A

Project Report
On
Preparation of cellulose nanocrystals and
cellulose nanofibers.

Guided by-
Prof. Sanjib Sen.
Prof. Jaykumar Bhasarkar.

Presented by – Adarsh Mishra

7th Semester B.Tech
Chemical technology (Pulp and Paper).
Laxminarayan Institute of technology Nagpur.

ACADEMIC SESSION 2020-2021

SR. NO. CHAPTERS Pg. NO.

1 Abbreviations 3

2 INTRODUCTION 4

3 CELLULOSE AND NANOCELLULOSE 8

4 Preparation of cnf and cnc 12

5 Process temperature and conditions 15

6 Conclusions References 18

INDEX
 Abbreviations

Nanocelluloses –NCs

Cellulose nanocrystals - CNCs,

Cellulose nanofibrils - CNFs

Bacterial cellulose - BC

Electrospun cellulose nanofibers - ECNFs

Nanofibrillated cellulose – NFC

Microfibrillated cellulose - MFC

INTRODUCTION

Presently, there is a strong need for replacing fossil oil-basedproducts with biodegradable
and/or bio-based ones, which canresolve numerous issues, such as reduction of oil stocks and
theirgeographical localization, plastic pollution, carbon footprint andsustainability.Cellulose
is the most abundant natural polymer and can be sustainably produced from various biomass.
The global annual output of cellulose is approximately 75 to 100 billion tonnes. The
development and utilization of cellulose is of great significance to the sustainable
development of human society, especially the energy scarcity in the future. Nanocelluloses
(NCs) could be produced by the degradation of cellulose from various sources of biomass and
have many unique properties, such as high specific surface area, high aspect ratio, high
tensile strength and stiffness, low density, and low thermal expansion coefficient. Recently,
the application of NCs has attracted great attention. NCs include cellulose nanocrystals
(CNCs), cellulose nanofibrils (CNFs), bacterial cellulose (BC), and electrospun cellulose
nanofibers (ECNFs).
In previous decades the challenge associated with isolating CNF was the high energy demand
required by mechanical disintegration process. However, with discovering strong impact of
pre-treatment methods, e.g., 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-mediated
oxidation or enzymatic hydrolysis. Which were aimed at facilitating the mechanical dis-
integration, CNF became a more attractive material for commercial applications. However,
research continues focusing on optimization of the existing techniques and on development of
alternative methods, which can benefit the production process or endow theCNF with new
properties.
CNCs and CNFs are more common than the other NCs. This is because CNCs and CNFs are
gained by disintegration of raw cellulose materials into nanosize particles (top-down
process), while BC and ECNFs are produced by a build-up of nanofibers from low molecular
weight sugars by bacteria and electrospinning, respectively.This review will focus on CNCs
and CNFs, while BC and ECNFs will not be covered. There is a significant difference
between CNCs and CNFs in terms of dimension and crystallinity. CNCs are highly
crystalline and usually have a length less than 500 nm, while CNFs are made up of
amorphous and crystalline cellulose chains and have a length of up to several microns. Both
of them have immense potential in the manufacture of renewable and biodegradable
materials. They have been applied in the fields of biomedical engineering, food, sensor,
packaging, optical and electronic devices, and so on. However, there aresome recent
advances that were not enough addressed, including certain mechanical disintegration
techniques (e.g., extrusion),biochemical pretreatments (e.g., periodate–chlorite
oxidation,sulfonation, quaternization, solvent-assisted pretreatments), frac-tionation
techniques, some issues of CNF quality assessment,production of CNF in different forms
(e.g., powders, hydrogels, aero-gels) etc. Thus, this review aims at complementing with the
aboveissues and focuses on the recent advances achieved in CNF production.
Cellulose and nanocellulose

2.1. Feedstock
Cellulosecan be derived from a variety of sources, such aswood (hardwood and softwood),
seed fibers (cotton, coir etc.), bastfibers (flax, hemp, jute, ramie etc.), grasses (bagasse,
bamboo etc.),marine animals (tunicate), algae, fungi, invertebrates and bacteria. Wood is
currently the most important industrial source of cellulose. Besides cellulose, it also contains
hemicellulose,lignin and a comparably small amount of extractives and inorganicsalts. Wood
species can be distinguished as hard- and softwoodsbased on their anatomical features.
Hardwood is more complexand heterogeneous in structure than softwood. Generally,
softwood fibers are 3–4 times longer thanhardwood. However, it is known that hard-woods
have more rigid structure than softwoods due to their highRunkel ratio (cell wall thickness
divided by lumen radius. Therefore, it was reported that softwood requires less mechanical
treatment than hardwood to produce equivalent fibrillation level. At the same time, non-wood
plants are receiving increasing interest as a source of cellulose since they, generally,
compriseless lignin. Consequently, fiber delignification and purification pro-cesses are easier
and less harmful for cellulose. Moreover, further fibrillation of such cellulose is less energy-
consuming. It should be also noted, that the use of never-dried cellulose comparing to once-
dried makes the fibrillation more favorable, since drying promotes irreversible hydrogen-
bonding between nanofibrils, known as hornification. However, the dry cellulose is much
easier to transport.Therefore, research focuses on both never-dried and dry celluloseas raw
material for CNF production.

2.2. Structure and chemistry

As mentioned above, cellulose can be found in some algae,fungi, tunicates etc. However,
commercial cellulose production concentrates on harvested sources such as wood, annual
plants or agricultural residues. Besides cellulose, they contain hemicelluloses, lignin, and a
comparably small amount of extractives. In suchproducts, cellulose is represented as a well-
organized architecture of fibrillar elements composing cells. Cellulose is the primary
structural component responsible for their mechanical strength.Each cell represents a fiber
with a width of 10–50 nm (depending on the source), consisting of cell wall layers, which
have thetotal thickness of 1–5 nm. These layersdiffer from each other with regard to their
structure and chemical composition. The cell wall is composed of several layers the middle
lamella (ML), the primary wall (P), the outer(S1), middle (S2) and inner (S3) layers of
secondary wall and thewarty layer (W). The middle lamella binds the neighboring
cellsbecause of the presence of high amount of lignin. The primary andsecondary walls
contains three main components: cellulose, hemi-cellulose, and a matrix, typically, composed
of pectin in the primarywall and lignin in the secondary wall.The primary cell wall is
approximately 30–1000 nm thick andcontains cellulose microfibrils (MF) located crosswise.
The secondary cell wall consists of three layers (S1, S2 and S3), which differin microfibrils
angle with respect to the fiber axis. In these layersthe microfibrils are aligned parallel and are
packed densely in aflat helix. The secondary wall contains most of the cellulose massin the
fiber and has a thickness varying from 100 nm (cotton) to300 nm (spruce wood). The warty
layer is a thin layer located inthe inner surface of the cell wall mainly composed of lignin
andhemicellulose.As described above, cellulose is present in the fibers in form ofthe
microfibrils. For instance, in the spruce wood the microfibrilshave a diameter of 10–20 nm.
These microfibrils in turn are made ofelementary fibrils, which are commonly considered as
the smallestmorphological units in the fiber. However, recent studies showed thatit is possible
to extract single cellulose polymer chains or 2 × 2chain-packing structures during CNF
production. The diameter ofelementary fibrils typically varies in the range of 3–35 nm
depending on cellulose source, and is in the rangeof 2.2–3.6 nm for spruce wood. Both
cellulose microfibrils and elementary fibrils are referred to as cellulosenanofibrils. However,
it is commonly desired to obtain individual elementary fibrils with a regular diameter, rather
than their (ormicrofibril) bundles.Cellulose is a semicrystalline polymer comprising
crystalline(ordered) and amorphous (disordered) regions within the microfibril, where the
individual cellulose molecule is considered to passthrough several crystalline and amorphous
parts according to fringe micelle theory. The native degreeof crystallinity is usually in the
range of 40–70% and depends on theorigin of cellulose and the isolation method.The building
blocks of cellulose polymer chain are D-glucopyranose (glucose) molecules. When linked
together by_-1,4-glucosidic bonds they turn into anhydroglucose units. Twoanhydroglucose
units compose anhydrocellobiose, which is therepeating unit of cellulose polymer.
Nevertheless, cellulose degree of polymerization (DP) is usually expressed as a numberof
anhydroglucose units. Each anhydroglucose unit has six carbonatoms with three hydroxyl
(viz., alcohol) groups (at C2, C3, and C6atoms), giving a high degree of functionality to
cellulose molecule.There are three types of anhydroglucose units: (i) a reducing endwith free
hemiacetal or aldehyde group at C1 atom, (ii) a non-reducing end with free alcohol group at
C4 atom, and (iii) internalrings. Due to the molecular structure, cellulose bears such prop-
erties as hydrophylicity, insolubility in water and most organicsolvents, degradability and
chirality.The DP of cellulose varies depending on the cellulose source(e.g., 10,000 in native
wood; 20,000 in cotton; 44,000 in Valonia)and the isolation/purification method (e.g., 200–
500 in regeneratedcellulose, 1000 in bleached kraft pulps).

2.3. Nanocellulose
Cellulose particles with at least one dimension in nanoscale (1–100 nm) are referred to as
nanocellulose. Depending on the pro-duction conditions, which influence the dimensions,
composition and properties, nanocellulose can be divided into two main cate-gories: (i)
cellulose nanocrystals (CNC) or cellulose whiskers and(ii) cellulose nanofibrils (CNF), also
known as nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC) or cellulose
nanofibers.Due to various terminology used to describe cellulose nanomateri-als, several
technical committees and organizations (ISO TC 6 andTC 229; TAPPI and CSA Z5100-14)
initiated a standardization of different types of nanocellulose. Even though this work has not
beenfinalized yet, the majority of experts are inclined to the term “cel-lulose nanofibrils” for
the second type of nanocellulose describedabove, which is a subject of this review.Bacterial
cellulose (BC) and electrospun cellulose nanofibers (ECNF) are also considered as
nanocellulose. However, CNC and CNFare much more common, since they are produced by
disintegration of cellulose fibers into nanoscale particles (top–down process),whereas BC and
ECNF are generated by a buildup of nanofibers(bottom–up process) from low molecular
weight sugars by bacte-ria or from dissolved cellulose using electrospinning,
respectively.Thus, large-scale production of BC and ECNF remains questionable.Regardless
of the nanocellulose type, it exhibits hydrophilicity,relatively large specific surface area,
broad potential of surfacechemical modification etc.

2.3.1. Cellulose nanocrystals

CNC were first produced by using acid hydrolysisof cellulose fibers dispersed in water. In
this method, concentratedsulfuric acid is commonly used, which degrades amorphous
regionsof cellulose and leaves intact the crystalline ones. By such treatment, rod-like rigid
CNC with sulfate groups at their surface areproduced. Their morphology generally depends
on the source ofcellulose. Commonly, CNC with a diameter of 3–35 nm and a lengthof 200–
500 nm are produced.
2.3.2. Cellulose nanofibrils
CNF as a new cellulosic material was introduced by Turbaket al. (1983) and Herrick et al.
(1983)who produced cellulosewith lateral dimensions in nanometer range by passing a
softwoodpulp aqueous suspension several times through a high-pressurehomogenizer. During
such treatment, strongly entangled networksof nanofibrils, having both crystalline and
amorphous domains, areproduced due to high shearing forces. They possess high aspectratio
and form gels in water with shear-thinning and thixotropicbehavior. Depending on the
processing conditions, cellulose fiberscan be disintegrated to flexible CNF with lateral
dimensions startingfrom ca. 5 nm, representing elementary fibrils, to tens of nanome-ters,
which correspond to single microfibrils and their bundles.Typically, CNF have a diameter of
5–50 nm and a length of fewmicrometers.

2.3.3. Bacterial cellulose

BC is high-purity cellulose generated by bacteria in aqueousculture media containing a sugar
source. The time of such a pro-cess ranges from few days up to two weeks BC has the same
chemical composition as plant cellulose. However, it is free of functional groups other than
alcohol,e.g., carboxyl or carbonyl, which are usually introduced to woodor plant-derived
cellulose during the purification process. BC isalso free of the other polymers, such as lignin,
hemicelluloses orpectin, which facilitates its use in biomedical applications. BC isproduced
in the form of twisting ribbons with cross-sections of3–4 nm × 70–140 nm and a length of
more than 2 _m. It has a DP of 3000–9000 anda distinct crystallinity of 80–90%.
Cellulose and nanocellulose

CNCs have high crystallinity with diameter less than 100nm and length less than 500 nm,
which are formed though intra and intermolecular interaction of cellulose macromolecules.

Fig. 1. Hierarchical structure of wood, showing: different layers.

pulp aqueous suspension several times through a high-pressurehomogenizer. During such

treatment, strongly entangled networksof nanofibrils, having both crystalline and amorphous
domains, areproduced due to high shearing forces. They possess high aspectratio and form
gels in water with shear-thinning and thixotropicbehavior. Depending on the processing
conditions, cellulose fiberscan be disintegrated to flexible CNF with lateral dimensions
startingfrom ca. 5 nm, representing elementary fibrils, to tens of nanometers, which
correspond to single microfibrils and their bundles.Typically, CNF have a diameter of 5–50
nm and a length of fewmicrometers. An in-depth review of CNF production techniques
andproperties is presented below in Section. Bacterial celluloseBC is high-purity cellulose
generated by bacteria in aqueousculture media containing a sugar source. The time of such a
pro-cess ranges from few days up to two weeks. BC has the same chemical composition as
plant cellulose. However, it is free of functional groups other than alcohol,e.g., carboxyl or
carbonyl, which are usually introduced to woodor plant-derived cellulose during the
purification process. BC isalso free of the other polymers, such as lignin, hemicelluloses
orpectin, which facilitates its use in biomedical applications. BC isproduced in the form of
twisting ribbons with cross-sections of3–4 nm × 70–140 nm and a length of more than 2 _m.
It has a DP of 3000–9000 anda distinct crystallinity of 80–90%.2.3.4. Electrospun cellulose
nanofibersThe other possibility to produce cellulose withnanoscale/submicron lateral
dimensions is electrospinning.Recently, the electrospun fibers from cellulose and its
derivatives.

CNF (cellulose nanofibers)

CNF (cellulose nanofibers) and CNC (cellulose nanocrystals) are derived from nanocellulose
and have gained tremendous amount of attention due to their renewable and chemical
properties. CNF as a new cellulosic material was introduced by Turbaket al. (1983) and
Herrick et al. (1983)who produced cellulosewith lateral dimensions in nanometer range by
passing a softwoodpulp aqueous suspension several times through a high-
pressurehomogenizer. During such treatment, strongly entangled networksof nanofibrils,
having both crystalline and amorphous domains, areproduced due to high shearing forces.
They possess high aspectratio and form gels in water with shear-thinning and
thixotropicbehavior. Depending on the processing conditions, cellulose fiberscan be
disintegrated to flexible CNF with lateral dimensions startingfrom ca. 5 nm, representing
elementary fibrils, to tens of nanome-ters, which correspond to single microfibrils and their
bundles.Typically, CNF have a diameter of 5–50 nm and a length of fewmicrometers.

Mechanical Treatments
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 relatively poor mechanical properties. Thus, CNF are
preferentially produced in aqueous suspension at low concentrations (,5 wt.%) using
mechanical treatments coupled 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 Different authors have published comparative studies among mechanical
treatments and their energy demand. The processing cycles are affected by the pulp used as
raw material, its fiber morphology and fiber swelling. Spence et al. concluded that nine
passes through a microgrinder was one of the most costefficient production processes of CNF
from recycled fibers. In addition, they reported that the microgrinding of wood fibers was
more efficient in terms of energy consumption than the homogenization of refined fibers. In
addition, films formed by CNF produced through microgrinding presented better mechanical
properties. Moreover, CNF produced by homogenization presented the highest specific
surface area and the lowest porosity of the films. On the other hand, Wang et al. observed that
microgrinding fibrillation time and energy expense trigger a decrement in the size, the DP,
and the crystallinity index (CrI) of CNF.
Properties of cnc and cnf compared to other materials
 The mineral acid hydrolysis is the most common method for the
preparation of CNCs.
 The typically used mineral acids are sulfuric acid, hydrochloric acid,
phosphoric acid, hydrobromic acid, and their mixed acids. Sulfuric acid is
the most typically used as it produces a negative surface charge on the
particles which leads to more stable suspension.
 Hydrochloric acid also was commonly used for the preparation of CNCs.
Due to the lack of charge on the surface of CNCs, the CNCs prepared by
hydrochloric acid are easily flocculation in water. But the thermal
stability of CNCs by HCl is higher than that by H2SO4.
 Phosphoric acid, which belongs to middle strong acid, could be used for
the manufacture of CNCs with high thermal stability and stable
suspension.
Preparation of Cellulose nanocrystals by Acid Hydrolysis
How acid hydrolysis works

 Acid hydrolysis is executed to remove the amorphous regions from the crystalline
regions
 Crystalline region possess the desired properties of cellulose nanocrystals, hence it is
preferred to make cellulose nanocrystals.

PROCESSES TEMPERATURE, CONDITIONS AND CHEMICALS

USED DURING PREPARATION OF CNC’S
Method Major Typical Yiel 𝑇max Other
chemical conditions d (∘C) advantages/disadvantages
reagents (%)

Mineral H2SO4, 64wt.% 15.7 253.2 It is difficult to treat waste

acid HCl, H2SO4, at     acid. H2SO4 has a serious
hydrolysis H3PO4, 45∘C for     corrosion problem to
HBr 30 min.     equipment.The CNCs have
      excellent suspension
      stability.
6MHCl,     It is difficult to treat waste
110∘C, 3 80 347.2 acid. HCl has a serious
h. corrosion problem to
equipment. The CNCs have
bad suspension stability.
Conclusion

This review summarizes the preparation methods of CNCs and CNFs. For the preparation of
CNCs, promising techniques were discussed besides the conventional mineral acid
hydrolysis, such as organic acid hydrolysis, subcritical hydrolysis, AVAP method, and ionic
liquid hydrolysis. Most of them have great possibility for further industrialization. However,
there are still some problems that need to be solved. For example, the corrosion of equipment
is serious and the post processing of waste acid is difficult for mineral acid hydrolysis, the
preparation time is long and the technological requirements is rigorous for enzymatic
hydrolysis, Therefore, in order to achieve the industrialization of various CNCs, a lot of
research works need to be done. The appropriate catalysts should be developed to reduce the
amount of acid or increase the efficiency of organic acid hydrolysis.
For the preparation of CNFs, various mechanical treatments are discussed, including high
pressure homogenization, grinding method, ball milling, twin-screw extrusion, cryocrushing,
blending, and aqueous counter collision. Among them, the twin-screw extrusion is the
method with the most potential for the preparation of CNFs due to a high solid content of
obtained CNFs. In order to reduce energy consumption of mechanical disintegration, the
pretreatment of cellulose materials is necessary. Various pretreatment methods are
summarized in this review.
REFERENCE’S
1Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology,
Tianjin 300457, China
2State Key Laboratory of Pulp & Paper Engineering, South China University of Technology,
Guangzhou 510640, China
3Key Laboratory of Industrial Fermentation Microbiology of Ministry of Education and
Tianjin Key Lab of Industrial Microbiology,
Tianjin University of Science and Technology, Tianjin 300457, China
4Department of Chemical Engineering, Auburn University, Auburn, AL 36849, USA5.
HITOSHI TAKAGI, ANTONIO N. NAKAGAITO & YUYA SAKAGUCHI
Graduate School of Science and Technology, Tokushima University, Japan
5. Oleksandr Nechyporchuk∗, Mohamed Naceur Belgacem, Julien BrasUniversité Grenoble
Alpes, Laboratory of Pulp and Paper Science and Graphic Arts (LGP2), CNRS, Agefpi, F-
38000 Grenoble, France
6. Advanced Structures and Composites Center, University of Maine, 35 Flagstaff Road,
Orono,
ME 04469-5793, USA
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5755, USA
8. Forest Products Laboratory, U.S. Forest Service, 1 Gifford Pinchot Drive, Madison,
Wisconsin 53726, USA
Department of Natural Resources, Behbahan Khatam Alanbia University of Technology,
Behbahan, Iran Corresponding author: P. Rezayati Charani, rezayati@bkatu.ac.ir
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