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NANOCELULOSA: PRODUCCIÓN, CARACTERIZACIÓN Y SU POTENCIAL EN LA FABRICACIÓN DE PAPEL Y NANOPAPEL
Formación continuada
FROM PAPER TO NANOPAPER: EVOLUTION OF MECHANICAL AND
PHYSICAL PROPERTIES
Madrid, 15th – 16th October
ONGOING MODIFICATION OF CELLULOSE NANOFIBERS AND THEIR POTENTIAL APPLICATIONS
Fabiola Vilaseca
Cellulose (2014) 21:2599–2609
I. Gonzalez • M. Alcala • G. Chinga-Carrasco • F. Vilaseca • S. Boufi • P. Mutje
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Contenido de la sesión Introduction to Nanopapaer
What is Nanopaper? Current studies on nanopaper
Fabrication of Nanopapers Dispersion of nanofibres Sheet formation Drying
Characterization of Nanopapers Physical properties
• Thickness • Density and Bulk • Opacity • Porosity
Mechanical properties • Tensile strength • Tensile index and breaking length • Young’s modulus • Strain • Effect of mechanical treatment intensity on nanopaper’s properties
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What is Nanopaper ?
The term refers to papers with a 51 wt% content or more of cellulose nanofibres.
Nanopapers can be fabricated and characterized at laboratory level using techniques similar to those used for normal papers.
Sehaqui et al. Biomacromolecules, 2010
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Remarkable works on nanopapers • Henriksson et al. 2008. Nanopapers fabricated from CNF with different polymerization degree (DP).
Henriksson et al. Biomacromolecules, 2008 a- Microphotography (FE-SEM) of nanopaper. b- Microphotography (FE-SEM) of failure point in a mechanically tested nanopaper sample.
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Remarkable works on nanopapers Olsson et al. 2010. Nanopapers with magnetic properties.
Olsson et al. Nature nanotechnology, 2010
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Remarkable works on nanopapers Sehaqui et al. 2010. Fast method for preparation of nanopapers
Sehaqui et al. Biomacromolecules, 2010
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Remarkable works on nanopapers Sehaqui et al. 2011. Highly porous nanopapers.
Sehaqui et al. Biomacromolecules, 2011 a- NFC gel b- transparent nanopaper sample. c- Highly porous nanopaper
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Remarkable works on nanopapers Youssef et al. 2013. Properties comparison among nanopapers fabricated from rapeseed fibres and bacterial cellulose.
Youssef et al. Industrial Crops and Products, 2013
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Nanopaper fabrication
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Nanopaper fabrication 1. Dispersion of CNF in water with a pulp disintegrator at 180000 revolutions. This is an important stage which defines many of the nanopaper’s final properties.
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Nanopaper fabrication
2. Nanopaper is formed in a Rapid-Köthen like equipment assisted with a vacuum pump that generates -0,35 bars of negative pressure.
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Nanopaper fabrication
3. A 0.65 μm porous diameter nitrocellulose membrane is laid at the bottom of the stock container in order to retain the nanofibres during the filtering process.
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Fabricación del nanopapel
4. Filtering takes between 3 and 4 hours. At the end of this time a transparent, wet nanofibre cake is obtained. This cake is carefully peeled off the nitrocellulose membrane and put between two absorbing papers.
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Nanopaper fabrication
5. Next, nanopaper is vacuum dried at 90ºC during 15-20 minutes depending on the moisture content of the wet cake.
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Nanopaper fabrication
6. Once dried, the nanopaper is weighted and conditioned in a climate chamber.
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Nanopaper characterization Physical properties: evolution of physical properties from ordinary paper to 100% nanopaper and their different grades.
Sample Thickness
(μm)
Density
(gr/cm3)
Bulk
(cm3/gr)
Opacity
(%)
Porosity
Gurley
(s)
Porosity
(%)
100%Fibres 101 0,640 1,562 84,50 2,00 57,30
75%fibres/25%NFC 88 0,730 1,569 51,02 1912 51,30
50%fibres/50%NFC 75 0,810 1,233 45,66 4284 46.00
25%fibres/75%NFC 62 0,950 1,051 40,20 <5000 36,66
100%NFC 52 1,200 0,832 33,20 <5000 20,00
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Nanopaper characterization Thickness: Its accurate determination is decisive in order to calculate other nanopaper’s properties such as density and tensile strength.
The technique used to determine thickness can vary significantly the result.
Chinga-Carrasco & Syverud, J Nanopart Res, 2009 Chinga-Carrasco et al. Microsc. Microanal., 2011
Thickness: It is reduced when the NFC content increases.
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Nanopaper characterization Opacity: It is the amount of light scattered by paper. It is measured by equipments that detect the scattered light, such as the ERIC.
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Nanopaper characterization Porosity: The increase in the NFC amount makes paper more robust and compact and thus less porous.
SEM microphotography of: a- ordinary paper with 100% bleached ecualyptus polp. b- 50 % fibres 50% NFC c- nanopaper 100 % NFC
a b c
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Nanopaper characterization SEM microphotography: The images show the structure of nanopapers with 100% NFC content.
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Nanopaper characterization SEM microphotography: The images show the structure of nanopapers with 50% NFC content.
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Nanopaper characterization SEM microphotography: The images show the structure of nanopapers with 0% NFC content.
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Nanopaper characterization Mechanical properties: evolution of strength from paper to nanopaper.
σ (Mpa)= tensile strength E (GPa)= Young’s modulus
ε (%) = strain
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Nanopaper characterization Mechanical properties: evolution of strength from paper to nanopaper.
Samples σ
(MPa)
T.I.
(N·m/gr)
E
(GPa)
ε
(%)
Breaking L.
(m)
100%Fibres 41,20 25,5 2,85 0,65 2601
75%fibres/25%NFC 80,50 55,8 6,90 3,23 5691
50%fibres/50%NFC 91,80 64,5 8,2 3,57 6579
25%fibres/75%NFC 113,50 81,15 10,90 1,90 8277
100%NFC 132,60 95,85 11,90 2,55 9776
σ (Mpa)= tensile strength E (GPa)= Young’s modulus
ε (%) = strain T.I. (N·m/gr)= Tensile Index
Breaking L.= Breaking length
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Nanopaper characterization Tensile strength: The results obtained in the present work correspond to those reported by other authors for nanopapers with similar degree of polymerization.
Muestra σ
(MPa) 100%Fibras 41,20
75%fibras/25%NFC 80,50
50%fibras/50%NFC 91,80
25%fibras/75%NFC 113,50
100%NFC 132,60
Henriksson et al. Biomacromolecules, 2008
Sehaqui et al. Biomacromolecules, 2010
DP : 423 -COOH content: 0,4mmol/g
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Nanopaper characterization Young’s modulus: comparison of Young’s modulus results obtained in the present work and others reported in the literature.
Sample E
(GPa)
100%Fibres 2,85
75%fibres/25%NFC 6,90
50%fibres/50%NFC 8,20
25%fibres/75%NFC 10,90
100%NFC 11,90
Henriksson et al. Biomacromolecules, 2008
Sehaqui et al. Biomacromolecules, 2010
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Nanopaper characterization Strain to failure: Defines the percentage of elongation before mechanical failure.
Sample ε
(%)
100%Fibres 0,65
75%fibres/25%NFC 3,23
50%fibres/50%NFC 3,57
25%fibres/75%NFC 1,90
100%NFC 2,55
Henriksson et al. Biomacromolecules, 2008
Sehaqui et al. Biomacromolecules, 2010
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Nanopaper characterization Mechanical properties: Effect of the number of passes of NFC through a high pressure homogenizer on the mechanical properties of nanopaper.
Sample
(nº of passes and pressure in bars)
σ
(MPa)
T.I.
(N·m/gr)
E
(GPa)
ε
(%)
Breaking length
(m) 5 (300) 74,65 49,62 7,45 2,02 5061
10 (5-300+5-600) 100,36 69,40 10,13 2,00 7078
15 (5-300+10-600) 125,00 88,35 11,00 2,32 9011
20 (5-300+15-600) 132,60 95,85 11,90 2,55 9776
Tensile strength: the number of passes through the homogenizer influences the degree of delamination in NFC which determines also the strength of nanopaper.
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Nanopaper characterization Tensile strength: the number of passes through the homogenizer influences the degree of delamination in NFC which determines also the strength of nanopaper.
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Nanopaper characterization Young’s modulus: more passes of NFC through the homogenizer also increases nanopaper’s stiffness.
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Key aspects to remember A pulp slurry with CNF content higher than 51% was considered as nanopaper, and it can be obtained by similar experimental procedures than standard paper. From paper to nanopaper you will get: higher density but lower thickness, bulk, porosity, opacity and porosity. Alo tensile index, strength and stiffness will increase, although deformation / strain increases up to 50% of CNF, and then start decreasing. The number of passes through the homogenizer affects the microfibrillation process and so the mechanical properties of the ensued nanopaper.
From different article (Cellulose (2013) 20:2909-2921), the intrinsic properties of CNF were calculated to be:
7 GPa strength , 160 GPa stiff
Thank you very much for your attention!!