Industrial Crops & Products 187 (2022) 115426

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Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Potential application of cellulose nanocrystals obtained from cultivated

fibers in Amazon forest
Samir Leite Mathias a, Marcelo de Assumpção Pereira-da-Silva b, c, Alessandra de Almeida
Lucas d, Aparecido Junior de Menezes a, *
a
Universidade Federal de São Carlos – UFSCar, Sorocaba, SP, Brasil
b
Instituto de Física de São Carlos –IFSC-USP, São Carlos, SP, Brasil
c
Centro Universitário Central Paulista – UNICEP, São Carlos, SP, Brasil
d
Universidade Federal de São Carlos – UFSCar, São Carlos, SP, Brasil

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

Keywords: The Amazon fibers, Jute (Corchorus capsularis L.) and Malva/Caesarweed (Urena lobata L.), obtained from
Lignocellulosic fibers Phoenix Amazon Project were scrutinized and the biomass components were quantified according to the TAPPI
Amazon fibers standards. The cellulose amount from jute and caesarweed was, respectively, around 49% and 41%. Scanning
Cellulose nanocrystals
Electron Microscopy (SEM) analysis has evaluated the removal of lignin of the fiber through the micro holes
Acid hydrolysis
Renewable sources
located at holocellulose’s samples and the hemicellulose partial removal through the samples’ fibrillation at
Characterization alphacellulose’s micrographs. The Fourier Transform Infrared spectroscopy (FTIR) results corroborated the
Jute delignification and hemicellulose removal through the alphacellulose obtention process. X-Ray Diffraction (XRD)
Caesarweed patterns reiterate type I cellulose for the raw/holo samples, and type II cellulose for the bleached ones, with an
increase of the crystallinity index from ~60% to ~85% for the samples. Thermogravimetry (TG) showed that the
thermal stability of the samples increased until the bleaching process, and decreased after the cellulose nano­
crystals (CNCs) extraction because of the ester sulphate groups insertion. The CNCs were successfully extracted,
as can be seen on the Atomic Force Microscopy (AFM) images, and the aspect ratio and specific surface area
calculated showed that these CNCs present some potential application in polymers matrices.

1. Introduction Results reported on the literature using models of Halpin-Tsai

equation show that there are no, or insignificant, mechanical proper­
As well known the world is in a rising tide of pursuing solutions to­ ties improvements using nanocellulose with aspect ratio under 50 to
wards climate change, pollution control and energy saving. In this reinforce polymers, but polymeric materials filled with CNCs with the
respect, researches that leads to applications of renewable materials same aspect ratio range shows a better improvement on barrier prop­
have been increased, helping head the society to a sustainable and erties, creating into the polymer matrix tortuous paths that hampers the
conscious development, stopping the indiscriminate seek for resources. passage of fluids (Eichhorn et al., 2010; Sanchez-Garcia et al., 2008;
The use of lignocellulosic fibers (LF) leads to an interesting field of Sánchez-García et al., 2010).
research that works with renewable material, has interesting mechani­ Created by Instituto Nacional de Pesquisas da Amazonia (INPA), the
cal/thermal properties and can be used in pharmaceutical/food industry Amazon Phoenix Project tries to build a synergetic sustainable network
or acting as a texturing agent. The CNCs can be obtained from LF by acid between human activities and the remaining natural ecosystems aiming
hydrolysis process and applied in various areas like: drug carrier in for harmonious economic development. The combined planting of fast-
pharmaceutical industry, papermaking industry, food industry, sup­ growing pioneer amazon forest species with slower-growing hardwood
porting matrix for catalysts, CNCs can improve mechanical/thermal it’s one of the project’s proposals that aims an intelligent production
properties and biodegradability of matrices without generate a consid­ chain for environmentally friendly wood products and soil enrichment
erable increase in the cost of the process (Longaresi et al., 2019; Silva of degraded areas by farming (Nobre, 2012).
et al., 2009; Xie et al., 2018). Jute (Corchorus capsularis L.) and Caesarweed (Urena lobata L.) are

* Corresponding author.
E-mail address: [email protected] (A.J. de Menezes).

https://doi.org/10.1016/j.indcrop.2022.115426
Received 4 April 2022; Received in revised form 20 July 2022; Accepted 25 July 2022
Available online 30 July 2022
0926-6690/© 2022 Elsevier B.V. All rights reserved.
S.L. Mathias et al. Industrial Crops & Products 187 (2022) 115426

Table 1
Percentual values of the biomass content of the samples.
Holocellulose (%) Hemicellulose (%) Alphacellulose (%) Lignin (%) Ash (%)

Caesarweed 81.82 ± 0.89 40.68 ± 1.31 41.15 ± 1.84 9.60 ± 0.52 0.53 ± 0.04
Jute 77.02 ± 0.86 27.64 ± 1.46 49.37 ± 0.66 21.83 ± 1.98 0.90 ± 0.01

some of the fibers utilized on the project, both cultivations are lowland farming and also have the three pillars of the sustainable economy: low
crops integrated into the Amazon biome, which does not cause wildfires carbon, rational use of natural resources and socially inclusive (Araújo
or deforestation, in addition to being a source of income for about et al., 2017; Bentes et al., 2017; Viegas et al., 1992). The production of
15,000 riverside families, known as “Ribeirinhas”, in the states of Caesarweed and Jute between the years of 2000 and 2014 were around
Amazon and Para. They are fast-growing species, used as familiar 10 tonnes/year, more than 95% of this production come from Amazon

Fig. 1. FTIR spectra from Jute and Caesarweed fibers. Black, red, blue and green lines correspond, respectively, to raw, holocellulose, alphacellulose and
CNCs samples.

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S.L. Mathias et al. Industrial Crops & Products 187 (2022) 115426

Fig. 2. SEM micrographs of the raw (first column), holocellulose (second column) and alphacellulose (third column) samples.

state and are Caesarweed fibers. After a seed crisis occurred in the state 2.2.3. FTIR characterization
of Para, the production has dropped and is stagnant at around 5 ton­ It was performed on a Shimadzu spectrometer using KBr pellets
nes/year. (Araújo et al., 2017). The aim of this study was to characterize (1:100 w/w) with a range of 4000–400 cm− 1, 2 cm− 1 resolution and 64
and obtain CNCs from these fibers and evaluated the possible applica­ scans, in a N2 atmosphere.
tion for each one.
2.2.4. SEM analysis
2. Methodology The micrographs of the powder samples were obtained through a
Hitachi TM3000 Tabletop Microscope with an acceleration voltage of 5
2.1. Materials kV and without sputtering.

The biomass of jute and caesarweed, provided by the Amazon 2.2.5. TG measurements
Phoenix Project, were cut/ground into approximately 30 mm pieces and Thermal behavior was studied using aluminum pans with 2 mg of the
placed in the oven (Solab SL-100) for drying for 48 h at 80 ◦ C, and after powder samples on a TA Instruments TGA-55 with heating rate of the
was grounded by blades in a vertical rotor cutting mill (Cienlab CE-430) 10 ◦ C.min− 1 from 30◦ to 500◦ C in a N2 atmosphere flow (30 mL.min− 1).
until MESH 80 (0.180 mm). NaClO2 (80.0%), H3CCOOH (99.7%), NaOH
(97.0%) and H2SO4 (98.0%). All the reagents were used as received. 2.2.6. XRD characterization
The powder sample’s diffractograms was obtained by a Shimadzu
DRX-6100. Cu-Kα radiation generated (40 kV and 30 mA) with a scan­
2.2. Methods
ning rate of 2 ◦ .min− 1 and 2θ from 5◦ to 35◦ in a disc sample holder.
Segal and Revol’s methods were used to calculate the Crystallinity
2.2.1. Chemical composition
Index (CI) of cellulose type I (French and Santiago Cintrón, 2013; Segal
Lignocellulosic biomass of the native species was characterized ac­
et al., 1959) and type II (Revol et al., 1987), respectively.
cording to the TAPPI standards: T257 om-85 (holocellulose), also writ­ I(22.5◦ ) − I(18.6◦ )
ten as chlorite treatment, T203 cm-99 (alphacellulose), also written as CISegal = I(22.5◦ ) .
alkaline treatment, T13 m-54 (soluble lignin), T222 om-02 (insoluble Where I(22.5 ◦ ) and I(18.6 ◦ ) correspond to the crystalline/amorphous
lignin) and T211 om-93 (ash). The difference between alphacellulose fraction of cellulose type I and I(20.0 ◦ ) and I(15.0 ◦ ) correspond to the
and holocellulose amount was used to determine the hemicellulose’s crystalline/amorphous fraction of cellulose type II.
content. All the results are a mean value calculated through the biomass
components determination and its standard deviation by triplicate 2.2.7. AFM analysis
experiments. It was carried out using a Dimension ICON from Bruker through
intermittent contact mode (tapping mode) with a 40 N.m− 1 spring
2.2.2. CNC extraction constant silicon rectangular cantilever vibrating at 330 KHz.
It was carried out through acid hydrolysis treatment of the alpha­ The muscovite mica was used as sample holder for the CNCs and the
cellulose with using H2SO4 (64% w/w) at 50 ºC for 10 min and the re­ height images acquired were treated utilizing the Nanoscope Analysis
action was stopped using ice cubes of deionized water. The CNC software.
suspension was dialyzed against deionized water using a dialysis
membrane (Sigma-Aldrich) with 12–14 kDa molecular weight cut off
until neutral pH.

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S.L. Mathias et al. Industrial Crops & Products 187 (2022) 115426

Fig. 3. AFM height image of the samples.

Fig. 1 represents the FTIR spectra of the jute and caesarweed before
Table 2
any chemical treatment (raw fiber), after the chlorite treatment (hol­
Length, diameter, aspect ratio, specific surface area and yield of the
ocellulose), after the alkaline treatment (alphacellulose) and after acid
nanocrystals.
hydrolysis (CNC). The raw samples show the respective bands at
CNCs Measurements Jute Caesarweed
1730 cm− 1 (Fig. 1(2)) and 1370 cm− 1 (Fig. 1(1)), referent to the C– –O
Length (nm) 80.86 ± 3.65 61.49 ± 2.04 stretching and OH phenolic bending, respectively. Lignin bands in­
Diameter (nm) 5.80 ± 0.31 4.82 ± 0.24 tensity decreased after the chlorite treatment. The CH2 asymmetric
Aspect ratio 13.95 ± 0.10 12.77 ± 0.08
stretching located at 2800 cm− 1 (Fig. 1(4)) is related to alphacellulose
Specific surface area (m2.g¡1) 459.96 ± 105.79 553.69 ± 123.78
Yield (wt%)a 9.9 8.3 groups, CH stretching located at 2900 cm− 1 (Fig. 1(3)) is related to
a
hemicellulose groups which one is partial removed after the alkaline
with respect to the cellulose content.
treatment. The band found at 890 cm− 1 (Fig. 1(5)) is related to the
glycosidic bonding, a cellulose signature band (Dufresne, 2017).
3. Results and discussion SEM microscopies were performed to scan the structure of the sam­
ples (Fig. 2). It can be seen in the raw fiber column, a compact structure
According to the literature, jute fibers contain 59–71 % alphacellu­ that corresponds to the high cohesion among alphacellulose, hemicel­
lose, 10–16 % lignin, 12–20 % hemicellulose (Abraham et al., 2011; lulose and lignin. Lignin partial removal through chlorite treatment
Arun et al., 2020; Chand and Fahim, 2021; Chowdhury and Hamid, causes the cell walls’ deconstruction of the raw fiber samples that is
2016; Razera et al., 2014) and caesarweed fibers are composed of 56% corroborated through the micro holes shown in the micrographs of the
alphacellulose, 9–24 % lignin, 13 % hemicellulose (Fasanya et al., 2020; holocellulose column, this made the fibers more accessible increasing
Njoku et al., 2020). All of these values corroborated with the ones shown the effectiveness of the hemicellulose removal through alkaline treat­
at Table 1 and some results might be different because of climatic ment (Ciftci et al., 2018). After the alkaline treatment occurs the
changes, age of the fibers, methodology or even the plant species (Chand hemicellulose removal which causes the fibrillation of the holocellulose
and Fahim, 2021).

Table 3
Jute and Caesarweed’s thermogravimetry events.
Jute Raw Holocellulose Alphacellulose Nanocrystals

Water and low molecular compounds evaporation Tonset (◦ C) 25.4 25.4 27.9 35.3
Tmax (◦ C) 45.6 47.0 35.5 52.4
WL (%) 4.0 2.9 7.8 0.8
Decomposition of low molecular weight fatty acids and esters Tonset (◦ C) 108.0 114.0 130.6 –
Tmax (◦ C) 254.1 241.6 276.3 –
WL (%) 3.8 3.7 3.6 –
Cellulose degradation Tonset (◦ C) 254.1 241.6 276.3 142.4
Tmax (◦ C) 338.8 321.9 337.6 307.4
Tend (◦ C) 362.1 345.7 360.0 355.1
WL (%) 64.6 60.0 68.5 42.4
Caesarweed Raw Holocellulose Alphacellulose Nanocrystals
Water and low molecular compounds evaporation Tonset (◦ C) 27.1 27.2 24.6 26.64
Tmax (◦ C) 37.4 37.0 56.6 34.83
WL (%) 8.7 6.6 3.1 1.9
Decomposition of low molecular weight fatty acids and esters Tonset (◦ C) 111.7 107.0 139.7 –
Tmax (◦ C) 256.2 233.0 294.5 –
WL (%) 3.9 2.6 3.2 –
Cellulose degradation Tonset (◦ C) 256.2 233.0 294.5 147.4
Tmax (◦ C) 331.7 318.4 337.8 289.9
Tend (◦ C) 353.9 348.6 382.1 381.6
WL (%) 67.0 56.7 77.6 49.1

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S.L. Mathias et al. Industrial Crops & Products 187 (2022) 115426

Fig. 4. Thermogravimetry analysis (TG and dTG) of the raw, holocellulose, cellulose and nanocrystals.

samples, this effect can be corroborated through the fibers formation on CNCs the values of the specific surface area can be seen in the Table 2. As
the alphacellulose micrographs (Budtova and Navard, 2016; Zhang said by Cadek et al. (2004) the reinforcement of a polymer increases
et al., 2005). linearly with the filler’s surface specific area due to the improvement of
As can be seen in the Fig. 3, the extraction, through sulfuric acid the interfacial interaction polymer-filler(Cadek et al., 2004).
hydrolysis, of the jute and caesarweed’s CNCs were successfully done, The TG measurements were performed to investigate the thermal
showing a rod-like nanocrystals, and after the image treatment the most stability of the jute and caesarweed fibers and CNCs. It was scrutinized
dispersed nanocrystals (those that were surrounded by the darkest part the thermal events that occurred along the temperature range, the cor­
of Fig. 3) were searched, thus it was possible to measure the length and responding events data are presented in Table 3, these data were taken
diameter of the nanocrystals without the possible interference of from the analysis of Fig. 4.
another nanocrystal under which it was being measured, several nano­ It can be distinguished three main events for raw fiber, holocellulose
crystals were observed because the largest amount of nanocrystals were and alphacellulose throughout the temperature range, for the nano­
agglutinated even after the dispersion dilution, thus obtaining Table 2. crystals it can only be seen two events (the first and the third).
The specific surface area of the CNCs were calculated using the The first event, observed between 27 and 118 ◦ C, is related to the
following equation (Dufresne, 2017): evaporation of water and low molecular compounds, the second, be­
tween 118 and 259 ◦ C, is associated with the decomposition of low
4
Asp = molecular weight fatty acids and esters and the third, between 259 and
ρ.d
359 ◦ C for raw fibers, holocellulose and alphacellulose and between 145
This equation assumes the CNCs’ geometry as rod-like and neglect and 369 ◦ C for nanocrystals, it is a consequence to the decomposition of
the acute sides, using “ρ” as 1.5 g.cm− 3 and “d” as the diameter of the hemicellulose, pectin, lignin and glycosidic units, besides the

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S.L. Mathias et al. Industrial Crops & Products 187 (2022) 115426

Fig. 5. X-ray Diffractograms of jute and caesarweed. Raw fiber, holocellulose, alphacellulose and nanocrystals are, respectively, black, red, blue and green lines.

degradation of alphacellulose involving dehydration and depolymer­ degradation temperature, whereas cellulose is made up of long chains of
ization reactions. Above these temperatures there are only residual glucose without ramifications, which generates a more ordained struc­
lignin decomposition (César et al., 2015; de Morais Teixeira et al., 2010; ture and a greater thermal stability (Yang et al., 2007).
Garcia Filho et al., 2020; Kalia et al., 2011; Sun et al., 2010; Yang et al., It is known that the greater the crystallinity of a polymer the greater
2007). The weight loss percentual of each event can be seen on Table 3. the thermal stability (Callister and Rethwisch, 2018), but analyzing
The high amount of residues that can be seen on the “Nanocrystals” Fig. 4 (or Table 3), at the “Nanocrystals” legend curves, it can be seen
curves at 500 ◦ C can be attributed to dehydration catalysis caused by the that the thermal stability of those does not tend to this statement, this
sulfuric acid, favoring residue formation (Julien et al., 1993; Kim et al., happens because the ester sulfate groups addition (occurred at the acid
2001; Roman and Winter, 2004; Scheirs et al., 2001). hydrolysis) significantly decreases the cellulose thermostability (Roman
All the difference in degradation temperature with the bleaching and Winter, 2004), exerting a catalytic effect in the thermal degradation
processes is due to the difference in the structures of the three main reactions (de Morais Teixeira et al., 2010).
components of the lignocellulosic fiber (alphacellulose, hemicellulose The x-ray diffractograms of the jute and caesarweed’s samples are
and lignin). Lignin is full of aromatic rings and ramifications, which shown in Fig. 5. The raw and holocellulose patterns are typically semi­
leads to greater stability, hence a higher degradation temperature, crystalline material of native cellulose type I with crystallographic
hemicellulose is made up of several small saccharides proving the low planes (200) and (110) at, respectively, 2θ ~22.5 ◦ and 2θ ~15 ◦ , shaped

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S.L. Mathias et al. Industrial Crops & Products 187 (2022) 115426

Table 4 Acknowledgment
Crystallinity Index (CI) of the raw, holocellulose, alphacellulose and nano­
crystals sample. We would like to thank Coordenação de Aperfeiçoamento de Pessoal
Raw Holocellulose Alphacellulose Nanocrystals de Nível Superior - CAPES, Brasil for the financial support through the
Sample (%) (%) (%) master degree, the Amazon Phoenix Project (Projeto Fênix Amazônico)
(%) for the fibers’ donation, IFSC/USP for the AFM measurements and
Caesarweed 60.9 72.9 77.7 89.1 Laboratory of Biomaterials, Faculty of Medical Sciences and Health
Jute 68.2 76.4 79.9 82.4 (FCMS), Pontifical Catholic University of São Paulo - PUC-SP, Sorocaba,
SP, by the TG measurements.
as an amorphous wide halo with an acuminate crystalline peak over­
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