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RESEARCH REPORT VTT-R-05013-14 
Guide to cellulose nanomaterials 
– English summary 
Authors: Heli Kangas 
Confidentiality: Public
RESEARCH REPORT VTT-R-05013-14 
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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
RESEARCH REPORT VTT-R-05013-14 
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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.
RESEARCH REPORT VTT-R-05013-14 
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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
RESEARCH REPORT VTT-R-05013-14 
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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.
RESEARCH REPORT VTT-R-05013-14 
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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.
RESEARCH REPORT VTT-R-05013-14 
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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
RESEARCH REPORT VTT-R-05013-14 
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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.
RESEARCH REPORT VTT-R-05013-14 
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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.
RESEARCH REPORT VTT-R-05013-14 
31 (35) 
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.
RESEARCH REPORT VTT-R-05013-14 
32 (35) 
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.
RESEARCH REPORT VTT-R-05013-14 
33 (35) 
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
RESEARCH REPORT VTT-R-05013-14 
34 (35) 
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.
RESEARCH REPORT VTT-R-05013-14 
35 (35) 
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

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Guide to cellulose nanomaterials

  • 1. RESEARCH REPORT VTT-R-05013-14 Guide to cellulose nanomaterials – English summary Authors: Heli Kangas Confidentiality: Public
  • 2.
  • 3. RESEARCH REPORT VTT-R-05013-14 2 (35) 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
  • 4. RESEARCH REPORT VTT-R-05013-14 3 (35) 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
  • 5. RESEARCH REPORT VTT-R-05013-14 4 (35) 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
  • 6. RESEARCH REPORT VTT-R-05013-14 5 (35) 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).
  • 7. RESEARCH REPORT VTT-R-05013-14 6 (35) 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.
  • 8. RESEARCH REPORT VTT-R-05013-14 7 (35) 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.
  • 9. RESEARCH REPORT VTT-R-05013-14 8 (35) 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.
  • 10. RESEARCH REPORT VTT-R-05013-14 9 (35) 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.
  • 11. RESEARCH REPORT VTT-R-05013-14 10 (35) 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.
  • 12. RESEARCH REPORT VTT-R-05013-14 11 (35) 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.
  • 13. RESEARCH REPORT VTT-R-05013-14 12 (35) 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
  • 14. RESEARCH REPORT VTT-R-05013-14 13 (35) 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.
  • 15. RESEARCH REPORT VTT-R-05013-14 14 (35) 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
  • 16. RESEARCH REPORT VTT-R-05013-14 15 (35) 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.
  • 17. RESEARCH REPORT VTT-R-05013-14 16 (35) 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
  • 18. RESEARCH REPORT VTT-R-05013-14 17 (35) 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.
  • 19. RESEARCH REPORT VTT-R-05013-14 18 (35) 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.
  • 20. RESEARCH REPORT VTT-R-05013-14 19 (35) 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.
  • 21. RESEARCH REPORT VTT-R-05013-14 20 (35) 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.
  • 22. RESEARCH REPORT VTT-R-05013-14 21 (35) 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/
  • 23. RESEARCH REPORT VTT-R-05013-14 22 (35) 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.
  • 24. RESEARCH REPORT VTT-R-05013-14 23 (35) 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).
  • 25. RESEARCH REPORT VTT-R-05013-14 24 (35) 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.
  • 26. RESEARCH REPORT VTT-R-05013-14 25 (35) 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.
  • 27. RESEARCH REPORT VTT-R-05013-14 26 (35) 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.
  • 28. RESEARCH REPORT VTT-R-05013-14 27 (35) 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.
  • 29. RESEARCH REPORT VTT-R-05013-14 28 (35) 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
  • 30. RESEARCH REPORT VTT-R-05013-14 29 (35) 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.
  • 31. RESEARCH REPORT VTT-R-05013-14 30 (35) 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.
  • 32. RESEARCH REPORT VTT-R-05013-14 31 (35) 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.
  • 33. RESEARCH REPORT VTT-R-05013-14 32 (35) 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.
  • 34. RESEARCH REPORT VTT-R-05013-14 33 (35) 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
  • 35. RESEARCH REPORT VTT-R-05013-14 34 (35) 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.
  • 36. RESEARCH REPORT VTT-R-05013-14 35 (35) 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