IMPACT OF MICRO/NANOFIBRILLATED CELLULOSE PREPARATION ON THE

REINFORCEMENT PROPERTIES OF PAPER AND COMPOSITES FILMS.

Denilson DA SILVA PEREZa,* Sandra TAPIN-LINGUAa, Anne LAVALETTE a,c,

Thiago BARBOSAa,c,d, Israel GONZALEZb, Gilberto SIQUEIRAb, Julien BRASb,
Alain DUFRESNEb.

a) Institut Technologique FCBA, New Materials Division, Grenoble, France.

b) INP Grenoble PAGORA, Grenoble, France.
c) ESB - Ecole Supérieure du Bois, Nantes, France.
d) UFPR - Universidade Federal do Parana, Curitiba, Brazil.
* E-mail : denilson.dasilvaperez@fcba.fr

Introduction
Micro- and nano-fibrillated cellulose (M/NFC) seem to be one of the ways of better exploiting the
potential of cellulosic fibres than the usual paper-based application (1-6). Depending on the fibrous
raw materials, pre-treatment and fibrillation conditions, different types of micro/nanofibrillated
cellulose can be obtained in terms of microfibrilles individualisation, dimensions, crystallinity, etc.
Moreover, the chemical modification of micro- and nano-fibres surfaces can not only impart different
functionalities but also be used as pre-treatment for their production. In particular TEMPO-mediated
oxidation allow selectively creating carboxyl groups on C6 carbon of cellulosic fibres, which can be
used for further grafting of specific moieties either by amidation or esterification (5-8). The work
described here aims at understanding the impact of M/NFC preparation on the properties of these
materials and consequently on their reinforcement capabilities for paper and composites applications.

Materials and Methods

Bleached kraft pulps from hardwoods or softwoods were used as raw materials for the production of
M/NFC. The pulps were firstly highly refined then enzymatically treated (Celluclast-Novozymes, 5%
pulp consistency, 10 mL enzyme for 100 g–dry pulp, 50°C, 2 hours.). Different M/NFC grades were
produced by homogenization using laboratory-scale A equipment Microfluidizer M110EH at 2 %
concentration equipped with different interaction chambers (Z-shaped, internal diameter of 100, 200,
and 400 µm) allowoing microfibrils individualisation by high pressure shearing (up to 2200 bars) of
the cellulosic suspensions. Three contrasted types of M/NFC were produced and used as reinforcement
agents for paper and latex composites films. Moreover, these M/NFC were chemically modified in
surface by TEMPO-oxidation and amidation of the carboxyl groups to graft polyethyleneglycol (PEG)
or aromatic groups based on the protocol of the work described earlier for fibres (9).

Results and discussions

1) M/NFC preparation
Different optical and electronic microscopy devices were used to follow the conversion of pulp fibres
into nanofibrillated cellulose (Figure 1).
A B C

Figure 1 – A :Light micrographyexamination of MFC obtained using 400 µm chamber; B : SEM examination of
M/NFC obtained using 200 µm chamber; C : TEM examination of NFC obtained using 100 µm chamber.
The cellulosic material obtained after 3 passes in 400 µm chamber is essentially composed of short cut
fibres and some microfibrils (MFC). After 5 passes in a 200 µm chamber NFC is obtained, but
important non-destructured material is still present. Finally, 5 passes in a 100 µm chamber allow
obtaining a homogenous material constituted essentially of cellulose nanofibres.
2) Paper reinforcement
The different M/NFC were applied as reinforcement agent at 1, 5 and 20 % in weight on refined
hardwoods and softwoods pulps aiming at improving the physical properties (bulk and tensile, tear,
burst indexes). Figure 2 clearly demonstrates that the smaller and more homogeneous the M/NFC, the
higher the reinforcement effects. Thus, the addition of 20 % of M/NFC produced after 5 passes on 100
µm chamber allows improving simultaneously the tensile and tear indexes higher than 90 %. For the
M/NFC produced using 400 µm and 200 µm chambers which are less homogenous, the improvements
are respectively 38 % and 56 % for the tensile index and 37 % and 80 % for the tear index. TEMPO-
oxidation of M/NFC allows further gains in physical properties (+ 10-25 %).
Gain in tensile index (N.m/g) compared without MFC

Gain in tear index (mN.m2/g)compared without MFC

5% MFC (HW_R_26) 20% MFC (HW_R_26) 5% MFC (HW_R_26) 20% MFC (HW_R_26)
100 5% MFC (SW_R_25) 1% MFC(HW_R_26) 5% MFC (SW_R_25) 1% MFC(HW_R_26)
1% MFC(SW_R_25) 100 1% MFC(SW_R_25)
90
90
80
80
70
70
60
60

(%)
(%)

50
50
40 40
30 30
20 20
10 10
0 0
SW_100x5 HW_400x3 HW_200x3 HW_100x5 SW_100x5 HW_400x3 HW_200x3 HW_100x5

Figure 2: Effect of the addition of hardwood and softwood MFC on the pulp mechanical properties (HW-R-26:
hardwood bleach Kraft pulp refined at 26 °SR; SW-R-25: softwood bleach Kraft pulp refined at 25 °SR /
SW_100-5: MFC from softwood pulps; HW_100-5: MFC from hardwood pulps)
3) Composites films
An important reinforcement was obtained when using M/NFC (Table 1). At 3 % of M/NFC, the
Young’s modulus compared to latex is multiplied by 6 and the tensile strength is by 2. At 12 % of
non-modified M/NFC, the Young’s modulus can reach 60-fold the latex one. If TEMPO-oxidized
M/NFC are used, values up to 100-fold the modulus of latex were obtained, while the tensile strength
is multiplied by 12. Moreover, these composites films preserve certain elasticity, measured by the
strain at break values, contrarily to the non-modified M/NFC. Finally, the grafting of PEG or aromatic
chains by amidation generated films with high tensile strength and strain at break, but considerably
lower Young’s modulus.

Table 1 – Mechanical properties of composites films reinforced with different MFC/NFC.

Type and characteristics of the reinforcement E (MPa) ƐR (%) δR (MPa)
Latex alone 0.77 409 0.65
(3%) 4.47±2.05 230±88.05 1.18±0.2
Natural
(12%) 47.64±5.25 76±15.55 2.35±0.04
TEMPO (3%) 5.32±0.49 307±50.91 1.75±0.25
Oxidised (12%) 75.75±19.61 191±62.93 7.82±0.53
Microfibrils
(3%) 8.51±2.85 377±96.43 1.77±0.04
Amided aniline
(12%) 17.82±3.31 51±9.19 7.07±0.91
Amided (3%) 6.22±1.34 349±0 2.01±0.33
PEG (12%) 12.11±0.45 16.5±0.7 7.45±0.55

Acknowledgments
The authors thank ADEME (contract AGRICE 06.01C.0039)/CTPi members for the financial support.

References
1) Herrick FW et al. (1983). J Appl Polym Sci: Appl Polym Symp 37:797-813.
2) Turbak AF et al. (1983). J Appl Polym Sci: Appl Polym Symp 37:815 - 827.
3) Henriksson M. et al. (2007). Europ Polym J 43:3434-3441.
4) Paakko M. et al. (2007). Biomacromolecules 8:1934-1941.
5) Saito T. et al. (2006). Biomacromolecules 7:1687-1691.
6) Saito T. et al (2007). Biomacromolecules 8:2485-2491.
7) da Silva Perez, D. et al. (2003) Biomacromolecules, 4, 1417-1425 (2003).
9) da Silva Perez, D. Guillemain, A., Petit-Conil, M., Strategies for surface fibre functionalisation using
TEMPO-mediated oxydation. 11th European Workshop on Lignocellulosics and Pulps, Hamburg, Germany
(2010) Proceedings, pp 377-380.
Impact of micro/nanofibrillated cellulose
preparation on the reinforcement
properties of paper and composites films

Sandra Tapin-Lingua, Denilson Da Silva

Perez
Introduction

Micro/nanofibrillated cellulose

• Chemical pre-treatments
9 Controlled acid hydrolysis
9 Alkaline swelling and/or
hydrolysis
9 Surface cellulose chemical
modifications

• Enzymatic pre-treatments
9 Cellulases
9 Hemicellulases

• Mechanical treatments
9 Fibers refining/beating/grinding
9“Homogenizers” Pääkkö et al., Biomacromolecules, 2007, 8, 1934-1941
Tappi Nano2010 - 28/09/2010 - STL - 2
OBJECTIVES

• Produce micro/nanofibrillated cellulose from bleached

chemical pulps

• Develop analytical techniques for the characterization

of M/NFC

• Evaluate the potential as reinforcement agents for

papermaking and composites films applications

• Contribute to the emergence of new products and

markets for the pulp and paper industry

Tappi Nano2010 - 28/09/2010 - STL - 3

Materiels and methods to M/NFC production

Bleached
9 Pulp pre-treatment Kraft Pulp
Mechanical refining
ƒ Strong refining
– Enhance fibre accessibility and treatment Refined BKP
efficiency
ƒ Enzymatic pre-treatment with cellulases Cellulase treatment
50 °C, 2h
– Weaken the fibres and enhance
microfibrillation Refined and
enzymaticaly
– Facilitate fibres transit into the vessel of
treated BKP
the Microfluidizer

Tappi Nano2010 - 28/09/2010 - STL - 4

 Materiels and methods to M/NFC production
Bleached
Kraft Pulp
9 Mechanical treatment processed by high- Mechanical refining
pressure homogenizer: Microfluidizer M- Refined BKP

110EH Cellulase treatment

50 °C, 2h
ƒ At constant liquid flow Refined and
ƒ Pressure applied depends on the internal enzymaticaly
diameter of the fluidization chambers treated BKP
– 100 bars for the 400 µm chamber, Homogenizing:
3 times through 400 µm
– 1500 bars for the 200 µm chamber
– 2200 bars for the 100 µm chamber + 5 *: 200 µm + 5 *: 200 µm
+ 5 *: 100 µm
ƒ Concentrations of the suspensions: 2 %
MFC NFC
9 NFC Oxidation with TEMPO
ƒ COOH rate: 1.0 mmol/g TEMPO
Oxidation

NFC ox
Tappi Nano2010 - 28/09/2010 - STL - 5
M/NFC Characterization

• Evaluation of the micro-/ nano- fibres size

9 MorFi analysis
ƒ Detection limit: ≈ 7 µm
9 Optical microscopy analysis
9 TEM analysis
9 SEM examinations
• Determination the suspension viscosity
• Evaluation of the impact of M/NFC on pulp properties
depending:
9 Pulp origin used to produce M/NFC
9 M/NFC suspension quality (size and heterogeneity)

Tappi Nano2010 - 28/09/2010 - STL - 6

M/NFC Characterization
• Light microscopy observations
9 Effect of the different passages through the homogenizer

400-1 400-3

200-1
200-5 MFC

100-1
100-5 NFC

9 Reduction of cellulosic particles size

9 Increase in homogeneity
Tappi Nano2010 - 28/09/2010 - STL - 7
 M/NFC Characterization

• SEM examination
9 Samples directly observed

Run 200-5 MFC 100-5 NFC

9 Reduction of cellulosic particles size

9 Increase in homogeneity
Tappi Nano2010 - 28/09/2010 - STL - 8
 N/MFC Characterization

• TEM examination
9 Samples directly observed without/with Uranyl acetate
staining

Run 200-5 100-5 100-9

Average MFC 20nm 17nm

Diameter
MFC NFC

Tappi Nano2010 - 28/09/2010 - STL - 9

Effect of M/NFC on pulp properties

• Introduction of M/NFC in pulp to evaluate their impact

on paper properties:
Pulp
M/NFC 26 °SR BKP
SW or SW or HW
HW

9 2 pulp origins:
ƒ Softwood (SW) and hardwood (HW)
9 3 different M/NFC qualities
9 3 concentrations introduced
ƒ 1%, 5% or 20 % weight

•M/NFC retention controlled by gravimetric measurement

Tappi Nano2010 - 28/09/2010 - STL - 10
 Effect of M/NFC on pulp properties

• Impact of M/NFC addition in pulp

5% MFC (HW_R_26) 20% MFC (HW_R_26)

Gain in tensile index (N.m/g) compared without MFC

100 5% MFC (SW_R_25) 1% MFC(HW_R_26) 9 On tensile index

1% MFC(SW_R_25)
90

80
ƒ in M/NFC
concentration: tensile
70

60
index enhancement
ƒ Pulp properties :
(%)

50

40
NFC > MFC
30

20
ƒ Not effect of the pulp
10
origin of the NFC
0
SW_100x5 HW_400x3 HW_200x3 HW_100x5

SW HW HW
NFC MFC NFC

Tappi Nano2010 - 28/09/2010 - STL - 11

 Effect of M/NFC on pulp properties

• Impact of M/NFC addition in pulp

9 On tensile index 9 On tear index

5% MFC (HW_R_26) 20% MFC (HW_R_26)

Gain in tensile index (N.m/g) compared without MFC

5% MFC (HW_R_26) 20% MFC (HW_R_26)

100 5% MFC (SW_R_25) 1% MFC(HW_R_26) 5% MFC (SW_R_25) 1% MFC(HW_R_26)

Gain in tear index (mN.m2/g)compared without MFC (%)

1% MFC(SW_R_25) 100
90 1% MFC(SW_R_25)
90
80
80
70
70
60
60
(%)

50
50
40
40
30
30
20 20
10 10
0 0
SW_100x5 HW_400x3 HW_200x3 HW_100x5 SW_100x5 HW_400x3 HW_200x3 HW_100x5

+ 20 % MFC Æ mechanical properties x2

Increase of tensile and tear index but bulk remained
Tappi stable- STL - 12
Nano2010 - 28/09/2010
 Effect of M/NFC on composite films

• Introduction of M/NFC in polymer matix to evaluate their impact

on composite properties:

NFC
Polymer
HW

or Fibres

Nanocomposite film

water evaporation (T>Tg) → particle coalescence

9 Matrix = aqueous dispersed polymer (latex)

9 Reinforcements
ƒ Cellulosic Fibres unmodified and modified (TEMPO oxidized)
ƒ NFC unmodified and modified
ƒ 3 and 12 % weight
Tappi Nano2010 - 28/09/2010 - STL - 13
Effect of fibre introduction on composite
films
• Unmodified fibres • TEMPO-oxidized fibres
9Phases 9Homogenous
separation: no film
reinforcement

HWF 12%
HWF-0x 12%
HWF 3%

HWF-Ox 3%

Latex (NR) Latex (NR)

Reference E (MPa) ƐR (%) 9With fibres addition:

Natural Latex 0.77 409
HWF 3% 2.2 ± 0.6 213 ± 9.2 9Young modulus:
HWF 12% 9.4 ± 0.6 66 ± 3.5
HWF-Ox 3% 2.9 ± 0.3 302 ± 82.0 9Elongation:
HWF-Ox 12% 34.5 ± 9.2 275 ± 44.5 Tappi Nano2010 - 28/09/2010 - STL - 14
Effect of M/NFC on composite films

• Unmodified NFC • TEMPO-oxidized NFC

9Homogenous films
NFC-ox 12%

NFC 12%

NFC 3% NFC-ox 3%
Latex (NR) Latex (NR)

Reference E Mpa ƐR (%) δR (MPa)

Natural Rubber 0.7 409 0.65
NFC 3% 4.5 ± 2.0 230 ± 88.0 1.2 ± 0.2
NFC 12% 47.6 ± 5.3 76 ± 15.5 2.4 ± 0.04
NFC-Ox 3% 5.3 ± 0.5 307 ± 50.9 1.7 ± 0.2
NFC-Ox 12% 75.7 ± 19.6 191 ± 62.9 7.8 ± 0.5

NFC-OX 12%: Strain at break Tensile strength

Tappi Nano2010 - 28/09/2010 - STL - 15
 CONCLUSION

• MFC Production
9 Development of a M/NFC production protocol
9 Characterisation of M/NFC

• M/NFC induced properties on pulp strength

9 Mechanical properties: x 2 with NFC addition
9 Impact of NFC characteristics on pulp properties Æ the smaller and
more homogenous give the best results

• M/NFC induced properties on composites films

9 Mechanical properties
ƒ Young modulus:
» x 62 with 12 % NFC »x 98 with 12 % Oxidized NFC
ƒ Tensile strength:
» x 12 with 12 % oxidized NFC
9 Oxidation of fibres/MFC improves the strength properties of
composites
Tappi Nano2010 - 28/09/2010 - STL - 16
ACKNOWLEDGEMENTS

9 Co-autors: Anne Lavalette, Thiago Brabosa, Israel

Gonzalez, Gilberto Siqueira, Julien Bras and Alain
Dufresne

9 Partial financial support from French energy agency-

ADEME

9 Industrial partners

9 Laboratory and R&D Institutes

ƒ PAGORA
ƒ CERMAV-CNRS

Tappi Nano2010 - 28/09/2010 - STL - 17