Industrial Crops and Products 93 (2016) 225

Contents lists available at ScienceDirect

Industrial Crops and Products

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

Production of cellulose nanobrils: A review of recent advances

Oleksandr Nechyporchuk , Mohamed Naceur Belgacem, Julien Bras
Universit Grenoble Alpes, Laboratory of Pulp and Paper Science and Graphic Arts (LGP2), CNRS, Agefpi, F-38000 Grenoble, France

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

Article history: This review describes the recent advances in production of cellulose nanobrils (CNF), otherwise known
Received 10 November 2015 as nanobrillated cellulose (NFC), microbrillated cellulose (MFC) or cellulose nanobers, a material
Received in revised form 1 February 2016 with signicant barrier, mechanical and colloidal properties, low density, renewable and biodegradable
Accepted 6 February 2016
character. The above properties make CNF promising for applications in such elds as papermaking, com-
Available online 19 February 2016
posites, packaging, coatings, biomedicine and automotive. In this review, CNF production methods are
summarized, covering raw materials selection, structural and chemical aspects necessary for understand-
Keywords:
ing the nanobril extraction process, conventional and novel mechanical disintegration techniques, as
Cellulose nanobrils (CNF)
Nanobrillated cellulose (NFC)
well as biological and chemical pretreatments aimed at facilitating nanobril isolation. The issues of frac-
Microbrillated cellulose (MFC) tionation, performed with the objective of retrieving the residual microscopic ber fragments from CNF
Cellulose nanobers suspensions, are addressed. Additionally, the preparation of CNF in various forms, such as suspensions,
Mechanical disintegration water-redispersible powders, lms or nanopapers, hydrogels and aerogels, is discussed.
Enzymatic and chemical pretreatments 2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Cellulose and nanocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Structure and chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Nanocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.1. Cellulose nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.2. Cellulose nanobrils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.3. Bacterial cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.4. Electrospun cellulose nanobers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Production of cellulose nanobrils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Mechanical disintegration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1. Homogenization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.2. Grinding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.3. Rening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1.4. Extrusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10
3.1.5. Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1.6. Ultrasonication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1.7. Cryocrushing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1.8. Steam explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1.9. Ball milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1.10. Aqueous counter collision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2. Biological and chemical pretreatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Corresponding author. Present address: Division of Applied Chemistry, Department of Chemistry and Chemical Engineering, Chalmers University of Technology, SE 412
96 Gothenburg, Sweden.
E-mail addresses: o.nechyporchuk@gmail.com (O. Nechyporchuk), naceur.belgacem@pagora.grenoble-inp.fr (M.N. Belgacem), julien.bras@pagora.grenoble-inp.fr
(J. Bras).

http://dx.doi.org/10.1016/j.indcrop.2016.02.016
0926-6690/ 2016 Elsevier B.V. All rights reserved.
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225 3

3.2.1. Enzymatic hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3.2.2. Carboxylation via TEMPO-mediated oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.3. Carboxylation via periodatechlorite oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.4. Sulfonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.5. Carboxymethylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.6. Quaternization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.7. Solvent-assisted pretreatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.3. Post-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.4. Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.5. Scaling up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.6. Quality assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.6.1. Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.6.2. Degree of brillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.6.3. Rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4. Cellulose nanobrils in different forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1. Suspensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.2. Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.3. Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.4. Hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.5. Aerogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

1. Introduction integration, CNF became a more attractive material for commercial

applications. However, research continues focusing on optimiza-
Presently, there is a strong need for replacing fossil oil-based tion of the existing techniques and on development of alternative
products with biodegradable and/or bio-based ones, which can methods, which can benet the production process or endow the
resolve numerous issues, such as reduction of oil stocks and their CNF with new properties.
geographical localization, plastic pollution, carbon footprint and A number of review articles or book chapters have been
sustainability. Cellulose is the most abundant natural polymer published lately dedicating to production and characterization
which can be used to propose rational solutions for these issues. of CNF (Moon et al., 2011; Lavoine et al., 2012; Isogai, 2013;
Cellulose is a renewable, biodegradable and non-toxic material. Lindstrm et al., 2014; Osong et al., 2015), including some with
It is also a vast source for environmentally friendly and biocom- an emphasis on industrialization and market issues (Chauve and
patible products. The production of cellulose by photosynthesis is Bras, 2014; Lindstrm and Aulin, 2014). However, there are
estimated to be 1011 1012 t/year (Klemm et al., 2004). The major some recent advances that were not enough addressed, includ-
sources of cellulose are wood and cotton. These materials have been ing certain mechanical disintegration techniques (e.g., extrusion),
used for centuries as a source of heat or as a construction material, biochemical pretreatments (e.g., periodatechlorite oxidation,
or for manufacturing of several commodities in textile and paper sulfonation, quaternization, solvent-assisted pretreatments), frac-
industry. Furthermore, cellulose is a versatile source for different tionation techniques, some issues of CNF quality assessment,
products obtained by chemical modication, as witnessed by the production of CNF in different forms (e.g., powders, hydrogels, aero-
variety of commercial cellulose derivatives (Klemm et al., 1998a). gels) etc. Thus, this review aims at complementing with the above
The use of cellulose in high added value applications is still issues and focuses on the recent advances achieved in CNF produc-
rare due to its insolubility in water and most organic solvents, tion.
hygroscopic character and no melting. Meanwhile, the interest in
nanocellulose has sharply increased lately due to the specic chem-
ical and physical properties of such material. Typically, two main 2. Cellulose and nanocellulose
types of nanocellulose are distinguished: (i) the one obtained by
acid treatment, referred to as cellulose nanocrystals (CNC), and (ii) 2.1. Feedstock
the one produced mainly by mechanical disintegration, called cel-
lulose nanobrils (CNF). This review focuses on the second type of Cellulose can be derived from a variety of sources, such as
nanocellulose. wood (hardwood and softwood), seed bers (cotton, coir etc.), bast
In recent years there has been a real breakthrough in the indus- bers (ax, hemp, jute, ramie etc.), grasses (bagasse, bamboo etc.),
trial production of CNF. This material is readily available on the marine animals (tunicate), algae, fungi, invertebrates and bacteria
market as a commercial product and has more and more inter- (Varshney and Naithani, 2011). Wood is currently the most impor-
est in industrial applications, as shown by recent patent studies tant industrial source of cellulose (Sir and Plackett, 2010; Stelte
(Charreau et al., 2013) or certain book chapters (Bardet and Bras, and Sanadi, 2009). Besides cellulose, it also contains hemicellulose,
2014; Chauve and Bras, 2014; Lindstrm et al., 2014). In previous lignin and a comparably small amount of extractives and inorganic
decades the challenge associated with isolating CNF was the high salts. Wood species can be distinguished as hard- and softwoods
energy demand required by mechanical disintegration process. based on their anatomical features. Hardwood is more complex
However, with discovering strong impact of pretreatment meth- and heterogeneous in structure than softwood (Wiedenhoeft and
ods, e.g., 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-mediated Miller, 2005). Generally, softwood bers are 34 times longer than
oxidation (Saito et al., 2006; Isogai et al., 2011) or enzymatic hydrol- hardwood (Shackford, 2003). However, it is known that hard-
ysis (Janardhnan and Sain, 2007; Henriksson et al., 2007; Pkk woods have more rigid structure than softwoods due to their high
et al., 2007), which were aimed at facilitating the mechanical dis- Runkel ratio (cell wall thickness divided by lumen radius) (Wang
et al., 2012). Therefore, it was reported that softwood requires less
4 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
mechanical treatment than hardwood to produce equivalent bril-
lation level (Stelte and Sanadi, 2009).
At the same time, non-wood plants are receiving increasing
interest as a source of cellulose since they, generally, comprise
less lignin. Consequently, ber delignication and purication pro-
cesses are easier and less harmful for cellulose. Moreover, further
brillation of such cellulose is less energy-consuming.
It should be also noted, that the use of never-dried cellulose
comparing to once-dried makes the brillation more favorable,
since drying promotes irreversible hydrogen-bonding between
nanobrils, known as hornication (Diniz et al., 2004; Spinu et al.,
2011). However, the dry cellulose is much easier to transport.
Therefore, research focuses on both never-dried and dry cellulose
as raw material for CNF production.
2.2. Structure and chemistry
As mentioned above, cellulose can be found in some algae,
fungi, tunicates etc. However, commercial cellulose production
concentrates on harvested sources such as wood, annual plants
or agricultural residues. Besides cellulose, they contain hemicellu-
loses, lignin, and a comparably small amount of extractives. In such
products, cellulose is represented as a well-organized architecture
of brillar elements composing cells. Cellulose is the primary struc-
tural component responsible for their mechanical strength.
Each cell represents a ber with a width of 1050 m (depend-
ing on the source), consisting of cell wall layers, which have the
total thickness of 15 m (Chinga-Carrasco, 2011). These layers
differ from each other with regard to their structure and chemi-
cal composition. The cell wall is composed of several layers (see
Fig. 1): the middle lamella (ML), the primary wall (P), the outer
(S1), middle (S2) and inner (S3) layers of secondary wall and the
warty layer (W). The middle lamella binds the neighboring cells
because of the presence of high amount of lignin. The primary and
secondary walls contains three main components: cellulose, hemi-
cellulose, and a matrix, typically, composed of pectin in the primary
wall and lignin in the secondary wall.
The primary cell wall is approximately 301000 nm thick and
contains cellulose microbrils (MF) located crosswise. The sec-
ondary cell wall consists of three layers (S1, S2 and S3), which differ
in microbrils angle with respect to the ber axis. In these layers
the microbrils are aligned parallel and are packed densely in a
at helix. The secondary wall contains most of the cellulose mass
in the ber and has a thickness varying from 100 nm (cotton) to
300 nm (spruce wood). The warty layer is a thin layer located in
the inner surface of the cell wall mainly composed of lignin and
hemicellulose (Sjstrm, 1981; Klemm et al., 1998b).
As described above, cellulose is present in the bers in form of
the microbrils. For instance, in the spruce wood the microbrils
have a diameter of 1020 nm. These microbrils in turn are made of
elementary brils, which are commonly considered as the smallest
morphological units in the ber (Frey-Wyssling and Mhlethaler,
1963). However, recent studies (Usov et al., 2015) showed that
it is possible to extract single cellulose polymer chains or 2 2
chain-packing structures during CNF production. The diameter of
elementary brils typically varies in the range of 335 nm depend-
ing on cellulose source (Klemm et al., 2005), and is in the range
of 2.23.6 nm for spruce wood (Fernandes et al., 2011). Both cellu-
lose microbrils and elementary brils are referred to as cellulose
nanobrils. However, it is commonly desired to obtain individual
elementary brils with a regular diameter, rather than their (or
microbril) bundles.
Cellulose is a semicrystalline polymer comprising crystalline
(ordered) and amorphous (disordered) regions within the microb-
ril, where the individual cellulose molecule is considered to pass
through several crystalline and amorphous parts according to
fringe micelle theory (Shmulsky and Jones, 2011). The native degree
of crystallinity is usually in the range of 4070% and depends on the
origin of cellulose and the isolation method.
The building blocks of cellulose polymer chain are D-
glucopyranose (glucose) molecules. When linked together by
-1,4-glucosidic bonds they turn into anhydroglucose units. Two
anhydroglucose units compose anhydrocellobiose, which is the
repeating unit of cellulose polymer (see Fig. 2). Nevertheless, cellu-
lose degree of polymerization (DP) is usually expressed as a number
of anhydroglucose units. Each anhydroglucose unit has six carbon
atoms with three hydroxyl (viz., alcohol) groups (at C2, C3, and C6
atoms), giving a high degree of functionality to cellulose molecule.
There are three types of anhydroglucose units: (i) a reducing end
with free hemiacetal or aldehyde group at C1 atom, (ii) a non-
reducing end with free alcohol group at C4 atom, and (iii) internal
rings. Due to the molecular structure, cellulose bears such prop-
erties as hydrophylicity, insolubility in water and most organic
solvents, degradability and chirality.
The DP of cellulose varies depending on the cellulose source
(e.g., 10,000 in native wood; 20,000 in cotton; 44,000 in Valonia)
and the isolation/purication method (e.g., 200500 in regenerated
cellulose, 1000 in bleached kraft pulps) (Fengel and Wegener, 1983;
Wertz et al., 2010).
2.3. Nanocellulose
Cellulose particles with at least one dimension in nanoscale
(1100 nm) are referred to as nanocellulose. Depending on the pro-
duction conditions, which inuence the dimensions, composition
and properties, nanocellulose can be divided into two main cate-
gories: (i) cellulose nanocrystals (CNC) or cellulose whiskers and
(ii) cellulose nanobrils (CNF), also known as nanobrillated cellu-
lose (NFC), microbrillated cellulose (MFC) or cellulose nanobers.
Due to various terminology used to describe cellulose nanomateri-
als, several technical committees and organizations (ISO TC 6 and
TC 229; TAPPI and CSA Z5100-14) initiated a standardization of dif-
ferent types of nanocellulose. Even though this work has not been
nalized yet, the majority of experts are inclined to the term cel-
lulose nanobrils for the second type of nanocellulose described
above, which is a subject of this review.
Bacterial cellulose (BC) and electrospun cellulose nanobers
(ECNF) are also considered as nanocellulose. However, CNC and CNF
are much more common, since they are produced by disintegra-
tion of cellulose bers into nanoscale particles (topdown process),
whereas BC and ECNF are generated by a buildup of nanobers
(bottomup process) from low molecular weight sugars by bacte-
ria or from dissolved cellulose using electrospinning, respectively.
Thus, large-scale production of BC and ECNF remains questionable.
Regardless of the nanocellulose type, it exhibits hydrophilicity,
relatively large specic surface area, broad potential of surface
chemical modication etc.
2.3.1. Cellulose nanocrystals
CNC were rst produced by Rnby (1949) using acid hydrolysis
of cellulose bers dispersed in water. In this method, concentrated
sulfuric acid is commonly used, which degrades amorphous regions
of cellulose and leaves intact the crystalline ones. By such treat-
ment, rod-like rigid CNC with sulfate groups at their surface are
produced. Their morphology generally depends on the source of
cellulose. Commonly, CNC with a diameter of 335 nm and a length
of 200500 nm are produced.
2.3.2. Cellulose nanobrils
CNF as a new cellulosic material was introduced by Turbak
et al. (1983a,b) and Herrick et al. (1983) who produced cellulose
with lateral dimensions in nanometer range by passing a softwood
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225 5

Fig. 1. Hierarchical structure of wood, showing: the middle lamella (ML), the primary wall (P), the outer (S1), middle (S2) and inner (S3) layers of secondary wall, the warty
layer (W), cellulose (C), hemicellulose (H), lignin (L), microbril (MF), elementary bril (EF), crystalline domain (Cr) and amorphous domain (Am). Some elements of the
gure were adapted from Prez et al. (2002) with kind permissions from Springer Science and Business Media and the authors.

Fig. 2. Molecular structure of cellulose polymer. Degree of polymerization (DP) = 2n + 2.

pulp aqueous suspension several times through a high-pressure
homogenizer. During such treatment, strongly entangled networks
of nanobrils, having both crystalline and amorphous domains, are
produced due to high shearing forces. They possess high aspect
ratio and form gels in water with shear-thinning and thixotropic
behavior. Depending on the processing conditions, cellulose bers
can be disintegrated to exible CNF with lateral dimensions starting
from ca. 5 nm, representing elementary brils, to tens of nanome-
ters, which correspond to single microbrils and their bundles.
Typically, CNF have a diameter of 550 nm and a length of few
micrometers. An in-depth review of CNF production techniques and
properties is presented below in Section 3.
2.3.3. Bacterial cellulose
BC is high-purity cellulose generated by bacteria in aqueous
culture media containing a sugar source. The time of such a pro-
cess ranges from few days up to two weeks (Gatenholm and
Klemm, 2010). BC has the same chemical composition as plant cel-
lulose. However, it is free of functional groups other than alcohol,
e.g., carboxyl or carbonyl, which are usually introduced to wood
or plant-derived cellulose during the purication process. BC is
also free of the other polymers, such as lignin, hemicelluloses or
pectin, which facilitates its use in biomedical applications. BC is
produced in the form of twisting ribbons with cross-sections of
34 nm 70140 nm and a length of more than 2 m (Brown and
Laborie, 2007; Stevanic et al., 2011). It has a DP of 30009000 and
a distinct crystallinity of 8090%.
2.3.4. Electrospun cellulose nanobers
The other possibility to produce cellulose with
nanoscale/submicron lateral dimensions is electrospinning.
Recently, the electrospun bers from cellulose and its derivatives
6 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
have gained evident interest. To produce ECNF, cellulose is rst
dissolved in an appropriate solvent. Then, a high voltage is applied
to a droplet of cellulose solution to overcome the surface tension
and to form a jet of the solution. While it is passed through air,
the solvent evaporates, forming a lament, which is collected on
an electrically grounded target (Lim et al., 2010). This method
can be used to prepare bers with diameter of several tens of
nanometers (Doshi and Reneker, 1993). However, ECNF starting
from few hundreds of nanometer to few microns in diameter are
commonly produced (Frey, 2008). Even so, they are often referred
to as nanobers. Recently, a lot of studies in this eld have been
devoted to investigation of appropriate solvents for cellulose
(Park et al., 2007; Konwarh et al., 2013; Ghorani et al., 2013).
Electrospinning can be also used to produce polymer composite
bers containing nanocellulose (Medeiros et al., 2008; Fortunato
et al., 2012; Xu et al., 2014).
3. Production of cellulose nanobrils
Cellulose is present in wood or plants in combination with
hemicellulose and lignin. The latter are generally removed before
the production of CNF by various cooking and bleaching methods,
which are similar to those used in papermaking industry. In this
section all the operations are reviewed, which are typically carried
out on previously puried cellulose pulp. CNF production meth-
ods usually comprise several operations, e.g., successive rening,
enzymatic hydrolysis, again rening and nally homogenization
(Pkk et al., 2007); TEMPO-mediated oxidation, followed by
blending (Saito et al., 2006) or homogenization (Besbes et al.,
2011), carboxymethylation or quaternization, followed by homog-
enization (Aulin et al., 2010a). Thus, the production process is
a combination of different operations, by varying which differ-
ent kinds on CNF are obtained, as shown in Fig. 3. Various
grades of CNF differ in morphology (particularly nanobril dimen-
sions and the amount of residual microscopic ber fragments),
surface chemistry, crystallinity, DP etc. Table 1 summarizes various
processing conditions used in publications for CNF production.
3.1. Mechanical disintegration
Dry cellulose pulp can be disintegrated to small fragments using
mechanical methods. However, it usually leads to ber shredding,
rather than elementary bril delamination. Consequently, it yields
CNF with low degree of polymerization, crystallinity and aspect
ratio and results in relatively poor mechanical properties of the
ensuing nanomaterials. The interbrillar hydrogen bonding energy
should be exceeded in order to delaminate the nanobrils, rather
than to cut them. Moreover, to benet from the delaminated b-
rils, reverse coalescence should be prevented. For this reason, CNF is
commonly produced in aqueous medium, which loosens the inter-
brillar hydrogen bonding. Typically, cellulose is dispersed at low
concentrations (<5 wt.%) due to its high water absorption capacity,
which results in highly viscous suspensions that are hard to handle
due to low solid concentration.
Rening, homogenization (using homogenizers and microu-
idizers) and grinding are the most common techniques used for
mechanical production of CNF. These techniques are the most ef-
cient for delamination of ber cell wall and CNF isolation, as well as
are suitable for upscaling. Thus, they are used nowadays for indus-
trial production of CNF. Meanwhile, other methods are studied in
order to nd more benecial solutions for CNF production.
3.1.1. Homogenization
High pressure homogenization is used to disintegrate cellulose
bers mechanically into CNF. In this context, two types of equip-
ment are employed: homogenizers and microuidizers. These
devices are commonly used in industries such as food, cosmetic,
pharmacy and biotechnology.
Turbak et al. (1983a,b) and Herrick et al. (1983) rst reported the
production of CNF by passing a water suspension of wood pulp at
a concentration of 2 wt.% through a Manton-Gaulin homogenizer.
Previously, cellulose was rened in PFI mill up to 10,000 revolu-
tions and passed through homogenizer at a pressure of 8000 psi
with water cooling to maintain a stable temperature of 7080 C
(Turbak et al., 1983b). As a result, for the rst time they obtained
individualized nanobrils with a diameter less than 100 nm.
During the homogenization process, a cellulose slurry is passed
through a tiny gap between the homogenizing valve and an impact
ring (see Fig. 4), subjecting the bers to shear and impact forces,
which ensure cellulose brillation. Homogenizers were widely
used by other researchers to produce CNF without biochemical
pretreatments (Dufresne et al., 2000; Nakagaito and Yano, 2004;
Iwamoto et al., 2005; Wang and Sain, 2007) or with preliminary
enzymatic hydrolysis (Henriksson et al., 2007; Hassan et al., 2011),
carboxylation (Besbes et al., 2011; Liimatainen et al., 2012), quat-
ernization (Liimatainen et al., 2014) etc.
As an alternative for a homogenizer, Zimmermann et al. (2004)
reported the use of a microuidizer (Microuidics Inc., USA) for
CNF production (see Fig. 4). Sulphite pulp suspensions were rst
treated with an ultra-turrax (FA IKA) at 24,000 rpm for 8 h and
further passed through M-100Y microuidizer processor at a pres-
sure of 1000 bar for 60 min. As a result, nanobrils of 20100 nm in
diameter and several tens of micrometers in length were obtained.
The principle of this technique consists in passing the cellulose
suspension through a thin chamber with a specic geometry, e.g.,
Z- or Y-shape, with an orice width of 100400 m. By applying
high pressure, strong shear forces and impact of the suspension
against the channel walls are achieved, yielding cellulose bril-
lation. Microuidizers were used in other works to individualize
cellulose nanobrils without preliminary biochemical pretreat-
ments (Taipale et al., 2010) or after enzymatic hydrolysis (Pkk
et al., 2007; Siqueira et al., 2010), carboxymethylation (Aulin et al.,
2010a; Eyholzer et al., 2010; Taipale et al., 2010) quaternization
(Aulin et al., 2010a; Ho et al., 2011) etc.
For a long period of time, the main barrier for commercial
success of homogenization process was the high energy consump-
tion, which could reach 70 MW h/t (Eriksen et al., 2008). However,
with the development of pretreatment methods (e.g., enzymatic
or oxidation) this value has decreased drastically reaching ca.
2 MW h/t (Lindstrm, 2011). Another disadvantage of homogeniza-
tion (mainly with microuidizers) is the clogging of the system
when using long bers (Spence et al., 2011). This issue remains
the main challenge for upscaling of such a process.
3.1.2. Grinding
Ultra-ne friction grinding is another technique which is used
for the production of CNF. Supermasscolloider grinders (Masuko
Sangyo Co. Ltd., Japan) are commonly used for such treatment (see
Fig. 4). Taniguchi and Okamura (1998) described the production of
CNF by passing 510 wt. % natural ber suspensions from different
sources through a grinder 10 times and obtained CNF with a diam-
eter in the range of 2090 nm. During such a process, the cellulose
slurry is passed between static and rotating grinding stones (disks).
The distance between these disks can be adjusted, which enables
avoiding the problem of clogging. By the shearing forces generated
between the discs, the cell wall is delaminated and the nanobrils
are individualized. A number of researchers reported the produc-
tion of CNF by such a method while using never-dried (Iwamoto
et al., 2007; Spence et al., 2011; Bulota et al., 2012; Jonoobi et al.,
2012) or once-dried cellulose (Wang et al., 2012; Nechyporchuk
et al., 2015a) pulp as a starting material.
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225 7

Fig. 3. Schematic diagram of CNF production tree.

Fig. 4. Mechanical processes for CNF production. The photographs were adapted from www.niro-soavi.com, www.microuidicscorp.com and www.masuko.com.
8 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225

Table 1
Different processing conditions used for the production of CNF.

Raw material Purication Mechanical Biological/chemical Principal Post-treatment Reference

pretreatment pretreatment mechanical
treatment

Softwood Sulte/kraft Rening (PFI mill) No Homogenization No Turbak et al.

process (homogenizer) (1983b)
Softwood Kraft process Rening (disk No Homogenization No Nakagaito and
rener) (homogenizer) Yano (2004)
Softwood/hardwood Bleaching Blending, grinding No Homogenization No Stelte and Sanadi
(homogenizer) (2009)
Softwood pulp Kraft process Rening No Homogenization No Iwamoto et al.
(homogenizer), (2005)
grinding
Potato pulp Sodium hydroxide, Blending No Homogenization No Dufresne et al.
sodium chlorite (homogenizer) (2000)
treatments
Soybean pods Sodium hydroxide, Rening (PFI mill) No Homogenization No Wang and Sain
hydrochloric acid, (homogenizer) (2007)
chlorine dioxide
treatments
Hardwood pulp No bleaching/kraft No/rening (Valley No Homogenization No Spence et al. (2011)
process beater) (homogenizer/
microuidizer)/
grinding
Softwood pulp Sulte process Homogenization No Homogenization No Zimmermann et al.
(Ultra-Turrax) (microuidizer) (2004)
Wood/cotton/ Various No No Grinding No Taniguchi and
tunicin/chitosan/ Okamura (1998)
silk/collagen
Softwood pulp Bleaching Blending No Grinding No Iwamoto et al.
(2007)
Hardwood pulp Kraft process No No Grinding Centrifugation/ Bulota et al. (2012)
acetylation
Dissolving pulp Bleaching Blending No Grinding No Jonoobi et al.
(2012)
Hardwood pulp Kraft process Blending No Grinding No Wang et al. (2012)
Cotton Hydrogen peroxide No No Rening (disk No Karande et al.
bleaching rener) (2011)
Needle-leaf Kraft process Rening No Extrusion (twin No Ho et al. (2015)
screw)
Softwood pulp Sodium chlorite No No Blending and/or No Uetani and Yano
treatment grinding (2011)
Rice straw Toluene, ethanol; No No/carboxylation Blending Centrifugation Jiang and Hsieh
sodium chlorite; (TEMPO) (2013)
potassium
hydroxide
treatments
Regenerated/ No No No Ultrasonication Centrifugation Cheng et al. (2009)
microcrystalline
cellulose
Hardwood pulp Benzene, ethanol; No No Ultrasonication No Chen et al. (2011a)
sodium chlorite;
potassium
hydroxide
treatments
Sugar beet pulp Sodium hydroxide, Blending No Cryocrushing, No Dufresne et al.
sodium chlorite homogenization (1997)
treatments (homogenizer)
Hemp/spring Sodium hydroxide, No No Cryocrushing No Bhatnagar and Sain
ax/rutabaga/ hydrochloric acid (2005)
softwood pulp treatments/kraft
process
Pineapple Sodium hydroxide, No No Steam explosion, No Cherian et al.
leaf/banana acetic acid, sodium blending (2010) and Deepa
hypochlorite, et al. (2011)
oxalic acid
treatments
Softwood pulp Kraft process Blending No/sodium Ball milling No Zhang et al. (2015)
carbonate
treatment
Bacterial cellulose No Homogenization No Aqueous counter No Kose et al. (2011)
(Physcotron) collision
Microcrystalline Various No/cutting No Aqueous counter No Kondo et al. (2014)
cellulose/bacterial (scissors) collision
cellu-
lose/Halocynthia
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225 9

Table 1 (Continued)

Raw material Purication Mechanical Biological/chemical Principal Post-treatment Reference

pretreatment pretreatment mechanical
treatment

Softwood pulp Sulte process No/rening (PFI No/enzymatic/sodium Rening (PFI mill), No Henriksson et al.
mill) hydroxide, homogenization (2007)
hydrochloric acid (microuidizer)
treatments
Softwood pulp Sulte process Rening (disk Enzymatic Rening (disk No Pkk et al. (2007)
rener) rener),
homogenization
(microuidizer)
Softwood pulp Kraft process Rening Enzymatic Rening, Filtration Janardhnan and
cryocrushing Sain (2007)
Sisal bers (Agave Sodium hydroxide, No No/enzymatic Homogenization No/sulfuric acid Siqueira et al.
sisalana) chlorite treatments (microuidizer) hydrolysis (2010)
Hardwood pulp Kraft process Blending No/enzymatic/ Grinding and/or No Qing et al. (2013)
carboxylation homogenization
(TEMPO) (microuidizer)
Softwood pulp Sulte process Blending, rening Enzymatic/ Grinding and/or No Nechyporchuk
(PFI mill) carboxylation homogenization et al. (2015a)
(TEMPO) (homogenizer)
Softwood/cotton/ Various No Carboxylation Blending/ Centrifugation Saito et al. (2006)
tunicin/bacterial (TEMPO) ultrasonication
cellulose
Hardwood pulp Kraft process, No Carboxylation Blending/ Filtration Saito et al. (2009)
sodium chlorite (TEMPO) ultrasonication
treatments
Needles grass Sodium chlorite, No Carboxylation Blending/ No Chaker et al. (2013)
(Stipa tenacis- acetic acid, sodium (TEMPO) homogenization
sima)/sunower hydroxide (homogenizer)
treatments
Hardwood Various No Carboxylation Homogenization No Besbes et al. (2011)
pulp/softwood (TEMPO) (homogenizer)
pulp/needles grass
(Stipa tenacissima)
Hardwood pulp Kraft process No Carboxylation Ball milling Fractionation (tube Keklinen et al.
(TEMPO) ow) (2015)
Softwood pulp Sulte process No Carboxylation Blending, extrusion No Cobut et al. (2014)
(TEMPO) (single screw)
Softwood pulp Kraft process, No Carboxylation Grinding (Wiley No Johnson et al.
sodium chlorite (TEMPO) mill), ultrasonica- (2008)
treatment tion/homogenization
(microuidizer)
Softwood pulp Kraft process No Carboxylation Blending/ No Tejado et al. (2012)
(periodate- homogenization
chlorite) (Brinkmann
Polytron)
Hardwood pulp Kraft process No Carboxylation Homogenization No Liimatainen et al.
(periodate- (homogenizer) (2012)
chlorite)
Hardwood pulp Kraft process No Sulfonation Homogenization No Liimatainen et al.
(homogenizer) (2013b)
Hardwood pulp Kraft process No Sulfonation/ Homogenization No Sirvi et al. (2014)
carboxylation (homogenizer)
(TEMPO)
Softwood pulp Sulte process Blending Carboxymethylation Homogenization No Wgberg et al.
(microuidizer) (2008)
Hardwood pulp Bleaching Rening, No/carboxymethylation Homogenization No Eyholzer et al.
homogenization (microuidizer) (2010)
(Ultra-Turrax)
Hardwood pulp Kraft process Rening (double No/carboxymethylation Homogenization Ultrasonication Taipale et al. (2010)
disc) (microu-
idizer)/grinding
Dissolving pulp Bleaching Blending Quaternization/ Homogenization No Aulin et al. (2010a)
carboxymethylation (microuidizer)
Oat straw pulp No No Quaternization Homogenization No Ho et al. (2011)
(Ultra-Turrax and
microuidizer)
Hardwood pulp Kraft process No Quaternization Homogenization No Liimatainen et al.
(homogenizer) (2014)
Hardwood/softwood Unbleached/kraft No Solvent-based Homogenization No Carrillo et al.
pulp process system (Ultra-Turrax), (2014)
(microemulsion) homogenization
(microuidizer)
Hardwood pulp Bleaching No Solvent-based Homogenization No Sirvi et al. (2015)
system (deep (microuidizer)
eutectic solvent)
10 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
The grinding process is very close to double-disk rening. How-
ever, the main difference is the possibility of a lower gap between
the discs when using grinders. To increase the brillation efciency,
Wang et al. (2012) reported the use of reducing the gap between the
grinding stones to 100 m from the zero position of motion. The
motion zero position is the contact position between two stones
before cellulose loading and the negative gap is set after cellulose
loading. Due to the presence of cellulose, there is no direct contact
between the grinding disks even at a negative setting of the disks
gap.
Another solution to facilitate the brillation is by performing
the grinding operation in the presence of a corrosive ller, typically
kaolin or calcium carbonate, as patented by several ller suppliers
(Gane et al., 2010; Husband et al., 2010). The resulting material
is a composite of CNF and a mineral, designated for use in the
papermaking industry (Bardet et al., 2013). Such an approach was
successfully industrialized and is present on the market under the
name FiberLean MFC.
3.1.3. Rening
The rening process, common in the paper industry, is well-
known to swell and peel the bers cell wall in aqueous medium.
Rening increases the bers specic surface and volume (Carrasco
et al., 1996) and makes the microbrils more accessible for fur-
ther biological or chemical treatment. That is why it is commonly
used prior to major operations of CNF production. However, ren-
ing also decreases the ber length through cutting and increases
the amount of nes. Several devices are used to rene cellulose
pulp at the initial stages of CNF production: disk reners (Hamada
et al., 2012; Nakagaito and Yano, 2004), PFI mills (Henriksson et al.,
2007; Janardhnan and Sain, 2007; Turbak et al., 1983b) and Valley
beaters (Joseleau et al., 2012; Spence et al., 2010). Grinders were
also reported to be used for pulp rening prior to more intensive
mechanical disintegration (Hassan et al., 2011; Stelte and Sanadi
2009).
The rening process was also studied as a single mechanical
treatment for CNF production. Karande et al. (2011) reported the
use of a disc rener to disintegrate once-dried bleached cotton
bers suspended in water at a concentration of 0.5 wt.%. The aver-
age ber diameter was reduced from ca. 25 m to 242 nm after
30 passes in the rener. The disintegration process was accompa-
nied by a decrease of DP from 2720 to 740 as well as a decrease
of cellulose crystallinity. Despite the attempts to use only the
rening process for CNF production, this widespread technique
commonly results in highly heterogeneous cellulosic material,
which is sometimes referred to as cellulose micro-/nanobrils
or micro-/nanobrillated cellulose. Thus, rening is commonly
applied as a mechanical pretreatment at the rst stages of CNF
production.
3.1.4. Extrusion
Twin-screw extrusion process can also be used for CNF produc-
tion. During such an approach, cellulose pulp is brillated by two
intermeshing, co-rotating screws mounted in a closed barrel. Due
to a wide range of screw and barrel designs, various screw proles
can be established. Extrusion has several advantages comparing to
homogenization or grinding techniques. First, CNF at a high solid
content, e.g., 2540 wt.% (Ho et al., 2015), can be processed, which
can be a signicant benet for transportation as well as storage
and production itself. Second, cellulose in situ brillation can be
performed while melt compounding of composites. The remaining
challenge of this technique is optimization of the screw prole and
other processing conditions to achieve the sufcient shear forces
necessary to induce delamination of the bers along with prevent-
ing the cellulose degradation.
Ho et al. (2015) reported the production of CNF from never-dried
rened needle-leaf bleached kraft pulp by twin-screw extrusion
process. A combination of kneading and feeding screws was used
and an operating temperature of 0 C was set. The pulp was fed
in the extruder at a concentration of 28 wt.% and brillated for
up to 14 passes. Further processing was not performed since the
temperature exceeded 40 C. By increasing the passes number, the
evaporation of moisture in the pulp occurred. Finally, a solid con-
tent of 45 wt.% was obtained and CNF were in the form of humid
powder. Scanning electron microscopy (SEM) revealed the produc-
tion of nanobers.
Extrusion was also used to produce composites with in situ CNF
production. Pulp nanobrillation and further melt compounding
with polypropylene was reported by Suzuki et al. (2013). Never-
dried rened needle-leaf bleached kraft pulp was disintegrated
to nano- and micrometer size while processing in a twin-screw
extruder with polypropylene, using maleic anhydride polypropy-
lene as a compatibilizer.
Hietala et al. (2014) studied twin-screw extrusion process for
the production of composites from thermoplastic starch and cel-
lulose bers. Bleached cellulose was obtained from softwood our
(particle size of 200400 m) and was further used in the extrusion
process to examine the direct cellulose brillation while pro-
cessing the composites. The results showed that CNF were not
produced during extrusion, but good dispersion of bers in the
starch matrix was achieved. The composites from thermoplastic
starch and TEMPO-oxidized cellulose bers were reported by Cobut
et al. (2014) when using single screw extruder. The brillation
of TEMPO-pretreated cellulose bers in CNF with diameter of ca.
30 nm during extrusion process was reported.
This technique seems to be very promising for CNF produc-
tion. Therefore, a new long-term project on this subject has been
recently launched in France (LGP2, Grenoble, supported by Tec21
and Institut Carnot PolyNat).
3.1.5. Blending
Uetani and Yano (2011) presented the successful use of a high-
speed blender to produce CNF with a uniform diameter of 1520 nm
from never-dried bleached softwood pulp. The blending at various
cellulose concentrations, stirring speeds and durations was ana-
lyzed. It was shown that the processing of cellulose pulp suspension
at a concentration of 0.7 wt.% at 37,000 rpm were the optimal condi-
tions for CNF production using such a method. Blending for 30 min
showed the same degree of brillation and less damage of CNF
comparing to that of grinded in Supermasscolloider for 1 pass.
A similar process to isolate CNF from rice straw cellulose was
reported by Jiang and Hsieh (2013). They blended the cellulose sus-
pension at 37,000 rpm for various periods of time (up to 2 h) and
heated up to 97 C. The obtained CNF had bimodal size distribution:
(i) a diameter of 2.7 nm and length of 100200 nm and (ii) diameter
of 8.5 nm and length of few micrometers. To increase the efciency
of such a process and to reduce the blending time, the design of the
blender bottle was improved by Nakagaito et al. (2015). As a result,
the time required for brillation was reduced by half.
Chaker et al. (2013) showed that it is possible to produce CNF by
blending of 2 wt.% cellulose suspension for 20 min and to obtain a
similar yield, compared to a suspension passed 10 times at 600 bar
in a homogenizer. This can be achieved by using a pulp with high
hemicelluloses content (ca. 25%) after mild TEMPO-mediated oxi-
dation (carboxyl content up to 500 mol g1 ).
3.1.6. Ultrasonication
Ultrasonication consists in exposing a liquid to ultrasonic waves
(>20 kHz), which results in alternating low-pressure and high-
pressure waves, leading to the creation and collapse of small
vacuum bubbles (Wang and Cheng, 2009; Kaboorani et al., 2013).
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Such treatment creates strong hydrodynamic shear forces, which
can be used to delaminate the ber cell wall. A number of
researchers used this method to produce CNF without biochemi-
cal pretreatments (Cheng et al., 2009; Wang and Cheng, 2009; Chen
et al., 2011a) or after TEMPO-mediated oxidation (Saito et al., 2006;
Johnson et al., 2008; Zhou et al., 2012; Saito et al., 2013). After ultra-
sonication, the cellulose suspensions were commonly centrifuged
and the CNF were recovered from the supernatant.
3.1.7. Cryocrushing
Another method for production of CNF was proposed by
Dufresne et al. (1997) and is called cryocrushing. In this method,
cellulose is frozen using liquid nitrogen and further crushed by
applying high shear forces. Under mechanical impact, ice crystals
exert pressure on the cell walls, causing them to break and release
cell wall fragments. Dufresne et al. (1997) showed that CNF can
be produced from hydrated and cryocrushed raw sugar beet pulp,
which was further passed through a Manton-Gaulin homogenizer
at 500 bar for 2 h. Cryocrushing is often used by the research group
of Sain (Bhatnagar and Sain, 2005; Wang et al., 2007; Janardhnan
and Sain, 2007; Alemdar and Sain, 2008) mostly for brillation of
agricultural crops.
3.1.8. Steam explosion
During the steam explosion process, pulp is exposed to pressur-
ized steam for short periods of time, followed by a rapid release
of pressure, which causes a rupture of the ber cell wall. This
treatment also results in the hydrolysis of signicant amounts of
hemicellulose to elementary sugars and water-soluble oligomers
and in depolymerization of some lignin (Fernandez-Bolanos et al.,
2001; Sun et al., 2005). Steam explosion is used mainly as a pulping
process for the extraction of cellulose bers from lignocellulosic
materials. However, it was also proposed for CNF production from
such sources as pineapple leafs (Cherian et al., 2010), banana bers
(Deepa et al., 2011), Helicteres isora (Kaushik and Singh, 2011) and
jute (Manhas et al., 2015). The quality of the obtained CNF remains
questionable.
3.1.9. Ball milling
Ball milling is another technique which was reported very
recently for the production of CNF. In this method, a cellulose
suspension is placed in a hollow cylindrical container, partially
lled with balls (e.g., ceramic, zirconia or metal). While the con-
tainer rotates, cellulose is disintegrated by the high energy collision
between the balls.
Zhang et al. (2015) studied the process of CNF production from
once-dried bleached softwood kraft pulp suspension at a solid con-
centration of 1 wt.% using ball milling. They showed the inuence
of the process conditions, such as the ball size and ball-to-cellulose
weight ratio, on the morphology of the produced CNF. An aver-
age diameter of 100 nm was reported for the disintegrated bers.
The control of the processing parameters was necessary to pre-
vent cellulose decrystallization and to produce cellulose nanobers
rather than short particles. Keklinen et al. (2015) proposed the
production of CNF from TEMPO-pretreated never-dried bleached
hardwood kraft pulp at high solid contents (50%) using ball milling
process. The inuence of grinding time, moisture content and car-
boxylic charge on disintegration process and CNF morphology was
examined in this work. Individual CNF with a diameter of 3.2 nm
were produced, as well as the bundles of nanobrils with a diameter
of 10150 nm. Thus, the quality and homogeneity of the produced
CNF remains a major challenge for this method.
3.1.10. Aqueous counter collision
Another mechanical method reported for CNF preparation is
aqueous counter collision (ACC). In this technique two jets of
11
cellulose aqueous suspensions collide against each other under
high pressure, resulting in wet pulverization and liberation of
CNF. Kose et al. (2011) produced individual CNF using ACC from
0.4 wt.% bacterial cellulose aqueous suspension, which was pre-
viously homogenized to obtain objects of ca. 180 m in width.
These suspensions were processed in ACC system at an ejecting
pressure of 200 MPa for up to 80 passes. As a result, individual
CNF with a diameter of ca. 30 nm were produced. After ACC, cel-
lulose I crystalline phase changed to cellulose I phase, whereas
the crystallinity was kept at >70%. Using such a method CNF from
microcrystalline cellulose (obtained from wood pulp) were also
produced (Kondo et al., 2014). The resulting CNF had a diameter
of ca. 15 nm and a length of ca. 700 nm. One of the shortcomings
of this method is the size of processed cellulosic material, which
should be lower that the nozzle diameter (ca. 150 m) to avoid
clogging.
3.2. Biological and chemical pretreatments
Production of CNF using only mechanical disintegration requires
high energetic costs (Spence et al., 2011; Tejado et al., 2012). This
explains the absence of signicant interest in patenting of CNF-
based developments during few decades after introducing this type
of material in early 1980s (Charreau et al., 2013). However, inten-
sive research has been performed to enhance brillation and to
reduce energy demand. Recent methods of CNF production involve
various biological and chemical pretreatments. These types of pre-
treatments inuence strongly the resulting CNF. Fig. 5 shows a
typical visual appearance of CNF aqueous suspensions prepared
using different pretreatment methods.
3.2.1. Enzymatic hydrolysis
It has been known that some enzymes catalyze the hydroly-
sis of cellulose and enhance its brillation. Bolaski et al. (1962)
patented the use of cellulase to improve cellulose brillation in
the papermaking process. Since then, an extensive investigation
has been carried out ranging from mild enzymatic hydrolysis, in
order to facilitate rening process, to strong hydrolysis in order to
convert cellulose into glucose for further production of bioethanol
(Tangnu, 1982). Recently, the production of CNF by applying mild
enzymatic hydrolysis was reported (Henriksson et al., 2007; Pkk
et al., 2007). In these works, a monocomponent endoglucanase
(Novozym 476 from Novozymes A/S, Denmark) was used as an
enzyme.
Pkk et al. (2007) proposed a method to disintegrate cel-
lulose bers with the following steps: (i) rening, performed to
increase cellulose swelling and to make it more accessible for the
enzyme; (ii) enzymatic hydrolysis, to facilitate the cellulose bers
delamination; (iii) washing and again rening followed by (iv)
homogenization of 2 wt.% aqueous suspension by 8 passes through
a microuidizer, equipped with two sequential Z-type interaction
chambers of different size. Henriksson et al. (2007) proposed a
similar procedure, applying different enzyme concentrations, and
using a homogenizer for 20 passes. During the enzymatic hydroly-
sis, the decrease of the DP and the increase of the crystallinity index
were usually observed (Henriksson et al., 2007; Qing et al., 2013;
Nechyporchuk et al., 2015a).
Fungi are the main microorganisms which produce cellu-
lases, although some bacteria and actinomycetes have also been
reported to yield cellulase activity (Jayant et al., 2011). Generally,
cellulases can be divided into three classes: (i) endoglucanases
(endocellulases), which hydrolyze amorphous regions of cellu-
lose; (ii) cellobiohydrolases (exoglucanases), which progressively
cleave the ends of cellulose crystalline or amorphous regions, pro-
ducing disaccharides (cellobiose) and tetrasaccharides, and (iii)
-glucosidases (cellobiases), which hydrolyze the di- and tetrasac-
12 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225

Fig. 5. Typical visual appearance of CNF suspensions (placed in Petri dishes, top view) produced using different processing conditions.

Fig. 6. Schematic diagram of different cellulase impacts on cellulose. Adapted from Lynd et al. (2002) with permissions from American Society for Microbiology and the
authors.

charides into glucose (Zhou and Ingram, 2000), as shown in Fig. 6.
At least two cellobiohydrolases are found in natural cellulases: cel-
lobiohydrolase I and cellobiohydrolase II, which attack reducing
and non-reducing ends of cellulose chain, respectively (Vljame
et al., 1998). In the process of enzymatic hydrolysis, cellulases can
be irreversibly bound to lignin; therefore, it is necessary to remove
the latter before the hydrolysis (Berlin et al., 2006).
Some studies (Siqueira et al., 2010; Qing et al., 2013) reported
the use of cellulase solution (Celluclast 1.5 L from Novozym A/S,
Denmark), which is a mixture of endoglucanase, exoglucanase and
cellobiase with the major activity of endoglucanase and exoglu-
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
canase (Rosgaard et al., 2007; Turon et al., 2008). Nechyporchuk
et al. (2015a) compared the production of CNF using the mono-
component endoglucanase and a mixture of endoglucanase,
exoglucanase and cellobiase. They showed that the monocompo-
nent endoglucanase has better effect on the nanobril separation
while inducing less depolymerization.
3.2.2. Carboxylation via TEMPO-mediated oxidation
The introduction of negatively charged (e.g., carboxyl or car-
boxymethyl) groups on cellulosic bers is known to improve
delamination of the nanobrils. This happens due to electrostatic
repulsion between the negatively charged cellulose nanobrils
(Bckstrm et al., 2012). Based on the same principle, it is known
that sulte pulps are easier to delaminate than kraft homologues.
Since 1993, when Davis and Flitsch (Davis and Flitsch, 1993)
reported the use of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)
radical for selective oxidation of the primary alcohol groups of
monosaccharides, this process has become one of the most stud-
ied topics in the eld of selective oxidation of cellulose. De Nooy
et al. (1994) reported a selective oxidation of polysaccharides pri-
mary alcohol groups to carboxylates using TEMPO, hypobromide
and hypochlorite at basic pH. This approach was further used by
Saito et al. (2006) to oxidize cellulose (a carboxyl content of up to
1.52 mmol/g) and to produce CNF using blending. The oxidation
reaction was carried out at room temperature for several hours
on never-dried cellulose from different sources (bleached sulte
wood pulp, cotton, tunicin, and bacterial cellulose). Finally, it was
disintegrated into individual nanobrils with a regular width of
35 nm.
The basic principle of TEMPO/NaBr/NaClO treatment (see Fig. 7a,
for shortening, cellulose repeating unit is displayed as anhydroglu-
cose instead of cellobiose) is the oxidation of cellulose bers by
the nitrosonium ion (+ N O), generated in situ through the reac-
tion of TEMPO radical with the oxidants. Consequently, the primary
alcohol groups of cellulose are converted into aldehydes, which are
further oxidized to carboxylic groups. It has been found that the
depolymerization of cellulose during the oxidation reaction takes
place. Two phenomena were assumed to be associated with cellu-
lose depolymerization: (i) -elimination due to the presence of C6
aldehyde groups under alkaline conditions and (ii) anhydroglucose
unit cleavage due to the presence of hydroxyl radicals formed as
side reactions (Isogai et al., 2011; Coseri et al., 2013).
In order to overcome the depolymerization occurring during
TEMPO/NaBr/NaClO reaction, several approaches were used. Zhao
et al. (1999) reported the use of TEMPO/NaClO/NaClO2 system
for oxidation of primary alcohol groups of different organic com-
pounds. Saito et al. (2009) successfully used a similar method for
cellulose oxidation (see Fig. 7b). The reaction was performed under
neutral or weakly acidic conditions at 60 C for up to 72 h. It was
shown that the original DP was mostly maintained when using the
TEMPO/NaClO/NaClO2 reaction.
After TEMPO-mediated oxidation, some unconverted aldehyde
groups remain, which can induce yellowing of the ensuing CNF
during oven drying, e.g., at 105 C (Mishra et al., 2012). Aldehyde
presence also disturbs the correct determination of DP from vis-
cosity measurements in copper ethylenediamine (CED) solution,
causing cellulose depolymerization (Shinoda et al., 2012). Thus, it
was proposed to perform: (i) a reduction reaction using sodium
borohydride in order to convert the residual aldehyde groups back
to alcohols or (ii) further oxidation reaction using sodium chlorite
in order to turn the aldehyde groups into carboxyl moieties (Saito
and Isogai, 2006; Mishra et al., 2012; Shinoda et al., 2012). It was
also reported that through nanobril surface oxidation the reduc-
tion in the CNF network strength was observed due to decrease of
the friction coefcient between the bers (Bckstrm et al., 2012).
13
A large number of reaction conditions was examined by the
research group of Prof. Akira Isogai using TEMPO and its derivatives
in order to nd energy-efcient ways of CNF production (Isogai
et al., 2011). Thus, for the innovative research on TEMPO-mediated
oxidation of cellulose and its further use for CNF production, Prof.
Akira Isogai received the Marcus Wallenberg Prize and Anselme
Payen Award in 2015.
3.2.3. Carboxylation via periodatechlorite oxidation
Sequential periodatechlorite oxidation of cellulose can be used
to convert cellulose secondary alcohols to carboxyl groups (Kim
and Kuga, 2001). Such a method was used by Tejado et al. (2012)
and Liimatainen et al. (2012) as a pretreatment to enhance the fur-
ther mechanical disintegration of cellulose. During the reaction,
cellulose secondary alcohols are rst oxidized using sodium peri-
odate to aldehyde groups, which are subsequently converted to
carboxyl groups using sodium chlorite (see Fig. 8a). In the work
of Liimatainen et al. (2012) the oxidized cellulose with a carboxyl
content of up to 1.75 mmol/g was produced. It was further washed,
redispersed in water and brillated using a two-chamber high-
pressure homogenizer for up to 4 passes. They produced CNF with a
width of 35 nm (Liimatainen et al., 2013a), as deduced from atomic
force microscopy (AFM).
It should be noted that this method leads to the opening of
the glucopyranose ring resulting in 2,3-dicarboxylic acid cellulose.
However, ring opening seems not to decrease the strength prop-
erties of nanobrils (Liimatainen et al., 2013a). On the contrary,
Liimatainen et al. (2013a) studied the lms, prepared from such CNF
and talc and observed that the tensile strength and elastic modulus
were remarkably higher than those reported previously for such
materials. Assumedly, the ring opening can increase the ductility
of the nanobrils, as shown by Larsson et al. (2014) for sheets pro-
duced from microscopic cellulose bers. In their work, the bers
were oxidized with sodium periodate, followed by a reduction with
sodium borohydride, yielding the 2,3-dialcohol cellulose.
3.2.4. Sulfonation
One more way to introduce negatively charged groups on the
surface of cellulose nanobrils and to promote the brillation pro-
cess is sulfonation (Liimatainen et al., 2013b; Sirvi et al., 2014).
In the work of Liimatainen et al. (2013b), bleached kraft hard-
wood pulp was successively treated with periodate and bisulte
(see Fig. 8b) and was passed through a homogenizer 5 times. CNF
with typical widths of 1060 nm were obtained from sulfonated
cellulose having low anionic charge densities of 0.180.51 mmol/g.
The elastic modulus and tensile strength of (13.5 0.4) GPa and
(164 4) MPa, respectively, were measured for a transparent lm,
obtained from CNF with the anionic charge density of 0.51 mmol/g
using vacuum-ltration. Such pretreatment was shown to be a
potential green method to facilitate CNF production, since the used
periodate can be efciently recycled (90100% recovery), as shown
in the preliminary experiments (Liimatainen et al., 2013b).
3.2.5. Carboxymethylation
Carboxymethyl cellulose was rst prepared in 1918, and was
already produced commercially in the early 1920s in Germany
(Heinze and Koschella, 2005). The production of CNF from car-
boxymethylated cellulose as a new type material was reported by
Wgberg et al. (2008). It has been produced using high-pressure
homogenization of carboxymethylated cellulose bers (see Fig. 8c)
followed by ultrasonication and centrifugation to remove the
residual non-brillated bers. The nanobrillated cellulose had a
cylindrical cross-section with a diameter of 515 nm and a length
of up to 1 m.
Eyholzer et al. (2010) used carboxymethylation pretreatment to
produce water-redispersible CNF in powder form (see Section 4.2).
14 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225

Fig. 7. Schematic diagrams of the regioselective oxidation of cellulose primary alcohol groups by: (a) TEMPO/NaBr/NaClO in water at basic pH and (b) TEMPO/NaClO/NaClO2
in water at neutral or slightly acidic pH.

Fig. 8. Schematic diagrams of cellulose: (a) carboxylation via periodatechlorite oxidation, (b) sulfonation via periodatebisulte treatment, (c) carboxymethylation using
chloroacetic acid and (d) quaternization using (2-3-epoxypropyl) trimethylammonium chloride.
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Carboxymethylation was also used by other researchers to produce
CNF (Aulin et al., 2009, 2010b; Eyholzer et al., 2011; Sir et al., 2011).
It was reported that the ensuing CNF had slightly lower and more
uniform dimensions compared to those of enzymatically pretreated
CNF (Aulin et al., 2009). Such a strategy has also been implemented
at pilot scale by Innventia AB, Sweden, in 2010s.
3.2.6. Quaternization
Compared to carboxymethylation or carboxylation, which are
used to endow cellulose with anionic surface charge, quaterniza-
tion is performed to cationize cellulose (Cai et al., 2003; Abbott et al.,
2006; Song et al., 2008). Such an approach was applied recently to
facilitate CNF production during further mechanical disintegration
(Aulin et al., 2010a). After quaternization, the pulp disintegration
process becomes easier due to electrostatic repulsion between the
quaternary ammonium cations at the surface of the nanobrils.
Aulin et al. (2010a) performed quaternization of bleached
sulphite dissolving pulp using (2-3-epoxypropyl) trimethylammo-
nium chloride in the presence of water, isopropanol and sodium
hydroxide (see Fig. 8d). After washing with deionized water, the
2 wt.% pulp suspensions were disintegrated in a microuidizer for
6 passes. In this work, the obtained cationic CNF were used together
with anionic homologue, made by carboxymethylation, to produce
polyelectrolyte multilayer coatings using layer-by-layer deposition
technique. The morphological and physical properties of these CNF
were further studied by Olszewska et al. (2011), who reported
nanobrils with a diameter of 2.63.0 nm, which was deduced
using cryogenic transmission electron microscopy (cryo-TEM). The
cationic charge density was measured to be 0.35 meq/g.
Another method to produce quaternized CNF was proposed by
Ho et al. (2011). They performed a modication of oat straw pulp
using (2-chloroethyl) trimethylammonium chloride (chlorocholine
chloride) in the presence of dimethyl sulfoxide (DMSO) and sodium
hydroxide. After reaction, the cellulose bers were washed with
deionized water and disintegrated using a microuidizer through
different combinations of Y- and Z-shaped interaction chambers.
The ensuing cationic CNF had much lower lateral dimensions and
uniform network structure, compared to that of the non-modied
counterpart.
Liimatainen et al. (2014) produced the quaternized CNF
using successive periodate oxidation and a reaction with
(2-hydrazinyl-2-oxoethyl)-trimethylazanium chloride (Girards
reagent T), followed by mechanical disintegration using a two-
chamber high-pressure homogenizer for 3 passes at a pressure
of 400680 bar. The obtained nanobrils had a typical width
of 1050 nm. The cationic charge density ranged from 1.10 to
2.13 meq/g depending on the reaction conditions (most notably the
reaction temperature). The CNF had crystallinity indices of 3830%.
It was also recently shown that lms produced from quaternized
CNF exhibit antibacterial properties without any leaching of qua-
ternary ammonium into the environment (Saini et al., 2016). The
antimicrobial activity of composites reinforced with quaternized
CNF was also reported (Chaker and Bou, 2015). These ndings
make CNF promising for applications in active food packaging,
wound healing, tissue engineering etc.
3.2.7. Solvent-assisted pretreatments
Diverse efforts were done to use solvent systems as a pretreat-
ment for CNF production. Acidic or basic treatment is traditionally
used to extract hemicellulose, lignin and the other impurities from
cellulose pulp (Wang et al., 2007; Hassan et al., 2011; De Campos
et al., 2013; Nakagaito et al., 2015). Thus, such treatment can give
a benecial effect on pulp disintegration, despite the fact that it
also partially dissolves cellulose. For instance, Hassan et al. (2011)
treated bleached kraft bagasse pulp with 5% sodium hydroxide
solution for 45 min at 50 C before further grinding in order to
15
extract the residual hemicellulose and lignin present in the pulp.
The ensuing CNF were compared with those of: (i) untreated and
(ii) hydrolyzed with xylanase enzyme before mechanical brilla-
tion. The alkali-pretreated CNF had the highest cellulose content
and DP, with similar lateral dimensions compared to the oth-
ers. These CNF samples were compared in terms of reinforcing
effect in chitosan-based composites. The CNF pretreated with alkali
or xylanase improved wet and dry tensile strength of the com-
posites in a stronger manner, comparing to those measured for
non-pretreated CNF.
Carrillo et al. (2014) proposed a method based on the use of
microemulsions (surfactantoilwater systems) with incorporated
urea or ethylenediamine as a pulp pretreatment prior to mechanical
disintegration. Urea and ethylenediamine were used due to their
ability to loosen the hydrogen bonds between cellulose nanobrils
and to solubilize cellulose under certain conditions. Bleached and
unbleached kraft pulps from softwood and hardwood were treated
with the described above microemulsions at room temperature
and under atmospheric pressure, followed by washing and pass-
ing through a microuidizer with two interaction chambers (200
and 100 m) at 2000 bar for 7 passes. It was shown that urea and
ethylenediamine pretreatment at mild conditions was efcient to
facilitate the CNF isolation. Moreover, the microemulsion medium
was effective to reduce the energy consumed during the mechan-
ical processing, due to the ability of microemulsions to penetrate
the capillary structures of wood.
In a study conducted by Sirvi et al. (2015) a bio-based deep
eutectic solvent (DES) based on choline chloride and urea (molar
ratio of 1:2) was reported to promote brillation of cellulose pulp.
The pretreatment with DES was carried out at 100 C for 2 h, fol-
lowed by its removal through ltration and washing with water.
The cellulose suspension was then passed for up to 6 passes in a
microuidizer through interaction chambers of different geome-
tries. The resulting CNF had lateral dimensions of 25 nm and some
nanobril bundles with width of 15200 nm. It was shown that
the original DP of cellulose was preserved after treating with DES,
whereas an enhancement of ber brillation was observed.
3.3. Post-treatments
While pretreatments are applied to reduce the energy demand
during the CNF production process, different post-treatments,
mainly surface chemical modication, are performed to endow
CNF with new properties (e.g., to improve the compatibility with
polymeric matrixes in composites application) or to conserve
their intrinsic characteristics (e.g., to prepare water-redispersible
CNF). The CNF surface chemical modication can include such
treatments as physical adsorption, molecular grafting or polymer
grafting. These pretreatments can also include surface modi-
cations, already described above as pretreatment methods (see
Section 3.2). Since this topic is very vast, the reader having a
particular interest in CNF surface modication is referred to the
corresponding review articles (Hubbe et al., 2008; Missoum et al.,
2013; Kalia et al., 2014). Additionally, centrifugation, ltration or
other techniques can be performed as a post-treatment to fraction-
ate the obtained cellulosic material.
3.4. Fractionation
A wide range of production techniques results in CNF with dif-
ferent morphology. The currently available techniques generally
yield a wide size distribution of produced CNF with some non-
brillated residual bers. Thus, it is very important to develop
efcient fractionation tools (integrated in the mechanical disin-
tegration process or as a post-treatment) for evaluation of the
16 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
produced CNF and for retrieving the undesired large fragments,
which may be further disintegrated.
A limited number of studies devoted to the issues of CNF frac-
tionation is available in literature. Tanaka et al. (2012) developed a
fractionation method based on the use of a cross-ow ultraltration
system to characterize nano- and microscale cellulose elements.
Different grades of CNF suspensions, produced by grinding of
enzymatically hydrolyzed, TEMPO-oxidized and non-pretreated
cellulose pulps, were processed. The fractionation system (see
Fig. 9a) had two optional fractionation modules: a rotating frac-
tionation element (see Fig. 9b) and cylinder tube unit (see Fig. 9c).
The fractionation was performed using a pump circulation system
with one fractionation module at a time, allowing the cellulose,
which does not pass through, to return back into the feed tank.
During the experiment, the decrease of volume due to permeate
removal was compensated by water addition. Initial CNF suspen-
sion concentration of 0.1% was used. Each stage was terminated
when the permeate turbidity was lower than 30 nephelometric
turbidity units (NTU). Morphology of the fractionated samples was
examined using SEM. The use of such a setup was efcient to sep-
arate the cellulose elements with specic dimensions, depending
on the membrane pore dimensions.
Madani et al. (2011) performed fractionation of commercial
CNF with an average ber length of 221 m (diameter was not
specied), indicating the presence of large microscopic objects.
Three different fractionation techniques were used: processing
in a hydrocyclone (see Fig. 9d), pressurized screening and cen-
trifugation in viscoplastic carrier uid. Cellulose suspensions at
concentrations ranging from 0.1 to 1 wt.% were used. Centrifuga-
tion was found to be the most efcient method to eliminate large
bers from the CNF suspensions.
Cross-ow ultraltration process, using several ceramic mem-
branes (pore size was not specied), was studied by Zhu et al.
(2012) in order to separate nanobers from the pulp, which was
pretreated using different methods. The pulp suspension with an
initial concentration of 0.1 wt.% was continuously circulated in the
fractionation system (see Fig. 9a), while the permeate was recov-
ered. The permeate with CNF concentration of 0.10.3 wt.% was
obtained, depending on the applied pretreatment. It was shown
that the fractionated CNF had a more narrow size distribution,
compared to that in the initial cellulose suspensions.
Haapala et al. (2013) reported the use of tube ow fractiona-
tion system (initially proposed by Laitinen et al., 2011) and ow
cytometry (FCM) method for CNF fractionation and both size and
structure characterization, respectively. In tube ow fractionation
(see Fig. 9e) a dilute cellulose suspension is subjected to ow
through a long plastic tube, where particles arrange within the tube
length according to their size. Accordingly, the largest particles
accumulate at the front part, whereas the smallest ones concen-
trate at the rear part of the tube. In the work of Haapala et al.
(2013), cellulose suspensions with a solid consistency of either 0.1%
or 0.2% were used for fractionation. Four batches of the suspensions
with different dimensions were obtained and were further exam-
ined in terms of cellulose relative size, degree of brillation and
aspect ratio. The results of FCM were compared with those of laser
diffraction and microscopy techniques. Although the interpreta-
tion of FCM data is complicated, this method can provide practical
knowledge for quality control and improvement of the produc-
tion process. Chinga-Carrasco et al. (2014) carried out a screening
using McNett classier (according to SCAN-CM 6:05 standard) to
remove the residual bers from 0.30.4 wt.% CNF aqueous suspen-
sion and studied the inuence of fractionation on the roughness of
the ensuing nanopaper.
Low solid content of fractionated CNF remains the main draw-
back of these techniques, which may limit their application in
simultaneous CNF production. However, these fractionation tech-
niques can be feasible for characterization and comparison of
different CNF grades.
3.5. Scaling up
Production of CNF is a batch process which employs the use
of several operations to produce the nal product, as discussed
previously (see Fig. 3). No single technique/equipment has been
developed yet for CNF isolation. Thus, various sequential processes
have been proposed by researchers. It should be kept in mind that
these processes should be scalable to allow industrialization of CNF
production. Moreover, their energy efciency remains an impor-
tant issue.
As of the end of 2015, around ten companies were positioned to
produce CNF (or similar products) at commercial/pre-commercial
scale, including Paperlogic, Forest Products Laboratory (coop-
erating with the University of Maine), American Process (all
USA), Borregaard (Norway), Innventia (Sweden), Nippon Paper,
Oji Paper (both Japan), CTP/FCBA (France) and others. Moreover,
numerous organizations have pilot scale production, which is
not disclosed and is employed for development of various CNF
applications. Rening, grinding and homogenization are typically
used as mechanical disintegration techniques in combination with
enzymatic or TEMPO-mediated oxidation pretreatments for the
production of CNF at commercial scale.
The cost aspect and other CNF industrialization issues have been
extensively discussed recently by Chauve and Bras (2014). Despite
multiple actors producing CNF nowadays, there is a great variety of
possible CNF grades. Moreover, no optimal processing conditions
were reported yet for the specic CNF applications. Thus, it is still
difcult to assess the end-use price of CNF. Nevertheless, it is esti-
mated to range between 712 USD per kg of dried material (Chauve
and Bras, 2014).
3.6. Quality assessment
A number of studies have been devoted to the comparison of dif-
ferent methods for CNF characterization (Chinga-Carrasco, 2013;
Moser et al., 2015), addressing the issues of evaluation of the extent
of brillation, which may be critical in quality control during the
production process. A range of properties are important for CNF
characterization: morphology, DP, crystallinity, chemical composi-
tion, rheology of CNF aqueous suspensions etc. In this section some
of them are discussed.
3.6.1. Morphology
Morphology of the obtained CNF is one of the most impor-
tant parameters to control during the production process. CNF
morphology depends strongly on the cellulose source and the
production process. Moreover, slightly different observations can
be obtained when using different microscopy techniques, e.g.,
transmission electron microscopy (TEM), eld emission scanning
electron microscopy (FE-SEM) or atomic force microscopy (AFM), as
well as the way of sample preparation for the analysis. For instance,
CNF can aggregate to some extent during some dehydration proce-
dures, e.g., freeze drying.
Generally, CNF, which are prepared using only mechanical treat-
ment or with a preliminary enzymatic hydrolysis, have a slightly
higher diameter compared to that of CNF pretreated with chemical
methods. Fig. 10 shows AFM height sensor images of CNF, produced
using different pretreatments, followed by homogenization in a
microuidizer, as reported by Phler et al. (2010). CNF diameter
is measured from the height prole of the images. Non-pretreated
CNF (see Fig. 10a; enzymatically hydrolyzed CNF have similar mor-
phology) have a higher diameter compared to that of the chemically
pretreated counterparts (see Fig. 10bd), which was also conrmed
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Fig. 9. Schematic diagrams of: (a) typical fractionation setup, consisting of feed tank, pump and fractionation module, such as (b) rotating fractionation element or (c) cylinder
tube unit. Schematic diagrams of: (d) hydrocyclone and (e) tube ow fractionator. Figures (b) and (c) were adapted from Tanaka et al. (2012) with permission from Nordic
Pulp and Paper Research Journal.
by other studies. For instance, Aulin et al. (2009) performed homog-
enization of bleached wood pulp and produced CNF with a diameter
of 1030 nm and 1015 nm when disintegrating non-pretreated
and carboxymethylated pulp, respectively, as measured from AFM
images. Henriksson et al. (2007) carried out enzymatic hydrolysis
and homogenization of bleached wood sulphite pulp to produce
CNF with a diameter of 530 nm, as deduced from AFM. Whereas,
Liimatainen et al. (2013a) showed that CNF with a diameter of
35 nm can be produced using periodatechlorite oxidation, fol-
lowed by homogenization.
A diameter of 35 nm was also measured from TEM analysis
for CNF from bleached sulte wood pulp and cotton, produced
by TEMPO-mediated oxidation and blending (Saito et al., 2006).
Olszewska et al. (2011) reported CNF, produced by quaternization
and homogenization, with a diameter of 2.63.0 nm, deduced from
cryo-TEM. Thus, the nanobrils with a diameter of 35 nm may
relate to the elementary brils, while the thicker ones may repre-
sent the bundles of elementary brils and microbrils (as shown
in Fig. 1). Determination of CNF length is problematic due to high
aspect ratio of nanobrils. At relatively high magnication, the
diameter of a cellulose nanobril can be detected, while the length
is out of measured range. When the magnication decreases in
order to capture the whole length, the nanobril becomes unde-
tectable due to its small diameter.
In summary, it should be noted that by introducing charged
groups, CNF with smaller diameter can be produced, compared to
that of non-modied or enzymatically hydrolyzed CNF, which also
results in more transparent aqueous suspensions as shown pre-
viously in Fig. 5. Moreover, mechanically delaminated as well as
previously enzymatically hydrolyzed CNF possess more entangle-
ments and can form occulated structures, as particularly shown by
Nechyporchuk et al. (2015a). Besides the nanobrils, the produced
17
material generally has some portion of non-brillated microscopic
bers or ber fragments.
3.6.2. Degree of brillation
As mentioned above, there is a great variety of production
methods, which affect strongly the morphology of the obtained
CNF. The characterization of this parameter is usually performed
in nanoscale using microscopy techniques in order to prove the
presence of nanobrils in the obtained material. However, such an
evaluation may exclude the residual microscopic bers and ber
fragments. Since it is time consuming to perform the microscopy
characterization at different magnications, as well as to carry out
the repetitive measurements to obtain representative results, other
reliable methods are necessary to quantify the obtained cellulose
particles, typically using a concept of degree of brillation.
Different methods were reported to evaluate the brillation
degree of CNF, e.g., through centrifugation to determine a water
retention value (WRV) (Saito et al., 2007; Hoeger et al., 2013;
Carrillo et al., 2014) or so-called yield of brillation (Besbes et al.,
2011; Chaker et al., 2013; Benhamou et al., 2014); measuring light
transmittance or scattering/turbidity of CNF aqueous suspensions
(Saito et al., 2006; Besbes et al., 2011; Chaker et al., 2013) or CNF
lms (Sir et al., 2011; Qing et al., 2013).
WRV is an empirical measure of celluloses capacity to hold
water. During pulp disintegration, the WRV value increases due
to an increase of cellulose surface area. Therefore, WRV measure-
ments (adopted from TAPPI UM 256 standard) can be used as an
indication of CNF degree of brillation. To determine the WRV, dif-
ferent conditions were used by different researchers, e.g., 6.25 g
of CNF aqueous suspension at 4 wt.% (Hoeger et al., 2013) or 10 g
at 1.4 wt.% (Carrillo et al., 2014) were centrifuged at 900 g for
30 min; Saito et al. (2007) performed centrifugation at 4500 g for
20 min. Then, the supernatant was removed and the wet sediment
18 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Fig. 10. AFM height images of CNF, produced from hardwood kraft pulp using homogenization of: (a) non-pretreated, (b) carboxymethylated, (c) carboxylated via TEMPO-
mediated oxidation or (d) quaternized cellulose. Adapted from Phler et al. (2010) with permissions from TAPPI (www.tappi.org) and the authors.
was weighed and oven dried at 105 C until reaching a constant
weight. The WRV was calculated as follows:
ww wd
WRV(%) = 100,
wd
where ww is a weight of the wet sediment and wd is a weight of the
dried sediment.
Another method to evaluate an extent of brillation using cen-
trifugation process is through calculating a yield of brillation
(Besbes et al., 2011). In the proposed method, a cellulose suspension
at 0.10.2 wt.% was centrifuged at 4500 rpm (centrifuge model or
relative centrifugal force were not specied) for 20 min to separate
CNF (in supernatant) from non-brillated residue (in sediment).
Then, the supernatant was removed and the sediment was dried
to a constant weight at 90 C in a halogen desiccator and weighed.
The yield of brillation was calculated as follows:
wc ws
Yield(%) = 100,
wc
where wc is a weight of dried cellulose in the suspension before
centrifugation and ws is a weight of dried sediment after centrifu-
gation.
The capacity of CNF suspensions and lms to transmit or scatter
visible light can also give an insight into the degree of brillation.
When more microscopic bers and their fragments remain intact
in the suspension, the higher the light scattering, which results in
less transparent CNF suspensions or lms. Ultravioletvisible spec-
troscopy was commonly used for this purpose to examine both CNF
suspensions (Saito et al., 2006; Besbes et al., 2011; Liimatainen et al.,
2012) and lms (Sir et al., 2011; Qing et al., 2013). Syverud et al.
(2011) used a desktop image scanner for quantication of CNF lm
transparency and visualization of non-brillated ber fragments.
Chinga-Carrasco (2013) compared different optical techniques for
(1) quantication of the degree of brillation of CNF in suspensions and
lms, such as ultravioletvisible spectroscopy and turbidimetry, as
well as different devices, including image scanner, ber optic test-
ing apparatus (FiberMaster) and a light sourcedigital CCD camera
system for dynamic measurements. It was reported that all the opti-
cal techniques and devices were suitable for quantifying the light
transmittance of CNF suspensions and lms, which is inuenced
by residual non-brillated bers. However, the image scanner was
found to be the most appropriate for evaluating the brillation
degree of CNF lms, as the residual bers are easily detected. More-
over, the light sourcecamera system for dynamic measurements,
based on analysis of grey level of the images, was demonstrated.
Such a system appeared to be promising for simultaneous evalua-
tion of the brillation degree in CNF production process.
(2)
3.6.3. Rheology
CNF are initially produced in the form of aqueous suspen-
sions. They retain a large amount of water because of the highly
hydrophilic nature of cellulose. CNF suspensions are known to
exhibit gel properties even at low cellulose concentrations, e.g.,
0.125 wt.% (Pkk et al., 2007), which occurs when the percola-
tion threshold concentration of nanobers is exceeded. Thereby,
an entangled network structure is formed, associated with the high
aspect ratio of CNF. The strength of this network enhances progres-
sively as cellulose concentration increases.
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Rheology is a key characteristic of CNF suspensions, since it
can reect a behavior of this material in different industrial pro-
cesses, e.g., in mixing, pumping or coating. CNF suspensions have
shear thinning properties, i.e., their viscosity decreases while shear
rate increases. CNF suspensions are thixotropic, i.e., the longer they
undergo shear stress, the lower their viscosity, and it takes some
time to attain an equilibrium level. Viscosity recovers as the shear-
ing forces are removed. Thus, shear stress and viscosity of CNF
suspensions are commonly measured at equilibrium by applying a
stepped shear rate. It was demonstrated that viscosity of CNF sus-
pensions increases when the pH is lowered (Pkk et al., 2007).
This is a result of reducing the electrostatic repulsion between the
nanobrils due to neutralization of negative charges by hydrogen
ions, which leads to higher interbrillar interactions.
An increase of viscosity of TEMPO-oxidized CNF suspensions,
produced from bleached sulte pulp, when subjecting the sus-
pension to more intense mechanical disintegration, was observed
by Lasseuguette et al. (2008). Such behavior was explained by
the continuous disintegration of cellulose bers into CNF. At
higher mechanical treatment, less residual microscopic bers were
detected using microscopy observations. Thus, an increase of vis-
cosity was associated with an increase of CNF concentration in
water. Shogren et al. (2011) observed an increase of viscoelas-
tic properties followed by progressive decrease when passing the
CNF suspension, produced from corn cobs, through a homoge-
nizer. Similar behavior was reported by Benhamou et al. (2014) for
CNF, prepared from date palm tree, when the oxidation level was
increased. The reduction of suspension stiffness was assigned to
the decrease of aspect ratio and an increase of electrostatic repul-
sion of the nanobrils. Although the rheological behavior of CNF
suspensions still requires further investigation, the above observa-
tions suggest that rheometry can be used as a tool to control the
CNF production process. It can be efcient to ensure CNF isolation
while preserving its further deconstruction and the reduction of
the aspect ratio.
Furthermore, CNF suspensions have a complex rheology, which
is justied by its heterogeneous ow behavior. It occurs due to the
presence of multiple ow bands, i.e., regions with different ow
velocity. Thus, the presence of such phenomena in CNF suspen-
sions using visualization techniques was a subject of several studies
(Karppinen et al., 2012; Saarikoski et al., 2012; Nechyporchuk et al.,
2014, 2015b; Martoa et al., 2015). Moreover, CNF suspensions tend
to slip over smooth surfaces of rheometer geometry, which is signif-
icant at low shear rates. Thus, roughening of the geometry surfaces
can be performed to overcome this issue (Nechyporchuk et al.,
2014, 2015b).
4. Cellulose nanobrils in different forms
4.1. Suspensions
As mentioned above, depending on the production process, the
obtained CNF aqueous suspensions have different properties. The
rheological behavior is one of the key parameters used to char-
acterize CNF suspensions. Regardless of the production methods,
as well as biological or chemical pretreatments, all of them pos-
sess gel-like, shear thinning and thixotropic behavior at low solid
content (as discussed previously in Section 3.6.3). However, these
suspensions can be further converted to other CNF products, e.g.,
hydrogels, aerogels, powders or lms. The production of various
types of CNF products is briey reviewed hereafter.
19
4.2. Powders
The use of CNF in a range of industrial applications is limited
due to several reasons. First, CNF has a high hydrophilic character,
which results in highly viscous aqueous suspensions at low solid
content. Second, cellulose has a tendency to irreversibly aggregate
while drying (hornication phenomenon). Thus, one of the chal-
lenges is to produce dry CNF powder with preserved nanoscale
structure and to ensure its redispersibility. This can provide advan-
tages in CNF storage, transportation and industrial applications.
A number of methods was studied for CNF drying, e.g., oven dry-
ing, spray drying, freeze drying or supercritical drying (Quivy et al.,
2010; Peng et al., 2012; Zepic et al., 2014). However, all of them led
to aggregation or formation of strong highly-networked structures.
Though, Eyholzer et al. (2010) showed that a water-redispersible
CNF in powder form can be prepared from bleached hardwood pulp
using carboxymethylation and mechanical disintegration, followed
by oven drying. SEM measurements of freeze-dried suspensions
from redispersed CNF conrmed that carboxymethylation pre-
vented the hornication during drying. Butchosa and Zhou (2014)
produced water redispersible CNF with adsorbed carboxymethyl
cellulose. In their work, the water redispersibility of dried CNF
was characterized by a sedimentation test. It was shown that
above a critical threshold of carboxymethyl cellulose adsorption
of 2.3 wt.%, the oven dried CNF sample was fully redispersible in
water. Moreover, after the redispersion, the initial CNF properties
were preserved.
Another way to produce water-redispersible CNF without any
chemical surface modication or adsorption was proposed by
Missoum et al. (2012). In their work, sodium chloride was used
to exchange cellulose counterion from H+ to Na+ , which decreases
signicantly the intermolecular hydrogen bonding. It was shown
that the freeze-dried CNF with added sodium chloride can be easily
redispersed in water and produces similar suspensions compared
to those prepared from non-dried CNF.
4.3. Films
CNF suspensions can be dried to obtain lms, also known as
nanopaper. Several methods can be applied to produce such lms,
e.g., air drying (Aulin et al., 2010c, 2012), pressurized ltration fol-
lowed by hot pressing (Henriksson et al., 2008; Nogi et al., 2009;
sterberg et al., 2013) or spray coating (Beneventi et al., 2014). CNF
lms typically possess high level of transparency (8090%) in the
visible wavelength spectrum, since the small nanober dimensions
and their dense packing signicantly reduce light scattering (Nogi
et al., 2009; Huang et al., 2013). Apart from the residual micro-
scopic ber fragments, some lack of transparency is associated with
surface light scattering. Nogi et al. (2009) showed that the trans-
parency of CNF lms can be enhanced by polishing of their surface,
e.g., by lamination or deposition of transparent resins/plastics (see
Fig. 11a).
As shown by Sir and Plackett (2010), the elastic modulus of CNF
lms may approach 20 GPa and their strength can reach 240 MPa.
However, in general, values of 10 GPa and 100 MPa are obtained
for the elastic modulus and tensile strength, respectively, with a
strain at break of 5%. CNF lms also possess low thermal expansion
coefcients (12.028.5 ppm K1 ) (Miao et al., 2015).
CNF lms are known to have high barrier properties, as
described in details by Lavoine et al. (2012). CNF lms were found
to be good barriers for oxygen gas, e.g., Syverud and Stenius
(2009) reported the values of oxygen transmission rate (OTR) of
17.75 0.75 cm3 m2 day1 at 23 C and 0% of relative humidity
(RH), which fulls the requirements for OTR in modied atmo-
sphere packaging. CNF lms are not redispersible in water due
to strong hydrogen bonding between the nanobrils. Henriksson
20 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225

Fig. 11. Examples of CNF products/applications: (a) polished with acrylic resin (left) and unpolished (right) CNF lms; adapted from Nogi et al. (2009) with permissions
from John Wiley and Sons; (b) light-emitting diode (LED) light circuits on CNF lm with: (1) gold sputtered lines, (2) inkjet-printed silver nanoparticle lines and (3) inkjet-
printed metallo-organic decomposition (MOD) silver lines; adapted from Hsieh et al. (2013) with permission of The Royal Society of Chemistry; (c) 3D printed human ear from
hydrogel of CNF and alginate, adapted with permission from Markstedt et al. (2015); 2015 American Chemical Society and (d) tiny chair (dimentions of ca. 25 10 15 mm, for
height width depth, respectively) made of CNF aerogel produced using 3D bioprinting; the photograph was kindly provided by Prof. Paul Gatenholm (Chalmers University
of Technology).

and Berglund (2007) reported that the mechanical properties of
CNF lms were reduced when immersed in water but the major
part of the structure was retained. Aulin et al. (2012) also reported
water vapor transmission rate (WVTR) of 70.3 g m2 day1 and
>2000 g m2 day1 at 50% RH and 80% RH, respectively. An advan-
tage of these lms is their resistance to various solvents, such as
methanol, toluene and dimethylacetamide (sterberg et al., 2013).
Moreover, through chemical or physical modication, these prop-
erties could be enhanced. Therefore, CNF lms can potentially be
used as barriers for packaging, in printed electronics (see Fig. 11b)
etc.
4.4. Hydrogels
CNF suspensions at low cellulose concentrations appear as vis-
cous uids (see Fig. 12a). However, they can be converted to the
so-called hydrogels (see Fig. 12b), i.e., hydrophilic materials with
highly networked structure, which can hold a large amount of
water, e.g., 99.9% (Saito et al., 2011), while maintaining their shape.
Thus, the CNF hydrogels can remain freestanding with no (negligi-
ble) uidity.
Abe and Yano (2011, 2012) reported hydrogel production by
treating mechanically disintegrated CNF aqueous suspensions with
alkali followed by neutralization. Two hydrogel types with differ-
ent crystal forms, namely cellulose I and cellulose II, were prepared,
using sodium hydroxide below and above a specic concentration
of ca. 12 wt.%, respectively. Above this concentration, the hydro-
gels were formed due to cellulose shrinkage and coalescence due
to mercerization. While at weaker alkaline media, before the mer-
cerization threshold, the formation of hydrogels was suggested to
occur due to some swelling, hence the enhancement of CNF entan-
glement and, additionally, some aggregation.
Saito et al. (2011) reported the production of hydrogels from
TEMPO-oxidized CNF by lowering the pH to around 2. Thus, the
formation of hydrogels was associated with the reduction of elec-
trostatic repulsion between the nanobrils due to the protonization
of the carboxylate groups. Hydrogels from TEMPO-oxidized CNF
suspensions were also produced by cross-linking using metal
cations (Dong et al., 2013a,b). Such hydrogels have a great potential
for application in such elds as tissue engineering (see Fig. 11c),
drug delivery, sorbents, sensors, contact lenses and purication
(Dong et al., 2013b).
4.5. Aerogels
CNF aerogels (see Fig. 12c) are porous sponge-like materials pro-
duced by replacing the liquid medium in suspensions or hydrogels
with air. Thus, by preserving the CNF three-dimensional (3D) net-
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Fig. 12. Visual appearance of: (a) TEMPO-oxidized CNF aqueous suspension at 0.25 wt.% and fabricated from it: (b) hydrogel and (c) aerogel.
work during dehydration, aerogels with high specic surface area,
low density and high porosity can be obtained. CNF aerogels were
rst prepared by Pkk et al. (2008) from CNF aqueous suspen-
sions using freeze drying. Aerogels with a density of ca. 0.02 g cm3 ,
porosity of 9898.7% and a specic surface area of 2070 m2 g1
were obtained when applying several freeze drying protocols. A
number of studies has been published describing the aerogels pro-
duction using similar approach (Aulin et al., 2010b; Sehaqui et al.,
2010; Chen et al., 2011b).
However, the presence of water during freeze drying results
in signicant CNF aggregation during sublimation. The extent of
aggregation can be reduced by solvent exchange to tert-butanol
prior to freeze drying. Thereby, Sehaqui et al. (2011) produced
CNF aerogel with much higher specic surface area of 284 m2 g1
with reduced level of cellulose aggregation, as proved by SEM. This
method was also used in other studies (Fumagalli et al., 2013; Wan
et al., 2015). Saito et al. (2011) proposed another route where CNF
aqueous suspensions were converted to hydrogels, which were
afterwards solvent exchanged to tert-butanol and freeze dried in
order to obtain aerogels.
An advantage of CNF aerogels is their exibility and ductil-
ity compared to those made of silica or metal oxides, which are
relatively brittle. Thus, CNF aerogels have a potential for use as
adsorbents, carriers for catalysts and drug release and thermal and
acoustic insulation (Sehaqui et al., 2011; Chen et al., 2011b).
It was recently shown that CNF aerogels can be produced using
3D bioprinting (Svensk Papperstidning, 2015; Rees et al., 2015), as
illustrated by the example in Fig. 11d. Due to shear thinning proper-
ties of CNF aqueous suspensions, which gives possibility to change
viscosity depending on the applied shear, as well as pH sensitiv-
ity and cross-linking capacity for hydrogel formation, CNF can be
applied in 3D printing to produce various 3D porous objects from
cellulose. This nding appears to be very promising and is expected
to revolutionize the manufacturing industry.
5. Conclusions
This review reports the most recent advances in the production
of CNF. Besides the conventional mechanical treatments, such as
homogenization or grinding, which are traditionally used to pre-
pare CNF, other promising techniques were discussed, which can
appear of great interest for further industrialization of this type of
material. The authors believe that the extrusion process has great
potential in this regard. The pretreatment methods appear to be one
of the prerequisites for economically efcient production of CNF,
since they can strongly reduce energy consumption required dur-
ing mechanical disintegration process. The search for new efcient
and environmentally friendly pretreatments remains an important
21
objective. In this context, the use of microemulsions, with incorpo-
rated urea or ethylenediamine, or deep eutectic solvents appears
to be promising for pulp pretreatment.
CNF is not a single material with unique properties. A large vari-
ety of CNF grades can be obtained, especially depending on the
type of biochemical pretreatment and mechanical disintegration
technique used. The ensuing cellulosic materials differ generally
in morphology (particularly CNF dimensions and the amount of
residual ber fragments) and surface chemistry. Mechanically dis-
integrated CNF produced with or without enzymatic pretreatment
usually possess agglomerated (occulated) structures with larger
nanobrils compared to CNF obtained using chemical pretreat-
ments, which generally have more regular and lower dimensions
as well as are more individualized.
The quantitative characterization of the obtained material dur-
ing conversion of microscopic bers to CNF is a current issue
both for scientic community and industry. Therefore, studies on
the development of fractionation processes have been particularly
addressed. However, to the best of our knowledge, all of them
require a considerable dilution of the suspension, which makes the
proposed methods not favorable for simultaneous application in
the CNF production process.
Despite all the above shortcomings, CNF are readily available on
the market, which allows use of all their outstanding properties.
Thus, this review summarized the production of different types
of products from CNF suspensions, including water-redispersible
powders, nanopapers or lms, hydrogels and aerogels.
Acknowledgments
LGP2 is a part of the LabEx Tec 21 (Investissements dAvenir,
Grant Agreement ANR-11-LABX-0030) and of the nergies du
Futur and PolyNat Carnot Institutes (Investissements dAvenir,
Grant Agreements ANR-11-CARN-007-01 and ANR-11-CARN-030-
01). This research was possible due to facilities of the TekLiCell
platform funded by the Rgion Rhone-Alpes (ERDF, European
Regional Development Fund).
References
Abe, K., Yano, H., 2011. Formation of hydrogels from cellulose nanobers.
Carbohydr. Polym. 85, 733737, http://dx.doi.org/10.1016/j.carbpol.2011.03.
028.
Abe, K., Yano, H., 2012. Cellulose nanober-based hydrogels with high mechanical
strength. Cellulose 19, 19071912, http://dx.doi.org/10.1007/s10570-012-
9784-3.
Abbott, A.P., Bell, T.J., Handa, S., Stoddart, B., 2006. Cationic functionalisation of
cellulose using a choline based ionic liquid analogue. Green Chem. 8, 784786,
http://dx.doi.org/10.1039/b605258d.
22 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Alemdar, A., Sain, M., 2008. Isolation and characterization of nanobers from
agricultural residueswheat straw and soy hulls. Bioresour. Technol. 99,
16641671, http://dx.doi.org/10.1016/j.biortech.2007.04.029.
Aulin, C., Ahola, S., Josefsson, P., Nishino, T., Hirose, Y., Osterberg, M., Wgberg, L.,
2009. Nanoscale cellulose lms with different crystallinities and
mesostructurestheir surface properties and interaction with water. Langmuir
25, 76757685, http://dx.doi.org/10.1021/la900323n.
Aulin, C., Johansson, E., Wgberg, L., Lindstrom, T., 2010a. Self-organized lms from
cellulose I nanobrils using the layer-by-layer technique. Biomacromolecules
11, 872882, http://dx.doi.org/10.1021/bm100075e.
Aulin, C., Netrval, J., Wgberg, L., Lindstrm, T., 2010b. Aerogels from
nanobrillated cellulose with tunable oleophobicity. Soft Matter 6, 32983305,
http://dx.doi.org/10.1039/c001939a.
Aulin, C., Gllstedt, M., Lindstrm, T., 2010c. Oxygen and oil barrier properties of
microbrillated cellulose lms and coatings. Cellulose 17, 559574, http://dx.
doi.org/10.1007/s10570-009-9393-y.
Aulin, C., Salazar-Alvarez, G., Lindstrm, T., 2012. High strength, exible and
transparent nanobrillated cellulosenanoclay biohybrid lms with tunable
oxygen and water vapor permeability. Nanoscale 4, 66226628, http://dx.doi.
org/10.1039/c2nr31726e.
Bckstrm, M., Bolivar, S., Paltakari, J., 2012. Effect of ionic form on brillation and
the development of the bre network strength during the rening of the kraft
pulps. O Papel: Revista Mensal de Tecnologia em Celulose e 73, 5765.
Bardet, R., Belgacem, M.N., Bras, J., 2013. Different strategies for obtaining high
opacity lms of MFC with TiO2 pigments. Cellulose 20, 30253037, http://dx.
doi.org/10.1007/s10570-013-0025-1.
Bardet, R., Bras, J., 2014. Cellulose nanobers and their use in paper industry. In:
Handbook of Green Materials. World Scientic, pp. 207232, http://dx.doi.org/
10.1142/9789814566469 0013.
Beneventi, D., Chaussy, D., Curtil, D., Zolin, L., Gerbaldi, C., Penazzi, N., 2014. Highly
porous paper loading with microbrillated cellulose by spray coating on wet
substrates. Ind. Eng. Chem. Res. 53, 1098210989, http://dx.doi.org/10.1021/
ie500955x.
Benhamou, K., Dufresne, A., Magnin, A., Mortha, G., Kaddami, H., 2014. Control of
size and viscoelastic properties of nanobrillated cellulose from palm tree by
varying the TEMPO-mediated oxidation time. Carbohydr. Polym. 99, 7483,
http://dx.doi.org/10.1016/j.carbpol.2013.08.032.
Berlin, A., Balakshin, M., Gilkes, N., Kadla, J., Maximenko, V., Kubo, S., Saddler, J.,
2006. Inhibition of cellulase, xylanase and -glucosidase activities by softwood
lignin preparations. J. Biotechnol. 125, 198209, http://dx.doi.org/10.1016/j.
jbiotec.2006.02.021.
Besbes, I., Vilar, M.R., Bou, S., 2011. Nanobrillated cellulose from alfa, eucalyptus
and pine bres: preparation, characteristics and reinforcing potential.
Carbohydr. Polym. 86, 11981206, http://dx.doi.org/10.1016/j.carbpol.2011.
06.015.
Bhatnagar, A., Sain, M., 2005. Processing of cellulose nanober-reinforced
composites. J. Reinf. Plast. Compos. 24, 12591268, http://dx.doi.org/10.1177/
0731684405049864.
Bolaski, W., Gallatin, A., Gallatin, J.C., 1962. Enzymatic conversion of cellulosic
bers. Patent U.S. 3041246.
Brown, E.E., Laborie, M.P.G., 2007. Bioengineering bacterial cellulose/poly
(ethylene oxide) nanocomposites. Biomacromolecules 8, 30743081, http://dx.
doi.org/10.1021/bm700448x.
Bulota, M., Kreitsmann, K., Hughes, M., Paltakari, J., 2012. Acetylated
microbrillated cellulose as a toughening agent in poly(lactic acid). J. Appl.
Polym. Sci. 126, E449E458, http://dx.doi.org/10.1002/app.36787.
Butchosa, N., Zhou, Q., 2014. Water redispersible cellulose nanobrils adsorbed
with carboxymethyl cellulose. Cellulose 21, 43494358, http://dx.doi.org/10.
1007/s10570-014-0452-7.
Cai, X., Riedl, B., Ait-Kadi, A., 2003. Effect of surface-grafted ionic groups on the
performance of celluloseberreinforced thermoplastic composites. J. Polym.
Sci. B: Polym. Phys. 41, 20222032, http://dx.doi.org/10.1002/polb.10566.
Carrasco, F., Mutj, P., Plach, M.A., 1996. Rening of bleached cellulosic pulps:
characterization by application of the colloidal titration technique. Wood Sci.
Technol. 30, 227236, http://dx.doi.org/10.1007/BF00229345.
Carrillo, C.A., Laine, J., Rojas, O.J., 2014. Microemulsion systems for ber
deconstruction into cellulose nanobrils. ACS Appl. Mater. Interfaces 6,
2262222627, http://dx.doi.org/10.1021/am5067332.
Chaker, A., Alila, S., Mutj, P., Vilar, M.R., Bou, S., 2013. Key role of the
hemicellulose content and the cell morphology on the nanobrillation
effectiveness of cellulose pulps. Cellulose 20, 28632875, http://dx.doi.org/10.
1007/s10570-013-0036-y.
Chaker, A., Bou, S., 2015. Cationic nanobrillar cellulose with high antibacterial
properties. Carbohydr. Polym. 131, 224232, http://dx.doi.org/10.1016/j.
carbpol.2015.06.003.
Charreau, H., Foresti, M.L., Vazquez, A., 2013. Nanocellulose patents trends: a
comprehensive review on patents on cellulose nanocrystals, microbrillated
and bacterial cellulose. Recent Pat. Nanotechnol. 7, 5680, http://dx.doi.org/10.
2174/187221013804484854.
Chauve, G., Bras, J., 2014. Industrial point of view of nanocellulose materials and
their possible applications. In: Handbook of Green Materials. World Scientic,
pp. 233252, http://dx.doi.org/10.1142/9789814566469 0014.
Chen, W., Yu, H., Liu, Y., Chen, P., Zhang, M., Hai, Y., 2011a. Individualization of
cellulose nanobers from wood using high-intensity ultrasonication combined
with chemical pretreatments. Carbohydr. Polym. 83, 18041811, http://dx.doi.
org/10.1016/j.carbpol.2010.10.040.
Chen, W., Yu, H., Li, Q., Liu, Y., Li, J., 2011b. Ultralight and highly exible aerogels
with long cellulose I nanobers. Soft Matter 7, 1036010368, http://dx.doi.org/
10.1039/C1SM06179H.
Cheng, Q., Wang, S., Rials, T.G., 2009. Poly(vinyl alcohol) nanocomposites
reinforced with cellulose brils isolated by high intensity ultrasonication.
Compos. A: Appl. Sci. Manuf. 40, 218224, http://dx.doi.org/10.1016/j.
compositesa.2008.11.009.
Cherian, B.M., Leo, A.L., de Souza, S.F., Thomas, S., Pothan, L.A., Kottaisamy, M.,
2010. Isolation of nanocellulose from pineapple leaf bres by steam explosion.
Carbohydr. Polym. 81, 720725, http://dx.doi.org/10.1016/j.carbpol.2010.03.
046.
Chinga-Carrasco, G., 2011. Cellulose bres, nanobrils and microbrils: the
morphological sequence of MFC components from a plant physiology and bre
technology point of view. Nanoscale Res. Lett. 6, 417, http://dx.doi.org/10.
1186/1556-276X-6-417.
Chinga-Carrasco, G., 2013. Optical methods for the quantication of the brillation
degree of bleached MFC materials. Micron 48, 4248, http://dx.doi.org/10.
1016/j.micron.2013.02.005.
Chinga-Carrasco, G., Averianova, N., Kondalenko, O., Garaeva, M., Petrov, V.,
Leinsvang, B., Karlsen, T., 2014. The effect of residual bres on the
micro-topography of cellulose nanopaper. Micron 56, 8084, http://dx.doi.org/
10.1016/j.micron.2013.09.002.
Cobut, A., Sehaqui, H., Berglund, L.A., 2014. Cellulose nanocomposites by melt
compounding of TEMPO-treated wood bers in thermoplastic starch matrix.
BioResources 9, 32763289, http://dx.doi.org/10.15376/biores.9.2.3276-3289.
Coseri, S., Biliuta, G., Simionescu, B.C., Stana-Kleinschek, K., Ribitsch, V., Harabagiu,
V., 2013. Oxidized cellulosesurvey of the most recent achievements.
Carbohydr. Polym. 93, 207215, http://dx.doi.org/10.1016/j.carbpol.2012.03.
086.
Davis, N.J., Flitsch, S.L., 1993. Selective oxidation of monosaccharide derivatives to
uronic acids. Tetrahedron Lett. 34, 11811184, http://dx.doi.org/10.1016/
S0040-4039(00)77522-8.
De Campos, A., Correa, A.C., Cannella, D., De M. Teixeira, E., Marconcini, J.M.,
Dufresne, A., Mattoso, L.H.C., Cassland, P., Sanadi, A.R., 2013. Obtaining
nanobers from curau and sugarcane bagasse bers using enzymatic
hydrolysis followed by sonication. Cellulose 20, 14911500, http://dx.doi.org/
10.1007/s10570-013-9909-3.
De Nooy, A.E.J., Besemer, A.C., Van Bekkum, H., 1994. Highly selective TEMPO
mediated oxidation of primary alcohol groups in polysaccharides. Recueil des
Travaux Chimiques des Pays Bas 113, 165166, http://dx.doi.org/10.1002/recl.
19941130307.
Deepa, B., Abraham, E., Cherian, B.M., Bismarck, A., Blaker, J.J., Pothan, L.A., Leao,
A.L., de Souza, S.F., Kottaisamy, M., 2011. Structure, morphology and thermal
characteristics of banana nano bers obtained by steam explosion. Bioresour.
Technol. 102, 19881997, http://dx.doi.org/10.1016/j.biortech.2010.09.030.
Diniz, J.F., Gil, M.H., Castro, J.A.A.M., 2004. Hornicationits origin and
interpretation in wood pulps. Wood Sci. Technol. 37, 489494, http://dx.doi.
org/10.1007/s00226-003-0216-2.
Dong, H., Snyder, J.F., Tran, D.T., Leadore, J.L., 2013a. Hydrogel, aerogel and lm of
cellulose nanobrils functionalized with silver nanoparticles. Carbohydr.
Polym. 95, 760767, http://dx.doi.org/10.1016/j.carbpol.2013.03.041.
Dong, H., Snyder, J.F., Williams, K.S., Andzelm, J.W., 2013b. Cation-induced
hydrogels of cellulose nanobrils with tunable moduli. Biomacromolecules 14,
33383345, http://dx.doi.org/10.1021/bm400993f.
Doshi, J., Reneker, D.H., 1993. Electrospinning process and applications of
electrospun bers. Industry Applications Society Annual Meeting Conference
Record of the 1993 IEEE, 16981703.
Dufresne, A., Cavaill, J.Y., Vignon, M.R., 1997. Mechanical behavior of sheets
prepared from sugar beet cellulose microbrils. J. Appl. Polym. Sci. 64,
11851194, http://dx.doi.org/10.1002/(SICI)1097-
4628(19970509)64:6<1185:AID-APP19>3.0.CO;2-V.
Dufresne, A., Dupeyre, D., Vignon, M.R., 2000. Cellulose microbrils from potato
tuber cells: Processing and characterization of starchcellulose microbril
composites. J. Appl. Polym. Sci. 76, 20802092, http://dx.doi.org/10.1002/
(SICI)1097-4628(20000628)76:14<2080:AID-APP12>3.0.CO;2-U.
Eriksen, ., Syverud, K., Gregersen, ., 2008. The use of microbrillated cellulose
produced from kraft pulp as strength enhancer in TMP paper. Nordic Pulp Pap.
Res. J. 23, 299304, http://dx.doi.org/10.3183/NPPRJ-2008-23-03-p299-304.
Eyholzer, C., Bordeanu, N., Lopez-Suevos, F., Rentsch, D., Zimmermann, T., Oksman,
K., 2010. Preparation and characterization of water-redispersible
nanobrillated cellulose in powder form. Cellulose 17, 1930, http://dx.doi.
org/10.1007/s10570-009-9372-3.
Eyholzer, C., Borges de Couraca, A., Duc, F., Bourban, P.E., Tingaut, P., Zimmermann,
T., Mnson, J.A.E., Oksman, K., 2011. Biocomposite hydrogels with
carboxymethylated, nanobrillated cellulose powder for replacement of the
nucleus pulposus. Biomacromolecules 12, 14191427, http://dx.doi.org/10.
1021/bm101131b.
Fengel, D., Wegener, G., 1983. Wood: Chemistry, Ultrastructure, Reactions. Walter
de Gruyter.
Fernandes, A.N., Thomas, L.H., Altaner, C.M., Callow, P., Forsyth, V.T., Apperley, D.C.,
Kennedy, C.J., Jarvis, M.C., 2011. Nanostructure of cellulose microbrils in
spruce wood. Proc. Natl. Acad. Sci. U. S. A. 108, E1195E1203, http://dx.doi.org/
10.1073/pnas.1108942108.
Fernandez-Bolanos, J., Felizon, B., Heredia, A., Rodrguez, R., Guillen, R., Jimenez, A.,
2001. Steam-explosion of olive stones: hemicellulose solubilization and
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
enhancement of enzymatic hydrolysis of cellulose. Bioresour. Technol. 79,
5361, http://dx.doi.org/10.1016/S0960-8524(01)00015-3.
Frey, M.W., 2008. Electrospinning cellulose and cellulose derivatives. Polym. Rev.
48, 378391, http://dx.doi.org/10.1080/15583720802022281.
Frey-Wyssling, V.A., Mhlethaler, K., 1963. Die elementarbrillen der cellulose.
Makromol. Chem. 62, 2530, http://dx.doi.org/10.1002/macp.1963.020620103.
Fortunato, G., Zimmermann, T., Lbben, J., Bordeanu, N., Hufenus, R., 2012.
Reinforcement of polymeric submicrometer-sized bers by microbrillated
cellulose. Macromol. Mater. Eng. 297, 576584, http://dx.doi.org/10.1002/
mame.201100408.
Fumagalli, M., Ouhab, D., Boisseau, S.M., Heux, L., 2013. Versatile gas-phase
reactions for surface to bulk esterication of cellulose microbrils aerogels.
Biomacromolecules 14, 32463255, http://dx.doi.org/10.1021/bm400864z.
Gane, P.A.C, Schoelkopf, J., Gantenbein, D., Schenker, M., Pohl, M., Kuebler, B., 2010.
Process for the Production of Nano-Fibrillar Cellulose Suspensions.
WO2010112519 (A1).
Gatenholm, P., Klemm, D., 2010. Bacterial nanocellulose as a renewable material
for biomedical applications. MRS Bull. 35, 208213, http://dx.doi.org/10.1557/
mrs2010.653.
Ghorani, B., Russell, S.J., Goswami, P., 2013. Controlled morphology and mechanical
characterisation of electrospun cellulose acetate bre webs. Int. J. Polym. Sci.
2013, e256161, http://dx.doi.org/10.1155/2013/256161.
Haapala, A., Laitinen, O., Karinkanta, P., Liimatainen, H., Niinimki, J., 2013. Optical
characterisation of size, shape and brillarity from microbrillar and
microcrystalline cellulose: and ne ground wood powder fractions. Appita J.
66, 331339.
Hamada, H., Tahara, K., Uchida, A., 2012. The effects of nano-brillated cellulose as
a coating agent for screen printing. 12th TAPPI Advanced Coating
Fundamentals Symposium.
Hassan, M.L., Hassan, E.A., Oksman, K.N., 2011. Effect of pretreatment of bagasse
bers on the properties of chitosan/microbrillated cellulose nanocomposites.
J. Mater. Sci. 46, 17321740, http://dx.doi.org/10.1007/s10853-010-4992-4.
Heinze, T., Koschella, A., 2005. Carboxymethyl ethers of cellulose and starcha
review. Macromolecular Symposia, vol. 223. WILEY-VCH Verlag, pp. 1340,
http://dx.doi.org/10.1002/masy.200550502.
Henriksson, M., Berglund, L.A., 2007. Structure and properties of cellulose
nanocomposite lms containing melamine formaldehyde. J. Appl. Polym. Sci.
106, 28172824, http://dx.doi.org/10.1002/app.26946.
Henriksson, M., Berglund, L.A., Isaksson, P., Lindstrom, T., Nishino, T., 2008.
Cellulose nanopaper structures of high toughness. Biomacromolecules 9,
15791585, http://dx.doi.org/10.1021/bm800038n.
Henriksson, M., Henriksson, G., Berglund, L.A., Lindstrm, T., 2007. An
environmentally friendly method for enzyme-assisted preparation of
microbrillated cellulose (MFC) nanobers. Eur. Polym. J. 43, 34343441,
http://dx.doi.org/10.1016/j.eurpolymj.2007.05.038.
Herrick, F.W., Casebier, R.L., Hamilton, J.K., Sandberg, K.R., 1983. Microbrillated
cellulose: morphology, and accessibility. In: Sarko, A. (Ed.), Proceedings of the
Ninth Cellulose Conference. Applied Polymer Symposia, vol. 37. Wiley, N.Y., pp.
797813.
Hietala, M., Rollo, P., Keklinen, K., Oksman, K., 2014. Extrusion processing of
green biocomposites: compounding, brillation efciency, and ber
dispersion. J. Appl. Polym. Sci. 131, 19, http://dx.doi.org/10.1002/app.39981.
Ho, T.T.T., Zimmermann, T., Hauert, R., Caseri, W., 2011. Preparation and
characterization of cationic nanobrillated cellulose from etherication and
high-shear disintegration processes. Cellulose 18, 13911406, http://dx.doi.
org/10.1007/s10570-011-9591-2.
Ho, T.T.T., Abe, K., Zimmermann, T., Yano, H., 2015. Nanobrillation of pulp bers
by twin-screw extrusion. Cellulose 22, 421433, http://dx.doi.org/10.1007/
s10570-014-0518-6.
Hoeger, I.C., Nair, S.S., Ragauskas, A.J., Deng, Y., Rojas, O.J., Zhu, J.Y., 2013.
Mechanical deconstruction of lignocellulose cell walls and their enzymatic
saccharication. Cellulose 20, 807818, http://dx.doi.org/10.1007/s10570-013-
9867-9.
Hsieh, M.-C., Kim, C., Nogi, M., Suganuma, K., 2013. Electrically conductive lines on
cellulose nanopaper for exible electrical devices. Nanoscale 5, 92899295,
http://dx.doi.org/10.1039/C3NR01951A.
Huang, J., Zhu, H., Chen, Y., Preston, C., Rohrbach, K., Cumings, J., Hu, L., 2013.
Highly transparent and exible nanopaper transistors. ACS Nano 7,
21062113, http://dx.doi.org/10.1021/nn304407r.
Hubbe, M.A., Rojas, O.J., Lucia, L.A., Sain, M., 2008. Cellulosic nanocomposites: a
review. BioResources 3, 929980.
Husband, J.C., Svending, P., Skuse, D.R., Motsi, T., Likitalo, M., Coles, A., 2010. Paper
Filler Composition. WO2010131016 (A2).
Isogai, A., 2013. Wood nanocelluloses: fundamentals and applications as new
bio-based nanomaterials. J. Wood Sci. 59, 449459, http://dx.doi.org/10.1007/
s10086-013-1365-z.
Isogai, A., Saito, T., Fukuzumi, H., 2011. TEMPO-oxidized cellulose nanobers.
Nanoscale 3, 71, http://dx.doi.org/10.1039/c0nr00583e.
Iwamoto, S., Nakagaito, A.N., Yano, H., 2007. Nano-brillation of pulp bers for the
processing of transparent nanocomposites. Appl. Phys. A 89, 461466, http://
dx.doi.org/10.1007/s00339-007-4175-6.
Iwamoto, S., Nakagaito, A.N., Yano, H., Nogi, M., 2005. Optically transparent
composites reinforced with plant ber-based nanobers. Appl. Phys. A 81,
11091112, http://dx.doi.org/10.1007/s00339-005-3316-z.
Janardhnan, S., Sain, M.M., 2007. Isolation of cellulose microbrils an enzymatic
approach. BioResources 1, 176188.
23
Jayant, M., Rashmi, J., Shailendra, M., Deepesh, Y., 2011. Production of cellulase by
different co-culture of Aspergillus niger and Penicillium chrysogenum from
waste paper, cotton waste and baggase. J. Yeast Fungal Res. 2, 2427.
Jiang, F., Hsieh, Y.-L., 2013. Chemically and mechanically isolated nanocellulose
and their self-assembled structures. Carbohydr. Polym. 95, 3240, http://dx.
doi.org/10.1016/j.carbpol.2013.02.022.
Johnson, R.K., Zink-Sharp, A., Renneckar, S.H., Glasser, W.G., 2008. A new bio-based
nanocomposite: brillated TEMPO-oxidized celluloses in
hydroxypropylcellulose matrix. Cellulose 16, 227238, http://dx.doi.org/10.
1007/s10570-008-9269-6.
Joseleau, J.-P., Chevalier-Billosta, V., Ruel, K., 2012. Interaction between
microbrillar cellulose nes and bers: inuence on pulp qualities and paper
sheet properties. Cellulose 19, 769777, http://dx.doi.org/10.1007/s10570-
012-9693-5.
Jonoobi, M., Mathew, A.P., Oksman, K., 2012. Producing low-cost cellulose
nanober from sludge as new source of raw materials. Ind. Crops Prod. 40,
232238, http://dx.doi.org/10.1016/j.indcrop.2012.03.018.
Kaboorani, A., Riedl, B., Blanchet, P., 2013. Ultrasonication technique: a method for
dispersing nanoclay in wood adhesives. J. Nanomater. 2013, e341897, http://
dx.doi.org/10.1155/2013/341897.
Kalia, S., Bou, S., Celli, A., Kango, S., 2014. Nanobrillated cellulose: surface
modication and potential applications. Colloid Polym. Sci. 292, 531, http://
dx.doi.org/10.1007/s00396-013-3112-9.
Karande, V.S., Bharimalla, A.K., Hadge, G.B., Mhaske, S.T., Vigneshwaran, N., 2011.
Nanobrillation of cotton bers by disc rener and its characterization. Fibers
Polym. 12, 399404, http://dx.doi.org/10.1007/s12221-011-0399-3.
Karppinen, A., Saarinen, T., Salmela, J., Laukkanen, A., Nuopponen, M., Seppl, J.,
2012. Flocculation of microbrillated cellulose in shear ow. Cellulose 19,
18071819, http://dx.doi.org/10.1007/s10570-012-9766-5.
Kaushik, A., Singh, M., 2011. Isolation and characterization of cellulose nanobrils
from wheat straw using steam explosion coupled with high shear
homogenization. Carbohydr. Res. 346, 7685, http://dx.doi.org/10.1016/j.
carres.2010.10.020.
Keklinen, K., Liimatainen, H., Biale, F., Niinimki, J., 2015. Nanobrillation of
TEMPO-oxidized bleached hardwood kraft cellulose at high solids content.
http://doi.org/10.1515/hf-2014-0269.
Kim, U.-J., Kuga, S., 2001. Ion-exchange chromatography by dicarboxyl cellulose
gel. J. Chromatogr. A 919, 2937, http://dx.doi.org/10.1016/S0021-
9673(01)00800-7.
Klemm, D., Heublein, B., Fink, H.-P., Bohn, A., 2005. Cellulose: fascinating
biopolymer and sustainable raw material. Angew. Chem. Int. Ed. 44,
33583393, http://dx.doi.org/10.1002/anie.200460587.
Klemm, D., Philipp, B., Heinze, T., Heinze, U., Wagenknecht, W., 1998a.
Comprehensive Cellulose Chemistry: Functionalization of Cellulose, vol. 2.
Wiley-VCH Verlag GmbH, Weinheimhttp, http://dx.doi.org/10.1002/
3527601937.
Klemm, D., Philipp, B., Heinze, T., Heinze, U., Wagenknecht, W., 1998b.
Comprehensive Cellulose Chemistry: Fundamentals and Analytical Methods,
vol. 1. Wiley-VCH Verlag GmbH, Weinheimhttp, http://dx.doi.org/10.1002/
3527601929.
Klemm, D., Schmauder, H.-P., Heinze, T., 2004. Cellulose. In: de Baets, S.,
Vandamme, E., Steinbchel, A. (Eds.), Biopolymers, vol. 6. Polysaccharides II:
Polysaccharides from Eukaryotes. Wiley-VCH Weinheim, pp. 275319.
Kondo, T., Kose, R., Naito, H., Kasai, W., 2014. Aqueous counter collision using
paired water jets as a novel means of preparing bio-nanobers. Carbohydr.
Polym. 112, 284290, http://dx.doi.org/10.1016/j.carbpol.2014.05.064.
Konwarh, R., Karak, N., Misra, M., 2013. Electrospun cellulose acetate nanobers:
the present status and gamut of biotechnological applications. Biotechnol. Adv.
31, 421437, http://dx.doi.org/10.1016/j.biotechadv.2013.01.002.
Kose, R., Mitani, I., Kasai, W., Kondo, T., 2011. Nanocellulose as a single nanober
prepared from pellicle secreted by gluconacetobacter xylinus using aqueous
counter collision. Biomacromolecules 12, 716720, http://dx.doi.org/10.1021/
bm1013469.
Laitinen, O.T., Kemppainen, K., Stoor, T., Niinimki, J., 2011. Fractionation of pulp
and paper particles selectively by size. BioResources 6, 672685, http://dx.doi.
org/10.15376/biores.6.1.672-685.
Larsson, P.A., Berglund, L.A., Wgberg, L., 2014. Highly ductile bres and sheets by
core-shell structuring of the cellulose nanobrils. Cellulose 21, 323333,
http://dx.doi.org/10.1007/s10570-013-0099-9.
Lavoine, N., Desloges, I., Dufresne, A., Bras, J., 2012. Microbrillated celluloseits
barrier properties and applications in cellulosic materials: a review. Carbohydr.
Polym. 90, 735764, http://dx.doi.org/10.1016/j.carbpol.2012.05.026.
Lasseuguette, E., Roux, D., Nishiyama, Y., 2008. Rheological properties of
microbrillar suspension of TEMPO-oxidized pulp. Cellulose 15, 425433,
http://dx.doi.org/10.1007/s10570-007-9184-2.
Liimatainen, H., Ezekiel, N., Sliz, R., Ohenoja, K., Sirvi, J.A., Berglund, L., Hormi, O.,
Niinimki, J., 2013a. High-strength nanocellulose-talc hybrid barrier lms. ACS
Appl. Mater. Interfaces 5, 1341213418, http://dx.doi.org/10.1021/am4043273.
Liimatainen, H., Visanko, M., Sirvi, J., Hormi, O., Niinimki, J., 2013b. Sulfonated
cellulose nanobrils obtained from wood pulp through regioselective
oxidative bisulte pre-treatment. Cellulose 20, 741749, http://dx.doi.org/10.
1007/s10570-013-9865-y.
Liimatainen, H., Visanko, M., Sirvi, J.A., Hormi, O.E., Niinimaki, J., 2012.
Enhancement of the nanobrillation of wood cellulose through sequential
periodate-chlorite oxidation. Biomacromolecules 13, 15921597, http://dx.doi.
org/10.1021/bm300319m.
24 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Liimatainen, H., Suopajrvi, T., Sirvi, J., Hormi, O., Niinimki, J., 2014. Fabrication
of cationic cellulosic nanobrils through aqueous quaternization pretreatment
and their use in colloid aggregation. Carbohydr. Polym. 103, 187192, http://
dx.doi.org/10.1016/j.carbpol.2013.12.042.
Lim, Y.M., Gwon, H.J., Jeun, J.P., Nho, Y.C., 2010. Preparation of cellulose-based
nanobers using electrospinning. In: INTECH Open Access Publisher.
Lindstrm, T., 2011. Nanocellulose research and developments at innventia. In:
TAPPI International Conference on Nanotechnology for Renewable Materials,
Washington D.C., USA.
Lindstrm, T., Aulin, C., 2014. Market and technical challenges and opportunities in
the area of innovative new materials and composites based on nanocellulosics.
Scand. J. For. Res. 29, 345351, http://dx.doi.org/10.1080/02827581.2014.
928365.
Lindstrm, T., Aulin, C., Naderi, A., Ankerfors, M., 2014. Microbrillated cellulose.
In: Encyclopedia of Polymer Science and Technology. John Wiley & Sons, Inc.,
http://dx.doi.org/10.1002/0471440264.pst614.
Lynd, L.R., Weimer, P.J., Van Zyl, W.H., Pretorius, I.S., 2002. Microbial cellulose
utilization: fundamentals and biotechnology. Microbiol. Mol. Biol. Rev. 66,
506577, http://dx.doi.org/10.1128/MMBR.66.3.506-577.2002.
Madani, A., Kiiskinen, H., Olson, J.A., Martinez, M.D., 2011. Fractionation of
microbrillated cellulose and its effects on tensile index and elongation of
paper. Nordic Pulp Pap. Res. J. 26, 306.
Manhas, N., Balasubramanian, K., Prajith, P., Rule, P., Nimje, S., 2015. PCL/PVA
nanoencapsulated reinforcing llers of steam exploded/autoclaved cellulose
nanobrils for tissue engineering applications. RSC Adv. 5, 2399924008,
http://dx.doi.org/10.1039/C4RA17191H.
Markstedt, K., Mantas, A., Tournier, I., Martnez vila, H., Hgg, D., Gatenholm, P.,
2015. 3D bioprinting human chondrocytes with nanocellulosealginate bioink
for cartilage tissue engineering applications. Biomacromolecules 16,
14891496, http://dx.doi.org/10.1021/acs.biomac.5b00188.
Martoa, F., Perge, C., Dumont, P.J., Orgas, L., Fardin, M.A., Manneville, S.,
Belgacem, M.N., 2015. Heterogeneous ow kinematics of cellulose nanobril
suspensions under shear. Soft Matter, http://dx.doi.org/10.1039/C5SM00530B.
Medeiros, E.S., Mattoso, L.H., Ito, E.N., Gregorski, K.S., Robertson, G.H., Offeman,
R.D., Wood, D.F., Orts, W.J., Imam, S.H., 2008. Electrospun nanobers of poly
(vinyl alcohol) reinforced with cellulose nanobrils. J. Biobased Mater.
Bioenergy 2, 231242, http://dx.doi.org/10.1166/jbmb.2008.411.
Miao, M., Zhao, J., Feng, X., Cao, Y., Cao, S., Zhao, Y., Ge, X., Sun, L., Shi, L., Fang, J.,
2015. Fast fabrication of transparent and multi-luminescent TEMPO-oxidized
nanobrillated cellulose nanopaper functionalized with lanthanide complexes.
J. Mater. Chem. C 3, 25112517, http://dx.doi.org/10.1039/C4TC02622E.
Mishra, S.P., Manent, A.S., Chabot, B., Daneault, C., 2012. The use of sodium chlorite
in post-oxidation of TEMPO-oxidized pulp: effect on pulp characteristics and
nanocellulose yield. J. Wood Chem. Technol. 32, 137148, http://dx.doi.org/10.
1080/02773813.2011.624666.
Missoum, K., Belgacem, M.N., Bras, J., 2013. Nanobrillated cellulose surface
modication: a review. Materials 6, 17451766, http://dx.doi.org/10.3390/
ma6051745.
Missoum, K., Bras, J., Belgacem, M.N., 2012. Water redispersible dried
nanobrillated cellulose by adding sodium chloride. Biomacromolecules 13,
41184125, http://dx.doi.org/10.1021/bm301378n.
Moon, R.J., Martini, A., Nairn, J., Simonsen, J., Youngblood, J., 2011. Cellulose
nanomaterials review: structure, properties and nanocomposites. Chem. Soc.
Rev. 40, 39413994, http://dx.doi.org/10.1039/C0CS00108B.
Moser, C., Lindstrm, M.E., Henriksson, G., 2015. Toward industrially feasible
methods for following the process of manufacturing cellulose nanobers.
BioResources 10, 23602375.
Nakagaito, A.N., Ikenaga, K., Takagi, H., 2015. Cellulose nanober extraction from
grass by a modied kitchen blender. Mod. Phys. Lett. B 29, 1540039, http://dx.
doi.org/10.1142/S0217984915400394.
Nakagaito, A.N., Yano, H., 2004. The effect of morphological changes from pulp
ber towards nano-scale brillated cellulose on the mechanical properties of
high-strength plant ber based composites. Appl. Phys. A 78, 547552, http://
dx.doi.org/10.1007/s00339-003-2453-5.
Nechyporchuk, O., Belgacem, M.N., Pignon, F., 2014. Rheological properties of
micro-/nanobrillated cellulose suspensions: wall-slip and shear banding
phenomena. Carbohydr. Polym. 112, 432439, http://dx.doi.org/10.1016/j.
carbpol.2014.05.092.
Nechyporchuk, O., Pignon, F., Belgacem, M.N., 2015a. Morphological properties of
nanobrillated cellulose produced using wet grinding as an ultimate
brillation process. J. Mater. Sci. 50, 531541, http://dx.doi.org/10.1007/
s10853-014-8609-1.
Nechyporchuk, O., Belgacem, M.N., Pignon, F., 2015b. Concentration effect of
TEMPO-oxidized nanobrillated cellulose aqueous suspensions on the ow
instabilities and small-angle X-ray scattering structural characterization.
Cellulose 22, 21972210, http://dx.doi.org/10.1007/s10570-015-0640-0.
Nogi, M., Iwamoto, S., Nakagaito, A.N., Yano, H., 2009. Optically transparent
nanober paper. Adv. Mater. 21, 15951598, http://dx.doi.org/10.1002/adma.
200803174.
Olszewska, A., Eronen, P., Johansson, L.S., Malho, J.M., Ankerfors, M., Lindstrm, T.,
Ruokolainen, J., Laine, J., sterberg, M., 2011. The behaviour of cationic
NanoFibrillar cellulose in aqueous media. Cellulose 18, 12131226, http://dx.
doi.org/10.1007/s10570-011-9577-0.
Osong, S.H., Norgren, S., Engstrand, P., 2015. Processing of wood-based
microbrillated cellulose and nanobrillated cellulose, and applications
relating to papermaking: a review. Cellulose, 131, http://dx.doi.org/10.1007/
s10570-015-0798-5.
sterberg, M., Vartiainen, J., Lucenius, J., Hippi, U., Seppl, J., Serimaa, R., Laine, J.,
2013. A fast method to produce strong NFC lms as a platform for barrier and
functional materials. ACS Appl. Mater. Interfaces 5, 46404647, http://dx.doi.
org/10.1021/am401046x.
Pkk, M., Ankerfors, M., Kosonen, H., Nyknen, A., Ahola, S., sterberg, M.,
Ruokolainen, J., Laine, J., Larsson, P.T., Ikkala, O., Lindstrm, T., 2007. Enzymatic
hydrolysis combined with mechanical shearing and high-pressure
homogenization for nanoscale cellulose brils and strong gels.
Biomacromolecules 8, 19341941, http://dx.doi.org/10.1021/bm061215p.
Pkk, M., Vapaavuori, J., Silvennoinen, R., Kosonen, H., Ankerfors, M., Lindstrm,
T., Berglund, L.A., Ikkala, O., 2008. Long and entangled native cellulose I
nanobers allow exible aerogels and hierarchically porous templates for
functionalities. Soft Matter 4, 24922499, http://dx.doi.org/10.1039/B810371B.
Park, J.Y., Han, S.W., Lee, I.H., 2007. Preparation of electrospun porous ethyl
cellulose ber by THF/DMAc binary solvent system. J. Ind. Eng. Chem. 13,
10021008.
Peng, Y., Gardner, D.J., Han, Y., 2012. Drying cellulose nanobrils: in search of a
suitable method. Cellulose 19, 91102, http://dx.doi.org/10.1007/s10570-011-
9630-z.
Prez, J., Munoz-Dorado, J., de la Rubia, T.D.L.R., Martinez, J., 2002. Biodegradation
and biological treatments of cellulose, hemicellulose and lignin: an overview.
Int. Microbiol. 5, 5363, http://dx.doi.org/10.1007/s10123-002-0062-3.
Phler, T., Lappalainen, T., Tammelin, T., Eronen, P., Hiekkataipale, P., Vehniinen,
A., Koskinen, T.M., 2010. Inuence of brillation method on the character of
nanobrillated cellulose (NFC). TAPPI International Conference on
Nanotechnology for the Forest Products Industry.
Qing, Y., Sabo, R., Zhu, J.Y., Agarwal, U., Cai, Z., Wu, Y., 2013. A comparative study of
cellulose nanobrils disintegrated via multiple processing approaches.
Carbohydr. Polym. 97, 226234, http://dx.doi.org/10.1016/j.carbpol.2013.04.
086.
Quivy, N., Jacquet, N., Sclavons, M., Deroanne, C., Paquot, M., Devaux, J., 2010.
Inuence of homogenization and drying on the thermal stability of
microbrillated cellulose. Polym. Degrad. Stab. 95, 306314, http://dx.doi.org/
10.1016/j.polymdegradstab.2009.11.020.
Rnby, B.G., 1949. Aqueous colloidal solutions of cellulose micelles. Acta Chem.
Scand. 3, 649650, http://dx.doi.org/10.3891/acta.chem.scand.03-0649.
Rees, A., Powell, L.C., Chinga-Carrasco, G., Gethin, D.T., Syverud, K., Hill, K.E.,
Thomas, D.W., 2015. 3D bioprinting of carboxymethylated-periodate oxidized
nanocellulose constructs for wound dressing applications. BioMed Res. Int.
2015, e925757, http://dx.doi.org/10.1155/2015/925757.
Rosgaard, L., Pedersen, S., Langston, J., Akerhielm, D., Cherry, J.R., Meyer, A.S., 2007.
Evaluation of minimal Trichoderma reesei cellulase mixtures on differently
pretreated barley straw substrates. Biotechnol. Prog. 23 (6), 12701276, http://
dx.doi.org/10.1021/bp070329p.
Saarikoski, E., Saarinen, T., Salmela, J., Seppl, J., 2012. Flocculated ow of
microbrillated cellulose water suspensions: an imaging approach for
characterisation of rheological behaviour. Cellulose 19, 647659, http://dx.doi.
org/10.1007/s10570-012-9661-0.
Saini, S., Ycel Falco, C., Belgacem, M.N., Bras, J., 2016. Surface cationized cellulose
nanobrils for the production of contact active antimicrobial surfaces.
Carbohydr. Polym. 135, 239247, http://dx.doi.org/10.1016/j.carbpol.2015.09.
002.
Saito, T., Hirota, M., Tamura, N., Kimura, S., Fukuzumi, H., Heux, L., Isogai, A., 2009.
Individualization of nano-sized plant cellulose brils by direct surface
carboxylation using TEMPO catalyst under neutral conditions.
Biomacromolecules 10, 19921996, http://dx.doi.org/10.1021/bm900414t.
Saito, T., Isogai, A., 2006. Introduction of aldehyde groups on surfaces of native
cellulose bers by TEMPO-mediated oxidation. Colloids Surf. A: Physicochem.
Eng. Aspects 289, 219225, http://dx.doi.org/10.1016/j.colsurfa.2006.04.038.
Saito, T., Kimura, S., Nishiyama, Y., Isogai, A., 2007. Cellulose nanobers prepared
by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8,
24852491, http://dx.doi.org/10.1021/bm0703970.
Saito, T., Kuramae, R., Wohlert, J., Berglund, L.A., Isogai, A., 2013. An ultrastrong
nanobrillar biomaterial: the strength of single cellulose nanobrils revealed
via sonication-induced fragmentation. Biomacromolecules 14, 248253,
http://dx.doi.org/10.1021/bm301674e.
Saito, T., Nishiyama, Y., Putaux, J.-L., Vignon, M., Isogai, A., 2006. Homogeneous
suspensions of individualized microbrils from TEMPO-catalyzed oxidation of
native cellulose. Biomacromolecules 7, 16871691, http://dx.doi.org/10.1021/
bm060154s.
Saito, T., Uematsu, T., Kimura, S., Enomae, T., Isogai, A., 2011. Self-aligned
integration of native cellulose nanobrils towards producing diverse bulk
materials. Soft Matter 7, 88048809, http://dx.doi.org/10.1039/c1sm06050c.
Sehaqui, H., Salajkov, M., Zhou, Q., Berglund, L.A., 2010. Mechanical performance
tailoring of tough ultra-high porosity foams prepared from cellulose I nanober
suspensions. Soft Matter 6, 18241832, http://dx.doi.org/10.1039/B927505C.
Sehaqui, H., Zhou, Q., Berglund, L.A., 2011. High-porosity aerogels of high specic
surface area prepared from nanobrillated cellulose (NFC). Compos. Sci.
Technol. 71, 15931599, http://dx.doi.org/10.1016/j.compscitech.2011.07.003.
Shackford, L.D., 2003. A comparison of pulping and bleaching of kraft softwood and
eucalyptus pulps. In: 36th International Pulp and Paper Congress and
Exhibition, So Paulo, Brazil.
 O. Nechyporchuk et al. / Industrial Crops and Products 93 (2016) 225
Shinoda, R., Saito, T., Okita, Y., Isogai, A., 2012. Relationship between length and
degree of polymerization of TEMPO-oxidized cellulose nanobrils.
Biomacromolecules 13, 842849, http://dx.doi.org/10.1021/bm2017542.
Shmulsky, R., Jones, P.D., 2011. Forest Products and Wood Science. John Wiley &
Sons.
Shogren, R.L., Peterson, S.C., Evans, K.O., Kenar, J.A., 2011. Preparation and
characterization of cellulose gels from corn cobs. Carbohydr. Polym. 86,
13511357, http://dx.doi.org/10.1016/j.carbpol.2011.06.035.
Siqueira, G., Tapin-Lingua, S., Bras, J., da S. Perez, D., Dufresne, A., 2010.
Morphological investigation of nanoparticles obtained from combined
mechanical shearing, and enzymatic and acid hydrolysis of sisal bers.
Cellulose 17, 11471158, http://dx.doi.org/10.1007/s10570-010-9449-z.
Sir, I., Plackett, D., 2010. Microbrillated cellulose and new nanocomposite
materials: a review. Cellulose 17, 459494, http://dx.doi.org/10.1007/s10570-
010-9405-y.
Sir, I., Plackett, D., Hedenqvist, M., Ankerfors, M., Lindstrm, T., 2011. Highly
transparent lms from carboxymethylated microbrillated cellulose: the
effect of multiple homogenization steps on key properties. J. Appl. Polym. Sci.
119, 26522660, http://dx.doi.org/10.1002/app.32831.
Sirvi, J.A., Kolehmainen, A., Visanko, M., Liimatainen, H., Niinimki, J., Hormi,
O.E.O., 2014. Strong, self-standing oxygen barrier lms from nanocelluloses
modied with regioselective oxidative treatments. ACS Appl. Mater. Interfaces
6, 1438414390, http://dx.doi.org/10.1021/am503659j.
Sirvi, J.A., Visanko, M., Liimatainen, H., 2015. Deep eutectic solvent system based
on choline chloride-urea as a pre-treatment for nanobrillation of wood
cellulose. Green Chem. 17, 34013406, http://dx.doi.org/10.1039/C5GC00398A.
Sjstrm, E., 1981. Wood Chemistry: Fundamentals and Applications. Academic
Press.
Song, Y., Sun, Y., Zhang, X., Zhou, J., Zhang, L., 2008. Homogeneous quaternization
of cellulose in NaOH/urea aqueous solutions as gene carriers.
Biomacromolecules 9, 22592264, http://dx.doi.org/10.1021/bm800429a.
Spence, K.L., Venditti, R.A., Habibi, Y., Rojas, O.J., Pawlak, J.J., 2010. The effect of
chemical composition on microbrillar cellulose lms from wood pulps:
mechanical processing and physical properties. Bioresour. Technol. 101,
59615968.
Spence, K.L., Venditti, R.A., Rojas, O.J., Habibi, Y., Pawlak, J.J., 2011. A comparative
study of energy consumption and physical properties of microbrillated
cellulose produced by different processing methods. Cellulose 18, 10971111,
http://dx.doi.org/10.1007/s10570-011-9533-z.
Spinu, M., Santos, N.D., Moigne, N.L., Navard, P., 2011. How does the never-dried
state inuence the swelling and dissolution of cellulose bres in aqueous
solvent? Cellulose 18, 247256, http://dx.doi.org/10.1007/s10570-010-9485-8.
Stelte, W., Sanadi, A.R., 2009. Preparation and characterization of cellulose
nanobers from two commercial hardwood and softwood pulps. Ind. Eng.
Chem. Res. 48, 1121111219, http://dx.doi.org/10.1021/ie9011672.
Stevanic, J.S., Joly, C., Mikkonen, K.S., Pirkkalainen, K., Serimaa, R., Rmond, C.,
Toriz, G., Gatenholm, P., Tenkanen, M., Salmn, L., 2011. Bacterial
nanocellulose-reinforced arabinoxylan lms. J. Appl. Polym. Sci. 122,
10301039, http://dx.doi.org/10.1002/app.34217.
Sun, X.F., Xu, F., Sun, R.C., Fowler, P., Baird, M.S., 2005. Characteristics of degraded
cellulose obtained from steam-exploded wheat straw. Carbohydr. Res. 340,
97106, http://dx.doi.org/10.1016/j.carres.2004.10.022.
Suzuki, K., Okumura, H., Kitagawa, K., Sato, S., Nakagaito, A.N., Yano, H., 2013.
Development of continuous process enabling nanobrillation of pulp and melt
compounding. Cellulose 20, 201210, http://dx.doi.org/10.1007/s10570-012-
9843-9.
Svensk Papperstidning, 2015. Chalmersforskare bryter ny mark med cellulosa frn
tr i 3D-skrivare, 6. http://spt.spci.se/pdf article/buy/2197-Chalmersforskare
bryter ny mark med cellulosa fran trae i 3D skrivare.
Syverud, K., Chinga-Carrasco, G., Toledo, J., Toledo, P.G., 2011. A comparative study
of Eucalyptus and Pinus radiata pulp bres as raw materials for production of
cellulose nanobrils. Carbohydr. Polym. 84, 10331038, http://dx.doi.org/10.
1016/j.carbpol.2010.12.066.
Syverud, K., Stenius, P., 2009. Strength and barrier properties of MFC lms.
Cellulose 16, 7585, http://dx.doi.org/10.1007/s10570-008-9244-2.
Tanaka, A., Seppnen, V., Houni, J., Sneck, A., Pirkonen, P., 2012. Nanocellulose
characterization with mechanical fractionation. Nordic Pulp Pap. Res. J. 27,
689694, http://dx.doi.org/10.3183/NPPRJ-2012-27-04-p689-694.
Tangnu, S.K., 1982. Process development for ethanol production based on
enzymatic hydrolysis of cellulosic biomass. Process Biochem. 17, 3645.
Taniguchi, T., Okamura, K., 1998. New lms produced from microbrillated natural
bres. Polym. Int. 47, 291294, http://dx.doi.org/10.1002/(SICI)1097-
0126(199811)47:3<291:AID-PI11>3.0.CO;2-1.
Tejado, A., Alam, M.N., Antal, M., Yang, H., Van De Ven, T.G.M., 2012. Energy
requirements for the disintegration of cellulose bers into cellulose nanobers.
Cellulose 19, 831842, http://dx.doi.org/10.1007/s10570-012-9694-4.
Taipale, T., sterberg, M., Nyknen, A., Ruokolainen, J., Laine, J., 2010. Effect of
microbrillated cellulose and nes on the drainage of kraft pulp suspension
and paper strength. Cellulose 17, 10051020, http://dx.doi.org/10.1007/
s10570-010-9431-9.
25
Turbak, A.F., Snyder, F.W., Sandberg, K.R., 1983. Microbrillated cellulose, a new
cellulose product: properties, uses, and commercial potential. In: Sarko, A.
(Ed.), Proceedings of the Ninth Cellulose Conference. Applied Polymer
Symposia, vol. 37. Wiley, N.Y., pp. 815827.
Turbak, A.F., Snyder, F.W., Sandberg, K.R., 1983. Microbrillated cellulose. Patent
U.S. 4374702.
Turon, X., Rojas, O.J., Deinhammer, R.S., 2008. Enzymatic kinetics of cellulose
hydrolysis: a QCM-D study. Langmuir 24, 38803887, http://dx.doi.org/10.
1021/la7032753.
Uetani, K., Yano, H., 2011. Nanobrillation of wood pulp using a high-speed
blender. Biomacromolecules 12, 348353, http://dx.doi.org/10.1021/
bm101103p.
Usov, I., Nystrm, G., Adamcik, J., Handschin, S., Schtz, C., Fall, A., Bergstrm, L.,
Mezzenga, R., 2015. Understanding nanocellulose chirality and
structure-properties relationship at the single bril level. Nat. Commun. 6,
7564, http://dx.doi.org/10.1038/ncomms8564.
Vljame, P., Sild, V., Pettersson, G., Johansson, G., 1998. The initial kinetics of
hydrolysis by cellobiohydrolases I and II is consistent with a cellulose
surface-erosion model. Eur. J. Biochem. 253, 469475, http://dx.doi.org/10.
1046/j. 1432-1327.1998.2530469.x.
Varshney, V.K., Naithani, S., 2011. Chemical functionalization of cellulose derived
from nonconventional sources. In: Kalia, S., Kaith, B.S., Kaur, I. (Eds.), Cellulose
Fibers: Bio- and Nano-Polymer Composites. Springer, Berlin, Heidelberg, pp.
4360.
Wan, C., Lu, Y., Jiao, Y., Jin, C., Sun, Q., Li, J., 2015. Ultralight and hydrophobic
nanobrillated cellulose aerogels from coconut shell with ultrastrong
adsorption properties. J. Appl. Polym. Sci., 132, http://dx.doi.org/10.1002/app.
42037.
Wang, S., Cheng, Q., 2009. A novel process to isolate brils from cellulose bers by
high-intensity ultrasonication, part 1: process optimization. J. Appl. Polym. Sci.
113, 12701275, http://dx.doi.org/10.1002/app.30072.
Wang, B., Sain, M., 2007. Isolation of nanobers from soybean source and their
reinforcing capability on synthetic polymers. Compos. Sci. Technol. 67,
25212527, http://dx.doi.org/10.1016/j.compscitech.2006.12.015.
Wang, B., Sain, M., Oksman, K., 2007. Study of structural morphology of hemp ber
from the micro to the nanoscale. Appl. Compos. Mater. 14, 89103, http://dx.
doi.org/10.1007/s10443-006-9032-9.
Wang, Q.Q., Zhu, J.Y., Gleisner, R., Kuster, T.A., Baxa, U., McNeil, S.E., 2012.
Morphological development of cellulose brils of a bleached eucalyptus pulp
by mechanical brillation. Cellulose 19, 16311643, http://dx.doi.org/10.1007/
s10570-012-9745-x.
Wgberg, L., Decher, G., Norgren, M., Lindstrm, T., Ankerfors, M., Axns, K., 2008.
The build-up of polyelectrolyte multilayers of microbrillated cellulose and
cationic polyelectrolytes. Langmuir 24, 784795, http://dx.doi.org/10.1021/
la702481v.
Wertz, J.-L., Bdu, O., Mercier, J.P., 2010. Cellulose Science and Technology. EPFL
Press, pp. 21.
Wiedenhoeft, A.C., Miller, R.B., 2005. Structure and function of wood. In: Rowell,
R.M. (Ed.), Handbook of Wood Chemistry and Wood Composites. CRC Press, pp.
933.
Xu, X., Wang, H., Jiang, L., Wang, X., Payne, S.A., Zhu, J.Y., Li, R., 2014. Comparison
between cellulose nanocrystal and cellulose nanobril reinforced poly
(ethylene oxide) nanobers and their novel shish-kebab-like crystalline
structures. Macromolecules 47, 34093416, http://dx.doi.org/10.1021/
ma402627j.
Zhao, M., Li, J., Mano, E., Song, Z., Tschaen, D.M., Grabowski, E.J., Reider, P.J., 1999.
Oxidation of primary alcohols to carboxylic acids with sodium chlorite
catalyzed by TEMPO and bleach. J. Org. Chem. 64, 25642566, http://dx.doi.
org/10.1021/jo982143y.
Zhang, L., Tsuzuki, T., Wang, X., 2015. Preparation of cellulose nanober from
softwood pulp by ball milling. Cellulose 22, 17291741, http://dx.doi.org/10.
1007/s10570-015-0582-6.
Zhou, S., Ingram, L.O., 2000. Synergistic hydrolysis of carboxymethyl cellulose and
acid-swollen cellulose by two endoglucanases (CelZ and CelY) from Erwinia
chrysanthemi. J. Bacteriol. 182, 56765682, http://dx.doi.org/10.1128/JB.182.
20.5676-5682.2000.
Zhou, Y.M., Fu, S.Y., Zheng, L.M., Zhan, H.Y., 2012. Effect of nanocellulose isolation
techniques on the formation of reinforced poly (vinyl alcohol) nanocomposite
lms. Express Polym. Lett. 6, 794804, http://dx.doi.org/10.3144/
expresspolymlett.2012.85.
Zhu, H., Helander, M., Moser, C., Stahlkranz, A., Soderberg, D., Henriksson, G.,
Lindstrom, M., 2012. A novel nano cellulose preparation method and size
fraction by cross ow ultra-ltration. Curr. Org. Chem. 16, 18711875, http://
dx.doi.org/10.2174/138527212802651197.
Zepic, V., Fabjan, E.S., Kasunic, M., Korosec, R.C., Hancic, A., Oven, P., Perse, L.S.,
Poljansek, I., 2014. Morphological, thermal, and structural aspects of dried and
redispersed nanobrillated cellulose (NFC). Holzforschung 68, 657667, http://
dx.doi.org/10.1515/hf-2013-0132.
Zimmermann, T., Phler, E., Geiger, T., 2004. Cellulose brils for polymer
reinforcement. Adv. Eng. Mater. 6, 754761, http://dx.doi.org/10.1002/adem.
200400097.