BARRIER PROPERTIES OF SPECIALTY PAPERS COATED WITH MICROFIBRILLATED CELLULOSE:

INFLUENCE OF BASE PAPER AND COAT WEIGHT

Raphael Bardet1, Nathalie Lavoine1 , Isabelle Desloges1, Naceur Belgacem1, Julien Bras1*
1GRENOBLE INSTITUTE OF TECHNOLOGY – PAGORA - 461 rue de la Papeterie, 38402 Saint Martin d'Hères, FRANCE

KEY WORDS: MFC, SPECIALTY PAPERS, BARRIER PROPERTIES

Introduction & Background Strategies & Objectives

New packaging materials from sustainable grease The MFC presents a high surface area and has the ability to form a
CO2
resources, biodegradable and designed for NEW
nanoporous network. It was firstly used with nanocomposites1,2 and as
food contact are expected. dispersion stabilizer3.
Since the 2000s, one innovative solution has More recently, MFC has shown its capacity to improve the barrier
OLD
been more and more studied and consists in O2 H2O
properties of composites or films4,5. Its combination with cellulosic materials,
using microfibrillated cellulose (MFC) as however, remains rare6,7. The present work investigates thus this still unknown
surface layer onto a substrate. Renewable – Biobased Light weight packaging Barrier properties
domain and proposes a study on the barrier properties of various MFC
coated specialty papers.
Fig. 1 Main objectives for new packaging materials Fig. 2: Strategies and objectives of the study

Materials & Methods Results & Discussions

1. Light weight specialty papers
Organic Elements (Dark Areas): fibers, MFC Part 1: Structure & Morphology of MFC layers
The substrates were selected among various kinds of industrial specialty papers in order to study the
influence of the substrate (table 1). FE-SEM AFM

Thickness Papermaking treatment

Ref Application
Basis weight
(µm)
Fillers Nanoporous network Three observation techniques ranging from micrometric to nanometric
(g/m²) content
Refining level Surface treat. scale were used to characterize the MFC coated layer.
A Specialty 11 16 ●●● Surface sized ●○○ It confirms that a MFC suspension deposited onto a porous substrate leads
B Cheese wrap 22 25 ○○○ Base paper ○○○ x1000 to :
C Thin printing 28 35 ●●○ Base paper ●●●  the formation of homogeneous layer for a coat weight higher than 1
D Thin printing 28 28 ●●○ Calandered ●●● g/m² (fig.6)
E Specialty 42 57 ○○○ Calandered ○○○  a nanoporous network of entangled MFCs with an average pores
Table 1 : Main features of selected base substrates Minerals Elements (Bright Areas): dimension at the surface of 50 nm +/-14 nm (fig.7).
2. Microfibrillated Cellulose (MFC) fillers, pigments ( CaCO3, TiO2,…)
Fig. 6: SEM pictures of substrate surface (ref. C) coated with increasing coating weight of MFC Fig. 7: FE-SEM (left) and AFM (right) pictures of substrate (ref. C) coated with 1.6 g/m² of MFC
The MFC suspension has been produced following process8 detailed in table 2 and characterized in table 3.
MFC production MFC characterization  BSE mode is used to highlight the homogeneity of the MFC surface layers.  FE-SEM & AFM are used to highlight the surface nanoporous network.
Diameter : 20 +/- 5 nm
Softwood dissolving pulp Dimension
Raw material Length > 1 µm
(Domsjö Cellulose plus® )
Viscosity 2400 mPa.s (Brookfield Viscosity, 60 rpm, 23°C) Part 2: Barrier properties
Cellulase (Novozym 476® ), Dry matter 2.7 %
Enzymatic Pretreatment
Cons. 3.5%, pH = 5, 1h
Table 3: Identity card of the MFC suspension Air permeability Carbon Dioxide diffusivity Water absorption
Masuko Grinder®
Mechanical treatment
20 passes at 0-dynamic point 600 600 30% 0.6 g/m² of MFC
0.4

Water absorption
Ref. A ref A - 11 g/m² 1.6 g/m² of MFC
Table 2: MFC Production parameters
Ref. B
20%
Air Permeability (cm3/m².Pa.s)

MFC coated ref B - 22 g/m²

Air permeability (cm3/m².Pa.s)

500

gain (%)
500
Base paper 10%
Water surface sized ref C - 28 g/m²

CO2 Diffusivity (cm/s)

0.3
400 400 ref E - 42 g/m² 0%
-10%
Fig. 3: The 2.7 % gel-like suspension of MFC Fig. 4: AFM image of individualized
MFCs 300 300 0.2 -20%
Ref A - 11 g/m² Ref B - 22 g/m² Ref C - 28 g/m² Ref E - 42 g/m²
3. Surface treatment operation & investigated properties 200 200 Fig. 11: Relative water absorption gain of MFC coated samples compared to water surface sized samples
Minimal ratio of MFC
0.1
• Before the coating and characterization  The relative gain of water absorption represents between 5 to 20% in
100 100
steps, the paper samples were kept during 24h at comparison to a water surface treatment for ref E. and ref B. respectively.
23°C, 50%HR. 0 0 0.0 Grease Resistance
• Due to the high water content of the MFC x0 x1 x2 x3 x4 x5 x6 x7 x8 0 3 6 9 12 15 0 0.5 1 1.5 2
suspension, MFC coated papers were systematically Number of passes MFC coat weight Base paper + 1.6 g/m² of MFC
MFC layer/paper ratio (% w/w) MFC coat weights (g/m²) Base Water
Ref
compared to water surface sized papers with a view Fig. 8: Air permeability as a function of the number of passes for Fig. 9: Air permeability (cm3/m².Pa.s) as a function of the Fig. 10: CO2 Diffusivity as a function of the MFC coat weight (ref .B )
paper surface sized 0.6 g/m² 1.6 g/m²
to taking into account the impact of the hornification8 MFC coated and water surface sized papers (Ref . A) MFC layer /paper ratio (% w/w) Covered Area (%)
(water uptaking and drying). A -11 g/m² 26 ± 2 24 ±3 7±1 4 ±1

• The MFC suspension is previously homogenized  Compared to the base paper, the air permeability is about 3 times lower with only  The MFC layers have a strong impact B- 22 g/m² 89 ± 2 88 ± 1 60 ± 1 41 ± 3
Covered area: 89% Covered area: 41%
during 2 min, at 10,000 rpm (IKA, Ultra-Turrax T18). 0.2 g/m² of MFC (fig.8). on the CO2 diffusivity with a drop of C- 28 g/m² 43 ± 2 25 ± 1 22 ± 4 18 ± 2
 No differences between a water surface treatment and a MFC coating treatment 300% compared to the base and water E- 42 g/m² 86 ± 2 77 ± 1 55 ± 1 34 ± 1
Fig. 11: Pictures showing different
• A specific test has been proposed to check the levels of oil migration without (left) or
are noticed for 8 passes (fig.8). surface sized papers. Table 4: Results obtained for the grease resistance evaluation with MFC coating (ref. A)
grease barrier. A sample is coated with colored
 An improvement of the standard variations is also revealed (fig.8).
commercial oil during 3 min onto an absorbent  Although neat MFC has no chemical greaseproof property, nanoporous network of
 Starting from a MFC ratio of 6-8 %, the air permeability is reduced to 6-12 times
paper. The grease resistance is evaluated by the MFC surface layer leads to a substantial reduction of oil migration (fig. 11).
depending on the basis weight (fig. 9).
measuring (ImageJ®) the surface of the grease  Whatever the base paper, this represents a significant improvement of grease
reported onto the absorbent paper. resistance ranging from 54% to 85% (table 4).
Fig. 5: Working plan

References Conclusions & Perspectives

1 Siró, I. and D. Plackett, Cellulose, 2010.
2 Siqueira, G., J. Bras, and A. Dufresne, Cellulosic Bionanocomposites, 2010.
3 Andresen, M., et al., Cellulose, 2006.
4 Syverud, K. and P. Stenius, Cellulose, 2009.
5 Aulin, C., M. Gällstedt, and T. Lindström, Cellulose, 2010.
 A thin MFC layers has an impact on the gas and liquid barrier properties.  Additional barriers & mechanical tests have to be carried out to emphasize further
6 Hamada, H. and D.W. Bousfield, Tappi Journal., 2010.
7 Lavoine, N. et al., Carbohydrate Polymers, 2012. (accepted)
8 Pääkkö, M., et al., Biomacromolecules, 2007.
 In order to have a homogeneous surface layer, a minimal ratio of 6-8% of MFC is required whatever the basis weight. the influence of a thin MFC layer.
9 Fernandes Diniz, et al.,. Wood Science and Technology, 2004.

 Barrier properties are certainly due to the homogeneous layer and the nanoporous network.  This new kind of lightweight coated papers may represent an interest for :
Acknowledgements
The authors gratefully acknowledge the industrial partnership and the French National Research Agency
 Some limits are however highlighted: final barrier properties are closely linked to the interactions between water and the base paper.  High added value packaging such as active packaging
(ANRT) for the financial and material support for the PhD thesis. We would like to thank Berthine Khelifi
(PAGORA) for her expertise in E-SEM & FE-SEM imaging.
 Filtration application markets

*Contact: julien.bras@pagora.grenoble-inp.fr