Novel Func Material Based in Cellulose

SPRINGER BRIEFS IN
APPLIED SCIENCES AND TECHNOLOGY
Haisong Qi
Novel Functional
Materials Based
on Cellulose
123
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Haisong Qi
Novel Functional Materials

Based on Cellulose
123
Haisong Qi
State Key Laboratory of Pulp and Paper
Engineering, School of Light Industry
Science and Engineering
South China University of Technology
Guangzhou
People’s Republic of China
ISSN 2191-530X ISSN 2191-5318 (electronic)

SpringerBriefs in Applied Sciences and Technology
ISBN 978-3-319-49591-0 ISBN 978-3-319-49592-7 (eBook)
DOI 10.1007/978-3-319-49592-7
Library of Congress Control Number: 2016957501
© The Author(s) 2017

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Preface
Cellulose is one of the oldest raw materials that have been used by human since
ancient times. Meanwhile, it is also the most common organic compound on earth.
Due to its unique structure and excellent properties, such as renewability, bio-
compatibility, biodegradability, chemical stability, and derivatizabilty, cellulose has
diverse applications, e.g., papers, textiles, building materials, composites, and so
on. However, there are still great challenges that hinder this readily available and
renewable natural polymer to be further used. One drawback of cellulose is its
limited processability, which is mainly caused by the large proportion of intra- and
inter-molecular hydrogen bonding systems. Until now, the traditional processes for
cellulose conversion such as viscose process still dominate the cellulose products
market.
Nowadays, the trend of science and technology is tending towards renewable
resources and eco-friendly processes. Materials based on natural polymers
including cellulose thus have attracted great attention. Especially, the development
of new and “green” solvents for cellulose provides efcient and eco-friendly plat-
forms for cellulose shaping and chemical modication. More recently, new frontiers
such as nanocelluloses and advancements in nanotechnologies also offer great
opportunities in the eld of functional materials over a broad range of applications.
This book is intended to review the novel functional materials based on cellulose
that were developed during the last few decades. Chapter 1 provides a general
introduction to the sources and structure of cellulose, including molecular struc-
tures, hydrogen bond systems, and crystalline structures as well as the hierarchical
organization of wood cellulose. In Chaps. 2 and 3, several dissolution-regeneration
processes (including viscose, Carbacell, N-methylmorpholine-N-oxide, aqueous
alkali system and ionic liquids) and the resulting regenerated cellulose products
(bers, lms, beads, etc.) are summarized. Chapter 4 covers the novel functional
and smart materials based on cellulose, such as electrically conducting materials,
v
vi Preface
magnetic materials, photofunctional materials, and so on. Chapter 5 is about the

new family of nature-based materials, nanocelluloses, and the functional materials
derived from them.
Guangzhou, China Haisong Qi

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Structure of Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.1 The Molecular Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.2 Hydrogen Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.3 Crystalline Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2 Platforms for Functionalization of Cellulose . . . . . . . . . . . . . . . . . . . . 11
2.1 Derivate Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.1 Viscose Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.2 Cellulose Carbamate Process . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2 Direct Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.1 NMMO System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2 Aqueous Alkali System . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.3 Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3 Novel Regenerated Cellulosic Materials . . . . . . . . . . . . . . . . . . . . . . . . 25
3.1 Cellulose Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.2 Regenerated Cellulose Fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.3 Regenerated Cellulose Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.4 Regenerated Cellulose Beads . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.5 Other Regenerated Cellulosic Materials . . . . . . . . . . . . . . . . . . . . . 37
3.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
vii
viii Contents
4 Cellulose-Based Functional and Smart Materials . . . . . . . . . . . . . . . . 45

4.1 Cellulose-Based Electrically Conducting Materials . . . . . . . . . . . . . 46
4.1.1 Multifunctional CNT/Cellulose Composites . . . . . . . . . . . . 46
4.1.2 Functional CNT-Coated Cellulose Materials . . . . . . . . . . . . 48
4.1.3 Electro-Active Papers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.1.4 Other Electro-Conducting Materials
Based on Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.2 Cellulose-Based Magnetic Materials . . . . . . . . . . . . . . . . . . . . . . . . 55
4.3 Photofunctional Cellulosic Materials . . . . . . . . . . . . . . . . . . . . . . . . 59
4.4 Other Functional Materials Based on Cellulose . . . . . . . . . . . . . . . 61
4.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5 Nanocellulose-Based Functional Materials . . . . . . . . . . . . . . . . . . . . . . 69
5.1 Cellulose Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.1.1 Introduction of CNCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.1.2 Surface Chemistry of CNCs . . . . . . . . . . . . . . . . . . . . . . . . 72
5.1.3 Functional Materials Based on CNCs . . . . . . . . . . . . . . . . . 73
5.2 Microbrillated Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.2.1 Introduction of MFC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.2.2 Functional Materials Based on MFC . . . . . . . . . . . . . . . . . . 77
5.3 Bacterial Nanocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.3.1 Introduction of BNC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.3.2 Biomedical Applications of BNC . . . . . . . . . . . . . . . . . . . . 80
5.3.3 BNC-Based Functional Materials . . . . . . . . . . . . . . . . . . . . 82
5.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Chapter 1
Introduction
Abstract As the most abundant polymeric raw material, cellulose has been
attractive to the global industry in many aspects over the past decades. Sources of
this ubiquitous biopolymer are mentioned, with attention to the special hierarchical
organization of wood cellulose. Details of its structure are given, including the
molecular structures, hydrogen bond systems, and crystalline structures.
Keywords Cellulose  Source  Structure  Hydrogen bonding  Crystalline

structures
Cellulose was isolated in 1838 for the rst time by the French chemist Anselme
Payen [1], who extracted it from green plants and reported its elemental composition
four years later. As the most common organic polymer on earth, cellulose represents
about 1.5  1012 tons of the total annual biomass production, and is considered an
almost inexhaustible source of raw material [2]. It has fascinating structure and many
attractive properties such as renewability, availability, non-toxicity, low-cost,
environmental friendliness, biocompatibility, biodegradability, thermal and chemi-
cal stability, and derivatizabilty. Versatile structuring of cellulose by various
physical and chemical methods has enabled its use in a variety of applications, e.g.,
papers, textiles, lms, llers, building materials, composites, and so on. Before the
discussion of the fabrication and application of cellulose-based materials, the sources
and structure of cellulose will be introduced briefly in this chapter.
1.1 Sources
Plants are the major source of cellulose, which contributes approximately 33% of
all plant materials. Within the plant kingdom, cellulose plays a key role in structural
support and the oriented deposition of cellulose microbrils is crucial to patterning
through anisotropic growth during development [3]. Fig. 1.1 shows the hierarchy of
cellulose for wood. Cell walls of wood are made with macrobers of cellulose,
hemicellulose, and lignin as well as small amounts of extractives, which form a
© The Author(s) 2017 1

H. Qi, Novel Functional Materials Based on Cellulose, SpringerBriefs in Applied
Sciences and Technology, DOI 10.1007/978-3-319-49592-7_1
2 1 Introduction
Fig. 1.1 Cellulose: hierarchical organization, applications and a closed carbon cycle
cellulose ber composite. The macrobers are composed of microbrils, which

have 2–20 nm diameter and 100–40,000 nm long. The microbrils are formed by
brillar units (nanocrystals), in which cellulose chains are arranged. Besides wood,
other cellulose-containing materials include agriculture residues, water plants,
grasses, and other plant substances. Each year, an impressive amount of cellulose is
produced, including wood ber from trees (ca. 1,750,000 kt world production),
bamboo (10,000 kt), cotton linters (18,450 kt), jute (2300 kt), etc. [4].
It should note that the percentages of the cellulose strongly depend on the type of
plants. For instance, wood contains about 40–55 wt% cellulose, whereas cotton is a
fairly pure cellulose source, containing 85–95 wt%. Table 1.1 shows the contents of
cellulose, hemicellulose, and lignin in common agricultural residues [5]. Together,
cotton and wood are the major resources for all cellulose products such as paper,
textiles, construction materials, and cardboard, in addition to cellulose derivatives
such as cellophane, rayon, and cellulose acetate. The presence of lignin and hemi-
cellulose makes the functionalization of cellulose difcult. Thus, removal of lignin
1.1 Sources 3
Table 1.1 The contents of cellulose, hemicellulose, and lignin in wood and common agricultural
residues
Lignocellulosic materials Cellullose (%) Hemicellulose (%) Lignin (%)
Hardwoods stems 40–55 24–40 18–25
Softwood stems 45–50 25–35 25–35
Nut shells 25–30 25–30 30–40
Corn cobs 45 35 15
Grasses 25–40 35–50 10–30
Paper 85–99 0 0–15
Wheat straw 30 50 15
Sorted refuse 60 20 20
Leaves 15–20 80–85 0
Cotton seed hairs 80–95 5–20 0
Table derived with permission from [5]
and hemicellulose is usually involved in the production of cellulose-based materials.

Furthermore, cellulose-based materials are biodegradable and can readily convert
into small molecules such as CO2 and H2O by combustion or degradation. The
produced CO2 can be absorbed by plants and stored in the form of cellulose through
the process of photosynthesis. Therefore, a closed carbon cycle is integrated
(Fig. 1.1).
Apart from higher plants, cellulose can be also obtained from other natural
resources, e.g., several animals, fungi, bacteria (such as Acetobacter,
Acanthamoeba), unicellular plankton, algae (such as Valonia, Chaetamorpha) and
minerals. Same as that found in photosynthesis of land plants, unicellular plankton
or algae in the oceans are capable of synthesizing cellulose using carbon dioxide
xation. However, several animals, fungi, and bacteria can only assemble cellulose.
These organisms are devoid of photosynthetic capacity and usually require glucose
or some organic substrate synthesized by a photosynthetic organism to assemble
their cellulose [6, 7]. Only one group of animals (urochordates) has the ability to
biosynthesize cellulose [8]. Bacterial cellulose, which is produced directly as a
brous network, contains no lignin, pectin, hemicelluloses, or other biogenic
products; it is very highly crystalline and possesses a high degree of polymeriza-
tion. The formation of cellulose by laboratory bacterial cultures is an interesting and
attractive access to pure cellulose for both organic and polymer chemists [2].
1.2 Structure of Cellulose
1.2.1 The Molecular Structure
The chemical and physical properties of cellulose can only be properly understood
by acquiring knowledge of the chemical nature of the cellulose molecule in addition
4 1 Introduction
Fig. 1.2 Molecular structure of cellulose (n = DP, degree of polymerization)
to its structure and morphology in the solid state. As well-known, cellulose is a

long-chain polymer with repeating units of D-glucose, a simple sugar. It has the
basic molecular format of C6H10O5. In the cellulose chain, the glucose units are in
six-membered rings, called pyranoses. As the molecular structure of cellulose given
in Fig. 1.2, the glucose units are linked together by b-(1  4) glycosidic bonds
formed between the carbon atoms C-1 of one pyranose ring and the C-4 of the next
ring. Since a molecule of water is lost when an alcohol and a hemiacetal react to
form an acetal, the glucose units in the cellulose polymer are referred to as anhy-
droglucose units (AGU). When considering only one of these glucopyranose
structures, repeated AGU are rotated 180° with respect to each other due to the
constraints of b-linkage. Cellobiose with a length of 1.3 nm can be considered the
repeating unit of cellulose. The stereochemistry of cellulose causes an extended
conformation molecular chain (a semi-rigid conformation), making it a good
ber-forming polymer.
Each of the AGU units within the cellulose chain has three reactive hydroxyl
(OH) groups (with the exception of the terminal ones), a primary group at C6 and
two secondary groups at C2 and C3 that are positioned in the plane of the ring
(Fig. 1.2). As is typical for a polymer formed by “polycondensation,” terminal
groups at the either end of the cellulose molecule are quite different in nature from
each other. The C-1 OH at one end of the molecule is an aldehyde group with
reducing activity. Aldehyde groups form a pyranose ring through an intramolecular
hemiacetal form. In contrast, the C-4 OH on the other end of the chain is an
alcoholborne OH constituent and thus is called the non-reducing end. Due to long
chain length, however, the chemistry of the alcohol groups of the internal units
predominates, so long as the chains are not cleaved by the reaction conditions.
The number n of repeat units per chain is called the degree of polymerisation
(DP) of the molecule, which depends on the cellulose source. For example, DP
value of cellulose is approximately 10,000 in wood and 15,000 in native cotton in
nature. However, cellulose isolated from native sources is always polydisperse, i.e.,
it consists of a mixture of macromolecules that has the same basic composition but
differs in the chain length. The determination of the DP is usually performed
viscosimetrically after dissolving the sample in complexing aqueous solvents, like
cuprammonium hydroxide (Guam) or Cuen. The value of DP for isolated cellulose
1.2 Structure of Cellulose 5
is greatly dependent on the method of isolation and treatment. Normally, the cel-
lulose used in practice has an average DP value ranging between 800 and 3000. The
average molecular mass results from the product of the DP and the molecular mass
of the repeating AGU. Besides viscosity measurements, there are several other
techniques such as size-exclusion chromatography and light scattering, which can
give information about the molar masses and their distribution.
1.2.2 Hydrogen Bonding
As mentioned above, cellulose is an unbranched chain of glucose units. Each

cellulose chain approximates to a flat ribbon, with alternate glucose units facing in
opposite directions. They are locked in this position by a hydrogen bond between a
hydroxyl group (O3–H) of one glucose unit and the ring oxygen (O5′) of the next
(shown in Fig. 1.3). The intramolecular O3–HO5′ hydrogen bond shown is
present in all crystalline forms of cellulose, but the pattern of hydrogen bonding
from O2 to O6 varies [9]. These intra- and inter-molecular hydrogen bonds cause
the chains to aggregate together in a highly ordered structure, which results in a
crystalline and stable structure. Since the chains are usually longer than the crys-
talline regions, they are thought to pass through several different crystalline regions,
with areas of disorder in between (“fringed-micelle” model).
For native cellulose, the crystal is made up from metastable cellulose I with all the
cellulose strands parallel. This cellulose I contains two coexisting phases cellulose
Ia and cellulose Ib. Figure 1.4 shows the symmetry and directions of hydrogen
bonding in both cellulose Ia and Ib, which determined using atomic-resolution
synchrotron and neutron diffraction data [9–11]. In cellulose Ia, all chains are
crystallographically identical but alternating glucose units in each chain, shaded gray
and yellow, differ slightly in conformation. In cellulose Ib, however, chains of two
distinct kinds are arranged in alternating sheets. Chains passing through the origin
and center of the unit cell are shaded respectively yellow and gray.
Fig. 1.3 Numbering system

for carbon and oxygen atoms
in two consecutive glucosyl
units of cellulose: hydrogen
atoms are shown in gray.
Images taken with permission
from [9]
6 1 Introduction
Fig. 1.4 Symmetry and directions of hydrogen bonding in cellulose: a cellulose Ia; b cellulose Ib.
Images taken with permission from [9]
The intramolecular hydrogen bonding of cellulose molecule results in its relative

stiffness and rigidity. Cellulose is thus regarded as a semi-flexible polymer, which is
reflected in its high viscosity in solution, a high tendency to crystallize, and its
ability to form brillar strands. The large amount of intra- and inter-molecular
hydrogen bonds in the crystalline regions are strong, also render cellulose materials
good strength and insolubility in most solvents, including water and common
organic agents. They also prevent cellulose from melting (non-thermoplastic). In
the less ordered regions (amorphous regions), the chains are further apart and more
available for hydrogen bonding with other molecules, such as water. Thus, cellulose
can swell by absorbing large quantities of water, but not dissolve in water.
Cellulose with different crystalline structure shows a different hydrogen bonding
system. Compared to that of cellulose I, the hydrogen bonding networks in other
cellulose crystallites are more complex. Furthermore, the hydrogen bonding for-
mation also involves in other state of cellulose, such as blends, gels, amorphous,
and liquid crystals. However, the detailed structure of them and their influence on
properties are still subjects of discussion.
1.2.3 Crystalline Structures
The intra- and inter-molecular hydrogen bonding networks in cellulose give rise to
various ordered three-dimensional arrangements, including different crystals. The
order of the polymer chains inside is not uniform throughout the whole structure.
A distinction between low-order (amorphous) and high-order (crystalline) regions
in cellulose is often made. It is normally interpreted by a two-phase model, the
fringed bril model, which neglects the rather small amount of matter with an
intermediate state of order [12]. Crystalline cellulose exists as different allomorphs.
X-ray diffraction patterns and solid-state 13C-NMR revealed cellulose conforma-
tions that were used to elucidate the detailed crystalline structure and the basis
for transformation in the various allomorphs [13]. Mainly, four polymorphs of
1.2 Structure of Cellulose 7
cellulose have been found and they are named as cellulose I, II, III, and IV.
Cellulose I has a parallel crystalline structure and is composed of two distinct
crystalline forms Ia and Ib [9, 14, 15]. Ia has a triclinic unit with one chain; whereas
Ib has a monoclinic unit with two chains. Compared to Ia, Ib is more thermody-
namically stable. The proportion between the two crystalline phases Ia and Ib
depends on the cellulose origin. Normally, Ia is found more in primitive organisms
(bacteria, algae, etc.); whereas Ib is the major form in higher plants (woody tissues,
cotton, ramie, etc.).
Besides cellulose I, cellulose II can easily be achieved by the so-called
mercerization process, i.e., soaking cellulose I in aqueous NaOH (17–20%, w/v)
followed by decomposition of the intermediate by neutralization or washing out the
NaOH [16]. Cellulose II has an antiparallel crystalline structure organized in a
monoclinic unit with two chains. In comparison to cellulose I, the cellulose II
molecules are more densely packed and strongly inter-bonded and, therefore, cel-
lulose II is more thermodynamically stable. The process of transformation of cel-
lulose I to cellulose II is generally considered to be irreversible. From a technical
and commercial point of view, cellulose II is the most important crystalline form of
cellulose. Man-made cellulose bers and lms are all cellulose II, which is
regenerated from the solution of cellulose in coagulation bath.
As shown in Fig. 1.5, the crystalline modication of cellulose III is obtained by
treating native cellulose with liquid ammonia or an organic amine such as ethylene
diamine [17–19]. Cellulose III can be divided into cellulose IIII and IIIII obtained
from cellulose I and cellulose II, respectively. The transformation of cellulose I to
Fig. 1.5 Transformation of cellulose into its various polymorphs. Reprinted with permission from
[17] Copyright (2004) American Chemical Society
8 1 Introduction
IIII and of cellulose II to IIIII is reversible. The unit cell for both cellulose IIII and
IIIII structures is the same but the meridional reflections differ. Heating of cellulose
III in a suitable liquid (such as glycerol) produces the crystalline structure of
cellulose IV, thermodynamically stable [20]. Similar to that for cellulose III, the two
allomorphs IVI and IVII originate from cellulose I and cellulose II, respectively.
Regarding the use of cellulose and its chemical derivatization, nevertheless, cel-
lulose I and II are the important crystal structures of cellulose.
1.3 Perspective
As a chemical raw material, cellulose is a fascinating biopolymer and has many

opportunities in a variety of applications. However, there are still great challenges
that hinder this readily available and renewable natural polymer to be further used.
One drawback of cellulose, mainly obtained from higher plants, is its chemical
impurity. As detailed previously, natural bers consist of an assembly of cellulose
microbrils concentrically arranged in a matrix of other organic compounds. Pure
cellulose can only be extracted from the cell wall using various mechanical,
chemical, and enzymatic processes. Most of these processes involved the utilization
of high temperature and pH, the release of organic sulfur compounds or the water
contamination, as well as the degradation of lignin and hemicellulose. How to
separate and purify the cellulose and other biomass using more benign strategies is
one major challenge in the eld of bio-based materials. Another drawback is its
limited processability. Although cellulose is a linear polymer with a simple
molecular structure, it is obvious that its hydroxyl groups and their ability to form
hydrogen bonds play a major role in directing the crystalline packing and also
governing the physical properties of this polymer. This results a major problem of
cellulose that it is degrading before melting. That is, cellulose has to be either
dissolved in direct solvents or derivatized and then processed. However, traditional
processes for cellulose conversion meet the environmental problems. The devel-
opment of more efcient and eco-friendly processes for cellulose shaping and
chemical modication will be discussed in the chapter followed.
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4. Eichhorn SJ, Baillie CA, Zafeiropoulos N et al (2001) Current international research into
cellulosic bers and composites. J Mater Sci 36:2107–2131
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9. Jarvis M (2003) Chemistry: cellulose stacks up. Nature 426:611–612
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system in cellulose Ia from synchrotron X-ray and neutron ber diffraction. J Am Chem Soc
125:14300–14306
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cellulose Ib from synchrotron X-ray and neutron ber diffraction. J Am Chem Soc 124:9074–
9082
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Chapter 2
Platforms for Functionalization
of Cellulose
Abstract The shaping, chemical modication, and functionalization of cellulose

are largely depended on the process of dissolution in an efcient solvent. Viscose
process as the most important method for production of cellulose-regenerated
materials was introduced. The dissolution of cellulose in several other most fre-
quently used eco-friendly solvents was also discussed, including cellulose carba-
mate, N-methylmorpholine-N-oxide, aqueous alkali system, and ionic liquids.
These processes provide efcient platforms for development of new regenerated
materials and other products based on cellulose.
 
Keywords Cellulose solvents Viscose process Carbamate NMMO Aqueous  

alkali system Ionic liquids
Due to its large proportion of intra- and intermolecular hydrogen bonding, cellulose
is difcult to process as a melt or solution. That is, the reason that only around 200
million tons of the 40 billion tons renewed annually are used as raw materials
(pulps) in the manufacture of materials and goods such as textile bers, packaging,
paper, and body care products [1]. Normally, the processing of regenerated cellu-
lose includes two ways: chemical derivatization and direct physical dissolution in a
suitable solvent, as shown in Fig. 2.1. The viscose process is the oldest and most
important derivate methods for producing cellulose bers and lms. An alternate
derivatization method without the use of sulfur-containing compounds is the
CarbaCell process, which retains the viscose spinning technology. Compared to
derivatization, the direct dissolution and shaping of cellulose is much simpler.
However, cellulose is not soluble in water or conventional organic solvents. As a
very early direct spinning route of cellulose (Cupro silk, Cuprophane), copper
ammonia technology is rarely used anymore for posing environmental hazards.
Some solvents such as DMA/LiCl, zinc chloride, and phosphoric acid are also
reported as direct solvents. More recently, new eco-friendly direct solvents, such as
N-methylmorpholine-N-oxide (NMMO), ionic liquids, and aqueous alkali system,
are developed and show great potential to shape cellulose or to produce functional
celluloses by chemical modication.

12 2 Platforms for Functionalization of Cellulose
Fig. 2.1 Process principles

in regenerated cellulose
technologies: left, derivate
methods; right, direct
methods
2.1 Derivate Methods
2.1.1 Viscose Process
Although Anselme Paven discovered cellulose in 1838, the rst cellulose-based

thermoplastic material was produced in 1870 by the Hyatt Manufacturing
Company. This material was manufactured by treating cellulose with nitric acid to
form cellulose nitrate and commercialized under the trade name “celluloid” [2]. In
1892, the viscose process as a new process to regenerate cellulose bers in a larger
scale was developed [3]. As shown in Fig. 2.2, this process mainly involves a
derivatization process of cellulose with sodium hydroxide and CS2 to cellulose
xanthogenate.
Generally, cellulose used in the manufacture of viscose process is alpha cellu-
lose, which is obtained from pulping of wood (or cotton linters and bamboo), where
Fig. 2.2 Viscose solution is formed during dissolution of cellulose xanthogenate

2.1 Derivate Methods 13
special care is taken in pulping and bleaching so that the pulp is of higher strength
with high cellulose content. Rayon is one of the most common and popular uses of
viscose, which is used for many types of clothing and other textile products. The
process of manufacturing viscose rayon consists of several steps, such as steeping,
pressing, shredding, aging, xanthation, dissolving, ripening, ltering, degassing,
spinning, and washing. Viscose bers have excellent properties for a broad product
range, from wet-strength cotton like textile bers (Modal bers) to technical bers
in the form of cord (Rayon) for use in high-performance tires. Besides the appli-
cation in textile industry, viscose technology is still in use today for lm (cello-
phane) production, which is particularly important for food casing products. In
addition, viscose process also rendered possible the utilization of cellulose in dif-
ferent elds such as construction, ceramics, paints, cosmetics, etc.
The viscose process has developed more than 100 years, and still dominates the
regenerated cellulose products market with an annual world production of about 2.2
million tons (2002) [2]. However, viscose process causes environmental pollution
and damage to human health due to the use of heavy metal salts (in the precipitation
process), CS2, and other harmful chemical substances. In addition, the viscose route
is technologically complex, and one produce cycle would last for more than one
week. Despite continuous improvement in the past decades, waste water and
exhaust air treatment is complex owing to tough environmental requirements. The
increased cost of viscose technology incurred by the purication of exhaust gas and
waste water is also a disadvantage. Due to the economic and ecological drawbacks
of the viscose process, scientists have long been engaged in efforts to make
cellulose-based materials production more cost effective and eco-friendly.
2.1.2 Cellulose Carbamate Process
As an alternate method to viscose process, the cellulose carbamate (CC) process

employs urea instead of CS2 to react with cellulose (Fig. 2.3) [4]. The obtained
product calls cellulose carbamate, which is soluble and shapeable in sodium
hydroxide solution. The patented CarbaCell process is a specic carbamate tech-
nology using a novel synthesis route for CC with xylene as the transfer medium. As
shown in Fig. 2.4, the technical sequence of the CC process is similar to the viscose
technology [5]. Thus the regenerated cellulose products based on CC can be pro-
cessed on the existing viscose wet-spinning systems. It should be noted that, there
are no zinc or other heavy metals in the spin-bath. An important advantage of the
cellulose carbamate is the relatively high stability at room temperature allowing
storage for over a year. Thus, the synthesis of cellulose carbamate can be carried out
on a large scale in a central location, from which products can then be shipped to
decentralized facilities for processing (such as spinning factories) [2, 5].
Although there are several advantages over the viscose process, the CarbaCell
process has not yet been industrially established until now. It is mainly due to
certain requirements such as a catalyst, organic solvents, long reaction times, and
Fig. 2.3 Formation of cellulose carbamate by transformation of cellulose with urea
Fig. 2.4 Comparison of the viscose and carbamate process steps. Images taken with permission
from [5]
high temperatures. It was reported that CC could be synthesized by supercritical

CO2-assisted impregnation [6]. More recently, Zhou et al. presented a novel process
for the synthesis of CC by using microwave irradiation [7]. Due to a well con-
trollable heating process, conversion of the cellulose is successful within a few
minutes under catalyst-free and solvent-free conditions. This efcient synthesis
process is greatly signicant for the commercialization of the carbamate process. In
addition, the microwave-assisted process is highly ecological, especially since side
products and harmful waste are avoided and no raw material is lost. They found that
the solubility of CC could be signicantly improved with the addition of a small
amount of ZnO to the NaOH solution [8–10].
2.2 Direct Solvents 15
2.2 Direct Solvents
2.2.1 NMMO System
Many attempts have been made to invent new solvents to directly dissolve cellu-
lose; and some successful results have been reported. Indisputably, the most
industrially successful of all non-derivatizing solvents for cellulose is
N-methylmorpholine-N-oxide, commonly known as NMMO. This particular
organic solvent has proven to be a viable commercial solvent system, mainly due to
its ability to dissolve high concentrations of cellulose directly and without alteration
of the chemical properties of the cellulose chain. The rst patent involved the
dissolution of cellulose in tertiary amine oxides was issued to Greanacher and
Sallmann in 1936 [11]. About 30 years later, Johnson et al. led patents describing
solutions of different synthetic and natural polymers in different cyclic tertiary
amine oxides, including NMMO [12]. These compounds are better solvents than
tertiary amine oxides, since they can dissolve not only cellulose but also other
polymers. Nowadays, the NMMO process has ripened technically and has made its
technical breakthrough, leading to a new class of man-made cellulose bers [13].
Well known as an oxidizing agent in organic chemistry, NMMO is extremely
hygroscopic and completely soluble in water. NMMO in combination with water
can dissolve cellulose without prior activation or derivatization, mainly due to its
strong N–O dipoles (Fig. 2.5). There is not a very clear mechanism for dissolution
of cellulose and the structure of cellulose–water–NMMO solutions. Commonly, it
is agreed upon that the solvation power of NMMO originates in its ability to disrupt
the hydrogen bonding networks of cellulose, and to form solvent complexes by
establishing new hydrogen bonds between the polymer and the solvent [14]. There
are two stable hydrates of NMMO, the monohydrate (NMMOH2O) and the
2.5-hydrate (NMMO2.5H2O). The oxygen in NMMO is able to form hydrogen
bonds with nearby hydroxyl groups that in water or cellulose [15]. The competition
of water and cellulose for these hydrogen bonds thus determine the state of dis-
solution and precipitation of cellulose in the NMMO system. Figure 2.6 shows the
solubility of cellulose in the binary NMMO-water [13]. Cellulose is soluble all the
Fig. 2.5 Structure of

N-methylmorpholine-N-oxide
way up to NMMO1.2H2O, and can be easily regenerated by precipitation for

higher amounts of water. Hence, the monohydrate can dissolve cellulose while the
2.5-hydrate cannot.
The dissolution procedure of cellulose in NMMO is much simpler comparing
with viscose process. Solutions with cellulose content of up to 23% can be produced
starting with the dispersion of conventional cellulose in NMMO with a large excess
of water (such as 50%) [2]. As indicated in the phase diagram (Fig. 2.6), cellulose
can only be dissolved completely in a relatively small region. The excess water
provides low viscosity and thereby superior mixing. Surplus water is then removed
by heat between 100 and 120 °C and reduced pressure until the point of complete
cellulose dissolution is reached. After dissolution, the cellulose/NMMO/water
solution can be used for production of various cellulose materials, such as cellulose
bers, lms, food casings, membranes, sponges, beads, and others without haz-
ardous by-products [13].
Compared with conventional viscose process, many steps in NMMO process
may be left out since NMMO is non-derivatizing. Fibers (such as Lyocell) spun
from NMMO solution have outstanding properties in certain respects, such as
strength in both wet and dry states, modulus of elasticity, sorption behavior,
wearing properties, gloss, and touch. In addition, the industrial recovery of NMMO
is 99.6–99.7% from the precipitation bath in a closed circle, with its upgrade and
cleaning by an ion-exchange process [2]. These clear advantages make NMMO a
serious competition to the viscose process. NMMO is now successfully applied as a
direct cellulose solvent on industrial scale. Besides the man-made bers with
generic name Lyocell mentioned above, several other commercial cellulose bers
based on NMMO were developed till now, such as Tencel, Alceru, and Cocel.
Fig. 2.6 Phase diagram of cellulose/NMMO/water. Images taken with permission from [13]
However, the NMMO process also has some shortcomings, which hinder it from
the replacement of the viscose process to date. For example, NMMO is thermally
unstable, which can cause deconstruct of the solvent molecule at high temperature.
Although the stabilizers were added, there are no guarantees of avoiding dangerous
runaway reactions [14, 16]. Another reason is the severe brillation of the bers
manufactured and the ber prole which is closer to cotton. In addition, the high
viscosity of the cellulose solution in NMMO system sets limits in both the process
economy and the strength properties of the bers. Therefore, the extension of the
NMMO to direct cellulose solvents of high thermal and chemical stability com-
prising lower solution viscosity is very attractive from a safety, environmental, and
economic point of view.
2.2.2 Aqueous Alkali System
In recent years, aqueous alkali systems have attracted much attention because they
can serve as eco-friendly and low-cost solvents for cellulose. Sodium hydroxide
(NaOH) as a common strong base is largely used in the pulp and paper industry.
NaOH can cause cellulose to swell and in a narrow range of the phase diagram,
even can dissolve cellulose. The earliest cellulose-NaOH-water phase diagram was
plotted by Sobue [17]. Cellulose would interact with NaOH in different way to form
different complex depended on the NaOH concentration and temperature. In the
region of NaOH concentration between 6 and 10% and temperature from −10 to 4 °C,
cellulose is highly swollen and form so-called “cellulose Q”.
Normally, cellulose can only be dissolved in NaOH aqueous solution (7–10%
NaOH) below room temperature. NaOH can penetrate the amorphous area of cel-
lulose, then solvate to cellulose and destruct the neighboring crystalline regions.
The amount of cellulose that is soluble in NaOH/H2O depends on DP, the con-
centration and the crystallinity of cellulose [18]. Some treated cellulose (such as
regenerated cellulose and steam-exploded cellulose) and microcrystalline cellulose
(MCC) can be dissolved in NaOH/H2O directly or by the method of freezing–thaw
(Table 2.1) [18–21]. It is found that cellulose with DP lower than 200 could easily
be dissolved completely in the NaOH solution, while that with higher DP might
only be partially dissolved. Cellulose bers were also prepared based on
NaOH/H2O. However, the quality of these bers is poor [19]. Consequently,
aqueous NaOH solutions are not suitable for technical applications.
More recently, Zhang and coworkers found that NaOH/urea can dissolve cel-
lulose more efciently than the binary NaOH/H2O system itself [22, 23]. For
example, 7 wt% NaOH/12 wt% urea aqueous system can dissolve cellulose within
2 min after precooled to −12 °C. The main advantage of this method is its rapid
dissolution, relative simplicity, and cost effectiveness; and it is an eco-friendly
process [24]. Especially, this solvent can dissolve cellulose with relatively high DP
(DP = 500 − 900) completely, which render it a good platform for fabrication of
cellulose materials with high performance. In addition, some other additives such as
Table 2.1 Dissolution Cellulose in NaOH-based aqueous systems

Solvents Method Cellulose Ref.
8–10 wt% NaOH Direct dissolution Treated cellulose [18]
7–9 wt% NaOH Direct dissolution Treated cellulose [19]
8–9 wt% NaOH Freezing–thaw MCC [20]
7.9–14.9 wt% NaOH Freezing–thaw MCC [21]
6 wt% NaOH/4 wt% urea Freezing–thaw Cotton linter [22]
7 wt% NaOH/12 wt% urea Direct dissolution −10 °C Cotton linter [23]
9.5 wt% NaOH/4.5 wt% Direct dissolution Cotton linter [25]
thiourea −4 to −5 °C
9 wt% NaOH/1 wt% PEG Freezing–thaw Cellulose powder [26]
12–18 wt% NaOH, 16–28 wt% Two-step, −2 to 5 °C Cotton linter, [27]
urea Avicel
Table derived with permission from [27]
thiourea and poly(ethylene glycol) (PEG) were also used to enhance the solubility
of aqueous NaOH solutions for cellulose [25, 26]. Lithium hydroxide and potas-
sium hydroxide are expected to have a similar effect as sodium hydroxide. A strong
impact of the choice of salt has been observed, and the dissolution power of the
different systems is in the order LiOH/urea > NaOH/urea KOH/urea. Both LiOH
and NaOH in combination with urea are able to rapidly dissolve cellulose, while
KOH is not [23].
It should be noted that there are mainly three processes for dissolution of cel-
lulose in NaOH-based aqueous system (Table 2.1): (1) freezing–thaw; (2) direct
dissolution in solvents; (3) two-step dissolution process. Although the compositions
and dissolution conditions are different, furthermore, all NaOH-based aqueous
systems mentioned previously have similar NaOH concentrations (ranging from 6
to 10 wt%) and can only dissolve cellulose at low temperatures [27]. Figure 2.7
shows a schematic diagram of the solubility of cellulose in NaOH-based aqueous
Fig. 2.7 Schematic diagram 20

of the solubility of cellulose in
NaOH-based aqueous systems
depending on NaOH 10
concentration and III
temperature: I, complete
dissolution area; II, partial
0
dissolution area; III,
non-dissolution area. Images I
taken with permission from
[27] -10
II
-20
0 5 10 15 20
NaOH (wt%)
systems depending on NaOH concentration and temperature. It exhibits that cel-

lulose can be dissolved completely in wide range of NaOH concentration (from 6 to
18%, area I), through three dissolution processes. Cellulose can only dissolve
partially in area II, while can not dissolve in area III. Furthermore, the proper
method for cellulose dissolution is determined by the NaOH concentration: (1) 6–
10 wt% NaOH for freezing–thaw; (2) 6.5–10 wt% NaOH for direct dissolution; and
(3) 10–18 wt% NaOH for two-step process. Whatever process being used, how-
ever, the NaOH concentration in the nal cellulose solution must keep in a range of
from 6 to 10% to maintain the stability of the solution [27].
It was suggested that the dissolution mechanism is based on that the hydrates of
NaOH in low temperatures are able to form hydrogen bonds with the cellulose
chain, while the urea molecules surrounds the cellulose/NaOH/H2O inclusion
complex, screening it from other cellulose molecules and thereby prevent cellulose
aggregation [28]. Regeneration takes place by precipitation in non-solvents, e.g.,
dilute H2SO4, ethanol, butanol, or acetone. From the cellulose dope based on this
solvent, a series of regenerated cellulose products have been fabricated, including
novel cellulose bers, lms, and aerogels [24, 25, 29]. Therefore, aqueous alkali
systems provide a novel eco-friendly and economic platform for shaping and
functionalization of cellulose. However, there exists an upper DP limit of cellulose
for these aqueous alkali systems. The resulting cellulose solutions are also sensitive
to temperature, cellulose content, and DP of cellulose. In addition, the existence of
lignin in cellulose pulp will reduce the solubility.
2.2.3 Ionic Liquids
In the past decade, ionic liquids (ILs) have emerged as effective and green solvents,
mainly due to their high thermal and chemical stability, nonflammable nature, and
miscibility with many other solvent systems [30]. Liquids consisting only of ions
are called ILs. In the broader sense, this term includes all kind of salt melts, like
sodium chloride at temperatures above its melting point of 800 °C. Today, the term
“ionic liquid” refers particularly to salts composed of organic nitrogen inorganic
cations and inorganic anions, with a melting point below 100 °C. Salts with a
melting point below 25 °C are called “room-temperature ionic liquids” (RTILs)
[31].
In 1934, Graenacher found that liqueed quaternary ammonium salts, alone or
diluted in suitable solvents, could dissolve cellulose. In 2002, Swatloski et al.
discovered the ability of some ILs, in particular 1-N-butyl-3-methylimidazolium
([C4mim]+) combined with different anions, to dissolve cellulose, which opened
new paths for the shaping of polysaccharides and provoked a high interest in this
area [32]. In the following years, more ILs for dissolution of cellulose have been
reported, such as imidazolium salts (including 1-ethyl-3-methylimidazolium salts,
1-butyl-3-methylimidazolium salt, 1-allyl-3-methylimidazolium salt, etc) pyri-
dinium salts, and ammonium salts [33]. Among them, compounds based on
dialkylimidazolium cations are the majority; while chloride and acetate are the most
frequently reported anions.
ILs appear to be highly polar due to their ionic character, resulting in their
enhanced biopolymer dissolving capacity [34]. It is thought that both anions and
cations are involved in the dissolution process. Figure 2.8 shows the proposed
dissolution mechanism of cellulose in ionic liquid ([BMIM]Cl) [35]. The oxygen
and hydrogen atoms of the cellulose form electron donor–electron acceptor com-
plexes with the charged species of the IL. The anion acts as a hydrogen bond
acceptor and the cation as a hydrogen bond donor. This interaction causes the
disruption of the hydrogen bonding networks in cellulose, leading to dissolution of
cellulose in IL.
A number of factors influence the cellulose dissolution, such as temperature,
time, cellulose source, DP, and the structure of ILs. Microwave was also applied as
a heating method instead of pretreatment to improve cellulose dissolution. This
internal heating may be responsible for the more effective breakdown of the H-bond
network between the microbrils, although care must be taken because heating
occurs rapidly and can easily lead to cellulose pyrolysis. Sonication-assisted dis-
solution, however, seems only to have little benign influence on the dissolution
[34]. The number of reported low melting organic salts for cellulose dissolution is
growing rapidly. More recently, a new generation of ILs as cellulose solvents has
been developed by conjugation of the organic acids and organic super-base
(1,1,3,3-tetramethylguanidine). It can be technically “distillable” to high purity
(>99% purity, >99% yield), not yet observed for earlier generations of ILs for
cellulose [36]. Furthermore, tetrabutylphosphonium hydroxides containing 30–50
wt% water are capable of dissolving cellulose rapidly at ambient temperature
without derivation or degradation. In particular, tetrabutylphosphonium hydroxides
containing 40 wt% water can dissolve cellulose and remain stable throughout the
process, treating a natural biomass containing a considerable amount of water [37].
Fig. 2.8 Proposed dissolution mechanism of cellulose in ionic liquid ([BMIM]Cl). Images taken
with permission from [35]
This relatively new class of solvent has already shown great versatility in the
eld of cellulose technology, including cellulose-regenerated materials, homoge-
neous derivatization, and biomass processing [38–40]. However, ILs also possess
various disadvantages for a commercial application, such as side products and
recycling of solvents [1]. Thus, further research and development is needed for both
economic and environmental sustainability, including the design of a “next gen-
eration” of cellulose dissolving ILs as well as the more conscious use of established
ones, based on their specic advantages and disadvantages [33].
2.3 Summary
By using the two main approaches, chemical derivatization and direct dissolution,
native cellulose can be converted into various regenerated cellulose products which
are used in our ordinary life. As the oldest and most important commercial method,
viscose process mainly involves a derivatization process of cellulose with sodium
hydroxide and CS2 to cellulose xanthogenate. However, viscose process causes
environmental pollution and damage to human health. CarbaCell process is an
eco-friendly derivatization method, which was developed recently as an alternate
process for viscose and can retain the viscose spinning technology. Compared with
the chemical derivatization methods, the direct solvents are much simpler in dis-
solution and shaping of cellulose. Especially, three new eco-friendly direct solvents,
e.g., NMMO, aqueous alkali system, and ILs, are developed more recently and
attracted much attention over the past decades. The dissolution mechanism and
regeneration process of these solvents were investigated by many researchers.
Although having the great potential to shape cellulose, these solvents also have
some challenges, which must be addressed before the nal replacement of the
viscose process. On the other hand, the development of other new efcient and
“green” solvents for cellulose is still an important issue in eld of cellulose science
and technology.
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Chapter 3
Novel Regenerated Cellulosic Materials
Abstract The regeneration and shaping process for man-made cellulosic materials
was introduced. The morphology, structure, properties, and potential applications of
the resulting regenerated cellulosic materials were summarized, including cellulose
regenerated bers, cellulose regenerated lms, cellulose regenerated beads, cellu-
lose hydrogels, cellulose aerogels, nonwoven membrane, cellulose sponges, ultra-
thin cellulose bers or mats, and cellulose-based bioplastics.
 
Keywords Regenerated cellulose Cellulose bers Cellulose lms Cellulose 
beads  Cellulose hydrogels 
Cellulose aerogels 
Cellulose membrane 
Electrospinning
Based on the dissolution in suitable solvents, various man-made cellulosic materials

can be fabricated directly via so-called regeneration process. The regeneration of
cellulose is generally carried out by coagulation with anti-solvent or non-solvent
after the dissolution. It provides a simple pathway to transform native cellulose to
useful materials in various forms, as shown in Fig. 3.1. These products with
inherent renewability and sustainability present the most important segment by
volume in the chemical–technical processing of cellulose and nd applications in a
series important commercial areas.
3.1 Cellulose Regeneration
A basic understanding of the process, structure changes, and mechanism of the

regeneration from the cellulose solution to its aggregation state is essential for the
successful preparation of the regenerated cellulose material, which dominates the
morphology and properties [1]. Generally, the regeneration of polymer occurs when
its solution contacting with a non-solvent coagulation bath, leading to an asymmetric
structure, i.e., a more or less dense skin is supported by a porous sub-layer [2].
The formation of the skin results from the high interfacial concentration stimulated

26 3 Novel Regenerated Cellulosic Materials
Fig. 3.1 Scheme of fabrication process for regenerated cellulosic materials
by an extremely rapid solvent depletion. The bulk of the polymer solution is still in a
fluid with nearly initial concentration. The growth of the sub-layer in the fluid region
is expected to occur by the rapid inflow of the coagulant through the weak points at
the skin interface [3]. Two predominant morphologies—nger-like and sponge-like
—are usually observed in the sub-layer, which are forming depends on the rate of
precipitation of the polymer [2]. Finger-like morphologies are formed when the
non-solvent enters into a polymer solution faster than the solvent diffuses out.
Sponge-like structures are formed when the solvent diffuses out faster than the
non-solvent diffuses in [4].
For the regeneration of cellulose from its solution, the exchange of solvent with
non-solvent leads to a desolvation of the cellulose molecules and to the supposed
reformation of the intra- and intermolecular hydrogen bonds [5]. While most types
of regenerated cellulose have crystal form of cellulose II, having antiparallel chain
packing, their mechanical and surface chemical properties are known to depend
strongly on the type of cellulose solvent and coagulant, as well as the conditions of
regeneration such as temperature and time. About the regeneration of cellulose from
NMMO system, for instance, several publications describing the morphological
features of bers and lms are available [2, 6, 7]. The regeneration of cellulose
using water as the coagulation system results from a phase separation process. The
type of morphology of a regenerated cellulose object is strongly dependent on the
state of the solution prior to regeneration. If the solution has crystallized, a dense
morphology is observed while a dense skin surrounding a core made of large voids
with cellulose walls is obtained from a molten solution. In this case, the cellulose
wall structure (small ordered spherical objects) is due to a spinodal decomposition
[3]. It was reported that bers precipitated in water show a dense cellulose network
structure with small nely distributed voids with dimensions ranging from 10 to
100 nm [6]. Comparison with a water bath, the microporosity of the bers increased
in a bath of isopropyl alcohol [7]. The regeneration of cellulose–NMMO system
was also investigated in various alcohols. It was observed that the increase of their
molecular mass leads to the formation of a distinct skin-core structure [6].
3.1 Cellulose Regeneration 27
The regeneration process for cellulose from NMMO system is a physical pro-
cess, with no accompanying chemical reaction. Similarly, the dissolved cellulose in
ILs can be coagulated and regenerated quantitatively by adding water or any other
solvents miscible with the ionic liquids, like methanol, ethanol, or acetone. In IL
systems, for example, the introduction of water over a set concentration range
induces changes in the ordered cation anion polar interaction network and disrupts
the interactions between ILs and cellulose [8]. While water diffuses inside the rst
solvation shell of cellulose, the number of hydrogen bonds among water molecules
and cellulose increases and the number of hydrogen bonds between the anion and
the sugar decreases [3, 8]. Thus, water acts as an anti-solvent and causes the
cellulose to be recovered. The regenerated cellulose object has almost the same DP
as the initial pulp, indicated that there are no obvious polymer degradation.
However, the morphology changes signicantly according to the coagulation bath
used. The degree of crystallinity can be manipulated by putting more or less stress
on the regenerating material. Without any loading of stress, cellulose is obtained as
nearly amorphous polymer, which offers the opportunity to produce amorphous
cellulosic materials.
Regenerated cellulosics such as bers and lms were also prepared from alkali
aqueous systems recently. In a more or less similar way as mentioned above,
cellulose is not initially derivatized but directly dissolved and then regenerated due
to phase separation. The coagulation baths used include water, aqueous acid, salt
solutions, and some organic liquid combinations such as ethanol and acetone
[9–11]. The main principle is that the regenerating liquid must be miscible with the
aqueous NaOH solution and be a non-solvent for cellulose [12]. As suggested, the
inclusion complex associated with cellulose, NaOH and urea (or thiourea) hydrates
is disrupted by adding a non-solvent such as water, leading to the self-association of
cellulose. In the case of aqueous acid as non-solvent, the H+ assumes a key role to
trigger cellulose regeneration by neutralizing the alkaline content. Moreover,
heating can also cause the cellulose chains aggregate rapidly to form hydrogels, and
then regenerated cellulose materials may be obtained by drying [1]. Obviously, the
choice of coagulation bath and coagulating conditions will considerably influence
the nal properties of the regenerated cellulose materials. As reported, aqueous
H2SO4/Na2SO4 resulted in a high optical transmittance and homogeneous structure
as well as good mechanical properties. Since the regeneration mainly relates to the
diffusion between the coagulant and the solvent, the relatively higher temperature
leads to the increasing of the diffusion coefcient [13]. Therefore, the lower tem-
perature is demonstrated to be favorable for denser network structure than higher
temperature, as a result of compact and ordered arrangement of macromolecules.
Furthermore, Isogai and coworkers reported that the prepressing and press vacuum
drying procedure endowed the regenerated cellulose lms with high performance
compared with no orientation [14]. Thus, the structure and properties of the
regenerated cellulose materials can be controlled by varying the conditions of
regeneration process.
3.2 Regenerated Cellulose Fiber
For a long time, cellulose bers have been involved in our daily life for textiles.
Cellulose bers are known to have good mechanical properties with relatively low
density, due to the hollow nature of the ber composition. Even although synthetic
polymer bers from fossil fuels are used widely now, regenerated cellulose ber
still remain unique among the mass-produced bers because they are the only ones
directly from the natural polymer, which is renewable, abundant, and biodegrad-
able. Different to that of natural bers, the properties of regenerated cellulose bers
are homogeneous and can be adjusted by processing parameters. Cuprammonium
rayon (Fig. 3.2) as the rst commercial regenerated ber is made from cellulose
dissolved in cuprammonium solution. The resultant solution is passed through the
spinnerets, and the cellulose is regenerated in the coagulations to remove the copper
and ammonia. However the relatively high costs associated with the need to use
copper salts prevented it from reaching a large scale of manufacture.
As one of oldest methods, the viscose process has developed more than
100 years, and still dominates the regenerated cellulose products market [16, 17].
Through this route cellulose pulp is converted in a series of controlled and coor-
dinated steps to a spinnable dope and then into longer laments which may be
Fig. 3.2 The SEM images of the viscose rayon (a) cuprammonium rayon (b) Lyocell ber (c) and
the novel cellulose laments based on NaOH/urea. Images taken with permission from [15]
3.2 Regenerated Cellulose Fiber 29
precisely controlled in terms of length, denier, physical properties and

cross-sectional shape. During the formation process of viscose rayon, its cross
section was shrunk as a result of the reverse of xanthation reaction, leading to the
lobulate skin-core structure as shown in Fig. 3.2a [15, 18]. In the past years, the
viscose process has undergone many renements. However, the basic chemistry is
still the same. Viscose rayon is produced today worldwide on a 5 million ton scale,
and its types range from high performance tire yarn to textile laments and staple
bers with excellent properties close to those of cotton [17]. Usually, there are three
types of viscose rayon: regular rayon, high wet modulus rayon and high tenacity
rayon. Regular rayon has the largest market share, and it is widely used in apparel
and home furnishings. High wet modulus rayon (Modal) is a modied regular rayon
with high wet strength, in which the laments are stretched to a lager degree than
regular rayon. High tenacity rayon is also a modication of regular rayon to provide
exceptional strength, such as the rayon with an average tenacity of 40 to 42 cN/tex
[19]. Nowadays, the development of viscose is focus more on novel bers with
specialities and high quality.
In recent decades, the NMMO technology turned out to be a simple physical
alternative to the yet dominating viscose technology for producing regenerated
cellulosic bers (Lyocell ber) without hazardous byproducts. This process not
only overcome the tedious technology for producing conventional Viscose bers,
but also exhibited a series of unique performance. Figure 3.3 shows the dry jet wet
ber spinning process for cellulose–NMMO solution schematically [6]. The
structure formation of Lyocell bers differs from that encountered in the conven-
tional viscose process. The smooth surface and round cross section as shown in
Fig. 3.3 Scheme of the dry jet wet ber spinning process for cellulose–NMMO solution. Images
taken with permission from [6]
Fig. 3.2c are attributed to the physical dissolution and regeneration. Compared with
the viscose bers, the Lyocell ber shows larger tenacity and modulus and lower
elongation [20]. Besides the traditional textile, Lyocell also demonstrates potentials
as technical textile, e.g., functional coating materials, technical knits, as well as a
high volume ber type for carpets, a brous powder for plastics as reinforcement, a
special textile ber for seat covers and a nonwoven application for battery sepa-
rators, etc. [1].
As another direct dissolution solvent, NaOH/urea aqueous system is also a
promising and eco-friendly platform of cellulose ber spinning. As shown in
Fig. 3.2d, the obtained cellulose multilaments have a circular cross section, which
is markedly different from the lobulate shape of the viscose rayon, but similar to
cuprammonium rayon and Lyocell bers [18]. This can be explained that the cel-
lulose multilaments were regenerated directly from cellulose ‘solution’ in a
quasi-gel state, which was formed mainly by physical cross-linking through
hydrogen bonds between cellulose chains [15]. The novel multilament bers are
easy to dye to deep vibrant colors. Moreover, the sulfate content in them was
determined to be essentially zero, while viscose rayon is about 8 mg/100 g cellu-
lose bers. The tensile strength values of the single ber are similar to that of
Lyocell. It is known that the mechanical properties depend on the micromorphology
structure which is influenced by the processing technology. With a drawing pro-
gress, the orientation factor increases and tensile strength of the multilament bers
are signicantly improved [21]. Figure 3.4 shows small-angle X-ray scattering
(SAXS) patterns of the laments and commercial viscose rayon. The sharp and long
equatorial streaks and very short meridional peaks indicate the presence of
Fig. 3.4 Small-angle X-ray scattering (SAXS) patterns of laments (a–e) from NaOH/urea
aqueous system and the commercial viscose rayon (f). Images taken with permission from [21]
3.2 Regenerated Cellulose Fiber 31
needle-shaped voids or a brillar structure aligned parallel to the ber direction and
with a periodic lamellar arrangement of crystalline and amorphous cellulose
regions. It is noted that the higher draw ratio could induce stronger lamellar
arrangements [21]. Recently, a pilot scale industrialized trial with a dissolution tank
of 1000 L capacity yielded regenerated bers spun successfully from the cellulose
dope based on NaOH/urea aqueous system [22]. In addition, NaOH/thiourea
aqueous solvent was successfully applied to pilot scale spinning, and to obtain
regenerated multilaments with tensile strength reached 19–22 cN/tex [23].
Cellulose dopes in ILs are also suitable for ber spinning [20, 24–26]. Similar to
Lyocell bers, the regenerated bers from ILs have a high degree of crystal ori-
entation and total crystallinity. The microvoids length and misorientation degree of
the bers were lower than that of viscose ber. Thus, the surface shape and cross
section of bers is regular and well-proportioned, and the bers presented strong
tear strength and initial modulus [20]. The spinning speed influenced the spinning
of cellulose/ILs solution. When higher spinning speeds applied the higher spinline
stress led to a higher capacity as well as higher tenacity of the regenerated bers, as
a result of the crystallinity and orientation enhancement [26].
Cellulose carbamate process as an alternate method to viscose process was also
investigated for production of regenerated cellulose bers. Industrial tests have
shown that cellulose carbamate can be processed without any problems on viscose
spinning machines [16]. Recently, a novel process for the synthesis of cellulose
carbamate by using of microwave irradiation was developed [27]. Based on this
method, novel regenerated cellulose laments (Fig. 3.5) were prepared from cellu-
lose carbamate in a NaOH/ZnO aqueous solution on a pilot scale [28]. The laments
Fig. 3.5 Photograph of the novel regenerated cellulose laments produced by a pilot machine
from cellulose carbamate. Reprinted with permission from [28] Copyright (2014) American
Chemical Society
demonstrated a relatively high degree of orientation. The tenacity of the bers is

determined in the range of 17–23 cN/tex, which is comparable with that of com-
mercial viscose rayon. This simple and eco-friendly method may offer an alternate to
the environmental drawbacks of the viscose process.
Compared to natural bers, regenerated cellulose bers show less variability of
ber properties. In addition, as mentioned above, the diameter, shape, elastic
modulus, tensile strength, and failure strain of regenerated cellulose bers can be
tuned during ber production by varying process parameters. Generally, the aver-
age tensile strength of regenerated cellulose bers is comparable to natural ligno-
cellulosic bers, whereas their elastic modulus is usually below that of natural bers
[29]. However, failure strain of regenerated cellulose bers is up to ten times higher
than in natural bers, which makes them particularly useful for applications where
high fracture toughness is required [30]. Due to the population growth and
increased prosperity megatrends, the demand for sustainable cellulose bers is
predicted to largely exceed the available supply in the future. And the natural bers
such as cotton production are increasingly questioned. In this respect, regenerated
cellulose bers are regarded to potentially play a leading role for textile
applications.
3.3 Regenerated Cellulose Films
As another main product from regeneration of cellulose, transparent regenerated

cellulose lms played a major role in packaging applications. Because of its
biodegradability, regenerated cellulose lms offer an environmental solution to the
plastic waste issue. Cuprammonium solution is still the rst solvent used to dissolve
solid cellulose and to prepare cellulosic lm (cuprophane) by extrusion. Similar to
regenerated cellulose bers, however, regenerated cellulose lms were produced
mainly by the viscose method. Typically, viscose lms (cellophane) are produced
using wide nozzle silts and spinning lips. The cellulose dope, in the form of a
coagulated and regenerated ribbon, is pulled off from the nozzle by a series of
consecutive rollers, then taken off and transported further [6]. The produced cel-
lophane is transparent, lustrous, durable, flexible, and impervious to air, grease,
germs, and dirt [31]. Thus, it can be used in food packaging and non packaging
such as adhesive tapes and an artistic wrap. Regenerated cellulose lms are
moisture permeable because cellulose is a poor barrier to moisture. This property is
exploited where controlled moisture permeability is a required characteristic.
Compared with other polymer lms, cellulose is less prone to static, which greatly
assists machinability. Unique among lms for flexible packaging, transparent col-
ored cellulose lms can be produced by incorporating dyes into the material during
manufacture. In addition, cellulose lms are also important for some special
applications such as small sausage casings and cupro membranes for separation
(dialysis) [6].
3.3 Regenerated Cellulose Films 33
Despite their advantageous properties, cellophane involves problems such as

high production costs and environmental problems of the processing route.
Nowadays, the interest has been concentrated on the preparation of cellulose
solution in a simple, environmentally benign and economical way [32].
The NMMO technology provides one promising platform for cellulose lm man-
ufacture. Fink et al. shown that it is possible to produce a high-yield cellulose lm
from NMMO solution with the blow-extrusion process [6, 33]. The principle of the
process is illustrated in Fig. 3.6. This new route starts from a melt solution of
cellulose in NMMO/H2O. The tube of highly viscous and highly elastic cellulose
dope emerging from the ring-shaped nozzle can then be blown up into an air gap
like a bubble due to its special rheological properties before it is coagulated from
the outer and the inner side in an aqueous precipitation bath. The tube of regen-
erated cellulose thus obtained is folded by drawing it over a rst godet and then is
further processed by washing, posttreatment, and drying [33]. Moreover, the per-
formance properties of the lms can be tuned by varying process the numerous
parameters of dope preparation, blow extrusion, coagulation, and posttreatment [6].
Besides the blown lm method, classical lm casting is applied to cellulose
solutions based on eco-friendly solvents such as NMMO, ionic liquids, and aqueous
Fig. 3.6 Scheme of the

blow-extrusion process for
cellulose lms formation.
Images taken with permission
from [6]
alkali systems [6, 34–37]. By dissolving different celluloses (pine, cotton, bamboo,
MCC) in ionic liquids, regenerated cellulose lms were prepared by casting
method. The obtained lms exhibit excellent thermal stability and mechanical
properties [35]. It was found that the higher tensile stress of cellulose lms is
mainly ascribed to higher DP and crystallinity values combined with hydrophobic
forces.
Recently, Qi et al. reported a ‘green’ process to prepare a cellulose solution by
dissolving cotton into aqueous NaOH/urea solution, which was then casted on a
glass plate to fabricate regenerated cellulose lms [34]. As shown in Fig. 3.7, the
resultant lms with good tensile strength (100 MPa) possess homogenous structure
and excellent optical transmittance (about 90%) that matches the appearance of
plastics. It is reported that transparent regenerated cellulose lms prepared from
alkali (NaOH or LiOH)/urea aqueous solutions exhibit high oxygen barrier prop-
erties, which are superior to those of commercial cellophane, poly(vinyl chloride)
(PVC) lms, and poly(vinyl alcohol) (PVA) lms [37]. Water-swollen cellulose
lms prepared from LiOH/urea solution were uniaxially drawn to investigate the
effect of orientation on their supramolecular structure and properties [38].
A signicant orientation of cellulose chains is occurred in its amorphous regions
rather than in crystalline regions. The porosity and swelling degree of the lms
decrease with an increase of the draw ratios, indicating a dense structure as a result
of the orientation. With an increase of the drawn ratios from 1 to 1.22, the tensile
strength and modulus of elasticity of the cellulose lms increases from 89 to
213 MPa and 4.4 to 11 GPa at dry state, respectively, and from 2.9 to 33.9 and 3 to
208 MPa at wet state. In addition, the orientated cellulose lms are capable of
supporting cell adhesion and proliferation, which indicates the potential application
in biotechnology.
Fig. 3.7 Optical

transmittance and photograph
of regenerated cellulose lms
(packaging a flower) prepared
from aqueous NaOH/urea
system. Reproduced from
Ref. 33 with permission from
The Royal Society of
Chemistry
3.4 Regenerated Cellulose Beads 35
3.4 Regenerated Cellulose Beads
Regenerated cellulose beads are spherical particles with diameters in the micro- to
millimeter scale, which are used in many advanced applications ranging from
chromatography over solid supported synthesis and protein immobilization to
retarded drug release [39]. The rst attempt to prepare cellulose beads was
described in 1951 [40]. By simply hand dropping a viscose solution into an aqueous
coagulation bath, the spherical materials were prepared and named cellulose pellets.
Since then, various procedures have been developed using different solvents and
techniques to obtain cellulose beads. In principle, regenerated cellulose bead pro-
duction can be simplied into three steps: (i) dissolution of cellulose (or a cellulose
derivative), (ii) shaping of the polymer solution into spherical particles, and
(iii) sol–gel transition and solidication of the solution particles to beads. In
addition, several post- and pretreatments can be applied to ne-tune certain prop-
erties [39].
The procedures commonly used for the preparation of regenerated cellulose
beads are shown in Fig. 3.8. Despite the fact that various starting polymers, sol-
vents, and regeneration methods can be applied, the shaping of the beads from a
polymer solution is either achieved by dropping (Fig. 3.8a–d) or dispersion tech-
niques (Fig. 3.8e). For the dropping procedures, beads can be obtained by solidi-
cation of spherical droplets of a cellulose solution in a coagulation bath of a
non-solvent. The droplets can be formed by pressing the solution through a thin
opening such as a syringe nozzle. For example, cellulose beads were prepared based
on NaOH/urea aqueous system by this way [41]. Optimization of ejection speed,
falling height, and solution viscosity are consequently important for the preparation
of cellulose beads using a dropping technique [41, 42]. For smaller droplets, the
cellulose solution was transferred to the nozzle by applying pressurized nitrogen [43].
Fig. 3.8 Schematic drawings of different procedures for the preparation of regenerated cellulose
beads by different techniques: dropping (a), jet cutting (b), spinning drop atomization (c), spinning
disc atomization (d), and dispersion (e). Reprinted with permission from [39] Copyright (2013)
American Chemical Society
Fig. 3.9 An optical

micrograph of the cellulose
beads. One division on the
scale is 1 mm. Images taken
Centrifugation (spinning drop atomization) has also been applied to prepare cel-
lulose beads (shown in Fig. 3.9) having narrow particle-size distribution from
viscose solutions [44]. Nowadays, cellulose beads prepared from viscose by dis-
persion techniques are commercially available.
In general, the diameter of cellulose beads obtained by dropping techniques is
limited to a range of approximately 0.5–3 mm, since it is restricted to the size of
droplets that can be prepared [39]. Different technical devices can be applied to
obtain droplets of a dened size and shape. Especially for large batch productions,
the utilization of automated systems that work at higher operation speeds is
favorable, as shown in Fig. 3.8c. Adjusting the rotational speed, geometrical
parameters of the cup, and size of its outlets allows particle sizes to be controlled
efciently [45, 46]. With high forces applied to the cellulose solution, it is also
possible to obtain droplets of comparably small diameters of 500 lm or less. In
addition, regenerated cellulose spheral nanoparticles with diameter ranging from
100 to 300 nm can be electrospun from the cellulose solution in NaOH/urea
aqueous system [47].
While for dispersion procedures, the solution of cellulose (or cellulose deriva-
tive) was dispersed in an immiscible solvent under high rotational speed to form
emulsions that can be stabilized with the aid of surfactants. The resulting emulsions
can be solidied to obtain cellulose beads. The diameter of the droplets within the
dispersion ranges from about 10 to several 100 lm, which can be controlled by the
mixing speed, type and amount of surfactant, ratio of hydrophobic to hydrophilic
3.4 Regenerated Cellulose Beads 37
Fig. 3.10 SEM images and

size distributions of
regenerated cellulose beads
by dispersion techniques
based on NaOH/urea aqueous
system. Images taken with
permission from [48]
solvent, and viscosity of the dispersion medium and cellulose solution [39]. By
dispersion techniques, regenerated cellulose beads (Fig. 3.10) with diameters range
from 5 lm to 1 mm were prepared from cellulose in NaOH/urea aqueous system
[48]. A preparative size exclusion chromatography (SEC) column packed with
these beads and exhibited high efciency and large throughput in fractionations of
polymers.
Similarly, several other cellulose solvents such as NMMO and ILs as well as
cellulose carbamate have also been employed for the preparation of cellulose beads
via both dispersion and dropping techniques [49–52]. Different to dropping pro-
cedures, no special equipment is required to produce cellulose beads with repro-
ducible properties. And cellulose beads based on dispersion procedures has already
been commercialized and products with different sizes (about 30–250 lm) are
available on the market.
3.5 Other Regenerated Cellulosic Materials
Besides the regenerated cellulose bers, lms and beads which were mentioned
above, a series novel regenerated cellulosic materials were also reported in the past
decades. Among them, cellulose hydrogels are attracting because they are bio-
compatible and biodegradable materials which are promising for a large number of
industrial uses, in particular the cases where environmental issues are concerned, as
well as in biomedical applications. In general, cellulose hydrogels are fabricated by
physical aggregation or chemical crosslinking, to obtain a three-dimensional net-
work of hydrophilic polymer chains, which is able to absorb and retain a signicant
amount of water. The solvent system provides great opportunities to prepare
regenerated cellulose hydrogel through physical cross-linking. By heating or
freezing process, cellulose hydrogels can be formed from the solution in
NaOH/urea aqueous system, which was due to destruction of stability of cellulose
solution [53]. Similarly, flexible gels can be obtained by dissolving cellulose in

1-butyl-3-methylimidazolium chloride when keeping it at room temperature for
7 days [54]. The gelation can be enhanced by using cross-linkers such as
epichlorohydrin (ECH) [55, 56]. In these cases, the hydrogel networks were built by
a synergy of chemical and physical cross-linking processes, that is, the etherica-
tion reaction between cellulose and ECH as well as the self-association and
entanglement of cellulose chains via hydrogen bonding reconstruction. By tuning
the crosslinker and cellulose concentrations as well as temperature, it is possible to
optimize the mechanical properties and swelling capabilities of hydrogels.
Structurally, due to the extended crosslinked network of polymers, cellulose
hydrogels are similar to the extracellular matrix of the human body. These struc-
tures may be modied or designed in accordance to the external physical and
chemical factors that may influence their activity during a certain application [57].
As porous ultralight materials derived from hydrogels, in which the liquid
component has been replaced with gas, aerogels of regenerated cellulose have also
gained attention for their ultrasmall density, high porosity, and high specic surface
area. Usually, regenerated cellulose aerogels can be fabricated by supercritical
drying or freeze–drying from the precursor of cellulose hydrogels. A serials of
attempts to direct dissolution of cellulose and its conversion into aerogels has been
reported, such as in alkali aqueous systems, NMMO, ILs and LiCl/DMSO solution
[58–62]. By using supercritical CO2 drying, the network structure in the hydrogel
was well preserved in the cellulose aerogels. The aerogels produced from
NaOH/urea aqueous solution exhibited large surface areas in range of 400–500
m2g−1 and high mechanical strength [58]. The typical value of the Young’s mod-
ulus was 200–300 MPa, which is more than two orders of magnitude greater than
those of silica aerogel (around 1 MPa). However, a specic surface area of about
only 150–200 m2g−1 was obtained by the similar supercritical drying procedure,
from the cellulose solution in NMMO, ILs and 8% NaOH/water [61]. That is, the
structure and properties of the cellulose aerogels are strongly dependent on the
formation of hydrogel precursor (such as the cellulose dissolution, cellulose content
and regeneration conditions) and the fabrication process (supercritical drying or
freeze–drying used). Due to the unique structure and inherent properties of
renewable resource, regenerated cellulose aerogels provide great potentials to be
used as adsorbents, heat/sound insulators, lters, catalyst supports, or carbon
aerogel precursors.
Other regenerated porous cellulose materials such as sponges and nonwoven
fabrics have great potential for applications within the eld of pharmaceuticals.
Apart from the biocompatibility, the good match of their mechanical properties with
those of hard and soft tissue has been demonstrated [63, 64]. A resorbable
macroporous cellulosic material was developed for use as a resorbable hemostatic
agent in bone sites, by using calcium carbonate powder as inverse matrix. It was
found that this regenerated cellulose material has cytotoxicity, biocompatibility, and
resorption properties which are similar to control, while its hemostatic power was
3.5 Other Regenerated Cellulosic Materials 39
higher [65]. Viscose cellulose sponges were investigated in connective tissue for-
mation [66]. By modifying the cellulose content and size of the sponge it is possible
to design suitable implants for various applications. The use of regenerated cellu-
lose as scaffolds for growing structurally mature and functional cardiac cell con-
structs in vitro was also demonstrated [67]. In addition, the nonwoven cellulose
fabrics were used as novel scaffold architectures for in vitro cartilage tissue engi-
neering. A homogeneous distribution of the seeded cells was possible and the
development of cartilaginous tissue could be proved [64].
Compared to nonwoven cellulose fabrics, electrospun regenerated cellulose mats
have a larger specic surface area and small pore size. It is reported that nonwoven
mats of submicronsized cellulose bers (250–750 nm in diameter) can be obtained
by electrospinning cellulose from NMMO/water system [68]. Similar to other
regenerated process, electrospinning of cellulose was found to bring about the
transformation from cellulose I to cellulose II. The degree of crystallinity of mats
can be controlled by various process conditions including spinning temperature,
flow rate, and distance between the nozzle and collector. Electrospinning of native
cellulose has been attempted by using IL system as the solvent [69]. The size and
morphology of the electrospun cellulose bers were influenced by the concentration
of cellulose in ionic liquid which directly affected the viscosity for electrospinning
[70]. For the nonvolatile nature of ionic liquid systems, a rotating drum composed
of parallel copper wires was used as a collector in order to avoid the contraction of
the wet bers, thus smooth cellulose nanobers were successfully fabricated (as
shown in Fig. 3.11) [70]. With the addition of cosolvent such as dimethyl for-
mamide (DMF) and dimethyl acetamide (DMAc) and dimethyl sulfoxide (DMSO),
the electrospinnability of cellulose solution can be enhanced, resulting in ner bers
with better web uniformity, thermal stability and crystallinity [70–72]. For instance,
nonwoven nanosized cellulose bers with average diameters of 470 ± 110 nm
were electrospun by using [C2mim][CH3CO2], while bers with average diameters
Fig. 3.11 SEM images of

cellulose bers electrospun
from cellulose solution in
AMIMCl/DMSO and
collected by a rotating copper
wire drum. Images taken with
of 120 ± 55 nm were obtained by the addition of a surface active ionic liquid

([C10mim]Cl) [72]. Due to their unique structure, ultrathin cellulose bers prepared
from electrospinning provide large-scale potential applications of in hemodialysis
membranes, ultraltration membranes, grading purication materials, catalyst car-
riers, and other biomedical possibilities [70].
Recently, novel cellulose bioplastics were developed from the regenerated
cellulose hydrogels based on cellulose solution in aq. NaOH/urea via simple hot
pressing [73]. On the basis of the removal of cellulose molecules in the hydrogel
state, the hot pressing induces the transition of its aggregated structure, with a
radial orientation of the cellulose aggregates occurred in the planar direction of the
plate, leading to the plastic deformation. The cellulose bioplastics exhibites
excellent mechanical properties (tensile strength of 240 MPa and modulus of
3.7 GPa), good thermal stabilities and low coefcients of thermal expansion, which
are comparable to common commercial plastics. It provides a potential alternative
to petroleum-derived plastics, which is not eco-friendly.
3.6 Summary
Most regenerated cellulose materials have crystal form of cellulose II, which
converted from native cellulose with crystal form of cellulose I. Their mechanical
and surface chemical properties are known to depend strongly on the type of
cellulose solvent and coagulant, as well as the conditions of regeneration such as
temperature and time. By using different apparatus and technology, cellulose can be
shaped to a wide range of forms, such as bers, lms and beads. These regenerated
cellulose materials are now widely used in our ordinary life, such as textile,
medicine and packing materials. Especially, some new solvents provide novel
platform for regeneration of cellulose, which have unique structure and excellent
properties. Meanwhile, the design of regenerated cellulose materials with special
morphology, for instance, cellulose hydrogels, cellulose aerogels, nonwoven
membrane, cellulose sponges, ultrathin cellulose bers or mats, and even
cellulose-based bioplastics, also offers great potential for cellulosic materials to be
used in many applications.
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Chapter 4
Cellulose-Based Functional and Smart
Materials
Abstract To convert the traditional cellulose material into functional and smart
materials, a series of procedures involved modication or functionalization of
cellulose have been developed. By integrating nanoparticles or other functional
materials, the cellulose-based materials can achieve tailored properties such as
electrical conductivity, magnetic properties, photosensitivity, catalytic activity,
sensing ability, and other special properties. The fabrication processes, properties,
and applications of the recently reported cellulose-based functional materials are
summarized in this chapter.
Keywords Cellulose composites 

Functional materials 
Smart materials 
   
Nanocomposites Blending Dip coating Nanoparticles Electrical conductivity 

Magnetic materials Photosensitivity Sensor 
Nowadays, functional and smart materials based on renewable bioresources and

eco-friendly processes have attracted considerable attention. As the most abundant
natural polymer in nature, cellulose is renewable, biodegradable, and biocompati-
ble. It can be extensively derivatized and to form strong and stable stiff-chain
homomolecular structure with ber-, lm-, and hydrogel-forming properties, which
has the potential to be a stable and robust carrier, matrix, or scaffold component for
the fabrication of functional materials [1–3]. Functional cellulose composites can be
easily prepared according to the same general procedure described in Chap. 3, with
the exception that a mixed solution of cellulose and an organic/inorganic material
with specic functionalities in an appropriate solvent is used. Specially, the
development of nanostructured inorganic materials in the form of nanocrystals,
nanowires, and nanotubes provides a list of functional llers or inks for integration
into the polymeric materials [4, 5]. Thus, the fabrication of functional and smart
materials based on cellulose, which combine the unique structure and properties of
nanomaterials and the inherent features of cellulose, is of great interest to polymeric
science.

46 4 Cellulose-Based Functional and Smart Materials
4.1 Cellulose-Based Electrically Conducting Materials
4.1.1 Multifunctional CNT/Cellulose Composites
Cellulose is insulating polymer. In general, the fabrication of cellulose-based

electro-conductive materials is involved with the introduction of specic conduct-
ing materials such as nanocarbons and conducting polymers. Among them, carbon
nanotubes (CNTs) have unique electrical, mechanical, and thermal properties. In
the past decade, a series of CNT-integrated cellulose composites have been
reported. By direct mechanical mixing methods, for example, CNT/cellulose
composite paper which possesses electrical conductivity has been prepared [6, 7].
However, these processes can only obtain microscale interaction between CNTs
and cellulose matrix, leading to poor dispersion and nonuniform electrical con-
ductivities [3]. Negatively charged cellulose xanthate was therefore employed as a
solubilizing agent of carbon nanotubes to prepare a highly stable aqueous sus-
pension and cellulose–carbon nanotube composites [8]. And the cellulose dissolved
in some special solvents, such as LiCl/DMAc, NMMO, ILs, and NaOH/urea
aqueous solution, were also used as the matrix to fabricate cellulose/CNT com-
posites [3, 9–13]. In these cases, CNTs could interact with cellulose in nanoscale
level to obtain a more uniform dispersion. The resulting composites thus exhibited
improved mechanical properties and thermal stability [9].
Compared with that of other solvents, the components of NaOH/urea aqueous
solution are more common and cheaper. Especially, water as the main component
of this solvent was also widely used in the dispersion of CNTs. Uniform dispersion
of CNTs, in combination with favorable CNT-cellulose matrix interaction, causes
the better ductility and higher toughness of the materials, as well as the enhanced
thermal stability. It was found that the resulting composite lms with 2–10 wt%
CNT have both normal flexible paper and conducting CNT characteristics, which
show a volume resistivity that can be controlled over a wide range of 1.35–
540 X cm. The network formation of the CNTs in cellulose matrix not only
introduces good conductivity to the materials, but also leads to the impressive
multifunctional sensing capacities to tensile strain, temperature, and environmental
humidity. Especially, the fractional resistance of the composite lms exhibits highly
linear and repeatable correlation to tensile strain. The useful linear strain range for
these composite lms is 7–13% strain with the value of GF in the range of 0.6–1.2.
This unique characteristic indicates their excellent sensing ability as strain gages
[3]. Furthermore, these electro-conductive lms were demonstrated to be served as
highly sensitive, well reversible and reproducible sensors for water, as shown in
Fig. 4.1. This unique water-induced sensibility of CNT-cellulose composites offers
a solution to sense liquid water in a reliable and efcient way, which can be widely
used in many elds such as detection of water leakages and water content deter-
mination. [14]. In the case of liquid sensing, the swelling of the polymer matrix in
4.1 Cellulose-Based Electrically Conducting Materials 47
Fig. 4.1 The CNT/cellulose composite lm (3 wt% CNT) as water sensor: a the photo and
b TEM image of the U-shaped sample; c the schematic of liquid sensing test; d relative resistance
change (Rrel) of the sample during immersion/drying (600/1200 s) cycle in water at 20 °C, where
R0 is the initial resistance of the sample and Rt is the transient resistance upon exposure to water.
Images taken with permission from [14]
contact with solvent molecules causes a local gap enlargement between conducting
llers, resulting in a detectable increase of electrical resistance. This direct trans-
duction of chemical information into an electrical signal when combined with
existing low power microelectronics and sensing technology makes it an attractive
material.
By using a lab-scale wet-spinning apparatus, CNT/cellulose composite bers
were spun based on NaOH/urea system [15]. The resulting bers (Fig. 4.2) are
lightweight, flexible, and exhibit good mechanical properties. Similar to that of
CNT/cellulose composite lms, the embedded CNT network introduces a high
electrical conductivity and multifunctional sensing abilities to composite bers.
However, composite bers exhibit a much higher sensitivity to water, and even can
be served as unique water “switches,” as shown in Fig. 4.3. Based on their unique
(structural) properties, the bers may be processed into “wearable electronic
devices” (textile sensors and actuators).
In addition, CNT/cellulose composite aerogels with good electrical conductivity
and excellent mechanical properties were reported [13, 16]. By combining the
nature of CNTs with the 3-D porous matrix, CNT/cellulose composite aerogels
show good sensitivity to ambient pressure; and they can also be served as simple,
reliable, highly sensitive, well reversible, and reproducible sensors for volatile
organic compounds (VOCs) analysis at room temperature. They provide a novel
concept for developing a new class of multifunctional chemical sensors [16].
Fig. 4.2 SEM images of a, b surface and c, d cross section of a CNT/cellulose composite
multilament ber (3 wt% CNT). The right side in b shows the charge contrast imaging SEM of
the ber surface. Reprinted with permission from [15] Copyright (2014) American Chemical
Society
4.1.2 Functional CNT-Coated Cellulose Materials
Besides the blending method mentioned above, conductive cellulose-based mate-

rials could also be fabricated by process of dip coating [17–23]. This process is
simple and scalable, similar to those widely used for dyeing bers or fabrics in the
textile industry. In addition, it is more effective in creating conductive CNT-to-CNT
junction networks where the CNTs are not encapsulated by polymer chains, leading
to remarkably low CNT loadings compared to the previously reported percolation
threshold values for composites. If the electronic properties of the CNTs on the
surface of cellulose bers can be harnessed, it is possible to design wearable sensors
or to build power generators and energy storage capabilities into the clothing [17,
18]. As shown in Fig. 4.4, intelligent e-textiles were fabricated from general
commodity cotton threads using a polyelectrolyte-based coating with CNTs [18].
Efcient charge transport through the network of nanotubes (20 X/cm) and the
possibility to engineer tunneling junctions make them promising materials for many
high-knowledge-content garments. Along with integrated humidity sensing,
CNT-cotton threads can be used to detect albumin, the key protein of blood, with
high sensitivity and selectivity. Similarly, highly conductive textiles with conduc-
tivity of 125 S/cm and sheet resistance less than 1 X/sq were produced by an
extremely simple “dipping and drying” process CNT ink [19]. Such conductive
Fig. 4.3 CNT/cellulose composite bers as unique water sensors: a ber acts as sensor
(R = 12 X cm); b ber acts as switch (R = 230 X cm); c schematic diagram of CNT/cellulose
composite bers as a simple water detection device. Reprinted with permission from [15]
Copyright (2014) American Chemical Society
Fig. 4.4 Photographs of CNT-cotton yarn: a comparison of the original and surface modied
yarn; b 1 m long piece as made; c demonstration of LED emission with the current passing
through the yarn. Reprinted with permission from [18] Copyright (2008) American Chemical
Society
textiles show outstanding flexibility and stretchability. Supercapacitors made from

these conductive textiles show high areal capacitance, up to 0.48 F/cm2, and high
specic energy.
Electrically conductive CNT-cellulose bers were prepared by dip coating [22,
23]. The interconnected networks are formed on cellulose ber surfaces. This
uniform and efcient conductive pathways result in the controllable resistance of
the CNT-cellulose ber in a large scale of 50–200,000 kX/cm. The modied cel-
lulose bers exhibit excellent sensing abilities to external stimuli [22]. For example,
the piezoresistance properties of CNTs may be used to detect variations of electrical
conductance as a function of mechanical deformation of the bers. These CNT–
coated cellulose bers exhibit highly linear and repeatable electrical resistance
correlation to tensile strain, with good reversibility and repeatability. And the useful
linear strain range for the ber is about 18% strain with the value of GF of 0.6. This
could be used to monitor the motion of muscles and limbs for rehabilitative and
telemedicine applications [17]. In addition, the CNTs covered on the ber surface
can come into contact directly and quickly with chemicals, which makes them more
sensitive to gases or liquids compared with composites. As chemical vapor sensors,
the CNT-coated cellulose bers exhibit simple, sensitive, and selective sensing
ability to chemical vapors, indicating their potential to be design new type of
electronic nose (e-nose) for VOCs and other gases [22]. As sensors for water, they
are highly sensitive, well reversible and reproducible, with a sensitivity of 100–
8000% [23]. And the CNT-cellulose ber with high resistance can even be served
as simple and efcient electrochemical water “switches.” Moreover, these func-
tional bers exhibited good sensibility to electrolytes aqueous solution. This unique
sensibility of CNT-cellulose ber provides the potential to sense liquid water or
Table 4.1 Potential Materials Selected applications

applications of electrically
conducting CNT-cellulose 1-D bers • Conductors; wearable electronics
materials • Structure health monitoring
• Smart textiles
• Detection of liquids (such as water) leakages
• Strain sensor
• Thermistor
• Humidity or vapors sensors
2-D lms • Detection of liquids leakages
• Strain sensor
• Humidity or vapors sensors
• Biosensors
3-D aerogels • Chemical sensors (gases or vapors)
• Batteries
• Energy storage
• Supercapacitors
aqueous solution in a reliable and efcient way, which can be widely used in water
monitoring or other elds such as smart textiles and wearable technology.
A humidity sensor on cellulose paper is demonstrated using CNTs functional-
ized with carboxylic acid [24]. As compared to the sensor made on a glass sub-
strate, the cellulose mediated charge transport on the paper substrate enhances the
sensitivity and provides a breakthrough toward future paper electronics for low cost
disposable applications. Similarly, regular paper and textiles can be turned into a
highly conductive medium by coating a thin layer of CNTs. These conductive paper
and textiles are highly porous, flexible, and even stretchable, and can serve as a
novel conductors to replace traditional electrodes. Due to their novel double porous
structure, high performance energy and environmental devices have been demon-
strated, including flexible thin energy storage devices, stretchable supercapacitors,
3-D energy textiles, microbial fuel cells using waste water, and high-speed water
ltration devices. These devices can be fabricated with simpler processes compared
to their counterparts with traditional conductors [25].
By using different approaches mentioned above, various CNT-integrated cellu-
lose materials are expected, including 1-D ber, 2-D lms, and 3-D aerogels. As
shown in Table 4.1, the creating of electrically conducting CNT network in poly-
mer matrix or on the surface, in combination of the inherent feature of cellulose,
offers the resulting materials unique and excellent properties, which render them
great potential to be used in many elds.
4.1.3 Electro-Active Papers
Piezoelectricity is observed in the uniaxially oriented systems of crystallites of

cellulose and elongated lms of optical synthetic polymers. The shear piezoelec-
tricity in cellulose-based biopolymers, such as wood, ramie, chitin, amylase, and
Fig. 4.5 Concept of EAPap bending actuator: a EAPap actuator, b cellulose microbril, and
c water molecules bonded with hydroxyls. Reprinted with permission from [28] Copyright (2006)
American Chemical Society
starch, is comparable to that in quartz crystal [26]. Recently, Kim et al. reported the
discovery of cellulose as a smart material that can be used for biomimetic
sensor/actuator devices and microelectromechanical systems. This smart cellulose
was termed as electro-active paper (EAPap) [27]. Considering the cellulose struc-
ture and processing of cellulose-based EAPap, its actuation mechanism is combi-
nation of ion migration and dipolar orientation. Figure 4.5 depicts the concept of
EAPap bending actuator [28]. Cellulose EAPap is a lm of regenerated cellulose
and morphologically, regenerated cellulose consists of ordered and disordered
regions. The ordered domains are composed of crystalline and amorphous sections,
and water molecules attached to hydroxyl groups can be found in large disordered
regions. During the fabrication process, sodium ions were injected in the ber.
When electric eld was applied, these ions migrate to anode, selective ionic, and
water transport across the polymer, which direct to bending of actuator.
Consequently, the large ordered region is responsible for the dipolar orientation,
leading to permanent polarization, which results into piezoelectric behavior [29].
The early investigation on EAPap actuator characterized by chemically treated
paper with thin electrodes on its both sides shows reasonable [27]. It was observed
that there is more than 3 mm tip displacement when 2 MV/m of excitation electric
eld was applied to the paper actuator with 30 mm length. However, the perfor-
mance is sensitive to the thickness of the EAPap material because the thickness is
associated with the bending stiffness that strongly affects the bending deformation
and the force output of the actuator. At an optimal thickness, the force and fre-
quency bandwidth was drastically improved in the EAPap material at the cost of
low actuation voltage and large bending displacement [30]. In order to enhance the
Fig. 4.6 Electro-active cellulose paper applications: a micro-flying object; b micro-insect robots;
c biodegradable MEMS. Reprinted with permission from [28] Copyright (2006) American
Chemical Society
performance of EAPap actuator, conducting polymer such as polypyrrole coating

on cellulose paper was suggested, which was previously gold electrodes coated
[31]. It was found that the electrode thickness plays a key role in the displacement
behavior of these types of actuators. CNTs are also involved in the fabrication of
EAPap actuators [32, 33]. Carbon nanotubes-mixed cellulose-EAPap actuator
exhibited the highest mechanical power output. Furthermore, the in-plane strains of
the EAPap materials were investigated in the presence of electric elds [34]. It
reveals that high Young’s modulus of EAPap is promising for its use as articial
muscle. The electrical power consumption was less than 8 mW/cm2, which is
beyond the safety limit of microwave power in air. This offers the possibility for
achieving microwave driven EAPap actuators.
Considering the current integration technology, cellulose-based EAPap actuators
and sensors have great potential for cheap, disposable, and biocompatible devices,
with recycling also being available after use [26]. By combining of ion migration
and the piezoelectric effect as well as its smart characteristics, cellulose EAPap is
suitable for many applications including micro robotics, MEMS devices, flexible
speaker, micro pumps, remotely controlled actuators, and so on (Fig. 4.6) [28, 29].
4.1.4 Other Electro-Conducting Materials Based

on Cellulose
Graphene has a two-dimensional (2-D) nanostructure and possesses unique struc-

tural and mechanical, electrical, thermal and optical properties, which are different
from those of other carbon allotropes such as CNT. To fabricate mutilfunctional
graphene-integrated cellulose materials, which combine the specic properties of
graphene and the characteristics of cellulose, are of great interest to polymeric
science. Till now, several attempts to prepare graphene/cellulose composites have
been reported [35–37]. Functional graphene/cellulose nanocomposite papers were
prepared by direct dispersion of graphene and cellulose nanobres [35, 36]. In order
to obtain a uniform dispersion in which graphene could interact with cellulose in
nanoscale level, some solvents such as NMMO, DMAC/LiCl, and ILs were also
used for both dissolution of cellulose and dispersing of graphene [37–40]. In these
cases, the graphene/cellulose composites exhibit good electrical properties and
excellent mechanical properties as well as enhanced thermal properties. Signicant
enhancement in gas barrier properties of the cellulose/graphene nanocomposites
was also observed [40]. The resulting nanocomposite may nd potential applica-
tions in the areas of carbon ber precursor, conductive bers, electrical tools, and
biodegradable composites.
The popular attempts conducting cellulose composites also include the cellulose
modication with conducting polymers, such as polyaniline (PANI) and polypyrrole
(PPy), by different techniques [41–44]. Dark green and transparent composite lms
were constructed facilely from PANI/cellulose solution, displaying highly homo-
geneous structure, good miscibility, excellent mechanical properties, and conduc-
tivity [41]. Furthermore, these flexible lms exhibit highly specic capacitance and
good cycle stability [42]. With the addition of CNTs, the specic capacitance of the
lms as supercapacitor materials was signicantly improved. PANI-cellulose
hydrogels with a homogeneous macroporous structure and good miscibility were
fabricated by the association of PANI chains with crosslinked cellulose networks.
The composite hydrogels display electromechanical actuation under a low voltage
electric eld, showing a continuous and linear crawling motion and the character-
istics of a rapid electrical response. This new avenue to construct hydrogels from
hydrophilic cellulose and hydrophobic PANI through new hydrogen bonding for-
mation is important for the fabrication of a soft intelligent system [43].
Electrically conductive nanoporous materials were fabricated by coating nano-
porous cellulose gels (NCG) with polypyrrole (PPy) nanoparticles [44]. After being
prepared from the aqueous alkali/urea solution, as shown in Fig. 4.7, the PPy/NCG
hydrogels were converted to aerogels by solvent exchanging with ethanol and drying
with supercritical CO2, resulting in materials with a low density, a large surface area, a
high mechanical strength, and sufcient electrical conductivity. While the PPy/NCG
composite hydrogels demonstrated good mechanical stability under bending, rolling,
and torsional loading (Fig. 4.7c–e), its aerogel was robust (Fig. 4.7f). In vitro studies
show that PC12 cells cultured on PPy/NCG composites have good adhesion and
proliferation. Furthermore, the cellular morphologies of PC12 cells show a remark-
able neuronal phenotype on the surface of PPy/NCG composite doped with dode-
cylbenzenesulfonic acid under electrical stimulation [44].
Some metal nanoparticles are also involved in the fabrication of electrically
conducting materials based on cellulose. For example, cellulose solution in
NMMO/DMSO co-solvent was spin-coated and then coagulated in an Au
nanoparticles aqueous colloid. The resultant cellulose composite lms are electri-
cally conductive with the Au loading higher than 20 wt%. In addition, they exhibit
either band-like or variable-range hopping conductivity, which depends on the
loading of Au nanoparticles. These properties lead to potentials in “smart” papers
and textiles, microelectronic components, catalysts, and chemical sensors [45].
4.2 Cellulose-Based Magnetic Materials 55
Fig. 4.7 a Preparation of PPy/NCG composite aerogels; b schematic representation of pyrrole

polymerization with FeCl3; Macroscopic views of PPy/NCG composite hydrogels under c bending,
d, e torsional loading, and f PPy/NCG composite aerogel. Images taken with permission from [44]
4.2 Cellulose-Based Magnetic Materials
As mentioned above, the combination of organic and inorganic materials provides

the opportunity to develop new materials that not only retain the inherent properties
of their component precursors but may also exhibit new properties due to the
synergistic interaction of the precursors. By integrating magnetic nanoparticles,
cellulose-based materials can convert into another subset of smart materials, which
can adaptively change their physical properties due to an external magnetic eld.
These magnetically responsive materials are expected to exhibit interesting mag-
netic eld-dependent mechanical behavior with a wide range of potential applica-
tions, such as protective clothing for military use, magnetic lters, sensors,
information storage, and health care or biomedical products [46–48].
Lumen-loading technology is one of the common processes used in the pro-
duction of magnetic cellulose materials. This process mainly involves the disper-
sion of cellulose pulp in a concentrated suspension of iron oxide particles such as
magnetite and maghemite particles, followed by a mild washing step to remove all
the unbound-magnetic particles [49–52]. Based on this method, commercially
available magnetic pigments can be introduced into the lumens of softwood bers
to prepare magnetic paper. Lumen-loaded bers act as magnetic dipoles allowing
manipulation of ber orientation in papermaking [50]. However, the diffusion
kinetics of the process is mainly limited by the transport of ller particles through
the pit apertures in the ber walls [51, 52]. It often results in a heterogeneous
composite with deleterious particle dispersion, aggregation and therefore inferior
performance.
By precipitation of magnetic nanoparticles with the presence of cellulose bers
from a premixed precursor, more uniform dispersion can be obtained for the
resulting materials. Composite lms prepared through this way with nano-sized
ferrite (Fe3O4 and CoFe2O4) particles exhibit better magnetic properties [53]. It was
found that the magnetic property of the lms increases with the loading of the
magnetic particles. The coercivity of the magnetic lms prepared with CoFe2O4 is
higher than that with Fe3O4, and the thermal stability of the magnetic lm depends
on the degree of crystallinity of the precipitated particles. The magnetic particles
deposited on the surface of the bers have detrimental effects on the lm strength.
Another approach to prepare magnetic cellulose materials involves synthesis of
iron oxide particles within the cellulosic matrix itself. In this so-called in situ
co-precipitation process, iron ions are converted to iron oxide particles within
cellulosic matrix by the addition of an excess NaOH solution. It was found that the
processing conditions have a major effect on size distribution of magnetic
nanoparticles. In order to make homogeneous dispersion and control the crystalline
phase of magnetic nanoparticles in cellulose matrix, ammonia gas-enhancing in
co-precipitation method operated in a closed system without oxygen has been used
[54]. By this method, magnetic particles in the crystal form of magnetite (Fe3O4)
can be obtained, with the average particle size in the range of 20–39 nm. Moreover,
the particle size and particle size distribution of magnetic nanoparticles are con-
trollable by adjusting the concentration of aqueous iron ion solution.
Besides the natural cellulose ber and bacterial cellulose, regenerated cellulose
is also used as the matrix for in situ co-precipitation. For instance, the regenerated
cellulose is hydrogels prepared from LiOH/urea and NaOH/urea aqueous solution
have unique brous network structure, which offers macro/mesoporous spaces.
Thus, it can be used as reaction chambers for precipitation of nanoparticles, with the
cellulose matrix providing a support structure to hold the particles [55–60]. As
shown in Fig. 4.8, magnetic Fe2O3 nanoparticles can be synthesized in situ in the
cellulose bers for the preparation of magnetic cellulose bers [55, 56]. The syn-
thesized Fe2O3 nanoparticles with a mean diameter of 18 nm are uniformly dis-
persed in the cellulose matrix. There has strong interaction between Fe2O3
nanoparticles and cellulose matrix. The composite bers with enhanced mechanical
strength exhibit superparamagnetic properties, relatively high dielectric constant
and a strong capability to absorb UV rays. The magnetic composite bers can be
used as protective materials for low frequency magnetic shielding.
Similarly, magnetic cellulose lms and microspheres can also be fabricated by
in situ co-precipitation. The obtained Fe2O3 nanoparticles in the composite lms
prepared from FeCl2 or FeCl3 solution are c-Fe2O3. The Fe2O3 nanoparticles are
plate-like, and distribute randomly in the cellulose matrix before drying [57]. The
possible mechanism for the formation of plate-like magnetic nanoparticles is
ascribed to the non-negligible magnetic dipole–dipole interactions between the
magnetic nanoparticles, transforming from Fe(OH)3 or Fe(OH)2 to Fe2O3. While
4.2 Cellulose-Based Magnetic Materials 57
Fig. 4.8 SEM images of regenerated cellulose ber (a and b) and photographs of the composite
bers (c–e). Reprinted with permission from [55] Copyright (2008) American Chemical Society
for the preparation of Fe3O4/cellulose lms, Fe3O4 nanoparticles are directly

formed in the cellulose matrix when treated with NaOH solution; therefore, the
morphology of the magnetic nanoparticles is irregular particles [58]. Novel mag-
netic cellulose microspheres have been created by in situ synthesize of Fe3O4
nanoparticles into the cellulose pore as a reaction micro-chamber [59]. The Fe3O4
nanoparticles with diameter about 20 nm can be synthesized from FeCl3/FeCl2
aqueous solution by in situ co-precipitation in the cellulose pores. As shown in
Fig. 4.9, the magnetic cellulose microspheres exhibit sensitively magnet induced
transference, extremely small hysteresis loop, as well as good adsorption and
release capabilities for bovine serum albumin. The Fe3O4 nanoparticles in the
cellulose microspheres play important roles in both the creation of the
magnetic-induced transference and the improvement of the targeting protein
delivery and release.
Fig. 4.9 Photos of magnetic cellulose microspheres in water at a magnetic eld (left) and the
magnetic hysteresis loop at 25 °C (right). The inset illustrates SEM image of the morphology of
magnetic cellulose microspheres. Images taken with permission from [59]
In this method, other llers, such as activated carbon (AC) can be added into the
mixed solution for the preparation of composite cellulose beads with improved
properties [60]. The cellulose beads containing Fe2O3 nanoparticles exhibit sensi-
tive magnetic response, and their recovery can be facilitated by applying a magnetic
eld. Dyes are adsorbed effectively by the AC/magnetic cellulose beads. The Fe2O3
nanoparticles and AC in the AC/magnetic cellulose beads can play important roles
in both the formation of spherical shape beads and the improvement of the
adsorption capacity. Furthermore, the sorbent can be regenerated and used
repeatedly. The magnetic properties of the beads allow the separation from the
effluent by applying a magnetic eld, leading to the development of a clean and safe
process for water pollution remediation.
Apart from the procedure mentioned above, magnetic cellulose materials can
also be prepared by adding ferromagnetic powders into the cellulose solution, and
then regenerated in coagulation bath. This technique is one of the most effective
methods of imparting new features to materials as it guarantees stability of their
properties, due to the fact that the stabile magnetic modier is rmly integrated in
the polymer matrix. Based on NMMO system, a ferromagnetic compound can be
added into the solution, and magnetic cellulose bers can be spun directly from the
mixed solution [61]. The obtained composite bers can be used to build textile
magnetic coils with a textile core. The magnetic properties of the composite bers
depend on the kind of implemented magnetic ller and the percentage content by
volume in the ber matter, and the composite bers have an increase in the ef-
ciency of shielding the magnetic eld.
4.3 Photofunctional Cellulosic Materials 59
4.3 Photofunctional Cellulosic Materials
Cellulose is a colorless polysaccharide due to the absence of groups in cellulose that

will absorb light in the visible range. Hence, cellulose-based materials such as
regenerated cellulose and cellulose ber with a diameter of micro/nanoscale size
can be used to prepare transparent paper by casting, ltration, extrusion, etc. [62,
63]. By introducing different fluorescent/luminescent inorganic compounds or other
functional materials, photofunctional cellulosic materials with tailored properties
can be prepared for various types of applications. Fluorescent cellulose lms have
been fabricated by treating the never-dried regenerated lms with fluorescent dyes,
which exhibited strong fluorescence under irradiation with UV lights [64]. By the
regeneration of solution containing photoluminescent (PL) pigments (alkaline earth
aluminates), luminescent cellulose composite lms with long after-glow emission
were prepared [64]. The PL pigments embedded in the cellulose matrix offer the
advantages of a short activation period, a long after-glow, and high brightness. As
shown in Fig. 4.10, it can absorb light (sunlight, fluorescent, incandescent, etc.) for
about 10–15 minutes and then emits a visible light for more than 10 hours in the
dark. Moreover, they are free of radioactive and nontoxic materials and are
chemically stable. Therefore, the novel PL lms can be used to make PL signs,
photos, etc., which can be widely used in the eld of information technology,
anti-counterfeiting techniques and functional packaging.
Among various luminescent materials, quantum dots (QDs) have attracted great
attention due to their semiconductor behavior and unique optical properties.
Hydrogels having strong fluorescence were fabricated from cellulose and QDs in a
NaOH/urea aqueous system via a mild chemical cross-linking process [65]. The
CdSe/ZnS nanoparticles were embedded rmly in the cellulose matrices, as a result
of strong interactions between the CdSe/ZnS nanoparticles and cellulose after
Fig. 4.10 After-glow decay curve (left) and photograph (right) of after-glow of luminescent lms.
Samples were irradiated by 365 nm UV light for 10 min before measurement (at time of 5 s).
Reproduced from Ref. [64] with permission from The Royal Society of Chemistry
Fig. 4.11 The appearances

of the QD-cellulose hydrogels
under a 302 nm UV
lamp. Images taken with
hydrolysis of the QDs ligands. As shown in Fig. 4.11, the QD-cellulose hydrogels
emit strong fluorescence with different colors of green, greenish-yellow, yellow and
red, depending on the size of the CdSe/ZnS nanoparticles, and exhibit relatively
high PL quantum yields. These QD-cellulose hydrogels are promising for appli-
cations in the elds of fluoroimmunoassay and biological labeling. Based on the
LiOH/urea aqueous system, QD-cellulose composites have been fabricated by
studying the surface ligand dynamics of aqueous QDs, and applied as the color
conversion layer to fabricate light-emitting diodes (LEDs) [66]. The as-prepared
QD-cellulose composites possess narrow full width at half maximum, excellent
stability, high PL quantum yields, tunable composition, and emission color, which
permit to fabricate LEDs with high color purity and controllable emission color. By
dip coating of regenerated cellulose lms in the as-prepared solution of QDs,
metal-free transparent luminescent cellulose lms are fabricated with N and S
doping carbon quantum dots (C-QDs) as the high-efciency luminescent materials
[67]. Similarly, luminescent biocompatible transparent membranes can be obtained
by the inclusion of SiQDs in the structure of a regenerated cellulose support
membrane [68].
In recent years, several visible light-driven photocatalytic semiconductors were
used for development of cellulose functional materials. For instance,
Ag3PO4/cellulose nanocomposite hydrogels has been synthesized in situ in two
steps using the cellulose reduction itself and H2O2 oxidation capacity [69]. These
nanocomposite hydrogels have good degradation efciency in the photocatalytic
degradation on Rh B, which provides the potential for application in the eld of
visible light photocatalytic water treatment and solar energy conversion.
Regenerated N-TiO2/cellulose nanocomposite thin lm is prepared by phase
4.3 Photofunctional Cellulosic Materials 61
inversion technique and utilizing recycled newspaper as cellulose source [70].

Under UV and visible irradiation, the obtained composite lm exhibits remarkable
photocatalytic activity for the degradation of methylene blue solution with degra-
dation percentage of 96 and 78.8%, respectively. By sol-gel biotemplating method
using regenerated cellulose membrane (RCM) as nanoreactor, visible light-driven
C-doped mesoporous TiO2 (C-MTiO2) nanorods are synthesized [71]. In this case,
the existence of electron rich hydroxyl groups of RCM plays an important role for
the synthesis of TiO2 nanorods within the cellulose matrix. The porous RCM
possesses low mean pores size of 2.48 ± 0.41 nm which provided cavities for the
growth of C-MTiO2 in nanoscale size and unique forms. In addition, RCM also
provides the in situ carbon source for the development of visible light-driven
photocatalyst with high crystallinity and rutile phase under hot and acidied sol
environment. The resulting C-MTiO2 nanorod exhibits excellent photocatalytic
activity, which is highly potential for used in the removal of organic pollutants in
wastewaters under visible light irradiation.
4.4 Other Functional Materials Based on Cellulose
Regenerated cellulose gels normally have micro/nanoporous structure and large

surface area, which make them attractive candidate for nanoparticle
synthesis/support medium. As reported, silver, gold, and platinum nanoparticles can
be synthesized in cellulose hydrogel by hydrothermal- or NaBH4-reduction [72].
Both methods give nanoparticles embedded with high dispersion in cellulose gels.
The amount and size of metal particles can be controlled through concentration,
temperature, and duration of reaction. By the process of supercritical CO2 drying,
the metal-carrying gel can be converted into corresponding aerogels with high
transmittance, porosity, surface area, moderate thermal stability, and good
mechanical properties. The obtained nanostructured materials will be useful as
antibacterial, electro-optical, and catalytic applications. Similarly, silver/cellulose
nanocomposite bers with excellent antibacterial activity are fabricated by soaking
the cellulose bers in AgNO3 aqueous solution, which is heated at 80 °C for 24 h to
synthesize Ag nanoparticles in situ [73].
In contrast to these methods of in situ reduction, electroless plating (EP) is
capable of creating dense metal nanoparticle coatings which is essential for elec-
trical conductivity by percolation of conducting paths as well as for highly active
catalysts and sensors [74]. By a modied EP procedure, cellulose aerogels can be
coated with a homogeneous layer of silver nanoparticles. The combination of
cellulose aerogel supports and EP is strikingly tting: the polar surface feature of
the cellulose promotes a dense nucleation and an efcient metal particle attachment,
while the conformal deposition is able to utilize the complex aerogel structure. In
the course of deposition, the morphological characteristics of the aerogel are pre-
served, such as the continuous self-supporting network structure, as shown in
Fig. 4.12. While achieving a high metal loading, the large specic surface area as
Fig. 4.12 SEM analysis of pure cellulose aerogel (a) and Ag-cellulose aerogel composite (b); and
TEM analysis of the Ag-cellulose aerogel composite in different magnication (c and d). The
insets show the EDX analysis (c the Cu signal stems from the TEM grid) and the particle size
distribution (d n = 200). Images taken with permission from [74]
well as the low density is retained in the cellulose-metal aerogel composite. This
approach can be extended to other metals (Au, Pt) and other substrate aerogels to
realize aerogel-metal composites of varying morphology, which can be employed in
plasmonic, sensing, and catalytic applications.
“Smart” materials based on cellulose have vast applications in the sensing eld
as a result of their behavior changes in response stimulus. Simple optical pH
sensors are fabricated by immobilizing pH-indicator Methyl Red on cellulosic
textile fabrics using a sol-gel technique [75]. These materials are found to show a
fast and clearly visible color change in response to pH-variation. This method offers
a highly effective technique for the development of flexible pH sensors. A simple
and novel paper-based pH sensor based on the cellulose-tin oxide hybrid composite
was investigated [76]. Cellulose-tin oxide hybrid composite is prepared by wet
chemical method, which involves immersion of a wet regenerated cellulose lm
into a solution of SnF2. The sensitivity (which dened as the change of resistance
the pH level) of this pH sensor is associated with three response regions with
different slope rates depending on the pH value. Specially, the relatively good
sensitivity in the pH range of 4–8 indicates the feasibility and potential of the tin
oxide-cellulose hybrid composite for disposable, cheap, and environment friendly
pH sensor applications.
4.4 Other Functional Materials Based on Cellulose 63
Flexible humidity sensors based on cellulose and PPy are also reported [77]. As
the humidity sensitive layer, nanoscaled PPy is introduced onto a cellulose surface
to fabricate PPy-cellulose nanocomposite via an in situ polymerization technique
without disrupting the cellulose structure. The capacitance of the humidity sensors
increases with increasing the humidity. Due to the polymerized surface, the
adsorption and of desorption of water molecules shows good repeatability with
cyclic humidity testing. Similarly, hybrid gallium nitride (GaN) coated cellulose
nanocomposite can be used as chemical gas sensor [78]. As gas sensor for NO2 and
NH3 gases, this nanocomposite shows good sensitivity, fast response, and recovery
times. The gas sensing mechanism of the GaN-cellulose gas sensor is explained as a
defect-related charge depletion layer for NO2 gas and a surface adsorption of
oxygen species of GaN nanoparticles for NH3 gas.
Using cellulose paper, glucose oxidase (GOx) immobilized SnO2-cellulose
hybrid nanocomposite has been developed as a glucose biosensor [79]. Porous GOx
is attached to the SnO2-cellulose hybrid nanocomposite via covalent bonding
between GOx and SnO2. Upon exposing the GOx immobilized SnO2-cellulose
hybrid composite to glucose, an enzymatic reaction occurs between GOx and
glucose. With immobilizing urease on the SnO2 layers by physical absorption
method, tin oxide-cellulose nanocomposite can be used as a urea detecting sensor,
which is found to be sensitive in the 0–42 mM urea concentration and can detect as
low as 0.5 mM [80]. By using an ionic liquid as solvent, 1-(2-pyridylazo)-
2-naphthol as a valuable extractant and indicator for metal ions was dissolved and
blended homogeneously to give cellulose hybrid lms, that could be applied to the
colorimetric determination of Hg2+, Zn2+, Mn2+, and Ni2+ in aqueous solution [81].
By adding metal oxide or other functional materials into a cellulose matrix, the
material properties in terms of chemical stability, electrical conductivity,
photo-catalytic activity and photosensitivity can be enhanced, leading to various
paper-based flexible and disposable sensors [82]. Therefore, there are great
opportunities to combine advantages of them, and further to develop novel func-
tional materials for tailored applications.
4.5 Summary
Based on cellulose, a series of functional and smart materials could be developed by

dissolution and regeneration process, in particular, using the eco-friendly solvents
developed recently. With the introduction of specic conducting materials such as
nanocarbons and conducting polymers, cellulose-based electrically conducting
materials were fabricated and can be used in many elds, such as conductors,
wearable electronics, sensors, energy storage, supercapacitors, actuators, etc. By
integrating magnetic nanoparticles, cellulose-based materials can convert into
another subset of smart materials, which can adaptively change their physical
properties due to an external magnetic eld. Similarly, photofunctional and other
functional cellulosic materials can be prepared with PL pigments, QDs, metals, or
other functional materials. These materials can be employed in information tech-

nology, anti-counterfeiting techniques, packaging, plasmonic, sensing, and catalytic
applications. Overall, the combination of cellulose and inorganic/organic materials
provides great opportunity to produce new materials that not only retain the
inherent properties of their component precursors but may also exhibit new prop-
erties due to the synergistic interaction of the precursors.
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Chapter 5
Nanocellulose-Based Functional Materials
Abstract Three kinds of nanocelluloses, i.e., cellulose nanocrystals, microbril-

lated cellulose, and bacterial nanocellulose, have attracted many attentions over the
last decades. The formation, dimension, morphology, and properties of them were
introduced in this chapter briefly. Depending on their unique and excellent char-
acteristics, these nanocelluloses have been employed as raw materials to produce
various novel functional materials, including lms, membranes, hydrogels, aero-
gels, microcapsules, and nanocomposites, by using different fabrication approaches.
Their properties and potential application were also discussed comprehensively.
 
Keywords Nanocellulose Cellulose nanocrystals Microbrillated cellulose 
  
Bacterial nanocellulose Functional materials Biomaterials Nanocomposites
As a new family of nature-based materials, nanocelluloses is the cellulose brils

with widths in the nanometer range, mainly including cellulose nanocrystals
(CNCs), microbrillated cellulose (MFC), and bacterial nanocellulose (BNC) [1].
These cellulose-based nanomaterials have excellent features such as superior
chemical and electrochemical stability, excellent mechanical strength and stiffness,
large surface area and its light weight, as well as wide availability, renewability, and
biodegradability. In addition, the unique structure of nanocelluloses renders them a
strong interaction with surrounding species, such as water, organic, and polymeric
compounds, nanoparticles, and living cells. Thus, nanocelluloses have drawn
extensive attention as their great potential in many applications, such as reinforcing
agents in nanocomposites and paper, biodegradable lms and barriers for packag-
ing, medical, and life-science devices as well as other functional materials.

70 5 Nanocellulose-Based Functional Materials
5.1 Cellulose Nanocrystals
5.1.1 Introduction of CNCs
Cellulose nanocrystals are often referred to as microcrystals, whiskers, nanocrys-

tals, nanoparticles, microcrystallites, or nanobers from cellulose. Hereafter, they
are called “cellulose nanocrystals” (CNCs). Owing to the hierarchical structure and
semicrystalline nature of cellulose, nanoscale materials can be extracted from this
naturally occurring polymer by applying specic top-down approaches [2]. The
main steps involved in the preparation of CNCs and MFC are presented in Fig. 5.1.
Purication of cellulose from plant bers involves chemical treatments consisting
of alkali extraction and bleaching. Multiple mechanical shearing actions applied to
the obtained cellulose pulp release more or fewer individual microbrils. This
material is usually called microbrillated cellulose (MFC). While a controlled
strong acid hydrolysis treatment is applied, the amorphous domains of cellulosic
ber can be dissolved, leading to the longitudinal cutting of the microbrils. The
ensuing nanoparticles are generally called cellulose nanocrystals (CNCs) and are
obtained as an aqueous suspension.
In general, acid hydrolysis of native cellulose induces a rapid decrease in its
degree of polymerization (DP). Typical procedures currently employed for the
production of CNCs consist of subjecting pure cellulosic material to strong acid
hydrolysis under strictly controlled conditions of temperature agitation and time.
The nature of the acid and the ratio of acid to cellulosic bers are also important
parameters that affect the preparation of CNCs. A resulting suspension is subse-
quently diluted with water and washed with successive centrifugations. Dialysis
against distilled water is then carried out to remove any free acid molecules from
the dispersion [3]. Although several strong acids (such as, phosphoric, hydrobromic
and nitric acids) have been shown to successfully degrade cellulose bers and used
for the preparation of crystalline cellulosic nanoparticles, sulfuric, and hydrochloric
acids are extensively used. By hydrolysis in hydrochloric acid, the CNCs prepared
Fig. 5.1 Scheme of

preparation of MFC and
CNCs from natural plant
5.1 Cellulose Nanocrystals 71
have limited ability to disperse and are tend to flocculate in their aqueous sus-
pensions. While for sulfuric acid as hydrolyzing agent, the chemical reaction with
hydroxyl groups occurred on the surface of CNC allow the grafting of anionic
sulfate ester groups. The presence of these negatively charged groups induces the
formation of a negative electrostatic layer covering the nanocrystals and promotes
their dispersion in water [2].
CNCs can be prepared from a variety of sources, such as wood, cotton, sisal,
hemp, ramie, microcrystalline cellulose, tunicin, algal cellulose, and bacterial cel-
lulose. To a certain extent, geometrical characteristics such as size, dimensions, and
shape of CNCs depend on the origin of the cellulosic substrate and conditions under
which the hydrolysis is performed. The morphological characteristics are usually
studied by microscopy (TEM, AFM, E-SEM, etc.) or light scattering techniques,
including small angle neutron scattering and polarized and depolarized dynamic
light scattering [3]. Nevertheless, acid-hydrolyzed CNCs take elongated rod-like
shapes with a typical width of a few nanometers and length of the order of hundreds
of nanometers [4]. Figure 5.2 shows TEM images of three types of CNCs obtained
from different cellulosic sources [5]. Since the CNCs are devoid of chain folding,
they contain only a small number of defects. An important parameter for CNCs is
Fig. 5.2 TEM images of CNCs obtained by sulfuric acid hydrolysis of a cotton b avicel
c–e tunicate cellulose. Reprinted with permission from [5] Copyright (2008) American Chemical
Society
the aspect ratio, which is dened as the ratio of the length to the diameter (L/d). As
reported, CNCs derived from tunicate and bacterial cellulose is usually larger in
dimension compared to those obtained from wood and cotton [6, 7]. This is because
tunicate and bacterial cellulose are highly crystalline, hence there are lower frac-
tions of amorphous regions that need to be cleaved resulting in the production of
larger nanocrystals [8].
Apart from the classical way of acid hydrolysis, several methods allowing the
release of crystalline domains from cellulosic bers have been reported more recently,
including enzymatic hydrolysis treatment [9], 2,2,6,6-tetramethylpiperidine-
1-oxyl (TEMPO) oxidation [10], and treatment with ionic liquids [11].
5.1.2 Surface Chemistry of CNCs
The chemical functionality of CNC surfaces dictates its suspension properties and
the composites or other materials fabricated based on it. When extracted from the
native bers, CNCs generally are functionalized by the acid. As mentioned above,
for instance, sulfate ester units are introduced for CNCs during hydrolysis with
sulfuric acid. Hydrolysis by the sulfuric acid forms sulfate esters that give the
surface a high acid content. CNCs are derived using different methods and show
different surface chemistries. In order to enhance the dispersibility of CNCs in
organic media and polymers, some surfactants as electrostatics are used to stabilize
the nanoparticles. Another common method for adsorptive modication involves
the use of electrostatic adsorption of macromolecules, which is borrowed from the
manufacture of paper [12].
Because of a natural advantage of an abundance of hydroxyl groups at the
surface of CNCs, chemical modication and/or covalent attachment of molecules
can be used to directly modify them. As shown in Fig. 5.3, techniques that react
with alcohols, e.g., isocyanates, epoxides, acid halides, and acid anhydrides are the
most common for direct attachment [12]. These reactions can be used to form a host
of alternate surface chemistries such as amine, ammonium, alkyl, hydroxyalkyl,
ester (acetate, propionate, etc.), acid, etc. Rather than surfactant or polymer coating,
the covalent attachment paradigms used can lead to covalently link polymers to the
surface of the cellulose nanocrystals, which further to increase their compatibility
with a polymer resin. Alternatively, grafting-from approaches to grow polymers
from CNC surface have been performed [13]. For example, acid halides have been
used to attach bromoesters as initiators for atom transfer radical polymerization
(ATRP) of styrene and single-electron transfer living radical (SET-LP) of N,
N-dimethylaminoethylmethacrylate [14, 15]. Most of these surface modication
approaches are focused on the improvement of their dispersability and compatibility
in different solvents or matrices that are suitable in the production of nanocom-
posites. In addition, the modication of CNCs also renders them great potential to
be used in other elds such as personal care and biomedical.
Fig. 5.3 Common modication chemistries of CNC surfaces: (clockwise from top-right) sulfuric
acid treatment provides sulfate esters, carboxylic acid halides create ester linkages, acid anhydrides
create ester linkages, epoxides create ether linkages, isocyanates create urethane linkages,
TEMPO-mediated hypochlorite oxidation creates carboxylic acids, halogenated acetic acids create
carboxymethyl surfaces, and chlorosilanes create an oligomeric silylated layer. Images taken with
5.1.3 Functional Materials Based on CNCs
The Young’s modulus of CNCs is in the range of 100–130 GPa, with a density of
around 1.5–1.6 g cm−3. This is much higher than that of glass bers, around
70 GPa with a density around 2.6 g cm−3, which are classically used in composite
applications [2]. Due to these features, CNCs are often used as high-quality rein-
forcing llers for polymers. It should be noted that, the homogeneous dispersion of
cellulose nanocrystals within a continuous polymeric matrix is the key step to
benet from their outstanding properties [16]. Due to the hydrophilic character of
CNCs, aqueous medium is the most suitable processing medium to form stable
colloidal dispersions of such nanoparticles. After mixing the CNC dispersion with
polymer solution/dispersion, a solid nanocomposite lm can be obtained by simple
casting. Apart from water, other polar liquid media can also be used for dispersing
CNCs and processing medium, such as N,N-dimethyl sulfoxide (DMF), dimethyl
sulfoxide (DMSO), N-methyl pyrrolidine (NMP), and formic acid [16]. A solvent
exchange procedure can be applied to suspend cellulosic nanoparticles in the proper
liquid medium for further surface chemical modication, or mixing with a polymer
solution or monomer for subsequent in situ polymerization [17].
Until now, several polymer matrices were explored, including starch, PLA, poly
(hydroxyalkanoate) (PHA), soy protein, chitosan, regenerated cellulose, and silk
broin as natural matrices, and poly(oxyethylene), polycaprolactone (PCL)-based
water-borne polyurethane (WPU), polypropylene (PP), PVC, and PVA as synthetic
polymers. For example, nanocomposite lms were prepared from a suspension of
CNCs as the ller and a PCL-based WPU as the matrix. The lms show a sig-
nicant increase in Young’s modulus and tensile strength from 0.51 to 344 MPa
and 4.27 to 14.86 MPa, respectively, with increasing ller content from 0 to 30 wt%
[18]. All-cellulose nanocomposite lms were fabricated by blending CNCs and
cellulose solution in NaOH/urea with cooling on the basis of the solubility
dependence on the temperature. The regenerated cellulose composite lms exhibit
high tensile strength (124 MPa) and elastic modulus (5 GPa), and the tensile
strength can reach 157 MPa through a simple drawing process [19]. Nevertheless,
the properties of composites depend on the nature of the matrix and the CNCs, and
on the strength and extent of their interfacial interactions.
CNCs can also be used to develop functional and smart composite materials,
which have potential applications in drug release, actuator, sensors, etc. CNC/poly
(sodium acrylate) hydrogels were investigated as wound dressing lms with con-
trollable drug release properties [20]. The release of an antibiotic drug (minocy-
cline, Mic) from the composite hydrogel can be controlled mainly by the variation
of CNC content. Moreover, the Mic-loaded lms showed fair antifungal and
antibacterial properties, which are fundamental properties for wound healing
applications. It was reported that CNC-reinforced all-cellulose composite gels can
be used as a high-performance porous material for drug delivery systems [21]. As
reinforcement in shape memory materials, CNC can change their shape upon
external stimulus. The rigidity of shape memory polymers by adding small amounts
of well-dispersed CNCs is improved signicantly [22]. A stimuli-responsive
mechanically adaptive CNCs composite was inspired by biological sea cucumbers,
which has the potential to reversibly change the stiffness [23]. In addition,
nanocomposites of poly(vinyl acetate) (PVA) and cotton CNCs demonstrated a
mechanically adaptive behavior in response to thermal and chemical stimuli [24].
Functionalization of the surface of CNC by either carboxylic acid (–COOH) or
amine (–NH2) renders the CNCs pH-responsive [25]. These modied CNCs can be
incorporated into a PVA matrix to yield mechanically adaptive pH-responsive
nanocomposite lms.
Cellulose-based electroconductive nanocomposites can be prepared by com-
bining conducting electroactive materials with CNCs. The deposition of conductive
polymers, such as PANI, PPy and poly(3,4-ethylenedioxythiophene) (PEDOT), on
the surface of CNCs have been widely investigated in the last few years due to its
potential to the fabrication of new functional devices, including flexible electronic
devices, batteries, sensors, and supercapacitor [26–28]. Another approach regards
the preparation of electroconductive cellulose-based nanocomposites. For instance,
CNT/CNC nanocomposites with tailorable electrical conductivity can be fabricated
via an aqueous suspension vacuum ltration method [29]. The surface electrical
resistivity for the hybrid lms can be tuned within a range from 102 to 1011 X/sq by
manipulating the CNT weight fraction as well as the environmental humidity.

Composite lms of CNC and graphene oxide (GO) can be produced by drop casting
of a water dispersion of GO in the presence of CNCs [30]. The composites show
electrical conductivity after thermal reduction of GO. By Layer-by-Layer
(LbL) spraying of modied GO-lled CNCs on lithographic patterns of interdigi-
tated electrodes on polymer substrates, a transparent and eco-friendly sensor can be
made and it helps to realize the precise location of approaching objects [31]. Stable
and reproducible signals generated by keeping the nger in close proximity to the
sensor can be controlled by humidity, temperature, and the distance and number of
sprayed layers.
Self-assembly and -organization of CNCs have also attracted much attention
recently. Above a critical concentration, the rod-like shape of the charged CNCs
leads to the formation of an anisotropic liquid-crystalline phase [32]. This
self-organization phenomenon was revealed by the appearance of “ngerprint”
patterns obtained from suspensions observed by polarized optical microscopy,
indicative of a chiral nematic ordering [3]. The liquid-crystalline properties of
cellulose nanocrystals are most readily observed for low-ionic-strength suspensions
of the relatively short nanocrystals isolated by acid hydrolysis. Suspensions of
longer nanocrystals tend to gel before attaining the equilibrium liquid-crystalline
structure [1]. The cooperative nature of the liquid-crystalline phase enhances the
response to applied elds. For example, cellulose-nanocrystal suspensions are
readily oriented by applied magnetic eld or electric eld [3]. After complete water
evaporation, this chiral nematic structure can be preserved to provide iridescent
lms of CNCs, which have numerous potential applications such as coating
materials for decorative materials and security papers.
By using LbL assembly, single component robust cage-like microcapsules using
high aspect ratio CNCs can be fabricated, as shown in Fig. 5.4 [33]. Due to the
highly open “haystack” shell morphology with large through pores, these resilient
Fig. 5.4 Scheme of preparation of CNC microcapsules via LbL assembly and their
encapsulation/release behavior under different pH conditions. Reprinted with permission from
microcapsules are capable of loading and unloading large solid particles with a
diameter up to 100 nm, in contrast to traditional ultrathin shell polymer micro-
capsule with random porous morphology and pore sizes below 10 nm with limited
molecular permeability of individual macromolecules. Moreover, the transport
properties of solid nanoparticles through these shells can be pH-triggered without
disassembly of these shells. These CNC microcapsules present a novel candidate
for functional materials relevant to prospective applications in bioengineering for
controlled encapsulation of solid nanoparticles with nanoscale and submicron
dimensions.
5.2 Microbrillated Cellulose
5.2.1 Introduction of MFC
Microbrillated cellulose (MFC), also called microbrillar cellulose, cellulose

microbril, nanobrils, or nanobrillated cellulose (NFC), is normally extracted
from wood by a mechanical disintegration process, as shown in Fig. 5.1. MFC can
be viewed as a cellulosic material, composed of expanded high-volume cellulose,
moderately degraded and greatly expanded in surface area [34]. Contrary to straight
CNCs, MFCs are long and flexible nanoparticles, which exhibit both amorphous
and crystalline parts. Due to the high aspect ratio (L/d), MFCs have very low
percolation threshold, thus they are highly entangled and have good ability to form
rigid networks and gels. The inherent interactions result in much stronger gels than
those formed only by weak hydrogen bonds between water and brils.
On the other hand, the development of disintegration methods that are less
energy-consuming also becomes a priority in securing the industrialization of MFC
production [35]. Thus, some combinations of pretreatments and mechanical treat-
ments have been suggested. Until now, several pretreatments, such as enzymatic
hydrolysis, TEMPO oxidation, carboxymethylation and acetylation, have been
applied to obtain bers that are less stiff and cohesive, thus decreasing the energy
needed for brillation. The dimensions of MFC vary according to the mechanical
treatment and pre-treatment that is applied. For example, non-pretreated MFC
obtained with a blender showed a uniform diameter of 15–20 nm [36], whereas
with TEMPO oxidation and the same mechanical treatment, the microbrils pre-
sented diameters of about 3–5 nm [37].
In addition, depending upon the source of the cellulose, MFC displays similar
morphologies but various dimensions. Figure 5.5 shows TEM images of
TEMPO-oxidized MFCs from wood pulp, cotton, tunicin, and bacterial cellulose,
respectively. In these cases, there is no lateral aggregation that is often observed in
acid-hydrolyzed samples. Other natural cellulose, such as wheat straw, soy hulls,
sisal, carrots and beet pulp, can also be used to produce MFC. Until now, however,
the raw material used for producing MFC does not contain lignin, or if it does, it is
5.2 Microbrillated Cellulose 77
Fig. 5.5 TEM images of MFCs disintegrated after TEMPO-mediated oxidation of never-dried
samples: a bleached sulte wood pulp, b cotton, c tunicin, and d bacterial cellulose. The
preparations were negatively stained with uranyl acetate. Reprinted with permission from [37]
Copyright (2006) American Chemical Society
only in low quantities [35]. With lignin-containing pulp, the diameter of MFC
produced is larger, regardless of the origin of the pulp used. Moreover, hemicel-
luloses also influence the MFC diameter distribution by limiting the association
between cellulose nanobers.
5.2.2 Functional Materials Based on MFC
MFC possesses high strength, aspect ratio, specic area, and flexibility, as well as a
high amount of hydroxyl groups. These intrinsic properties make it attractive for
many applications. For example, cellulose nanopaper lms can be fabricated
directly from MFCs in water suspension [38]. These lms exhibit high toughness
with a strain-to-failure as high as 10%. Despite a porosity of 28% for the toughest
nanopaper, the Young’s modulus (13.2 GPa) and tensile strength (214 MPa) are
remarkably high. Optically transparent nanober paper can be prepared from 15 nm
MFC, as shown in Fig. 5.6 [39]. Using TEMPO-oxidized MFCs, nanopaper with
Fig. 5.6 Optically transparent nanober paper (left) composed of 15 nm cellulose nanobers
(upper left, scale bar in inset: 100 nm) and conventional cellulose paper (right) composed of
30 mm pulp bers (upper right, scale bar in inset: 200 mm). Images taken with permission from
[39]
higher transmittance (84–89%) and surface smoothness can also be obtained [40].
In contrast to conventional cellulose paper which composed of 30 mm pulp bers,
nanopaper shows much lower surface roughness and much higher transparency.
These novel nanopapers could play the same role as or an even greater role than
conventional paper in information storage and transfer.
As a reinforcing phase in nanocomposites, MFC has numerous well-known
advantages, such as low density, renewable nature, high specic properties,
biodegradability, relatively reactive surface which can be used for grafting specic
groups, and almost unlimited availability. Similar to that of CNCs, the production
process of nanocomposites normally involves the dispersion of MFC and casting of
lms from a medium in which the matrix material can be dissolved. Several
matrices, such as starch, hydroxypropylated cellulose (HPC), regenerated cellulose,
and phenol–formaldehyde resin, were reinforced by MFCs. The mechanical per-
formance of MFC-reinforced polymer nanocomposites can be enhanced [41]. In
addition, MFCs can be chemically modied with different reagents, including
N-octadecyl isocyanate and others that enable combination with synthetic polymers
and produce precursor materials for lm casting [17]. Charged groups, reactive vinyl
moieties, and polymer chains can be installed on the surface of MFC via treatment
with maleic anhydride, glycidyl methacrylate, and succinic anhydride [42].
In order to render electrical conductivity in cellulose paper, conducting materials
such as conductive metal oxide, graphene, CNTs, metal nanowires, and conductive
5.2 Microbrillated Cellulose 79
polymers can be integrated. By freeze-drying the mixture of CNTs and MFCs, a

highly conductive cellulose aerogel can be fabricated [43]. Further deposition of
silicon onto the MFCs using plasma-enhanced chemical vapor deposition can
produce a highly flexible silicon electrode, which has stable cycling at around
1500 mAh/g for more than 100 cycles. By direct chemical polymerization of
pyrrole on wood-derived MFCs in hydrogels, electronically conductive composite
material with high-surface area can be fabricated [44]. It was found that this
composite is electroactive with an ion-exchange capacity for Cl− of 289 C/g.
Similarly, conductive aerogel composites of TEMPO-oxidized MFC and PPy can
be prepared by chemically polymerizing and supercritical CO2 drying [45].
Due to the unique structure and excellent optical transmittance as well as
mechanical strength, MFC-based nanopapers have great potential for electrically
conductive patterns to realize lightweight and flexible electronics and optoelec-
tronics devices. As reported, a fully transparent organic eld-effect transistor can be
fabricated on properly designed nanopaper from TEMPO-oxidized MFCs [40]. The
transmittance of the device is 83.5% at 550 nm. The transistor also shows excellent
mechanical properties, with only around a 10% decrease in mobility when the
device was bent in directions parallel or vertical to the conduction channel. By
depositions of transparent and conductive materials including tin-doped indium
oxide, CNTs and silver nanowires, transparent conductive nanopaper can be
achieved [46]. They open up a wide range of applications in optoelectronics such as
displays, touch screens, and interactive paper as well as organic solar cell. In
addition, other devices such as integrated transparent sensors and 3D microfluidic
devices may also be fabricated on MFC-based papers. As a potential replacement
for plastic substrates, MFC-based paper holds great promise for fabricating fully
integrated flexible electronics and displays with unique properties, and at the same
time is compatible with high throughput processes such as roll-to-roll printing [47].
5.3 Bacterial Nanocellulose
5.3.1 Introduction of BNC
Besides natural plant, cellulose can also be produced through a new process that
reduces the environmental impact to a minimum, using a biotechnology technique
(microorganisms). That is bacterial nanocellulose (BNC, also known as bacterial
cellulose, microbial cellulose, biocellulose), which is synthesized by bacteria
belonging to the genera Acetobacter, Rhizobium, Agrobacterium and Sarcina [48].
The Acetobacter xylinum (A. xylinum) was reported as the most efcient producer.
The production of BNC could be carried out in either solid-phase cultivation or
submerged culture. The quality and quantity of the cellulose highly depend on the
methods of production process. From the viewpoint of constituents, BNC is pure
cellulose free from other plant components such as hemicelluloses, lignin, and
pectin [49]. However, the BNC obtained is not completely pure and contains some
impurities, such as culture broth components and whole bacteria cells. Some
purication methods are required to remove these unwanted impurities.
Macroscopically, the BNC network is constructed as a pellicle that acquires the
shape of the recipient where the bacteria are grown. As shown in Fig. 5.7, the BNC
produced in a static cultivation method exhibits a hydrogel sheet [49]. In terms of
microstructure, BNC possesses a unique and sophisticated 3D porous network
structure, which consists of cellulose nanobers of around 20–100 nm in diameter
and around 100 lm in length. These ribbons are made up of bundles of cellulose
microbrils of 2–4 nm in diameter [50, 51]. Additionally, BNC also demonstrates
some other unique physical properties, including high crystallinity (60–90%), high
degree of polymerization (up to 8000), high water content to 99%, and mold ability
[52, 53]. Meanwhile, as a type of cellulose, BNC also exhibits good biocompati-
bility, hydrophilicity, and nontoxicity. Due to the aforementioned characteristics,
BNC has been employed as raw materials to fabricate diverse BNC-based materials,
which are widely used in many elds such as biological and medical elds, envi-
ronmental sciences, and optoelectronics.
5.3.2 Biomedical Applications of BNC
Due to the hydrophilic nature of cellulose, BNC can bind water strongly and behave
as hydrogels. In addition, BNC also exhibits good biocompatibility and tissue
integration, as well as unique mechanical properties which are similar to soft tis-
sues. All these features enable BNC to serve as a natural scaffold material for the
regeneration of a wide variety of tissues. As reported, a new mammalian cell culture
substrate was developed with BNC. The results showed that a serum-soaked BNC
membrane was an effective substrate for use in tissue engineering [54]. The
Fig. 5.7 Photograph a and SEM image b of BNC produced in static cultivation. Images taken
5.3 Bacterial Nanocellulose 81
biological properties of BNC can be improved by integrating with other biomate-

rials. For instance, composites based on BNC and type I collagen were developed
for potential bone tissue engineering, in which collagen was homogeneously and
covalently introduced into the BNC network [55]. Heparin (Hep) was also hybri-
dized with the BNC network to build Hep-BNC nanobrous scaffolds with anti-
coagulant properties for potential use in vascular tissue engineering [56].
One of the best known biomedical applications of BNC is as a topical covering
for severe wounds. Now there are even several commercially available BNC-based
coverings, such as Xcell®, Bioprocess®, and Bioll® [51, 57]. It was reported that
the biocompatibility of BNC-based wound dressings is related to its distinctive
nanobrillar structure, which serves as an optimal wound healing environment [58].
As shown in Fig. 5.8, it has the benet of conforming remarkably well to almost
any contour and is an ideal moisturizing applicant as it can maintain a proper water
balance by either absorbing or releasing fluid according to the behavior of the
wound [57, 59]. Compared with conventional wound dressings such as wet gauze
and ointments, BNC can accelerate the process of healing of the skin. In addition,
studies have shown that BNC-based coverings can reduce wound pain, accelerate
re-epithelization, and reduce scarring [51, 57, 58]. However, BNC itself has no
antimicrobial activity to prevent wound infection. To achieve antimicrobial activity,
BNC were used as a template for the precipitation of silver (Ag) nanoparticles via
in situ liquid phase redox reaction between AgNO3 and NaBH4 [60]. The ether
oxygen and the hydroxyl group not only anchor silver ions tightly onto bacterial
cellulose bers via ion–dipole interactions, but also stabilize silver nanoparticles by
strong interaction with their surface metal atoms. Good dispersion and
Fig. 5.8 A never-dried BNC membrane used for wound healing. Reprinted with permission from
nanodimension provide Ag particles an extremely developed specic surface, and

consequently guarantees the hybrid nanobers an efcient antimicrobial property
[49].
The use of BNC-based tubes as blood vessels and for nerve surgery has not yet
reached clinical trials in humans, but there have been very promising results in
animal studies [59]. BNC tubes named BASYC® with different dimensions were
prepared for blood vessel substitutes [61–63]. The study of BASYC® small caliber
blood vessel replacements in ve mice (carotid artery) and eight pigs (carotid
artery) demonstrated patency in all of the mice endoprosthesis after 1 year and
seven of the eight pig prostheses after 90 days. Epithelialization of the internal
lining of the prosthesis was also observed histologically as well as the development
of three distinct structural layers mirroring the normal three-layer structure of native
arteries [62]. Other studies of BNC tube prosthesis for rat blood vessels (carotid
arteries and jugular veins) have also showed patency of all implants. The tubes also
improved outcomes in nerve surgery when placed around suture sights, presumably
by reducing invasion of connective tissue [61]. Recently, BNC tubes are also
investigated by seeding with human urine-derived stem cells to form a
tissue-engineered conduit for use in urinary diversion. These urothelial-lined BNC
tubes seem to do well after 2 weeks’ implantation [64].
The potential of BNC-based materials in other biomedical applications is also
investigated recently, including cartilage replacement, heart valve replacement,
contact lenses and so on. However, there are also some challenges should be
addressed, such as the biocompatibility and degradation rate, before BNC as
biomedical materials to be used in human beings.
5.3.3 BNC-Based Functional Materials
Due to their unique 3D structure, BNC can contain other monomeric, reactive, and
potentially polymerizable monomers within its networks, occupying its void vol-
ume and interacting with nanober chains. Therefore, diverse BNC-based electrical
conducting materials can be fabricated by combing with inorganic nanoparticles,
metal ions and oxides, carbon nanotubes, graphene and graphene oxide, conducting
polymers, and ionic liquids [65]. For instance, electrically conducting polymeric
membranes were prepared by incorporating CNTs into bacterial cellulose pellicles
produced by Gluconacetobacter xylinum [66]. Transparent and electrically con-
ducting lms were also fabricated by the adsorption of CNTs on BNC membranes
embedded in silk broin [67]. The light transmittance and electrical conductivity
varied according to the concentration of the CNT dispersion. In addition, the
composite lms showed remarkable flexibility without any loss of their initial
properties. By using the three-dimensional structure of BNC as a template for
polymerization of aniline, flexible PANI/BNC composites were prepared, with a
high conductivity (5.0  10−2 S/cm) and good mechanical properties, which could
be applied in sensors and flexible electrodes [68].
5.3 Bacterial Nanocellulose 83
Flexible displays have been produced by using BNC as the substrate or the basic
optical lm [69]. The device has the potential to be extended to various applica-
tions, such as e-book tablets, e-newspapers, dynamic wall papers, rewritable maps,
and learning tools. Organic light-emitting diodes were fabricated by deposition of
indium tin oxide (ITO) thin lms onto the BNC membrane using radio frequency
magnetron sputtering [70]. Visible light transmittance of about 40% was observed.
Resistivity, mobility, and carrier concentration of deposited ITO lms were com-
parable with commercial ITO substrates. To improve the light transmittance,
BNC-based composites were developed by reinforcing various types of resins [71].
The resulting nanocomposites exhibit a low coefcient of thermal expansion
comparable to silicon and mechanical strength comparable to mild steel. Due to the
nanober size effect, high transparency was obtained against a wide distribution of
resin refractive, being also less sensitive to refractive index variations caused by the
elevation of ambient temperature up to 80 °C. Moreover, they have succeeded in
depositing an electroluminescent layer on these transparent BNC nanocomposites,
as shown in Fig. 5.9 [72].
Electroactive biopolymer actuator based on BNC was developed to be activated
in the wet environment for biomedical applications [73]. It was found that the
LiCl-treated BNC can be adjusted to achieve a better actuation performance by
controlling the crystallinity and stiffness of the pristine BNC. Freeze-dried BNC
aerogels can be used as templates for making lightweight porous magnetic aerogels
[74]. Unlike solvent-swollen gels and ferrogels, this magnetic aerogel is dry,
lightweight, porous (98%), flexible, and can be actuated by a small household
magnet. Moreover, it can absorb water and release it upon compression. Owing to
their unique features, these aerogels are expected to be useful in microfluidics
devices and as electronic actuators. BNC layers have also been investigated as
loudspeaker vibration lms, which can be simply manufactured by bacterial bio-
fabrication. Apart from the good fundamental characteristics of a sound-vibration
Fig. 5.9 Luminescence of an

organic light-emitting diode
deposited onto a transparent
BNC nanocomposite. The
luminescence area is
40  25 mm2. Images taken
lm, these lms also have the several advantages, such as good mechanical
properties, thermal stability, high specic elasticity and loss factor, long service life,
and environmental friendliness [1].
5.4 Summary
Nanocelluloses, extracted from the natural bers or synthesized using a biotech-

nology technique, are a new class of sustainable functional nanomaterials featuring
exciting properties. Taking elongated rod-like shapes, acid-hydrolyzed CNCs
possess excellent mechanical properties and can be used as high-quality reinforcing
llers for polymers. Surface modication can improve their dispersability and
compatibility in different solvents or matrices, further to produce functional
nanocomposites. MFC is normally extracted from natural bers by a mechanical
disintegration process. Due to the high aspect ratio, they exhibit gel-like charac-
teristics and have specic area and good flexibility. Cellulose nanopapers and
related smart materials can be easily fabricated from them. In contrast to CNCs and
MFC, BNC is synthesized by bacteria and possess unique and sophisticated 3D
porous network structure. Their good biocompatibility and hydrophilicity render
them to be widely used in biological and medical elds. Especially, the in situ
biofabrication of BNC opens up unique possibilities for the control of shape, the
structure of the nanober network, and functional composite formation. Due to their
excellent features and great opportunities in applications, nanocelluloses will attract
more attentions and improve the development of both nanomaterials and bioma-
terials in the future.
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Novel Func Material Based in Cellulose

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SPRINGER BRIEFS IN

APPLIED SCIENCES AND TECHNOLOGY

A timely report of state-of-the art methods

SpringerBriefs are characterized by fast, global electronic dissemination, standard

More information about this series at http://www.springer.com/series/8884

Novel Functional Materials

ISSN 2191-530X ISSN 2191-5318 (electronic)

Library of Congress Control Number: 2016957501

© The Author(s) 2017

Printed on acid-free paper

This Springer imprint is published by Springer Nature

magnetic materials, photofunctional materials, and so on. Chapter 5 is about the

Guangzhou, China Haisong Qi

4 Cellulose-Based Functional and Smart Materials . . . . . . . . . . . . . . . . 45

Keywords Cellulose  Source  Structure  Hydrogen bonding  Crystalline

© The Author(s) 2017 1

cellulose ber composite. The macrobers are composed of microbrils, which

and hemicellulose is usually involved in the production of cellulose-based materials.

1.2 Structure of Cellulose

1.2.1 The Molecular Structure

Fig. 1.2 Molecular structure of cellulose (n = DP, degree of polymerization)

to its structure and morphology in the solid state. As well-known, cellulose is a

1.2.2 Hydrogen Bonding

As mentioned above, cellulose is an unbranched chain of glucose units. Each

Fig. 1.3 Numbering system

The intramolecular hydrogen bonding of cellulose molecule results in its relative

1.2.3 Crystalline Structures

As a chemical raw material, cellulose is a fascinating biopolymer and has many

1. O’Sullivan AC (1997) Cellulose: the structure slowly unravels. Cellulose 4:173–208

5. Sun Y, Cheng J (2002) Hydrolysis of lignocellulosic materials for ethanol production: a

Abstract The shaping, chemical modication, and functionalization of cellulose

© The Author(s) 2017 11

Fig. 2.1 Process principles

2.1 Derivate Methods

2.1.1 Viscose Process

Although Anselme Paven discovered cellulose in 1838, the rst cellulose-based

Fig. 2.2 Viscose solution is formed during dissolution of cellulose xanthogenate

2.1.2 Cellulose Carbamate Process

As an alternate method to viscose process, the cellulose carbamate (CC) process

Fig. 2.3 Formation of cellulose carbamate by transformation of cellulose with urea

high temperatures. It was reported that CC could be synthesized by supercritical

2.2 Direct Solvents

2.2.1 NMMO System

Fig. 2.5 Structure of

way up to NMMO1.2H2O, and can be easily regenerated by precipitation for

2.2.2 Aqueous Alkali System

Table 2.1 Dissolution Cellulose in NaOH-based aqueous systems

Fig. 2.7 Schematic diagram 20

systems depending on NaOH concentration and temperature. It exhibits that cel-

2.2.3 Ionic Liquids

1. Hermanutz F, Gähr F, Uerdingen E et al (2008) New developments in dissolving and

6. Yin C, Shen X (2007) Synthesis of cellulose carbamate by supercritical CO2-assisted

31. Bentivoglio G, Röder T, Fasching M et al (2006) Cellulose processing with chloride-based

Based on the dissolution in suitable solvents, various man-made cellulosic materials

3.1 Cellulose Regeneration

A basic understanding of the process, structure changes, and mechanism of the

© The Author(s) 2017 25

Fig. 3.1 Scheme of fabrication process for regenerated cellulosic materials

3.2 Regenerated Cellulose Fiber

precisely controlled in terms of length, denier, physical properties and

demonstrated a relatively high degree of orientation. The tenacity of the bers is

3.3 Regenerated Cellulose Films

As another main product from regeneration of cellulose, transparent regenerated

Despite their advantageous properties, cellophane involves problems such as