Progress in Polymer Science 53 (2016) 169–206

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Progress in Polymer Science

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

Recent advances in regenerated cellulose materials

Sen Wang, Ang Lu ∗ , Lina Zhang ∗
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China

a r t i c l e i n f o a b s t r a c t

Article history: The dual threats of the depletion of nonrenewable energy and environmental pollution
Received 2 September 2014 caused by petroleum-based polymers motivate utilization of naturally occurring polymers
Received in revised form 7 July 2015 to create new materials. Cellulose, as the most abundant natural polymer on earth, has
Accepted 9 July 2015
attracted attention due to its renewability, wide availability, low-cost, biocompatibility
Available online 5 August 2015
and biodegradability, etc. Regenerated cellulose may be constructed simply via physical
dissolution and regeneration, an environmentally friendly process avoiding the consuming
Keywords:
of chemicals since most of the reagents (solvents, coagulant, etc.) may be recycled and
Regenerated cellulose materials
reused. “Green” solvents and techniques for the preparation of the environmentally friendly
Physical dissolution and regeneration
Cellulose solvent regenerated cellulose materials have been developed successfully, showing great potentials
Relationship of structure and properties in the fields of polymer science and technology.
Functional composites In this article, the widely used non-derivatizing cellulose solvents are summarized,
including their dissolution mechanisms. Regenerated cellulose materials with different
functions and properties have been designed and fabricated in different forms, such as fil-
aments, films/membranes, microspheres/beads, hydrogels/aerogels and bioplastics, etc., to
meet various demands. The concept of regeneration through a physical process is illus-
trated, and a number of novel regenerated cellulose materials are introduced for wide
applications in textiles, packaging, biomedicine, water treatment, optical/electrical devices,
agriculture and food, etc. The methodology of material processing and the resultant prop-
erties and functions are also covered in this review, with emphasis on the neat regenerated
cellulose materials and the composite materials. The 277 references cited concerning the
direct preparation of cellulose materials via physical dissolution and regeneration are rep-
resentative of the wide impact and benefits of the regenerated cellulose materials to society.

© 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
2. Cellulose solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
2.1. N-methylmorpholine-N-oxide (NMMO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
2.2. Ionic liquids (ILs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
2.3. LiCl/N,N-dimethylacetamide (LiCl/DMAc) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
2.4. NaOH aqueous solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
2.5. Alkali/urea and NaOH/thiourea aqueous solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
2.6. Tetra butyl ammonium fluoride/dimethyl sulfoxide system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175

∗ Corresponding authors.
E-mail addresses: anglu@whu.edu.cn (A. Lu), zhangln@whu.edu.cn (L. Zhang).

http://dx.doi.org/10.1016/j.progpolymsci.2015.07.003
0079-6700/© 2015 Elsevier Ltd. All rights reserved.
170 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

2.7. Metal complex solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

2.8. Molten inorganic salt hydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3. Regenerated cellulose materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.1. Cellulose regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.2. Cellulose fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
3.3. Cellulose films and membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.4. Cellulose hydrogels and aerogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.5. Cellulose microspheres and beads . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
3.6. Cellulose bioplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
4. Cellulose based composite materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
4.1. Cellulose composite fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
4.2. Cellulose composite films and membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
4.3. Cellulose composite hydrogels and aerogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
4.4. Cellulose composite microspheres and beads . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
5. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200

1. Introduction gained particular attention, due to its renewability, avail-

ability, non-toxicity, low-cost, environmental friendliness,
In the 21st century, the trend of science and technol- biocompatibility, biodegradability, thermal and chemical
ogy is tending towards environmentally friendly materials, stability and derivatizabilty [4,5]. Plants produce over tens
renewable resources and energy, as well as sustainable of billions of tons of cellulose per year globally, making this
techniques and processes. The depletion of non-renewable polysaccharide the largest organic carbon reservoir [6,7].
resources (petroleum, coal and gas) in the future and the Cellulose is a linear chain comprising two anhydroglu-
environmental pollutions caused by the petroleum-based cose rings ((C6 H10 O5 )n ), linked together through an oxygen
polymers motivate increasing demands from renew- covalently bonded to C1 of one glucose ring and C4 of the
able resources, which are biodegradable, non-petroleum adjoining ring (1–4 linkage), with the so called the ␤ 1–4
based, carbon neutral, and posing low environmental, ani- glucosidic bond giving rise to a flat ribbon-like conforma-
mal/human health and safety risks [1]. The themes of the tion [1,8,9]. The number n of repeat units per chain depends
239th (2010), 241st (2011), 243rd (2012), 245th (2013), on the source, e.g., n is approximately 10,000 in wood and
247th (2014) and 249th (2015) American Chemistry Soci- 15,000 in native cotton in nature.
ety National Meetings were “Chemistry for a Sustainable The relatively high persistence length of the cellu-
World”, “Chemistry of Natural Resources”, “Chemistry of lose molecular chain conformation and their close packing
Life”, “Chemistry of Energy & Food”, “Chemistry & Materi- through numerous hydrogen bonds have made the dissolu-
als for Energy” and “Chemistry of Natural Resources” again, tion of cellulose to be a difficult process. Thus, development
respectively. They are regarded as directions and guid- of environmentally friendly low cost solvents for cel-
ance to the advances and developments in chemistry all lulose is essential for the successful utilization of the
over the world, suggesting the wide utilization of renew- cellulose as a component of polymeric materials. Usually,
able resources to produce environment-friendly materials regenerated cellulose materials may be prepared directly
via physical approaches with no chemical reactions, to from cellulose solution via a physical dissolution, shaping
avoid using or producing any hazardous substances, a com- and regeneration process. The process is environmen-
ponent of the new international frontier of “green” and tally friendly by avoiding consuming chemicals since most
sustainably developing processes. In that case, the research of the agents (solvents, coagulant, etc.) may be recycled
and development of renewable biomass was highly val- and reused, with no accompanying chemical reaction. By
ued by governments, business communities and academia. changing the regeneration parameters, the regenerated
The Technology Road Map for Plant/Crop-based Renew- cellulose vary in different shapes, such as powder, fibers,
able Resources 2020, sponsored by the U.S. Department of films, hydrogels, spheres, etc. Especially, the dissolution
Energy, has targeted to achieve 10% of basic chemical build- and regeneration is a “green”, clean and physical pro-
ing blocks arising from plant-derived renewable sources cess when “green” cellulose solvents are applied, leading
by 2020, with development concepts in place by then to to sustainable development, environmental preservation
achieve a further increase to 50% by 2050 [2]. This addresses and energy conservations. Thus, regenerated celluloses
renewable natural resources to the topics important to life have drawn attention, since they are easy to fabricate,
in the 21st century. biocompatible, biodegradable, thermal and chemical sta-
In the last several decades, increasing attention turned ble, etc. However, the difficulty in dissolving cellulose has
to natural polymers in the development of environmen- hindered the advancement and development of regener-
tally friendly and biocompatible products and fuels [3], ated cellulose. Therefore, there is a growing urgency to
among which cellulose constitutes the most abundant develop novel and green techniques to physically prepare
renewable polymer resource available today and has regenerated cellulose. “Green” solvents for the preparation
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
of regenerated cellulose materials have been developed
[10–18]. For example, Robin D. Rogers received US Pres-
idential Green Challenge award in 2005 for proving that
ionic liquids are capable of physically dissolving cellu-
lose. Thomas Heinze received the 2010 Anselme Payen
Award of the ACS for developing tetra butyl ammonium
fluoride/dimethyl sulfoxide as a non-derivatizing solvent,
and cellulose derivation reactions in a number of different
mediums. Lina Zhang was awarded with the 2011 Anselme
Payen Award of the ACS who opened a new pathway for the
physical cellulose dissolution in NaOH/urea aqueous solu-
tion with cooling, remarked as “a milestone in the history of
cellulose processing technology”. Hans-Peter Fink received
the Anselme Payen Award of the ACS in 2012 for developing
the environmentally friendly cellulose carbamate technol-
ogy as a derivatizing approach, and the combination of it
with NMMO (N-methylmorpholine N-oxide) solvent sys-
tem as a novel way to manufacture high modulus technical
cellulose fibers via liquid crystalline solutions. Fink and
Thomas Rosenau were rewarded with the 2013 and 2014
Anselme Payen Awards of the ACS for contributions in the
cellulose processing in NMMO as well as other solvents. In
that case, a number of regenerated cellulose materials and
functional materials have been fabricated directly from cel-
lulose solution for applications such as textile, packaging,
biomedicine, water-treatment, optical/electrical devices
etc. These cellulose materials gained attentions not only
because of their unsurpassed quintessential physical and
chemical properties, inherent renewability and sustain-
ability in addition to their abundance, but also because the
physical dissolution and regeneration technique from non-
derivatizing cellulose solvents is simple, low-cost, “green”,
easy for industrialization and possessing great potentials.
Following developments such as these, this review focuses
on the physical dissolution and regeneration of cellulose, as
well as their relevant dissolution mechanisms, followed by
preparation of the cellulose materials and demonstration
of their structure, properties and application potentials.
2. Cellulose solvents
As a result of its persistant chain conformation and close
chain packing through massive inter- and intra-molecular
hydrogen bonds, as well as other intermolecular interac-
tions cellulose cannot be dissolved in common solvents
[19–22]. The widely-used cellulose dissolution viscose pro-
cess, developed over 100 years ago, still dominates the
regenerated cellulose products market. During the first 10
years of the 21st century the global viscose staple capac-
ity increased by around 1.5 million tonnes (an average of
7.7% per annum) to more than 3.5 million tonnes, as an all
time record high. Simultaneously, the production of viscose
staple also increased, of 6.7% per annum, well above the all-
fiber average of 4.1% per annum, slightly higher than that of
polyester staple (6.6% per annum) and well ahead of acrylic
staple which went into decline at an average rate of −2.5%
per annum [23]. In the viscose procedure, cellulose is con-
verted with CS2 to cellulose xanthogenate via a derivative
reaction, resuting in solublity in aqueous NaOH, leading to
a viscose solution, subsequently treated with acidic solu-
tion to reform the regenerated cellulose. However, the use
171
Fig. 1. The mechanism of NMMO dissolving cellulose [26], Copyright
2006. Reproduced with permission from Elsevier Ltd.
of toxic, flammable and explosive CS2 causes environmen-
tal problems. The viscose technique was greatly improved
in the past decades as producers investicated a number of
techniques to decrease pollution, such as decreasing the
undesirable emission of gas, and ca. 70–75% recovery of CS2 .
However, the waste water and exhaust air are still prob-
lems, as well as the degradation of the cellulose backbone
concurrent in the viscose process [3]. Therefore, a series
of novel cellulose solvent systems have been introduced
for sustainable development and environmental preserva-
tion, and the most important feature of the novel cellulose
solvents in the 21st century should lie in the range of
simplicity and convenience, as well as low-toxicity and
environmental friendliness.
2.1. N-methylmorpholine-N-oxide (NMMO)
The first patent on the capacity of NMMO in dissolv-
ing cellulose was assigned in 1969 [24]. From then on,
NMMO has been widely investigated as an organic sol-
vent for the preparation of cellulose solutions. NMMO is
used as a non-derivatizing solvent in the cellulose disso-
lution procedure and the cellulose is supposed to undergo
an entirely physical process during dissolution, due to the
hydrogen bonding and ionic interactions between NMMO
and cellulose, as shown schmatically in Fig. 1, as a result of
the strong N O dipoles [13,25,26]. It is commonly 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 macromolecules and
the solvent [27]. Above 85 ◦ C, NMMO·H2 O can destroy the
cellulose inter-molecular hydrogen bonds, and the NMMO
dipole formed complex with cellulose hydroxyls, leading
to dissolution [28]. Holladay and coworkers indicated that
the NMMO crystal structure in cellulose/NMMO mixture
collapses between 70 and 100 ◦ C to become very mobile
(liquid-like form). The mobile NMMO could transform
crystalline cellulose into the amorphous phase. Cellulose
started to replace H2 O hydrogen-bonded to NMMO in
a cellulose/NMMO mixture heated to 150 ◦ C, with the
released H2 O existing as both adsorbed H2 O on cellu-
lose and unbound H2 O physically confined in the cellulose
matrix [29]. Microwave heating accelerated the cellu-
lose dissolution in NMMO, and the process significantly
shortened the dissolution time and energy consump-
tion [30]. However, thermal instability and relevant side
172 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
reactions (homolytic and heterolytic) occurred, resulting
in the formation of considerable byproduct since NMMO
slowly oxidized the cellulose during the dissolution, with
detrimental effects such as NMMO decomposition, cel-
lulose degradation, decreased product performance and
increased consumption of stabilizers [27].
Rosenau and co-workers have reported the stabilization
of the cellulose solutions in NMMO system by trapping
radicals, formaldehyde and N-(methylene)iminium ions
efficiently, to prevent the side reactions and their harm-
ful effects [31]. To date, the NMMO process has ripened
technically by overcoming some of the initial difficul-
ties, and the industrial process and emission-free technical
NMMO recovery system (99.6–99.7% NMMO recovery from
the coagulation) have led to the commercialization of the
Lyocell® process and Tencel® fibers, attributed to the Aus-
trian company Lenzing AG [32]. Usually, the range of water
content in NMMO used to dissolve cellulose is between
4 and 17%, and cellulose solution up to around 30% can
be produced, depending on the water content and the
characteristics of the cellulose pulp. In most industrial
and pilot-scale Lyocell processes, a typical composition
is 50–60% NMMO, 20–30% water and 10–15% cellulose,
specifically 14% cellulose, 10% water and 76% NMMO [27].
2.2. Ionic liquids (ILs)
Ionic liquids (IL) are a group of salts that exist as liquid at
relatively low temperatures (less than 100 ◦ C), with many
attractive properties, including nonvolatile, chemical and
thermal stability, non-flammability, and immeasurably
low vapor pressure [33]. In 2002, Rogers and co-workers
reported the use of ILs as cellulose solvents for both phys-
ical cellulose dissolution and regeneration, opening up
a new class of solvents to the cellulose research com-
munity [14]. Later, 1-allyl-3-methylimidazolium chloride
(AMIMCl) was developed to be a new and effective cellu-
lose solvent. Cellulose samples without any pretreatment
have been readily dissolved, and the regenerated cellulose
films, prepared by coagulation in water, exhibited good
mechanical properties [34]. Ohno and co-workers synthe-
sized a series of alkylimidazolium salts containing dimethyl
phosphate, methyl methylphosphonate, or methyl phos-
phonate via one-pot procedure as ILs, potentially capable
of solubilizing cellulose under mild conditions [35]. A new
generation of ionic liquids as cellulose solvents has been
developed by conjugation of the commercially available
organic acids and 1,1,3,3-tetramethylguanidine as a com-
mercially available organic super-base. It can be technically
“distillable” to high purity (>99% purity, >99% yield), not yet
observed for earlier generations of ionic liquids solvents
for cellulose [36]. Furthermore, tetrabutylphosphonium
hydroxides containing 30–50 wt% water are capable of dis-
solving cellulose rapidly at ambient temperature (25 ◦ C),
without derivation or degradation. In particular, tetra-
butylphosphonium hydroxides containing 40 wt% water
can dissolve cellulose and remain stable throughout the
process, treating a natural biomass containing a consider-
able amount of water [37]. Moreover, microwave heating
also significantly accelerates the cellulose dissolution in ILs
[38].
The dissolution mechanism of cellulose in ILs has
been extensively investigated to improve the dissolution
capacity. Studies on the mechanism of the cellulose dis-
solution in ILs have indicated that interactions between
the IL anions and the hydroxyls of cellulose play an
important role in this process, and requirements of hydro-
gen bonding acceptor ability (or basicity) of the anion
has been borne out by experimental results [3,35]. The
investigation of cellulose in chloride-based IL using NMR
spectroscopy revealed that the solvation of cellulose
by 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl)
involves stoichiometric hydrogen-bonding between the
hydroxyl protons of the solute and the chloride ions of the
IL [39]. Furthermore, the solvation of cellobiose, the repeat-
ing unit in cellulose, in 1-ethyl-3-methylimidazolium
acetate (EmimAc) under various cellobiose concentra-
tions and temperatures suggest that hydrogen bonding
formed between the hydroxyls of cellobiose and both
the anions and the cations of EmimAc [40]. 13 C NMR
results of cellulose and cellulose oligomers dissolved in
1-butyl-3-methylimidazolium chloride showed that the
␤-(1,4)-linked glucose oligomers were disordered in this
medium [41]. Molecular simulation applied to cellulose
in 1-butyl-3-methylimidazolium chloride suggested that
ILs tended to target the glucose residues in cellulose,
and the anions strongly interacted with the hydroxyl
groups [42]. Wang and coworkers prepared 13 kinds
of ILs with various cations, but an identical anion, and
found the cations significantly affected cellulose dissolu-
tion, either increased the cellulose solubility by forming
hydrogen bonds with hydroxyl oxygen and ether oxygen
of cellulose, or decreased the solubility by anionic com-
petition/steric hindrance [43]. Therefore, it is generally
agreed that anions and cations are both involved in the
dissolution process through synergistic inter-molecular
interactions, e.g., hydrogen bonding, the van der Waals
interaction, etc., as shown schematically in Fig. 2 [44–46].
Furthermore, Singh and coworkers found that the inter-
action energy between the cellulose chain and the IL was
stronger than that for chain/water or chain/methanol inter-
actions. In addition to the anion forming strong hydrogen
bonds with the cellulose hydroxyl groups, some cations
were found to be in close contact with the polysaccha-
rides through hydrophobic interactions, confirming the
significant role of the cations in cellulose dissolution [47].
Rabideau et al. studied the breakup of small cellulose
I␣ and I␤ bundles in ILs in the following process: the
anions can bind strongly to the hydroxyl groups of the
exterior bundle strands, forming negatively charged com-
plexes, while the cations then intercalate between the
individual strands, likely due to charge imbalances, pro-
moting the bulk to push the individual moieties apart
and initiate the separation [48]. The solubility of cellu-
lose in ILs has been supposed to be dominated not only
by the effective polarity and the hydrogen bonding capac-
ity of the IL, but also by the melting temperature, the
viscosity, the additives and other factors [49–53]. Righi
et al. analyzed the environmental impacts of the cellu-
lose dissolution in 1-butyl-3-methylimidazolium chloride
compared with NMMO through a “cradle to gate” life
cycle assessment, leading to conclusions that both of the
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
Fig. 2. Proposed dissolution mechanisms for cellulose in imidazolium-
based ionic liquids: (A) interactions between the basic anion and the
cellulose hydroxyl groups break up the hydrogen bond network between
the cellulose chains. (B) Hydrophobic interactions take place between the
hydrophobic face of cellulose and the imidazolium ring. (C) The acidic pro-
ton at the C2 position on the imidazolium ring interacts with the cellulose
hydroxyl groups [45], Copyright 2015. Reproduced with permission from
the Royal Society of Chemistry.
processes exhibited similar impacts, and the major contri-
butions to the environmental impacts came from precursor
syntheses [54]. The results obviously encourage further
investigation of ILs as a powerful and green cellulose sol-
vents.
For example, effort is needed in several key areas to fur-
ther understand the process and to meet the sustainability
and green chemistry requirements for the development
of the next generation of industrial chemical processes.
Heinze and coworkers summarized the disadvantages that
may hamper the use of ILs as solvents for cellulose [55].
First, the purity grade of the ILs should be further increased,
and water remains as a problem with ILs since water, a
“precipitation agent” for cellulose/IL solutions, is almost
unavoidable in working with ILs [37,56]. Second, the vis-
cosities of ILs and the relevant cellulose solutions show
non-Arrhenius temperature behavior and increases unex-
pectedly rapidly in particular when approaching 0 to
40 ◦ C [57,58], dramatically affecting ion diffusion and mass
transfer, especially important in industrialization. Third,
potential thermal instability and side reactions have been
reported when using recycled ILs, such that the thermo-
stability of cellulose/IL solutions significantly decreases,
indicating that partial decomposition may start even below
the cited processing temperatures [59,60]. Moreover, the
development of more efficient and energy-saving methods
of recycling the ILs is also required, because the current
methods to recycle ILs in biomass processing mainly center
on the evaporation of the anti-solvents, leading to a large
energy consumption [3,61].
173
2.3. LiCl/N,N-dimethylacetamide (LiCl/DMAc)
LiCl/DMAc is a well-established non-derivatizing, non-
aqueous solvent system that has been widely employed
to dissolve different cellulose types without significant
degradation for cellulose modification under homogenous
reaction conditions to prepare a wide range of deriva-
tives [10,62]. This makes it an important medium for
cellulose analysis by various methods, e.g., size-exclusion
chromatography, nuclear magnetic resonance and light
scattering. It is noted that LiCl/DMAc can dissolve cellu-
lose with high molecular weight (>1000,000) molecularly
at ambient temperature without noticeable degradation
[63]. The standard approach to LiCl/DMAc dissolution of
cellulose is usually described by a sequence of mechan-
ical disintegration, activation, solvent exchange starting
with swelling in water followed by ethanol, methanol or
acetone, and final dissolution [64]. To accelerate the disso-
lution, Raus and co-workers reported an optimized version
of the activation method, based on solvent exchange from
water to dioxane, suitable for larger quantities of cellu-
lose. It is easy to tailor to specific needs, and is virtually
waste-free [65]. Molecular dispersion of cellulose can be
achieved in dilute solutions, but solutions with a higher cel-
lulose concentration (>2 wt%) and a low LiCl concentration
(e.g. 6 wt%) have shown a noticeable amount of optically
anisotropic particles [66]. In the well-received dissolution
mechanism proposed by McCormick ion–dipole complexes
are formed between Li+ and carbonyl of DMAc, whereas
hydrogen bonds occur between Cl− and hydroxyls of cellu-
lose [67]. Liu and coworkers have revisited the dissolution
of cellulose in LiCl/DMAc, concluding that the cellulose
hydroxyl protons induced strong hydrogen bonds with the
Cl− during which the intermolecular hydrogen bonding of
cellulose was broken with simultaneous splitting of the
Li+ –Cl− ion pairs, while Li+ were further solvated by free
DMAc molecules to accompany the hydrogen-bonded Cl−
to meet the electric balance, as shown in Fig. 3 [68].
As a non-aqueous cellulose solvent, water in LiCl/DMAc
has a distorting effect on the dissolution state of cellulose,
even though there is relatively little effect on the struc-
ture of dissolved cellulose if the water concentration is
below about 0.1 M. Usually, the typical LiCl/DMAc solvent
is composed of 5–9% LiCl, capable of dissolving 15–17%
cellulose. Kosma and coworkers developed a readily appli-
cable and general method for the precise determination
of water in DMAc and LiCl/DMAc, demonstrated the maxi-
mum solubility of LiCl in dry DMAc is 8.46 wt%, leading to
the conclusion that literatures which give higher solubil-
ity must have used – more or less – wet DMAc and/or LiCl
[69]. However, the high cost and difficulties in recycling
LiCl/DMAc solvent due to its low volatility also limits its
further development for commercial applications. In addi-
tion to refined cellulose samples, LiCl/DMAc is also capable
of dissolving paper containing different kinds of additives,
typically found in historic papers, without degradation and
aggregation even after several months [70]. Furthermore,
cellulose gels can be formed as a result of the molecu-
lar aggregates originated by the large-scale fluctuation of
the molecular chain density in the solution [71]. Ramos
et al. investigated the aceylation reaction of cellulose in
174 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
Fig. 3. Schematic of the interaction among Li+ cation, Cl− anion and DMAc
when cellulose dissolves into the DMAc/LiCl system [68], Copyright 2014.
Reproduced with permission from the American Chemical Society.
LiCl/DMAc with three different cellulose samples, indicat-
ing the correlation between the reaction efficiency and the
aggregation number of the dissolved cellulose [72].
2.4. NaOH aqueous solution
Kamide et al. reported that low molecular weight
(<40,000) non-crystalline cellulose dissolved in 8–10 wt%
NaOH aqueous solution at about 4 ◦ C. Fig. 4 shows the
13 C NMR spectrum of the cellulose solution in NaOH/D O.
2
C4 carbon peak located at much higher magnetic field
(79.9 ppm) than that of the original cellulose solid (87.9
and around 84.0 ppm) [73], indicating the increase of
the electron cloud density, as a result of the interactions
between cellulose chains with NaOH, which led to the rup-
ture of the intermolecular hydrogen bonds. On that basis,
cellulose filaments with small swelling ratio and low fibril-
lation nature in water were spun [74]. Later, microcrystal
cellulose was dissolved in 8–9 wt% aqueous NaOH by a
freeze–thaw–dilution process [75]. Heux and coworkers
used 13 C NMR solid-state spectroscopy to show that the
initial cellulose was replaced successively by Na-cellulose
I followed by Na-cellulose II with increasing NaOH concen-
tration [76]. Navard and coworkers demonstrated that a
combination of NaOH hydrates was able to penetrate into
the cellulose structure, preferentially forming some type
of network among the hydrates rather than binding only
to the cellulose [77]. They also demonstrated that the ZnO
addition improved the thermodynamic quality of cellu-
lose solution in NaOH [78]. However, the restriction of low
molecular weight, chain aggregation and the easy gelation
[79] suggested that this system might be unsuitable for the
characterization of cellulose molecular weight and chain
conformation.
Due to the confinement of the dissolution capacity
of NaOH aqueous solvent, many methods of cellulose
Fig. 4. 13 C NMR spectrum of the cellulose solution in NaOH/D2 O [73],
Copyright 1984. Reproduced with permission from the Nature Group.
treatment form have been reported to transform it into
an alkaline soluble form to increase cellulose reactivity
and solubility, including steam explosion, hydrothermal
treatment and enzymatic modifications etc. [80,81] In
steam explosion a mixture of cellulose in aqueous NaOH
is exposed to steam at high temperature for a short time
under pressure (e.g., 2.9 MPa for 30 s), followed by fast
decompression, to obtain maximum solubility of cellu-
lose in aqueous NaOH [82]. In the hydrothermal method
prolonged exposure of a mixture of cellulose in aqueous
NaOH can decrease the molecular weight of cellulose, poly-
dispersity and crystallinity, thus increasing the solubility
of the cellulose (e.g., 100–200 ◦ C under 0.1–1.5 MPa for
30–70 min) [83,84]. The treated cellulose at this condition
can be directly soluble in NaOH solvents, and the resultant
cellulose dope has been successfully spun into regener-
ated fibers [85]. Milling can enhance cellulose solubility by
decreasing the crystallinity as well as the inter- and intra-
molecular hydrogen bonds, leading to an increase in free
hydroxyl groups [86,87]. For the enzymatic treatment in
a specific procedure, the cellulose is first swollen and dis-
integrated in water followed by mechanical tearing, then
subjected to cellulolytic enzyme in acetate buffer at pH 4.8;
after filtration and washing the treated cellulose is ready for
dissolution in NaOH [88], as a result of the reduction of the
molecular weight and the crystallinity degree of cellulose
as well as the number of hydrogen bonds [89,90]. Later,
this process was intensively investigated within the 6th
European Framework Programme, in the project Biotech-
nological Process for Manufacturing Cellulosic Products with
Added Value, giving the acronym Biocelsol® as the name of
the process as well as the resultant fibers and films. Usually,
the treated cellulose containing 75 wt% water is dissolved
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
in 10.2 wt% NaOH aqueous solution containing ZnO for 60
to 180 min at 0 ◦ C [88], to give a viscous cellulose solutions,
and an optimal cellulose solution is composed of 6–6.5 wt%
cellulose, 7.8 wt% NaOH and 0.87 wt% ZnO. Enzymatic pre-
treatment, which decreased the molecular weight rather
than the crystallinity, also improved the cellulose disso-
lution in NaOH/urea, suggesting the effect of crystallinity
on the cellulose dissolution in NaOH/urea solution is much
less than molecular weight [91]. Moreover, Fardim and
coworker also reported a one-step chemical pretreatment
method using ethanol/hydrochloric acid for the cellulose
dissolution in NaOH/urea, due to a combination of degra-
dation of remnant primary fiber wall layer and reduction
of the molecular weight [92].
2.5. Alkali/urea and NaOH/thiourea aqueous solution
Zhang and coworkers developed a series of aqueous
cellulose solvents to dissolve cellulose rapidly (in 2 min)
at low temperature, providing a completely new avenue
for investigating the most intransigent macromolecules
of cellulose using non-toxic and low cost solvents via a
“green” technology. Cellulose pulps with molecular weight
smaller than 114,000 dissolved in 7 wt% NaOH/12 wt% urea,
and cellulose pulp smaller than 372,000 can be dissolved
in 4.6 wt% LiOH/15 wt% urea aqueous solution, pre-cooled
to −12 ◦ C, within 2 min, respectively [15,93]. The dissolu-
tion mechanism of cellulose at low temperature has been
revealed as follows: NaOH “hydrates” could be more eas-
ily attracted to cellulose chains through the formation
of new hydrogen-bonded networks, relatively stable at
low temperatures, while the urea hydrates as shell sur-
rounded the NaOH hydrogen-bonded cellulose to form an
inclusion complex (IC) with sheath like structure, leading
to the dissolution of cellulose. The experimental results
from dynamic and static light scattering (DLS and LLS)
and transmission electron microscopy (TEM) indicated that
the cellulose ICs existed as a worm-like conformation in
the aqueous solution, as shown in Fig. 5 [16,17]. Liu and
coworkers further confirmed by 15 N NMR the direct inter-
actions between the OH− ions of NaOH and the amino
groups of urea through hydrogen bonds, whereas no direct
interaction existed between urea and cellulose, however,
Na+ ion interacted with both cellulose and urea. Further-
more, cryo-TEM observation confirmed that the cellulose
IC appeared as extended wormlike shape with mean diam-
eter of about 3.6 nm and mean length of about 300 nm,
consisted with the diameter (2.8 nm) of the ICs estimated
using the M06-2X/6-31 + G(d) theoretical method [94].
The cellulose solubility in NaOH/urea strongly
depended on the temperature, crystallinity and molecular
weight [95,96], as well as additives [97,98]. As mentioned
in the preceding, the highest solubility of cellulose with
molecular weight of 114,000 in NaOH/urea is below 4 wt%,
and further increasing the cellulose amount leads to
increasing undissolved cellulose. The cellulose solution is
stable for one week at 0 to 5 ◦ C, but heating over 20 ◦ C can
induce irreversible cellulose gelation [99]. In addition, the
rapid dissolution was not ideally achieved in an industrial-
ization process, due to the uneven dispersion of cellulose
in the precooled solvent and easy gelation tendency.
175
The NaOH/urea system requires further investigation to
enhance the dissolving capacity and the stability of the
cellulose solution.
In addition to NaOH/urea and LiOH/urea, NaOH/
thiourea can also dissolve cellulose at low temperature
(−5 ◦ C), and inclusion complexes associated with cellu-
lose, NaOH, thiourea and water occurred through hydrogen
bonds [100]. Yan et al. found that both NaOH and thiourea
had a homogeneous distribution around the cellulose fibers
during the dissolution process, and their synergic interac-
tions played a key role in dissolving the cellulose aggregates
[101]. In the alkali/urea or NaOH/thiourea systems, the cel-
lulose formed a meta-stable solution, and aggregates or
gels occurred with increasing temperature, concentration
or storage time, as a result of the partial destruction of
the inclusion complex structure [102–106]. Furthermore,
the dissolution mechanism of biopolymers in alkali/urea
aqueous solution at low temperature was also confirmed
by more recent work including chitin and chitosan, in
which the alkali and chitin (or chitosan) formed hydrogen-
bonded complex, surrounded by the urea hydrates to form
a sheath-like structure, leading to the dissolution. More-
over, the extended wormlike chitin (or chitosan) chains
easily aggregated in parallel to form nanofibers in the
aqueous solution, providing an important guidance for con-
structing novel nanomaterials [107–109].
2.6. Tetra butyl ammonium fluoride/dimethyl sulfoxide
system
Heinze et al. reported that cellulose with a molecu-
lar weight up to 105,300 dissolves in dimethyl sulfoxide
(DMSO) containing 10 to 20% (w/v) tetrabutylammo-
nium fluoride trihydrate (TBAF·3H2 O) within 15 min at
room temperature without any pretreatment [110], as
a non-derivatizing solvent and reaction medium for the
homogeneous functionalization of cellulose [111–113]. A
simple pretreatment (cellulose in DMSO at 60–80 ◦ C and
stirring) prior to the addition of TBAF·3H2 O is favor-
able [114]. In the mixture DMSO/TBAF·3H2 O, the F−
mainly interacted through hydrogen bond with water
and after adding cellulose, similar interaction (F− ·H O-
cell) easily replaced that with water, leading to chain
separation and cellulose dissolution [115]. Later, the com-
parison of cellulose dissolution in water-free DMSO/TBAF
to DMSO/TBAF·3H2 O led to the conclusion that F− domi-
nated the cellulose dissolution in DMSO/TBAF while water
played a minor role, at least up to the TBAF trihydrate
[116,117]. Ostlund and coworkers revisited the cellulose
dissolution in this solvent system via NMR, revealing the
cellulose dissolution power of the TBAF/DMSO system
was primarily due to the strong ion–dipole interaction
between F− from TBAF and the hydroxyl groups of cellu-
lose, and the highly electronegative F− formed hydrogen
bonds with the cellulose hydroxyl groups to deconstruct
the hydrogen-bonded cellulose network [118,119]. Water
can induce gel formation in the TBAF/DMSO/cellulose
solution, as a result of a competitive system since F−
not only interacted with the water molecules but also
the cellulose hydroxyl groups. Heinze and coworker
also tested the other ammonium fluorides in DMSO as
176 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 5. 1D WAXD intensity profiles of NaOH (powder), urea (powder) and cellulose in NaOH/urea solution and then frozen and dried (left) and TEM images
of cellulose solution at 5.0 × 10−4 g ml−1 in 7 wt% NaOH/12 wt% urea aqueous solution pre-cooled to −12 ◦ C (middle, inset presents the electron diffraction
pattern of the surface), and scheme of the worm-like cellulose complexes (right). Right: [16], Copyright 2007. Reproduced with permission from John Wiley
& Sons Inc; Middle: [17], Copyright 2008. Reproduced with permission from the American Chemical Society.

cellulose solvents, such as tetramethylammonium fluoride
(TMAF) and benzyltrimethylammonium fluoride monohy-
drate (BTMAF·H2 O). Up to 1 wt% cellulose was soluble in
DMSO/BTMAF·H2 O when the mixture was heated to 85 ◦ C,
whereas TMAF was not appropriate for the preparation of a
cellulose solution, due to the low solubility in DMSO [117].
a similar manner as in ladder polymers [121]. Among the
metal complex solvents, the Cupro processes, utilizing
Cuam as the solvent, has been commercialized by such
as Asahi Kasei Fibers Corporation, although with a high
cost.

2.8. Molten inorganic salt hydrates

2.7. Metal complex solutions
Aqueous metal complex solutions, composed of tran-
sition metal ions and nitrous ligands, are also applied for
cellulose dissolution, characterization and regeneration,
among which, the best known are cuprammonium hydrox-
ide (Cuam) and cupriethylenediamine hydroxide (Cuen).
The common metal complexes with their formula are as fol-
lows: Cadoxen: [Cd(H2 N(CH2 )2 NH2 )3 ](OH)2 ; Cdtren: [Cd
(NH2 CH2 CH2 )3 N](OH)2 ; Cooxen: [Co(H2 N(CH2 )2 NH2 )2 ]
(OH)2 ; Cupren: [Cu(H2 N(CH2 )3 NH2 )2 ](OH)2 ; Nioxam:
[Ni(NH3 )6 ](OH)2 ; Nioxen: [Ni(H2 N(CH2 )2 NH2 )3 ](OH)2 ;
Nitren: [Ni(NH2 CH2 CH2 )3 N](OH)2 ; Cuam (Cuoxam, Schw-
eitzer’s reagent): [Cu(NH3 )4 ](OH)2 ; Cuen: [Cu(H2 N(CH2 )2
NH2 )2 ](OH)2 ; Pden: [Pd(H2 N(CH2 )2 NH2 ](OH)2 ; Zincoxen:
[Zn(H2 N(CH2 )2 NH2 )2 ](OH)2 [120]. A feature of these
cellulose solvents is their strong color, which may cause
problems in analytical applications, e.g., Cuam and Nitren
are deep blue so that light scattering measurements of
Cuam and Nitren carried out with the blue line of an argon
ion laser required an absorption correction according to
the Lambert–Beer law [121]. Burchard and co-workers
showed that the metal complexes aqueous solution dis-
solved cellulose by forming a complex with the cation
through the C2 and C3 hydroxyl groups of the cellulose
and thereby replaced ligands from the coordination sphere
of the cation [122,123]. They also studied the cellulose
solution in several metal complex solvents, demonstrating
Cdtren dissolved cellulose with highest molecular weight,
exhibiting stronger dissolving power than Nitren and
Cuam in turn. In the solution, the cellulose chain stiffness
was very likely caused by an enhanced strength of the
hydrogen bonds between the deprotonated olate O3 − and
the ring oxygen of the next anhydroglucose unit, and the
hydrogen bonding system reduces segmental mobility in
Besides the solvents above, molten inorganic salt
hydrates have also gained much attention as new sol-
vents and media for cellulose dissolution. Some of
the widely used cellulose-dissolving inorganic molten
salt hydrates are ZnCl2 ·4H2 O, Zn(NO3 )2 ·xH2 O (x < 6),
FeCl3 ·6H2 O, LiClO4 ·3H2 O, LiI·2H2 O, LiBr, LiSCN·2H2 O,
ZnCl2 ·3H2 O, Ca(SCN)2 ·3H2 O, as well as mixtures such as
LiClO4 ·3H2 O/MgCl2 ·6H2 O, LiClO4 ·3H2 O/Mg(ClO4 )2 /H2 O,
LiCOl4 ·3H2 O/NaClO4 /H2 O, LiCl/ZnCl2 /H2 O, NaSCN/KSCN/
LiSCN/H2 O, NaSCN/KSCN/Ca(SCN)2 /H2 O etc. [120,124]
LiClO4 ·3H2 O is a very effective solvent, and yields a trans-
parent solution of cellulose within a few minutes. In the
early 1970s, Richard and Williams investigated the com-
plexes formed between aqueous ZnCl2 and cellulose using
methyl ␤-d-glucopyranosides as a model, demonstrating
the concentration and stability of the complexes were pro-
portional to the ZnCl2 concentration, and the complexes
were formed between ZnCl2 and the vicinal hydroxyl
groups on C2 and C3 of the d-glucopyranoside repeating
unit [125]. Later, ultraviolet spectra was applied to inves-
tigate the complex structure between ZnCl2 (67 wt%) as
well as cellulose, cellobiose, maltose, ␤-methyl glucoside
and glucose. The results showed that Zn2+ formed loose
complexes with the C2 or C3 hydroxyl of glucose or methyl
glucopyranoside, and that with the hemiacetal oxygen
atom of the anhydroglucose at the non-reducing end and a
hydroxyl group of an anhydroglucose unit at the reducing
end of cellulose or cellubiose as well as similar complexes
involving the anomeric oxygen at the reducing end of
cellobiose [126]. Shen and coworker dissolved bacteria
cellulose in ZnCl2 ·3H2 O with a maximal concentration of
5.5 wt% at 80 ◦ C, followed by spinning at 50 ◦ C to fabricate
fibers. However, the regenerated fibers had relatively
poor tensile strength and elongation at break due to
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
surface cracks and fibrillation, as well as lower crystallinity
[127].
Furthermore, the dissolution of cellulose in Ca(SCN)2
was extensively studied by Hattori et al. They found that
55 wt% Ca(SCN)2 solution at room temperature swelled
to wood pulp, to form a new structure with larger inter-
planar spacings of (1 1̄ 0) and (1 1 0) planes and slightly
smaller spacings of (2 0 0) planes than for the original cellu-
lose. The regenerated cellulose from the cellulose/Ca(SCN)2
solution with water, methanol and acetone led to cellulose
II, cellulose I and almost amorphous cellulose, respec-
tively [128]. They also found out that only Ca(SCN)2 ·xH2 O
(x ≤ 4) + yH2 O (y ≤ 6), exhibiting mainly a non-dissociated
type of SCN−1 with a high specific viscosity can dissolve
cellulose. Swelling of cellulose took place by first attacking
the ring oxygen in the cellulose towards Ca(SCN)2 ·xH2 O
(x ≤ 4) to fulfill the 4-hydrates-like form (6-valence coor-
dination of Ca2+ ), with cellulose forming a 5-membered
cyclic structure by coordinating two oxygen atoms (O5 and
O6) in glucopyranose units to centered Ca2+ , and then dis-
solving on heating [129]. Almost all tested celluloses were
soluble in 55 wt% Ca(SCN)2 solution at 100 ◦ C, however,
60 wt% NaSCN solution only dissolved limited cellulose
mainly regenerated from cellulose solution. Detailed inves-
tigation of NMR showed that Ca2+ coordinated with oxygen
atoms in skeletal glucose rings and in primary alco-
hol at C6 position, whereas Na+ closely interacted with
all hydroxyl oxygen atoms of the glucopyronose ring of
cellulose in solution, leading to differences in solubility
[130].
Among different lithium-containing salt hydrates,
LiClO4 ·3H2 O, LiSCN·2H2 O and mixtures of LiSCN/KSCN/
NaSCN/H2 O are able to dissolve cellulose, but solubil-
ity does not occur with either LiCl·xH2 O (2 ≤ x ≤ 5) or
LiNO3 ·3H2 O [131]. The 7 Li NMR spectra revealed a larger
shielding of the Li+ for systems that dissolve or swell cel-
lose, than for those that do not do so, showing interaction
between cellulose and solvents. By taking cellobiose as a
model, the presence of cellobiose in the first co-ordination
sphere of the Li+ was verified, and thus cellulose was
hypothesized to take part in the solvation of Li+ , as one of
the driving forces [132]. Later, Fischer et al. illustrated that
except the specific structure of the molten salt hydrate, the
cations and the water content are the most important fac-
tors for the dissolving capability of a molten salt hydrate
when utilizing LiClO4 ·3H2 O, NaSCN/KSCN/LiSCN·2H2 O and
LiCl/ZnCl2 /H2 O as cellulose solvents. They also proved the
existence of direct interactions between Li+ and hydroxyl
of cellulose, however, Raman spectroscopic investigations
gave no indication for the formation of stable addition
compounds between molten salts and cellulose [133].
Generally, the inorganic molten salt hydrates act as non-
derivatizing solvents for cellulose dissolution [134]. It is
widely recognized that the dissolution of cellulose depends
on the direct interaction of the cellulose hydroxyl groups
with the metal ions. However, arguments existed with the
statement that the hydrogen bonding of cellulose hydroxyl
groups with the water molecules directly bonded to the
metal cations also played important roles in the cellulose
dissolution [135]. Therefore, further study is necessary to
clarify the mechanism of cellulose dissolution.
177
3. Regenerated cellulose materials
The regeneration of the cellulose solution by coagu-
lation with anti-solvent or non-solvent is an important
pathway for the preparations and the industrialization of
cellulose materials. Materials fabricated directly from the
cellulose solution via physical regeneration gain unsur-
passed physical and chemical properties, inherent renewa-
bility and sustainability, exhibiting astonishing impacts
and benefits to society. The regeneration provides a simple
pathway to transform native cellulose to useful mate-
rials in various forms, such as fibers, films/membranes,
beads/microspheres, hydrogels/aerogels, bioplastics, etc.
Moreover, chemical or physical treatments can be applied
to generate many functional materials, such as inor-
ganic/cellulose hybrids, organic/cellulose blends, porous
membranes, biocompatible materials, during regeneration
of cellulose solution. Therefore, the regeneration technique
and the resultant regenerated cellulosic materials have
played important roles in the comprehensive utilization of
cellulose.
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 suc-
cessful preparation of the regenerated cellulose material,
which dominates the morphology and properties. Usually,
the cellulose regeneration is a physical process, with no
accompanying chemical reaction. Taking the regeneration
of cellulose solution from alkali/urea and NaOH/thiourea
as an example, when the urea hydrates on the surface of
the NaOH hydrogen-bonded cellulose complex with sheath
like structure in the cellulose solution are broken by heat-
ing or other action, the cellulose chains aggregate rapidly to
form hydrogels, and then regenerated cellulose materials
may be obtained by drying. Thus, the structure and prop-
erties of the cellulose materials depend on the coagulants,
temperature, time and pathway. The factors influencing the
regeneration of cellulose are summarized in the following
section.
Usually, non-solvents are chosen as coagulants for
the regeneration of cellulose from its solution. Zhang
and coworkers [136,137] developed a series of coag-
ulants for the regeneration of cellulose in NaOH/urea,
including H2 SO4 , CH3 COOH, H2 SO4 /Na2 SO4 , Na2 SO4 ,
(NH4 )2 SO4 ·H2 O, C2 H5 OH and (CH3 )2 CO aqueous solutions,
respectively. Among all the coagulants, H2 SO4 /Na2 SO4
resulted in the highest optical transmittance, the most
homogeneous structure and the best mechanical proper-
ties, thus it became the first choice as a coagulant for the
cellulose solution. Since the regeneration mainly related
to the diffusion between the coagulant and the solvent, the
relatively higher temperature led to the increasing of the
diffusion coefficient [138,139]. By using H2 SO4 /Na2 SO4
as the coagulant, the lower temperature was demon-
strated to be favorable for denser network structure than
higher temperature, as a result of compact and ordered
arrangement of macromolecules. Similarly, acid/salt were
also chosen as the coagulation of Biocelsol® process: the
178 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
tenacity and porosity of the Biocelsol® fibers spun with
15% H2 SO4 /10% Na2 SO4 were higher and average size of
crystallites was smaller than that of 5% H2 SO4 /10% Na2 SO4 ,
due to the perfect solidification of fibers in the higher
coagulation concentration [140]. In addition, Budtova and
coworker investigated the regeneration of cellulose from
cellulose/NaOH/water gels immersed in a non-solvent
coagulation (different alcohols), showing that the “porous
membrane” (i.e. free volume or hydrodynamic approach)
was applicable, caused by the phase separation during
regeneration of gels placed in a non-solvent liquid [141].
Orientation is very important in the polymeric prod-
uct fabrication, especially for the fiber and film, to
enhance the mechanical properties by creating ordered
microstructure/supra-molecular structure and stronger
inter-molecular interactions. By using the water-swollen
regenerated cellulose films as templates, the drawing
process led to substantial re-orientation of the cellulose
molecular chains, resulting in a significant improvement of
their mechanical properties (the tensile strength increased
from 89 to 213 MPa when increasing the drawn ratios
from 1 to 1.22) and water-resistance [142]. Furthermore,
the drying process affected the structure and properties
of the regenerated cellulose films. Isogai and coworkers
reported that the pre-pressing and press-vacuum drying
procedure endowed the films with the tensile strength of
263 MPa, Young’s modulus of 7.3 GPa, coefficient of ther-
mal expansion of 10.3 ppm K−1 and oxygen permeability of
0.0007 ml ␮m m−2 day−1 kPa−1 , demonstrating the high-
est performance of regenerated films compared with no
orientation [143]. Zhong and coworkers investigated the
influence of the water content on the cellulose structure
fabricated via the cellulose dissolution in NaOH/urea fol-
lowed by gelation, coagulation and freeze–drying. The gel
was treated at 50 ◦ C to give different water content, and
the 3D nanofibrillar networks of the freeze-dried porous
samples gradually transformed to the denser 3D sheet-like
network structure with the decrease of the water contents,
suggesting the important influence of water [144].
3.2. Cellulose fibers
Cellulose fibers have been involved in the daily life for
a long time. The most widely-used regenerated cellulose
fibers are fabricated via viscose procedure during which the
cellulose xanthogenate are spun, appears over 100 years
ago [145]. Usually, there are three types of rayon: regular
rayon, high wet modulus rayon and high tenacity rayon.

Regular rayon, identified on labels by the term “Viscose®
rayon, has the largest market share, and it is widely used in
apparel and home furnishings. In a typically Viscose® rayon
manufacturing process, the cellulose dissolving pulp were
soaked in NaOH to produce alkali cellulose, followed by
aging for 2 to 3 days, and then are churned with liquid CS2
to get sodium cellulose xanthogenate. The resulting viscose
solution after bathing in NaOH is subjected to regenerated
filaments fabrication, by forcing the liquid through a spin-
neret into an acid coagulation. High wet modulus rayon is
a modified Viscose® rayon with high wet strength, primar-
ily supplied by Lenzing® with the trade name of Modal® ,
in which the filaments are stretched to a lager degree than
Viscose® rayon. High tenacity rayon is also a modification of
Viscose® rayon to provide exceptional strength, such as the
Viscont® HT with an average tenacity of 4.0 to 4.2 cN dtex−1
produced by Glanzstoff Industries [146].
Tencel® fibers can be obtained by successively dry jet-
wet spinning the Lyocell® dopes of cellulose/NMMO/water
by coagulating (in water or NMMO aqueous solution),
washing, drying and post-treatment. The spinning process
for making Tencel® fiber is considered to be environmen-
tally friendly because the solvent is recovered, purified
and recycled as an integral part of the manufacturing
process. The smooth surface and round cross-section as
shown in Fig. 6 were attributed to the physical dissolution
and regeneration, and their dry and wet tensile strength
reaches 4.2 and 3.6 cN dtex−1 , respectively [13]. Tencel®
fibers can also be swelled and dissolved in NMMO/H2 O,
starting at the outer parts of the fiber and progressed
inside the fiber, different from the native cellulose fiber
[147]. Beside the traditional textile, Tencel® also demon-
strates potentials as technical textile, e.g. foam materials,
functional coating materials, technical knits, as well as a
high volume fiber type for carpets, a fibrous powder for
plastics as reinforcement, a special textile fiber for seat
covers and a nonwoven application for battery separators,
etc.
Another commercial regenerated fiber, Cuprammo-
nium rayon, is a rayon 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 ammo-
nia. The fabric is commonly known by the trade name
“Bemberg”, currently produced by Asahi Kasei Fibers Cor-
poration, extensively used in diverse fields such as high
quality linings and lingerie, as well as in apparel applica-
tions. It can also take various forms, such as the Bemliese,
a binder free spunbonded nonwoven fabric, as well as a
hollow fiber for artificial kidneys, earned on outstanding
reputation in their fields.
The mechanical properties of some commercial sta-
ple fibers were listed, e.g. the dry and wet tensile
strength of cotton is 2.4–3.6 and 2.6–4.0 cN dtex−1 ,
2.4–2.6 and 1.0–1.3 cN dtex−1 for Viscose rayon, 3.4–3.6
and 1.9–2.1 cN dtex−1 for Modal fiber, 4.0–4.2 and
3.4–3.6 cN dtex−1 for Tencel, 2.6–3.0 and 1.8–2.2 for Bem-
berg staples, 2.8–5.5 and 3.0–5.5 cN dtex−1 for Polyethy-
lene terephthalate (PET), 2.5–6.0 and 2.5–6.0 cN dtex−1 for
polypropylene (PP) and 3.2–3.6 cN dtex−1 (dry state) for
polylactic acid (PLA), respectively. And the water reten-
tion of cotton, viscose, Modal, Tencel, PET and PP are
45%, 100%, 65%, 70%, 5% and 0%, respectively [148]. Obvi-
ously, the wet tensile strength of the regenerated fibers
was lower than dry state, due to the water retention fea-
ture. On the other hand, life cycle assessment is usually
applied to assess the environmental impact of industrial
products, and according to Lenzing [148] an integrated
fiber-pulp production leads to much lower environmen-
tal impacts than the separate production of pulp and
fibers. The Lenzing fiber products (Viscose, Modal and Ten-
cel fibers) have better environmental profiles than PET
and cotton, regarding environmental impact indicators as
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
Fig. 6. SEM image of the Lyocell fibers [13], Copyright 2001. Reproduced with permission from Elsevier Ltd.
global warming potential, abiotic depletion, ozone layer
depletion, human toxicity, fresh water aquatic ecotoxicity,
terrestrial ecotoxicity, photochemical oxidation, acidifi-
cation, and eutrophication. Specifically, the regenerated
cellulose fibers cause comparatively insignificant impacts
to human toxicity, fresh water aquatic ecotoxicity and
eutrophication, and all regenerated cellulose fibers, PET, PP
and cotton have minor contribution to ozone layer deple-
tion and photochemical oxidant formation, while the fresh
water aquatic ecotoxicity and terrestrial ecotoxicity of cot-
ton is very high.
Müller et al. recruited the non-woven fabrics (Tencel® ,
Lenzing, Austria) as scaffolds for in-vitro cartilage tissue
engineering, after being activated in Ca(OH)2 and sub-
sequently coated with a calcium phosphate layer from
a supersaturated physiological solution, leading to sig-
nificantly improved cell adherence of chondrocyte cells
[149]. Via the Biocelsol® procedure, enzymatic treated
cellulose was dissolved in NaOH/ZnO, followed by a
large-laboratory-scale wet spinning technique, to give
regenerated fibers with tenacity of 1.8 cN dtex−1 , elonga-
tion of 15% and titer of 1.4 dtex. The average molecular
weights and shape of molecular weight distribution curves
of the resultant fibers were close to the commercial viscose
rayon, demonstrating the Biocelsol® process as a poten-
tial option for replacing the viscose method, due to the the
elimination of CS2 [140,150].
Zhang and coworkers successfully fabricated regener-
ated cellulose multi-filaments via a pilot-scale spinning
equipment from cellulose solution in NaOH/urea, as
shown in Fig. 7 [151,152]. The multi-filament have a
circular cross-section and a smooth surface, as well as
good mechanical properties (tensile strength reaches
1.9–2.2 cN dtex−1 ), with no sulfur or nitrogen remaining
in the sample [151,153]. Chu and coworkers confirmed
with the WAXD results that an increase in flow rate during
spinning produced a better crystal orientation and a higher
degree of crystallinity, and the regenerated fibers coagu-
lated in the H2 SO4 /Na2 SO4 coagulant at 15 ◦ C exhibited the
highest crystallinity and a crystal orientation comparable
to commercial viscose rayon [154]. Moreover, a pilot-scale
industrialized trial with a dissolution tank of 1000 L
179
capacity yielded regenerated fibers spun successfully from
the cellulose dope [155]. NaOH/thiourea solvent was also
successfully applied to pilot-scale spinning, and to obtain
regenerated multi-filaments with tensile strength reached
1.9–2.2 cN dtex−1 [18,156].
Cellulose dopes in ionic liquids are also suitable for fiber
spinning via a dry-wet spinning process [157]. In a specific
procedure, a cellulose dope was transferred to a single-hole
spinning cylinder under a nitrogen atmosphere and heated
to 100 ◦ C, to extrude fibers spun at 100 ◦ C under nitrogen
(0.5 MPa) through a single-hole spinneret. The extruded
dope passed through a 5 cm long air gap before entering
a distilled-water coagulation bath at room temperature
to fabricate the fibers with smooth surfaces and round
cross-sections, as shown in Fig. 8 [158], as well as good
tensile strength [159]. The spinning speed influenced the
spinning of cellulose/1-butyl-3-methylimidazolium chlo-
ride solution, and when higher spinning speeds applied
the higher spinline stress led to a higher capacity as well
as higher tenacity of the regenerated fibers, as a result of
the crystallinity and orientation enhancement [160]. Sixta
and coworkers reported strong cellulose filaments fab-
ricated from cellulose/1,5-diazabicyclo[4.3.0]non-5-enium
acetate via dry jet-wet spinning, showing equal or better
properties than Tencel. This spinning process was robust
and simple, with stretching to a draw ratio of 5 effect-
ing most improvement in the tenacities and moduli [161].
Furthermore, regenerated cellulose fibers with diameter
ranged in hundreds of nanometers have been fabricated
using ionic solutions by an electro-spinning step and water
as coagulant, with dimensions dominated by the cellulose
concentration in the ionic liquids [162,163].
3.3. Cellulose films and membranes
Transparent films fabricated from cellulose mainly via
viscose method (cellophane) and cuprammonium process
(cuprophane) are still important roles for food casing,
cosmetics, medicals/pharmaceuticals packaging and pres-
sure sensitive tapes. However, polyolefine films edged
cellulose films off the market, due to the less complicated
and less expensive manufacturing process. Compared
180 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 7. Photographs of pilot-scale spinning machine and regenerated cellulose fibers (up), SEM images of regenerated cellulose fibers with different draw
ratio (middle), and SAXS and optical microscopy images of the fibers (down) [151], Copyright 2007. Reproduced with permission from John Wiley & Sons
Inc.

with common synthetic polymer films (PP and PET),
cellophane exhibits lager tensile strength (20–100 MPa)
and smaller elongation (15–40%) [32], as do Lyocell® films
(50–300 MPa and 2–40%) [13].
Zhang and coworker have developed new cellulose
films via low temperature solvents. The cellulose solution
in NaOH (or LiOH)/urea was cast on a glass plate to give
a gel sheet with thickness of 200–300 ␮m, and then
immersed in coagulant to regenerate, followed by wash-
ing, plasticizing and drying. The resultant films possessed
homogenous structure, excellent optical transmittance
(90% at 800 nm), good tensile strength (100 MPa) and could
be completely biodegraded in soil at about 30 ◦ C within one
month, showing a promising application in packaging field
[164]. All-cellulose nanocomposite films were fabricated
by blending the cellulose whiskers and cellulose solution
in NaOH/urea with cooling on the basis of the solubility
dependence on the temperature and the molecular weight
of cellulose. The cellulose composite films reinforced by
the cellulose whiskers had high tensile strength (124 MPa)
and elastic modulus (5 GPa), and the tensile strength
could reach 157 MPa through a simple drawing process
[165]. Moreover, transparent regenerated cellulose films
were prepared by Isogai and coworkers, which exhibited
high oxygen barrier properties ranging from 0.003 to
0.03 mL ␮m m−2 day−1 kPa−1 at 0% relative humidity,
depending on the coagulants (H2 SO4 , H2 SO4 /Na2 SO4 ,
ethanol, t-butanol and acetone at different temperatures).
The oxygen permeability values of the films were nega-
tively correlated with their densities and correlated with
the relative humidity, as shown in Fig. 9, demonstrating
promising potentials as packaging materials [166]. The
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 181

Fig. 8. Regenerated cellulose fibers produced from cellulose/ionic liquid (left) and SEM images of cross-sectional fracture of the regenerated cellulose fibers
(right). Left: [157], Copyright 2010. Reproduced with permission from Acta Polymerica Sinica; Right: [158], Copyright 2007. Reproduced with permission
from John Wiley & Sons Inc.

films regenerated from cellulose in LiOH/urea exhibited
pore size from 21 to 52 nm, and can be applied to waste
water treatment, in which the organic matters with
molecular weight lager than 20,000 effected significantly
on the membrane pore density [167]. Yan and coworkers
fabricated flexible, transparent and very strong regener-
ated films by cross-linking cellulose with epichlorohydrin
(ECH) in NaOH/urea, resulting in a low coefficient of
thermal expansion of about 6.9 ppm K−1 , superior to that
of glass [168]. Furthermore, Xu and coworkers presented
a novel method to prepare cellulose hydrated membranes
in NaOH/thiourea by employing a pre-gelation process,
during which a non-solvent induced phase separation
mechanism led to the formation of the hydrated mem-
brane. The membranes were densely packed, and exhibited
a homogeneous bulk structure and good mechanical prop-
erties, suggesting potential application in the drug delivery
devices and food engineering [169].
Yousefi and coworkers constructed all-cellulose films
with cellulose microfibers in ionic liquid by nano-welding.
The cellulose microfiber suspension was vacuum fil-
tered, dried and hot-pressed to yield microfiber films.
The microfiber films were immersed in 1-butyl-3-
methylimidazolium chloride and then regenerated in
methanol, followed by cold-pressing and drying, to give a
hybrid structure reinforced with undissolved nano-fibrils
(with the average diameter of 53 nm). The films exhibited
high mechanical properties, high transparency, biodegrad-
ability and complete barrier to air, showing potential
applications in packaging. Omitting the step of cellulose
nanofiber production made the direct production of all-
cellulose nanocomposite from cellulose microfibers easier,
shorter, and cheaper than using cellulose nanofibers as
starting material [170,171]. Similar processes were also
recruited in different solvents to give all-cellulose films,
such as LiCl/DMAc [172] and NaOH/poly(ethylene glycol)

Fig. 9. (a) Effects of relative humidity on oxygen permeabilities of the cellulose film and cellophane. The cellulose film was prepared from 6 wt% filter
paper pulp cellulose solution in LiOH/urea by regeneration with acetone at 20 ◦ C. (b) UV–vis transmittance and appearance of an approximately 50 ␮m
thick cellulose film prepared from 5 wt% filter paper pulp cellulose solution in NaOH/urea by regeneration with 5 wt% H2 SO4 at 0 ◦ C [166], Copyright 2011.
Reproduced with permission from the American Chemical Society.
182 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
Fig. 10. Optically transparent nanofiber paper (left) composed of 15 nm
cellulose nanofibers (upper left, scale bar in inset: 100 nm) and conven-
tional cellulose paper (right) composed of 30 mm pulp fibers (upper right,
scale bar in inset: 200 ␮m) [174], Copyright 2009. Reproduced with per-
mission from John Wiley & Sons Inc.
[173], with improved mechanical properties due to the
undissolved cellulose fibers acted as reinforcement in the
matrix. Furthermore, Nogi et al. dispersed fibrillated cel-
lulose fibers with diameter around 15 nm in water with
stirring, and optically transparent paper can be obtained
after vacuum filtration and hot-pressing. The transpar-
ent paper was foldable and with low thermal expansion
(<8.5 ppm K−1 ) with the same chemical constituents as
conventional paper but different fiber width and pore size,
as shown in Fig. 10. The optically transparent nanofiber
paper could be a perfect match as substrates for continuous
roll-to-roll processing, as well as potential substitution to
glass substrates [174].
3.4. Cellulose hydrogels and aerogels
Hydrogels network structures obtained by physi-
cal aggregation or chemical cross-linking contain large
amounts of retained water [175,176]. Cellulose hydrogels
are attracting attention due to their low cost, hydrophility
and inherent advantages of safety, biocompatibility and
biodegradability, etc. Zhang and coworkers fabricated a
series of cellulose hydrogels directly from the cellulose
solution followed by cross-linking with ECH via heating
or freezing; heating led to macro-porous inner struc-
ture while a fiber-like structure was induced by freezing
[177,178]. The cellulose hydrogels prepared via heating
were transparent, with the equilibrium swelling ratios
in distilled water in the range from 30 to 60 g·H2 O/g
dry hydrogel at 25 ◦ C [179]. Moreover, novel onion-like
and multi-layered tubular cellulose hydrogels were con-
structed from the cellulose solution in NaOH/urea by
changing the shape of the agarose gel cores. Specifically,
rod or sphere gel core with a thin layer of cellulose solu-
tion was immersed in 10 wt% acetic acid to prepare the first
cellulose layer, with a multi-layered cellulose hydrogels
generated by repeating this process, followed by immers-
ing in hot water to remove the agarose gel core, as shown in
Fig. 11. The size, layer thickness and inter-layer space of the
hydrogels were controlled by adjusting the cellulose con-
centrations, the gel core diameter and the contacting time
of the solid-liquid interface, and the multi-layered cellulose
hydrogels displayed good architectural stability and sol-
vent resistance, as well as high compressive strength and
excellent biocompatibility, exhibiting potentials as bioma-
terials [180].
Gindl et al. fabricated regenerated cellulose hydrogels
from LiCl/DMAc by slow coagulation with water. After
exposing to an alternating current electric field, the orien-
tation of cellulose molecules developed in both crystalline
and amorphous regions. The orientation hardly changed
for several days after storage in water and persisted
after drying of the gel [181]. Kadokawa et al. prepared
flexible cellulose hydrogel composed of cellulose, water
and ionic liquid from 1-butyl-3-methylimidazolium chlo-
ride by keeping the cellulose/ionic liquid/water system at
room temperature for days, in which the cellulose crys-
talline structure in the material was largely disrupted.
When heated to 120 ◦ C, the material became soft, and was
converted into a fluid at 150 ◦ C, giving a “smart” phase tran-
sition behavior [182].
As porous ultra-light materials derived from hydrogels,
in which the liquid component has been replaced with
gas, aerogels have gained attention, due to the ultra-small
density, high porosity, high specific surface area [183],
showing potential applications in separation, absorption,
catalyst, photo-electricity, sensors or biomedicine. Usu-
ally, cellulose aerogels can be fabricated by critical point
drying or specific freeze–drying protocols, and their struc-
ture and properties are dependent on both the hydrogel
of aerogel precursor as well as the fabrication process
[184–186]. Kuga and coworkers fabricated cellulose hydro-
gel composed of interconnected fibrils in alkali/urea by
coagulating. After solvent exchange the gel was subjected
to supercritical CO2 drying to obtain a cellulose aerogel.
The surface areas of the aerogels may be controlled in
the range of 400–500 m2 g−1 , potentially useful as adsor-
bents, heat/sound insulators, filters, catalyst supports, or
carbon aerogel precursors [187]. By solvent-exchange and
supercritical drying, Panayiotou and coworkers fabricated
nano-porous aerogels, while a foaming procedure (under
high pressure at the desired conditions) produced micro-
porous structures of cellulose and cellulose composites
with high surface area, low density, and large porosity [5].
The structures of cellulose aerogels prepared by regenerat-
ing hydrogels from ionic liquid, NaOH aqueous solution and
NMMO, followed by drying in supercritical CO2 were com-
pared by Budtova and coworkers. Their porosity strongly
depended on the regeneration conditions, and can be
varied by foaming in the presence of surfactants. The “bead-
like” morphology of aerogel from cellulose/ionic liquid was
similar to the one from “molten” cellulose/NMMO mono-
hydrate, different from the “net-like” morphology of aero-
gel from solid cellulose/NMMO monohydrate or gelled cel-
lulose/NaOH/water solutions, as shown in Fig. 12 [188,189].
Ratke prepared cellulose hydrogel from cellulose
solution in hydrated calcium thiocyanate melt, and
fabricated aerogel and cryogel by supercritical dry-
ing and freeze–drying, respectively. The freeze–drying
led to a cryogel with cracks and brittleness, while the
super-critical drying was the most effective method for
homogeneous aerogels, with the surface area of aerogels
reaching 250 m2 g−1 compard with 160 m2 g−1 for cryogels
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 183

Fig. 11. Schematic model to describe the formation of the multi-layered cellulose hydrogel via fast solution−solid interfacial interaction (upper left);
photographs of the multi-layered tubular cellulose hydrogels (upper right), SEM images of the cross-section of the freeze-dried multi-layered tubular
cellulose gels (lower left), and fluorescent images of cells cultured on cellulose hydrogels for 2 days (lower right) [180], Copyright 2014. Reproduced with
permission from the American Chemical Society.

[190]. By using LiCl/dimethyl sulfoxide (LiCl/DMSO) as
cellulose solvent, Wang et al. also prepared translucent
cellulose hydrogels with ethanol as coagulant, and then
converted to highly porous aerogels via solvent exchange
drying, composed of relatively straight fibril segments
with 20 nm wide and 100–1000 nm long [191]. On the
basis of an ice-template, the cellulose aerogels with an
aligned, columnar and open porosity were fabricated from
cellulose/NaOH/urea solution frozen from the bottom
side, leading to a directional ice crystal growth. Then a
structured porous cellulose network was achieved after a
complete solidification and sublimation of the ice crystals
by freeze–drying, providing a novel pathway to control
the material structures in macro-scale [192]. Chatenet
and coworkers prepared carbonized aerogels after pyrol-
ysis of the cellulose aerogels under nitrogen flow, and
subsequently doped by platinum nanoparticles, showing
potential applications in proton exchange membrane fuel
cell [193].
3.5. Cellulose microspheres and beads
Microspheres/beads have wide applications in various
fields, such as chromatography, separation technology,
sorbent, biocatalyst immobilization and carriers [194].
According to the definition by Fardim and coworkers cel-
lulose microspheres and beads are defined as: (i) spherical
particles with diameters larger than several micrometers;
(ii) prepared via the dissolution, shaping and regeneration
of cellulose; (iii) exclusively composed of cellulose and
fixed in their spherical shape by re-establishment of the
hydrogen bonding network and typical cellulose–cellulose
interactions [195]. Usually, dropping and dispersion
procedures are applied in the fabrication of regenerated
cellulose microspheres/beads, with the latter already
commercialized.
Budtova and coworkers fabricated cellulose beads from
very thin plates to spheres, from cellulose/NaOH solution
by dropping in water bath. The spherical shape of the beads
improved with increased solution viscosity and weaker
shock of the falling droplet on the bath surface [196].
Regenerated cellulose microspheres were fabricated from
cellulose solution in NaOH/urea by the dispersion approach
in paraffin oil, and the mean diameter of the microsphere
with nano-scale pore size was controlled from 5 ␮m
to 1 mm. A preparative size-exclusion chromatography
column packed with the microspheres demonstrated
high efficiency for the fractionations, suggesting potential
184 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 12. SEM images of cellulose aerogels from 3% cellulose/EMIMAc solutions (upper left), cellulose aerogels from 5% cellulose/NaOH/water (upper right),
cellulose aerogels from molten 3% cellulose/NMMO (lower left) and cellulose aerogels from solid 3% cellulose/NMMO. Upper left: [188], Copyright 2008.
Reproduced with permission from the American Chemical Society; Remainder: [189], Copyright 2011. Reproduced with permission from Elsevier Ltd.

applications in the fields of purification, separation and
fractionation of polymers [197]. Regenerated cellulose
beads were prepared using 1-butyl-3-methylimidazolium
chloride and an improved double emulsification method,
and followed by modification with diethylaminoethyl
chloride after cross-linking. The beads demonstrated a
pore diffusivity for bovine serum albumin was over 6.7
times higher than that for Sepharose 6 Fast Flow (a com-
mercial absorbent) [198]. Yao and coworkers preapared
macro-porous beads from cellulose xanthogenate viscose
densified by high-density tungsten carbide via water-in-oil
suspension thermal regeneration, with starch as porogenic
agent, with subsequent elimination of the starch after
bead formation, as shown in Fig. 13. The properties of
the composite beads, such as water content, porosity and
mean pore diameter were significantly improved with the
introduction of starch, and the mass transfer kinetic inside
the macro-porous matrix was enhanced, which could ben-
efit the chromatographic operation under high flow rate
[199].

Fig. 13. Morphology of prepared macroporous composite beads (left) and expansion factors of macroporous composite beads (right) [199], Copyright 2007.
Reproduced with permission from Elsevier Ltd.
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
3.6. Cellulose bioplastics
Plastics, well-known to be shaped or undergo plastic
deformation when processed under appropriate condi-
tions, dominate the annual consumption market [200],
and bioplastics, produced from renewable resources rather
than fossil–fuel sources, are capable of solving serious
environmental problems [201,202]. Zhang and cowork-
ers constructed novel cellulose bioplastics (CBP) from the
cellulose hydrogels prepared from cellulose solution in
NaOH/urea via simple hot-pressing [203]. On the basis of
the removal of cellulose molecules in the hydrogel state,
the hot-pressing induced the transition of its aggregated
structure, with a radial orientation of the cellulose aggre-
gates occurred in the planar direction of the plate, leading
to the plastic deformation, as shown in Fig. 14. The CBP
exhibited excellent properties compared with common
commercial plastics, such as excellent mechanical proper-
ties (the tensile strength and modulus of the CBP reached
240 MPa and 3.7 GPa), good thermal stabilities and low
coefficients of thermal expansion. The coefficient of ther-
mal expansion of the CBP were 13–48 × 10−6 K−1 , lower
than common plastics (acrylonitrile–butadiene–styrene
(ABS) copolymer, polycarbonate (PC), polyethylene (PE),
polyvinyl chloride (PVC) and polybutylene terephthalate
(PBT), (47–317 × 10−6 K−1 )). Furthermore, the environ-
mental impact of biomass conversion to CBP as well as
petroleum to PE were evaluated via life cycle assessment
and analytic hierarchy process, revealing the environ-
mental load of the CBP was at least 70% less than PE
from the local, regional and global perspectives, indicat-
ing CBP is not only environmentally friendly but also could
reduce the adverse effects contributing to global warm-
ing.
4. Cellulose based composite materials
Regenerated cellulose composites can be physically
constructed from cellulose solutions in the presence of
organic/inorganic/polymeric molecules via blending with
subsequent modification, etc. [204] Regenerated cellulose
fibers, films/membranes, hydrogels, etc., may be used for
in-situ synthesis as micro-reactors due to the micro-/nano-
porous structure, to obtain cellulose hybrid materials. Such
approaches endow the regenerated cellulose materials
with various functions and properties, greatly expand their
applications in different fields.
4.1. Cellulose composite fibers
Cellulosic composite fibers may be obtained by blend-
ing cellulose solutions with organic/inorganic substances.
Linhardt and coworkers spun core–sheath multi-walled
carbon nanotubes (MWNT)/cellulose fibers with diam-
eters from several hundreds of nanometers to several
micrometers by coaxial electro-spinning from cellulose/(1-
methyl-3-methylimidazolium acetate) solutions as a
sheath and MWNT gelable in the same ionic liquid as the
core solution. The resultant fibers had a cable structure
with a conductive core and insulating sheath, with the
excellent conductivity that is critical in actuator design
185
[205]. Cellulose/NaOH/urea solution did not produce
fibers via electro-spinning. However, after introduction
of high molecular weight polyethylene glycol (PEG),
PEG/cellulose composite fibers with diameter around
400 nm were electro-spun [206]. A dry-jet wet-spinning
process incorporated MWNT in regenerated cellulose fibers
in 1-allyl-3-methylimidazolium chloride (Fig. 15). The
MWNT/cellulose fibers exhibited improved mechanical
properties and thermal stability, due to the strong inter-
actions between cellulose and MWNTs [158]. Kumar and
coworkers also spun MWNT/cellulose fibers by the same
technique in ethyl methylimidazolium acetate, and the
MWNT orientation was higher than cellulose in the com-
posite fiber, leading to lower thermal shrinkage and an
axial electrical conductivity over 3000 S/m, which can
be used as electronic textiles or thermal barrier fabrics
[207]. Following a similar pathway, Rogers and cowork-
ers fabricated magnetically active cellulose fibers by dry-jet
wet spinning cellulose/Fe3 O4 blend solution in 1-ethyl-3-
methylimidazolium chloride, as shown in Fig. 16, showing
deterioration in both the tensile strength and failure strain
following the addition of the magnetite powder [208].
Furthermore, Araki et al. obtained cellulose/polyrotaxane
composite fibers by wet-spinning the blend solution in
LiCl/DMAc, with methanol as coagulant, resulting in fibers
with tunable mechanical properties [209].
The micro/nano-porous structure in the wet cellulose
fibers and the pores can be utilized as micro-reactors for
in-situ synthesis of inorganic nanoparticles or a secondary
polymer network. Fe2 O3 nanoparticle with size of 18 nm
were synthesized and immobilized in the cellulose fibers,
and the nanocomposite fibers had not only good mechani-
cal strength but also strong absorbance of UV, important to
functional fabrics and protective clothing [210]. Further-
more, 1D fiber-like Fe2 O3 nanomaterials prepared from
the Fe2 O3 /cellulose fibers by calcination to remove the
cellulose matrix displayed superior electrochemical activ-
ity (a discharge capacity of 2750 mAh g−1 ) as shown in
Fig. 17 [211]. Mäder and coworkers fabricated cellulose
fibers with carbon nanotube networks for water sensing, by
dip coating commercial viscose cellulose fibers in MWNT
suspensions for different dipping repetitions. The compos-
ite fibers exhibited rapid response, high sensitivity and
good reproducibility to water, with a relative electrical
resistance change of about 100–8000% depending on the
initial resistance, attributed to the disconnection of MWNT
networks caused by swelling effects of the cellulose fibers
[212].
Cellulose-based complex fibers from hydrophilic cel-
lulose and hydrophobic polyaniline (PANI) have been
prepared with objective of fibers with antistatic proper-
ties. PANI doped with acidic phosphate ester was dissolved
in the cellulose/NaOH/urea solution at low temperature,
forming a PANI/cellulose supra-molecular complex solu-
tion through hydrogen bonds. The PANI/cellulose solution
was more stable than the cellulose solution, indicating
good processability of PANI [213,214]. The PANI/cellulose
composite filament fibers were spun by wet spinning,
which did not require external doping to render the con-
ductivity, demonstrating a non-toxic and simple pathway
for the antistatic fiber fabrication [215].
186 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 14. Photogram of the cellulose bioplastic (a), an image perpendicular to the cellulose bioplastic surface under polarized light (b), representative
stress–strain curves of CBP, PBT, PVC, PC and ABS (c), SEM image of the inner part of CBP (d), swollen ratios of CBP, PC, PVC, PBT, and ABS in DMSO, acetone,
THF, toluene, hexane and H2 O at ambient temperature after 24 h (∞ = dissolution) (e), the CTE values of CBP, PC, PE, PVC, PBT, and ABS in the direction of
the thickness of the sample (f) [203], Copyright 2013. Reproduced with permission from the Royal Society of Chemistry.

4.2. Cellulose composite films and membranes
Fluorescent and photo-luminescent cellulose films have
been fabricated by treating the never-dried regenerated
films with fluorescent dyes, which exhibited strong fluores-
cence [164]. Composite cellulose films with long after-glow
emission were prepared from the cellulose solution con-
taining photoluminescent (PL) alkaline earth aluminates
embedded in the cellulose matrix in the PL films, as shown
in Fig. 18. The photo-luminescent films could emit a visi-
ble light for more than 10 h in the dark after being exposed
to sunlight for 10 min. Dark green and transparent com-
posite films were constructed facilely from PANI/cellulose
solution, displaying highly homogeneous structure, good
miscibility, excellent mechanical properties and conduc-
tivity, as shown in Fig. 19 [213].
Mäder and coworkers reported that the multifunctional
regenerated MWNT/cellulose films had both normal flex-
ible paper and conducting MWNT characteristics with
2–10 wt% MWNTs, showing a controlled volume resistiv-
ity over a wide range (1.35–540  cm), as shown in Fig. 20.
The films achieved multifunctional sensing ability for
monitoring stress–strain, temperature and humidity, lead-
ing to potentials in electronic, magnetic, semiconducting
and biotechnological applications [216]. The regenerated
MWNTs/cellulose films can also be applied as water sensor,
whose sensitivity was mainly caused by the hygroscopic
swelling of the cellulose matrix, demonstrating a high
selectivity for water/ethanol solutions with different water
fraction [217].
Isogai and coworkers fabricated transparent and water
repellent gas barrier cellulose films, by surface modifying

Fig. 15. A schematic of the dry-jet wet-spinning process for cellulose fiber (left), photograph of the regenerated cellulose and cellulose/MWNT composite
fibers (middle), and SEM images of cross-sectional fracture of the cellulose/MWNT composite fibers (right) [158], Copyright 2007. Reproduced with
permission from John Wiley & Sons Inc.
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 187

Fig. 16. Magnetite-embedded cellulose fiber (upper left), SEM images of magnetite-embedded MCC fibers (upper right), magnetic property of the fibers
(lower left) and hysteresis loops of peach pulp fibers made with 10% (a), 20% (b), and 30% (c) Fe3 O4 (lower right) [208], Copyright 2008. Reproduced with
permission from the Royal Society of Chemistry.

Fig. 17. (a) Schematic illustration for the formation of the fiber-like Fe2 O3 nanomaterials. (b and c) photographs of the regenerated cellulose composite
fibers. (d) SEM images of the fiber-like Fe2 O3 macroporous nanomaterials, (e) cycle performance of the electrode made from fiber-like Fe2 O3 nanomaterials,
respectively [211], Copyright 2008. Reproduced with permission from the American Chemical Society.
188 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
Fig. 18. Afterflow decay curve (left) and photograph (middle) of afterglow for 5 s of luminescent films: (a) RC-F4 (films prepared from alkaline earth
aluminate CaAl2 O4 :Eu2+ ); (b) RC-F5 (films prepared from alkaline earth aluminate SrAl2 O4 :Eu2+ ) (Samples were irradiated by 365 nm UV light for 10 min
before measurement), and SEM images of the luminescent films (right) [164], Copyright 2009. Reproduced with permission from the Royal Society of
Chemistry.
cellulose films regenerated from alkali/urea via succes-
sively soaking in cationic alkylketene dimer dispersion,
drying and heating. The cellulose films exhibited oxy-
gen transmission rates of 0.0005 mL m−2 day−1 kPa−1 at
0% relative humidity and water contact angles of 110◦
[218]. During the heating treatment, the alkylketene dimer
molecules melted and transformed into spherical nanopar-
ticles (∼37 nm in diameter) on the film surface, forming
“sea/island”-like structures, contributing to the hydropho-
bicity of the films [219]. They also prepared transparent and
flexible cellulose/montmorillonite nanocomposite films,
via dissolving cellulose in montmorillonite dispersed
LiOH/urea aqueous solution followed by regeneration in
acetone. The formation of regular intercalated nanolayered
structures of montmorillonite platelets in the cellulose
matrix led to improvements of film properties, as a result
of the high aspect ratio of the montmorillonite platelets
and their nanolayered structure [220]. Moreover, Yan and
coworkers prepared cellulose/graphite oxide blended film
by dissolving cellulose in NaOH/urea/graphite oxide aque-
ous suspension, followed by coagulation in H2 SO4 to obtain
composite films with a 98% increase in the tensile strength
and a 60% improvement in Young’s modulus, in which
7.5 wt% graphite oxide was immobilize in the cellulose
matrix [221]. Coma and coworkers reported the bio-based
films by blending and casting chitosan/cellulose solution
in NaOH/thiourea, and an increase in chitosan content led
to higher tensile strength and the percentage of elongation
[222,223].
Ionic liquids were also widely utilized to fabri-
cate cellulose functional films. Highly ordered, flexible,
homogeneous and reinforced cellulose/graphene oxide
composite films were fabricated by Hao and coworkers by
blending in 1-butyl-3-methylimidazolium chloride, with
obviously enhanced mechanical properties [224]. Push-
paraj et al. grew vertically aligned MWNTs on silicon by
thermal-chemical vapor deposition, and then embedded
and infiltrated the MWNT matrix with cellulose solution
in 1-butyl,3-methylimidazolium chloride. After regenera-
tion, a nano-composite paper as the super-capacitor was
obtained, serving as building blocks for a variety of thin
mechanically flexible energy storage devices, as a result
of the parallel alignment of the MWNTs in the cellulose
matrix, as shown in Fig. 21. These ultrathin, flexible, safe
energy storage devices were capable of meeting the various
design and power needs of modern gadgets [225].
Wang and coworkers constructed composite mem-
branes via casting and coagulating after blending cellulose,
starch and lignin in 1-allyl-3-methylimidazolium chloride,
to give membranes with a wide range of CO2 :O2 perme-
ation ratios (1.05–1.67), exhibiting potential applications
as fresh food packaging [226]. By blending cellulose solu-
tion in 1-butyl-3-methylimidazolium chloride with laccase
solution in a secondary IL, Rogers and coworkers pre-
pared low-leaching bioactive cellulose films after casting
and regeneration. Pre-coating the enzyme with a sec-
ond, hydrophobic IL prior to dispersion in the cellulose/IL
solution improved the enzyme activity relative to the
untreated film, making it ready for reactions and sensing
systems [227]. They also prepared surface-active cellulose
films by co-dissolution of cellulose with polyamidoamine
dendrimers in 1-butyl-3-methylimidazolium chloride fol-
lowed by regeneration, with 1,3-phenylene diisocyanate
as a linker to obtain the films, which exhibited better per-
formances for immobilization of laccase [228]. By using
the same cellulose solution, 1-(2-pyridylazo)-2-naphthol
as a valuable extractant and indicator for metal ions was
dissolved and blended homogeneously to give cellulose
hybrid films, that could be applied to the colorimetric
determination of Hg2+ , Zn2+ , Mn2+ and Ni2+ in aqueous
solution as shown in Fig. 22 [229,230].
In addition, the nitrogen oxide (NOx ) sensors and
storage devices have been fabricated by utilizing the
ability of ILs to co-dissolve cellulose and gas-sensing
calix[4]arenes (which reacted with NOx to form stable
calix[4]arene–NO+ complexes, mechanistically stabilized
through the strong charge-transfer interactions between
NO+ and the -surfaces of the calix[4]arene cavity [231]),
followed by blending, casting and regeneration. The sen-
sors may be exposed directly to NOx gas for quick
colorimetric calixarene–NO+ complexation, that may be
rapidly or slowly reversed by humidity, depending on the
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 189

Fig. 19. Photo (a) and SEM image (b) of PANI/cellulose films, stress–strain curves of the cellulose and PANI/cellulose films (c), and dependence of logarithmic
conductivity varied as a function of the PANI content in the PANI/cellulose (bottom) and PANI/cellulose/carbon black (up) films (d) [213], Copyright 2011.
Reproduced with permission from the American Chemical Society.

desired application (e.g., sensing vs. storage) [232]. Rice
husk and natural wool were reported to disperse in IL
to blend with dissolved cellulose to form eco-composite
films with improved mechanical properties, giving the
potentials in the comprehensive utilization of the agri-
cultural wastes [233,234]. Moreover, Kim and coworkers
constructed cellulose/MWNT paper transistors via cur-
ing and drying processes in sequence after spin-coating
the cellulose/MWNT solution, prepared by chemical reac-
tion between dissolved cellulose and imidazolide attached
MWNTs, in LiCl/DMAc. The leakage current and the on/off
ratio of the paper transistors were strongly associated
with the MWNT concentration, and the estimated electron
mobility of the paper was comparable to other organic tran-
sistor materials, indicating potentials for flexible electronic
paper, as well as chemical sensors [235,236].
Mann and coworkers reported another pathway to
fabricate blend films by dispersing nanoparticles in the
coagulant. Specifically, cellulose solution in NMMO/DMSO
co-solvent was spin-coated and then coagulated in an Au
nanoparticles aqueous colloid. The resultant cellulose com-
posite films were electrically conducting with Au loading
of higher than 20 wt%, and exhibited either band-like or
variable-range hopping conductivity, depending on the
Au loading. These properties led to potentials in “smart”
papers and textiles, microelectronic components, catalysts
and chemical sensors, as shown in Fig. 23 [237].
Zhou and coworkers reported regenerated films
coated with copper nanoparticles by coagulation
cellulose/cuprammonium solution in NaOH and sub-
sequent reduction in NaBH4 . Cu2+ migrated from the inner
to the surface during the coagulation, and then reduced
190 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 20. Photo and SEM image of MWNT/cellulose films, and temperature and humidity sensitivity of the MWNT/cellulose composite film: (a) dependence
of electrical resistance on temperature and (b) dependence of fractional resistance (R/R0 ) and moisture adsorption (W/W0 ) on relative humidity (RH)
[216], Copyright 2013. Reproduced with permission from the Royal Society of Chemistry.

from Cu2+ to Cu0 . The composite films showed effi-
cient antibacterial activity against Staphylococcus aureus
and Escherichia coli [238]. Furthermore, single-sided Cu
nanoparticles-coated regenerated cellulose composite
films were prepared through a one-step reduction taking
advantages of the copper compound in the cuprammonium
solution. The coagulant-contacting (front) surface had a
porous structure coated with a layer of Cu nanoparticles
exhibiting high conductivity (105.6 ± 63.9 S cm−1 ), but the
back side was not coated with Cu due to its dense skinned
structure. Moreover, the conductivity of the conductive
surface had close relation to the bending curvature,
showing promising application as flexible electronic and
sensors [239].
Lucia and coworkers developed the preparation tech-
nology for core–shell cellulose/cellulose nanocrystal
nanocomposite films via a co-electrospinning technique.
Specifically, cellulose solution in NMMO was used in the
external concentric capillary needle as the shell solution,
and nanocrystal aqueous suspension as the core liquid
in the internal concentric capillary needle, and cellulose
films were collected on a metal screen under a cold water
bath, that could be an option for fabricating reinforced
nanofabric structure [240].
The micro/nanoporous structure of the regenerated
cellulose films can be used to fabricate inorganic nanopar-
ticles, because the abundant pores of the cellulose matrix
at the wet state supplied not only cavities for the formation
of nanoparticles, but also a shell to protect their nanostruc-
ture. Thus, cellulose/Fe2 O3 films have been synthesized by
using regenerated films at the wet state as templates and
FeCl2 as precursor followed by the NaOH treatment. The
Fe2 O3 nano-disks with 24 nm in width and 2.5–3.5 nm in
thickness were well aligned in the cellulose matrix to form
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 191

Fig. 21. (a) Schematic of the supercapacitor and battery assembled by using nanocomposite film units. (b) Photographs of the nanocomposite units
demonstrating mechanical flexibility. Flat sheet (top), partially rolled (middle), and completely rolled up inside a capillary (bottom) are shown. (c) Cross-
sectional SEM image of the nanocomposite paper showing MWNT protruding from the cellulose/RTIL thin films. (Scale bar, 2 ␮m.) The schematic displays
the partial exposure of MWNT [225], Copyright 2007. Reproduced with permission from the National Academy of Sciences.

Fig. 22. Structure of 1-(2-pyridylazo)-2-naphthol (PAN) and from left to right: unreacted sensor, partially reacted sensor, fully reacted sensor (left).
Absorption spectra of sensors after contact with various buffered pH solutions containing 50 ppm Hg(II) (black blank; red pH 3.4; green pH 4.0; yellow
pH 4.5; blue pH 5.0; cyan pH 5.5; purple pH 5.9) (Right) [229], Copyright 2007. Reproduced with permission from the Royal Society of Chemistry. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
192 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
Fig. 23. Photograph of wet Au nanoparticles AuNP/cellulose hybrid films
produced after 96 h by regeneration in aqueous colloids of variable AuNP
concentration; (i) 0.043, (ii) 0.058, (iii) 0.086, and (iv) 0.173 mg mL−1 (up),
and temperature dependence of plane resistivity () for AuNP/cellulose
films with Au content of 33 and 44 wt% showing changes in the nature of
electronic conduction [237], Copyright 2010. Reproduced with permission
from the American Chemical Society.
ordered multi-bilayer structure, and the composite films
displayed anisotropic magnetic properties [241]. Further-
more, the CdS nanoparticles were synthesized in-situ in
the pores of the regenerated cellulose substrate to prepare
the CdS nanoparticles/cellulose films, by treating cellu-
lose films with successive CdCl2 and Na2 S [242]. The CdS
nanoparticles with a mean particle diameter about 6 nm
were well dispersed and tightly immobilized in the cel-
lulose matrix, resulting in a portable photocatalyst with
high photocatalytic efficiency for H2 evolution under visi-
ble light irradiation. As shown in Fig. 24, the rate of the H2
evolution increased rapidly from 202 ␮mol h−1 for CD-005
to 808 ␮mol h−1 for CD-02, whereas the H2 yield gener-
ated by CdS particles alone was determined to be only
7.42 ␮mol h−1 under the same conditions. Moreover, the
photocatalytic ability for H2 evolution of the CdS nanopar-
ticles/cellulose films were much higher than those of both
Fig. 24. Schematic picture describing the photocatalytic reaction of the cellulose composite film containing CdS nanoparticles under sunlight (left). Time
course of hydrogen yield over Pt-loaded composite film CD-03 (middle). The rate of H2 evolution on CdS, CD-005, CD-02 and CD-03 under visible light
( > 420 nm) at room temperature (right) [243], Copyright 2011. Reproduced with permission from Springer.
the normal CdS catalyst and CdS nanoparticles embed-
ded in zeolite [243]. TiO2 /cellulose composite film were
also prepared by immersing the cellulose films in TiO2 sol
solution, followed by the NaOH treatment. The composite
films exhibited good photo-catalytic activity for photo-
degradation of phenol under weak UV light irradiation,
leading to potential applications in photo-degradation of
organic pollutant [244].
Graphene oxide/cellulose composite films may also be
used as template for in-situ synthesis, and, after treatment
with CuSO4 and NaOH to generate CuO, Cu2 O nanoparti-
cles were generated in the film via reduction by diluted
hydrazine hydrate. The graphene oxide in the cellulose
matrix proved to improve the photocatalyst activity, lead-
ing to potential applications for wastewater purification
utilizing solar energy [245]. Furthermore, highly hydropho-
bic cellulose composite films with biodegradability were
fabricated, to solve the hydrophilicity drawback of cel-
lulose. Stearic acid/cellulose films were constructed via
solvent-vaporized controllable crystallization of stearic
acid in the porous structure of cellulose films followed by
hot-pressing, due to the formation of a rough surface that
could trap abundant air, exhibiting potential applications in
packaging [246]. Subsequently, 12-hydroxyoctadecanoic
acid (HOA) was induced to grow along the hydrophilic
cellulose pore wall to form regular vertical wormlike-
like crystals with an average diameter of about 200 nm,
resembling the “short hair-growth” on the skin in the
nature, as shown in Fig. 25. The cellulose/HOA composite
films containing 4-(1,2,2-triphenylethenyl) benzoic acid,
an aggregation-induced emission luminogen, exhibited
high hydrophobicity, as a result of the formation of the
solid/air composite surface, leading to the bifunctional
photoluminescence and self-cleaning properties [247].
Regenerated cellulose films can also be used as sub-
strates for organic/inorganic coatings [248]. By means
of physical vapor deposition, Kim et al. deposited gold
electrodes on both sides of cellophane, producing a
large bending displacement with low actuation volt-
age and low power consumption. The cellulose papers
can be used for biomimetic sensor/actuator devices and
micro-electromechanical systems [249]. Moreover, SnO2
nanoparticles were created on regenerated films by immer-
sion in SnF2 solution at 90 ◦ C, and then enzyme glucose
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 193

Fig. 25. Scheme to describe the mechanism of the HOA crystal growth on cellulose gel (left), FESEM images of surface for the cellulose film with HOA
crystals (middle), and the photograph of the film with a water droplet under an UV lamp (right) [247], Copyright 2014. Reproduced with permission from
the American Chemical Society.

oxidase was immobilized on the cellulose/SnO2 films
by physical absorption, followed by covalent bonding
between glucose oxidase and SnO2 . The composite films
were able to cover the clinical region of glucose concentra-
tion, indicating potential use as an inexpensive, flexible and
disposable glucose biosensor [250]. Furthermore, Kitaoka
and coworkers prepared lactose-modified cellulose films
by incubating regenerated cellulose films with lactose
using a surfactant-enveloped cellulase in LiCl/DMAc, which
exhibited superior cell adhesion properties. In the absence
of serum, hepatocytes were significantly attached only on
the lactose-modified cellulose films, as shown in Fig. 26,
providing potentials as a bioactive scaffold for cell culture
engineering [251].
4.3. Cellulose composite hydrogels and aerogels
Functional cellulose hydrogels may be fabricated by
blending or incorporating a second phase in cellulose
solution. By blending cellulose and sodium alginate in
NaOH/urea with ECH as a cross-linker, composite hydrogels
were fabricated with a macro-porous structure and highly
swelling behavior, in which cellulose acts as the backbone
whereas sodium alginate contributes to the higher equilib-
rium swelling ratio [252]. Strongly fluorescent hydrogels
were fabricated by blending cellulose and quantum dots
(QDs) in NaOH/urea, followed by crosslinking with ECH.
The hydrogels exhibited strong photo-luminescence (PL)
emission and nearly pure color from green to red, depend-
ing on the size of the quantum dots (Fig. 27), providing a
new pathway for the preparation of safe and biocompatible
biopolymer/quantum dot hydrogels with a high efficiency
of photo-luminescence emission [253].
Safe and biocompatibile cellulose based hybrid hydro-
gels (CPH) have been constructed from cellulose solution
containing rare-earth doped phosphor (PP) in LiOH/urea,
exhibiting good compressive strength and processabil-
ity [254]. As shown in Fig. 28, the PP particles were

Fig. 26. Scheme of the fabrication of lactose modified cellulose (lac-modified) film (left), fluorescent microscopic images of modified and unmodified
cellulose films labeled with RCA120-FITC (middle), and microscopic images of IAR-20 cells cultured on lac-modified and unmodified cellulose film (right)
[251], Copyright 2009. Reproduced with permission from the American Chemical Society.
194 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 27. The appearances of the cellulose/QDs hydrogels under a 302 nm UV lamp (left), and PL spectra of CdSe/9nS (core/shell) QDs in buffer solution
(right, top) with emission peaked at 541 nm, 568.5 nm, 577 nm, 596 nm, and in the cellulose/QDs hydrogels (right, bottom) with emission peaked at
549.5 nm, 566.5 nm, 577 nm, 599 nm with a laser line at 400 nm used for excitation. The average diameters of the QDs nanocrystals are 2.8 nm (green),
3.0 nm (yellowish-green), 3.2 nm (yellow) and 3.6 nm (red) [253], Copyright 2009. Reproduced with permission from the Royal Society of Chemistry. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

tightly embedded in the macroporous cellulose matrix
through strong intermolecular hydrogen bonding interac-
tion, protecting the structure and character of PP, leading
to the emission of the relatively strong brightness and
long-lasting afterglow with lower cell autofluorescence
interference. Notably, CPH with a strong afterglow could
be detected both under the skin and in the stomach with
or without excitation light, showing a promising prospect
as a candidate for bioimaging.
It is noted that electro-mechanical hydrogels were con-
structed from PANI/cellulose solution. As shown in Fig. 29,
the pore walls were supported by the persistent chain
conformation of the cellulose and PANI entangled chains,
and the PANI/cellulose hydrogel exhibited a continuous
and linear crawling motion under a low applied electric
field [255]. Interestingly, ampholytic hydrogels with pH
and salt responsive properties by cross-linking quaternized
cellulose and carboxymethyl cellulose were synthesized,
in which the latter contributed to increased swelling as
a result of strong water adsorption, whereas the former
played a role in controlling the charges, leading to the pH
sensitivity [256].
Xu and coworkers fabricated cellulose hydrogels via
freezing cellulose/NaOH/thiourea solution, then swelled
them with low molecular weight poly(ethylene glycol)
(PEG) to obtain a high-strength cellulose/PEG gel. The com-
posite hydrogel exhibited better optical transmittance, and
the tensile strength increased sharply with the PEG molec-
ular weight as a result of the strong hydrogen-bonding
interaction between PEG and cellulose [257].
Functional hybrid aerogels may also be constructed
by incorporating organic/inorganic molecules in the

Fig. 28. Schematic diagram of the architecture of CPH (a), SEM images of the cross-section of CPH (b), photographs of CPH under visible light (c), photographs
of CPH in the dark after UV excitation (d), and merged images of the bright-field and the threshold false color of autofluorescence without a excitation light
under skin (e) [254], Copyright 2014. Reproduced with permission from the Royal Society of Chemistry.
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 195

Fig. 29. Photographs of PANI/cellulose hydrogel (upper left) and SEM images of cross-section for the hydrogel in freeze-dried state (upper right), and
the dependence of displacement and crawling velocity on driving time for the hydrogel under the a applied electric field (lower) [255], Copyright 2013.
Reproduced with permission from the Royal Society of Chemistry.

cellulose hydrogel matrix, followed by freezing–drying
or supercritical CO2 drying. Feng and coworkers blended
cellulose and graphene oxide sheets in NaOH/thiourea, and
the composite aerogels were obtained after regeneration
and the freeze–drying process. The hybrid aerogel was
attractive for a variety of biological and environmental
applications because of the improved mechanical prop-
erties (the compression strength and Young’s modulus
of the composite aerogels improved by about 30 and
90%, respectively, compared with the pristine cellulose
aerogels), due to the strong interactions between graphene
oxide and cellulose [258]. Mäder and coworkers blended
MWNTs with cellulose in NaOH/urea, and prepared electri-
cally conductive aerogels by lyophilizing the regenerated
blend hydrogel. The MWNT/cellulose aerogels had good
thermal stability and excellent mechanical properties, and
the conductivity (2.3 × 10−4 –2.2 × 10−2 S cm−1 ) endowed
the aerogel good sensitivity to ambient pressure, as
shown in Fig. 30, demonstrating promising applications in
detectors, energy storage, catalysis and biotechnological
fields [259].
Regenerated cellulose aerogels have a micro/nano
porous structure, and can be used as supporting medium
for the creation of nanoparticles. Kuga and coworkers
have reported that silver, gold and platinum nanoparticles
may be synthesized in the cellulose hydrogel by reduc-
tion reactions, and successive supercritical CO2 drying gave
corresponding aerogels with high transmittance, porosity,
surface area, moderate thermal stability and good mechan-
ical strength, as shown in Fig. 31 [260].
Cellulose/silica composite aerogels were also prepared
by serving regenerated cellulose hydrogel from alkali/urea
196 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 30. Photograph and TEM image of the aerogel (up), and a typical electrical response to ambient pressure for the composite aerogels (down) [259],
Copyright 2013. Reproduced with permission from the Royal Society of Chemistry.

system as scaffold via an in situ sol–gel process. Specif-
ically, a cellulose hydrogel was impregnated with silica
precursor tetraethyl orthosilicate in methanol/H2 O to form
silica via hydrolysis and condensation (sol–gel process with
NH3 ·H2 O) and then to give the cellulose/silica compos-
ited aerogel by drying with supercritical CO2 . The ease of
preparation and wide tunability of composition/properties
with this method is expected to form the basis for the devel-
opment of various advanced nano-porous materials [261].
Moreover, the robust conductive cellulose/polypyrrole
(PPy) composite aerogels were in situ synthesized by Cao
and coworkers as follows. The cellulose hydrogel (NCG)
fabricated in aqueous NaOH/urea solution was exchanged
with ethanol, and then impregnated with FeCl3 in ethanol,
followed by the in-situ vapor-phase polymerization of pyr-
role monomers. Then the polypyrrole/cellulose aerogels
were synthesized after washing, solvent-exchanged and
supercritical CO2 drying, as shown in Fig. 32. Electrical
stimulation demonstrated that PC12 cells (The PC12 cell
line is an immortalized cell line derived from a neuroen-
docrine tumor in the rat adrenal medulla [262]) attached
and extended longer neuritis when cultured on NCG/PPy
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 197

composite gels with dodecylbenzene-sulfonic acid dopant,

indicating potentials in nerve regeneration, carbon capture
and catalyst supports [263].

4.4. Cellulose composite microspheres and beads

Functional cellulose blend beads may be prepared via

Fig. 31. XRD patterns and photographs (inset) of the cellulose (A), sil-
ver/(B), gold/(C), and platinum/(D) cellulose aerogels [260], Copyright
2009. Reproduced with permission from the American Chemical Society.
the dissolution, shaping and regeneration procedure, with
the exception that a mixed solution of cellulose and
organic/inorganic molecules with specific functionalities is
used in an appropriate solvent [195]. Magnetic cellulose
beads were fabricated via an optimal dropping technol-
ogy by blending cellulose/NaOH/urea solution and Fe2 O3
nanoparticles in a submerged circulative impinging stream
reactor. The Fe2 O3 /cellulose magnetic beads exhibited sen-
sitive magnetic response, and their recovery could be
facilitated by applying a magnetic field. Moreover, the mag-
netic beads could efficiently adsorb the organic dyes in
the wastewater, and the sorbents could be recovered com-
pletely, leading to applications in the removal of hazardous
materials [264]. After activated with epoxy chloropropane
to enhance the biomacromolecules loading efficiency,
penicillin G acylase (PGA) as a biocatalyst was immo-
bilized successfully in these magnetic cellulose/Fe2 O3

Fig. 32. Preparation of NCG/PPy composite aerogels: (1) The NCG hydrogel with interconnected nanofibrillar network is solvent-exchanged with ethanol,
and then impregnated with a solution of FeCl3 in ethanol to form the NCG/FeCl3 alcogel; (2) PPy nanoparticles are formed by in situ vapor-phase polymeriza-
tion of pyrrole monomers supplied as vapor, giving the NCG/PPy-1 composite alcogel; (3) Repeating the second step two or three times gives NCG/PPy-2 and
NCG/PPy-3 composite alcogels, respectively; (4) Drying with supercritical CO2 gives NCG/PPy composite aerogel (a). Schematic representation of pyrrole
polymerization with FeCl3 (b). Macroscopic views of NCG/PPy-3 composite hydrogels under bending (63 mm × 28 mm × 0.9 mm) (c) and rolling (internal
diameter of 10 mm) (d). TEM images of the NCG/PPy-3 composite aerogel (e). Fluorescence micrographs of PC12 cells cultured on NCG/PPy-3 after electrical
stimulation (f) [263], Copyright 2014. Reproduced with permission from John Wiley & Sons Inc.
198 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206

Fig. 33. SEM (a) and TEM (b) images of the magnetic microsphere. Photos of magnetic microspheres in water (c) and in a magnetic field (d). The magnetic
hysteresis loops of the magnetic microspheres M10, M20 and M30 (with increasing Fe3 O4 loading) at 25 ◦ C (e) [266], Copyright 2014. Reproduced with
permission from John Wiley & Sons Inc.

Fig. 34. SEM images of the composite microspheres (upper left), photos of microsphere migration under a magnetic field (upper middle), mass spectra
of the tryptic digests of a mixture of ␤-casein and the BSA sample after enrichment by microspheres (upper right,  phosphorylated peptides, 䊉 their
dephosphorylated counterparts) and scheme illustration of the enrichment mechanism of phosphopeptides (lower) [267], Copyright 2015. Reproduced
with permission from the Royal Society of Chemistry.
 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206 199

Fig. 35. Schematic illustration of the preparation for the magnetic Fe3 O4 –cellulose–chitosan microspheres, the enzyme immobilization onto the magnetic
cellulose–chitosan microspheres, and their use for catalytic oxidation of glucose (left) and the dependence of glucose conversion on reaction time with
different catalysts (right). (a) Cellulose microspheres, (b) magnetic cellulose–chitosan microspheres with the ratio of cellulose to chitosan was 2:1, (c) 1:1,
and (d) 1:2 [270], Copyright 2012. Reproduced with permission from the Royal Society of Chemistry.

microspheres, and the immobilized PGA exhibited highly
effective catalytic activity, thermal stability and enhanced
tolerance to pH variations. The loaded microspheres could
be removed and recovered easily by introducing a mag-
netic field, demonstrating promising applications in the
enzyme immobilization and catalysis fields [265]. By using
the regenerated cellulose microspheres as micro-reactor,
magnetic Fe3 O4 /cellulose microspheres were fabricated by
in-situ synthesis. The magnetic microspheres had sensi-
tive magnetic-induced delivery, extremely small hysteresis
loop and low coercivity, as well as excellent adsorption and
controlled release capabilities on bovine serum albumin
(Fig. 33) [266]. Later, magnetic cellulose/TiO2 microspheres
were fabricated by sol–gel transition of cellulose/Fe3 O4
colloidal micro-droplets and in-situ synthesis of TiO2 in
precursor. The microspheres thus exhibited high efficiency
for selective enrichment of trace phosphopeptides from
tryptic digests of ␤-casein and human serum samples, and
1:1000 molar ratio of the selective enrichment of phos-
phopeptides from a mixture of ␤-casein and bovine serum
albumin (BSA) was achieved, better than the commercial
TiO2 nanoparticles, as shown in Fig. 34 [267].
Xu and coworkers fabricated porous cellulose micro-
spheres from NaOH/thiourea and paraffin oil emulsion by a
sol–gel transition, and Ag nanoparticles were incorporated
in the microspheres by hydrothermal method in AgNO3 .
The Ag in microspheres showed good catalytic activity due
to the large specific surface area, exhibiting potential appli-
cations for catalytic applications in practice [268].
Rogers and coworkers blended cellulose and bovine
serum albumin in 1-butyl-3-methylimidazolium chlo-
ride, to obtain beads by dispersion in a rapidly stirring
poly(propylene glycol) bath, followed by cooling and wash-
ing. The beads were ready for use as sensing devices to
detect various compounds, including polyphenols, aro-
matic amines and aminophenols and as solid support
materials for enzyme-catalyzed transformations, as well as
separation, chromatography, and/or constant flow reactors
[269]. By blending Fe3 O4 nanoparticles, cellulose and chitin
in the same IL, magnetic microspheres were fabricated by
the sol–gel transition technology, and glucose oxidase was
immobilized on the microspheres via the glutaraldehyde
technique. The enzyme presented higher thermal stability,
wider range of pH optima and improved storage stability in
comparison with free glucose oxidase, as shown in Fig. 35,
demonstrating potential applications in the biocatalysis
field [270].
Wang and coworkers also developed magnetic hydrogel
microspheres with chitosan and cellulose coating via the
sol-gel method. Briefly, cellulose and chitosan were dis-
solved in 1-butyl-3-methylimidazolium chloride, followed
by Fe3 O4 particles addition, and then ethanol was added
for regeneration to obtain composite hydrogels, in which
cellulose contributed to the mechanical strength and
chemical stabilities, while chitosan stabilized Fe3 O4 . The
hybrid hydrogel microspheres had high adsorption capac-
ities for different heavy metal ions (Cu2+ , Fe2+ and Pb2+ ),
and could be efficiently recycled and reused, showing
promising application in the areas of biotechnol-
ogy/biomedicine, health care, catalysis and magnetic
resonance imaging [271]. Through a similar procedure
by co-dissolving chitosan (chitin)/cellulose in 1-butyl-
3-methylimidazolium chloride followed by dropping in
water bath, Chen and coworkers fabricated composite
beads as biosorbent. As a result of the strong intermolec-
ular hydrogen bond between chitosan and cellulose as
well as the hydroxyl and amine groups to be the metal ion
binding sites, and the capacity of adsorption was found to
be Cu2+ > Zn2+ > Cr6+ > Ni2+ > Pb2+ [272]. Lee and coworkers
dissolved cellulose in 1-ethyl-3-methylimidazolim acetate
with and without the presence of biopolymers (chitosan,
carrageenan, agar and agarose), and the resultant solu-
tions were mixed with lipase, with enzyme-entrapped
composite beads prepared through a dropping proce-
dure. The incorporation of biopolymers increased the
immobilization yields (specific activity ratio of entrapped
lipase to free lipase) compared with cellulose beads, other
than cellulose–carrageenan, demonstrating potential
200 S. Wang et al. / Progress in Polymer Science 53 (2016) 169–206
applications including drug delivery, biosensors and tissue
engineering etc. [273].
Sun and coworkers prepared super-porous cellu-
lose beads from cellulose xanthogenate viscose via
emulsification–thermal regeneration with calcium carbon-
ate as porogenic agents, leading to more “craters” of several
microns scattering on the surface of the beads, resulting in
higher water content and effective porosity. After modi-
fication with diethylaminoethyl, the super-porous feature
of the beads contributed to higher column efficiency and
dynamic binding capacity, suggesting the potential appli-
cations as a potential stationary phase for high-speed
preparative protein chromatography [274]. Guo et al. fab-
ricated cellulose beads by heating a dispersed emulsion
of cellulose xanthogenate viscose in chloroben/pump oil
mixture. Iron oxyhydroxide was then immobilized in the
beads by treatment with Fe3 Cl and NaOH. The beads exhib-
ited selectivity toward both As3+ and As5+ species and high
adsorption capacity, as well as high regeneration efficiency
and high removal performance for arsenic, indicating prac-
tical applications for water purification [275]. Zhao et al.
also fabricated cellulose beads by dispersing cellulose xan-
thogenate viscose in chlorobenzene/pump oil, and after
being activated, ammonified and reacted with H3 PO3 and
chloride acid, the beads were treated with excessive FeCl3
to yield Fe3+ loaded ligand exchange beads, which acted as
adsorbents for fluoride and potentially cost-effective mate-
rials for drinking water purification [276].
Faced with the impending energy crisis, electrochemi-
cal capacitors have significant potential as energy storage
devices, and conductive polymers are commonly used as
pseudo-capacitive electrode materials, owing to their facile
synthesis and flexibility. To resolve the problem of the
pulverization and rapid capacity fading of the polymer
electrodes, Zhang et al. constructed novel electrode materi-
als from polyaniline/cellulose microspheres (PANI/PA/CM),
which were fabricated via in-situ synthesis of PANI on
cellulose matrix by using phytic acid (PA) as “bridge”.
The firm connection between hydrophobic polyaniline
and hydrophilic cellulose through the PA “bridge” created
micro- and nano-porous architecture, leading to the ion
channels for the electrolyte penetration. The PANI/PA/CM
composite electrodes exhibited excellent cycling stability
(over 12000 cycles) and high rate capability, showing great
potential in the energy-storage devices [277].
5. Conclusions and outlook
To realize a sustainable world, we are facing the
emerging challenges in agriculture, forestry, academia,
government and industry. Cellulose is the most abundant
natural and renewable resource, and is a prime candidate
for replacing the petroleum-based products to expand to
new applications without polluting the earth. In particular,
cellulose has inherent advantages of safety, biocompatibil-
ity and biodegradability, because it is intrinsically a part
of plants and animals (tunicates). Moreover, the abundant
OH groups endow cellulose with the affinity to inor-
ganic/organic substances, leading to the preparation of
hybrid materials, expands the potential application of cel-
lulose as functional materials.
In the last decades, the diversity and richness of
the regenerated cellulose materials fabricated via phys-
ical dissolution and regeneration have been astonishing,
demonstrating promising potentials among textiles, pack-
aging, biomedicine, water treatment, optical/electrical
devices, agricultures and food fields. The physical dissolu-
tion and regeneration process is environmentally friendly
by avoiding the consumption of chemicals since most of the
agents can be recycled and reused, and the nature of cellu-
lose is retained, as a result that no chemical reaction occurs,
promising to bring another Green Revolution to the compre-
hensive utilization of cellulose-like natural resources. The
impact and benefits of such physical processes to society
are truly fascinating, considering the preparation of new
materials via an environmentally friendly technology and
substitution to the petroleum-based materials.
This review has attempted to provide a broad vision of
physical dissolution and regeneration of cellulose to con-
struct regenerated materials that have been accomplished
to date, in order to stimulate the increasing interests in
the cellulose research and developments. It is worth not-
ing that the novel “green” cellulose solvents as well as the
physical dissolution/regeneration techniques will open up
a completely new avenue to create novel enticing materials
with desired properties and functions. The overall applica-
tions of the regenerated cellulose materials are virtually
limitless. A deeper understanding of the new mechanisms
involved in the cellulose dissolution and regeneration will
not only make the regenerated cellulose materials more
functional, but also more tunable with various applications.
In view of the work reviewed in this article, further
explorations in cellulose may improve the world to be
greener and more sustainable in the future. Therefore,
this review article could give a full perspective view of
the preparation of the environmentally friendly cellu-
lose materials and their potential applications, leading to
the increasing attentions to further investigations of the
renewable resources for a sustainable world.
Acknowledgments
This work was supported by the Major Program of
National Natural Science Foundation of China (21334005),
and the National Natural Science Foundation of China
(51203122).
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