DEVELOPMENT AND EVALUATION OF SOME OF THE MECHANICAL PROPERTIES OF KENAF/POLY...
Guide to cellulose nanomaterials
1. RESEARCH REPORT VTT-R-05013-14
Guide to cellulose nanomaterials
– English summary
Authors: Heli Kangas
Confidentiality: Public
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Preface
The report “Guide to cellulose nanomaterials” is an English summary of a report published in
Finnish. The Finnish report is based on an earlier report published in June 2012. Since then,
the field has developed rapidly, thus creating the need to update the information and also to
publish a summary of the report in English.
The contribution of numerous experts to the content of this report is gratefully acknowledged.
Espoo 31.10.2014
Heli Kangas
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Contents
Preface ................................................................................................................................... 2
Contents ................................................................................................................................. 3
1. Introduction ....................................................................................................................... 5
2. What are cellulose nanomaterials? ................................................................................... 6
2.1 Cellulose nanofibrils (CNF) ....................................................................................... 6
2.2 Cellulose nanocrystals (CNC) ................................................................................... 8
2.3 Bacterial cellulose ..................................................................................................... 9
3. The most important properties ........................................................................................ 10
3.1 Strong material ....................................................................................................... 10
3.2 Rheological properties ............................................................................................ 11
3.3 High specific surface area and tendency for network formation .............................. 11
3.4 Film formation ......................................................................................................... 12
4. Potential technical applications ....................................................................................... 12
4.1 Light materials with increased strength ................................................................... 12
4.1.1 Fibre-based packaging and composites ...................................................... 12
4.1.2 Polymer composites4, .................................................................................. 13
4.1.3 Strong yarns ............................................................................................... 14
4.2 Rheology modifier ................................................................................................... 14
4.3 Smooth, transparent films ....................................................................................... 15
4.3.1 Barrier materials.......................................................................................... 15
4.3.2 Substrates for printed electronics ................................................................ 16
4.3.3 Electronic displays ...................................................................................... 18
4.3.4 Coloured films ............................................................................................. 18
4.4 Water absorbing, retaining and releasing materials ................................................ 18
4.4.1 Medical applications .................................................................................... 18
4.4.2 Hygiene products ........................................................................................ 19
4.5 Reactive networks .................................................................................................. 19
4.5.1 Membranes ................................................................................................. 19
4.5.2 Porous structures ........................................................................................ 20
5. Commercial prospects .................................................................................................... 20
5.1 Availability ............................................................................................................... 20
5.1.1 Commercial production ............................................................................... 20
5.1.2 Demonstration/ pre-commercial production ................................................. 21
5.1.3 Pilot-scale production .................................................................................. 21
5.1.4 Production facilities under construction / planning ....................................... 22
5.1.5 Production................................................................................................... 22
5.2 Commercial application possibilities ........................................................................ 23
5.3 Important stakeholders ........................................................................................... 24
6. Characterization .............................................................................................................. 25
7. Advice on use ................................................................................................................. 29
7.1 Preservability .......................................................................................................... 29
7.2 Processing .............................................................................................................. 29
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7.2.1 Composites4,24 ............................................................................................ 29
7.2.2 Water suspensions ..................................................................................... 30
7.2.3 Drying and redispersion .............................................................................. 30
8. Environmental, health and safety aspects ....................................................................... 31
8.1 Published information ............................................................................................. 31
8.2 Regulatory information ............................................................................................ 33
8.3 Standardization ....................................................................................................... 34
9. Summary ........................................................................................................................ 34
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1. Introduction
According to the recommendation of the European Commission, nanomaterials are defined
as “natural, incidental or manufactured material containing particles, in an unbound state or
as an aggregate or as an agglomerate and where, for 50 % or more of the particles in the
number size distribution, one or more external dimensions is in the size range 1 nm-100
nm.”1
Cellulose nanomaterials are not a new invention but their manufacture was patented already
in the early 80’s.2 Back then, the high energy consumption in the manufacturing proved to be
barrier for their industrial production. During the last decade, the interest towards cellulose
nanomaterials has boomed, as can be seen by the significant increase in the related
publications and patents (Figure 1).
Figure 1. The amount of patents and other publications related to cellulose nanomaterials
1980-2013. Source: Chemical Abstracts, June 18, 2014 (Image source: VTT).
The decreased demand for traditional products of the paper industry and thus the need to
create new products could be one of the reasons for the increased interest towards cellulose
nanomaterials. At the same time, development in the manufacturing processes for cellulose
nanomaterials has led to decrease in the energy consumption, thus enabling production at
industrial scale. Cellulose nanomaterials have many unique properties that make potential for
numerous applications. The worldwide trend towards sustainability and bioeconomy favours
the utilization of biobased materials, such as cellulose nanomaterials, for the replacement of
oil-based materials in the existing products as well as for production of novel products.
Cellulose nanomaterials are also considered to be of national importance in Finland.3
1 European Commission (2011): Commission Recommendation of 18 October 2011 on the definition of
nanomaterial. http://eur-lex.europa.eu/legal
content/EN/TXT/?qid=1409558975674&uri=CELEX:32011H0696
2 Turbak, A.F. et al. (1983) Microfibrillated cellulose. Patent US4,374,702; Herrick, F.W. (1984) Process
for preparing microfibrillated cellulose. Patent US4,481,077; Kawai ja Sugawara (1983) Redispersion
of dried microfibrils of cellulose. Patent JPS58206601; Okumura ja Moriyama (1985) Microfibrillated
cellulose composition that can be redispersed and suspended in water. Patent JPS6044537.
3 Suomen biotalousstrategia (2014). www.biotalous.fi ; Linturi, R. et al. (2013) Suomen sata uutta
mahdollisuutta: Radikaalit teknologiset ratkaisut. Eduskunnan Tulevaisuusvaliokunta, Helsinki. ISBN
978-951-53-3514-2 (nid.), ISBN 978-951-53-3515-9 (PDF).
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2. What are cellulose nanomaterials?
Cellulose nanomaterials are cellulose-based materials that have one or more of their external
dimensions at the nano-scale, i.e. between 1 to 100 nm. Based on their production method,
size and other properties, cellulose nanomaterials are generally divided into three classes:
cellulose nanofibrils (CNF), cellulose nanocrystals (CNC) and bacterial cellulose (BC).
2.1 Cellulose nanofibrils (CNF)4
Cellulose nanofibrils are generally manufactured from wood pulps, but annual plants offer an
alternative source. They are manufactured by mechanical treatments, for example by
grinding, homogenization or microfluidisation. During mechanical treatment, the microfibrils
forming the fibre cell wall are separated from each other, and as a result a viscous gel is
formed, consisting of individual nano-scale fibrils with width generally between 20-40 nm and
length of several micrometers (Figure 2). However, usually the formed material also contains
a heterogeneous mixture of micro-scale fibrils and their aggregates, fibres with variable
fibrillation degree and even unfibrillated fibres. Fibrils manufactured by mechanical treatment
are flexible and highly branched and their aspect factor (length/width) is high. Due to the free
hydroxyl groups on the surface of cellulose fibrils, they have a strong tendency to
agglomerate forming larger fibril bundles. This takes place especially during drying of
cellulose nanofibrils.
Chemical and enzymatic treatments can be applied to ease the fibrillation, and thus decrease
the energy needed to achieve adequate fibrillation level. With chemical and enzymatic pre-treatments,
the resulting cellulose nanofibril material is generally more homogeneous than
that formed by mechanical treatment alone and more individual nanofibrils with smaller width
are formed. Common chemical treatments for preparation of cellulose nanofibrils are TEMPO
(2,2,6,6-tetramethylpiperidine-1-oxyl) mediated oxidation5 and carboxymethylation.6
Enzymatic pretreatments are often performed with endoglucananase, which is believed to
degrade cellulose from the amorphous parts of the cellulose fibrils.7 Cellulose nanofibril
widths of around 3-5 nm have been achieved by TEMPO mediated oxidation and 5-20 nm by
endoglucanase treatment. The size difference of cellulose nanofibrils produced by chemical
pre-treatments compared to mechanically manufactured cellulose nanofibrils can be
observed for example based on their colour (Figures 2 and 3) or their atomic force
microscope (AFM) images (Figure 4), able to reveal structural details on nanometer scale.
One challenge related to manufacturing of cellulose nanofibrils is how to produce material of
even quality from batch to batch.
http://www.eduskunta.fi/triphome/bin/thw.cgi/trip?${APPL}=erekj&${BASE}=erekj&${THWIDS}=0.1/140
9661001_258895&${TRIPPIFE}=PDF.pdf
4 Sirȩ, I. and Plackett, D. (2010). Microfibrillated cellulose and new nanocomposite materials: a review.
Cellulose 17 , 459; Klemm, D. et al. (2011). Nanocelluloses: A new family of Nature-based Materials.
Angew. Chem. Ind. Ed. 50, 5438.
5 Saito, T. and Isogai, A. (2004) TEMPO-mediated oxidation of native cellulose. The effect of oxidation
conditions on chemical and crystal structures of the water-insoluble fractions. Biomacromolecules 5,
1983; Saito, T. et al. (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed
oxidation of native cellulose. Biomacromolecules 7, 1687; Saito, T. et al. (2007) Cellulose
nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8, 2485;
Saito, T. et al. (2009) Individualization of nano-sized plant cellulose fibrils by direct surface
carboxylation using TEMPO catalyst under neutral conditions. Biomacromolecules 10, 1992.
6 Wågberg, L. et al. (2008). The build-up of polyelectrolyte multilayers of microfibrillated cellulose and
cationic polyelectrolytes. Langmuir, 784-795.
7 Pääkkö, M. et al. (2007). Enzymatic hydrolysis combined with mechanical shearing and high-pressure
homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8, 1934;
Henriksson, M. et al. (2008). Cellulose nanopaper structures of high toughness. Biomacromolecules 9,
1579.
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Figure 2. left: Cellulose nanofibril gel produced by Masuko grinding.8 Right: Scanning Elecron
microscope (SEM) image of cellulose nanofibrils. Scale: 100 nm (Image source: VTT).
Figure 3. Cellulose nanofibrils produced by TEMPO mediated oxidation (left) and
carboxymethylation as the pre-treatment.8
8 Pöhler, T. et al. (2010). Influence of fibrillation method on the character of nanofibrillated cellulose
(NFC). 2010 TAPPI International Conference on Nanotechnology for the Forest Products Industry.
Sept. 27-29, Espoo, Finland.
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Figure 4. AFM images of cellulose nanofibrils produced by fluidisation (left), TEMPO
mediated oxidation (middle) and carboxymethylation (right).8 Image area 2ȝmx2ȝm. Scale in
nanometers (nm).
2.2 Cellulose nanocrystals (CNC)9
Cellulose nanocrystals are produced by acid hydrolysis from a variety of raw materials,
including wood pulps and cotton, tunicates, bacterial cellulose and microcrystalline cellulose
(MCC). During acid hydrolysis of cellulose fibres, the microfibrils are cleaved in the
transverse direction on the location of the amorphous cellulose. After acid hydrolysis, the
fibrils are separated from each other by mechanical treatment, such as ultrasound or
sonication. The resulting material consists of rod-shaped cellulose crystals, with width around
2-20 nm and lengths varying from 100-600 nm to over 1 ȝm (Figure 5). The aspect ratio of
cellulose nanocrystals is potentially high, 10-100, but usually lower than that of cellulose
nanofibrils. Due to their manufacturing method, cellulose nanocrystals contain less
amorphous cellulose, and thus their crystallinity is high, 62-90%. When the acid hydrolysis is
performed with sulphuric acid (usually concentration of 64%), the hydroxyl groups on the
cellulose fibril surface are replaced with sulphate ester groups, leading to stable colloidal
dispersions in aqueous environment. However, cellulose nanocrystals prepared with
hydrochloric acid (HCl) hydrolysis are less stable towards aggregation.
There are a few challenges related to the manufacturing of cellulose nanocrystals. Firstly,
during the isolation of the cellulose nanocrystals, the solution is diluted with water and the
purification of the crystals as well as the acid recovery from the dilute solution can be costly.
Secondly, the yield of the process is quite low, typically around 20-50%.
9 Klemm, D. K. (2011). Nanocelluloses: A new family of Nature-based Materials. Angew. Chem. Ind. Ed.
50, 5438.; Moon, R. J. et al. (2013) Cellulose nanocrystals – a material with unique properties and
many potential applications. Production and Applications of cellulose nanomaterials. Toim. M.J.
Postek, R.J. Moon, A.W. Rudie ja M. A. Bilodeau,. Tappi Press, USA. s. 9-12.
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Figure 5. AFM image of cellulose nanocrystals from cotton. 8 Image area 2ȝmx2ȝm. Scale in
nanometers (nm).
2.3 Bacterial cellulose10
The manufacturing method of bacterial cellulose is completely different to that of cellulose
nanofibrils or crystals. Bacterial cellulose is produced by certain bacteria, such as
Acetobacterium xylium, as a bottom-up process of polymerization of glucose into cellulose.
The bacteria excrete the formed thick cellulose polymer gel, consisting of fine-structured
cellulose fibrils, outside its cell wall. The width of the bacterial cellulose fibrils is around 20-
100nm and they consist of even finer cellulose nanofibrils with width around 2-4 nm (Figure
6). The cellulose purity of bacterial cellulose, its molar mass, degree of polymerization and
crystallinity (60-80%) are high. The mechanical strength of bacterial cellulose is typically very
high, but at the same time, it is very elastic and formable. Compared to cellulose
nanomaterials originating from plants, the water retaining ability of bacterial cellulose is
excellent, due to its highly porous structure and large specific surface area. The formation of
different shapes from bacterial cellulose, such as hollow tubes and membranes, is possible
already during the growing stage.
The up-scalability of the process and commercial production are decelerated by the slow
production rate of bacterial cellulose, resulting in high production costs. Increase in the
production rate can be potentially achieved by development of the growing technology,
careful selection of raw materials and even by gene technology. It is however probable that
production of bacterial cellulose will be more expensive compared to cellulose nanofibrils and
crystals in the future also. Therefore, its applications need to be selected in such a way that
the higher price is justified. Medical applications are a good example of potential applications
for bacterial cellulose.
10 Klemm, D. et al. (2001). Bacterial synthesized cellulose - artificial blood vessels for microsurgery.
Progress in Polymer Science 26, 1561; Czaja, W. et al. (2006). Microbial cellulose - the natural power
to heal wounds. Biomaterials 27, 145; Chawla, P. R. et al. (2009). Microbial cellulose: Fermentative
production and applications. Food Technology and Biotechnology 47, 107; Shoda, M. ja Sugano, Y.
(2005). Recent advances in bacterial cellulose production. Biotechnology and Bioprocess engineering
10, 1.
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Figure 6. SEM image of bacterial cellulose. Sample provided by Alexander Bismarck,
Imperial College of London. Scale 20 ȝm. (Image source: VTT).
3. The most important properties
3.1 Strong material
Cellulose nanomaterials are considered as strong materials. Estimates for the elastic
modulus of individual cellulose nanofibrils range from 65 GPa to 145 GPa depending on the
raw material and measuring method.11 The elastic modulus of cellulose nanocrystals has
been estimated to be around 137-150 GPa12 and that of bacterial cellulose fibrils in the range
from 78 to 114 GPa. As a comparison, the elastic modulus of aluminium is 69 GPa, that of
steel 200 GPa and of glass 69 GPa.
The strength of cellulose nanomaterials has also been estimated by measuring the
mechanical properties of cellulose nanomaterial films. However, it is well known that the
results are very much depended on the film preparation and testing methods as well as the
properties of the films, such as grammage, density and thickness. Estimates for the tensile
11 Iwamoto, S. K. (2009). Elastic modulus of single cellulose microfibrils from tunicate measured by
atomic force microscopy. Biomacromolecules 10, 2571-2576; Josefsson, G. (2013) Prediction of
elastic properties of nanofibrillated cellulose from micromechanical modelling and nano-structure
characterization by transmission electron microscopy. Cellulose 20, 761
12 Sakurada, I. et al (1962). Experimental determination of the elastic modulus of crystalline regions in
oriented polymers. J. Polymer Sci. 57, 651; Iwamoto, S. K. (2009). Elastic modulus of single cellulose
microfibrils from tunicate measured by atomic force microscopy. Biomacromolecules 10, 2571-2576;
Sturcova, A. (2005) Elastic modulus and stress-transfer properties of tunicate cellulose whiskers.
Biomacromolecules 6, 1055.
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strength of the cellulose nanofibril films range from 129 MPa to 312 MPa, and those for
elastic modulus between 6 to 17 GPa.13
3.2 Rheological properties
In solution, cellulose nanofibrils form gels already at low concentrations, such as 0.125%,14
due to strong interfibrillar forces (Figure 7). The gel viscosity decreases under shear, a
phenomenon that has been observed both under low and high shear.15
Cellulose nanocrystals form a colloidal dispersion in solution, the stability of which depends
on the acid used during hydrolysis. The viscosities of cellulose nanocrystal suspensions are
lower than those of cellulose nanofibrils. Both suspensions express shear thinning behaviour.
Figure 7. Gel formation in water suspensions containing cellulose nanofibrils (Image source:
VTT).
3.3 High specific surface area and tendency for network formation
The mechanical treatment during manufacturing of cellulose nanofibrils leads to external and
internal fibrillation and increased specific surface area of fibrils. Cellulose nanocrystals also
13 Syverud, K. et al. (2009). Strength and barrier properties of MFC films. Cellulose 16, 75-85;
Henriksson, M. et al. (2008). Cellulose nanopaper structures of high toughness. Biomacromolecules 9,
1579-1585; Saito, T. et al. (2009). Individualization of nano-sized plant cellulose fibrils by direct
surface carboxylation using TEMPO catalyst under neutral conditions. Biomacromolecules 10, 1992-
1996; Sirȩ, I. ja Plackett, D. (2010). Microfibrillated cellulose and new nanocomposite materials: a
review. Cellulose 17 , 459-494; Dufresne, A. (2012): Nanocellulose, Walter de Gruyter Gmbh, Berlin,
43-75.
14 Pääkkö, M. et al. (2007). Enzymatic hydrolysis combined with mechanical shearing and high-pressure
homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8, 1934
15 Karppinen, A. et al. (2012): Flocculation of microfibrillated cellulose in shear flow. Cellulose 19, 1807;
Iotti, M. et al. (2011): Rheological studies of microfibrillar cellulose water dispersions. J. Polym.
Environ. 19, 137.
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have a high surface area in relation to its volume. Typical values given for the surface area of
cellulose nanofibrils are around 100-200 m2/g,16 but figures as high as 480 m2/g17 have also
been presented. Estimates between 150-250 m2/g for cellulose nanocrystals have been
published.18 The high specific surface area makes cellulose nanomaterials reactive and
easily chemically modified.
Due to the hydroxyl (OH) on its surface, cellulose is a hydrophilic material. The water
adsorption and retention of cellulose nanomaterials are enhanced by their high specific
surface area. Depending on the application, the water absorbency can be either a positive or
a negative property.
Via the hydroxyl groups on their surface, the cellulose nanomaterials also form strong
interfibrillar hydrogen bonds, resulting in strong and elastic fibrillar networks. High aspect
ratio of cellulose nanofibrils and bacterial cellulose is beneficial in forming strong network
structures.
3.4 Film formation19
Cellulose nanomaterials have a tendency for film formation upon drying. Films prepared from
cellulose nanofibrils are strong, thin, smooth and dense and their thermal stability is good.
The transparency of the films increases with the fibrillation degree of the material; the finer
the fibrils are, the more transparent the films will be.
Rod-shaped particles such as cellulose nanocrystals have a tendency to self-organize once
their critical concentration in the solution has been exceeded. The self-organisation gives the
solution liquid crystal properties. The self-organized structure can be preserved during film
formation giving the cellulose nanocrystal film interesting optical properties.
4. Potential technical applications
4.1 Light materials with increased strength
4.1.1 Fibre-based packaging and composites
In fibre-based products, cellulose nanofibrils can be applied for enhancement of both wet and
dry strength in paper products20 and multi-layer packaging materials.21 Addition of cellulose
16 Lavoine, N. et al. (2012) Microfibrillated cellulose, their barrier properties and applications in cellulosic
materials: a review. Carbohydrate Research 90, 735.
17 Sehaqui, H. et al. (2011) Strong and tough cellulose nanopaper with high specific surface area and
porosity. Biomacromolecules 12, 3638.
18 Terech, P. (1999) A small-angle scattering study of cellulose whiskers in aqueous suspensions.
Macromolecules 32, 1872; Eichorn, S. D. (2010). Review: current international research into cellulose
nanofibres and nanocomposites. J. Mater. Sci. 45, 1.
19 Tammelin, T. ja Vartiainen, J. (2014) Nanocellulose films and barriers. In: Handbook of green
materials, Vol.3: Self- and Direct-Assembling of Bionanomaterials, Chapter 13.
20 Eriksen, Ö. et al. (2008). The use of microfibrillated cellulose produced from kraft pulp as strength
enhancer in TMP paper. Nordic Pulp Paper Res J 23, 299; Ahola, S. et al. (2008). Cellulose nanofibrils
- adsorption with poly(amidamine) epichlorohydrin studied by QCM-D and application as paper
strength additive. Cellulose 15 , 303; Taipale, T. et al. (2010). Effect of microfibrillated cellulose and
fines on the drainage of kraft pulp suspension and paper strength. Cellulose 17, 1005; Torvinen, K. et
al. (2011) Nano fibrillated cellulose as a strength additive in filler-rich SC paper. 2011 Tappi
International Conference on Nanotechnology for Renewable materials, 6-8.6., Arlington, USA; Brodin,
F.W. et al. (2014) Cellulose nanofibrils: Challenges and possibilities as a paper additive or coating
material – a review. Nord. Pulp Paper Res. J. 29, 156
21 Wildlock, Y. et ja Hejnesson-Hulten, A. (2008). Method of producing a paper product. Patentti
WO2008076056; Heiskanen, I. et al. (2011) Process for the production of a paper or board product
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nanofibrils potentially increases the strength of the fibre-pigment network, by increasing both
the strength of the individual bonds and the bonding area (Figure 8), thus enabling higher
pigment contents and lower grammages. The addition of cellulose nanofibrils into the paper
furnish has been investigated at pilot scale, showing improved tensile strength and less
effect on water removal than was originally expected.22
Figure 8. Wood fibre-cellulose nanofibril-filler network.23
4.1.2 Polymer composites4,24
As strength additives for composite applications, cellulose nanomaterials should fulfil certain
criteria: firstly and most importantly, their aspect ratio (length/width) should be high,
preferably over 60.25 Secondly, as stiffness is required their crystallinity should be high, at
least 20% but preferably over 70%. In addition to these, cellulose nanomaterials have
numerous other properties making them potential for composites applications, such as
elasticity, good dispersability and high specific surface area.
Potential markets for composites containing cellulose nanomaterials are for example
automotive industry (tyres, indoor panelling), aviation, military (armours, ballistic glass) and
electronics (batteries). As an example, small amounts (0.5-3%) of chemically modified
cellulose nanofibrils have been applied in the preparation of very thin PVOH composite
films26 (Figure 9), suitable for packaging applications, durable coatings and polarizer
components such as TV screens and sun glasses. Cellulose nanocrystals are also suitable
for composites with added functionality with potential applications in biosensors, catalysis,
fotoelectronic devices, drug delivery, membranes and antimicrobial applications.27
and a paper or board produced according to the process. PatenttiWO2011056135A1; Svagan, A. A.
(2008). Biomimetic foams of high mechanical performance based on nanostructured cell walls
reinforced by native cellulose nanofibrils. Adv. Mater. 20, 1263.
22 Kajanto, I. ja Kosonen, M. (2012) The potential use of micro- and nano fibrillated cellulose as a
reinforcing element in paper and board based packaging. 2012 Tappi International Conference on
Nanotechnology for Renewable Materials. 4-6.6, Montreal, Canada.
23 Hentze, H.-P. (2010). From Nanocellulose Science towards applications. PulPaper 2010, 3-5.6.,
Helsinki.
24 Hubbe, M. et al. (2008). Cellulosic nanocomposites: A review. Bioresources 3, 929; Eichhorn, S. et al.
(2011). Cellulose nanowhiskers: promising materials for advanced applications. Soft Matter 7, 303.
25 Cavaille, J.-Y. et al. (2000) Cellulose microfibril-reinforced polymers and their applications. Patent
US6,103,790.
26 Virtanen, S. et al. (2014) Modified nanofibrillated cellulose – polyvinyl alcohol films with improved
mechanical performance. RCS Adv. 4, 11343; Virtanen, S. et al. (2013) Patent application
FI20135900.
27 Lin et al. (2012) Preparation, properties and application of polysaccharide nanocrystals in advanced
functional nanomaterials: a review. Nanoscale 4, 3274; Moon, R.J. (2011) Cellulose nanomaterials
review: structure, properties, and nanocomposites. Chem. Soc. Rev. 40, 3941.
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Figure 9. Thin PVOH composites films prepared with cellulose nanofibril addition.28
Despite their suitable properties for composite applications, there are certain challenges
related to cellulose nanomaterials in composites. For example, native cellulose is hydrophilic,
which limits its compatibility with hydrophobic polymer matrices. Surface modification of
cellulose nanomaterials may therefore be needed. The length of cellulose nanocrystals may
in some cases be too small for a load-bearing element in composites. However, the length of
cellulose nanofibrils may also pose a problem due to entanglement and aggregation of fibrils
during composite manufacturing. Water absorptivity of cellulose nanomaterials, especially of
cellulose nanofibrils, presents another problem for composite stability. Even though bacterial
cellulose has many superior properties, it is probably best suited for very high-value
applications, such as those in medical field, due to its high production costs.
4.1.3 Strong yarns
There is a long history of preparing cellulose fibres by recovery from dissolution such as in
the viscose process. Fibres have also been prepared from cellulose nanofibrils and
nanocrystals by various spinning methods.29 Recently, a method for preparing continuous
cellulose filaments from cellulose nanofibrils without solvents has been published.30
4.2 Rheology modifier
Cellulose nanomaterials can be utilized as rheology modifiers in applications such as
papermaking, oil drilling, paints, food, medicine and cosmetics. In papermaking, cellulose
nanofibrils could be used as an additive in the coating colour to improve its rheological
properties and ease its application into the paper surface, as well as enhance the paper
quality and printability.31 For food applications, cellulose nanofibrils can be applied as
28 Qvintus, P. et al. (2014) Nanocellulose – towards applications. 13th International Symposium on
Bioplastics, Biocomposites and Biorefining (ISBBB), 19-24.5., Guelph, Canada.
29 Iwamoto, S. (2011) Structure and mechanical properties of wet-spun fibers made from natural
cellulose nanofibers. Biomacromolecules 12, 831; Walther, A. et al. (2011) Multifunctional high-performance
biofibers based on wet-extrusion of renewable native cellulose nanofibrils. Adv. Mater.
23, 2924; Dong, H. et al. (2012) Cellulose nanocrystals as a reinforcing material for electrospun
poly(methyl methalacrylate) fibers: formation, properties, and nanomechanical characterization.
Carbohydrate Polym. 87, 2488; Peresin, M.S. et al. (2010) Nanofiber composites of polyvinyl alcohol
and cellulose nanocrystals: manufacture and characterization. Biomacromolecules 11, 674.
30 Håkansson, K.M.O. (2014) Hydrodynamic alignment and assembly of nanofibrils resulting in strong
cellulose filaments. Nature Comm. 5, 4018.
31 Matsuda, Y. et al. (2001) Super microfibrillated cellulose, process for producing the same and tinted
paper using the same. Patentti US6183596; Hamada, H. et al. (2012) The effects of nano-fibrillated
cellulose as a coating agent for screen printing. 12th TAPPI Advanced Coating Symposium, 10-12.9,
Atlanta, GA; Pajari, H. et al. (2012) Replacement of synthetic binders with nanofibrillated cellulose in
board coating: Pilot scale studies. TAPPI International Conference on Nanotechnology for Renewable
Materials, 4-7.6, Montreal, QC; Brodin, F.W. et al. (2014) Cellulose nanofibrils: Challenges and
possibilities as a paper additive or coating material – a review. Nord. Pulp Paper Res. J. 29, 156;
Pajari, H. et al. (2012) Replacement of synthetic binders with nanofibrillated cellulose in board coating:
Pilot scale studies. TAPPI International Conference on Nanotechnology for Renewable Materials,
June 4-7, Montreal, USA; SUNPAP (2012) Final summary report.
http://sunpap.vtt.fi/pdf/Final_report_M39_VTT_20121126.pdf
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stabilisers and texture modifiers.32 In cosmetics and medicine, the potential of cellulose
nanofibrils has been studied as stabilisers and thickeners.33 Cellulose nanocrystals can be
used to modify the rheological properties of different solutions, polymer melts and particle
mixtures with potential applications in paints, coatings, adhesives, food, cosmetics, medicine
and concrete.34 Bacterial cellulose has been studied for example as a rheology modifier in oil
drilling fluids.35 It is however probable that it is too expensive for this kind of application.
4.3 Smooth, transparent films
4.3.1 Barrier materials
Cellulose nanofibril films have proven to be excellent oxygen and grease barriers and could
be utilized in packages to prevent food spoilage.36 However, they are also sensitive to
moisture, thus limiting their field of application. For packaging purposes, multi-layered
structures consisting of cellulose nanofibrils and water-resistant polymers have therefore
been developed. For example, adequate moisture and oxygen barrier properties can be
obtained with three-layered structure containing polyethylene terephthalate (PET), cellulose
nanofibrils (CNF) and low-density polyethylene (LD-PE), with CNF contributing to the oxygen
barrier properties.37 The material can be used for packaging of dry food, such as nuts (Figure
10). The water-sensitivity of cellulose nanomaterials can also be improved by chemical
modification.
As barrier materials, the films containing cellulose nanofibrils have potential in replacing oil-based
plastics and aluminium, traditionally used in food-contact packaging materials.
Manufacturing of CNF films is already possible at larger scale as for example VTT and Aalto
University have developed a method for roll-to-roll production of plastic-like films at pilot
scale (Figure 11).38
Chemically modified cellulose nanocrystal films have also shown potential as barrier
materials.28,39
32 Kleinschmidt, D. et al. (1988) Filling-containing, dough-based products containing cellulose fibrils and
microfibrils. Patent US4774095; Yaginuma, Y. et al. (2005) Water-dispersible cellulose and process
for producing the same. Patentti US2005272836.
33 Turbak, A. et al. (1985) Suspensions containing microfibrillated cellulose Patentti US4500546;
Mondet, J. (1999) Cosmetic use of natural microfibrils and a film-forming polymer as a composite
coating agent for hair, eyelashes, eyebrows and nails. Patent US6001338; Akimoto, M. (2008)
Composition composed of highly dispersible cellulose complex and polysaccharide. Patent
US2008/0107789.
34 Moon, R. et al. (2013) Cellulose nanocrystals – a material with unique properties and many potential
applications. Production and Applications of cellulose nanomaterials. Toim. M.J. Postek, R.J. Moon,
A.W. Rudie ja M. A. Bilodeau,. Tappi Press, USA. s. 9-12.
35 Westland, J. et al. (1994) Method of supporting fractures in geological formations and hydraulic fluid
composition for same. Patentti US5350528; Westland, J. et al. (1994) Drilling mud compositions
Patentti US5362713.
36 Syverud, K. and Stenius, P. (2009). Strength and barrier properties of MFC films. Cellulose 16, 75;
Aulin, C. et al. (2010) Oxygen and oil barrier properties of microfibrillated cellulose films and coatings.
Cellulose 17, 559; Österberg, M. et al. (2013) A fast method to produce strong NFC films as a platform
for barrier and functional materials. ACS Appl. Mater. Interfaces 5, 4640.
37 Vartiainen, J. et al. (2014) Improving multilayer packaging performance with nanocellulose barrier
layer. 2014 TAPPI Place Conference, May 12-14, Ponte Vedra, FL.
38 Tammelin, T., et al. (2013) Method for the preparation of NFC films on supports. Patentti WO
2013/060934.
39 Siqueira, G. et al. (2010) Cellulosic bionanocomposites: a review of preparation, properties, and
applications. Polymers 2, 728; Hubbe et al. (2008) Cellulosic nanocomposites: A review. Bioresources
3, 929.
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Figure 10. Transparent PET/CNF/LDPE film can be used for packaging of dry food such as
nuts, dried fruits and spices (Image source: VTT).
Figure 11. Manufacturing of CNF film from roll to roll at pilot scale with VTT’s Sutco device.29
4.3.2 Substrates for printed electronics
Cellulose nanofibrils can be utilized in substrates for printed electronics, either together with
fillers or alone. High filler papers, consisting of wood fibres, cellulose nanofibrils and filler (up
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to 40%) as well as pigment composites containing 80% of filler and 20% of CNF have proven
to be good substrates for printed electronics.40 The composites can tolerate temperatures as
high as 270°C for short periods of time and temperatures around 230°C for 12 hours. The
function of electronics, e.g. LC resonator and RFID tag, printed on the composite substrate is
comparable to those printed on plastics (Figure 12). Due to their smoothness, density and
good temperature tolerance, films prepared from cellulose nanofibrils alone have also proven
to be good substrates for printed electronics (Figure 13).
Figure 12. Electronics printed on filler-CNF substrates. LC resonator (left) and RFID tag
(right), hot laminated into a plastic pocket. The content of the RFID tag can be read with
mobile phone.39
Figure 13. Flexo printed silver electrodes (left) and inkjet and gravure printed transistors
structures on CNF substrate (Image source: VTT).
40 Torvinen, K. et al. (2012) Flexible bio-based pigment-nanocellulose substrate for printed electronics.
International Conference on Flexible and Printed Electronics, 11-13.9, Tokyo, Japan. Finnish
Bioeconomy Cluster FIBIC (2013) Efficient Networking Towards Novel Products and Processes.
EFFNET Programme Report 2010-2013, pp. 51-54.
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4.3.3 Electronic displays41
Due to the controlled thermal expansion, strength, transparency and good balance between
flexibility and stiffness of cellulose nanofibril films, they are potential materials for the strength
enhancement of electronic devices in web-form, such as flexible electronic displays (OLED),
solar panels, electronic papers and sensory panels. Cellulose nanocrystal films could also
function as electronic displays due to their tendency to self-organise and their liquid crystal
properties. However, they are not suitable for liquid crystal displays as the formation and
changing of the crystals is too slow. Potential applications for bacterial cellulose films include
e-books and newspapers.42 The films can be modified by addition of ions to induce
conducting or semiconductor properties, or coloured with dyes to bring content to the film.
4.3.4 Coloured films
Films prepared from cellulose nanocrystals have interesting optical properties, such as film
colour that changes depending on the viewing angle. This type of film can be potentially
applied as optical marker in passports, credit cards etc. to prevent forgery.43
4.4 Water absorbing, retaining and releasing materials
4.4.1 Medical applications
Cellulose nanofibril gels in water have been found to be a good growing media for cells.44
Scaffolds for growing of cells can be manufactured from hydrogels containing 1-2% of
cellulose nanofibrils by 3D printing (Figure 14). The cells can be added to the hydrogel prior
to printing or alternatively, after printing and freeze-drying to aerogel. Cells growing in the
hydrogel can be used for production of tissue implants, based on the scaffold produced by
3D printing.45 Cellulose nanofibril films have also been applied as platform for immunoassays
and diagnostics,46 as well as for controlled drug release and delivery, similarly as cellulose
nanofibril particles and aerogels.47
41 Sirȩ, I. and Plackett, D. (2010). Microfibrillated cellulose and new nanocomposite materials: a review.
Cellulose 17 , 459.
42 Shah, J. et al. (2004). Towards electronic paper displays made from microbial cellulose. Appl
Microbiol Biotechnol 66, 352.
43 Revol, J. et al. (1997). Patentti US5629055; Habibi, Y. et al.(2010) Cellulose nanocrystals: chemistry,
self-assembly, and applications. Chemical reviews 110, 3479; Lima, M.M.D ja Borsali, R. (2004) Rod-like
cellulose microcrystals: structure, properties, and applications. Macromolecular
44 Bhattacharya, M. et al. (2012) Nanofibrillar cellulose hydrogel promotes three-dimensional liver cell
culture. J. Contr. Release 164, 291.
45 Hänninen, T. et al. (2013) 3D-printed scaffolds for generative medicine from ceramics and cellulose.
MiMe – Materials in Medicine. International Conference, 8-11.10., Faenza, Italy.
46 Orelma et a. (2012) Surface functionalized nanofibrillar cellulose (NFC) film as a platform for
immunoassays and diagnostics. Biointerphases 7, 61; Orelma, H. et al. (2012) Genetic method for
attaching biomolecules via avidin-biotin complexes immobilized on films of regenerated and
nanofibrillar cellulose. Biomacromolecules 13, 2802.
47 Kolakovic, R. et al. (2012) Nanofibrillar cellulose films for controlled drug delivery. Eur J Pharma
Biopharma 82, 308; Kolakovic, R. et al. (2012) Spray-dried nanofibrillar cellulose microparticles for
sustained drug release. Int J Pharma 430, 47; Valo, H. et al. (2013) Drug release from nanoparticles
embedded in four different nanofibrillar cellulose aerogels. Eur. J. Pharma Sci. 50, 69.
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Figure 14. Stable cellulose nanofibril gel (1%, height 7 cm, left). Freeze-dried cellulose
nanofibril aerogel.44
Bacterial cellulose can be potentially applied as scaffolds for cartilage and small vessels
during surgical operations as well as tissue implants.48 By providing ideal conditions for
moisture and oxygen transmission, bacterial cellulose is also suitable material for wound
dressings. The advantages of bacterial cellulose over cellulose nanofibrils and crystals in
medical applications include its purity and biocompatibility with human tissue.
4.4.2 Hygiene products
Fine-structured cellulose can absorb, retain and release liquids in a controlled manner,
making it a suitable material for various hygiene products such as diapers, sanitary napkins,
wound dressings and cleaning cloths.49 Usually in these products cellulose nanofibrils form
the absorbing matrix in which a small amount of super-absorbent polymer (SAP) is attached.
Cellulose nanofibrils absorb the incoming liquid fast and transfer it to the SAP in a controlled
way. Cellulose nanofibrils also enhance the strength properties of the products.
4.5 Reactive networks
4.5.1 Membranes
The pores in cellulose nanomaterial films are in the nanometer range and could thus be
utilized for separation of components, providing a biobased alternative for synthetic
membrane materials. For example, membranes produced from cellulose nanofibrils are
suitable for nanofiltration of organic solvents.50 Membrane properties, such as sensitivity to
water or temperature tolerance can be modified with chemical treatments. In the latter case,
48 Svensson, A. N. (2005). Bacterial cellulose as a potential scaffold for tissue engineering of cartilage.
Biomaterials 26, 419; Bäckdahl, H. H. (2006). Mechanical properties of bacterial cellulose and
interactions with smooth muscle cells. Biomaterials 27, 2141; Hoenich, N. (2006). Cellulose for
medical applications: Past, present and future. BioResources 1, 270.
49 Klemp, W. V. et al. (2004) Disposable absorbent article enploying an absorbent composite and
method of making the same. Patentti US .6,794,557; Suzuki, M. ja Mori, S. (2003) Highly absorbent
composite sheets and methods for manufacturing the same. Patentti US20030114059; Takai, H. et al.
(2003) Water-disintegratable sheet and manufacturing method thereof. Patentti US20030000665.
50 Mautner, A. (2014) Nanopapers for organic solvent nanofiltration. Chem. Commun. 50, 5778.
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for example, the surface properties of the membrane can be adjusted by the temperature of
the liquid being filtrated.51
4.5.2 Porous structures
Together with natural fibres and fillers, cellulose nanofibrils can be utilized in manufacturing
of porous structures to be used for example for sound insulation, packaging and air
filtration.29,52 Foam forming provides a technology to produce porous structures from natural
fibres and addition of cellulose nanofibrils has been found to increase the compression
strength of such structures, as well as to enhance the recovery of the structure after
compression.53 Hydrophobic cellulose nanofibril aerogels have also proven to be suitable for
transportation purposes in liquids and removing impurities such as oil from water.54
Aerogels prepared from cellulose nanocrystals form also very porous structures with
densities around 0.01-0.04 g/cm3 and specific surface area between 30-600 m2/g, and are
thus potential for many applications.55 Bacterial cellulose has been found a suitable material
for acoustic membranes in high frequency speakers and headphones.56
5. Commercial prospects
5.1 Availability
Currently there are few commercial producers of cellulose nanomaterials. In addition, many
companies have started pre-commercial or demonstration production at full or pilot scale.
Many more have announced the start of production in the near future. The following
describes the situation in August 2014. The information is mainly based on press releases
and company websites.
5.1.1 Commercial production
x Daicel Corporation, Japan. Cellulose microfibrils with brand names Celish and nano-
Celish www.daicel.com/en
x JRS – J. Rettenmaier & Söhne Gmbh + Co. KG, Germany. Product with brand name
Arbocel“ UFC-100 has the best resemblance to cellulose nanomaterials
http://www.jrs.de/jrs_en/index.php
x Chuetsu Pulp, Japan. 18 different grades of cellulose nanofibrils http://www.chuetsu-pulp.
co.jp/ (in Japanese)
51 Hakalahti, M. et al. (2014) Surface modification of nanocellulose membranes using thermoresponsive
poly(N-isopropylacrylamide). Nano 4 Water. 4th Joint Workshop, 23-24.4., Stockholm.
52 Pöhler, T. et al. (2013) New high volume fibre products by foam forming, European Paper Week,
CEPI and EFPRO Open Seminar “New ideas for the paper industry – Young researchers
presentations, 27.11, Brussels.
53 Pääkkönen, E. et al. (2013) Porous wood fibre structures for tomorrow markets. 17th International
Symposium on Fibre, Wood and Pulping Chemistry (ISFWPC), 12-14.6., Vancouver, BC.
54 Jin, H. et al. (2011) Superhydrophobic and superoleophobic nanocellulose aerogel membranes as
bioinspired cargo carriers on water and oil. Langmuir, 27, 1930; Korhonen, J. et al. (2011)
Hydrophobic nanocellulose aerogels as floating, sustainable, reusable, and recyclable oil absorbents.
ACS Appl. Mater. Interfaces 3, 1813.
55 Capadona et al. (2007) A versatile approach for the processing of polymer nanocomposites with self-assembled
nanofiber templates. Nature Nanotech. 2, 765; Kelley, J et al. (2010) Decrystallization of
cellulose nanocrystal aerogels in organic solvents. 239th ACS National Meeting, San Francisco, CA,
USA. s. CELL-276; Heath, L. ja Thielemans, W. (2010) Cellulose nanowhisker aerogels. Green Chem.
12, 1448.
56 Iguchi, M. et al. (2000). Bacterial cellulose - A masterpiece of nature's arts. J. Materials sci. 35, 261.
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x Sugino Machine, Japan. Nanofibres prepared from carboxymethyl cellulose (CMC) with
brand name BiNFi-s. Price around 25-35 €/kg http://www.sugino.com/site/biomass-nanofiber-
e/
x Daio Paper, Japan. Cellulose nanofibrils prepared from company’s own pulps.
x Dai-ichi Kogyo Seiyaku, Japan. 2% cellulose nanofibril suspension with brand name
RHEOCRYSTA for modification of rheological properties.
x Asahi Kasei, Japan. Cellulose nanoparticles with brand name NanoAct™ for diagnostic
purposes http://www.asahi-kasei.co.jp/asahi/en/
x Oji Holdings, Japan. Production of CNF films in collaboration with Mitsubishi Chemicals.
http://www.ojiholdings.co.jp/english/index.html
x CelluComp, Iso-Britannia. Production of cellulose nanofibres with brand name Curran“
from root vegetable waste http://cellucomp.com/
x University of Maine, USA. The capacity of CNF production is around 1t/day at pilot scale
http://umaine.edu/pdc/process-and-product-development/selected-projects/
nanocellulose-facility/
x Blue Goose Biorefineries (BGB), Canada. Production of cellulose nanocrystals based on
oxidative, nanocatalytic process. http://www.bluegoosebiorefineries.com/
x
5.1.2 Demonstration/ pre-commercial production
x Stora Enso, Finland. Pre-commercial production of microcellulose since 2011
http://biomaterials.storaenso.com/
x UPM, Finland. Cellulose nanofibrils with two brand names; Biofibrils™ and GrowDex®
http://www.upm.com/EN/PRODUCTS/biofibrils/Pages/default.aspx
x CelluForce, Canada. Demonstration plant for CNC production with brand name NCC™
since 2012 www.celluforce.com/en
x American Process Inc., USA. Production of cellulose nanofibrils and nanocrystals with
patented AVAP® technology since 2013. Provides also lignin-coated grades
http://www.avapco.com/
x Nippon Paper Group, Japan. Pre-commercial production of chemically modified cellulose
nanofibrils with brand name CELLENPIA since 2013. The capacity is over 30 tonnes
http://www.nipponpapergroup.com/english/
5.1.3 Pilot-scale production
x Innventia, Sweden. Production of cellulose microfibrils with capacity of 100 kg/day since
2011. In June 2014 announced plans to develop mobile facilities for nanocellulose
production in co-operation with BillerudKorsnäs www.innventia.com
x Borregaard Chemcell, Norway. Production of cellulose microfibrils in biorefinery
http://www.borregaard.com/Business-Areas/Borregaard-ChemCell
x Forest Products Laboratory (FPL), USA. Production of cellulose nanocrystals (capacity
25 kg/day) and cellulose nanofibrils (2 kg/day) since 2012 http://www.fpl.fs.fed.us/
x AkzoNobel, The Netherlands. Production of CNF at paper mill environment
https://www.akzonobel.com/
x CTP/FCBA, France. Pilot facilities (NaMiCell) for production of cellulose micro/nanofibrils
http://www.webctp.com/gb/default.cfm
x GL&V, USA. The company has developed a method for the production of cellulose
microfibrils capable of utilizing the existing commercial pulp refiners. Start-up of pilot plant
in 2013. http://www.glv.com/
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5.1.4 Production facilities under construction / planning
x Norske Skog, Norway. The company received a grant in December 2013 for setting up
pilot facilities for cellulose microfibril production from thermomechanical pulp (TMP)
http://www.norskeskog.com/Default.aspx
x Krueger and FPInnovation, Canada. Plans for construction of demonstration plant for the
production of cellulose filaments with capacity of 5 t/day http://www.kruger.com/
x Alberta Innovates – Technology Futures, Canada. Pilot facility plans to open in 2014 with
production of cellulose nanocrystals 100 kg/week
http://www.albertatechfutures.ca/Home.aspx
x BASF ja Zelfo Technology, Germany. BASF has purchased the rights for Zelfo’s
technology for production of cellulose microfibrils. Companies plan to co-operate in
developing and up-scaling the technology https://www.paper-chemicals.
basf.com/portal/basf/en/dt.jsp; http://www.zelfo-technology.com/
x InoFib, France. Start-up company expected to enter markets in 2014 with re-dispersible
cellulose microfibril product.
x Seiko PMC (a subsidiary of of DIC Corp.), Japan. Pilot facility under construction in
Ryugasaki, Japan, with start-up planned for 2016.
x Melodea, Israel. Patented method for extracting cellulose nanocrystals from the sludge of
pulp and paper mills. Facility with production of 100 kg/day under planning, expected to
be in operation in 2015 www.melodea.eu
5.1.5 Production
Estimates for production of cellulose nanomaterials according to Future Markets Inc., a
consulting company, are presented in Figure 15. Currently, most of the production consists of
cellulose nanofibrils and nanocrystals, the share of bacterial cellulose being only marginal.
FPInnovation, a Canadian research institute, has estimated that the cellulose nanomaterials
market will be worth $250 M in North America by year 2020.57
57 Future Markets Inc. The Global Market for Nanocellulose to 2024.
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Figure 15. Estimates for the production of cellulose nanomaterials (Source for the figures:
Future Markets Inc.56)
5.2 Commercial application possibilities
In this chapter, commercial applications that appear to be developing for cellulose
nanomaterials are discussed. The information given is based on the patent landscape of
cellulose nanomaterials, which reflects the future activities of companies in this field, as well
as on recently published market report.57
The topographic map of the patent landscape for cellulose nanomaterials is presented in
Figure 16. Similar patent documents are gathered together as clusters. The terms shown
next to the cluster describe its content the best. The size of the cluster is presented by its
colour; the redder the colour, the bigger the cluster.
When evaluated according to technology indicators, patent classifications and clustering
concepts, i.e. terms that best describe the content of the patent, the main application areas
for cellulose nanomaterials are paper applications and packaging, coatings and films,
pharmaceuticals and drug delivery, reinforced plastics, textiles, non-wovens and energy
storage.
Figure 16. Topographic map of the patent landscape for cellulose nanomaterials. STN
AnaVist visualisation based on 2082 patent documents (CAplus ja WPIndex database 2007–
16.6.2014, image source: VTT).
Future Markets Inc. has divided the most potential applications into those of high volume and
low volume and new applications (Table 1).
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Table 1. Most probable applications for cellulose nanomaterials.57
High volume Low volume New
Composites for automotive
industry: replacement of
glass fibre
Insulators in construction:
sound and heat
Stress sensors
Concrete: additive Composites for space
technology
Air and water filtration
Coatings and films in
packages: additive in wet
end, retention aid
Aerogels for gas and oil Flexible electronic displays
Transparent films in food
contact packaging: barrier
properties and durability
Functional pigments:
dispersion, coating durability
and viscosity
Flexible circuits, printed
electronics and conducting
platforms
Packaging composites Construction materials and
composites
Flexible solar panels
Printing papers:
improvement of ink adhesion
and optical properties
Hydrophobic and self-cleaning
surfaces
Intelligent packages
Electronic packaging:
strengthening agent
Optoelectronics
Pharmaceuticals: filler
Paper composites: improved
strength
Hygiene products and
absorbents
Textiles
Cosmetics: filler
5.3 Important stakeholders
Asian countries China, Japan and Korea are well represented among the countries with most
patents on cellulose nanomaterials in years 2007-2014, being on the first, second and fourth
place. Among the top ten patent counties are also USA (3rd place), Canada (5.), Australia
(6.), India (7.), Mexico (8.), Finland (9.) and Russia (10.). Finland is the only European
country to have made it to the top ten.
Out of the individual organisations, the Chinese University of Donghua is on the first place
and Chinese Academy of Science on the 10th place. Several Japanese organisations are in
the top ten: Nippon Paper Group, Konica Minolta, Oji Group, University of Kyoto and
Mitsubishi. The Finnish Paper companies UPM and Stora Enso are on the third and fifth
place, respectively, and the Canadian research institute FPInnovations on the 9th place.
In Finland, UPM produces cellulose micro- and nanofibrils under the brand name Biofibrils™
for industrial applications such as rheology modifiers, strength additives and barrier
materials. Cellulose nanofibrils with the brand name Growdex® are suitable for medical
applications. Stora Enso is testing the use of cellulose microfibrils in paper- and packaging
products and in the future, the use in totally new products is a possibility.
In Canada, Celluforce has a long list of potential applications for their cellulose nanocrystals
with brand name NCC™, ranging from paper products, composites and textiles all the way to
bone tissue implants and pharmaceuticals. A very unique application for cellulose
nanocrystals are iridescent films with modifiable properties to be used in various secure
documents and coatings.
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In Japan,58 the target applications for Nippon paper are functional additives such as rheology
modifiers, functional films like membranes and gas barriers, transparent films and
composites. Sugino Machine produces its cellulose nanofibrils for rheology modification,
such as for emulsification in pharmaceuticals, cosmetics and food, as well as for strength
enhancement in industrial applications. Seiko PMC focuses in composites for automotive
industry with its product, aiming at the replacement of resin composites with CNF
composites. Daio Paper lists the following applications for its product: water retention agents,
strength additives, battery parts, cosmetics, food and pharmaceutical applications. Kao
Corporation and Toppan are investigating the application of cellulose nanofibrils as coating to
improve the gas barrier properties of packages. Oji Holdings has a number of patents on
diapers containing CNF. Olympus holds patents related to composites and a very recent one
dealt with thermostable cellulose nanofibrils to be used as strengthening agent in
composites.
6. Characterization
Studies have shown that the phenomena behind the behaviour of cellulose nanofibrils are
complex and its properties cannot be characterized by any single method alone. Therefore, a
combination of characterization methods based on different measurement principles is
recommended.59 The most important properties of cellulose nanofibrils and methods for their
characterization are listed in Table 2. Out of these characterization methods, a combination
of four measurements is recommended for the basic characterization of cellulose nanofibrils,
including optical microscopy, electron microscopy, low shear viscosity and transmittance.
Combined, these methods provide information on the homogeneity, external dimensions and
size distribution as well as rheological properties of the cellulose nanofibrils.58
58 Valuenex (2014) Research report http://so-ti.com/report/detail173.html
59 Kangas, H. et al. (2014) Characterization of fibrillated celluloses. A short review and evaluation of
characteristics with a combination of methods. Nord. Pulp Paper Res. J. 29, 129.
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Table 2. The most important properties of cellulose nanofibrils and the methods used for their
characterization.59 The literature listed in the Table refers to the first or most important
publication related to the method.
Property Characterization method
Amount of nanomaterial Mechanical fractionation60
Fractionation by centrifugation61
Tube flow fractionation62
Particle size and size distribution Light-scattering methods (for low aspect ratio materials)
Transmittance (UV-vis spektroscopy)63
Fibre analysators
Fractionators
Turbidity
Microscopy: scanning electron microscope (SEM),
transmission electron microscope (TEM), atomic force
microscope (AFM)64
Rheological properties Low shear viscosity65
Gel strength, viscoelastic properties14
Appearance of fibrils; dimensions,
branching, aspect ratio
(length/width)
Microscopy; optical microscopy (OM) and
SEM/TEM/AFM14,61
Crystallinity X-ray diffraction (XRD)66
Specific Small-angle X-ray scattering (SAXS)67
N2 absorption, Brunauer-Emmett- Teller (BET)
isotherms14
Surface charge and chemistry
(chemically modified grades)
Conductometric titration68
Polyelectrolyte titration69
Zeta potential70
X-ray photoelectron spectroscopy (XPS)6
Fourier Transform Infrared spectroscopy (FT-IR)71
60 Tanaka, A. et al. (2012): Nanocellulose characterization with mechanical fractionation. Nord. Pulp
Paper Res. J. 27, 689.
61 Ahola, S. et al. (2008): Model films from native cellulose nanofibrils. Preparation, swelling, and surface
interactions. Biomacromolecules 9,1273.
62 Haapala, A.T. et al. (2013): Optical characterization of of size, shape and fibrillarity from microfibrillar
and microcrystalline cellulose, and fine ground wood powder fractions. Appita J. 66(4), 331.
63 Saito, T. et al. (2006): Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed
oxidation of native cellulose. Biomacromolecules 7, 1687.
64 Vartiainen, J., et al. (2011): Health and environmental safety aspects of friction grinding and spray
grinding of microfibrillated cellulose. Cellulose 18, 775.; Wang, Q.Q. et al. (2012): Morphological
development of cellulose fibrils of a bleached eucalyptus pulp by mechanical fibrillation. Cellulose 19,
1631.
65 Iotti, M. et al. (2011): Rheological studies of microfibrillar cellulose water dispersions. J. Polym.
Environ. 19, 137.
66 Iwamoto, S. et al. (2007): Nano-fibrillation of pulp fibers for the processing of transparent
nanocomposites. Appl. Phys. A 89, 461.
67 Leppänen, K., et al. (2010): Small-angle x-ray scattering study on the structure of microcrystalline and
nanofibrillated cellulose. J. Phys.: Conf. Ser. 247, 012030.
68 Saito, T. and Isogai, A. (2004): TEMPO-mediated oxidation of native cellulose. The effect of oxidation
conditions on chemical and crystal structures of the water-insoluble fractions, Biomacromolecules 5,
1983.
69 Junka, K. et al. (2013): Titrimetric methods for the determination of surface and total charge of
functionalized nanofibrillated/microfibrillated cellulose (NFC/MFC). Cellulose 20, 2887.
70 Eronen, P. et al. (2012): Comparison of multilayer formation between different cellulose nanofibrils
and cationic polymers. J. Colloid Interface Sci. 373, 84.
71 Saito, T. et al. (2006): Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed
oxidation of native cellulose. Biomacromolecules 7, 1687.
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Mechanical properties Strength properties of CNF films72
Dissolved and colloidal
substances (quality and amount)
Gel chromatography (GPC)
Size exclusion chromatography (SEC)
High performance liquid chromatography (HPLC)
Microscopy; SEM/TEM/AFM
Canadian organisation CSA Group published in June 2014 the first national standard on
characterization of cellulose nanomaterials.73 The important properties and related
characterization methods for cellulose nanocrystals listed in the standard are presented in
Table 3. Some of the methods are also recommended for cellulose nanofibrils. However,
regarding characterization of morphology, the standard clearly states that no standardized
method can be presented for CNFs.
72 Henriksson, M. et al. (2008). Cellulose nanopaper structures of high toughness. Biomacromolecules
9, 1579.
73 CSA Group (2014) Cellulosic nanomaterials – Test methods for characterization. Standard Z5100-14.
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Table 3. Characterization methods for cellulose nanomaterials listed in the Canadian
standard Z5100-14.73
Property Characterization method CNC/CNF
Purity Carbohydrate
content
Gas-liquid chromatography
(GLC), TAPPI T249 cm
Anion exchange
chromatography (AES)
CNC, CNF
Lignin content PAPTAC methods G.8, G.9
or G.18
CNC, CNF
Extractives content Soxhlet extraction, TAPPI
T204 cm or PAPTAC G.13
ja G.20
CNC, CNF
Metal content Inductively coupled mass
spectrometry (ICP-MS)
CNC, CNF
Crystallinity degree and
index
XRD, Nuclear magnetic
resonance spectroscopy
(NMR)
CNC, CNF
Free sulphate groups ICP-AES CNC
Dry matter content Oven drying and weighing CNC, CNF
ISO brightness, colour
ISO 2469, ISO 2470-1, ISO
CNC, CNF
(CIELAB)
5631-1
Morphology Length and width
distribution
SEM, TEM, AFM CNC
Size distribution Dynamic light scattering
(DLS)
CNC
Agglomeration and
aggregation
Turbidity (light scattering
and transmittance),
Turbiscan
CNC
pH PAPTAC H.4P CNC, CNF
Viscosity TAPPI T 648 (ISO 12058-1;
ISO 3105; ISO 2884-2; ISO
1628-3; ISO/TR 3666)
CNC, CNF
Total sulphur content ICP-AES CNC
Sulphate ester content Conductometric titration CNC
Carboxyl content Conductometric titration CNC
Degree of polymerization
(DP), distribution
Size exclusion
chromatography-multi-angle
light scattering (SEC-MALS)
CNC, CNF
Zeta potential CNC, CNF
Specific surface area BET (ISO 9277); NMR CNC
Thermal stability Thermogravimetry CNC, CNF
Dispersibility in water Shear birefringence (CNC),
turbidity, DLS (CNC); visual
evaluation, film strength,
fibre analysator
CNC, CNF
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7. Advice on use
7.1 Preservability
Generally the same rules of preservation apply to cellulose nanomaterials than to other
water-containing biomasses; even though they are prone to contamination, their shelf-life can
be extended with proper handling and preserving. Contamination of cellulose nanomaterials
can be observed as visible microbial growth but also as deterioration of their properties. For
example, their contamination has been found to have influence in papermaking applications
as effect on phenomena such as dewatering and bonding, thus decreasing the viscosity and
strength.74 The preservability of cellulose nanomaterials is most depended on the
preservation temperature and the materials should be cooled down immediately after
processing and kept at refrigeration temperature at all times, even during transportation. The
sources of microbial contamination should be kept at minimum, e.g. using clean containers
and avoiding touching by hand. Biocides or UV treatments can also be used to extent the
shelf-life.75
The stability of cellulose nanocrystals during a year-long storage has been recently studied.76
The deterioration of cellulose nanocrystal properties was found to depend on storage
conditions, surface charge of crystals (acid groups vs. neutralized) and the state of
preservation (water suspension vs. freeze dried). The neutralized cellulose nanocrystals
preserved their properties the best. Acidic cellulose nanocrystals should not be stored as
dried, and even in water suspension their shelf-life is limited. Especially for high-quality use,
such as optical applications, their storage time should be limited to less than 3 months.
7.2 Processing
7.2.1 Composites4,24
There are several challenges related to processing of composites containing cellulose
nanomaterials:
x The chemical compatibility of cellulose nanomaterials with the matrix material.
x Water absorptivity of cellulose nanomaterials leading to swelling.
x Uneven distribution of cellulose nanomaterials in the composite matrix, due to
chemical incompatability, entanglement of nanofibrils and/or improper addition and
mixing techniques.
x The thermal stability of cellulose in the composite processing temperatures.
With hydrophilic composite matrices, such as starch, the chemical compatibility with cellulose
nanomaterials is not a problem. However, usually the matrix consists of hydrophobic
thermoplasts and compatibility becomes an issue. Chemical incompatibility between
cellulose nanomaterials and the matrix material results in uneven distribution of the additive
in the matrix as well as poor adhesion, leading to deterioration of strength properties. In this
case the compatibility can be increased by chemical modification of the cellulose
nanomaterials or using dispersing aids such as latex.
Swelling of cellulose nanomaterials due to water absorption leads to weakening of adhesion
between fibrils and the matrix polymer. Selecting the right amount of cellulose nanomaterial
could provide a solution to this problem: adding the amount needed for clear improvement of
74 Finnish Bioeconomy Cluster FIBIC (2013) Efficient Networking Towards Novel Products and
Processes. EFFNET Programme Report 2010-2013, 79.
75 Chauve, G. et al. (2014) Separation of cellulose nanocrystals. In: Handbook of Green Materials. Vol.
1. Bionanomaterials: separation processes, characterization and properties. Ch. 6, 73-87.
76 Beck, S. and Bouchard, J. (2014) Effect of storage conditions on cellulose nanocrystal stability. Tappi
J. 13(5), 53.
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strength properties without deterioration of the composite structure due to water absorption
and swelling.
Even distribution of cellulose nanomaterials in the composite structure is critical for their
strength properties. Regarding cellulose nanofibrils, their length can present a problem, since
entanglement of long fibrils can lead to aggregation. Even distribution can be promoted by
selecting cellulose nanomaterial and matrix with optimal compatibility and the best possible
processing method for mixing. Sonication and surfactants can be utilized for improved
mixing.
In general, cellulose fibres have a rather low thermal stability for composite manufacturing as
they start to degrade at around 230°C. This limits the operating temperature during
manufacturing to 200°C. The thermal stability of cellulose nanomaterials can be improved for
example by chemical modification treatment by sulphuric acid.
7.2.2 Water suspensions
Currently, cellulose nanofibrils are delivered as water suspensions and when used at large
scale, are faced with processing challenges for example in dewatering and pumping.77
Cellulose nanofibril suspensions undergo shear thinning flow already at low shear and are
prone to flow-induced instabilities such as flow variations and related pressure fluctuations.
Flow instabilities can be prevented by selection of the pump type and sizing of the flow
piping. Due to the gelling behaviour of cellulose nanofibril suspensions, pumping also
presents a challenge. Pumping of thick suspensions can be best handled by high-consistency
pumps or screw pumps. Mixing of thick cellulose nanofibril suspensions,
especially after dilution with water, requires high-consistency mixers.
7.2.3 Drying and redispersion
Delivery of cellulose nanomaterials in dried form would be ideal in order to save on shipment
costs and potentially extending the shelf-life of the product. However, re-dispersion presents
a challenge due to hornification of cellulose fibrils. Some methods for producing dry, re-dispersible
cellulose nanomaterial powders have been published. For example, water-soluble
polymers, such as carboxymethyl cellulose (CMC) or xanthan, and/or hydrophilic substance,
such as dextrin or water-soluble sugar, can be added to dry cellulose powder 10-35% of the
dry weight of the powder.78 Cellulose nanomaterials can be also chemically modified to
increase their re-dispersibility, for example by acetylation or silylation.79 A simpler method is
provided by addition of NaCl to the suspension before drying.80 The salt functions as a barrier
to hydrogen bonds, which normally form between fibrils during drying.
Re-dispersion of cellulose nanocrystals into water is possible when their dry matter content is
96% or less. With higher dryness levels, re-dispersion can be achieved after ion exchange of
cellulose nanocrystal acid groups with Na ions into neutral nanocrystals.81
77 Finnish Bioeconomy Cluster FIBIC (2013) Efficient Networking Towards Novel Products and
Processes. EFFNET Programme Report 2010-2013, 78.
78 Tuason, Jr., D.C. et al. (2004) Fat-like agents for low calorie food compositions. Patentti US6,689,405;
Yaginuma, Y. et al. (2010). Water-dispersible cellulose and process for producing the same. Patentti
US7,838,666; Akimoto, M. (2008).Composition composed of of highly dispersible cellulose complex
and polysaccharide. Patenttihakemus US2008010779.
79 Zimmermann, T. et al. (2010) Applications of nanofibrillated cellulose in polymer composites. Tappi
International Conference on Nanotechnology for Forest Products Industry, 27-29.9., Espoo, Finland.
80 Missoum, K. et al, (2012) Water redispersible dried nanofibrillated cellulose by adding sodium
chloride. Biomacromolecules 13, 4118.
81 Beck, S. et al. (2012) Dispersibility in water of dried nanocrystalline cellulose. Biomacromolecules 13,
1486.
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8. Environmental, health and safety aspects
8.1 Published information
Results so far published on the safety of cellulose nanomaterials have revealed no
immediate danger to human health or to the environment.82 However, the results obtained
are dependent on the raw material and the processing method used as well as on the testing
method. Therefore, the results obtained cannot be generalized for all cellulose nanomaterials
and currently, the evaluation of safety must be conducted case-by-case. A summary of
published information on the environment, health and safety (EHS) of cellulose
nanomaterials is given in Table 4.
Table 4. Published information on the environmental, health and safety of cellulose
nanomaterials.
Material Human health Occupational
exposure
Environment
CNF, nano-sized
fraction83
Slight indications of
cytotoxicity in one out of
two tests in vitro. No
genotoxicity in vitro. No
systemic effects in vivo.
CNF,
unmodified,
anionic and
cationic84
No cytotoxicity in vitro
CNF85 At high dosage (> 2
mg/ml) in vitro decrease
in cell viability and effect
on expression of markers
connected to cell viability
and cell death
CNF86 No acute cytotoxicity in
vitro
CNF87 No cytotoxicity or effect
on cell viability in vivo
CNF88 No cytotoxicity or
immunotoxicity in vitro.
Slight genotoxicity in
Overall risk
considered low
/moderate by
82 Pitkänen et al. (2014) Toxicity and Health Issues. In: Handbook of Green Materials. Processing
Technologies, Properties and Applications, Vol 1. Chapter 12. World Scientific Publishing, 188-205.
83 Pitkänen et al. (2014) Characteristics and safety of nano-scale cellulose fibrils. Cellulose DOI
10.1007/s10570-014-0397-x.
84 Hua et al. (2014) Translational study between between structure and biological response of
nanocellulose from wood and green algae. RCS Adv. 4:2892. DOI: 10.1039/C3RA45553J
85 Pereira, M.M. (2013) Cytotoxicity and expression of genes involved in the cellular stress response and
apoptosis in mammalian fibroplast exposed to cotton cellulose nanofibers. Nanotechnology 24,
075103.
86 Alexandrescu, L. et al. (2013) Cytotoxicity tests of cellulose nanofibril-based structures. Cellulose 20:
1765.
87 Bhattacharya, M. et al. (2012) Nanofibrillar cellulose hydrogel promotes three-dimensional liver cell
culture. J Controlled Release 164:291. doi: 10.1016/j.jconrel.2012.06.039
88 SUNPAP (2012) Final summary report.
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vitro. Slight inflammatory
reactions in vivo
control band (CB)
method
CNF89 No cytotoxicity or
inflammatory effects in
vivo
Risk of exposure
low during pilot
production
No acute environmental
toxicity
CNF90 No cytotoxicity or
genotoxicity in vitro
CNC91 No cytotoxicity
CNC92 Slight cytotoxicity,
dependent on
concentration
CNC93 Clear cytotoxicity
CNC94 Slight dosage-dependent
cytotoxicity and
inflammatory effects in
vitro
CNC95 No acute dermal irritation
or toxicity by oral
administration or
inhalation in vivo. No
genetic mutation or
chromosomal damage in
vitro, in vivo.
Risk low as
evaluated by CB
method
Biodegradability 42% (28
days, OECD method). Low
toxicity effect towards
aquatic organisms. No
indications of interaction
with living organisms. No
passage to the next
generation.
CNC96 Biodegradability 54% (28
days, OECD method). No
toxicity towards oxygen-uptaking
micro-organisms.
BC97 No immunoreactive
effects in vitro, in vivo
BC98 Biocompatibility as
implant: mild and benign
89 Vartiainen, J. et al. (2011) Health and environmental safety aspects of friction grinding and spray
drying of microfibrillated cellulose. Cellulose 18, 775.
90 Pitkänen, M. et al. (2010) Nanofibrillar cellulose – Assessment of cytotoxic and genotoxic
properties in vitro. Tappi International Conference on Nanotechnology for the forest products
industry, 27-29.9, Espoo, Finland.
91 Dong, S. et al. (2012) Cytotoxicity and cellular uptake of cellulose nanocrystals. Nano LIFE 2(3):
1241006.
92 Ni, H. et al. (2012) Cellulose nanowhiskers: preparation, characterization and cytotoxicity evaluation.
Bio-Medical Mater. Eng. 22: 121.
93 De Lima, R. et al. (2012) Evaluation of the genotoxicity of cellulose nanofibers. Int. J. Nanomedicine
7:3555.
94 Clift, M.J.D. et al. (2011) Investigating the interaction of cellulose nanofibers derived from cotton with a
sophisticated 3D human lung cell coculture. Biomacromolecules 12:3666.
95 Kovacs, T. et al. (2010) An ecotoxicological characterization of nanocrystalline cellulose.
Nanotoxicilogy 4, 255; O’Connor, B. (2011) Ensuring safety of manufactured nanocrystalline cellulose.
A risk assessment under Canada’s new substances notification regulation. Tappi International
Conference on Nanotechnology for Renewable Materials, 6-8.6., Arlington, USA; O’Connor, B. (2012)
NCC: Environmental health and safety update. Tappi International Conference on Nanotechnology for
Renewable Materials, 5-7.6, Montreal, Canada.
96 Kümmerer, K. et al. (2011) Biodegradability of organic nanoparticles in the aqueous environment.
Chemosphere 82: 1387.
97 Kim, G.-D. et al. (2013) Evaluation of immunoreactivity of in vitro and in vivo models against bacterial
synthesized cellulose to be used as a prosthetic biomaterial. BioChip J.7(3), 201.
98 Pertile, R.A.N. et al. (2012) Bacterial cellulose: long-term biocompatibility studies. J. Biomater. Sci.
Polym. Ed. 23, 1339.
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inflammatory effects
which resolve over time.
No reactions towards
foreign body. No toxic
effects.
BC99 No cytotoxicity in vitro, in
vivo
BC100 No cytotoxicity in vitro.
Slight reduction in the
cell reproduction rate in
vitro.
8.2 Regulatory information
Cellulose pulps are generally considered as safe materials, and approved for example as
food contact packaging materials. Microcrystalline cellulose (MCC) and cellulose powder are
also approved as additives in food (with E code E460). Cellulose nanomaterials differ from
bulk cellulose materials by their size and other unique nano-specific properties, and
conclusions on the safety of cellulose nanomaterials cannot be made based on their similar
chemistry to bulk cellulose. Nanomaterials can react with the surrounding environment quite
differently compared to the bulk materials, and their safety must be assessed separately.
In EU, the production and import of chemicals is regulated by REACH (Registration,
Evaluation, Authorisation and Restriction of Chemicals) and CLP (Classification, Labelling
and Packaging of substances and mixtures). Cellulose pulp (CAS 65996-61-4) is exempted
from the REACH registration requirement. Currently, there are no specific registration
requirements for nanomaterials, and thus cellulose nanomaterials are also exempted from
REACH registration.
In addition, presently there are no other safety-related regulatory requirements specific to
nanomaterials. Thus, nanomaterials are regulated as their bulk materials and must therefore
fulfil the valid regulations such as the requirements set by REACH, regulations related to
occupational exposure as well as use-specific regulations, the strictness of which depends
on the intended use of the material. For example, the regulations for nanomaterials in food or
cosmetics are more stringent than for those in industrial applications, where their exposure to
humans and the risk of passage into human body is less probable.
The regulatory situation is likely to change in the near future, since the authorities all over the
world are currently evaluating the suitability of the current regulations for nanomaterials.
Some opinions and guidance on the matter have already been published.101
99 Jeong, S.I. et al. (2010) Toxicologic evaluation of bacterial synthesized cellulose in endothelial cells
and animals. Mol. Cell. Toxicol. 6, 373.
100 Moreira, S. et al. (2009) BC nanofibres: In vitro study of genotoxicity and cell proliferation. Toxicol.
Letters 189: 235.
101 OECD (2010) Guidance Manual for the Testing of Manufactured Nanomaterials: OECD’s Sponsorship
Programme. First Revision, 02-Jun-2010, Series on the Safety of Manufactured Nanomaterials 25
(2012). http://search.oecd.org/officialdocuments/displaydocumentpdf/?cote=env/jm/mono(2009)20/rev&doclanguage=en;
European Food Safety Authority (EFSA) (2010). Guidance on the risk assessment of the application of
nanoscience and nanotechnologies in the food and feed chain, 10 May 2011. EFSA Journal 9(5):
(2011) 2140, 36 pp. DOI:10.2903/j.efsa.2011.2140 http://www.efsa.europa.eu/en/efsajournal/pub/2140.htm ;
REACH Implementation Project on Nanomaterials (RIPoN) final reports (RIPON2 and RIPON3).
http://ec.europa.eu/environment/chemicals/nanotech/ ; European Chemical Agency (ECHA). Guidance on
information requirements and chemical safety assessment. http://echa.europa.eu/guidance-documents/
guidance-on-information-requirements-and-chemical-safety-assessment
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8.3 Standardization
Since 2011, a standardization workshop has been organized in the context of Tappi
International Conference on Nanotechnology for Renewable materials, in order to promote
the efforts towards international standardization of cellulose nanomaterials. The workshops
have brought together experts in this field and the work has continued in informal working
groups.
Technical report on characterization of cellulose nanocrystals – particle morphology, purity
and surface properties has been proposed to the Nanotechnology committee (TC229) of
International Standard Organisation (ISO). The organisation arranged a ballot on the report
in spring 2014.
Simultaneously, the North American organisations, Canadian CSA Group and Tappi from the
USA, are developing national standards. The Canadian standard on the characterization of
cellulose nanomaterials was published in June 2014.73 Tappi has developed a standard for
the nomenclature of cellulose nanomaterials. After publication, the standard will be taken to
ISO TC229 to be utilized in the development of the international standard.
In Finland, the progress of standardization related to cellulose nanomaterials is followed by
Kemesta ry (Forest and Chemical Industries) and METSTA (Nanotechnology).
9. Summary
The technical properties of cellulose nanomaterials make them potential for many industrial
applications. Compared to oil-based materials, they can also be considered as
environmentally friendly materials. Based on published research and patents, the most
interesting applications for cellulose nanomaterials seem to be light-weight fibre-based
packaging materials and composites with excellent strength properties and added
functionality, modification of rheological properties of liquids in various industrial sectors,
transparent films as barrier materials or electronic displays, hydrogels for medical
applications and aerogels as membranes or for insulation. Based on their properties and
manufacturing method, cellulose nanomaterials can be roughly divided into three different
category, cellulose nanofibrils, cellulose nanocrystals and bacterial cellulose, each with their
own optimal applications.
Development in manufacturing technology has enabled the production of cellulose
nanomaterials at industrial scale, and many companies have already started the production
or announced its start in the near future. There are still some challenges related to the
characterization of cellulose nanomaterial properties as well as to the assessment of their
safety. However, progress towards standardization of methods has already started.
As a conclusion, the strengths, weaknesses, opportunities and threats of cellulose
nanomaterials are summarized in Table 5.
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Table 5. The Strengths, Weaknesses, Opportunities and Threats (SWOT) matrix for cellulose
nanomaterials.
Strengths Weaknesses
Renewable raw materials
Bio-based material
Safe
Unique properties
Heterogeneity of materials
Drying and re-dispersion
Processing challenges
Opportunities Threats
Numerous potential applications
Replacement of oil-based materials
Novel innovative products
Added functionality
Developments in process technology
New products for forest industry
Resource efficiency
Markets with large volume (forest, chemical,
packaging, construction etc.)
Up-scaling of manufacturing processes
Price too high
Benefit must be multiple compared to
traditional
Feasibility of industrial production and
products
Slow progress of standardization and
regulation