matériaux biosourcés à base de pelures de végétaux · matériaux biosourcés à base de...
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Matériaux biosourcés à base de pelures de végétaux
Pr Mathieu Robert, Ph.D.
Titulaire de la Chaire de recherche du Canada sur les éco-composites polymères
Directeur scientifique Carrefour d’innovations en technologies écologiques (CITÉ)
Description • 17 000 pi.ca situés à Granby, Canada
• 2 Professeurs, 1 Chaire de recherche active
• Plus de 5 M$ en subvention de recherche
• ± 25 PHQ
• Collaborations avec plusieurs industriels
Objectifs Valorisation de la biomasse canadienne
Extraction de matériaux à valeur ajoutée (Fibres naturelles, NCC, huile, latex…) Transformation (textiles, m)
Elaboration de composites bio-sourcés Modifications de surface Composites polymères et cimentaires
Axes de recherche
Biomasse ou matière à valoriser
Produits finaux et mise en production
Inte
ract
ion
avec
les e
ntre
prise
s co
llabo
ratr
ices
Context Canada’s population is projected to increase by 50% by 2036, and will experience a rise of 90% by the end of 2061.
Statistic Canada website (http://www.statcan.gc.ca)
This gives a preview of a massive construction activity to accommodate the population which will result in an increased demand for building materials.
Since current building materials are mostly from non-renewable resources, the excessive consumption of them raises two major issues:
• It will create a shortage of building material (construction costs ↑).
• It will have environmental effects such as waste production, climate change and accelerated global warming.
Pacheco-Torgal et al. Construction and building materials, 40 (2013) 729-737
Composites
Metals
A composite material can be defined as a combination of two or more materials that results in better properties than those of the individual components used alone.
Hull D, Clyne TW (1996) An Introduction to Composite Materials. Cambridge University Press,
A composite which is combined from one or more biologically derived materials is called biocomposite.
Biocomposite Natural Fiber Reinforced Composites
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Why Crop waste
Eco-designed or bio-inspired products are announced as the materials of the future
Our Common Future/Brundtland Report.
Abundance Low cost Low energy consumption renewable
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Context
Hemp Fibers • Ontario Ministry of Agriculture, Food and Rural Affairs • Ministère de l’Agriculture, des pêcheries et de l’alimentation du Québec
(MAPAQ) promotes the culture of hemp as a substitute for tobacco producers.
Flax Fibers • Canada has a potential production of 1,200,000 tons of flax straw annually. • Overall more than 75 % of this amount is usually burnt or thrown away.
W.H.F. Martin J.T. Reaney wt et al. BIOCAP CANADA, 2006.
Milkweed Fibers • Canada is the native land of Milkweed fibers. • The companies which process industrially the milkweed are only in Canada.
"La soie d'Amérique passe en production industrielle". Radio-Canada. Retrieved 20 December 2015.
http://www.mapaq.gouv.qc.ca/fr/Productions
Unclassified and wasted vegetables • Close to 20% of the production of potatoes must be recovered annually. Canadian Food Inspection Agency, Regulatory guidance, Recycled food Products. MAPAQ, 2010. Règlement sur la culture de pommes de terre; MDDEP, 2008. Guide sur la valorisation des matières résiduelles fertilisantes.
With the courtesy of CITÉ
Context
3) Valorisation des nanocristaux cellulosiques – Axes 1 à 3
• Le lin canadien est cultivé pour sa graine Que faire des tiges inexploitées
• Pommes de terre déclassées Maintenant impossible de les enfouir ou d’en nourrir
le bétail
Projets en cours
Pommes de terre : Actuellement aucune valorisation
Plantes à Fibres : Valorisation ?
Projets en cours
15-25 % Filasse Longues fibres dm
10-15 % Étoupe Fibres cm-mm
45-50 % Anas Granulats mm
10 % Poussières Poudre
Paille
Graines : 5-8% Paillettes: 3-6%
Différents produits suite à une 1ère transformation des pailles de lin
Grande valeur établie
Recèlent de nanocristaux fonctionnels
Nanofibrillated cellulose
MFC, NFC, CNF, CF Properties of Nano fibrillated cellulose Surface area: 100-246 m2.g1 High modulus: 100-150 GPa Significant barrier properties Low density
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Projets en cours
Valorisation des nanocristaux cellulosiques : Extraction verte de nanocristaux/nanofibrilles
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APPLICATIONS
construction Coatings
Agriculture chemicals
Health care
Personal care
MULTITUDE APPLICATIONS
Reference- Exilva.com
Paints
Hydrogels – NFC can be treated with carbapol in presence of Ca2+ ions to yield hydrogels. Such hydrogels will help in tissue engineering, sensors, drug delivery, contact lenses. Cosmetics
Improved durability Improved syneresis Improved mud-crack resistance 100% natural
Improves non-dripping performance Ability to reduce wrinkles
Cementetious composites and concrete Micro- and nano-reinforcement Improved toughness Low cost
Paints
The anti mud-crack effect of adding NFC to a 45% PVC exterior acrylic paint was compared to the same formulation based on a standard HEC.
Reference- Exilva.com
Cementitious Composites
SEM image of CNF in cement matrix showing morphology of nanofiber.
CNFs at a concentration as low as 0.048wt% can be used to increase the flexural strength and the Young’s modulus of cement matrix up to 40% and 75%, respectively.
SPG-270-10, Infrastructure Technology Institute, USA
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Carrot pulping in a juicer
Nanofibrillated and nanocrystalline cellulose from Carrot
Nanocrystalline cellulose (C-NCC)
Nano fibrillated cellulose (C-NFC)
Case Study: CARROT
Morphology Structural crystalline Functional Thermal properties
Morphology Structural crystalline Functional Thermal properties
Graphical representation for the extraction of C-NFC and C-NCC
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Morphology of carrot fibers SEM for raw fibers
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SEM for purified fibers
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SEM: Cross section of Spring fibers
Carrot have both classical and unusual spring fibers composed with small nanofibers
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Assessment of fibrillation by SEM
1.5 min 3 min 5 min
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Structural morphology of C-NFC and C-NCC by TEM
C-NFC
C-NCC
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Functional properties
FT-IR: -OH of cellulose
-C=O in HC
-CH in CH2
-CO stretching of xylane in hemicellulose
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Nanofilms
Prepared by casting evaporation Room temperature
Bleached Ball milling for 1,5 mins
Ball milling for 3 mins
Ball milling for 5 mins
Transparency of nanofilms
UV-visible spectrophotometry
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sita
nce(
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wavelength (nm)
CNC film
purifiedfilm1.5 minfilm
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1.5NFC 3 NFC 5 NFC NCC
Morphology of nanofilms
SEM
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Mechanical properties of the films
NFC film
LDPE film
σ = 56,6 Mpa E = 899 MPa
σ = 23,1 Mpa E = 110-450 MPa
References: http://srjcstaff.santarosa.edu/~yataiiya/E45/PROJECTS/Strength%20of%20Plastics.pdf http://www.shimadzu.com/an/industry/petrochemicalchemical/chem0301006.htm
Material Why TiO2 ?
In general, TiO2 is a biocompatible material, with high physicochemical stability and rather good mechanical strength , specifically:
• Sol-Gel (dip-coating method is an effective method to synthesize and coat NF surface with TiO2 because it is cheap and takes place at low temperature.
Puetz , Dip coating technique 2004, springer.
Wang et al. Nature 388, 431-432
Fiber
TiO2 Film
Hydrophobic Matrix
No UV Irradiation
Fiber
TiO2 Film
Hydrophilic Matrix
UV Irradiation
• Photo-induced hydrophilicity.
Material Why TiO2 ?
SAMPLE
Et MPa
σM MPa
Ɛb %
Polyethylene film 30 10 1272
Polypropylene film 180 12.3 39.4
Neat film-5N cell 899 56,6 7,3
Neat film-100N cell 1350 150 22
Oxidized film without coating 470 38,2 8,7
Oxidized film with coating 1120 73,7 13
TiO2 coated film 1160 81,9 17
Neat film-100N cell 1100 91,6 15
Oxidized film with coating 1370 79,0 9,0
TiO2 coated film 1730 91,3 8,5
ASTM D882
ASTM D638
Neat film-Oven dried (65 deg 1hr) 1330 121 14
Oxidized film 10secs with coating 1200 110 16
Neat film-Oven dried 1660 117 9,3
Oxidized film 10secs with coating 1320 103 9,4
TiO2 coated film 1560 123 12
Oven dried (40deg overnight)
Oxidation time -10 secs
Tensile test
Nagalakshmaiah, M et al , 2016, Maia, T. H. S et al. Carbohydr. Polym. 2017
FTIR for oxidized films
Moisture absorption study
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er u
ptak
e (%
)
Time (hrs)
neat film
Contact angle measurement
SAMPLE θa θr
Neat 54 34 Oxidized and coated 92 53
TiO2 80 39
- More hydrophobic film leading to an increase of the moisture absorbtion and a better durability when subjected to humid environment.
SEM
Neat film
Oxidized and coated film
TiO2 coated film
Cross-section of the films
Starch granules from potato
SEM image of potato peel NFC
75%NFC+25% starch
Ongoing Project at CITÉ: 100% Waste Potato-based film
starch
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Ongoing Project: Dandelion Fibers/PLA Extruded Composites
- Grape is the world's largest fruit crop, with around 7.6 million ha dedicated to vineyards and an estimated 67 million tons annual production worldwide (FAOSTAT, 2009).
- Grape pomace includes stalks, skins, pulps and seeds and consists of mainly cellulose, lignin, hemicellulose and other polysaccharides.
Le champ d’action du CITÉ
• Mise au point de tissus de renfort à base de fibres naturelles d’asclépiade (Cavolié)
• Développer des composites polymères performants et ultra-légers • 50% plus légers que les composites lin/PP • Performances identiques ou supérieures au lin/PP
• Promouvoir l’utilisation des matrices polymères bio-sources (PLA, amidon) • Étude de la cristallisation de leur cristallisation • Développement des techniques de mise en forme
4) Exemple de projet: Autres
• Bétonature
• Valorisation de residus manufacturiers non-recyclables dans les
Projets en cours Exemple 4
Merci
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