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

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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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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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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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