Chapter 5
Nanocellulose for Industrial Use:
Cellulose Nanofibers (CNF), Cellulose
Nanocrystals (CNC), and Bacterial
Cellulose (BC)
Angeles Blanco, M. Concepcion Monte, Cristina Campano, Ana Balea, Noemi Merayo and Carlos Negro
Department of Chemical Engineering and Materials, Complutense University of Madrid, Madrid, Spain
5.1 INTRODUCTION: CELLULOSE
AND NANOCELLULOSE
Cellulose is the most available biopolymer on earth and
the primary reinforcement component in the cell wall of
plants [1]. It is produced not only by plants but also by
fungus, bacteria, and to a lesser degree by tunicates (small
and sessile marine animals) (Fig. 5.1) [2].
Cellulose is chemically defined as a linear homopoly-
saccharide composed of β-D-glucopyranose units linked
together by β-1
4-glycosidic bonds. Its main constituents
are carbon (44.44 %), hydrogen (6.17 %), and oxygen
(49.39 %). Its chemical formula is (C6H10O5)n (Fig. 5.2),
where n is called degree of polymerization (DP) and
represents the number of glucose units, ranging from hun-
dreds to thousands or even tens of thousands.
Each monomer bears three hydroxyl groups. These
hydroxyl groups and their ability to form hydrogen bonds
play a major role in crystalline packing and govern the
physical properties of cellulose [3]. Each cellulose fiber is
formed by the union of fibrils, which are long thread-like
bundle of molecules laterally stabilized by intermolecular
hydrogen bonds [3]. The elementary fibrils seem to be
composed of 36 β-1,4-glucan chains [4] and they are
formed during the biosynthesis in the plasmatic mem-
brane. Each fibril can be considered as a string of cellu-
lose crystals linked along the fibril axis by disordered
amorphous domains. The main portion of cellulose is con-
stituted by crystallites with interspersed amorphous
regions, called native cellulose or cellulose I, whereas cel-
lulose II, III, and IV are amorphous (with cellulose II the
most stable). Cellulose I shows two different crystalline
Handbook of Nanomaterials for Industrial Applications. DOI: https://doi.org/10.1016/B978-0-12-813351-4.00005-5
74
structures (Fig. 5.3): Iα assigned to one-chain triclinic cell
unit, and Iβ assigned to two-chain monoclinic cell. The
proportion of both crystalline types is related to the origin
of cellulose; thus, bacterial cellulose (BC) is rich in Iα
whereas Iβ is mainly present in the cell wall of superior
plants.
With the use of appropriate chemical, mechanical,
and/or enzymatic methods, cellulose can reduce its size in
diameter or both diameter and length, up to the nanoscale
[5]. The term “nanocellulose” generally refers to cellulose
materials having at least one dimension in the nanometer
range. The three main types of nanocelluloses are cellu-
lose nanofibers (CNF), cellulose nanocrystals (CNC), and
BC, that differ in their dimensions, functions, and prepa-
ration methods (Fig. 5.4 and Table 5.1 [19]). These nano-
materials have grown in popularity owing to their
exceptional properties for diverse applications. Some of
the imperative properties of cellulose-based materials
such as functionality, uniformity, and durability can be
improved by the use of nanocelluloses. They present
enhanced mechanical properties due to their high surface
area, large water holding capacity, and a reactive surface
of
OH side groups, where almost any desired functional
group can be attached [6].
Based on the literature, the term microfibrillated cellu-
lose, microfibers, and microfibrils (MFC) is generally
used to describe a cellulose structure 2
10 nm thick and
several microns in length [7]. The terms nanofibrillated
cellulose, nanofibrillar cellulose, nanofibers, nanofibrils,
cellulose nanofibrils, and CNFs are also used as syno-
nyms for MFC.
© 2018 Elsevier Inc. All rights reserved.
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5 75

FIGURE 5.1 Cellulose as a natural biopolymer

obtained from (A) wood, (B) agricultural residues,
(C) bacteria, and (D) tunicates. Sources: (A) and (B)
From https://pixabay.com/; (C) Reprinted from A.,
Balea Martı´n, C. Negro A´lvarez, N. Merayo Cuevas,
C. Campano Tiedra, M. Delgado-Aguilar, P. Mutje,
et al., Celulosa nanofibrilada y su papel en la indus-
tria papelera, Ind. Quı´m. 32 (2016) 58
63 with per-
mission from Industria Quı´mica; (D) From http://
www.freeimages.com.

β-1,4-Glycosidic bonds FIGURE 5.2 Molecular structure of cellulose (n 5 DP). DP,

degree of polymerization.

CH2OH
OH 1 OH
HO O HO OH
O 4
HO O O
HO O
CH2OH OH 1 4 CH2OH

n–2

FIGURE 5.3 Crystalline structure

of cellulose Iα and cellulose II: (A)
projection of the unit cell along the
a
b plane; (B) projection of the UC
parallel to the (1 0 0) lattice plane
(cellulose I) and the (0 1 0) lattice
plane (cellulose II). Reprinted from
D. Klemm, B. Heublein, H.P. Fink,
and A. Bohn, Cellulose: fascinating
biopolymer and sustainable raw
material, Angew. Chem. Int. Ed. 44
(22) (2005) 3358
3393 with per-
mission from Wiley.
76 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

FIGURE 5.4 Nanocellulose (A) cellulose nanocrystals, (B) cellulose nanofibers, and (C) bacterial cellulose. Reprinted from A., Balea Martı´n, C.
Negro A´lvarez, N. Merayo Cuevas, C. Campano Tiedra, M. Delgado-Aguilar, P. Mutje, et al., Celulosa nanofibrilada y su papel en la industria pape-
lera, Ind. Quı´m. 32 (2016) 58
63 with permission from Industria Quı´mica.

TABLE 5.1 Terminologies Used to Describe the Three Types of Nanocellulose

Type of Acronyms
Name Typical Sources Production and

Nanocellulose Dimensions
Cellulose MFC Microfibrillated Wood (hardwood and softwood), seed fibers Pretreatment: chemical or
nanofibers cellulose/ (cotton, coir, etc.), bast fibers (flax, hemp, enzymatic
microfibers/ jute, kenaf, ramie, etc.), grasses (bagasse,
microfibrils bamboo, etc.), marine animals (tunicate),
algae and fungi
NFC Nanofibrillated Mechanical treatment
cellulose/
Diameter: 5
60 nm
nanofibrillar
cellulose/nanofibers/ Length: several μm
nanofibrils
CNF Cellulose nanofibrils/
cellulose nanofibers

Nanocrystalline NCC Nanocrystalline Acid hydrolysis

cellulose cellulose
MCC Microcystalline Diameter: 5
70 nm
cellulose
CNC Cellulose Length: 100
250 nm (from
nanocrystals plant celluloses); 100
nm
several μm (from
CMC Cellulose
celluloses of tunicates,
microcrystal
algae, and bacteria)
Wh Whiskers
CNW Cellulose
nanowhiskers
Rod-like cellulose
crystals
Nanorods
Microcrystals,
nanocrystals
Bacterial BC Bacterial cellulose Bacteria: Komagataeibacter, Zoogloea, Bacterial culture
nanocellulose Sarcina, Salmonella, Rhizobium,
Microbial cellulose
Pseudomonas, Escherichia, Agrobacterium,
Biocellulose Aerobacter, Achromobacter, Azotobacter and
Alcaligenes
Low-molecular sugars and alcohols Diameter: 20
100 nm

Adapted from D. Klemm, D. Schumann, U. Udhardt, and S. Marsch, Bacterial synthesized cellulose—artificial blood vessels for microsurgery, Prog. Polym.
Sci. 26(9) (2001) 1561
1603.
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
When subjected to acid hydrolysis, CMF undergo
transverse cleavage along the amorphous regions and the
use of sonication results in a rod-like material with a rela-
tively low aspect ratio referred to as cellulose whiskers
[8]. Other synonyms for cellulose whiskers include nano-
whiskers [9], nanorods [10], and rod-like cellulose crys-
tals [11]. Strong hydrogen bonding between the
individual cellulose crystals promotes reaggregation [12]
which leads to another cellulose structure called micro-
crystalline cellulose (MCC).
Extraction of crystalline domains from a cellulose
material is based on dissolution of amorphous cellulose in
acid media. Some decades ago, Nickerson and Habrle
[13] suggested that amorphous sections which join the
crystallites in the longitudinal direction were attacked
first, thus reducing its length. The proportion of these
amorphous or disordered regions compared to crystallites
is relatively small, so further hydrolysis will allow crys-
tallites to remain as the only cellulose material. However,
after several hours of further hydrolysis, it is assumed
crystallites hydrolyze. In 1951, Ranby, at the Institute of
Physical Chemistry at the University of Uppsala, pub-
lished the controlled sulfuric acid-catalyzed degradation
of cellulose fibers to obtain a suspension of rod-like crys-
tallites [14]. These studies woke up the interest of Derek
Gray, who started the research on CNC in the 1970s at
the University of McGill. But it was not until 1992 when
Derek Gray and his colleague Jean-Francois Revol pub-
lished their work on extracting CNC from wood [15].
Since then, thousands of works regarding the production,
characterization, modification, and application of CNC
have been published. In addition, there are a few compa-
nies that are producing and applying this material on an
industrial scale [16].
Cellulose presented in nature is mostly associated with
lignin and hemicelluloses. The removal of these two com-
pounds is inherently difficult and it sometimes requires an
increment in costs regarding chemical, mechanical, and
time expenses. However, cellulose can also be produced
by bacteria (BC) as an extracellular polymer, being chem-
ically pure and with an identical molecular structure to
that of the cellulose present in plants [17]. Although BC
has been observed for centuries in the production of vine-
gar, Kombucha tea, and nata de coco, it was not con-
firmed until 1886 by Brown [18]. He reported BC
produced by Bacterium aceti as tough to tear, with the
touch and feel of animal tissue. Since then, different bac-
terial strains have been identified to produce cellulose
from different sugars or carbohydrates, but only
Komagataeibacter (K) genus has been considered for
industrial interests.
All these exceptional properties have enabled different
nanocelluloses to be applied in diverse applications,
like reinforcement in nanocomposite materials [20],
77
biomedicine [21], conducting devices [22], membranes
for batteries [23], food packaging [24], environmental
applications [25], or sensors [26]. However, each applica-
tion requires some specific properties of the material
used, so depending on the final use, only one or some
nanocelluloses (CNF, CNC, or BC) can be the most ade-
quate. In addition, due to the high surface reactivity of
nanocelluloses, they are often modified or combined with
other compounds to obtain synergistic properties that can
fit the requirements of determined applications.
5.2 NANOCELLULOSE PRODUCTION
5.2.1 Feedstock
Nanocellulose can be derived from a wide variety of cel-
lulose sources such as wood (hardwood and softwood),
seed fibers (cotton, coir, etc.), bast fibers (flax, hemp,
jute, kenaf, ramie, etc.), grasses (bagasse, bamboo, etc.),
marine animals (tunicate), algae, fungi, invertebrates, and
bacteria.
Wood is currently the most used source of cellulose
[27,28]. Moreover, cellulose is present in wood in combi-
nation with hemicellulose, lignin, and a comparably small
amount of extractives and inorganic salts. Therefore,
wood must be treated by mechanical and/or chemical pro-
cesses to remove noncellulosic material before being used
for nanocellulose production. Wood species can be distin-
guished as hard and softwoods based on their anatomical
features. Hardwood fibers are 3
4 times shorter than soft-
wood and have more rigid structure due to their high
Runkel ratio (cell wall thickness divided by lumen radius)
[29]. Moreover, hardwood is more complex and heteroge-
neous in structure than softwood, thus requiring harder
mechanical treatment to produce equivalent fibrillation
level [30]. It should be also noted, that the use of never-
dried cellulose makes the fibrillation more favorable com-
pared to once-dried cellulose, since drying promotes irre-
versible hydrogen-bonding between nanofibrils. This
process is known as hornification [31,32].
The nanocellulose production process from these
wood pulps and its characterization are well-known [33].
However, high costs are related with the use of these raw
materials due to their high demand from pulp and paper,
construction, and furniture industries. Thus, new trends
are focused on the production of both CNF and CNC
from annual plants, agroforestry residues, water plants,
grasses, and other cellulose sources (Table 5.2). These
materials are considered as an effective alternative source
of cellulose for producing nanocellulose with acceptable
properties. Some researchers have suggested the use of
annual plants such as flax, hemp, sisal, kenaf, and agri-
cultural crops including those obtained from the empty
fruit bunches, rice, sugar cane, pineapple, and wheat.
78 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

TABLE 5.2 Cellulose Sources for Cellulose Nanofibers and Cellulose Nanocrystals Production

Cellulose Source CNF and CNC (Ref.)

Wood Softwood: pine, Douglas fir, etc. [48
50]
Hardwood: eucalyptus, birch, poplar, etc. [48,50
56]
Nonwoody plants and crops Abaca [57]
Bamboo [58,59]
Cotton [60,61]
Ficus [62,63]
Flax [57]
Hemp [57,64]
Hibiscus leaf [44]
Jute [57]
Potato tubers [49,65]
Sisal [57,66,67]
Sugar beet [68
71]
Tomato peel [40]
Water hyacinth (Eichhornia crassipes) [72]
Agroforestry residues Banana (stalks, rachis) [73,74]
Corn (husk, stalk, etc.) [75,76]
Garlic straw [46]
Lemon peel [75]
Oil palm biomass [47]
Pineapple leaf [77]
Rape (stalks) [78]
Rice (straw, husk, etc.) [49,78]
Soy hulls [79,80]
Sugarcane bagasse [81]
Tabacco [82]
Triticale [83]
Wheat straw [79]
Wood bark [84]
Animals Exoskeleton (prawns, crabs, etc.) [85]
Tunicates [11]
Others OCC [42]
ONP [43]

OCC, old corrugated containers; ONP, old newspapers.

Comparatively to wood, nonwoody plants and crops resi- environmental benefits, and low energy consumption for
dues have generally lower lignin and hemicellulose con- the isolation of cellulose particles. In addition, further
tent [34] and offer several advantages, including short fibrillation of such cellulose is also less energy-
growth times with moderate irrigation requirements, consuming [35]. However, despite the abundance of
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
nonwoody plants, their use as raw materials for nanocellu-
lose production has several limitations because of the
high labor cost of collection in developed countries, and
the high silica content which provokes some processabil-
ity problems [36].
Industrial bioresidues have also been used to produce
nanocelluloses, presenting many advantages compared
with other cellulose feedstocks, such as their low or even
negative cost and the solution of disposal problems for
industries [37]. Currently, these industrial bioresidues are
either burned to obtain electricity or used as animal feed-
ing. Therefore, the development of new value-added pro-
ducts such as nanocellulose materials from these
bioresidues is presented as a potential route to increase
the value of agricultural resources and contribute to a cir-
cular economy [37]. In the recent review of Malucelli,
Lacerda [38], a study of the influence of the raw material
on CNC properties has been carried out and the agroin-
dustrial residues are presented as an environmentally
friendly alternative to wood sources. Some of the most
recent are waste cotton cloth [39], tomato peel [40], rice
husk [41], old corrugated containers [42], old newspapers
[43], hibiscus leaf [44], soy hulls [45], garlic straw [46],
or oil palm biomass [47].
Regarding BC, two “raw materials” are involved in
the cell culture: bacterial strain and culture media.
Different attempts have been made to isolate some bacte-
rial strains with the purpose of finding a new type of bac-
teria with increased cellulose production. Among them,
the most common and effective bacterial strains are of the
genus Komagataeibacter, including the species Xylinus,
Hansenii, Swingsii, Rhaeticus, Oxydans, Oboediens,
Persimmonis, etc. [86]. However, other genus like
Zoogloea, Sarcina, Salmonella, Rhizobium, Pseudomonas,
Escherichia, Agrobacterium, Aerobacter, Achromobacter,
Azotobacter, and Alcaligenes have also proved to produce
BC [17]. These types of bacteria can be found in places
where fermentation of sugars and plant carbohydrates
takes place, like fruits [87], flowers [88], fermented foods
[89], beverages [90], temple wash waters [91], and vine-
gar [87]. Characteristics and behavior of these bacteria
have been recently reviewed by Campano et al. [86].
Genetic modification has been applied to BC produc-
ing bacteria to solve some problems present during cul-
ture, like the production of water-soluble polysaccharides
instead of BC, and/or to increase the productivity of cellu-
lose [92]. Depending on the concrete objective, different
methods have been tried, such as UV radiation [93], ethyl
methanesulfonate [93], high hydrostatic pressure treat-
ment [94], and disruption of cellulase [95].
Two major components have to be present in culture
media to allow bacteria to grow: carbon and nitrogen
sources [96]. Typically, glucose has been the most used
carbon source since it is not only presented as an energy
79
source but also a cellulose precursor [86]. On the other
side, yeast extract and peptone are commonly used as
nitrogen sources due to their high nitrogen content and
growth factors. However, the required amount of these
nutrients is relatively high for a standard amount of BC,
and together with their high cost, make BC production
process almost inviable at industrial scale.
Many decades ago, Hestrin and Schramm (HS) [97]
developed a culture media, which is composed of 20 g/L
glucose, 5 g/L peptone, 5 g/L yeast extract, 2.7 g/L diso-
dium phosphate, and 1.15 g/L citric acid. It is the most
common medium used for these types of bacteria due to
these nutrients being present in most microbiological lab-
oratories. However, some variations have been adapted
for this standard medium to increase the productivity of
BC by specific bacterial strains [98].
On the other side, due to the large amount of nutrients
required to this media, some researchers have focused
their work on the use of cost-effective carbon and nitro-
gen sources from industrial wastes or by-products [99].
Some of them are the use of glycerol from biodiesel or
grape bagasse [100], konjac powder hydrolyzate [99], cot-
ton cloth hydrolysate [101], orange juice [102], waste
from beer fermentation broth [103], and pineapple or
watermelon peels [104]. Most of them not only reduce
considerably the cost of nutrients, but also increase the
BC yield, making the process more economically viable.
Table 5.3 shows some of the used media to culture bacte-
ria and produce BC.
5.2.2 Cellulose Nanofibers
Turbak et al. [116] and Herrick et al. [117] were the first
to report the production of CNF by refining a water sus-
pension of 2 wt.% wood pulp in a PFI mill up to 10,000
revolutions, and passing it through a Manton-Gaulin
homogenizer at 550 bar [118]. As a result, they obtained
individualized CNF with a diameter of less than 100 nm.
Today, CNF can be produced through several mechan-
ical processes, such as high-pressure homogenization,
microfluidization, refining, or grinding [119]. Other less
used mechanical treatments are electrospinning [120,121],
ultrasonication [53,122,123], cryocrushing [79], or steam
explosion [124,125]. The main drawback of mechanical
processes is the high energy demand. Therefore, different
chemical or enzymatic pretreatments of pulp [126], such
as cationization, hydrolysis, TEMPO-mediated oxidation,
acetylation, and silylation [127], have been used to ease
the mechanical treatment, reducing the energy consump-
tion and obtaining the desired surface chemistry of the
product. In addition, as already mentioned the cellulose
source has a big impact on the energy requirements
[128
130].
80 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

TABLE 5.3 Culture Media Used to Produce Bacterial Cellulose

Culture Media Bacterial Strain Ref.

Lignocellulosic biomass Bagasse acid hydrolysate K. xylinus CH001 [105]
Bagasse enzymatic hydrolysates K. xylinus CH001 [105]
Konjac powder hydrolyzate K. xylinus ATCC 23770 [99]
Cotton cloth hydrolysate K. xylinus ATCC 23770 [101]
Industrial byproducts Apple residues from cider production K. medellinensis ID13488 [106]
Glycerol from biodiesel production K. xylinus NRRL B-42 [100]
Grape bagasse from wine production K. xylinus NRRL B-42 [100]
Black strap molasses solution and CSL K. xylinus ATCC 10245 [107]
Molasses K. xylinus BPR 2001 [108,109]
Waste from beer fermentation broth K. hansenii PJK [103]
Fruit peels K. hansenii MCM B-967 [104]
Beet molasses K pasteurianus HBB6, K. lovaniensis HBB5 [110]
Dry olive mill residue K. sacchari [98]
Industrial wastewaters TS, from rice wine distillery, K. xylinus BCRC 12334 [111,112]
Waste fiber sludges K. xylinus ATCC 23770 [113]
Low-solids potato effluents K. xylinus ATCC 23770 [114]
Sugar rich sources Fruit juices K. xylinus NBRC 13693 [102]
Maple sirup K. xylinus BPR 2001 [115]

CSL, corn steep liquor; TS, thin stillage.

The properties of CNF depend not only on the used
raw material and the production process but also on the
fiber history [131]. When cellulose fibers are dried, they
suffer irreversible agglomeration due to the high hygro-
scopicity of cellulose allowing the formation of additional
hydrogen bonds [132,133]. This process, called hornifica-
tion, is avoided by the use of never dried pulps [134
136].
5.2.2.1 Mechanical Treatments
Dry cellulose pulps can be fibrillated to small fragments
using mechanical methods, like milling, but it usually
leads to fiber shredding, rather than elementary fibril
delamination. Consequently, the nanofibrils present low
DP, crystallinity, and aspect ratio, and this results in rela-
tively poor mechanical properties [35]. Thus, CNF are
preferentially produced in aqueous suspension at low con-
centrations (,5 wt.%) using mechanical treatments cou-
pled with a pretreatment. It results in highly viscous
suspensions that are hard to handle and especially pump.
High-pressure homogenization, microfluidization,
refining, and grinding are the most common techniques
used for mechanical production of CNF. These techniques
are the most efficient for CNF isolation, as well as being
suitable for upscaling. Meanwhile, other methods are
being studied in order to economize the CNF production.
The main mechanical treatments reported in the literature
are summarized in Table 5.4.
Different authors have published comparative studies
among mechanical treatments and their energy demand
[147,148]. The processing cycles are affected by the pulp
used as raw material, its fiber morphology and fiber
swelling [148]. Spence et al. [147] concluded that nine
passes through a microgrinder was one of the most cost-
efficient production processes of CNF from recycled
fibers. In addition, they reported that the microgrinding of
wood fibers was more efficient in terms of energy con-
sumption than the homogenization of refined fibers. In
addition, films formed by CNF produced through micro-
grinding presented better mechanical properties.
Moreover, CNF produced by homogenization presented
the highest specific surface area and the lowest porosity
of the films [147]. On the other hand, Wang et al. [29]
observed that microgrinding fibrillation time and energy
expense trigger a decrement in the size, the DP, and the
crystallinity index (CrI) of CNF.
TABLE 5.4 Mechanical Treatments for Cellulose Nanofibers Production
Equipment/Scheme
(a) High-pressure homogenization
Description
High-pressure process
Cellulose suspension is pump at
high-pressure and passed through
a tiny gap between the
homogenizing valve and an
impact ring, dropping the
pressure, increasing the
turbulence and the temperature;
and subjecting the fibers to shear
and impact forces, which ensure
cellulose fibrillation
Conditions Comments Ref.
High pressure: 30
150 MPa Fibers are exposed to repeated [137
140]
number of passes cyclic stresses
Energy consumption: Irreversible changes of the fibers;
12,000
70,000 kWh/t increasing the specific area and
the bonding potential and
decreasing the crystallinity degree
Cinlet (%): 1
3 Homogenization conditions
(collision of particles, magnitude
of the pressure drops, turbulent
flow and high shear forces)
influence the size, aspect ratio,
and morphology of the nanofibers
An appropriate concentration of
the fiber suspension is required to
avoid clogging
Degree of fibrillation depends on
the applied pressure and the
number of passes through the
homogenizer
(Continued )
TABLE 5.4 (Continued)
Equipment/Scheme Description
(b) Microfluidization Microfluidizer includes intensifier
pump to increase the pressure
and interaction chamber, with a
specific geometry, e.g., Z- or Y-
shape, to defibrillate the fibers
using shear and impact forces
against colliding streams and the
(a) Microfluidizer channel walls
(b) Z-shape chamber
Cellulose fibrillation is achieved
by applying high pressure, strong
shear forces and impact of the
suspension against the channel
walls
After the chamber, the sample
passes through a heat exchanger
that cools the suspension at
ambient temperature
(c) Refining Diluted fiber suspension is passed
through a gap which is between
stator and rotor disks. The
surfaces of these disks are fitted
with grooves and bars against
which the pulp is exposed to
sequential cyclic stresses
Conditions
Very high pressure . 100 MPa
number of passes
Cinlet (%): 1
3
Energy consumption:
500
2550 kW h/t
Maximum speed: 400 m/s
Z or Y-shape chambers: 400,
200 y 100 μm, with an orifice
width of 100
400 μm
High pressure: 30
50 MPa
High energy consumption due to
the high number of passes needed
(16
30 times)
Cinlet (%): .3
Comments Ref.
High shear forces inside the [52,141,142]
capillary tube ensured cellulose
fibrillation. Morphological
characterization showed that the
size distribution of nanofibers is
homogenous and the suspension
is well down dispersed and stable
Interaction chamber has different
geometries and dimensions to
produce different sized materials
Plugging can be resolved by using
reverse flow through the chamber
Degree of fibrillation depends on
the interaction chamber size
(higher fibrillation was achieved
with the smaller size) and the
number of passes through the
microfluidizer
Conventional refining process [139,140,143]
used in the paper industry for
kraft pulp can be used to produce
CNF
125.000 revolutions of PFI refiner
were required to produce CNF;
this value represents roughly
50
100 times the amount of
refining energy used in refing the
same kind of pulp for
papermaking
Easy scale-up for industrial
applications
Evaluation of low-consistency
refiners to reduce the energy costs
(d) Grinding Similar manufacturing process as High pressure Easy scale-up for industrial [82,84,85,140,144
146]
refining, except that the gap applications: simply and robust
clearance for the grinder is technology
narrower than that for refiners,
Cinlet (%): 2
5 (or even 10) Less clogging during CNF
and that the rotor and stator of the
production
grinder are ceramic
Mechanical working principle is Grinding could reduce the cost of
based on a rotor
stator rotation- the production of nanocellulose at
grinding pattern. Grinder industrial scale
Grinder: Supermasscolloider or disintegrates fibers using frictional
Masuko forces and the high impact of the
grinding action of the rotor on the
stator
(e) Electrospinning Electrohydrodynamic method for Control parameters of the process Simple and versatile method. [120,121]
producing cellulose nanofibers include: (a) the solution properties
through the action of electrostatic such as viscosity, elasticity,
forces conductivity, and surface tension;
and (b) governing variables such
as hydrostatic pressure in the
capillary tube, electric potential at
the capillary tip, and the gap
(distance between the tip and the
collecting screen)
To form nanofibers, the solution is Other factors are temperature, Diameter of the nanofibers and
pumped to flow from the needle humidity, and air velocity the mat thickness can be
to form a Taylor cone at the tip of controlled varying the control
the needle when the voltage parameters
reaches a critical level. The
electrostatic force then over
whelms the surface tension at this
critical voltage to form a jet of the
solution that stretches the droplets
at the needle tip and throws them
out on the collector. As the
solvent evaporates, the nanofibers
are collected onto a grounded
mesh or plate in the form of a
nonwoven mat

(Continued )
TABLE 5.4 (Continued)
Equipment/Scheme Description
(f) Ultrasonication Mechanical process in which
oscillating power is used to
isolate cellulose fibrils by
hydrodynamic forces of
ultrasound
Diluted pulp suspension is
exposed to ultrasonic waves
( . 20 kHz), which results in
alternating low-pressure and high-
pressure waves, leading to the
creation and collapse of small
vacuum bubbles
(g) Cryocrushing Cellulose fibers are frozen using
liquid nitrogen and further
crushed by applying high shear
forces. Under mechanical impact,
ice crystals exert pressure on the
cell walls, causing them to break
and release cell wall fragments
(h) Steam explosion Pulp suspension is exposed to
pressurized steam for short
periods of time, followed by a
rapid release of pressure, which
causes a rupture of the fiber cell
wall
Conditions
Cfeed (%): 0.2
0.5
Low temperature (N2 liquid)
High pressure with steam
Comments Ref.
Low consistency of the cellulose [53,58,59,119]
suspension is required
Fibrillation efficiency varies with
fiber concentration, power,
temperature, time and fiber size
After ultrasonication, cellulose
suspensions were centrifuged to
recover CNF from the supernatant
Low-volume manufacturing
Cryocrushing is combined with [27,50,72,143]
other mechanical treatments:
disintegration or high-pressure
homogenization
Low-volume manufacturing
Rupture of the fiber cell wall, [35,124,125]
hydrolysis of significant amounts
of hemicellulose to elementary
sugars and water-soluble
oligomers and in
depolymerization of some lignin
Quality of CNF remains
questionable
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5 85

Although the processing methods have influence on
the properties of CNF, there are other depending factors,
such as the chemical composition of pulps. Lignin con-
taining CNF resulted in a cost reduction by reducing
energy and chemical expenses. Moreover, they had higher
specific surface area than CNF without lignin [130].
Unexpectedly, as the lignin content increases, the water
vapor transmission rate increases as well, indicating that
the hydrophilic nature of the material is not the unique
important parameter for barrier properties.
5.2.2.2 Pretreatments
Production of CNF using only mechanical disintegration
requires high energetic costs [147,149]. Although energy
consumption of mechanical treatments can be reduced by
using a refined never-dried pulp with short length fibers,
it is still one of the main drawbacks for CNF production
[150]. Therefore, intensive research is being carried out to
facilitate fibrillation thus reducing energy expenses.
Either enzymatic or chemical pretreatments have been
used to smooth mechanical fibrillation, but they have a
strong impact on the properties of the resulting CNF.
Fig. 5.5 shows the visual appearance of CNF suspensions
prepared by different pretreatments [35].
5.2.2.2.1 Enzymatic Pretreatments
The most used enzyme to hydrolyze cellulose fibers thus
enhancing its posterior fibrillation has been cellulase.
Despite being mainly produced by fungi, some bacteria
and actinomycetes have also been reported to present cel-
lulase activity [151]. Generally, cellulases can be divided
into three classes: (1) endoglucanases (endocellulases),
which hydrolyze amorphous regions of cellulose; (2) cel-
lobiohydrolases (exoglucanases), which progressively
cleave the ends of cellulose crystalline or amorphous
regions, producing disaccharides (cellobiose) and tetrasac-
charides, and (3) glucosidases (cellobiases), which hydro-
lyze the di- and tetrasaccharides into glucose [152]. At
least two cellobiohydrolases are found in natural cellu-
lases: cellobiohydrolase I and cellobiohydrolase II, which
attack reducing and nonreducing ends of the cellulose
chain, respectively [153]. In the enzymatic hydrolysis, cel-
lulases can be irreversibly bound to lignin, so its removal
is strictly necessary for an efficient hydrolysis [154].

FIGURE 5.5 Visual appearance of CNF suspensions (placed in Petri dishes, top view) produced using different processing conditions. Reprinted
from O. Nechyporchuk, M.N. Belgacem, J. Bras. Production of cellulose nanofibrils: a review of recent advances, Ind. Crops Prod. 93 (2016) 2
25
with permission from Elsevier.
86 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

FIGURE 5.6 Reactions of the regioselective oxidation of cellulose primary alcohol groups by: (A) TEMPO/NaBr/NaClO in water at basic pH and
(B) TEMPO/NaClO/NaClO2 in water at neutral or slightly acidic pH. Reprinted from O. Nechyporchuk, M.N. Belgacem, J. Bras. Production of cellu-
lose nanofibrils: a review of recent advances, Ind. Crops Prod. 93 (2016) 2
25 with permission of Elsevier.

Bolaski et al. [155] patented the use of cellulase to
improve cellulose fibrillation in the papermaking process.
Since then, an extensive investigation has been carried
out to find an economic way to apply this process
[156,157]. Recently, the production of CNF with the used
of mild enzymatic hydrolysis was reported [127,158,159].
In these works, a monocomponent endoglucanase
(Novozym 476 from Novozymes A/S, Denmark) was
used. Some studies [160,161] reported the use of a cellu-
lase solution (Celluclast from Novozym A/S, Denmark),
which is a mixture of endoglucanase, exoglucanase, and
cellobiase with the major activity of endoglucanase and
exoglucanase. Nechyporchuk et al. [162] compared the
production of CNF using the monocomponent endogluca-
nase and a mixture of endoglucanase, exoglucanase and
cellobiase. They concluded that the monocomponent
endoglucanase has a better effect on the nanofibril separa-
tion since the reduction in PD is not very pronounced.
Enzymatic pretreatments reduce not only the energy
requirements for fibrillation but also the mean width of
the obtained CNF, thus minimizing the cellulose degrada-
tion [127]. They also improve the strength of the gel net-
work, prevent blocking problems during homogenization
and induce a high aspect ratio on the CNF [158,159].
5.2.2.2.2 Chemical Pretreatments
Different chemical pretreatments have been studied:
carboximethylation (TEMPO oxidation and periodate

chlorite oxidation), cationization, and acidic or basic pre-
treatments [163].
Saito and Kimura [164] studied the application of
TEMPO-mediated oxidation to the fibers prior to
mechanical homogenization (Fig. 5.6) and it resulted in
almost transparent and highly viscous dispersions. By the
use of this method, crystallinities of 65%
95% can be
found [164]. The energy required for the homogenization
or other mechanical treatment after TEMPO-mediated
oxidation decreases inversely with the increasing carbox-
ylation of primary hydroxyl groups of cellulose [149].
Moreover, Li et al. [165] evaluated several lab-scale CNF
fabrication routes through cradle-to-gate life cycle assess-
ment and they concluded that this pretreatment resulted in
a lower impact than carboxymethylation. The effect of the
raw material composition on CNF produced through a
TEMPO-mediated oxidation have been studied
[48,57,166]. As a result of these investigations, it is con-
cluded that the higher the hemicellulose and the carboxyl
content of the fibers, the higher is the yield of CNF and
the light transmittance of the CNF [48,57]. This type of
CNF can be used to form films with adsorbed cationic
surfactants in order to reduce the water wettability, with-
out affecting significantly the tensile index [167]. Li et al.
[168] studied the preparation of CNF by oxidation and
sonication and they observed that with a higher sonication
time, the yield increases [168].
During the sequential periodate
chlorite oxidation,
cellulose secondary alcohols are firstly oxidized using
sodium periodate (NaIO4) to aldehyde groups, which are
subsequently converted to carboxyl groups using sodium
chlorite (NaClO2). It should be noted that this method
leads to the opening of the glucopyranose ring resulting
in 2,3-dicarboxylic acid cellulose (Fig. 5.7A) [169]. It can
increase the ductility of the nanofibrils [170], the tensile
strength, and the elastic modulus of the films prepared
from such CNF and talc [171].
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
Sulfonation introduces negatively charged groups on
the surface of cellulose and promotes the fibrillation pro-
cess [56,172]. Liimatainen andVisanko [56] treated
bleached kraft hard-wood pulp with periodate-bisulfite
(Fig. 5.6) before homogenization. CNF films obtained
from sulfonated cellulose have low anionic charge
densities (0.18
0.51 mmol/g), high elastic modulus
(13.5 6 0.4 GPa), and high tensile strength (164 6 4 MPa).
This pretreatment is presented to be a potentially green and
economic method to produce CNF, since periodate can be
efficiently recycled (90%
100% recovery).
Carboxymethylation is based on the introduction of
charged groups into the fiber wall (Fig. 5.7C) in order to
increase the electrostatic repulsion, leading to fiber swell-
ing [159]. Carboxymethylation makes the fibrils easier to
separate, facilitating the subsequent high-pressure homog-
enization process [159]. These CNF have been used in
combination of oppositely charged polyelectrolytes to
form layers that could be used for new types of sensor
materials [173]. In addition, carboxymethylated CNF
have been used for paper coating and for preparing CNF
films, which could be applied as transparent and biode-
gradable packaging films to the improvement of barrier
87
properties [174]. Eyholzer et al. [129] investigated the
preparation of water-redispersible CNF in powder form
and they concluded that carboxymethylation prevented
CNF from irreversible agglomeration during drying.
However, the main drawback of this pretreatment is the
organic solvents used in the reaction, instead of water-
based processes which are always desired for environ-
mental reasons.
The cationization increases the efficiency in the
microfibrillation obtaining a nonaggregated and
stable CNF suspension [126]. The cationic CNF could be
potentially useful in high volume applications, such as
strengthening agents for nanocomposites or paper. In this
last context, as cellulosic fibers are inherently negatively
charged, cationic CNF can replace the commonly used
cationic polyelectrolytes as efficient strength additives
[136]. Quaternization has been applied to cationize the
surface of the cellulose with quaternary ammonium
cations (NH41) [175]. This reaction can be performed
using (2
3-epoxypropyl) trimethylammonium chloride in
the presence of water, isopropanol, and sodium hydroxide
(Fig. 5.7D). Other methods to produce quaternized CNF
used (2-chloroethyl) trimethylammonium chloride
FIGURE 5.7 Pretreatments of cellulose:
(A) carboxylation via periodate
chlorite
oxidation; (B) sulfonation via perioda-
te
bisulfite treatment; (C) carboxymethy-
lation using chloroacetic acid; and (D)
quaternization using (2
3-epoxypropyl)
trimethylammonium chloride. Reprinted
from O. Nechyporchuk, M.N. Belgacem, J.
Bras. Production of cellulose nanofibrils:
a review of recent advances, Ind. Crops
Prod. 93 (2016) 2
25 with permission
from Elsevier.
88 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
(chlorocholine chloride) in the presence of dimethyl sulf-
oxide and sodium hydroxide [176] or in the presence of
periodate and (2-hydrazinyl-2-oxoethyl)-trimethylazanium
chloride (Girard’s reagent T) [177]. Their diameter and
cationic charge density were 2.6
3.0 nm and 0.35 meq/g,
respectively [136]. It has been proved that films produced
from quaternized CNF exhibit antibacterial properties
without any leaching of quaternary ammonium to the
environment [178] with promising applications in food
packaging, wound healing, or tissue engineering.
Some researchers used acidic
basic pretreatment
before mechanical isolation of CNF to extract hemicellu-
lose, lignin, and other impurities from cellulose pulp
[70,79,179]. This treatment facilitate pulp disintegration,
despite the fact that it dissolves partially some cellulose
particles. It includes the following three steps [64,180]:
(1) soaking fibers in 12
17.5 wt.% NaOH solution for
2 h to make the surface area of cellulosic fibers more sus-
ceptible to hydrolysis; (2) hydrolyzing the fibers with HCl
1 M at 60
80 C to solubilize the hemicelluloses; and (3)
treating the fibers with 2 wt.% NaOH solution for 2 h at
60
80 C to disrupt the lignin structure, and breakdown
the linkages between carbohydrates and lignin. CNF pro-
duced from bleached kraft bagasse pulp using alkali as
pretreatment (5% NaOH for 45 min at 50 C) and grinding
improved strongly wet and dry tensile strength of the
chitosan-based composites, compared to those composed
of nonpretreated CNF [181]. Using acidic
basic pretreat-
ment, lignin and hemicelluloses were partially removed
from wheat straw and soy hull fibers. The diameter of
wheat straw and soy hull nanofibers was around 10
80
and 20
120 nm, respectively, when CNF was produced
from fibers pretreated by cryocrushing and posterior fibril-
lation [79].
5.2.2.2.3 Emerging Pretreatments
Bio-based deep eutectic solvents (DES) based on choline
chloride and urea (molar ratio of 1:2) were reported for
pulp pretreatment prior to mechanical disintegration. The
pretreatment with DES was carried out at 100 C for 2 h,
and after that the suspension was passed through a micro-
fluidizer. CNF had diameters of 2
5 nm, but some nano-
fibril bundles were found with a width of 15
200 nm. It
was shown that the original DP of cellulose was preserved
after treating with DES, whereas an enhancement on fiber
fibrillation was observed [182].
A method based on the use of microemulsions with
urea or ethylenediamine was developed by Carrillo and
Laine [183] as a pulp pretreatment. It reduces the energy
consumption, due to the ability of microemulsions to pen-
etrate the capillary structures of wood. Urea and ethylene-
diamine were used due to their ability to loosen the
hydrogen bonds between cellulose nanofibrils and to solu-
bilize cellulose under certain conditions.
Ionic liquids (IL) are organic salts with very interest-
ing and valuable properties such as nonflammability, ther-
mal and chemical stability, and infinitely low vapor
pressure. Li and Wei [81] combined the used of 1-butyl-
3-methylimidazolium chloride as IL with high-pressure
homogenization to isolate CNF from sugarcane bagasse.
5.2.2.3 Posttreatments
Different posttreatments are carried out to modify the
nanocellulose surface [36,184,185]. The surface modifica-
tion of CNF improves the compatibility and homogeneous
dispersion within polymer matrices [186]. Different chem-
ical methods such as esterification, cationization, silyla-
tion, polymer grafting, and TEMPO oxidation have been
reported for the surface modification of CNF
[126,187
189]. Moreover, some treatments for CNF sur-
face modification include physical adsorption, molecular
grafting, or polymer grafting. Additionally, centrifugation,
filtration, or other techniques can be performed as a post-
treatment to fractionate the obtained cellulosic material.
5.2.3 Cellulose Nanocrystals
5.2.3.1 Acid Hydrolysis
CNC have been traditionally produced by acid hydrolysis,
where disordered or para-crystalline regions are first solu-
bilized, leaving behind the crystalline domains or CNC,
which possess a higher resistance to acid [190]. Although
both sulfuric and hydrochloric acids have been the most
used for this purpose, other acids, like phosphoric or
hydrobromic acids, can be used. However, the dispersabil-
ity of CNC produced from these acids is different. Due to
the abundance of charged sulfate or phosphate groups on
its surface, CNC obtained from sulfuric or phosphoric
acid hydrolysis dispersed readily in water, while those
produced from hydrochloric or hydrobromic acid hydroly-
sis are not as easy to disperse since their aqueous suspen-
sions tend to flocculate. In addition, differences in the
thermal stability and rheological behavior between the
CNC produced from sulfuric acid and those from hydro-
chloric acid were observed [6].
A standard recipe for the acid hydrolysis of a pulp
starts with the milling of the dry sample. Then, a solution
of 60
66 wt.% H2SO4 at an acid to pulp ratio between 8
and 20 mL/g was slowly added to the dry pulp to avoid
overheating. The reaction was kept at 40
50 C for
15
90 min. These conditions are found to vary depending
on the source of cellulose. In the book of Alain Dufresne,
titled “Nanocellulose: From Nature to High Performance
Tailored Materials,” a complete table with the different
hydrolysis conditions used for more than 30 cellulose
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
sources has been reported [191]. Typically, when the pur-
pose of the study is to optimize reaction conditions, a
pure cellulose material is used [192]. However, new ten-
dencies are focused on the use of different wastes [39,46]
to obtain a high-added-value product at low cost.
5.2.3.2 Pretreatments
Typically, to produce CNC, cellulose has to be previously
isolated to be directly attacked. The composition of the
cellulose sources depends on their origin. In the cases of
cotton, BC, and MCC, only cellulose is present. However,
when CNC are desired to be obtained from biomass,
including wood and agricultural residues, not only cellu-
lose is present but also different extractives, hemicellu-
loses, lignin, or inorganic particles. In these cases,
different pretreatments have been applied prior to acid
hydrolysis. A general procedure is often the following:
the first step is the removal of extractives (dewaxing)
using dichloromethane, acetone, or ethanol/benzene,
depending on the raw material [193]. The mixture 2:1
benzene/ethanol often gives the maximum level of extrac-
tives since low-molecular-weight carbohydrates and poly-
phenols are also dissolved. Depending on the state of the
raw material, different proportions solid/liquid have to be
used to get the best results.
After that, an alkaline process solubilizes most of pec-
tines and hemicelluloses [191]. A standard procedure
would be the treatment of the pulp free of extractives in
2
5 wt.% NaOH or KOH with a solid to liquid ratio of
1:20, stirring the solution at 80 C for 2 hours [41]. After
washing until neutral pH, several bleaching cycles are
performed to remove lignin. Bleaching agents break down
phenolic molecules present in the lignin and removes the
by-products of this reaction, thus bleaching the material
[191]. Although pulp and paper industries nowadays
mostly use totally chlorine-free processes, in research
activities, NaClO/NaClO2 continue being the standard
model [194]. Thus, a solution composed of the same
amount of acetate buffer (2 M, pH 4.8) and aqueous chlo-
rite (1.7% w/v in water), was mixed with the alkali-
treated pulp at 80 C for 2
4 hours [195]. After several
washing and cleaning steps, the pulp is ready to
hydrolyze.
As described previously, cellulose sources are being
pretreated to isolate cellulose particles before acid hydro-
lysis treatment. However, these pretreatments increase
considerably the yield loss. In addition, depending on the
final application of the CNC, a high purity is not required,
but a great effectiveness. Therefore, new tendencies of
CNC production are focused on the isolation of CNC
without a previous cellulose purification.
Recently, Campano and Miranda [43] published the
variation in CNC properties using old newspapers and
89
newsprints as raw materials, and it was proved that CNC
purity increased from 77% to 93% when pretreatment was
used. However, a direct hydrolysis without pretreatments
almost doubled the process yield, from 35% to 60%, with-
out worsening crystallinity, CNC size, or thermal
behavior.
5.2.3.3 Emerging Methods
The use of mineral acid hydrolysis for the production of
CNC, usually triggers several disadvantages, such as
high-energy consumption, toxicity, and corrosion risk.
Therefore, new tendencies are being directed by the use
of less aggressive acids, organic solvents (IL), or oxida-
tion of particles.
5.2.3.3.1 Other Types of Acids
Due to the low water solubility of solid organic acids,
they can be easily recovered after acid hydrolysis through
crystallization at ambient temperature [196]. Chen and
Zhu [197] obtained carboxylated CNC (CCNC) and CNF
from a bleached eucalyptus kraft pulp using oxalic acid at
the concentrations between 50 and 70 wt.%. They
increased the onset thermal degradation temperature to
322 C compared to 218 C for CNC produced with tradi-
tional mineral acids. In addition, longer CNC and CNF
were obtained due to the lower strength of organic acids.
Phosphotungstic acid (PTA) was also used to produce
CNC as an example of heteropoly acid, due to its rela-
tively simple regeneration and notably less corrosive
action than mineral acids [198]. They proposed the
destruction of cellulose in acetic acid/PTA with H2O2.
Obtained CNC formed stable hydrosols that after freeze-
drying tend to agglomerate into different structures
depending on the concentration.
Bian and Chen [199] used 60 wt.% maleic acid at
120 C for 120 min to produce ligno-CNC (LCNC) and
ligno-CNF (LCNF) from two unbleached hardwood
chemical pulps of different lignin contents (3.9% and
17.2%). According to their results, a low LCNC yield was
obtained (lower than 6%), defibrillating the nonhydro-
lyzed material to CNF. A lower carboxylated and there-
fore charged LCNC and LCNF were obtained compared
to lignin-free CNC and CNF, but obtaining a more hydro-
phobic and thermally stable material, which is more
favorable for composite applications.
5.2.3.3.2 Hairy Cellulose Nanocrystaloids
Van de Ven and Sheikhi [200] published the development
of a new kind of cellulose-based nanoparticles (NP) with
a crystalline body, similar to that of CNC, but with differ-
ent polymer chains at their ends. They called them hairy
cellulose nanocrystalloids (HCNC). The procedure starts
with an oxidation of cellulose fibers with sodium
90 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

FIGURE 5.8 Reaction of periodate with cellulose

yields DAC, when going to full conversion. For par-
tial conversion, it results in DAMC, a copolymer of
glucose and dialdehyde glucose. DAC, dialdehyde
cellulose; DAMC, dialdehyde modified cellulose.
Reprinted from T.G.M. van de Ven, A. Sheikhi, Hairy
cellulose nanocrystalloids: a novel class of nanocel-
lulose, Nanoscale 8(33) (2016) 15101
15114 with
permission from The Royal Society of Chemistry.

OH OH

O Cl– pH = 4.5 O
O NH O
+2 H2N N+ + 2H2O
H H
O H O N H N
NH
NH
n n

O
Cl– N+ N+ Cl–

FIGURE 5.9 Schiff base reaction between aldehyde groups on modified cellulose fibers with Girard’s reagent T ((2-hydrazinyl-2-oxoethyl)-trimethy-
lazanium chloride). Note that it is difficult to attach the second quaternary ammonium group to the same glucose unit due to steric hindrance and elec-
trostatic repulsion. Reprinted from T.G.M. van de Ven, A. Sheikhi, Hairy cellulose nanocrystalloids: a novel class of nanocellulose, Nanoscale 8(33)
(2016) 15101
15114 with permission of The Royal Society of Chemistry.

FIGURE 5.10 Reaction of dialdehyde modified cellu-

lose fibers with chlorite. Hydrogen peroxide is also added
to the reaction to convert HClO to HCl, O2, and H2O and
to minimize its reverse effect on the oxidation of DAMC.
DAMC, dialdehyde modified cellulose. Reprinted from T.
G.M. van de Ven, A. Sheikhi, Hairy cellulose nanocrys-
talloids: a novel class of nanocellulose, Nanoscale 8(33)
(2016) 15101
15114 with permission of The Royal
Society of Chemistry.

periodate, accelerated with the addition of an inert salt,
converting cellulose to a water soluble cellulose deriva-
tive (Fig. 5.8).
When the periodate oxidation is followed by a heat
treatment at 80 C, sterically stabilized nanocrystalline
cellulose (SNCC) is produced [201]. The dialdehyde mod-
ified cellulose (DAMC) particles at the ends of the cellu-
lose fibers provide steric stability and no charge. Due to
the high reactivity of DAMC, it can be modified through
a Schiff base reaction with a primary amine (R-NH2),
where the group R is attached to the DAMC, producing
the cationic CNC (CNCC) (Fig. 5.9). In this case, R is a
quaternary ammonium group [202].
However, after a chlorite oxidation of DAMC, dicar-
boxylated cellulose chains keep at their ends, providing
electrostatic and steric stability, so they have been called
electrosterically stabilized NCC (ENCC) (Fig. 5.10)
[203]. As SNCC, CNCC, and ENCC have different func-
tionalization on the ends of the particles, the range of
applications is very wide.
5.2.3.3.3 Ionic Liquids
The use of IL as green solvents to dissolve cellulose is
very powerful [204]. Recently, Iskak and Julkapli [205]
have produced CNC with the desirable yield, crystallinity,
and particle size under catalytic hydrolysis using IL. They
found that the reaction temperature and time were the key
variables affecting the yield and thermal properties of
CNC.
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
TABLE 5.5 Effect of Enzymatic Hydrolysis on Final Properties of CNC
Enzymes Fiber Diameter
(nm)
Control 20
30
Cellulase 10
20
Endoglucanase 6
15
Cellobiohydrolase 10
27
DP, degree of polymerization.
Reprinted from Z. Karim, S. Afrin, Q. Husain, R. Danish. Necessity of enzymatic hydrolysis for production and functionalization of nanocelluloses, Crit.
Rev. Biotechnol. 37(3) (2017) 355
370 with permission of Taylor & Francis.
5.2.3.3.4 Enzymatic Hydrolysis
As already mentioned, the enzymatic hydrolysis has been
used to produce CNC due to its great potential for high
saccharification efficiency and high penetration, as well
as the low pollution level. In addition, high yields and
almost pure cellulose material have been obtained. Karim
and Afrin [206] explained in their review the effect of
enzymatic hydrolysis on the properties of the produced
CNC (Table 5.5). With the use of enzymatic hydrolysis,
the environmental impact is reduced and the products can
be used in biomedical applications.
5.2.4 Bacterial Cellulose
The technology used to process BC is quite different from
that used for either CNF or CNC. BC production entails
different steps in order to obtain a product with the
desired properties at a high yield. The first step is the cell
growth, where the increase in the number of bacterial
cells is the main objective. Although Komagataeibacter
xylinus has shown the ability to grow in a wide variety of
substrates, the maximum increase of cell density can be
achieved with the proper nutrient medium. Typically, bac-
teria are incubated for 24
72 h at 28
30 C in HS
medium [97], in static or shaken culture. Campano and
Balea [86] published a review regarding the different con-
ditions of nutrient media, time, pH, temperature and type
of culture used for different bacterial strains.
In general terms, BC is hydrophilic, has high purity
(no hemicellulose or lignin) and high crystallinity, as well
as a high molecular weight. However, the properties of
the produced BC are highly influenced by the culture con-
ditions [208]. Therefore, several studies have been
focused on the media optimization to reach the required
properties for a specific application [96].
The most common fermentation method to produce
BC is the static culture (SC), since it has been proved to
produce high yields of BC. In SC, BC is created on the
91
DP Viscosity Crystallinity Alkaline Solubility Ref.
(cm3/g) index (%) (%)
753 535 71.63 21 [207]
566 413 77.04 50.1
483 358 79.59 59.6
672 483 NA 30.2
surface of the culture broth in the shape of a pellicle,
which is denser on the side exposed to air. There are dif-
ferent hypothesis regarding this fact, like the creation of a
support for living in different environments being pre-
vented from drying, contamination, and the lack of oxy-
gen and food [209]. In addition, these pellicles hold
bacteria to be in contact with the oxygen-rich air
media
interface apart from protecting them from ultraviolet light,
retention of moisture, and colonization of substrates
[17,210]. Table 5.6 summarizes the different methods
used for BC production.
Hsieh and Wang [222] varied the traditional SC
through an intermittent feeding strategy, consisting of the
addition of supplementary nutrients directly to the top of
the BC film when it is already formed. Then, BC films
with different thickness are formed in a layer-by-layer
form with high productivity. They observed that depend-
ing on the amount of fresh medium added, a controlled
distance between all BC membranes can be created
(Fig. 5.11). Through this method, a BC membrane thick-
ness of around 30 mm after 30 days of cultivation can be
created compared to 2 mm with the conventional method.
In view of a large-scale production, the implementa-
tion of agitation during culture always seems to decrease
the production time due to the improvement of the mass
transfer, apart from a higher oxygen transfer rate [86].
However, shear stress can convert most of cellulose pro-
ducing bacterial strains into noncellulose producing
mutants (Cel 2) [211].
Antibiotics are widely used in genetic engineering in
order to carry out a nonnatural function and/or express a
synthetic gene resistant to a specific antibiotic. Thus, the
need for complete sterilization of the culture of some bac-
teria is not as important with the addition of low doses of
antibiotics. Antibiotics are defined as chemicals that inter-
fere with some cellular mechanisms making cell growth
slower and some cells may even die. Some unicellular
and simple multicellular organisms produce antibiotics in
TABLE 5.6 Bacterial Cellulose Production Under Different Fermentation Methods
Method/Equipment Description
(a) Static culture Culture media inoculated
with bacteria and kept for a
long period. BC produced
in the shape of a pellicle or
membrane at the surface of
the culture broth.
(b) Agitated culture: Culture media inoculated
Shaken/impeller with bacteria and shook
180
200 rpm or agitated
with an impeller at
300
500 rpm
(c) Airlift bioreactors Culture media agitated
through the air bubbling
from the bottom
Spherical type bubble column bioreactor
(d) Rotating disk bioreactor Disks rotating with their
half area submerged in the
inoculated medium. Low
rotating speed in preferred
(4 rpm)
(e) Stirred tank reactor with Agitated culture with the
a spin filter use of an impeller and a
spin filter of stainless steel
to collect all BC formed and
the implementation of
aeration (30 L/min)
(f) Biofilm reactor with PCS implemented in a
plastic composite biofilm reactor to increase
supports (PCS) the surface area of the
impeller.
(g) TBR Tank filled with corncobs
where culture broth is
pumped from bottom to the
top at the same time than
air
BC, bacterial cellulose; TBR, trickling bed reactor; DP, degree of polymerization.
a
WHC: water holding capacity.
b
CMC: carboxymethylcellulose.
Advantages Disadvantages Ref.
G Compact and G Long culture times: 5
20 [103,211]
homogeneous pellicle days
G Low energy and G Large space required
investment expenses
G BC with extremely high
WHCa
G Easy implementation for
in-situ production of
nanocomposites
G Cost-effective G Shear stress converts [211]
G Suitable for economical microbial strains into
scale production noncellulose-producing
(Cel 2 ) mutants
G BC is attached to the
impeller, being difficult
its recovery
G Higher oxygen G Aeration also causes the [212]
availability conversion of bacteria
G Decreased power supply into Cel 2
G Adhesion of BC to the
top of the reactor
G BC with low mechanical
strength
G Low shear stress G Lower crystallinity [213,214]
G Low concentrated G Lower mechanical
solution state culture properties
G High productivity G Lower DP
G High contact with G Lower mechanical [215,216]
atmosphere: high oxygen properties of BC
availability G Lower crystallinity
G High productivity
G Low production time:
3
4 days
G Semi-continuous mode
tried satisfactorily
G High cell density G Big amount of Cel 1 [217]
G High productivity cells converted in Cel 2
G High biomass density G BC attached to the PCS: [218
220]
G Natural form of cell avoided with the addition
immobilization of 2% CMCb to the
G Higher shear force than culture media
standard impellers at the
same agitation speed
G High productivity
G High water retention on
BC
G Better mechanical
properties
G High
OH associating G More research needed [221]
degree
G Increased oxygen supply
G Decreased shear force
G High biomass density
G Higher DP
G Higher WHCa
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
a natural way to compete with other organisms in their
environment [223]. However, some of these antibiotics
can have a negative impact on the product that bacteria is
producing, in this case BC. In this context, Henning and
Catchmark [224] evaluated the effect of ampicillin, chlor-
amphenicol and kanamycin, antibiotics to which
FIGURE 5.11 Distance effect between the existing pellicle and new
air
liquid interface. Different distances between the existing pellicle
and new air
liquid interface in test tube (distance from left to right: ,1,
1, 3, 5, 7, 9 mm). Reprinted from J.T. Hsieh, M.J. Wang, J.T. Lai, H.S.
Liu, A novel static cultivation of bacterial cellulose production by inter-
mittent feeding strategy, J. Taiwan Inst. Chem. Eng. 63 (2016) 46
51
with permission of Elsevier.
93
Gluconacetobacter hansenii is inherently resistant, on the
properties of the BC produced. Ampicillin increased bun-
dle thickness but some noncellulosic deposits appeared.
Both ampicillin and chloramphenicol inhibited biomass
production (Fig. 5.12) and induced filamentation behav-
ior. Antibiotic stress can cause the production of addi-
tional exopolysaccharides.
One of the main drawbacks of the intermittent/batch
fermentation mode is the time needed by bacteria to get
used to new fermentation conditions and nutrients.
Therefore, in view of the typical demand of a product for
industrial applications, a continuous or at least semicon-
tinuous fermentation mode will be required. Several
authors are currently studying different operation modes
focusing on the highest productivity. Çakar and Özer
[225] optimized a static semicontinuous operation mode
for K. xylinus FC01, finding the highest productivity of
1.637 g/L by changing the culture volume with 1/22 ratio
in 7 days.
Fed-batch fermentation has been also tried by Bae and
Shoda [108], who cultured K. xylinus BPR2001 keeping
the levels of sugar at 20 g/L by the addition of small
amounts of molasses (6.3 g/h). Shezad et al. proved the
increment in the yield with K. hansenii PJK and evaluated
the difference in the properties of both BC produced by
batch and continuous mode [226,227]. Despite CrI and
DP being not much affected, tensile strength was strongly
reduced, from 76.7 to 19.8 MPa.
FIGURE 5.12 Cellulose pellicles treated
with 100 mg/mL antibiotics. (A) Pellicle
from cells grown for 7 days without anti-
biotics; (B) pellicle from cells grown in
the presence of ampicillin; (C) pellicle
grown in chloramphenicol; and (D) pellicle
grown in kanamycin. Reprinted from A.L.
Henning, J.M. Catchmark, The impact of
antibiotics on bacterial cellulose in vivo,
Cellulose 24(3) (2017) 1261
1285 with
permission of Springer.
94 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
BC has been produced with different morphologies
depending on the bacterial strain, addition of some com-
ponents to the medium, growing conditions, and drying
methods [228]. Different authors have taken advantage of
this fact to create BC with a desired morphology. For
example, Zang and Sun [229] restricted the movement of
bacteria through a platform with microgrooves and oxy-
gen bubbles. They obtained a BC scaffold with the struc-
ture of grid and strip that could have potential interest for
the preparation of scaffolds in the biomedical field. In
addition, Bodin and Backdahl [230] made bacteria grow
in oxygenated silicon tubes, allowing the formation of
tubular shaped BC that can be used as a digestive tract
and vascular grafts.
Once BC is produced, it can be easily modified by
coatings or chemical methods like grafting [231].
However, the in situ modification of BC during its culture
is becoming more relevant as a way of modifying some
of its properties in its early stages of production by the
addition of the required component [232].
5.2.5 Nanocellulose Structures
5.2.5.1 Nanopaper and Film
The term nanopaper has been recently created to describe
membranes made entirely by high aspect ratio (beyond
100) intertwined nanofibrils and random surface nanofi-
bril orientation [233]. In the case of films based on nano-
cellulose, they could be produced in combination with
other components (e.g., sodium caseinate, titania NP),
being in almost all cases optically transparent [234,235].
Fukuzumi and Saito [166] reported a variance in light
transmittance of films based on nanocellulose from 90%
to 78% for softwood and hardwood raw materials, respec-
tively. They concluded that the lower light transmittance
of hardwood was related to the presence of xylan mole-
cules as the main hemicellulose in the TEMPO-oxidized
CNF (TOCNs) which perhaps interfered with the com-
plete and homogenous dispersion of TOCNs in water.
In the packaging industry, nanocellulose has been
used to make films or coat packaging materials to provide
biodegradable barriers with adequate mechanical and per-
meability properties. Moreover, the information and com-
munication industry is facing an increasing demand for
printed electronics, solar cells, organic light-emitting
diode, transistors, and other electronic components and
requires new types of thin polymer films. Nanocellulose
can produce performance films with high strength,
smoothness, optical transparency, and low coefficient of
thermal expansion.
Nanopapers and films based on nanocellulose present
different advantages in comparison to ordinary papers and
films such as a smoother surface, high foldablity, and
compactness. Additionally, they show good heat transfer-
ence (e.g., low thermal expansion coefficient) and are
transparent due to densely packed structure and small
space between nanofibers that avoid light scattering
[236]. In addition, the mechanical properties of these
nanopapers and films are significantly better than ordinary
papers or films, due to the higher interfibril adhesion,
greater fibril strength, and more homogeneity [233,237].
Therefore, nanopapers and films are the perfect candi-
dates as substrates used for roll-to-roll processing in
the production of electronic devices and could replace
the expensive conventional batch processing of glass
[236]. Henriksson and Berglund [233] found higher
toughness in nanopapers produced from carboxymethy-
lated CNF.
The most frequently used techniques for the prepara-
tion of nanopapers and films are vacuum-assisted filtra-
tion technique [233,238,239], solvent casting at room
temperature or inside an oven [70,240], electrospinning,
and spin-coating [241].
Henriksson and Berglund[233] produced nanopapers
with vacuum-assisted filtration using a nitrocellulose
membrane with porous diameter of 0.65 μm at the bottom
of the stock container to retain CNF. High tensile strength
and Young’s modulus were achieved and these properties
strongly depended on the DP of CNF and overall porosity
of the nanopaper.
Osterberg and Vartiainen [242] also produced nanopa-
pers by vacuum-assisted filtration using a 10-μm porous
diameter filter which retains about 60% of the CNF.
Drainage was applied for 1 hour and formed nanopapers
were then hot-pressed for different times. The authors
found that hot-pressing provokes a substantial enhance-
ment on tensile strength of nanopapers. Hot-pressing also
avoided wrinkage of nanopapers as well as promoted den-
sification and compactness. Osterberg and Vartiainen
[242] studied the behavior of nanopapers in polar sol-
vents, reporting that, though nanopapers swelled consider-
ably, the wet strength was still high. Barrier properties of
nanopapers were also improved by showing low perme-
ability to oxygen and grease.
In a solvent casting, a nanocellulose suspension is
poured on a finite flat substrate like a Petri dish. After
pouring, the solvent is evaporated under defined condi-
tions of humidity, temperature, and pressure, to finally
obtain the films. Despite the fact that this is a relatively
simple technique, reproducible thin films are difficult to
obtain. Dufresne and Cavaille [70] produced CNF suspen-
sions from sugar beet pulp using an alkaline pretreatment
followed by shear disintegration and cryocrushing. They
produced films by casting and drying at 37 C, and studied
their tensile strength. Although Young’s modulus
increased with the mechanical treatment, the results were
lower compared to other published studies.
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
Spin-coating technique, on the other hand, is a more
technical method for the preparation of films with nano-
metric thickness, unlike solvent casting. This technique is
based on the removal of the liquid phase by applying
high-speed spinning. This high-speed spinning may also
induce a radial orientation of the crystals in the film,
depending on the conditions used. The capability of this
technique to build ultrathin and well-defined films has
made it be used when the aim is to study the interactions
of different components with nanocelluloses on the sur-
face of these materials [241].
The effect of residual lignin and heteropolysaccharides
in CNF and nanopapers was studied by Ferrer et al. [239].
For this study, CNF were produced from both bleached
and unbleached, oxygen-delignified birch fibers as start-
ing materials. Interestingly nanopapers produced with
CNF from unbleached fibers presented higher densities
when compared to nanopapers produced from bleached
pulps. It was due to the higher fibrillation degree achieved
in unbleached fibers, thanks to a higher content of hemi-
celluloses. Moreover, stress at break and energy absorp-
tion was higher in the nanopapers made from unbleached
fibers CNF.
Several researchers extracted CNF from agricultural
sources to produce nanopapers. CNF from empty palm
fruit bunch (EPFB) could be a good candidate for high
performance applications of nanopaper having similar
strength and structure of wood CNF. Nanopapers from
EPFB-CNF had high modulus (12
18 GPa) and tensile
strength (103
137 MPa) as well as low water absorption
rate [243]. Hassan and Mathew [244] compared the opac-
ity, tensile strength, and porosity of a nanopaper made of
CNF from bagasse with other made from rice straw
through refining and homogenization processes. Both
nanopapers showed lower porosity when compared to
paper sheets produced from original pulps. Nanopaper
made from bagasse-CNF exhibited better dry and wet ten-
sile strength compared to those prepared from rice straw-
CNF. The presence of silica in the rice straw nanopaper
decreased the tensile strength and transparency compared
to those of bagasse-CNF sheets.
Recently, Pereira and Waldron [245] formed different
biodegradable films through the incorporation of CNC
and citric acid to hemicelluloses extracted from wheat
straw. On the one side, CNC improved tensile strength
and modulus, water resistance, and water vapor barrier.
On the other side, citric acid presented concomitant plasti-
cizing and crosslinking effects. The optimal conditions
for a minimum water sensitivity and permeability, with
good tensile strength were found to be 5.9 wt.% CNC and
30 wt.% citric acid.
The combination of random ecofriendly copolyesters
containing butylene succinate and triethylene succinate
(TES) with CNC has been proposed by Fortunati and
95
Gigli [246] as a new class of biodegradable materials for
flexible film manufacturing. They assessed the effect of
TES and CNC content on the mechanical, physical, and
thermal properties of the produced films, and found a tun-
able capacity of the properties by the interaction of CNC
with the matrixes.
Another type of biocomposite film was developed by
Wang et al. [247], by the combination of protein extracted
from buckwheat distiller’s dried grains and BC. High
compatibility and rigidity was showed in the films by the
addition of BC. FTIR and viscosity analysis proved the
interaction of both protein and BC through hydrogen
bonds, thus affecting negatively some film characteristics
such as moisture content, water solubility, and water
vapor permeability. However, tensile strength increased
from 4.26 MPa in pure protein films to 14.98 MPa in
films containing 1.8% BC.
5.2.5.2 Foam and Aerogel
The terms foam and aerogel are commonly used inter-
changeably to describe nanocellulose-based porous mate-
rials. Lavoine and Bergström [248] defined foam as “a
mesoporous solid material (e.g., pore size in the range
2
50 nm) of high porosity (.90%)” and aerogel as “a
multiphase porous material with a porosity larger than
50% in which gas is dispersed in a liquid, solid or hydro-
gel. The diameter of the bubbles (or the pore size) is usu-
ally larger than 50 nm.”
Processing of nanocellulose foams and aerogels
involves two main steps: (1) preparation of a gel or wet
foam from a dispersion; and (2) removal of the solvent by
evaporation (oven drying), freeze drying, and supercritical
drying preceded by solvent exchange. Moreover, foams
can be structured directly from the dispersion by, e.g.,
freezing of the solvents [248].
Nanocellulose foams and aerogels display densities
ranging from 1 to 200 kg/m3, depending on the initial
solid concentration, the possible expansion of the disper-
sion during the formation of the foam or structured gel,
and shrinkage during solvent removal [248]. The porosity
of aerogels and foams made of nanocelluloses can be
even higher than 99%.
Foams and aerogels made from nanocelluloses have
potential applications in several industrial sectors (e.g.,
environmental, building, medicine) by providing excellent
mechanical structural integrity as well as thermal and
sound insulation properties. High specific surface area is
desirable for foams used as, e.g., insulators, electrodes,
catalyst supports, and adsorbents [249]. Recent attempts
have used nanocellulose foams and aerogels as scaffolds
in biomedical applications, electrical devices, and
energy storage systems, as well as thermal insulation and
fire retardant materials. In addition, they have been
96 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

FIGURE 5.13 (A) POM image of a 3.0 wt.% CNCs suspension exhibiting the isotropic nature of a colloidal suspension. (B, C) POM images of the
anisotropic phase of a 10 wt.% CNCs suspension, which indicates the liquid crystalline ordering in focal conic texture and fingerprint texture. All the
images were taken under crossed polarized light. (D
F) Illustrations of the alignment in CNCs suspension for their corresponding texture. POM,
polarized optical microscopy; CNC, cellulose nanocrystals. Reprinted with permission from G. Chu, D. Qu, E. Zussman, Y. Xu, Ice-assisted assembly
of liquid crystalline cellulose nanocrystals for preparing anisotropic aerogels with ordered structures, Chem. Mater. 29(9) (2017) 3980
3988.
r 2017 American Chemical Society.

investigated as absorbent materials [250,251], templates
for inorganic or carbon porous materials [252,253], gas
membranes/filters [254,255], and packaging materials
[248].
Anisotropic aerogels are presented as promising novel
scaffolds in materials science. However, its facile fabrica-
tion continues being a challenge. A directional freeze-
casting process was used by Chu and Qu [256] to form a
CNC anisotropic aerogel taking advantage of its liquid
crystalline ordered conformation. The produced CNC
aerogels presented lamellar macrostructural features and
optical anisotropy (Fig. 5.13). In addition, they proved
that this directional freezing was kept in the system
CNC
silica, obtaining anisotropic silica aerogels with an
ordered mesopore-imprinted structure template by the liq-
uid crystalline CNC.
Recent works have shown that nanocellulose foams
and aerogels can display thermal conductivity below
25 mW/m/K, which classifies them as superinsulating
materials [257
260]. These studies have shown that the
thermal conductivity could be reduced by combining
nanocelluloses with other components (e.g., graphene
oxide and sepiolite [258], nanozeolites [259]) or using a
novel spray freeze-drying technique [260].
BC was also used to synthesize polyurethane (PU)
foams from castor oil polyol and MDI diisocyanate using
water as the blowing agent [261]. BC formed a nano-
metric distribution of cells within the struts, triggering a
decrease of the apparent density in 7.6%. Mechanical
properties, such as specific compression modulus and
strength were improved by 4.67% and 23.6%,
respectively, with only 0.2 wt.% BC. In addition thermo-
mechanical properties were also improved by 52.4% in
the specific E’ at 30 C.
5.2.6 Nanocelluloses at the Industry
Patent applications on nanocellulose include composite
materials (38%), nonwoven absorbent webs (18%), paper
and boards (16%), food products (13%), paper and board
coatings (8%), cosmetics and toiletries (3%), and filter
materials (4%) [262,263]. Around 10 companies were
positioned to produce CNF at commercial/precommercial
scale, including Paperlogic, Forest Products Laboratory
(FPL) (cooperating with the University of Maine),
American Process (USA), Borregaard (Norway),
Innventia (Sweden), Nippon Paper, Oji Paper (both
Japan), CTP/FCBA (France), Holmen Paper (Sweden),
and others.
Celluforce is the world’s largest CNC plant, capable
of producing 300 tonnes per year of their star product
CelluForce NCCt. It was built in 2011 and is situated in
Windsor, in the state of Quebec (Canada). According to
the Celluforce web page, this company controls approxi-
mately 20% of all CNC intellectual property (active
patents), more than any other organization in the world.
The CelluForce NCCTM are produced through a reaction
process to remove amorphous components and leave
high-purity cellulose crystals. Then, they are separated,
cleaned, and spray-dried to form a powder and save sig-
nificantly in costs of storage and transportation. At the
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
plant, they recycle the chemicals used in the reaction and
converts sugars into energy [16].
On the other side, there are some other attempts to
commercialize CNC at a large scale, but without reaching
the annual production of Celluforce. Between them, there
is The University of Maine (Process Development Center)
which supplies CNC and CNF to different academic, pub-
lic, and private research groups. While the CNF are man-
ufactured at the University, the CNC are produced at the
US Forest Service’s Cellulose Nanomaterials Pilot Plant
at the FPL, located in Madison, Wisconsin [264].
Despite multiple actors producing nanocellulose nowa-
days, there is a great variety of possible CNF and CNC
grades. Moreover, no optimal processing conditions were
reported yet for the specific nanocellulose applications.
Thus, it is still difficult to assess the end-use price of
CNF but it is estimated to range between US$7 and 12
per kg of dried material [265].
5.3 NANOCELLULOSE PROPERTIES
Nanocellulose properties are directly dependent on both
cellulose source and production process. The main nano-
cellulose properties and methods to measure them are
described in this section.
5.3.1 Morphology
Morphology of nanocelluloses is one of the most impor-
tant parameters to control during production and it
depends on the cellulose source and the production
method (Table 5.7). Indeed, depending on the source of
the cellulose, the initial fibers have different lengths,
MFC angles, and amounts of residual lignin and hemicel-
luloses, or other characteristics when they come from
wastes that also influence the final CNF and CNC
morphology.
Different techniques have been used to observe CNF,
CNC, and BC morphologies and to measure the nanofiber
widths: atomic force microscopy (AFM), transmission
electron microscopy (TEM), transmission cryo-electron
microscopy, scanning electron microscopy (SEM) (with
and without the use of a Field Emission Gun), field-
emission-SEM (FE-SEM), wide-angle X-ray scattering,
solid state 13C crosspolarization magic angle spinning
NMR spectroscopy.
CNF form spaghetti-like structures consisting of long
and flexible nanofibers that alternate crystalline and
amorphous domains. Although some image analysis soft-
ware can provide information on nanofiber widths, the
determination of CNF lengths is still a challenge due to
entanglements and difficulties in identifying both ends of
individual nanofibers.
97
Generally, the diameter as well as the length of CNF
vary according to the pretreatment and mechanical treat-
ment applied. The typical dimensions of CNF produced
with a homogenizer are 20
40 nm in width and several
micrometers in length. The diameter of a cellulose nanofi-
bril can be detected at relatively high magnification, while
the length is out of the measured range. However, when
the magnification decreases to capture the whole length,
the nanofibril becomes undetectable due to its small
diameter. Moreover, it is often reported that CNF suspen-
sions are not homogeneous containing both individual
nanofibers and nanofiber bundles. Dehydration proce-
dures, mechanical delamination, grinder treatments, or
enzymatic treatments can produce MFC aggregates,
entanglements, or flocculated structures [162,266]. Thus,
the produced material generally has some portion of non-
fibrillated fibers and large fiber fragments [267,268]. In
some cases, low diameter values are mainly due to the
centrifugation step used in these studies, which aims to
eliminate the larger CNF or fibers that are still present in
the CNF suspension [269,270].
In the case of CNC, different microscopic techniques
suggested that they are rod-shaped with remarkable uni-
form width but a wide distribution of lengths. AFM and
TEM have been the most used techniques to assess the
precise shape and dimensions of these CNC. In the case
of TEM, which is the best-suited method to identify indi-
vidual CNC, the grid is usually stained with uranyl ace-
tate to enhance contrast of the sample [191].
On the other hand, the macroscopic morphology of
BC mainly depends on the cultivation method, being in a
form of pellicle when it is produced in static conditions,
or in the form of irregular granules, stellate, and fibrous
strands when the culture is agitated in either shake culture
or rotating disk system. In addition, microscopic images
also revealed morphological differences between both cul-
ture systems. Nanofibrils produced under static conditions
are more extended and piled above one another in a cross-
ing manner, and have a larger cross-sectional width. The
cellulose pellicle obtained in agitated culture consists of
entangled and curved nanofibrils. These morphological
differences contribute to varying crystallinity and other
important properties of BC [17].
Some authors have measured the dimensions of CNF
extracted from different agricultural residues [79]. CNF
produced from wheat straw and soy hulls have diameters
of 10
80 nm and 20
120 nm [79] that are higher than
those of CNF from wood. However, CNF from sisal
[160,271], carrots [272], and Luffa cylindrical [273] have
smaller diameters, of 20
65, 3
36, and 55 6 15 nm,
respectively. Therefore, it is difficult to draw a clear over-
all picture, since each source is specific and individual,
and the mechanical treatment differs from one study to
another.
98 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

TABLE 5.7 Microscopy Techniques Used to Evaluate Nanocellulose Diameter

Microscopy Type of Cellulose Source Production Method Diameter (nm) Ref.

Technique Nanocellulose
AFM CNF, film Bleached wood pulp Carboxymethylation 1 homogenization 10
15 [277]
CNF, film Bleached wood pulp Not pretreatment 1 microfluization 10
30 [277]
CNF, Wood sulfite pulp Enzymatic 5
30 [158]
suspension hydrolysis 1 homogenization
CNF, film Bleached wood pulp Periodate
chlorite 1 homogenization 3
5 [171]
CNF, Bleached sulfite Enzymatic 20
30 [159]
suspension wood pulp hydrolysis 1 microfluidization
CNF, Bleached sulfite TEMPO oxidation 1 homogenization 3
5 [270]
suspension wood pulp
CNF, Cotton TEMPO oxidation 1 homogenization 3
5 [270]
suspension
BC, suspension Acetobacter xylinum Glucose medium/static conditions Two classes: [270]
50
100; 3
5
CNF, Tunicin TEMPO oxidation 1 homogenization Two classes: [270]
suspension 10
20; 3
5
cryo-TEM CNF, Bleached sulfite Quaternization 1 homogenization 2.6
3.0 [278]
suspension wood pulp
CNF, Bleached sulfite Enzymatic 10
20 [159]
suspension wood pulp hydrolysis 1 microfluidization
FE-SEM CNF, Wood pulp Not pretreatment 1 grinding 20
50 [279]
suspension
CNF, Wood pulp Not pretreatment 1 grinding 15 [280]
suspension
CNF, Wood pulp Not pretreatment 1 blender 15
20 [269]
suspension
13
C (CP/MAS) CNF, Bleached sulfite Enzymatic 17.3 [159]
NMR suspension wood pulp hydrolysis 1 microfluidization
SAXS BC formation Komagataeibacter Culture with secondary-wall 4
10 [276]
sucrofermentans hemicelluloses from wood

CNF, cellulose nanofibers; AFM, atomic force microscopy; BC, bacterial cellulose; FE-SEM, field-emission scanning electron microscopy; cryo-TEM, cryo-
electron microscopy; CP/MAS, crosspolarization magic angle spinning.

Moreover, the lignin and hemicellulose contents have
an influence on the morphology of CNF. The diameter of
MFC produced with lignin-containing pulp was larger,
regardless of the origin of the pulp used. Hemicelluloses
also influence the CNF diameter distribution by limiting
the agglomeration between nanofibers [130,274].
Only a few studies have compared the diameter of
CNF obtained using different techniques. Most of these
studies agreed that TEM obtains the highest degree of
precision in CNF characterization, followed by SEM and
AFM. Depending on the technique, the sample prepara-
tion is different, which can also have an impact on the
measurement accuracy. In the case of TEM, as already
mentioned, the preparation of the sample is delicate, com-
pared to AFM, but the resolution and precision of the
images using AFM are not as good as those of TEM.
Some research pointed out that the FE-SEM technique
overestimated the diameter of CNC because it requires to
cover the surface with a conductive metallic layer
[166,192]. However, a new method for acquiring FE-
SEM images without the use of this layer was developed
based on low acceleration voltage (,1 kV) and short
working distance (,1 mm) [275].
Some other authors have used small-angle X-ray scat-
tering (SAXS) to study the nanoscale morphology of BC.
Penttila and Imai [276] used this technique to assess the
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5 99

effect of spruce galactoglucomannan and beech xylan on relationship with the pattern recorded by the diffraction
the morphology of BC when it is produced in situ with experiment. This size has been defined firstly by Scherrer
these components. The intensities provided by SAXS [288], who found a relationship between the crystallite
were fitted with a model covering multiple levels of the size and the width of a given peak at half its maximum
hierarchical structure. With the additional support of other (pwhm), represented in the following equation:
techniques such as SEM, TEM, and infrared spectroscopy,
Kλ
they observed that the cellulose crystals structure was τ5 (5.1)
βcosθ
converted with the addition of both hemicelluloses from
Iα to Iβ. In addition, the formed BC presented a reduced where τ is the size perpendicular to the lattice plane
cross-sectional dimension that caused their packing into represented by the peak in question, K is a constant that
bundles. depends on the crystal shape, λ is the wavelength of the
incident beam in the diffraction experiment, β is the
pwhm in radians, and θ is the position of the peak (half of
5.3.2 Crystallinity
the plotted 2-θ value).
Crystallinity of cellulosic materials is an important prop- Some results of CrI and crystallite sizes of native cel-
erty since practical performance characteristics of these luloses have been compiled in Table 5.8.
materials depend on it. The degree of crystallinity (or the CNF is composed of both crystalline and amorphous
CrI of cellulose) and/or nanocellulose and the dimensions regions, and measurement of the CrI could explain the
of the crystallites have been the subject of extensive behavior and the properties of the material. A high degree
investigations for many years [281]. The CrI is the ratio of crystallinity of 78% and 70% has been obtained for
of the diffraction portion from the crystalline part of the CNF produced from wheat straw and soy hull, respec-
sample to the total diffraction of the same sample. tively [79], and higher values (about 90%) have been
The degree of crystallinity obtained differs depending on obtained using sisal or Luffa cylindrical as a cellulose
the cellulose source. source for CNF production [160,273]. A low degree of
Although there are numerous techniques to determine crystallinity of CNF, less than 40%, was obtained using
the degree of crystallinity, the most widely used is X-ray sugar beet pulp and homogenization treatment [269,289].
diffraction (XRD) [282], considering (1) a peak intensity A low degree of crystallinity values have been also
approach [283] and (2) a peak area approach [284,285] as obtained for wood pulp [159], 8%
12% for CNF pro-
the most used methods to interpret the results. duced from bleached sulfite softwood pulp.
Segal et al. proposed a method to evaluate a CrI Additionally, the CrI of CNF decreases with an
through results of a powder diffractometer X-ray experi- increase in the number of passes through a grinder [279]
ment [283]. The hypothesis that all cellulosic material is
composed of a crystalline and an amorphous region allow
to assimilate the intensities of peaks to the different mate- TABLE 5.8 Degrees of Crystallinity (CrI), Crystallite
rials. Thus, the height of the highest diffraction peak is sizes (D(hkl)), and Lateral Dimensions (d) of
related with the amount of crystalline material, while the Microfibrils of Native Celluloses
height of the minimum valley between both peaks is
assigned to the amount of amorphous material. Then, the Cellulose CrI Crystallite Sizes d
difference between these two intensities divided by the Source (%) (nm) (nm)
intensity of the highest peak gives as a result the CrI. D110 D020
Although Segal’s method can be easily implemented Algal cellulose , 80 9.7 8.9 10
35
and readily understood, many authors find fault with this
method. Driemeier and Calligaris [286] pointed out that a Bacterial 65
79 6.5 5.7 4
7
cellulose
peak area is more representative of the crystalline fraction
of a material, instead of the peak height. Therefore, they Cotton linters 56
65 5.4 6.0 7
9
employed a Rietveld fitting of X-ray data collected with a Ramie 44
47 5.0 3
12
digital area detector to obtain integrated peak areas, and Flax 44 4
5 4
5 3
18
through the comparison between the area under the peaks
with the total corrected integrated intensity, they were Hemp 44 3
5 3
5 3
18
able to obtain the absolute fraction of the crystalline Dissolving pulp 43
56 4.1
4.7 10
30
material.
Reprinted from D. Klemm, B. Heublein, H.P. Fink, and A. Bohn,
It has been also found that different cellulose sources Cellulose: fascinating biopolymer and sustainable raw material, Angew.
are composed of different and very small crystallite sizes Chem. Int. Ed. 44(22) (2005) 3358
3393 with permission of Wiley-VCH.

[287]. Thus, this crystallite size has presented a strong

100 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

which can be explained by the hornification of the CNF
under a high shear rate. TEMPO-mediated oxidation pre-
treatment showed that both degree of crystallinity (59%

92%) and crystal size (3.2
6.2 nm) of cellulose I of the
original native celluloses are unchanged [290].
The crystallite sizes calculated using Scherrer’s equa-
tion revealed that these sizes are modified to a slightly
greater degree by the agitation of the blender compared to
the grinding process. Therefore, blending and homogeni-
zation cause less damage to the crystalline structure of
cellulose than grinding treatment [269].
However, the value of CrI seems to be more important
for CNC since it can be related to the degree of hydrolysis
and then to the yield of reaction. Table 5.9 shows the
influence of the cellulose source and the CrI calculation
method with the CrI values.
In order to evaluate the effect of common variables in
BC cultures on crystallinity and type of cellulose (Iα or
Iβ), Zeng and Liu [306] developed a Plackett
Burman
design of experiments. XRD and FTIR were the used
techniques. While pH doesn’t seem to affect crystallinity
of the produced BC, a Na1 concentration of 0.174 mol/L
in the culture media was found to strongly decrease it.
The use of fructose as a carbon source leads to a higher
CrI than glucose. It suggests that the CrI of BC depends
on its production speed. In addition, culture time was
inversely related with CrI due to the movement restriction
of bacteria with densification of BC network.
5.3.3 Degree of Polymerization
The DP of cellulose varies depending on the source and
treatment of the original cellulose fiber. It has been
widely determined according to ISO 5351 method, that
consists of diluting the cellulose sample in cupri-ethyene-
diamine (CED) solution and measuring the intrinsic

TABLE 5.9 Crystallinity Indexes of CNC Produced From Different Sources

Source Method Crystallinity (%) Reference

BC Deconvolution 85 [291]
Bamboo Deconvolution 46 [292]
Bioresidue from wood bioethanol production Segal 75 [293]
Capim Dourado Segal 91 [294]
Cassava bagasse Segal 54 [295]
Coconut husk
50
57 [296]
Deconvolution 62
66 [297]
Cotton linter Segal 84 [298]
Curaúa Deconvolution 72
87 [299]
Kenaf Segal 75
82 [300]
Luffa cylindrica Segal 96 [273]
MCC Segal 87
92 [301]
Mulberry
73 [302]
Newsprint Segal 95 [43]
Rice husk Segal 59 [41]
Rice straw Segal 86
91 [303]
Sisal Segal 75 [66]
Softwood kraft pulp Segal 80
86 [304]
Deconvolution 69
89
Sugarcane bagasse Deconvolution 70
87 [305]

MCC, microcrystalline cellulose.

Updated from A. Dufresne, Preparation of cellulose nanocrystals, in: Nanocellulose: From Nature to High Performance Tailored Materials. 2012, Walter de
Gruyter.
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
viscosity of the solution with the use of a
Cannon
Fenske capillary viscometer [43]. These values
of intrinsic viscosity were translated into DP through the
Mark
Houwink
Sakurada equation, η 5 0.42  DP when
DP ,950 and η 5 2.28  DP0.76 when DP .950 [233].
Usual DP values in wood are reported to be between
300 and 1700. In nature, cellulose has a DP of approxi-
mately 10,000 glucopyranose units in wood cellulose and
of 15,000 units in plant cellulose, whereas BC shows DP
values of 2000
6000 [307,308].
The evaluation of a statistical size of both CNF and
CNC in terms of width and length has posed a challenge
for researchers, since most of these nanocelluloses are
aggregated or dispersed in water as bundles or as web-
like networks. Therefore, Shinoda and Saito [309] found a
relationship between DP and apparent length of CNF
(Fig. 5.14), which can provide an easy and fast way to
find an estimation of their dimensions. They used
TEMPO-mediated oxidation and mechanical disintegra-
tion to produce CNF, and evaluate their influence on the
DP and the apparent length. DP values decreased drasti-
cally from 1270 to 500
600 with the increasing concen-
tration of NaClO during the TEMPO-mediated oxidation,
decreasing even more by mechanical fibrillation. As
shown in Fig. 5.14, there is a linear relationship between
both parameters when CED is used at the concentration
of 0.5 M.
As it has been already explained, CNC are produced
by the dissolution of amorphous regions through their dis-
solution during acid hydrolysis. It induces a rapid
decrease in its DP, reaching the so-called level-off DP
(LODP) when hydrolysis yield is maximum. This LODP
has been found to correlate with the periodic crystal size
along the longitudinal direction of cellulose chains of cel-
lulose sources before hydrolysis [190]. It has been
101
actually confirmed by XRD, TEM, small-angle XRD, and
neutron diffraction analyses [190]. In addition, LODP
strongly depends on cellulose origin, having the typical
values of 160 for cotton [287], 300 for ramie fibers [310],
100
200 for bleached wood pulp [304], 180 for bamboo
fibers [311], and is much higher, i.e., 2000
6000, for BC
[312].
5.3.4 Degree of Fibrillation
Different methods were reported to evaluate the degree of
fibrillation of CNF: microscopy techniques, water retention
value (WRV) [164,183,313], centrifugation [48,314
317],
or measuring light transmittance or scattering/turbidity of
CNF aqueous suspensions [48,270,314
316] or CNF films
[161,318]. Since it is time-consuming to perform the
microscopy characterization at different magnifications, as
well as to carry out the repetitive measurements to obtain
representative results, other reliable methods have been
used [35].
WRV is an empirical measurement to evaluate the
hold-water capacity of cellulose [Eq. (5.2)]. During pulp
disintegration, the WRV value increases due to an
increase of cellulose surface area. Therefore, WRV mea-
surements (adopted from TAPPI UM 256 standard) can
be used as an indication of CNF degree of fibrillation.
Different conditions were used to determine the WRV,
e.g., 6.25 g of CNF suspension at 4 wt.% [313] or 10 g of
CNF suspension at 1.4 wt.% [183] were centrifuged at
900 3 g for 30 min. Saito et al. [164] performed centrifu-
gation at 4500 3 g for 20 min. After centrifugation, the
supernatant was removed and the wet sediment was
weighed and oven dried at 105 C until reaching a con-
stant weight.
FIGURE 5.14 Relationship between DP and the length-weighted aver-
age length of CNF. The dashed line shows chain lengths having the cor-
responding DP values, assuming that molecular chains are fully
extended along the longitudinal direction in each nanofibril. DP, degree
of polymerization; CNF, cellulose nanofibers. Reprinted with permission
from R. Shinoda, T. Saito, Y. Okita, A. Isogai, Relationship between
length and degree of polymerization of TEMPO-oxidized cellulose nano-
fibrils, Biomacromolecules 13(3) (2012) 842
849. r2012 American
Chemical Society.
102 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
Ww 2 Wd
WRVð%Þ 5 3 100 (5.2)
Wd
where Ww is a weight of the wet sediment and Wd is a
weight of the dried sediment.
Through a smooth centrifugation, the yield of fibrilla-
tion has been also determined. In the proposed method, a
cellulose suspension of 0.1
0.2 wt.% was centrifuged at
4500 rpm (centrifuge model or relative centrifugal force
were not specified) [48] or at 4500 3 g [163,314] for
20 min to separate CNF (in supernatant) from nonfibril-
lated residue (in sediment). The yield of fibrillation was
calculated as follows [Eqs. (5.3) and (5.4)]:
Wc 2 Ws
Yield of fibrillationð%Þ 5 3 100 (5.3)
Wc
Wd
Yield of fibrillationð%Þ 5 3 100 (5.4)
Wc
where Wc is the weight of dried cellulose in the suspen-
sion before centrifugation, Ws is the weight of dried sedi-
ment after centrifugation, and Wd is the weight of dried
supernatant after centrifugation.
The capacity of CNF suspensions and films to transmit
or scatter visible light can also give an insight into the
degree of fibrillation. CNF remain intact in the suspen-
sion, having a higher light scattering, which results in
more transparent CNF suspensions or films. Ultraviolet-
visible spectroscopy was commonly used for both CNF
suspensions [48,270,319] and films [161,318]. An image
scanner was also used for quantification of CNF film
transparency and visualization of nonfibrillated fiber frag-
ments [240]. Chinga-Carrasco et al. [320] compared dif-
ferent optical techniques for quantification of the degree
of fibrillation of CNF in suspensions and films, such as
ultraviolet-visible spectroscopy and turbidimetry, as well
as different devices, including image scanner, fiber
optic testing apparatus (FiberMaster), and a light
source
digital CCD camera system for dynamic measure-
ments [320]. Although all optical techniques and devices
were suitable for quantifying the light transmittance of
CNF suspensions and films, the image scanner was the
most appropriate.
5.3.5 Rheology
Rheology is a key characteristic of CNF suspensions,
since it can become an inconvenience in different indus-
trial processes, especially in mixing, pumping, or coating.
CNF suspensions have shear thinning properties where
viscosity decreases or shear rate increases, further recov-
ering the initial shape as the shearing forces cease.
Moreover, CNF suspensions are thixotropic, a time-
dependent shear thinning property.
CNF suspensions retain a large amount of water
because of the highly hydrophilic nature of cellulose and
exhibit gel properties even at low concentrations [159]. It
occurs when the percolation threshold concentration of
nanofibers is exceeded. Thus, shear stress and viscosity of
CNF suspensions are commonly measured at equilibrium.
Generally, the viscosity of the pulp fiber suspension
increases dramatically during CNF preparation
[158,321,322]. It was also demonstrated that viscosity of
CNF suspensions increases when the pH is lowered [159].
It is expected that CNC display a rich set of phase
behavior with salt and pH, since they have an anisotropic
shape and electrical double layer that results in liquid
crystallinity and self-assembly [323]. Therefore, it would
be possible to provide CNC with tunable rheological
properties for a wide variety of applications. Different
pH, salinity, and CNC concentrations were used and ana-
lyzed by AFM, Z-potential, dynamic light scattering, and
SEM. Some studied regions turned the suspension into a
viscous fluid and viscoelastic soft solid, while others pro-
voked regions of instability (salt concentration is high
enough to reduce the electrical double layer but with
insufficient CNC to form a load-bearing network).
In order to assess the influence of length/surface
chemistry of nanocellulose on the rheological behavior,
Moberg and Sahlin [324] produced three different nano-
celluloses: CNC through sulfuric acid hydrolysis, CNF
through mechanical shearing, and a kind of intermediate
nanocellulose between CNF and CNC also through
mechanical shearing. These three nanocelluloses formed
three groups in terms of size, with lengths between 200
and 850, measured by TEM and AFM. This parameter,
the length (or the aspect ratio) of the NP was found to
play a key role in the rheological behavior.
CNF have been successfully used to reinforce cement
due to their exceptional mechanical performance.
However, Sun and Wu [325] used CNF as a modifier of
rheological, curing, and also mechanical performance of
oil well cement (OWC). Rheological data were best fitted
by the Vom
Berg model. CNF addition increased the
yield stress of OWC and the degree of hydration of the
final composites. Only with the addition of 0.04 wt.%
CNF flexural strength was increased by 20.7%. However,
excessive addition of CNF triggers a detrimental effect on
mechanical properties, caused by the aggregation of CNF.
5.3.6 Thermal Properties
Investigation of the thermal stability of the cellulosic
fibers is essential to establish their applicability for com-
posite technology, in which the processing temperature
for thermoplastic polymers rises above 200 C. In addi-
tion, both CNF and CNC have potential as rheology
modifiers of some fluids like drilling fluids for use in oil
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
wells or as additives in injection water for enhanced oil
recovery. Therefore, these nanocelluloses have to support
temperatures over 100 C for days or even months,
depending on the specific application [326].
Thermal degradation of lignocellulosic materials
begins with an early decomposition of hemicelluloses,
followed by an early stage of pyrolysis of lignin, depo-
lymerization of cellulose, active flaming combustion, and
char oxidation [327]. It is widely accepted that the pri-
mary thermal decomposition of cellulosic materials occurs
between 200 and 400 C, as investigated by thermogravi-
metric analysis [328].
Many researchers have investigated the thermal stabil-
ity of cellulosic fibers and the respective nanocellulose.
The structure and chemical composition of cellulose
fibers highly affect the thermal degradation. Higher
extractive contents, associated with lower crystallinity
and smaller cellulose crystallite size, can accelerate the
thermal decomposition and reduce the thermal stability of
the lignocellulosic fibers [329,330].
The higher temperature of degradation onset obtained
for CNF reflects an improved thermal behavior of the
fibers due to the removal of hemicellulose, pectin, and
lignin during the nanofiber isolation process [37].
Besides, crystalline structure in CNC is a key factor deter-
mining their thermal stability since the cellulose chains
are packed in a highly ordered manner through the strong
hydrogen bonds preventing cellulose from melting and
thus increasing the thermal stability [55]. However, CNC
produced by sulfuric acid showed a two-stage degradation
with an initial onset degradation around 120 C and a sec-
ond degradation around 225 C, which induce the degrada-
tion of cellulose at lower temperature and lead to lower
thermal stability [37].
The presence of CNC in poly(lactic acid) (PLA) or
poly(hydroxyalkanoates) increased the thermal stability
and resistance toward heat, based on the high heat resis-
tance of CNC that could hinder the heat flow to the com-
posite. Moreover, the addition of CNC is also beneficial
for the reduction of thermal expansion and rapid heat dis-
sipation of polymer [331].
Thermostability and crystallinity of nanocellulose in
relation to different drying methods (e.g., air-drying,
freeze-drying, spray-drying, supercritical drying) were
studied by Peng and Gardner [332]. They found that
supercritical-drying generated CNF with the least thermal
stability and the lowest CrI. Air-drying or spray-drying
produced more thermally stable CNF compared to freeze-
drying. Independently of the drying technique used, CNC
have similar onset temperature of thermal degradation.
However, not only is the onset temperature of thermal
degradation important but also the temperature stability
over time to be used in determined applications like rhe-
ology modifiers. This issue was studied by Heggset and
103
Chinga-Carrasco [326] through the application of heat
aging to three different nanocelluloses, including CNF
produced mechanically with two different pretreatments
(TEMPO-mediated oxidation and carboxymethylation), as
well as CNC. Temperature stability was better for CNC,
being stable after heating to 140 C for three days. In addi-
tion, they evaluated the effect of different additives to
these nanocelluloses. Between all, cesium formate and
sodium formate further increased the temperature stability
of the dispersions.
In the case of BC, the combination of high crystallin-
ity and high water content provide a good thermal stabil-
ity, being able to sterilize it by an easy heating process
like autoclaving [333]. This fact can be a great advantage
in the biomedical field.
5.3.7 Mechanical Properties
With high strength and stiffness, nanocelluloses are
suitable to become a promising reinforcing element for
different matrices (e.g., chitosan, thermoplastic polymers,
paper) [148,334,335].
CNF not only have active chemical properties
endowed by the hydroxyl and carboxylate groups, but
have excellent mechanical properties, for example, the
Young’s modulus of single CNF prepared by TEMPO-
oxidation is 145.2 6 31.3 GPa [11].
CNC have exceptional mechanical properties because
of the removal of the amorphous parts of the nanofibers
that increase the interchain hydrogen bonds in the crystal-
line regions, which provide a strengthening effect. Its
values for tensile strength (7500
7700 MPa) together
with Young’s modulus (130
250 GPa) [3,336] are com-
parable with carbon fiber of TORAYCAs T1000G, one
of the world’s best mechanical properties material, with
values of 6370 MPa for tensile strength and 294 GPa for
Young’s modulus [86]. Additionally, the mechanical
properties of CNC also depend on their cellulose type,
because each type of cellulose has its own crystalline
organization and structure, which determine its mechani-
cal properties [3]. The incorporation of high strength
CNC could overcome the poor mechanical properties of
plant oil-based materials like soybean oil [337].
Nevertheless, because of their limited compatibility with
typical matrixes and their difficulty to disperse, the prop-
erties of the composites reinforced with CNC are usually
far below from that could be expected [337,338].
According to several studies, a typical tensile strength
of BC membranes is in the range of 200
2000 MPa,
while Young’s modulus is usually in the range of
15
138 GPa [308,312,339]. These excellent mechanical
properties are directly due to their high DP and CrI, apart
from nanofibril structure with high aspect ratio, which
make BC be used to reinforce materials.
104 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
Zeng and Laromaine [340] evaluated the influence of
bacterial strain and drying method of the membranes on
the porosity, transparency, water absorption capacity
(WAC), and mechanical properties. Gluconacetobacter
xylinus and Gluconacetobacter europaeus were used as
bacterial strains, and room temperature, freeze drying,
and supercritical were the drying methods used. They
observed that BC films produced from G. europaeus were
not much affected by the drying method. With the use of
supercritical drying, BC films were mechanically robust
and extremely lights, 0.05 g/mL, with 96% of porosity
and 110 times WAC of their dried weight. However, BC
films produced by G. xylinus were more sensitive to the
drying method. In general they were denser, 0.06
0.2 g/
mL, with porosities between 60% and 90% and WAC 66
times their dried weight.
5.3.8 Optical Properties
Particles with diameters less than one tenth of visible light
wavelengths are not expected to cause light scattering
[341]. CNF are typically in this size range and therefore,
unless significant nanofiber agglomeration occurs, CNF
suspensions are highly transparent. Therefore, films of
20 μm thick produced with TOCNs obtained from hard-
wood and softwood have 78% and 90% light transmit-
tance at 600 nm, respectively [166]. In addition, light
transmittance at 600 nm of 20 μm thick films could be
improved from 61% to 82% by subjecting the initial CNF
gel suspension to three additional homogenization passes
before film preparation [318]. Carboxymethylated CNF
with low hemicellulose content tend to form large fiber
fragments and aggregates of micron size, which can com-
promise film transparency.
Some researchers found that film surface roughness
significantly reduced the light transmittance of nanocellu-
lose films. When film surfaces were polished or impreg-
nated with an optically transparent polymer layer (e.g.,
using an acrylic resin) the total light transmittance could
be increased up to 89.7% [342].
BC has been presented as a promising material for
optically transparent composites. Patchan and Graham
[343] tried to prepare a material suitable for use on the
ocular surface. For this purpose, BC in the form of hydro-
gel, with high transparency, high mechanical strength,
biocompatibility, and wound-healing enhancement are
critically important. Enough moisture on the ocular sur-
face is also key for conjunctival and corneal wound heal-
ing. BC has been shown to be both biocompatible and
biodegradable (biosorbable) in vivo [344]. Patchan and
Graham [343] used cellulose materials from wood pulp,
cotton, and bacteria and dissolved them in lithium chlo-
ride/N,N-dimethylacetamide to form regenerated cellulose
hydrogels. They found that overnight activation time
increased optical transparency of the hydrogels from 77%
to 97% at 550 nm.
5.3.9 Surface Charge
Surface charge is one of the most important properties
affecting the performance of nanocellulose particles in
different applications, such as imaging and drug delivery.
A controlled surface charge can not only improve the
speed that nanocelluloses are cleared out by the host sys-
tem, but also they can increase colloidal stability in differ-
ent fluids and avoid their aggregation in the presence of
salt, blood or plasma [345].
Zeta potential has been used to evaluate the surface
charge of NP, and then assess the degree of agglomeration
of nanocelluloses. Zeta potential can be estimated by fol-
lowing the moving rate of charged particle (negative or
positive charge) across an electric field. A value of zeta
potential smaller than 215 mV means the NP start to
agglomerate, while higher than 230 mV shows enough
bilateral repulsion and colloidal stability [346]. According
to bibliography, zeta potential values are around 246 mV
for CNF produced by TEMPO-mediated oxidation due to
carboxyl groups, 235 mV for CNC because of sulfonate
groups, and 223 mV for ultrasonicated produced nano-
cellulose owing to its natural hydroxyl groups [346].
As both CNF and CNC produced through traditional
methods are negatively charged, cationic demand (CD)
was also used to measure the surface charge of these par-
ticles [314]. CD has been defined as the amount of highly
charged cationic polymer required to neutralize the sur-
face of a particle suspension. Poly-DADMAC has been
the most used titratant for such tests [347].
Despite the importance of a high surface charge on
CNC, traditional preparation methods do not offer a high
flexibility on surface charge control. Hosseinidoust and
Alam [345] reported a method to synthesize CNC with
remarkably high carboxyl content (6.6 mmol/g) and with
continuous control over surface charge. The CNC suspen-
sions were highly stable with low aggregation, even at
high salt concentrations or serum-containing media. This
procedure consisted of three reactions, with NaIO4,
NaClO2, and a third one with HCl, by varying the reac-
tion time to obtain different surface charges.
CNC were modified through the grafting of imidazole
functionalities using a one-pot functionalization strategy
[348]. Those modified CNC (m-CNC) were shown to
have a pH responsive surface charge, being positive
below pH 6 and negative above pH 7. Then, they proved
their efficiency on the reversible flocculation of Chlorella
vulgaris using CO2 to induce flocculation. With a CNC
dose as low as 200 mg/L, they reached a flocculation effi-
ciency up to 90%.
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
5.3.10 Gel Point
The lowest solid content at which a fiber suspension
forms an interconnected network is called the gel point,
and it is related to the fiber aspect ratio. This technique
has proved to be an excellent and simple tool to evaluate
the CNF quality through the comparison of the relative
shortening of fibers with diameter reduction [349].
Raj and Mayahi [350] first studied the required condi-
tions to measure the gel point through sedimentation.
High yield CNF were found to produce anomalous sedi-
mentation data because of the electrostatic repulsion from
surface charges. However, with the addition of high levels
of Na1 or Ca21 ions, the electrostatic interactions
between fibers were reduced, thus settling normally. The
aspect ratio of three different feedstocks used increased
with increasing homogenization, proving that the fiber
delamination dominated over fiber shortening. Then, the
slope of the aspect ratio versus energy consumption
showed the ease of processing of each feedstock.
This technique has been used to quantify flocculation
mechanisms, among others such as floc size, strength, and
reflocculation ability of MFC through Focused Beam
Reflectance Measurements [351]. Polyelectrolyte mor-
phology, charge density, molecular weight, and CMF con-
centration were studied in the adsorption and flocculation
of MFC. Linear Cationic Polyacrylamide and Branched
Polyethyleneimine (PEI) were used as polyelectrolytes.
The gel point technique allowed the authors of this study
to realize that the flocculation mechanism was not purely
charge neutralization. The reason was that the minimum
gel point was not the point of zero charge. This was
attributed to the high polydispersity of the commercial
polyelectrolyte PEI used, that formed some bridges
through the largest molecules thus changing the minimum
gel point.
5.4 NANOCELLULOSE APPLICATIONS
The applications of nanocelluloses are linked to their
properties, which include light weight, nontoxicity, high
strength and modulus, dimensional stability, thermal sta-
bility, high thermal conductivity, high optical transpar-
ency, low oxygen permeability, modest abrasivity, and
the fact that it is reusable, recyclable, environmentally
friendly, and biodegradable.
There are several potential markets for nanocellulose-
based materials (Table 5.10), where envisaged applica-
tions include high-volume processes in pulp and paper,
plastics, automotive, food industry, or building sectors
(e.g., strength additives in nanocomposites, barrier/coating
applications, food additives), and low-volume applications
in medicine, cosmetics, and pharmaceuticals sectors (e.g.,
drug delivery, implants). Moreover, there are some novel
105
and emerging applications based on the electrical and
photonic properties of nanocellulosic materials. Some of
them include organic LEDs, flexible electronics, photo-
voltaics, 3D-printing, photonic films, and recyclable
electronics.
5.4.1 Nanocomposites
Nanocelluloses have been largely known as promising
strengthening agents for different matrixes (Table 5.10a)
in several industrial sectors (e.g., plastics, automotive,
building, plastics) with numerous well-known advantages
as already mentioned [384,385]. Moreover, they can be
used as reinforcement in transparent nanocomposites due
to the size of the fibrils and crystals. However, there are
also some disadvantages, for instance, high moisture
absorption and limitation of processing temperature.
Nanocelluloses are hydrophilic which hampers interfacial
compatibility with most hydrophobic polymer matrices.
By providing hydrophobicity surfaces to the nanocellu-
loses, interfacial wetting and interactions with commodity
polymer matrices were improved [386]. Maleic anhydride
grafted coupling agent was used to process polypropylene
(PP)
CNF composites, which showed more than 50%
increase in the mechanical strength [387]. Indeed, ligno-
cellulosic materials start to degrade near 220 C, restrict-
ing the type of matrix that can be used [388].
Traditionally, the mechanical reinforcement of nano-
composites containing CNC is attributed to the formation
of a percolating network structure above the percolation
threshold resulting from hydrogen bonding between NP
[389], but poor interface compatibility usually limits their
reinforcing effect [20]. However, such assumptions are
valid only for CNC with high aspect ratio and often are
misinterpreting the reinforcement obtained at low volume
fraction of filler loading. CNC were evaluated as a rein-
forcement agent of different polymer matrices such as
natural rubber [390], poly(styrene-co-butyl acrylate)
[391,392], PLA [393], poly(vinyl alcohol) (PVA) [394],
and poly(epsilon-caprolactone) [395]. In most cases, the
mechanical properties could be substantially improved
depending on the concentration and homogeneity of CNC
dispersion.
Recently, CNC were also used as filler of poly(L-lac-
tide) (PLLA) to produce a highly biodegradable and tough
nanocomposite [396]. The procedure starts with the ring
opening polymerization of D-lactide and a ε-caprolactone
mixture to obtain CNC-P(CL-DLA), followed by further
polymerization of D-lactide to obtain CNC-rD-PDLA.
Then, different proportions of CNC-rD-PDLA were added
to a PLLA matrix. Through a chemical characterization,
they confirmed the successful grafting of the rubber and
the PDLA segments onto CNC. Mechanical analysis
showed improved tensile toughness and 20-fold increase
106 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

TABLE 5.10 Nanocellulose Applications in Different Industrial Sectors

Industrial Sector Application Ref.

High-volume manufacturing processes
(a) Nanocomposites G Polymeric matrix reinforcement [36,352
355]
G Techniques: extrusion, hot compression, solvent casting, electrospinning, etc.
G Types of polymeric matrix: PLA, polymethylmetacrylate, PVA, starch, PCL,
polyhydroxibutyrate, etc.
(b) Plastics G PE and PP reinforcement [36,356]
G Food packaging: barrier properties (air, oxygen and water) and mechanical properties
improvement.
(c) Paper and G Reinforcement agent for paper and paperboard (bulk and coating addition). [357
359]
cartonboard G Print quality of fiber sheets (e.g., linting control, ink density, paper gloss)
G Papermaking wet-end additives
G Food packaging: barrier properties (air, oxygen, and water) and mechanical properties
enhancement
(d) Building G Reinforcement material [325,356,360]
G Concrete formulation for reinforcement
G Thermal insulation: aerogels
(e) Automotive G Light and reinforcement agent [356,360]
(f) Textiles G Conductive fabrics [361,362]
G Antimicrobial fabrics
(g) Food G Emulsifying and stabilizing ingredient [363
365]
G Additive: low calorie content
G Food packaging
(h) Environmental G Water treatment: heavy metals, organic compounds, oil, etc. [366
372]
G Air treatment: CO2 capture, etc.
G Herbicides/pesticides adsorption
G Oil adsorption
Low-volume manufacturing processes
(i) Medicine/ G Tissue bioscaffolds for cellular culture [128,373
376]
Pharmaceuticals G Drug excipient and drug delivery
G Immobilization and recognition of proteins and enzymes
G Substitutes/medical biomaterials:

Blood vessel replacement

Soft tissue
ligament, meniscus, and cartilage replacements

Nucleus pulposus (intervertebral discs) replacement
G Advanced nanomaterials for tissue repair, regeneration and healing

Skin tissue repair and wound healing

Bone tissue regeneration and healing

Other tissue repair: wound-healing platform for traumatic tympanic membrane,
reconstruction of damaged peripheral nerves, etc.
G Antibacterial/antimicrobial nanomaterials
G Other biomedical applications

Capture DNA oligomers

Purify blood as hemodialysis membrane
(j) Cosmetics G Hygiene and absorbent products: high absorption capacity [377,378]
Novel and emerging
(k) Rheological G Functional pigments and paint products [325]
modifier G Oil extraction
(l) Biosensors/ G Biosensors [379
381]
electrodes G Flexible electrodes: processable polyaniline suspensions through in situ polymerization
onto nanocellulose

(Continued )
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
TABLE 5.10 (Continued)
Industrial Sector Application
(m) Electronic G Electrical conductors: processable polyaniline suspensions through in situ
devices polymerization onto nanocellulose
G Conductive particles synthesis
G Antistatic coatings
G Flexible printed electronics
(n) Nanopaper G Fire-retardant and ductile: clay nanopaper based on montmorillonite in matrix of CNF
and CMC
(o) Others G Advanced composite materials: aerospace structure and interiors
G 3D printing
G Organic LEDs
G Recyclable electronics
PE, Polyethylene; PP, Polypropylene; PLA, poly(lactic acid); PVA, poly(vinyl alcohol); PCL, poly(epsilon-caprolactone); PP, polypropylene; CNF, cellulose
nanofibers; CMC, carboxymethylcellulose.
in strain at break with the addition of 2.5% CNC-rD-
PDLA.
Quaternized tunicate CNC (QTCNC) have been
proved to act as both nanofillers and physical crosslinkers
in a poly(acrylic acid) (PAA) network [20]. Their inter-
face compatibility was assumed to be by electrostatic
interaction between the positive charges of QTCNC and
the negative charges of PAA. The nanocomposite hydro-
gel exhibited pH-sensitive swelling and enhanced
mechanical properties.
Rusmirovic and Ivanovic [397] m-CNC by the intro-
duction of reactive vinyl groups on the CNC surface
through esterification with oleic acid, linseed, or sun-
flower oil fatty acids, and by amidation of maleic acid/
ethylene diamine with methyl ester of fatty acid. The
m-CNC were vacuum or supercritical CO2 dried, obtain-
ing different morphologies from nonuniform layered to
spongy. Then, m-CNC were added to an insaturated poly-
ester, getting an increase of stress at break in the range
76%
93%, with 1 wt.% of m-CNC.
Crosslinking agents have been typically used to pre-
pare nanocomposites with determined densities that end
in the appropriate porous structure, mechanical perfor-
mance as well as thermal properties. Recently, the effect
of different crosslinking agents on morphological, struc-
tural, thermal, mechanical, and cytocompatibility (cell
adhesion and proliferation) properties of scaffolds of
CNC reinforced PVA/sodium alginate, fabricated by
freeze-casting and freeze-drying methods, has been inves-
tigated [398]. Among all studied crosslinking agents (cal-
cium chloride, orthophosphoric acid, and borax), borax
hybrid scaffold showed good fibrous porous structure
with high porosity (95.2%), the highest water uptake
capacity, good thermal stability, mechanical stability
(storage modulus), and in vitro cell adhesion and
107
Ref.
[379,382]
[383]
[360]
proliferation with fibroblast cells. However, a big varia-
tion was found between all of them that can be varied to
design and fabricate scaffolds for specific applications.
The reinforcing effect of CNF is strictly dependent on
the interactions of the CNF with the matrix, as well as the
CNF surface area, which result in stiffer composite mate-
rials due to a higher contact surface. CNF were also stud-
ied as nanoreinforcement in different matrices such as
PLA [355], PVA [399], hydroxylpropylcellulose [400],
and PU [401]. Hietala and Sain [402] demonstrated that
CNF dispersion in the PVA matrix was better when CNF
contained pectin and hemicelluloses due to the reduced
formation of hydrogen bonds by physical blocking and
electrostatic repulsion.
Cao and Zavattieri [403] assessed the effect of the
CNC agglomeration on the improvement of cement pastes
strength. According to rheological measurements,
agglomerates appear when CNC concentration exceeds
1.35% (v/v) with distilled water or 0.18% when a cement
paste pore solution is used. When CNC were added at this
concentration (0.18%), the maximum strength was
reached. With the use of ultrasonication, CNC were effec-
tively dispersed, obtaining enhancements up to 50%
instead of 20%
30% without its implementation.
Recently, CNF from eucalyptus pulp, produced by high-
pressure homogenization, also was used as cement
reinforcement. Results showed an improvement in the
compressive strength and the thermal conductivity by
more than 50% and 20%, respectively, with 0.3 wt.% of
CNF. Mohammadkazemi and Aguiar [404] developed a
green hybrid composite, composed of cement, bagasse
fibers, and BC incorporated in different states: as powder
or gel, or coated onto the bagasse fibers. Inverse gas chro-
matography results showed an increase in reactivity of the
fiber-cement surface with the BC addition. When BC was
108 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
added in gel state, the surface basicity was found to
decrease (Ka/Kb ratio between 2.88 and 5.75), increasing
the organic matter at the surface and being more suscepti-
ble to hydration. Moreover, when BC was added as a
coating of fibers, the fiber mineralization was prevented,
increasing the inorganic matter at the surface and
therefore the surface basicity (Ka/Kb ratio lower
than 2.00).
Recent studies have highlighted the potential of BC as
reinforcing agent in nanocomposites [405
409]. BC were
also used to reinforce an acrylic resin, thus forming
optically transparent composites [407]. To improve this
property, BC was acetylated until a degree of substitution
of 1.76. BC surface properties were changed and the
moisture content of the composite was reduced to about
one-third, but excessive acetylation resulted in an increas-
ing hygroscopicity.
The weak adhesion between intrinsically polar plant
fibers and nonpolar polymer matrices has limited its fabri-
cation. Therefore, different studies regarding the adhesion
improvement between both components to develop a use-
ful and stable composite have been reviewed. Juntaro and
Pommet [409] developed a truly green technique consist-
ing of modifying natural fibers by attaching BC to the
fiber surface. Unidirectional natural fiber reinforced com-
posites of cellulose acetate butyrate and PLLA were
developed to assess the effect of fiber modification on
their reinforcing effect. Tensile strength was found to
increase strongly by the addition of BC modified fibers,
obtaining an increase of 44% in parallel measurement and
68% in the off-axis composite strength. In a posterior
study, Juntaro et al. [408] demonstrated that BC can be
attached to the surface of sisal fibers through the in situ
culture of cellulose producing bacteria. The presence of
BC enhanced the interfacial adhesion between the cellu-
lose vegetal fibers and the polymer matrix, leading to
improved mechanical properties and reduced water
uptake.
Through the solvent casting and particulate leaching
methods, Abu Ghalia and Dahman [410] reinforced the
copolymer polylactic acid (PLA)/polyethylene glycol
(PEG) with different proportions of BC (1
10 wt.%)
using silane as coupling agent. Results showed an optimal
dose of BC of 5 wt.%, obtaining 230 mm pore size (with
uniform size and shape), 9.8 MPa of compressive strength
and a porosity of 80%. Thermodynamic stability and crys-
tallinity were also improved.
In order to reinforce PVA, BC was added to the cul-
ture medium to allow the in situ assembly of a nanocom-
posite [411]. Both Young’s modulus and tensile strengths
were improved, reaching increases of 680% and 40%,
respectively, with 14% BC loading.
One of the main factors influencing the reinforcing
effectiveness of fibers is their alignment in the
preferential direction. This fact has been previously stud-
ied by Rahman et al. [412], who also developed a facile
method to fabricate aligned BC through the cultivation of
bacteria inside polydimethylsiloxane tubes followed by an
optimum wet-stretching. An optimized stretching of the
tube-shaped BC at a crosshead speed of 0.03 mm/min and
draw ratio of 1.20 was translated into superior mechanical
properties compared to traditional BC pellicle. More spe-
cifically, tensile strength was increased by 230%, Young
modulus by 330%, and orientation indices of 135%. This
BC alignment was proved by the fabrication of high-
performance green composites with soy protein by a
vacuum-assisted resin impregnation process. Both tensile
strength and modulus improved by 275% and 300%,
respectively, compared with the composite fabricated
without BC alignment (Table 5.11).
5.4.2 Biomedicine
In recent years, nanocellulose has been successfully used
by many researchers in several biomedical and cosmetic
applications (Table 5.10i, j) [373].
Materials based on collagen can be of special interest
in biomedicine due to their inherent properties, such as
low toxicity, high structural capacity support, controlled
biodegradability, and biocompatibility. However, thermal
and mechanical properties are still a challenge. Recently,
Rodrigues and de Souza [438] added CNC with three dif-
ferent plasticizers by two different methods to a matrix of
collagen. The best results were obtained with glycerol as
plasticizer being first stirred with the CNC and then added
to the collagen solution. Tensile strength was improved
by 250% and strain at break in 6.5-fold. Thermal stability
was also enhanced, retarding the onset temperature from
285 to 313 C.
Khalid and Khan [439] proved the synergistic effect of
the inherent wound healing characteristics of BC and
antimicrobial properties of zinc oxide NP. They investi-
gated the in vivo wound healing and tissue regeneration of
the material in burn BALBc mice model, and they showed
66% healing activity. Nanocomposites exhibited 90%,
87.4%, 94.3%, and 90.9% activity against Escherichia
coli, Pseudomonas aeruginosa, Staphylococcus aureus,
and Citrobacter freundii, respectively. For uses in the ther-
apy of skin wounds, Sanchavanakit and Sangrungraungroj
[440] developed BC films with a thickness of 0.12 mm, an
average pore diameter of 224 Å and a total surface area of
12.62 m2/g. They evaluated the potential biological mech-
anism of action through the use of human keratinocytes
and fibroblasts and demonstrated that the BC film allows
the growth, spreading, and migration of human keratino-
cytes but not those of human fibroblasts.
Recently, Ullah and Badshah [441] prepared BC cap-
sule shells for immediate drug delivery, being a promising
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5 109

TABLE 5.11 Properties of Nanocellulose Composites

Matrix Type Cellulose Content Tensile Young’s Process Ref.

Nanocellulose Source (wt.%) Strength Modulus
(MPa) (GPa)
PVA CNF Curava 5 B80a B1.6a Solution casting [413]
CNF flax 5 33.07 0.536 [414]
MCC Avicels PH- 5 B80 a
B4 a
[415]
101
CNF Pulp 60 55.6 1.022 [416]
CNC Banana 3 46 2.940 [417]
CNF Aloe vera 10 B160 a
7.99 [418]
CNF Sugar beet 2 31.0 1.643 [402]
residue
CNC Cotton 5 1890 42 Gel spinning [419]
PLA CNC Flax 2.5
5.0 19.4
30.9 1.48
2.17 Solution casting [420]
MCC Pulp 20 38.1 4.7 Extrusion [421]
CNF Pulp 5 71.5 3.6 [335]
CNF Bamboo 2 53 2.2 [422]
BC 2 57 2.3
MCC 2 71 2.6
CNF Wood pulp 10 75 4.7 Compression [354]
molding
Poly MCC Avicels FD- 20 8.52 0.0596 Electrospinning [423]
(ethylene 100
oxide)
CNC 1 3.5 0.072 [424]
CNF 4 2.2 0.051
CNC 7 17.6 0.937 Solution casting [425]
CNF 7 27.3 1.727
Polyester CNC Cotton 1 59 1.9 Solution casting [397]
a a
Poly CNF Kraft pulp 5 65 3.10 Injection molding [426]
(propylene)
Methacrylate CNC Lignin 0.5 68.5a 1.19a 3D [427]
containing stereolithography
pulp (3D-SL) printing
Cement CNC Eucalyptus 0.18 19.3c
Mixing [403]
dry-lap
CNF Bleached 0.3 43b Mixing and curing [428]
eucalyptus
pulp
Chitosan CNF Avicels PH 10 57.45 1.627 Solution casting [334]
CNC Bleached 5 99 2.971 [429]
softwood kraft
pulp
Starch CNC Rice straw 10 26.8 0.898 Solution casting [430]
CNC Kneaf 6 8.2 0.326 [431]

(Continued )
110 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use

TABLE 5.11 (Continued)

Matrix Type Cellulose Content Tensile Young’s Process Ref.

Nanocellulose Source (wt.%) Strength Modulus
(MPa) (GPa)
Soy protein CNF Cotton 20 31.19 1.023 Solution casting [432]
CNF Bamboo 30 59.3 1.816 [433]
CNF Soy chaff 5 10.83 0.172 Hot solution [434]
casting
Jute CNF Jute waste 10 35a 5.58 Compression [435]
molding
Agarose BC Acetobacter 20 60.2 Solution casting [436]
xylinum
Castor bean CNF Balsa tree (raft 10 13a,c 1.7a,c Compression [437]
oil cake wood) molding

CNF, cellulose nanofibers; MCC, microcrystalline cellulose; PVA, poly(vinyl alcohol); PLA, poly(lactic acid); BC, bacterial cellulose.
a
Values estimated from charts presented in the original reference.
b
Compressive strength after 28 days of curing.
c
Flexural strength.

alternative to actual capsule shells composed of gelatin.
BC shells presented immediate drug release profile,
regardless of the drying method and thickness. But after
the addition of release-retardant polymers like hydroxy-
propylmethylcellulose and carboxymethyl cellulose
sodium, the process presented first-order kinetics. In the
work of Alkhatib et al. [442], a BC-based system that pro-
vides long-term controlled release of the antiseptic octeni-
dine has been presented. Different micelles and gels, such
as Poloxamers 338 and 407 were incorporated to BC, to
retard the delivery of the studied drug. A controlled
release of octenidine up to 1 week was proved, with addi-
tional high compression stability and water binding.
Ran and Jiang [443] combined the good bioaffinity of
BC/hydroxyapatite (BC/HAp) with the excellent mechani-
cal properties of BC/gelatin (BC/GEL) to synthesize a
multicomponent organic/inorganic composite BC-GEL/
HAp to be used in bone tissue engineering. In vitro cell
culture demonstrated that the rat bone marrow-derived
mesenchymal stem cells cultured on the BC-GEL/HAp
showed better adhesion and higher proliferation and dif-
ferentiation potential than the cells cultured on BC/GEL.
5.4.3 Conducting Devices
In recent decades, the demand for sustainable energy
devices has been increased, and nanocelluloses are pre-
sented as promising materials, due to their excellent phys-
ical, mechanical, and optical properties, important
parameters for high-performance energy devices.
Nanocelluloses are not conductive by themselves, but
many chemical or physical modifications can be applied
to provide them with conductivity. In the recent review of
Du and Zhang [22], the advances in the fabrication of
conductive nanocellulose have been reviewed, including
supercapacitors, lithium ion batteries, and solar cells.
Fig. 5.15 shows the general procedures to produce con-
ductive hybrid nanocelluloses.
CNC have been used to induce long-range order in the
semiconducting polymer, poly[3-(potassium-4-butanoate)
thiophene-2,5-diyl] (PPBT) [444]. Interestingly, it was
found that PPBT was incorporated into the liquid crystal
“template,” forming ordered structures since the polymer
chains followed the helicoidal twist of the chiral nematic
structure of CNC. Therefore, depending on CNC concen-
tration and temperature, different conformations can be
obtained since pitch becomes affected.
Li and Ahadi [445] prepared freestanding carbonized
hybrid nanocellulose films as electrode materials for
supercapacitors. They used both CNF and CNC to form
micro/mesopores in the film and then deposit a thin
atomic layer of Al2O3, which prevented the aggregation
of NC. They made a standard film of a mass loading of
4 mg/cm2 (typical for supercapacitors) and specific capac-
itance of 170 F/g, being kept almost completely even at
very high current.
Graphene has been used to provide biopolymers such
as starch, cellulose, BC, cotton, and carrageenan with
good electrical conductivity. Ccorahua et al. [446] pre-
pared BC nanocomposites with reduced graphene oxide
(RGO) prepared by a hydrazine treatment, thus increasing
their conductivity. This treatment removed the hydroxyl
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
FIGURE 5.15 Schematic illustration of the generalized fabrication routes to nanocellulose based conductive hybrid. Reprinted from X. Du, Z.
Zhang, W. Liu, Y.L. Deng, Nanocellulose-based conductive materials and their emerging applications in energy devices—a review, Nano Energy 35
(2017) 299
320 with permission Elsevier.
and epoxy groups present on the reduced graphene and
increased the content of nonoxygenated carbon. Before
the hydrazine treatment, the material behaved as insulat-
ing material, but the final composite reached an average
conductivity value of 12 S/m.
5.4.4 Batteries (Membranes)
With the increasing use of portable electronic devices, the
demand of lithium-ion batteries is growing. Recently, cel-
lulose materials have been used as separators for this type
of batteries, due to their electrochemical and thermal sta-
bility [447]. Xuand Wei [448] proved the efficiency of a
membrane composed of BC and Al2O3 as a separator for
lithium-ion battery. They coated Al2O3 on the BC nanofi-
ber surface through the thermal decomposition of Al
(NO3)3  9H2O. The membrane showed thermal stability
even at high temperature of 200 C. It also presented
larger ionic conductivity, good electrochemical stability,
and large discharge capacity.
The use of BC membranes as bioanodes for microbial
fuel cells is gaining attention from researchers. Mashkour
and Rahimnejad [449] created a bioanode composed of
BC produced in situ with different proportions of polypyr-
role (PPYR). BC-PPYR presented a power density of
136 mW/m2 and a current density of 662 mA/m2, much
superior to those of graphite (1 mW/m2 and 9 mA/m2,
respectively). In this study, wet BC with a water content
of more than 98% was utilized as a novel scaffold to
design bioanodes for microbial fuel cells. At first, unmod-
ified wet BC was used a bioanode. Then a simple in situ
synthesis of PPYR at various pyrrole concentrations was
subsequently performed on the BC‘s fibers to generate the
111
novel bioanodes. A power density of 136 mW/m2 and a
current density of 662 and 9 mA/m2 were found for BC-
PPYR, which are superior to those of graphite (1 mW/m2,
respectively). The results were attributed to the good
adhesion of bacterial cells to the fibrous surface of BC,
permanent capillary transfer of nutrients, the conductive
content of hydrogel BC, and good conductivity and cata-
lytic activity of PPYR in the nanocomposite.
5.4.5 Food Industry
In the food industry, nanocellulose can be used for three
different applications: (1) as an emulsifying and stabiliz-
ing agent; (2) as a functional food additive; and (3) in
food packaging (Table 5.10g) [364].
Several scientific publications and patents demon-
strated that nanocellulose has a potential use as emulsify-
ing and stabilizing agent in food such as salad dressings,
whipped toppings, sauces, foams, soups, puddings, dips,
and many others [116,363]. For example, oil/water emul-
sions containing up to 71.5 wt.% oil were stabilized by
adding between 0.25 and 2.00 wt.% of nanocellulose.
Recent studies showed that the addition of 0.10
0.30 wt.
% of nanocellulose increased the shape retention time
before a frozen dessert melted and fell. Because of the
small amount of nanocellulose used, it was unnecessary
to change the composition of the dessert mix, since good
flavor and texture could be achieved, and the properties
of the frozen dessert were not strongly affected [450].
Winuprasith and Suphantharika [363,451] suggested that
the suspension formation and stabilization could be per-
formed by the adsorption of nanocellulose at the oil

water interfaces, providing a steric barrier against droplet
112 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
coalescence by the Pickering mechanism. Nanocellulose
in dry form has also been used as a stabilizer in food for-
mulations [452].
The first scientific consideration of nanocellulose as a
food additive was published by Turbak et al. in 1983
[116]. Nanocellulose can be used also as a low-calorie
ingredient for the preparation of reduced-fat formulations
[452,453]. There is a relationship between the consump-
tion of a high energy-density diet and obesity. Thus, food
technologists recommended low energy-density diets
(,1.6 kcal/g) for weight management. Nanocellulose,
with a high water content, could be used to reduce the
energy density of many foods such as cheese, hambur-
gers, chocolate, baked goods, and sausages [452,454].
Activities involving low water content are often
required in baked goods to keep them crispy and crunchy.
Fat-based cream fillings can be used, but fat typically
accounts for approximately 33% of its weight.
Replacement of fat with nonfat ingredients such as nano-
celluloses could reduce the calories of different aliments
by 15
20 wt.% [455]. In addition, they are dietary fiber,
a fact that could play an important role in the overall
health of adults. Thus, nanocellulose can treat intestinal
disorders by adding to the foodstuff a mixture of 15 to
65 wt.% nanocellulose and 85 to 35 wt.% water-soluble
saccharide to prevent nanocellulose agglomeration [456].
Corral and Cerrutti [457] assessed the effect of the
addition of BC to wheat flours on the baking quality,
through the change of the viscoelastic behavior of the
mass. With the addition of BC, specific volume, and
moisture retention increased, while the browning index
decreased. Although BC provided elastic properties to the
different doughs, textural studies demonstrated that the
firmness of bread crumb was reduced.
The food packaging industry produces many synthetic
plastics that after being used, are wasted, causing a seri-
ous environmental problem if they are not recycled [458].
Then, nanotechnology in food packaging aims to increase
the shelf life and nutrition capacity of food and provide
food quality to customers [459]. Therefore, many recent
studies have focused on the development of biodegradable
films and coatings to be used in this industry. These bio-
polymers have to be renewable, abundant, low-cost, and
nontoxic. In addition, mechanical properties, like tensile
strength and elongation at break, are considered key para-
meters since the integrity of the packed food need to be
maintained. On the other side, the migration of compo-
nents to the food needs to be avoided. Nanocelluloses
possess all these properties, so research about their use in
food packaging is becoming more important.
Films of nanocelluloses improve both mechanical and
permeability properties [460,461]. The oxygen permeabil-
ity of nanocellulose films with thickness of 21 6 1 mm
was 17 6 1 mL/m2/day; this value is competitive with
synthetic polymers such as ethylene vinyl alcohol and
polyester-oriented, coated polyvinylidene chloride films
of roughly the same thickness [461]. However, the oxy-
gen permeability of nanocellulose films depends on rela-
tive humidity. High relative humidity values increase the
oxygen permeability of the films because of the plasticiz-
ing and swelling of the nanocellulose [174]. Although the
oxygen barrier properties of nanocellulose films are com-
petitive with the currently available commercial films
made of synthetic polymers, their water vapor barrier
remains low owing to the strong hydrophilic nature of
nanocellulose [461]. Therefore, several chemical treat-
ments, such as acetylation, can be used to increase water
barrier properties through the creation of a hydrophobic
surface [364].
A biocomposite containing thermoplastic corn starch
and bacterial CNC (BCNC) was prepared by melt mixing
to be used in food packaging [462]. Both water vapor and
oxygen permeability were decreased up to a maximum of
46% and 95% with a BCNC loading of 15 wt.%. Then, it
was hydrophobized by coating with electrospun poly(3-
hydroxybutyrate) (PHB) or electrospun PHB-BCNC fibers
(with a BCNC load of 15 wt.%). The addition of PHB-
BCNC coating further reduced the water vapor
permeability.
5.4.6 Papermaking
Papermaking is a sustainable industrial sector in which
paper recycling has been recognized as being of great
importance. In Europe, 54% of the paper industry’s feed-
stock comes from recovered paper, which corresponds to
a paper recycling rate of 72% [463]. However, one of the
main problems in the utilization of secondary fibers is to
maintain the quality levels of the paper products, which is
continuously increasing following customer demands. In
order to maintain their competitiveness, papermakers
must reduce production costs and develop new paper pro-
ducts that approach the high potential of paper as a biode-
gradable material, e.g., to replace plastics. In this
framework, nanocelluloses have a high potential as
strengthening agents, components of retention systems,
aids to control printing quality (decreasing linting pro-
blems) [357,464], coating binders [465], air permeability
controller aids [358,466,467], and special additives in
technology papers [359]. In fact, Lindström and Aulin
[468] indicate that the more feasible and practical uses of
nanocelluloses in the papermaking process are related to
their use as a strength additive and for barrier applications
in food packing (Table 5.10c).
The first researchers to use micro- and nanocelluloses
as reinforcing agents in papermaking produced them from
wood and applied them to virgin pulps to enhance the wet
and the dry strength of paper [52,54,469
473]. Although
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5
CNF and CMF increase draining time of the pulp and
enhance water retention by increasing hydrogen bonding
[469], it has been proved that the optimum selection of
CNF retention agent and operation conditions is key to
limit or avoid deteriorating the drainability of the pulp
suspension when CNF is used [52]. For example, the use
of 1 wt.% CNF in the recycled pulp in combination with
1 mg/g chitosan could be a way to obtain sheets with
superior tensile strength (an increase of 32.56% was
achieved) without decreasing drainage [474]. The CNF
production method affects their effect on drainage too.
González and Vilaseca [475] have demonstrated that
enzymatic pretreatment combined with high-pressure
homogenization can significantly improve mechanical
strength properties without greatly affecting the drainage
rate. Furthermore, CNF can be produced by bleaching and
homogenization of pulp from agrowastes, without requir-
ing TEMPO oxidation (with higher cost and environmen-
tal impact than bleaching), and the use of these CNF
increases strength without deteriorating drainage process
[315].
Recent studies have also assessed the potential
strength benefits of nanocellulose in recycled pulps
[314,476,477]. Delgado-Aguilar and Gonzalez [476] dem-
onstrated that paper containing 1.5 wt.% of CNF pre-
sented a higher tensile strength and stiffness than paper
from beaten pulp with similar freeness and WRVs.
Most studies in papermaking have focused on the
effect of CNF on paper properties, but the high specific
surface area of CNF and their nature favor their interac-
tion with flocculants in competition with other pulp com-
ponents. In recycled pulp, in most cases CNF increased
113
floc stability, while allowing the addition of a higher floc-
culant dose before reaching overdosing effects [474].
The use of BC as reinforcement of paper has been
tried too. Santos and Carbajo [478] have reinforced dam-
aged papers by producing BC on the surface of different
papers by the direct culture of K. sucrofermentans.
Tabarsa and Sheykhnazari [479] tried BC to reinforce
softwood pulp. Xiang and Liu [480] increased the tensile
strength of bleached sugarcane bagasse pulp with BC and
cationized BC. The results of these researches suggest the
economical prospect for BC to be used as reinforcement
in paper-based material.
All these aspects will be reviewed in the chapter
“Nanofibrilated Cellulose as an Engineered Nanomaterial
in Papermaking.”
5.4.7 Environmental Applications
Due to the high specific surface area, high functionaliza-
tion capacity, and strengthening action, nanocelluloses are
being used as a new class of biobased adsorbent, espe-
cially useful for environmental remediation. The most
common pollutants, including heavy metals, dissolved
organic pollutants, dyes, oil, and undesired effluents can
be adsorbed by nanocelluloses. However, usually some
modification has to be made to adsorb a specific com-
pound. In the review of Mahfoudhi and Boufi [25], a
complete outline of the surface modifications of nanocel-
lulose according to the pollutant has been highlighted.
Fig. 5.16 shows the functionalization strategies to remove
a specific pollutant.
FIGURE 5.16 Surface modifica-
tion strategies of nanocellulose
according to the pollutant class.
Reprinted from N. Mahfoudhi, S.
Boufi, Nanocellulose as a novel
nanostructured adsorbent for envi-
ronmental remediation: a review,
Cellulose 24 (3) (2017)
1171
1197 with permission of
Springer.
114 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
Liu and Jin [481] prepared a composite adsorbent
through an amidation reaction between CCNC and poly-
ethyleneimine (PEI), to remove Cr(VI) ions from aqueous
solutions. The encouraging results showed an uptake
capacity of 358.42 mg/g, reaching the adsorption equilib-
rium within 250 min. The calculated thermodynamic para-
meters show the adsorption of Cr(VI) onto CCNC-PEI
was a spontaneous exothermic process. In addition,
CCNC-PEI proved a good efficiency for repeated Cr(VI)
adsorptions.
Water-based or flexographic inks are more environ-
mentally friendly than organic solvents-based inks.
However, their use is still limited since they remain dis-
solved in water and alter the recycling process when
water-based printed papers are used. Moreover, conven-
tional deinking technologies such as flotation, adsorption,
coagulation/flocculation, or biological processes do not
effectively remove inks, are expensive, or have negative
health impacts because of the use of heavy metal com-
pounds. Balea and Monte [482] have shown the feasible
decolorization of flexographic inks using CNF through its
combination with a flocculant, namely cationic polyacrila-
mide. Ink concentration reductions of 100%, 87.5%, and
83.3% were achieved for copper phthalocyanine blue, car-
bon black, and diarlyide yellow pigments, respectively.
Moreover, flocculation studies have been carried out to
understanding the water-based ink solution decolorization
mechanism.
The industry of textile dyeing and finishing has been
demonstrated to be one of the most contributing sectors in
water pollution [483]. Even at low concentration, dyes
affect sunlight penetration and ultimately deplete marine
life of biochemical oxygen demand thus upsetting the
downstream food chain. Focusing on the dye degradation,
Li and Nandgaonkar [483] developed a membrane
through the oxidation of BC and posterior covalent immo-
bilization of laccase as well as TiO2. Results proved that
the oxidation process successfully improved the stability
of the immobilized laccase. The optimum pH for the max-
imum dye degradation was found to be 5
6, while the
optimum temperature was around 40 C. In addition, UV
illumination was found to improve dye degradation
efficiently.
5.4.8 Catalysis
A key feature in the development of novel catalysts
resides in the importance of engineering and easy recov-
ery step [484]. Among the many applications of nanocel-
luloses, nowadays their use in the design of recyclable
catalysts has attracted great attention of the research
groups.
There are mainly two categories of guest NP used for
catalytic applications: (1) photocatalysts such as TiO2 and
(2) precious metals (Au, Ag, Pt, etc.). When used for
catalysis, nanocellulose typically acts as a catalyst support
to hinder nanoparticle aggregation. In the study of Chen
and Chen [485], the deposition of gold NP onto the sur-
face of TEMPO-oxidized BC was successfully produced.
The catalytic activity to reduce 4-nitrophenol to 4-
aminophenol of the prepared nanohybrids was estimated
by UV-Vis spectrometry. The BC/Au nanohybrid exhib-
ited superior catalytic properties for this purpose, obtain-
ing a turnover frequency of 750 h21.
5.4.9 Sensors
Santos and Tercjak [486] developed an optical sensor
platform composed of CNC and 40 -(hexyloxy)-4-biphe-
nylcarbonitrile. The obtained material showed the syner-
gistic effect of properties of both compounds: the intense
structural coloration of photonic cellulose and thermal
and conductive properties of CNC. Film optical properties
were found to be switchable with the temperature during
heating/cooling cycles. Then, the created film is both
thermal and electrical responsive in photonic.
Low-cost piezoelectric devices are used as fast diag-
nostic tools for several diseases detection, but some
inconveniences, like unspecific antigen recognition, poor
molecular probe adsorption, and the need for sample dilu-
tion, may limit their use in routine diagnostics. Pirich and
de Freitas [487] coated piezoelectric sensors with thin
films of BC-CNC to improve the attachment of monoclo-
nal immunoglobulin G (IgGNS1) and to favor specific
detection of nonstructural protein 1 (NS1) of dengue
fever. The complete sensor was able to detect the NS1
protein in serum in the range of 0.01
10 μg/mL.
Due to the unique optical properties of CNC, they
have been used as photonic humidity sensors [488], but
their maximum water uptake was limited by the dissolu-
tion and decomposition of the CNC structure. Recently,
Lu and Pan [26] developed a novel humidity sensor by
the chemical bonding induced between CNC and poly-
acrylamide, using glutaraldehyde as a bridging agent. It
was found that when the humidity increases, the poly-
acrylamide swells enlarging the pitch of the chiral
nematic structure of CNC. That causes a change in color
which can be measured by reflectance spectra (Fig. 5.17).
In addition, this composite can be used in several cycles
of humidity without suffering degradation.
With the objective of being used as biological and
chemical sensors, where biocompatibility and electrical
conductivity are required, Jasim and Ullah [489] devel-
oped electrically conductive BC membranes through oxi-
dative polymerization with polyaniline (PAni). Then,
single-walled carbon nanotubes (SWCNTs) were uni-
formly distributed in the composites. Both degradation
resistance and electrical conductivity were enhanced with
 Cellulose Nanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Cellulose (BC) Chapter | 5 115

FIGURE 5.17 Schematic diagram of the working mechanism of the

novel photonic humidity sensor composed of CNC and polyacrylamide.
Reprinted with permission from T. Lu, H. Pan, J. Ma, Y. Li, S.W.
Bokhari, X. Jiang, et al., Cellulose nanocrystals/polyacrylamide compo-
sites of high sensitivity and cycling performance to gauge humidity,
ACS Appl. Mater. Interfaces 9(21) (2017) 18231
18237. r 2017
American Chemical Society.

FIGURE 5.18 Fluorescence characterizations of CDs and CDs with different metal ions (under the illumination of a 350 nm UV light). Reprinted
from P.F. Lv, Y.X. Yao, D.W. Li, H.M. Zhou, M.A. Naeem, Q. Feng, et al., Self-assembly of nitrogen-doped carbon dots anchored on bacterial cellu-
lose and their application in iron ion detection, Carbohydr. Polym. 172 (2017) 93
101 with permission of Elsevier.

the implementation of both components. Degradation
temperature was increased from 232 C to 310 C, and
electrical conductivity was improved to 1.41 3 1022 S/cm
with BC-PAni/SWCNTs at the dose of 0.1 mg/mL.
A smart fluorescence biosensor was developed by
[490], through the biosynthesis of BC with nitrogen-
doped carbon dots, previously synthesized by a hydrother-
mal method with citric acid and ethanediamine. The pre-
pared biosensor exhibited a blue emission under the
excitation wavelength of 350 nm. Results of spectroscopy
showed that the prepared material presented a sensitive
response to Fe31 (Fig. 5.18) in a wide range (from 0.5 to
600 μM) with an ultralow detection limit of 84 nM.
5.4.10 Other Applications
Power generator: Triboelectric nanogenerators convert
mechanical energy harvested from the environment to
electricity for powering small devices such as sensors or
for recharging consumer electronics. Recently, Kim and
Yim [491] have developed a biotriboelectric nanogenera-
tor based on BC film having unique functionalities such
as transparency, flexibility, and biocompatibility. BC was
produced in a gel state by Acetobacter xylinum KJ1 in the
Glucose-Fructose medium.
Thermal conductive: Uetani and Okada [492] pro-
duced a transparent thermally conductive nanocellulose
films mixing transparent acrylic resin with CNF produced
from tunicate of ascidian (sea animal). Nanocellulose
films have a transparency of 73% at a wavelength of
600 nm and an in-plane thermal conductivity as high as
2.5 W/m/K, which is more than 220% higher than previ-
ously reported composites. Song and Jiao [493] developed
anisotropic thermally conductive flexible films with CNF
and in situ RGO prepared via a vacuum-assisted self-
assembly technique. The thermal conductivity of prepared
film was 6.168 W/m/K.
Thermal stability: CNC produced via sulfuric acid-
assisted hydrolysis of cellulose have shown relatively poor
thermal stability. In order to overcome this drawback in a
simple low-cost environmentally friendly strategy, Goikuria
and Larranaga [494] coassembled five different metallic NP
(ZnO, SiO2, TiO2, Al2O3, and Fe2O3) in water with CNC to
obtain free-standing nanocomposite films. The increase in
thermal stability reached a maximum of 75 C for compo-
sites with 10 wt.% Fe2O3 and ZnO. These composites
showed a delayed degradation upon heating, confirmed by
the activation energies of the thermodegradation process.
Fire retardancy: Nanocellulose foams have been
shown to have excellent fire retardancy. The limiting
116 PART | I Different Kinds Of Engineered Nanomaterial For Industrial Use
oxygen index (LOI) was as high as 34, which is signifi-
cantly better than commercial flame-retardant containing
polymer-based foams, which display LOI in the range
22
25 [248]. The addition of inorganic fillers (e.g., clays,
graphene) enhances the fire retardant properties of com-
posites [495].
Tunable properties: Onggo and Mulyani [496]
described the growth of the microcrystals of the one-
dimensional spin crossover (SCO) compound [[Fe
(Htrz)2(trz)](BF4)]n in a matrix of BC. Reversible thermo-
magnetic (diamagnetic 2 paramagnetic) and thermo-
chromic bistability (purple 2 pale-yellow) were found in
the SCO-BC composite films. They were determined by a
well-defined hysteresis in the temperature range ca.
345
380 K where these properties depend on the history
of the sample (memory effect).
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