B. (2016). Extraction of cellulose
nanocrystals with a high yield of 88% by simultaneous mechanochemical activation
and phosphotungstic acid hydrolysis. ACS Sustainable Chemistry & Engineering, 4(4),
2165–2172. https://doi.org/10.1021/acssuschemeng.5b01620.
Lu, Z., Fan, L., Zheng, H., Lu, Q., Liao, Y., & Huang, B. (2013). Preparation, character-
ization and optimization of nanocellulose whiskers by simultaneously ultrasonic
wave and microwave assisted. Bioresource Technology, 146, 82–88. https://doi.org/
10.1016/j.biortech.2013.07.047.
Mahmud, M. M., Perveen, A., Jahan, R. A., Matin, M. A., Wong, S. Y., Li, X., & Arafata, M.
T. (2019). Preparation of different polymorphs of cellulose from different acid hy-
drolysis medium. International Journal of Biological Macromolecules, 130, 969–976.
https://doi.org/10.1016/j.ijbiomac.2019.03.027.
Mandal, A., & Chakrabarty, D. (2011). Isolation of nanocellulose from waste sugarcane
bagasse (SCB) and its characterization. Carbohydrate Polymers, 86(3), 1291–1299.
Meillisa, A., Woo, H. C., & Chun, B. S. (2015). Production of monosaccharides and bio-
active compounds derived from marine polysaccharides using subcritical water hy-
drolysis. Food Chemistry, 171, 70–77. https://doi.org/10.1016/j.foodchem.2014.08.
097.
Moon, R. J., Martini, A., Nairn, J., Simonsen, J., & Youngblood, J. (2011). Cellulose
nanomaterials review: Structure, properties and nanocomposites. Chemical Society
Reviews, 40(7), https://doi.org/10.1039/c0cs00108b.
Nayak, L., & Mishra, S. P. (2016). Prospect of bamboo as a renewable textile fiber, his-
torical overview, labeling, controversies and regulation. Fashion and Textiles, 3(2).
Ng, H.-M., Sin, L. T., Tee, T.-T., Bee, S.-T., Hui, D., Low, C.-Y., & Rahmat, A. R. (2015).
Extraction of cellulose nanocrystals from plant sources for application as reinforcing
agent in polymers. Composites Part B Engineering. https://doi.org/10.1016/j.
compositesb.2015.01.008.
Novo, L. P., Bras, J., Garcia, A., Belgacem, M. N., & Curvelo, A. A. S. (2015). Subcritical
water: A method for green production of cellulose nanocrystals. ACS Sustainable
Chemistry & Engineering, 3(11), 2839–2846.
Nuruddin, M., Hosur, M., Uddin, M. J., Baah, D., & Jeelani, S. (2016). A novel approach
for extracting cellulose nanofibers from lignocellulosic biomass by ball milling
combined with chemical treatment. Journal of Applied Polymer Science, 133(9),
https://doi.org/10.1002/app.42990.
Ogi, T., Zulhijah, R., Iwaki, T., & Okuyama, K. (2017). Recent progress in nanoparticle
dispersion using bead mill. KONA Powder and Particle Journal, 34, 3–23. https://doi.
org/10.14356/kona.2017004.
Park, S., Baker, J. O., Himmel, M. E., Parilla, P. A., & Johnson, D. K. (2010). Cellulose
crystallinity index: Measurement techniques and their impact on interpreting cellu-
lase performance. Biotechnology for Biofuels, 3(10).
Phanthong, P., Guan, G., Ma, Y., Hao, X., & Abudula, A. (2016). Effect of ball milling on
the production of nanocellulose using mild acid hydrolysis method. Journal of the
Taiwan Institute of Chemical Engineers, 60, 617–622. https://doi.org/10.1016/j.jtice.
2015.11.001.
Piras, C. C., Fern´andez-Prieto, S., & Borggraeve, W. M. D. (2019). Ball milling: A green
technology for the preparation and functionalisation of nanocellulose derivatives.
Nanoscale Advances. https://doi.org/10.1039/c8na00238j.
Pirich, C. L., Picheth, G. F., Machado, J. P. E., Sakakibara, C. N., Martin, A. A., de Freitas,
R. A., & Sierakowski, M. R. (2019). Influence of mechanical pretreatment to isolate
cellulose nanocrystals by sulfuric acid hydrolysis. International Journal of Biological
Macromolecules, 130, 622–626. https://doi.org/10.1016/j.ijbiomac.2019.02.166.
Rohaizu, R., & Wanrosli, W. D. (2017). Sono-assisted TEMPO oxidation of oil palm lig-
nocellulosic biomass for isolation of nanocrystalline cellulose. Ultrasonics
Sonochemistry, 34, 631–639. https://doi.org/10.1016/j.ultsonch.2016.06.040.
Rosli, N. A., Ahmad, I., & Abdullah, I. (2013). Isolation and characterization of cellulose
nanocrystals from Agave angustifolia fibre. BioResources, 8(2), 1893–1908.
Santos, R. M., Neto, W. P. F., Silvério, H. A., Martins, D. F., Dantas, N. O., & Pasquini, D.
(2013). Cellulose nanocrystals from pineapple leaf, a new approach for the reuse of
10
Carbohydrate Polymers 234 (2020) 115942
this agro-waste. Industrial Crops and Products, 50, 707–714. https://doi.org/10.1016/
j.indcrop.2013.08.049.
Segal, L., Creely, J. J., Martin, A. E., & Conrad, C. M. (1959). An empirical method for
estimating the degree of crystallinity of native cellulose using the X-ray dif-
fractometer. Textile Research Journal. https://doi.org/10.1177/
004051755902901003.
Sheltami, R. M., Abdullah, I., Ahmad, I., Dufresne, A., & Kargarzadeh, H. (2012).
Extraction of cellulose nanocrystals from mengkuang leaves (Pandanus tectorius).
Carbohydrate Polymers, 88(2), 772–779.
Sinha, A., Martin, E. M., Lim, K.-T., Carrier, D. J., Han, H., Zharov, V. P., & Kim, J.-W.
(2015). Cellulose nanocrystals as advanced "Green" materials for biological and
biomedical engineering. Journal of Biosystems Engineering, 40(4), 373–393. https://
doi.org/10.5307/jbe.2015.40.4.373.
Sofla, M. R. K., Brown, R. J., Tsuzuki, T., & Rainey, T. J. (2016). A comparison of cellulose
nanocrystals and cellulose nanofibres extracted from bagasse using acid and ball
milling methods. Advances in Natural Sciences Nanoscience and Nanotechnology, 7(3),
https://doi.org/10.1088/2043-6262/7/3/035004.
Song, K., Ji, Y., Wang, L., Wei, Y., & Yu, Z. (2018). A green and environmental benign
method to extract cellulose nanocrystal by ball mill assisted solid acid hydrolysis.
Journal of Cleaner Production, 196, 1169–1175. https://doi.org/10.1016/j.jclepro.
2018.06.128.
Sulaiman, H. S., Chan, C. H., Chia, C. H., Zakaria, S., & Jaafar, S. N. S. (2015). Isolation
and fractionation of cellulose nanocrystals from Kenaf core. Sains Malaysiana, 44(11),
1635–1642.
Sun, B., Hou, Q., Liu, Z., & Ni, Y. (2015). Sodium periodate oxidation of cellulose na-
nocrystal and its application as a paper wet strength additive. Cellulose, 22(2),
1135–1146.
Tan, X. Y., Hamid, S. B. A., & Lai, C. W. (2015). Preparation of high crystallinity cellulose
nanocrystals (CNCs) by ionic liquid solvolysis. Biomass & Bioenergy, 81, 584–591.
https://doi.org/10.1016/j.biombioe.2015.08.016.
Tang, Y., Shen, X., Zhang, J., Guo, D., Kong, F., & Zhang, N. (2015). Extraction of cel-
lulose nano-crystals from old corrugated container fiber using phosphoric acid and
enzymatic hydrolysis followed by sonication. Carbohydrate Polymers, 125, 360–366.
Trachea, D., Hussin, M. H., Haafiz, M. K. M., & Thakur, V. K. (2017). Recent progress in
cellulose nanocrystals. Nanoscale, 9(5), 1763–1786. https://doi.org/10.1039/
C6NR09494E.
Ververis, C., Georghiou, K., Christodoulakis, N., Santas, P., & Santas, R. (2004). Fiber
dimensions, lignin and cellulose content of various plant materials and their suit-
ability for paper production. Industrial Crops and Products, 19(3), 245–254.
Wang, R., Chen, L., Zhu, J. Y., & Yang, R. (2017). Tailored and integrated production of
carboxylated cellulose nanocrystals (CNC) with nanofibrils (CNF) through maleic
acid hydrolysis. ChemNanoMat, 3(5), 328–335. https://doi.org/10.1002/cnma.
201700015.
Xua, Y., Salmib, J., Kloser, E., Perrin, F., Grosse, S., Denault, J., & Lau, P. C. K. (2013).
Feasibility of nanocrystalline cellulose production by endoglucanase treatment of
natural bast fibers. Industrial Crops and Products, 51, 381–384.
Yang, J. (2017). Manufacturing of nanocrystalline celluloseMaster’s degree thesis. Espoo:
Aalto University.
Yeganeh, F., Behrooz, R., & Rahimi, M. (2017). The effect of sulfuric acid and maleic acid
on characteristics of nano-cellulose produced from waste office paper. International
Journal Nano Dimension, 8(3), 206–215.
Yu, H., Qin, Z., Liang, B., Liu, N., Zhou, Z., & Chen, L. (2013). Facile extraction of ther-
mally stable cellulose nanocrystals with a high yield of 93% through hydrochloric
acid hydrolysis under hydrothermal conditions. Journal of Materials Chemistry A,
1(12), https://doi.org/10.1039/c3ta01150j.
Yu, M., Yang, R., Huang, L., Cao, X., Yang, F., & Liu, D. (2012). Preparation and char-
acterization of bamboo nanocrystalline cellulose. BioResources, 7(2), https://doi.org/
10.15376/biores.7.2.1802-1812.
Zhang, L., Tsuzuki, T., & Wang, X. (2015). Preparation of cellulose nanofiber from soft-
wood pulp by ball milling. Cellulose, 22(3), 1729–1741. https://doi.org/10.1007/
s10570-015-0582-6.
Zhao, M., Kuga, S., Jiang, S., Wu, M., & Huang, Y. (2016). Cellulose nanosheets induced
by mechanical impacts under hydrophobic environment. Cellulose, 23(5), 2809–2818.
https://doi.org/10.1007/s10570-016-1033-8.
Zheng, Y., Fu, Z., Li, D., & Wu, M. (2018). Effects of ball milling processes on the mi-
crostructure and rheological properties of microcrystalline cellulose as a sustainable
polymer additive. Materials (Basel), 11(7), https://doi.org/10.3390/ma11071057a.