CELLULOSE NANOMATERIALS IN TEXTILE APPLICATIONS

ANDREA CRISTIANE KRAUSE BIERHALZ

Department of Textile Engineering, Federal University of Santa Catarina – Campus Blumenau,

Rua João Pessoa 2740, 89036-256, Blumenau, SC, Brazil
✉Corresponding author: A. C. Krause Bierhalz, [email protected]

Received August 1, 2021

Nanocellulose (NCC) has attracted increasing attention for use in several applications owing to its impressive
strength-to-weight ratio, ease of functionalization, and apparent biocompatibility. In the nanocomposite textile
field, NCC has exhibited outstanding potential for reinforced fibers, especially fibers processed by solution
spinning. Continuous NCC fibers with high modulus and strength can be obtained, while preserving the cellulose
I crystal structure. Owing to the various possibilities of surface modification, NCC is an efficient adsorbent of
cationic and anionic textile dyes, as it reaches maximum removal capacities comparable to those of commercial
adsorbents. In dyeing, NCC contributes in improving dye fixation and reducing the consumption of chemicals
and water. In this review, recent studies on the applications of NCC in the textile field are discussed. The main
methods, advances and limitations, regarding the NCC applications for fiber reinforcement of water-soluble and
insoluble materials, dye removal and textile finishing, are presented.

Keywords: cellulose nanocrystals, textile, fiber spinning, dye removal, finishing

INTRODUCTION
In recent years, nanotechnology has been significantly increasing the competitiveness of the textile
industry. Nanomaterials of various classes, such as metal oxides and carbon nanotubes, can provide
specific functionalities to conventional textile substrates, such as antimicrobial, anti-static, protection
against ultraviolet radiation, flame retardancy, and self-cleaning.1,2 Nanotechnology has also
contributed to improving the properties of fibers and fabrics, such as strength, softness, dyeability,
color fastness, and durability.3
Among the wide range of available nanomaterials, nanocellulose (NCC) is excessively versatile
and is used in several applications owing to its remarkable mechanical properties, which are related to
its high modulus (~150 GPa),4 strength (7.5-7.7 GPa), and low density (1.6 g cm−3).5 The Young's
modulus of NCC is much higher than that of natural fibers, such as cotton (12.6 GPa), flax (27.6 GPa),
jute (26.5 GPa), sisal (22 GPa),6 and is higher than that of high-performance fibers, such as fiberglass
(50-80 GPa)7 and aramid fibers (~67 GPa).8 Furthermore, NCC is broadly biocompatible, chemically
inert, has a low thermal expansion, good optical properties, and high chemical reactivity.
NCC is derived from renewable and widely available sources (wood, plants, algae, bacteria, and
tunicates), and is biodegradable and recyclable.9,10 Significant environmental and economic benefits
have also been associated with the use of agricultural and industrial wastes, such as corn husks,11 rice
husks,12 and sugarcane bagasse13 as NCC sources. Massive amounts of cotton fibers with high
cellulose contents (up to 90%) are annually processed in the industry. Therefore, textile cotton wastes
are also a promising source of NCC.14 These residues are obtained from different stages of cotton
processing, such as ginning, carding, and weaving, or even from discarded clothes and fabrics.15,16
According to Wang et al.,15 the production of NCC is an excellent alternative to recycle waste cotton
cloths, which are mostly disposed in landfills or incinerated.
Cellulose consists of a linear homopolysaccharide composed of -D-glucopyranose units linked
together by -1-4-linkages, with amorphous and crystalline regions. It is the most abundantly produced
homopolysaccharide, with an estimated annual production of 1011-1012 tons cellulose biomass.17 The
term “nanocellulose” refers to cellulosic materials with at least one dimension less than 100 nm, which
can be obtained when the amorphous regions are broken down by chemical, mechanical, or enzymatic
treatments.18
NCC is categorized into two major groups: cellulose nanocrystals (CNCs) and cellulose nanofibrils
(CNFs).19 CNCs are rod-like (or needle-like) nanoscale materials (Fig. 1a), which are approximately 3-
35 nm wide and 200-500 nm long, and are mainly obtained by acid hydrolysis with sulfuric acid.20,21
Figure 1(c) shows the appearance of a CNC suspension obtained by hydrolysis with sulfuric acid using
cotton as cellulose source. The dimensions and properties strongly depend on the cellulosic source,
preparation and processing conditions, and possible post- or pre-treatments.19 CNC suspensions, in
general, exhibit high crystallinity, narrow size distribution, and good dispersibility owing to the
negatively charged surface resulting from acid hydrolysis.10 Other terminologies employed to describe
the rod-like materials include “cellulose nanocrystals”, “cellulose nanowhiskers”, “nanowires” and
“nanorods”.22
CNFs, also called nanofibrils, nanofibrillated cellulose, microfibrillated cellulose, and nanofibrillar
cellulose,23 have fibril-like features (Fig. 1b), with lengths of a few micrometers and diameters in the
range of 5-50 nm.21 These nanomaterials are mainly produced using mechanical processes (high-
pressure homogenization, grinding, microfluidization etc.) often associated with chemical or biological
pretreatments.19,24 CNCs are stiff owing to the predominantly crystalline regions; however, CNFs are
flexible due to the entangled network with alternating crystalline and amorphous domains.25 The CNC
and CNF isolations are already well established at an industrial level, enabling excellent availability at
an affordable cost.
Bacterial cellulose (BC) is also considered as belonging to the nanocellulose class and is
characterized by high purity and crystallinity. It is produced extracellularly by bacteria (such as
Acetobacter xylinum), cultivated in aqueous culture medium containing nitrogen sources and carbon
sources, such as sugar. BC can be formed using a wide variety of substrates, and its properties, shape,
and size, can be tailored during synthesis.26 BC is hydrophilic and free of lignin, hemicelluloses, or
pectin. BC is suitable for a broad range of biomedical applications.21,27
These three classes of nanocellulose have been increasingly explored for different textile
applications (Fig. 2). In filament or yarn production, NCC can act as the base element for continuous
filaments of submicron diameter or as a reinforcement agent for nanocomposite structures with high
mechanical resistance. In the case of 100% NCC filaments, unlike well-established regenerated
cellulose, NCC maintains the cellulose I structure, which is much stiffer, compared to cellulose II.28

Figure 1: TEM images of (a) CNCs and (b) CNFs; and (c) aspect of CNC suspension after hydrolysis. Reprinted
with permission (a and b) from Xu et al.20 (copyright 2013 American Chemical Society)
 Figure 2: Sources, types of nanocellulose and textile applications

Fiber spinning includes melt spinning, solvent spinning (dry and wet spinning), and
electrospinning. The limitations of melt spinning are mainly related to the dispersion of NCC in
hydrophobic matrices. Therefore, several superficial modification methods have been proposed to
increase the compatibility between NCC and polymers. NCC deposition methods are also beneficial
for the mechanical properties of filaments or yarns obtained from natural fibers.
The high potential of NCC in the textile industry is not only due its outstanding mechanical
performance. Due to the high concentration of surface functional groups and the possibility of
chemical modification, NCC can strongly interact with various substrates. NCC is an excellent
adsorbent for textile dyes, both cationic and anionic. Considering textile finishing, NCC is significant
in more sustainable dyeing processes, as it reduces the consumption of dyes, water, chemicals, and
dyes discharged in effluents. In addition, the hydrophilicity of synthetic substrates can be improved,
which improves the perceived comfort of fabric.29 NCC can also impart superhydrophobicity to cotton
substrates.30
According to the Google Scholar database, the number of scientific documents involving the
keywords “nanocellulose” and “textile” increased from 168, in the period from 2000 to 2010, to 7110
in the period from 2011 to 2020, 84% of which were registered in the last five years (research carried
out on 2/20/2021). These numbers reflect the increasing interest and strong tendency to expand the
applications of NCC in the textile field.
In this review, the research progress involving the application of nanocellulose in the textile field in
recent years is described in terms of three aspects: fiber spinning, textile finishing, and dye removal. In
fiber spinning, important issues related to the processing and dispersion of NCC are discussed. The
impact of NCC and modification treatments on the mechanical properties is also analyzed. In dye
removal, the capacity of adsorption and strategies to increase the adsorption of cationic and anionic
dyes of NCC is discussed, and this nanomaterial is compared to other adsorbents. The potential
applications of NCC in textile finishing are also presented.

FIBER REINFORCEMENT
The addition of a second phase as a reinforcement in a polymeric matrix has been widely used to
improve the mechanical properties of the developed materials and expand their applications in several
areas. In fiber manufacturing, however, the success of this strategy is highly dependent on the size of
the reinforcing element. Owing to the small diameter of the fibers, slight aggregation caused by
macro-sized elements can lead to spin failure. Nanosized materials have the potential to be used as a
reinforcement phase, improving the mechanical properties of polymeric fibers, without affecting their
spinnability and surface finish.31
Owing to its high modulus, high aspect ratio, and large surface area, NCC has been increasingly
used to obtain fibers with new functionalities and improved mechanical properties. In addition to its
outstanding properties, NCC offers advantages in terms of environmental friendliness and biological
compatibility compared to other nanofillers, such as carbon nanotubes.32 Studies have demonstrated
that nanocellulose can increase fiber stiffness and strength by over 100%.33-35
Nanocomposite fibers containing NCC have been produced using different spinning techniques,
such as melt spinning, wet spinning, dry spinning (Fig. 3), and electrospinning. The choice of the
method depends on the processing conditions and component characteristics, such as the melting point
and degradation temperature. For all methods, achieving highly oriented nanofibrils is important
because it results in more effective stress transfer and better mechanical properties. 33 The main aspects
of each technique involving NCC processing are addressed in the subsequent sections.

Melt spinning
Melt spinning is one of the most economical and convenient methods for continuous manufacturing
of fibers from thermoplastic polymers in large quantities for the textile industry.28,37 In this technique,
molten polymer is pumped through a spinneret under high pressure. Therefore, it is more
environmentally friendly because it does not require solvents to dissolve the polymers. In addition, it is
easily scalable and offers fiber drawing and heat setting to increase dimensional stability.31,35
A common limitation in obtaining composite fibers with NCC by melt spinning is its thermal
degradation. Many polymers processed by melt spinning have a high melting point (above 200 °C),
whereas the NCC extracted by sulfuric acid-based hydrolysis has a thermal decomposition temperature
of approximately 180 °C. The sulfate groups grafted and adsorbed to the surface of NCC are
responsible for electrostatic repulsion and stability of suspensions, but they also catalyze thermal
degradation.35 Thus, the applications involving fiber reinforcement with NCC by melt spinning have
been limited to polymeric matrices with comparably low processing temperatures, such as polylactic
acid (PLA) and acetate butyrate, as shown in Table 1.
However, thermoplastic polymers with low melting points tend to be hydrophobic, making
homogeneous NCC dispersion in these matrices difficult to achieve. Therefore, the poor dispersion
and incompatibility of CNCs with most nonpolar thermoplastics limit the final mechanical
performance of these systems.
A variety of processing strategies have been adopted to minimize these dispersion and
incompatibility issues, including solvent exchange and surface modification.40,41 The first study that
used cellulose nanocrystals (CNCs) as an additive for melt-spun nanocomposite fibers was conducted
by John et al.31 To avoid aggregation, the nanofibers in aqueous medium were solvent-exchanged to
acetone, and a master batch of PLA with CNC was prepared for further melt spinning. No
improvements in the mechanical properties were obtained by the addition of CNCs. According to the
authors, this was caused by the poor dispersion of CNCs in the PLA matrix and lack of bonding
between them.

Figure 3: Common fiber spinning techniques: wet spinning (left), dry spinning (center), and melt spinning
(right). Reprinted with permission from Rosén et al.36 (copyright 2020 Wiley Online Library)
 Table 1
Examples of nanocomposite fibers obtained by melt spinning and their mechanical properties

Dispersion approach Matrix NCC source NCC content Main observations regarding mechanical properties Ref.
CNC extracted by acid
Solvent-exchange to acetone by Presence of aggregates. Addition of CNC did not improve tensile
PLA hydrolysis from 1-3 wt% [31]
centrifugation strength of the fibers. Slight improvement in modulus was observed.
microcrystalline cellulose
Tenacity improved 23.4% (10 wt% CNF).
A masterbatch containing 10 wt%
The elongation at break decreased from 153.21% to 112.54% and to
CNFs in Nylon 6 was compounded to Commercial spray-dried
Nylon-6 2.5-10 wt% 69.5% with the addition of 5 and 10 wt% of CNFs, respectively. [32]
improve the dispersion of CNFs CNF
The moisture absorption of the nanocomposite filaments increased with
during subsequent processes
the addition of CNFs.
Polyethylene glycol (PEG) acted as a
compatibilizating agent; Mechanically fibrillated 0.05-1.3% Tensile strength of the fibers did not improve with the addition of CNC.
PLA [33]
Surface modification of CNF with 12- CNF mCNF-C12 Stiffness was improved up to 600% (1.3%, maximum draw).
carbon aliphatic chain (mCNF-C12)
CNC extracted by acid Addition of 1 wt% CNC-g-PLLA resulted in improved stiffness (≈20%),
CNC grafting with PLLA PLA hydrolysis from commercial 1 wt% strength (≈100%), and elongation at break (1720%) compared to neat [34]
cellulose microcrystals PLA.
Thermoplastic
Dispersion of CNC in DMF by CNC extracted by acid Incorporation of 5 wt% CNC increased Young’s modulus by 500% and
polyurethane 1-5 wt% [35]
sonication hydrolysis from tunicates reduced the strain at break by 60%.
(PU)
CNC extracted by acid 1. Agglomerates of CNC affected mechanical properties negatively.
1. Reduction and exchange water
hydrolysis from Reduction of tensile strength, modulus and strain.
content to ethanol using centrifugation Cellulose acetate
microcrystalline cellulose 2 wt% 2. Few aggregations of CNC. Young’s modulus was improved by 17% [37]
2. Sol-gel process to exchange water butyrate (CAB)
and non-dried cellulose upon CNC addition.
content of CNC by ethanol
residue (sludge) Reduction of 35% in elongation at break.
PLLA fibers filled with 2 wt% C6-BC exhibited the highest yield
BC modification with hexanoic acid CNC extracted by acid 2 wt% and 7
strength.
(C6-BC) and dodecanoic acid (C12- PLLA hydrolysis from bacterial wt% (neat and [38]
Surface modification of BC with hexanoic acid, acted to improve the
BC) cellulose modified)
draw ratio.
Addition of CNC did not improve tensile strength and Young’s modulus
Compatibilizer CNC extracted by acid
of the fibers.
PLA‐grafted maleic anhydride PLA hydrolysis from commercial 1-3 wt% [39]
Elongation at maximum force increased ≈18% with 1 wt% CNC
(PLA‐g‐MA) microcrystalline cellulose
compared to neat PLA.
 Hooshmand et al.37,42 studied two different dispersion techniques to obtain homogenous melt
spinning cellulose acetate butyrate (CAB) nanocomposite fibers. One approach consisted in reducing
the water content of the CNC suspension and exchanging it with ethanol by centrifugation. In the
second approach, the water in the CNC suspension was completely exchanged with ethanol by the sol-
gel process. This technique increased Young’s modulus by 17%, without any surface modification or
use of a surfactant.37 In a subsequent study, using this technique, nanocomposite fibers with a high
concentration of CNC (10 wt%), defect-free smooth surface, enhanced thermal stability, tensile
strength (23%) and modulus (90%) were obtained.42
To increase the surface hydrophobicity of NCC and make it more compatible with polymers to be
processed by melt spinning, a variety of surface modification methods have been developed. These
methods include physical adsorption and chemical grafting of small molecules and macromolecules.43
For example, the superficial modification of bacterial cellulose with organic acids via esterification
can improve its interfacial adhesion with PLLA, which improves the mechanical properties of the
melt-spun fibers.8,38
Compatibilizers formed by the grafting of polymer chains on the surface of CNCs are promising to
improve the interfacial adhesion between the CNCs and polymer matrix. To improve the compatibility
between PLA and CNC, Mujica et al.34 grafted PLLA chains onto the CNC surface using a “grafting
from” reaction. A tensile strength improvement of 234% was reported for PLA nanocomposite fibers
with PLLA-grafted nanocrystals, compared to the nanocomposites with neat CNCs. This results in a
flexible interface between the grafted CNC and the PLA matrix, which offers high stretching and
enhanced strength.
To increase the thermal stability and enable the processing of CNCs by melt spinning, Redondo et
al.35 isolated CNCs from tunicates using phosphoric acid hydrolysis. The thermal analysis of the
isolated material with phosphoric acid indicated an onset degradation temperature of approximately
300 °C, while the CNC extracted with sulfuric acid showed an onset degradation temperature of
approximately 180 °C. The greater thermal stability can be attributed to the lower amount of
degradation-catalyzing charged groups on the CNC surface. These CNCs were processed with
thermoplastic polyurethane (PU) elastomer by melt spinning and were able to improve the Young’s
modulus of the fibers by more than 500%.
In addition to mechanical reinforcement, nanocellulose has also been associated with the comfort
of textile fibers by increasing their hydrophilicity. In general, the hydrophilicity of fibers provides a
better feel and results in a more breathable product. Zhu et al.32 studied the effect of CNF loading (0-
10 wt%) on the properties of Nylon 6/cellulose nanofibril melt-spun nanocomposite filaments. The
authors observed that the incorporation of CNF improved the tenacity and initial modulus and
increased the hydrophilicity of the nanocomposite filaments, which improved the fabric comfort.
Nanocellulose has also shown potential as a material with shape memory. Loads of 1 wt% CNC in
shape memory polyurethane ribbons improved flexural properties and showed that they can act as
springs incorporated in the material, offering a faster recovery rate and reduced recovery time.44

Solvent spinning
Solvent spinning can be classified as dry spinning or wet spinning. In these techniques, the polymer
precursor is first dissolved to produce a spinning dope and then extruded through a forming element.
The difference between dry and wet spinning is the form of solidification of the dope. In dry spinning,
the solution is extruded through a spinneret into a warm air chamber, where the solvent evaporates and
solidifies the fine filaments. In wet spinning, the solution is extruded and submerged in a liquid, where
the solvent is removed through the diffusion of the fiber solvent to the baht solvent, or through
precipitation by a chemical reaction. A combination of both wet and dry spinning, called the dry-jet-
wet-spinning, has been increasingly used to obtain composite fibers with CNCs. In this approach, the
spinning dope is extruded through an air gap between the spinneret and coagulation bath, where
threadline tension can induce molecular orientation.28
These spinning methods are used when the melt spinning is not possible, and when the final
properties justify the increase in cost, time, and chemical risks related to solvents.33 In general, the
solution processes result in improved mechanical performance, as they can result in highly drawn
fibers.28
 Studies based on solution techniques have focused primarily on synthetic and natural water-soluble
polymers, such as PVA,45 alginate,46,47 methylcellulose,48 casein,49 and silk fiboin.50 Nanocomposite
fibers of other polymers, including cellulose acetate,51 PAN,52 and PLA,53 were processed using water-
miscible organic solvents, such as acetone, dimethylformamide, and dimethylacetamide. In most cases,
the addition of CNCs increased the mechanical properties of the individual fibers, as can be seen in
Table 2. The molecular chain of the CNCs composed of glucose linked by -1-4 glucosidic bonds
resulted in hydroxyl groups on their surface, offering CNCs hydrophilic characteristics and
compatibility with hydrophilic polymers. In addition, CNCs obtained from hydrolysis with sulfuric
acid have sulfate groups on the surface, resulting in stable dispersions in water owing to repulsive
interactions.47

Electrospinning
Electrospinning is a simple, versatile, and widely used technique for the production of ultrathin
fibers. Owing to their high surface-to-volume ratio and interconnected and uniform porous structure,
electrospun fibers have gained increasing prominence in applications involving filtration, sensing
technology, energy generation, protecting clothes, tissue engineering scaffolds, and biomedical
applications.55
The formation of nanofibers by this method is based on the uniaxial stretching of a viscoelastic
solution by electrostatic forces. A typical electrospinning apparatus is composed of a spinneret
(syringe needle) connected to a high-voltage supplier and a grounded metallic collector. The polymeric
fluid (melt or solvent solution) is injected with a syringe pump through the spinneret at a controlled
flow rate. When a high voltage (typically more than 5 kV) is applied and the electrical potential
exceeds the surface tension of the liquid, a filament is formed and ejected from the spinneret to the
collector. The jet of the polymer elongates and dries during the trajectory, resulting in fibers that are
deposited in the form of a nonwoven mesh.56
Several processing parameters can be used to control the diameter of the fibers, such as the
viscosity of the polymer in solution, conductivity, surface tension, voltage, feed rate, distance between
the spinneret and the collector, and the ambient temperature and relative humidity. Depending on the
operating conditions and material properties, structural defects, such as beads, may be present in the
resulting fibers. These defects lead to inefficient load transfer throughout the fiber and weaken the
mechanical resistance of the membrane.57
In general, the CNC is added in small quantities to the polymer solution (1-5 wt%), as there is a
tendency of increasing viscosity, difficulty in spinnability, and of increasing diameter of the fibers.
However, concentrations of up to 50% NCC have produced electrospun fibers.58
CNCs have been successfully processed by electrospinning using various natural and synthetic
polymer matrices. When used as reinforcing phase, significant improvements in the mechanical
properties were obtained with the CNC-polymer composites, compared to the neat polymer. For
instance, the addition of 3 wt% CNC to electrospun fibers from hordein/zein increased the tensile
strength and Young’s modulus from 4.36 ± 0.29 to 7.79 ± 0.36 MPa and from 195.80 ± 13.02 to
396.64 ± 18.33 MPa, respectively.59 The addition of only 0.105 wt% of CNC to cellulose acetate
improved the fracture stress by 2.8 times and the fracture strain by 2.2 times, compared to the pristine
CA nanofiber.60
CNC–polymer interactions and the orientation of CNCs within electrospun fibers play an important
role in their mechanical properties. Strong interactions between the matrix and CNC lead to efficient
stress transfer within the composite fibers. The orientation of the nanocrystals along the fiber axis
direction enhances the anisotropic mechanical properties. Electrospinning offers several advantages in
terms of CNC alignment and the formation of nanocomposite fibers. The alignment is induced by large
electric fields and shear forces in the liquid jet. Furthermore, owing to the small diameter, the removal
of the solvent is very fast and contributes to the fixation of the fiber alignment.28,61
 Table 2
Examples of nanocomposite fibers obtained by solution spinning and their mechanical properties

Spinning NCC
Matrix NCC source Main observations regarding mechanical properties Ref.
technique content
CNC is more effective than OCNC to improve mechanical properties.
1. CNC extracted by acid
The tensile strength of modified fibers reached a maximum at 0.5 wt%
hydrolysis from bleached birch
Wet spinning Alginate 0.5-8 wt% CNC/OCNC loading. [47]
kraft paper
Elongation at break and maximum work at break increased by 208% and 523%
2. Oxidized derivative (OCNC)
for alginate/CNC fibers. Tensile strength was improved by 40%.
Pure methylcellulose did not allow fiber spinning and the optimal mechanical
CNC extracted by acid hydrolysis
Methyl- properties were achieved with 0.25 wt% CNC. This condition resulted in high
Wet spinning from Whatman® Grade 1 filter 0-3 wt% [48]
cellulose strain (36.1%) and modulus of toughness (48.3 MJ/m3), keeping a high strength
papers
(190 MPa).
The maximum tenacity of 5.84 ± 0.16 cN tex–1 was achieved at 10.5% of CNC.
CNC particles on dry sodium
Wet spinning Casein 0-37.5 wt% At this CNC content, elongation at break was reduced from 86.1% to 3.93%. [49]
form
Young’s modulus increased by 34%.
Silk CNC extracted by acid hydrolysis Young’s modulus, tensile strength and breaking strain were improved by 195%,
Wet spinning 1-7 wt% [50]
fibroin from waste mulberry branch bark 160% and 130%, respectively, with 5 wt% CNC.
Water-based suspensions of
Cellulose Maximum improvements were achieved at 34 wt% CNC, with increases of 137%
Dry spinning CNCs (solvent exchanged into 0-49 wt% [51]
acetate in tensile strength and 637% in elastic modulus.
N,N-dimethylacetamide (DMAc))
Fibers presented elastic modulus between 2 and 6.5 GPa and a maximum
CNC slurry at 11.8 wt% in water
strength of 100 MPa.
Dry-spinning PLA (Solvent exchange from water 0-5 wt% [53]
The increase in the CNC shifted the mechanical behavior of the fibers from
into DMF)
ductile to brittle.
Maximum improvements in tensile strength and elastic modulus were achieved
with 15 wt% CNC.
Dry-jet-wet- CNC extracted by acid hydrolysis Elastic modulus increased from 3.24 to 10.76 GPa (wood) and 14.31 GPa
PVA 0-20 wt% [54]
spinning from wood pulp and cotton (cotton). Tensile strength increased from 100.01 to 230.86 MPa (wood) and
274.38 MPa (cotton). In terms of reinforcing, cotton CNC exhibited better
properties than wood CNC.
 The evaluation of mechanical properties is usually centered on electrospun nanocomposite mats in
measurements using dynamic mechanical analysis or Instron tensile tests. The analysis of mats is
easier and more accessible than that of individual fibers.28 However, it should be considered that
structural properties, such as thickness, porosity, distribution and intersection of the fibers, influence
the mechanical properties of the mat. To eliminate the effect of these parameters and to better
understand the role of CNCs in the mechanical properties of PMMA electrospun fibers, Dong et al.55
investigated the nanomechanical properties of single composite fibers using nanoindentation. CNCs
were incorporated into electrospun PMMA fibers with weights up to 41%, and the results indicated a
moderate improvement of approximately 17% in storage modulus with the first 17 wt% CNCs.
In addition to mechanical reinforcement, NCC contributes to the improvement in specific
properties for different applications involving nanofibers. For biomedical applications, NCC has been
associated with increased biocompatibility, cell attachment, proliferation, and migration, with no toxic
responses. For example, Jia et al.62 produced electrospun vascular tissue scaffolds based on cellulose
acetate (CA) containing microcrystalline cellulose (MCC) and CNC. The CNC promoted cell
attachment and a synergistic effect of MCC and CNC was observed, as scaffolds containing both
particulates simultaneously exhibited enhanced cell viability and biocompatibility. Naseri et al.58
observed that CNC increased the permeability of electrospun fiber mats based on chitosan–
polyethylene oxide to O2 and CO2 by 20-fold and 22-fold, respectively. Higher gas permeation of
wound dressings is critical, as it accelerates tissue regeneration and prevents the proliferation of
anaerobic bacteria.
CNC also demonstrated the potential for smart electronic clothing applications. Ponnama et al.63
investigated the piezoelectric properties of cellulose nanocrystals (2 wt%) and Fe-doped ZnO (2 wt%)
embedded as fillers in electrospun nanofibers of polyvinylidene fluoride hexafluoropropylene (PVDF-
HFP). CNC played a significant role in enhancing the piezo potential. According to the authors, each
CNC acted as an electrical dipole, and during compressive stress, the CNC sensed a voltage and
resulted in voltage-induced electrical polarization.
In polyvinylidenefluoride-co-hexafluoropropylene (PVDF-HFP) electrified membranes for
distillation applications, the addition of CNC narrowed down the pore size distribution and improved
the liquid entry pressure (LEP), which ensured high salt rejection of the membranes in membrane
distillation.64 For separation, the addition of 4 wt% CNC to PVDF electrospun membranes resulted in
a four-fold increase in the flux of the membrane.65

Cellulose-based fibers
Regenerated cellulose fibers can be obtained from cotton linter or wood by two main regeneration
systems: direct dissolution process and derivatizing process. In direct dissolution, cellulose is directly
dissolved in solvent without modification, while in the derivatizing process, the chemical structure of
the starting cellulose is modified before dissolution.66
The viscose (xanthate) derivatizing process is the most traditional route for obtaining regenerated
cellulose fibers with low cost and good mechanical properties. However, the by-products generated by
this process have been associated with serious environmental problems.67 The oldest direct dissolution
process is the cuppramonium process, invented in the 1890s. In this process, cellulose is dissolved in
an aqueous solution of cuprammonium hydroxide using auxiliary hazardous chemicals, such as
ammonia and sulfuric acid. The cuppramonium process is in decline in several countries because of
the high cost of dissolution and related environmental and health issues.66
Alternative and more recent processes include the dissolution of cellulose in the N-methyl-
morpholine-N-oxide (NMMO),68 N,N-dimethylacetamide (DMAc)/LiCl,69 NaOH/urea aqueous
solution,67 NaOH/water70 and ionic liquids.71
There has been increasing interest in synthesizing single components using only cellulose
nanomaterials. This interest is due to the possibility of obtaining fibers with high rigidity and tenacity,
since the hydroxyl groups on the surface of CNC/CNF can form strong hydrogen bonds with each
other.72
Textile fibers from regenerated cellulose, such as rayon (cuprammonium process) and Lyocel®
(NMMO process), have cellulose II crystal structure, while natural cellulose has cellulose I crystal
structure. Because of the loss of hydrogen bonds, the Young’s modulus of cellulose II crystals of
regenerated cellulose (88 GPa) is much lower than that of cellulose I (130-150 GPa).72 The cellulose I
crystal structure can be retained by spinning CNC/CNF yielding fibers with a high degree of crystal
orientation, as well as high modulus and strength.72,73
Cellulose nanofibers are not soluble, but are highly dispersible in water. Thus, a suspension of
cellulose nanofibers in water has a viscosity similar to that of the cellulose solution and non-
flocculated uniformity. This suggests that the cellulose nanofiber suspensions are suitable for
spinning.73
Cellulose fiber spinning was first performed by Iwamoto et al.73 and Walther et al.7 The first group
prepared TEMPO-mediated oxidized wood and tunicate cellulose fibers by simple wet spinning (wet
extrusion, coagulation, and drying). The fibers exhibited tensile strength of ≈300 MPa and stiffness of
≈25 GPa. According to Walther et al.,7 the stiffness was one order of magnitude larger than that of
typical rayon fibers.
The 100% NCC fiber can be produced by wet or dry spinning. In wet spinning, the dispersion can
be spun into a coagulation bath containing solvents, such as acetone, ethanol, methanol/water, THF,
and isopropanol, where the fibers are formed by solvent exchange. According to Shen et al.,74 the
drawbacks of wet spinning are related to uncontrolled removal of water, which leaves the filament
hollow.
The dry spinning approach has also been successfully used for preparing CNF filaments.
Hooshmand et al.75 used piston-driven extrusion (capillary rheometer) for dry-spun cellulose
nanofibers (CNFs) based on banana waste. Shen et al.74 developed a dry spinning method with an
adhesion-controlled surface exhibiting low friction (slippery surface). This strategy eliminates the need
for shrinkage control, allowing the wet filament to dry in a controllable manner.
TEMPO-mediated oxidation is a widely applied chemical pretreatment of cellulose for filament
production. The reaction is performed under mildly alkaline conditions using sodium hypochlorite
(NaClO) as the primary oxidant and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) as the
catalyst. In this process, anionic carboxylate groups are introduced at the C6 primary hydroxyl groups
of glucose units on the surface of the crystalline cellulose microfibrils. The negative charges
introduced at the surface of cellulose fibers greatly reduced the energy required for their disintegration
into individual fibrils with very small diameters (typically 3-5 nm).28,76 Therefore, the tension applied
on a CNF filament had a stronger aligning effect due to the elevated fibril aspect ratio.77,78 However,
the high specific area and surface charge made the TEMPO-oxidized CNF filaments more sensitive to
water, impairing the strength under wet conditions.77
Several studies have demonstrated the significance of the high orientation of nanofibrils in
achieving better mechanical properties. In general, the nanofibers are aligned in the fiber direction of
the spun fibers at higher spinning rates.10,79 Iwamoto et al.73 observed that by increasing the spinning
rate from 0.1 to 100 m/min, the mechanical properties increased from 8.4 to 23.6 GPa and from 90 to
320 MPa, respectively. Hooshmand et al.75 investigated the effect of CNF concentration on CNF
alignment and mechanical properties of filaments. They observed that the modulus of the filaments
increased from 7.8 to 12.6 GPa and the strength increased from 131 to 222 MPa when the lowest
concentration and highest speed were used.
As a strategy to increase fiber alignment and mechanical properties, Tang et al.80 covalently grafted
polyethylene glycol onto the surface of cellulose nanofibrils. This approach facilitated the alignment
and compartmentalization of individual nanofibrils in cellulose ribbons. As a result, high tensile
strength of 576 ± 54 MPa and modulus of 32.3 ± 5.7 GPa were obtained. Håkansson et al.81 developed
a wet-extrusion process combining hydrodynamic fibril alignment (millimeter-sized flow focusing)
with a dispersion–gel transition to produce homogeneous and smooth CNF filaments. The highest
strength was 490 MPa and the modulus was 17.6 GPa.

Reinforcement of fibers and fabrics by deposition

Filaments or yarns from natural fibers can also be treated with CNC suspensions to improve their
mechanical properties, mainly strength. Cellulose nanofibrils (CNFs) and cellulose nanocrystals
(CNCs) were used to improve the mechanical properties of tapes and yarns produced from hemp and
flax slivers. Yarns and tapes were produced by soaking fiber strands in different nanocellulose
suspensions, which exhibited considerably higher tensile properties in terms of strength and initial
modulus than those of the controls. The flax tape treated with CNF that was ground for 100 min
showed an improvement in strength of approximately 45 times over the control.24
 Habeish et al.82 evaluated the reinforcement of cotton and polyester/cotton blend fabrics (50/50) by
soaking the fabrics in padding liquor containing CNC, with surface modifications of grafting and
etherification at different concentrations. Several properties of the fabrics, including roughness,
stiffness, abrasion resistance, crease recovery, tensile strength and elongation at break, were enhanced
by the reinforcement treatment. In general, these properties increased with increasing CNC
concentration, regardless of the type used.
CNC deposition on regenerated cellulose fibers was evaluated to create RCF-based composites
with hierarchical structures. Fibers treated with CNC using γ-methacryloxypropyltrimethoxysilane
(MPS) as a coupling agent absorbed two times less water than untreated fibers and enhanced the fibre-
epoxy resin adhesion at RH 64%.83

DYE REMOVAL
Thousands of tons of synthetic dyes are annually produced in the textile industry. These dyes are
classified according to their application and chemical structure of the chromophor groups, which are
responsible for the dye color. It is assumed that dye losses can vary from 2 to 50% of the initial
concentration while dyeing, depending on the dye class.84 The release of dyes in large quantities into
the aquatic environment causes serious damage. The presence of dyes in water, even at low
concentrations, is highly visible, reduces light penetration, and negatively affects the photosynthesis of
water systems. In terms of toxicity, these substances can be teratogenic, mutagenic, and carcinogenic.18
Owing to the high water consumption of textile dyeing and finishing, which is related to effluent
generation in large volumes with potentially toxic composition, the textile industry has been classified
as the most polluting industrial sector.
Various physical, chemical and biological treatments have been proposed for the removal or
remediation of dyes from textile effluents to reduce environmental impacts. Among the different
techniques, adsorption is known for its low cost, simple operation and high efficiency.18 The
adsorption consists in fixing molecules, atoms, or ions in a dissolved state in vacant sites on the
substrate surface by physical processes (physisorption) and chemical bonds (chemisorption). Recently,
several studies have focused on the development of non-conventional low-cost adsorbents, including
waste materials from agriculture and industry.85
CNCs have attracted attention as adsorbents for cationic and anionic textile dyes. In addition to the
high aspect ratio, large specific surface area, biodegradability, and low toxicological risk, the presence
of negative charge on the CNC surface facilitates the adsorption of positively charged dyes.86 In
general, the adsorption capacity increases with an increase in the CNC amount as an adsorbent, which
can be attributed to the presence of more active sites for the same number of molecules.86,87 The
versatility of CNC as an adsorbent for cationic and anionic dyes arises from the possibility of chemical
modification and functionalization. Conventional approaches to the surface modification of CNCs
include sulfonation, esterification, etherification, silylation, and polymer grafting.88 The modification
of cellulose nanomaterials for improved adsorption was recently reviewed by Köse et al.17
The introduction of carboxyl groups onto the CNC surface increases the adsorption ability of
cationic dyes, as it increases the number of adsorption sites and the electrostatic interactions between
the negative carboxyl groups and positively charged cationic dye molecules.18,86,89 Carboxylation via
esterification with maleic anhydride and succinic anhydride,88 via TEMPO oxidation,86 and ammonium
persulfate oxidation (APS)89 showed good results for cationic dye adsorption. Song et al.90 increased
the carboxyl content on the CNC surface using ascorbic acid and citric acid as branching groups. The
approach of Yu et al.87 for the preparation of carboxylated CNCs involved single-step
citric/hydrochloric acid hydrolysis.
For comparison, Table 3 shows the methylene blue absorption capacity of materials commonly
used as adsorbents and others, including nanocellulose, with data obtained from different studies.
Adsorption is a complicated process that depends on several factors, such as electrostatic and/or
non-electrostatic (hydrophobic) interactions and pore structure. Commercial activated carbon is the
preferred adsorbent for color removal, but it is expensive. As revised by Rafatullah et al.,85 the
adsorption capacities of commercial activated carbons and coals for methylene blue range from <10 to
~ 1000 mg/g, the majority having capacities between 200 and 400 mg/g. Two studies involving
nanocellulose exhibited an adsorption capacity of 800 mg/g,86,92 demonstrating the enormous potential
of nanocellulose as an adsorbent.
 Table 3
Comparison of adsorption capacities of NCC and other adsorbents for methylene blue

Maximum adsorption capacity

Adsorbent Ref.
qmax (mg/g)
Commercial activated carbon 980.3 [91]
NCC-carboxymethyl chitosan aerogel 785 [92]
TEMPO-CNC 769 [86]
TEMPO-periodate-hypochlorite oxidation CNF
502 [93]
(TPC-CNF)
Microporous fish waste-based activated carbon
476.2 [94]
material (MFC)
Hazelnut husk-activated carbon 476.2 [95]
Coffee husk waste 415.8 [96]
Porous carbon from tea waste 402.2 [97]
CNC-alginate hydrogel bead 256.4 [98]
Agar/κ-carrageenan hydrogel 242.3 [99]
Citrus limetta peel 227.3 [100]
Sago pith CNF aerogel 222.2 [101]
CNC 118 [86]
PMVEMA/PEG/CNC aerogel 116.2 [102]
CNC/polyurethane foam 110.5 [103]
NCC 101 [89]
CNC-ZnO nanocomposite 64.9 [104]

The increased number of adsorption sites in CNC has a positive impact when it is associated with
hydrogels. Mohammed et al.98 impregnated CNCs into alginate hydrogel beads and reported that
methylene blue removal was almost three times higher than that of hydrogel beads without CNCs. In
addition, the removal efficiency remained at ~97% after five adsorption–desorption cycles. Aerogels,
which are flexible and highly porous, usually derived by freeze-drying, are promising materials for dye
removal. To improve their structural stability and mechanical performance, CNC aerogels can be
cross-linked.102 Yang et al.92 prepared an aerogel based on CNC and carboxymethylchitosan by a
Schiff base reaction and obtained a maximum adsorption capacity of 785 mg/g, which retained the
adsorption capacity over a wide pH range for at least six cycles, demonstrating excellent reusability.
The adsorption of anionic dyes is also possible by the insertion of cationic groups onto the
backbone of CNCs, such as imidazolium and primary amino groups.105,106 The hydroxyl groups on the
surface of cellulose nanofibrils can be converted to quaternary ammonium groups using
glycidyltrimethylammonium chloride, resulting in a high cationic charge density for the adsorption of
anionic dyes Congo red and acid green 25.107

TEXTILE FINISHING
Improvement in dyeing
In addition to the potential for removing textile dyes, NCC can play an important role in more
sustainable dyeing and minimizing the environmental pollution caused by the textile industry. Kim et
al.108 reported an environment-friendly textile dyeing technology based on CNF that reduces the use of
water and chemicals in textile dyeing by one order of magnitude. This process involves coated and
anchored CNF-carboxymethyl cellulose-based hydrogels bearing reactive dye molecules on the
surface of cotton fibers. Comparable dyeing and colorfastness performance to conventional exhaust
dyeing was obtained with this approach using only 10% water, salt, and alkali. Liyanapathiranage et
al.109 demonstrated that post-treatment of CNF-colored cotton textiles with polycarboxylic acid
promotes grafting and chemical cross-linking of the CNF dye and cotton fabric surface by
esterification. This offers up to 30% improvement in reactive dye fixation and up to 60% reduction in
dye discharge.
Chattopadhyay and Patel110 prepared NCC from viscose rayon yarns and applied it to a polyester
fabric by the padding technique. NCC treatment improves the load-bearing capacity and absorbency of
the fiber. Polyester treatment enhances the color strength of the polyester fabric dyed with direct dyes
and improves the speed towards soaping.
According to Minko et al.,111 a nanocellulose solution may be employed to permanently bind dye to
textile surfaces as a uniform thin film, with binding forces much higher than those in conventional
dyeing. They produced nanocellulose (CNF and CNC) dye dispersion and applied it to cotton fabrics.
Compared to the cotton control dyed by the exhaustion method, CNF and CNC presented three- and
two-fold larger dye fixations.

Release of fragrance
Finishing textiles with fragrances is highly attractive and can result in value-added products. In
addition to the sensory aspect, which refers to the feeling of well-being and freshness in the wearer,
the essential oils used for the aroma finish can therapeutically act against stress, anxiety, depression,
and irritability.112 One of the significant challenges in obtaining fragrance products is the fast release
of fragrance and its duration, because aromatic compounds are highly volatile.
Kuhnt et al.113 developed an approach to slow down the release of fragrance by decorating cellulose
nanocrystals with β-damascone, a compound widely used in the perfume industry. Fragrance
molecules were bound to the CNC surface using a short thioeter linker, which facilitated slow
fragrance release via a retro 1,4-Michael-type reaction. Cotton sheets were washed with an aqueous
softener containing decorated CNCs. As a reference, the treatment was also performed using the neat
compound β-damascone. After 3 days of drying under ambient conditions, the amount of fragrance
released from the sheet treated with decorated CNCs was 80 times higher than that of the control
sample. The control sample contained a low fragrance concentration owing to evaporation during
drying.

Hydrophilicity and hydrophobicity

To improve the water and moisture absorption properties of polyester fabric, Zaman et al.29 treated
it with a hydrophilic surface finishing agent containing cationic CNC.
CNC, cationically modified via quaternization by grafting glycidyl trimethyl ammonium chloride,
(GTMAC) was used with a textile binder as a surface finishing system for polyester fabrics. This
treatment increased the fabric regain by more than 500% and reduced the contact angle from 132° to
42°, compared to the untreated PET fabric. The results of the analyses performed with the cationic-
CNC were much superior to those of the unmodified-CNC, in terms of hydrophilicity, as well as
durability of the treatment after multiple washing steps.29
CNC has also been used to mimic the lotus effect and create rough surfaces with
superhydrophobicity. Cheng et al.114 obtained a superhydrophobic cotton fabric using dip-coating with
cured epoxidized oil resin as a binder. The water contact angle of the cotton surface increased from 0°
to 157° after the treatment, and the fabric was able to separate the oil/water mixture with an efficiency
higher than 98%. The use of CNCs represents a more sustainable and ecologically correct alternative
to inorganic compounds normally used to obtain superhydrophobic textiles.

CONCLUSION
The textile industry is one of the oldest industries in the world. It is primarily based on the use of
commodities and is considered as one of the most polluting industries. In the last few decades, efforts
have been directed towards new products and innovations, aiming at high-performance fibers,
functionalized and value-added products, as well as more sustainable and environmentally friendly
processes. The interest in nanocellulose for textile applications has sharply increased due to their high
strength, stiffness, low weight and renewability. NCC can be isolated by simple processes from a
variety of resources, including pre- and post-consumption textile waste.
NCC has been applied as a reinforcing agent in a wide range of polymer matrices, mainly water-
soluble polymer matrices. Significant modifications, such as chemical grafting, have been developed
to overcome the limitations associated with the low thermal stability of NCC and its incompatibility
with many nonpolar thermoplastics. Methods using NCC in solution, such as wet spinning and dry
spinning, which do not involve high temperatures, have resulted in highly drawn fibers and improved
mechanical properties under optimal conditions. However, it must be assessed whether the final
properties of the fibers justify the increase in cost, time and risks associated with the solvents.
Electrospinning is the most explored method for spinning the NCC solutions with various polymers,
enabling the achievement of highly interconnected porous structures that are prominent for special
applications. In addition to the mechanical reinforcement with small amounts of NCC, these
interconnected porous structures contribute to biological features, such as biocompatibility and cell
proliferation.
Functionalization and chemical modification are also responsible for the versatility of NCC as an
adsorbent for cationic and anionic dyes. As adsorption is a complex process that depends on
interactions and involves several variables, the dye removal capabilities of NCC have a wide range,
but its capacity is similar to that of commercial adsorbents, such as activated carbon. The association
of NCC with hydrogels and aerogels tended to increase the adsorption capacity. Moreover, NCC has
played an important role in more sustainable dyeing, which offers better fixation of dyes, less
consumption of water and chemicals, and reduced dye discharge.
In general, the research and development of finishes in the textile sector with NCC can be further
explored. Each application presents unique challenges for obtaining the desired properties. The NCC
source influences the preparation and properties of the final products. NCC has a great potential for
textile applications owing to its sustainable appeal and unique properties. However, its expansion at
the industrial level still depends on the cost reduction of its processing and standardization for safety.

ACKNOWLEDGEMENTS: The author would like to thank CNPq for financial support (Process
438821/2018-1).

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