Heliyon 6 (2020) e05486

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Heliyon
journal homepage: www.cell.com/heliyon

Research article

Preparation and characterization of cellulose nanocrystal extracted from

ramie fibers by sulfuric acid hydrolysis
Kusmono *, R. Faiz Listyanda, Muhammad Waziz Wildan, Mochammad Noer Ilman
Department of Mechanical and Industrial Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jalan Grafika No. 2, Yogyakarta, 55281, Indonesia

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

Keywords: Cellulose nanocrystals (CNCs) were isolated from ramie fibers through chemical pretreatments accompanied by
Materials science sulfuric acid hydrolysis. The influences of both temperature and hydrolysis time on the properties of CNCs were
Materials chemistry discussed in the present study. The characterization of CNCs was conducted using FT-IR, XRD, TEM, and TGA. The
Biotechnology
results showed the characteristics of obtained CNCs were influenced significantly by both temperature and time of
Ramie fibers
Cellulose nanocrystal
hydrolysis. The crystallinity, dimensions, and thermal stability of CNCs were found to reduce by increasing both
Sulfuric acid hydrolysis temperature and reaction time of hydrolysis. The optimal hydrolysis parameters were achieved at 45
C for 30
min with 58% sulfuric acid to produce CNCs, rod-like particles with a high crystallinity (90.77%), diameter (6.67
nm), length (145.61 nm), and best thermal stability among all CNCs. The obtained CNCs had a higher potential
for application of alternative reinforcing fillers in the nanocomposites.

1. Introduction cassava bagasse [22], sugar palm fibers [23], apple pomace [3], cotton
pulp [24] and date palm [25]. Ramie fiber is a potential source of cel-
In recent years, cellulose has attracted great interest owing to its lulose to produce CNC due to its high cellulose (72.68%), hemicellulose
unique characteristics such as abundant availability in nature, renew- (13.70%), and very low contents of lignin (0.38%) [26]. In this work, the
able, environmentally friendly, biocompatibility, and cost-effective ramie fiber was chosen as a source of cellulose owing to high cellulose
reinforcement of composites [1]. Cellulose can be obtained from large content and low non-cellulose substances. CNCs prepared from ramie
types of plants, animals, and some bacteria that becoming the most fibers have been reported in several literatures. Habibi et al. [27] pro-
abundant biopolymer on earth [2]. Cellulose nanocrystals (CNCs) are duced CNC from ramie fibers via sulfuric acid hydrolysis (65% (w/w)
high crystalline, defect-free, needle-like particles with an average H2SO4 solution) and combined it with poly (3-caprolactone) (PCL) matrix
diameter of 5–10 nm and an average length of around 100 nm prepared to make PCL/CNC bio-nanocomposite films. They found that both elastic
with the elimination of amorphous parts in cellulose fibers via acid hy- and storage modulus of PCL increased significantly by the presence of
drolysis [3, 4]. CNC is a cellulose-based material that promises to be due CNC. In addition, Habibi et al. [28] prepared CNCs from three different
to its attractive properties including nanometer size, low toxicity, natural fibers such as cotton, sisal, and ramie fibers through sulfuric acid
biocompatibility, biodegradability, excellent mechanical, and optical hydrolysis. In addition, cellulose surfaces model based on CNCs were
properties [4, 5]. Owing to its attractive characteristics, CNC has been produced with the Langmuir-Schaeffer method. They concluded that the
proven to be extensively used in a lot of applications including optical Langmuir-Schaeffer (LS) horizontal deposition method was obtained
apparatuses, regenerative medicine, and as a reinforcement material of appropriate for preparing stable, strong monolayers of CNCs from sisal,
nanocomposites [6]. cotton, and ramie. Recently, cellulose nanofibers produced from ramie
CNCs can be isolated from various agro-industrial wastes. In the fibers by a combined chemical-ultrasonic method were demonstrated by
literature, CNCs have been prepared from many different resources such Syafri et al. [29]. They obtained the cellulose nanofibers with 9.9–89.1
as wheat straw [7], sisal [8], pineapple leaves [9], coconut husk fibers nm in diameter and 1 μm in length, respectively. Although the producing
[10], banana [11], sugarcane bagasse [12], bamboo [13], mengkuang CNCs from ramie fiber has been made by previous researchers, studies on
leaves [14], rice straw [15], cotton linter [16], kenaf bast [17], corn husk the influence of hydrolysis parameters on the characteristics of the
[18], Acacia mangium [19], oil palm fronds [20], doum leaves [21], gained CNCs have not yet been reported.

* Corresponding author.
E-mail address: kusmono@ugm.ac.id (Kusmono).

https://doi.org/10.1016/j.heliyon.2020.e05486
Received 7 March 2020; Received in revised form 28 May 2020; Accepted 6 November 2020
2405-8440/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
Kusmono et al. Heliyon 6 (2020) e05486

Several methods for producing nanocelluloses including cellulose alkali of 1:50 g/ml. The fiber suspension was stirred at 90
C for 2 h with
nanocrystals (CNCs), cellulose nanofibers (CNFs), and bacterial nano- magnetic stirrer. The fibers were rinsed with the distilled water, dried at
celluloses (BNCs) have been used by numerous researchers [2] such as 80
C for 3 h, and finally produced CPC. The illustration of the purifi-
the mechanical method [30, 31], TEMPO oxidative method [32], ionic cation process can be presented in Figure 1.
liquid method [33], enzymatic method [34], combination method
(oxidative or enzymatic and mechanical) [35, 36, 37], sulfuric acid hy-
2.3. Extraction of nanocrystalline cellulose
drolysis [13, 14, 15], hydrochloric acid hydrolysis [38, 39], phosphoric
acid hydrolysis [40, 41], formic acid hydrolysis [42], combined sulfuric
CNCs were produced by sulfuric acid hydrolysis of obtained CPC. Two
acid/oxalic acid hydrolysis [43], mixed sulfuric acid/acetic acid hydro-
hydrolysis parameters (temperature and hydrolysis time) were investi-
lysis [44], FeCl3-catalyzed deep eutectic solvent system (DES) treatment
gated at a constant concentration of 58 wt% and CPC to acid ratio of 1:20
[45], and mixed chemical-ultrasonic treatments [29]. Among all these
under magnetic stirring. Based on our previous studies [49], the optimal
methods, sulfuric acid hydrolysis has been recognized as the method
H2SO4 concentration was achieved at 58% with the highest crystallinity
most widely used for preparing CNCs because the process is simple and
index of 90.77%. The influences of temperatures (45, 55, 65
C) and
results in nanoparticle (100–1000 nm) with highly crystalline and stiff.
reaction times (30, 45, 60 min) of hydrolysis on the properties of CNCs
The extraction of CNC commonly consists of two processes, namely
were studied with a constant sulfuric acid concentration (58 wt%). The
chemical purification and acid hydrolysis [46]. The chemical purification
hydrolysis was conducted using a sulfuric acid solution (58% (w/w), 1:20
was carried out to eliminate non-cellulose contents (wax, lignin, and
g/ml (CPC: dilute sulfuric acid) under different temperatures of 45, 55,
hemicellulose) and produce chemically purified cellulose (CPC). The
and 65
C at a constant time of 30 min. Other hydrolyzes were performed
chemical purification process composes several steps including dewax-
at various hydrolysis times of 30, 45, and 60 min at a constant temper-
ing, bleaching, and alkali treatments [47]. The acid hydrolysis was per-
ature of 45
C and 58% sulfuric acid concentration. Furthermore, the
formed to the CPC to remove amorphous domains. Sulfuric acid
suspension was cooled into cold distilled water (about 5
C) by a ratio of
hydrolysis has become the most extensively used method to isolate CNCs
suspension to the cold water of 1:20 (v/v) to stop hydrolysis. Centrifu-
because it has been proven effective in the elimination of amorphous
gation was conducted at 4000 rpm for 15 min to abolish the acid solution.
components and resulting in stable CNC suspensions [48]. The charac-
CNC precipitates were collected and rinsed with distilled water to neutral
teristics of gained CNCs are strongly influenced by several parameters
condition. The ultra-sonication of CNCs suspension was then performed
including type and concentration of acid, temperature, time, and acid to
for 1 min by a 50% amplitude to obtain the uniform CNC suspensions.
pulp ratio.
Partly CNCs were accumulated for the TEM observation and others were
In this study, CNCs were prepared from ramie fibers by chemical
freeze-dried for FT-IR, XRD, and TGA analysis. The schematic represen-
purification accompanied by sulfuric acid hydrolysis. The chemical pu-
tation of CNCs isolation was displayed in Figure 2.
rification process was performed via de-waxing using toluene and
ethanol solution, bleaching using acidified sodium chlorite, and alkali
treatments. The purified fibers were then hydrolyzed using sulfuric acid 2.4. Characterization
at different conditions. The influences of hydrolysis conditions (tem-
perature and hydrolysis time) on the properties of obtained CNCs were 2.4.1. Fourier transform infrared (FT-IR) spectroscopy
evaluated by FT-IR, XRD, TEM, and TGA. Changes in chemical structures of the samples after the purification
and hydrolysis processes were investigated by FT-IR spectra. FT-IR
2. Experimental spectra were analyzed on an infrared spectrophotometer (IRPrestige21
machine from Shimadzu) at wavenumbers ranging from 400-4000 cm1.
2.1. Materials
2.4.2. X-ray diffraction (XRD)
Dried ramie fibers (Boehmeria nivea) were provided by Balai Pene- The diffraction patterns of untreated ramie fiber, CPC, and CNCs were
litian Tanaman Pemanis dan Serat (Balittas) Malang, East Java, measured in the range 2θ ¼ 10–40
with Emperyan (Malvern PAN-
Indonesia. In our previous results [26], the ramie fibers contained alytical) x-ray diffractometer using Ni-filtered Cu Kα radiation (λ ¼
α-cellulose (72.68%), hemicellulose (13.70%), lignin (0.38%), and 1.5406 Å) at 40 kV and 30 mA. The crystallinity index and crystallite size
others (13.24%). Sulfuric acid with a 96.1% concentration was supplied were analyzed using the diffraction pattern. The crystallinity index was
from Mallinckrodt, Ireland. Toluene (99.9%), sodium chlorite (NaClO2), computed according to the Segal empirical method [50] as in Eq. (1):
acetic acid (100%), and sodium hydroxide (99%) were bought from
ðI200  Iam Þ
Merck, USA. Ethanol (99.5%) was bought from Sigma-Aldrich, USA. CrI ¼  100% (1)
I200
2.2. Purification of cellulose where, I200 is the intensity of crystallites peak at approximately 2θ ¼
22.5
and Iam is the intensity of the amorphous cellulose at 2θ ¼ 18–19
.
Chemically purified cellulose (CPC) was prepared by application of The crystallite size (t) was calculated by the Scherrer equation [51] as in
several chemical pretreatments on the ramie fibers. The amorphous Eq. (2) below:
components of the ramie fibers were released via some chemical pre-
treatments (de-waxing, bleaching, and alkalization) to find chemically Kλ
t¼ (2)
purified cellulose (CPC). Initially, the dried ramie fibers were cut to a β1=2 cos θ
length of about 1 cm, ground, and then sieved into 30 mesh. The ramie
fibers were de-waxed in a Soxhlet equipment with a 2:1 (v/v) mixture of where K (0.91) is the Scherrer constant, λ (1.54060 Å) is the radiation
toluene and ethanol for 20 cycles. After that, the solvent and impurities wavelength, β1/2 is the full width at the half maximum (FWHM) of (200)
were eliminated by washing in 96 wt% alcohol and the fibers were diffraction peak in radians, and θ is the corresponding Bragg's angle.
heated at 80
C for 2 h. The de-waxed fibers were bleached using 0.7%
(w/v) (NaClO2 solution with the incorporation of acetic acid solution 2.4.3. Transmission electron microscopy (TEM)
with a ratio of fiber to acid of 1:50 gr/ml until the pH of 4. This mixture The structure and dimensions of CNCs were characterized using the
was stirred using the magnetic stirrer at 70
C for 1 h and rinsed with the TEM (JEOL type JEM-1400 Electron Microscope, Japan) at of 120–200
distilled water until it achieved the neutral pH. The fibers were then kV. A drop (10 μL) of CNC suspension was placed on the copper grids
treated by alkali using a 2% (w/v) NaOH solution with a ratio of fiber to covered by a carbon layer for examination. The diameter and length of

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Kusmono et al. Heliyon 6 (2020) e05486

Figure 1. Cellulose purification process of ramie fibers.

Figure 2. Isolation process of cellulose nanocrystals.

the CNC particles were determined with ImageJ software from the TEM 3. Results and discussion
images.
3.1. Fourier transform infrared (FT-IR) spectroscopy
2.4.4. Thermogravimetric analysis (TGA)
The thermal properties were analyzed by TGA (LINSEIS machine Figure 3 shows the FT-IR spectra of untreated ramie fibers, CPC, and
Type TA PT 1600) in the temperature range of 30–600
C in the same gained CNCs with variations in temperature and duration of hydrolysis.
heating rate of 10
/min at a flow rate of 4 L/h under the nitrogen All samples showed almost the same spectra showing no changes in their
atmosphere. chemical composition during the purification and hydrolysis of sulfuric

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Kusmono et al. Heliyon 6 (2020) e05486

Figure 3. FTIR spectra of untreated ramie fibers, CPC, and CNCs at various Figure 4. XRD patterns of untreated ramie fibers, CPC, and CNCs under
hydrolysis temperatures and durations. different hydrolysis temperature and duration.

acid. All samples showed similar vibration bands, namely at 3400, 2900, respectively. This indicated that the chemical purification increased the
1635, 1427, 1373, 1056, and 894 cm1. The peaks at 3400 and 1635 crystallinity owing to the dissolving of hemicellulose and lignin [58, 62].
cm1 were related to the stretching and bending vibrations of the OH The crystallinity index of CNCs prepared at various temperatures of 45,
groups of cellulose [52, 53], respectively. The peak at 2900 cm1 was 55, and 65
C was 90.77, 87.99, and 80.32%, respectively. This suggested
attributed to the C–H stretching [54]. The peaks at 1427 cm1 and 1373 that the crystallinity index of CNCs prepared with hydrolysis tempera-
cm1 reflected the symmetric bending of CH2 and the bending vibrations tures of 45 and 55
C was higher compared to that of both untreated
of the C–H and C–O groups of the aromatic rings in polysaccharides, ramie fibers and CPC. The removal of amorphous components due to
respectively [55]. The peak at 1056 cm1 was attributed to the C–O–C sulfuric hydrolysis and structural changes in organization and alignment
pyranose ring (anti-symmetric in phase ring) stretching vibration to produce highly ordered crystal bundles might be responsible for the
whereas the peak at 894 cm1 related to C–H rock vibration of cellulose increased crystallinity index of CNCs [15,63]. However, the crystallinity
(anomeric vibration, specific for β-glucosies) [56]. The untreated ramie index of CNCs hydrolyzed at a temperature above 45
C was reduced.
fibers showed a distinct band appearance compared to others where the This was related to the fact that at the higher temperature, acid hydro-
peak at 1735 cm1 appeared. The peak at 1735 cm1 corresponded to lysis removed amorphous components and also some parts of crystalline
carboxyl groups in the acids and esters of acetic, p-coumatic, ferulic, and accelerating the hydrolytic cleavage of the glycosidic bonds and finally
uronic acids, which were the primary components of extractives and resulted in the decreased crystallinity [64]. Furthermore, the impact of
hemicellulose [54, 57, 58]. The absence of a peak at 1735 cm1 in the hydrolysis time on the crystallinity index is presented in Table 1. The
spectra of CPC and CNCs indicated the elimination of hemicellulose and crystallinity index of CNCs made at various hydrolysis times of 30, 45,
lignin during chemical purification and hydrolysis [14, 23]. Moreover, and 60 min was 90.77, 87.55, and 83.52%, respectively. This indicated
the small shoulder at 811 cm1 was only observed in the CNCs repre- that the crystallinity index reduced as the reaction time increased. This
senting C–O–S group vibration owing to the establishment of sulfate trend is similar to that of increasing the hydrolysis temperature (Table 1).
esters on the CNCs surface during hydrolysis [19,59]. There were no At the reaction time more than 30 min, part of the cellulose crystalline
significant changes in the FT-IR spectra of the gained CNCs after sulfuric domains of CNCs was removed due to corrosion by sulfuric acid and then
acid hydrolysis under different both hydrolysis temperature and time. It resulted in the reduced crystallinity [65, 66]. These findings were also in
means that both hydrolysis temperature and time did not change the line with those found by other researchers [64, 65]. Kargarzadeh et al.
structure of cellulose. Moreover, the intensity of CNCs samples was [65] demonstrated that the optimal reaction time was achieved in 40 min
higher compared to that of both untreated ramie fibers and CPC. The at 45
C with 65% sulfuric acid on the production of CNC from kenaf bast
increased intensity might be related to the increased crystallinity of the fibers. Similar observations were demonstrated by Al-Dulaimi and
fiber after chemical purification and hydrolysis of sulfuric acid [60]. Wanrosli [64] where the optimum hydrolysis time was achieved in 80
min by 58% sulfuric acid concentration on the extraction CNCs from oil
3.2. X-ray diffraction (XRD) palm empty fruit bunches. It is interesting to be concluded that both
temperature and time of hydrolysis influenced the crystallinity of CNCs
The XRD patterns of untreated ramie fibers, CPC, and CNCs prepared and the optimum hydrolysis conditions were achieved under hydrolysis
under different both hydrolysis temperature and time are demonstrated conditions, namely at 45
C for 30 min with 58% sulfuric acid concen-
in Figure 4. All samples displayed peaks at 2θ ¼ 15, 16, 22, and 34
in tration. The highest crystallinity index obtained in this study was 90.77%
accordance with the (110), (110), (200), and (004) crystal planes, and this was a slight higher than that demonstrated by Habibi et al. [28].
respectively, which represented the characteristic of cellulose Iβ struc- CNC with 88% crystallinity index was prepared by Habibi et al. [28]. The
ture [61]. These results showed that the structure characteristics of cel- slight difference was probably due to the slight difference in sulfuric acid
lulose I did not changed by purification and sulfuric acid hydrolysis. The concentration where Habibi et al. [28] used 65% H2SO4 solution in the
crystallinity index of CNCs at different hydrolysis conditions was deter- hydrolysis process. The obtained crystallinity index was much higher
mined using Segal equation (Eq.1) and their results were presented in compared to that declared by Syafri et al. [29] producing cellulose
Table 1. As for control, the crystallinity index of untreated ramie fibers nanofibers from the ramie fibers with 73.65% crystallinity index. This
and CPC were also determined and it was found that the crystallinity difference was associated with the different methods used where Syafri
index of untreated ramie fibers and CPS were 79.75 and 86.68, et al. [29] used mixed chemical-ultrasonic method.

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Kusmono et al. Heliyon 6 (2020) e05486

Table 1. Crystallinity index and crystallite size of CNCs produced under different hydrolysis conditions.

Temperature (
C) Reaction time (min) Sulfuric acid concentration (%) Crystallinity (%) Crystallite size (nm)
45 30 58 90.77 5.33
55 30 58 87.99 4.95
65 30 58 80.32 4.73
45 45 58 87.55 5.22
45 60 58 83.52 4.62

The crystallite size of CNCs made at various hydrolysis conditions was 3.3. Transmission electron microscopy
computed according to the Scherrer equation (Eq. 2) and the results were
summarized in Table 1. The crystallite size of untreated ramie fibers and Figure 5 displays the TEM images of obtained CNCs produced with
CPC was also determined as for comparison and their results were 3.74 and 58% sulfuric acid under different temperatures and durations of hydro-
4.75, respectively. This indicated that the chemical purification increased lysis. It can be seen that all CNCs had a needle-like shape with a nanoscale
the crystallite size of CPC. The increase in CPC crystallite size might be dimension. Figure 5a displays the TEM image of CNC produced under
believed to be mainly owing to the tightening of the crystal size distri- hydrolysis by 58% sulfuric acid solution at 45
C for 30 min whereas
bution by chemical purification [15]. From Table 1, it was also found that Figure 5b presents the TEM image of CNC produced under 58% sulfuric
the crystallite size of CNCs made at various temperatures of 45, 55, and 65 acid solution at 65
C for 30 min. The TEM image of CNC made under


C was 5.33, 4.95, and 4.73 nm, respectively. This exhibited that the hydrolysis by 58% sulfuric acid solution at 45
C for 60 min is displayed
crystallite size of CNCs reduced by increasing hydrolysis temperature. This in Figure 5c. Furthermore, the diameter and length of CNCs particles
trend was similar to the results of the crystallite size of CNCs by increasing were analyzed by ImageJ taken from TEM images (Figure 5). Figure 6a-b
reaction time (Table 1). The crystallite size of CNCs was reduced by exhibits the distribution of diameter and length of CNC made under
increasing reaction time. This trend is similar to the crystallinity index. hydrolysis condition at 45
C for 30 min with 58% sulfuric acid) and it
The decrease in the crystallite size of CNCs with increasing both temper- was found average 6.67 nm in diameter and 145.61 nm in length. This
ature and reaction time during hydrolysis was associated with the stronger result was no significant difference with the result obtained by Habibi
hydrolysis at both higher temperature and reaction time that eliminated et al. [28] which produced CNCs with average 6.5 nm in diameter and
the amorphous components and even portions of the crystalline compo- average 185 nm in length. The diameter and length distributions of CNC
nent producing the reduced crystallite sizes [63]. prepared under hydrolysis by 58% sulfuric acid at 65
C for 30 min are

Figure 5. TEM images of obtained CNCs under different hydrolysis conditions with 58 wt% sulfuric acid at: (a) 45
C for 30 min (b) 65
C for 30 min, and (c) 45
C for
60 min.

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Kusmono et al. Heliyon 6 (2020) e05486

Figure 6. Diameter and length distribution of obtained CNCs under hydrolysis with 58 wt% sulfuric acid at: (a, b) 45
C for 30 min (c, d) 65
C for 30 min, and (e, f)
45
C for 60 min.

shown in Figure 6c-d. The average diameter and length of the CNC were eliminated the amorphous domains and some parts of the crystalline
4.9 nm and 108.78 nm, respectively. This indicated that by increasing domains, which then led to the reduced diameter and length of CNCs
hydrolysis temperature the diameter and length were decreased drasti- [64]. Figure 6e-f displays the classification of diameter and length of CNC
cally. At higher hydrolysis temperature (above 45
C), hydrolysis made at 45
C for 60 min by 58% sulfuric acid. The average diameter and

Figure 7. TGA curves of untreated ramie fibers, CPC, and obtained CNCs under hydrolysis with different (a) temperature and (b) duration.

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Kusmono et al. Heliyon 6 (2020) e05486

Table 2. Initial temperature (Ti), maximum degradation temperature (Tmax) and char yield (Wresidue) for untreated ramie fibers, CPC, and CNCs at various hydrolysis
conditions.
a b
Sample Ti T10 Tmax Wresidue





( C) ( C) ( C) (%)
Untreated ramie fibers 226 99 346 2,9
CPC 271 317 346 0,5
CNC 45
C, 30 min 220 270 320 31
CNC 55
C, 30 min 215 247 274 22
CNC 65
C, 30 min 218 253 304 16
CNC 45
C, 45 min 217 252 276 27
CNC 55
C, 60 min 211 228 263 25

Figure 8. DTG curves of untreated ramie fibers, CPC, and obtained CNCs under hydrolysis with different (a) temperature and (b) duration.

length of the gained CNC were 5.26 nm and 107.02 nm, respectively. was related to the release of some hemicelluloses with lower thermal
Compared to the CNC prepared under at 45
C for 30 min, the CNC hy- stability during the chemical purification, causing thermal stability to
drolyzed for 60 min had a smaller average diameter and length. This drop [70, 71]. Furthermore, the initial temperatures at the main degra-
indicated that the smaller dimension of CNCs was found with increasing dation of CNCs hydrolyzed with 58% sulfuric acid concentration for 30
reaction time. A similar observation was shown by the hydrolysis tem- min with different temperatures of 45, 55, and 65
C were 220, 215, and
perature effect as discussed earlier. 218
C, respectively. This suggested that thermal stability was reduced
with increasing hydrolysis temperature. This was ascribed to more
3.4. Thermogravimetry analysis (TGA) dissolution of crystalline regions of cellulose during hydrolysis at the
higher temperatures (more than 45
C) resulting in reduced crystallinity
Figure 7 shows the thermogravimetry (TG) curve from the untreated and then resulting in decreased thermal resistance. The onset degrada-
ramie fiber, CPC, and CNCs, and their results were displayed in Table 2. tion temperature of CNCs made at various hydrolysis times of 30, 45, and
Figure 7a exhibits the TG curves of CNCs prepared under hydrolysis with 60 min was 220, 217, and 211
C, respectively. A similar effect was also
different temperatures whereas Figure 7b displays the TG curves of CNCs exhibited by the hydrolysis time where the initial temperature at the
prepared under hydrolysis with different reaction times. From Figure 7, main degradation of CNCs was also reduced with an increase of hydro-
all samples depict similar behavior with three regions of thermal lysis time. The Ti values of all CNCs were lower compared to those of
degradation. Region I was 30–220
C that was particularly attributed to untreated ramie fibers and CPC. This indicated that all CNCs displayed
the vaporization of moisture absorbed by all samples with a slight mass lower thermal stability than the untreated ramie fibers and CPC. The
loss [67]. From Figures 7a and 7b, it can be seen that CNC prepared under lower thermal resistance of CNCs was related to the existence of sulfate
hydrolysis at 45
C for 30 min exhibited the lowest water weight loss groups on the CNCs surface that catalyzed degradation [72]. From
among all samples. This was associated with the highest crystalline Table 2, it can also be observed that the thermal resistance of CNC was
content of the CNC. This is consistent with the XRD analysis as discussed found to decrease with the increase of the hydrolysis time. This was due
earlier. Furthermore, all samples exhibited the main stage of thermal to the longer interaction between cellulose and sulfuric acid under hy-
degradation at a temperature range of 220–360
C (Region II). This re- drolysis resulted in more negatively charged sulfate groups on the CNCs
gion showed the highest thermal degradation among all samples and surface resulting in decreased thermal resistance [73, 74]. It was
cellulose experienced stronger depolymerization to produce volatiles concluded that both temperature and hydrolysis time have the same ef-
including carbon monoxide, methane, and carbon dioxide [68]. Region fect in reducing thermal stability. Similar findings were declared by
III was 360–600
C, which particularly demonstrated the further break- Kargarzadeh et al. [65], Li et al. [75], and Haafiz et al. [76] who
down of thermal degradation intermediates, like levoglucosan and coke concluded that the addition of sulfate groups on the CNCs surface
to produce volatile materials such as hydrogen, ethylene, ethane, and tar decreased the thermal resistance due to dehydration reaction.
[69]. Furthermore, changes in thermal stability are also observed at the
From Table 2, it can be found that the initial temperatures (Ti) at the 10% weight loss temperature (T10) as shown in Table 2. The T10 of the
main weight loss of the untreated ramie fibers, CPC, and CNCs were 226, untreated ramie fiber was lower than the CPC and all CNCs samples. The
271, and 211–220
C, respectively. The initial decomposition tempera- lower T10 of the untreated ramie fibers was caused by the high moisture
ture of CPC was higher compared to that of untreated ramie fibers. This content on the raw fibers owing to the existence of hemicellulose. The

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Kusmono et al. Heliyon 6 (2020) e05486

dissolution of hemicellulose after purification increased to 317
C for the (5.81 nm), average diameter (6.67 nm), and average length (145.61 nm).
CPC sample. However, the T10 of all CNCs samples was lower compared Both temperature and reaction time played an important role in the
to that of the CPC caused by the addition of sulfate groups. The highest crystallinity, crystallite size, dimensions, and thermal resistance of CNCs.
value in T10 of the CNCs samples was achieved for CNC hydrolyzed at 45 The crystallinity, crystallite size, dimensions, and thermal resitance of


C for 30 min. The T10 was then decreased as the increase in temperature CNCs were attained to be reduce with the increase of both temperature
and duration. This was ascribed to the removal of some parts of crys- and reaction time of hydrolysis. The results indicated that the obtained
talline during hydrolysis thereby reducing both crystallinity index and CNCs with high crystallinity (90.77%) had high potential as reinforcing
crystallite size as discussed in the XRD test results. According to Haafiz materials for nanocomposites.
et al. [76], the harsher condition of hydrolysis can lead to the dissolution
of the crystalline domain and result in smaller crystallite sizes making it Declarations
more susceptible to elevated temperature.
The decomposition peak temperature (Tmax) for all samples can be Author contribution statement
observed in the DTG curves (Figure 8) and these values are summarized
in Table 2. The major decomposition peaks of untreated ramie fibers and Kusmono: Conceived and designed the experiments; Contributed re-
CPC occurred at a similar temperature of 346
C and it was higher than agents, materials, analysis tools or data; Wrote the paper.
that of CNCs. The higher thermal resistance was probably associated with R. Faiz Listyanda: Performed the experiments.
the higher lignin content in both untreated raw fibers and CPC. Muhammad Waziz Wildan: Analyzed and interpreted the data.
Furthermore, lignin acted as a filler and linked to polysaccharides such as Mochammad Noer Ilman: Contributed reagents, materials, analysis
cellulose by covalent bonds, leading to the CNCs internal structure tools or data.
denser, which enhanced the thermal stability [77]. On the other hand,
CNCs prepared under different temperatures of 45, 55, and 65
C
Funding statement
exhibited major degradation peaks at 320, 274, and 304
C, respectively.
Compared to both untreated ramie fibers and CPC, CNCs showed lower
This work was supported by Universitas Gadjah Mada and Ministry of
thermal stability. Furthermore, the major degradation peaks of CNCs
Research, Technology and Higher Education, Indonesia Government
made at various hydrolysis times of 30, 45, and 60 min were 320, 276,
under Hibah Penelitian Dasar Unggulan Perguruan Tinggi (110/UN1/
and 263
C, respectively. This suggested that the maximum decomposi-
DITLIT/DITLIT/LIT/2018 and 2645/UN1.DITLIT/DIT-LIT/LT/2019).
tion temperature of CNCs reduced by increasing the reaction time of
hydrolysis. Both temperature and reaction time gave a similar effect in
reducing the Tmax of CNCs. This was ascribed to the smaller size CNCs Data availability statement
with increasing both temperature and hydrolysis time as previously
described in TEM images. Smaller CNC particles had a large surface area Data included in article/supplementary material/referenced in
which caused an increase in heat transfer rate and finally reduced Tmax as article.
both temperature and hydrolysis time increased [78]. In addition, the
thermal resistance of smaller size CNCs was lower than that of larger ones
Declaration of interests statement
because smaller size CNCs had a much larger specific surface area and
were more possible to expose during heating. This led to the accelerated
The authors declare no conflict of interest.
pyrolysis rate and finally resulting in reduced thermal stability [79, 80].
From the dimension measurements taken from TEM images as discussed
earlier, the smaller diameter and length were found by increasing both Additional information
temperature and reaction time of hydrolysis. Moreover, with increasing
hydrolysis time, the number of ester sulfate groups on the CNCs surfaces No additional information is available for this paper.
induced by hydrolysis increased, and then it led to the lower thermal
stability. This is in good agreement between the TGA results and TEM References
observations. Furthermore, the residual weight of all CNCs at around 600


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