Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology –A European Perspective
Denilson da Silva Pereza and Alain Dufresneb
a)FCBA – New Materials Division; b) INP Grenoble PAGORA
OECD Conference on Potential Environmental Benefits of Nanotechnology: Fostering Safe Innovation-Led GrowthOECD Conference Centre - Paris ,July 15th-17th 2009.
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 2
• BackgroundWhy cellulose micro- and nanofibres ?From trees to cellulose molecular levelCellulose microfibrils and nanocrystalsCellulose biosynthesis and polymorphism
• Cellulose micro/nanofibres and nanocrystalsLaboratory scale productionCharacterization and applicationsScaling-up technology : Main challenges
Outlines
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 3
1) Same reasons as for cellulosic fibres…
Non-fossil, low density, high specific strength and modulus, renewability, biodegradability, high availability in a variety of forms, flexibility, non abrasive nature, non-toxicity, easiness to handle, moderate ability for surface modification, possibility to generate clean bioenergy at endlife, no competition with food (for forestry fibers), relative low cost.
☺
Hydrophilic character : poor adhesion and dispersion in non-polar matrix, high moisture absorption, limited thermal stability : low permissible temperatures of processing and use, very high fiber-to-fibre affinity, (early) biodegradability.
Why cellulose micro- and nanofibres ?
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 4
2) To reduce intrinsic heterogeneity and create almost defect-free structuresKnobby swelling along flax fibers Hardwood fibres
Why cellulose micro- and nanofibres ?
Dufresne et al., 1997
Microfibrillated cellulose
Habibi et al., 2008
Cellulose nanocrystals(Lampke, 2001) (FCBA, 2009)
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 5
Cellulose crystals are potentially stronger than steel and similar to Kevlar®
Experimental Young’s modulus : 137 GPaTheroretical Young’s modulus : 167.5 GPa
Why cellulose micro- and nanofibres ?3) To create high performing bio-based materials
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 6
trunk
timber
growth ring
fibers
cell wall
microfibrils
molecule
10°-102
10-2
10-3
10-6
10-9
10-10
macrofibrils 10-8
10°-101(m
eters)
From trees to cellulose molecular level…
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 7
Cell wall structure
Paroi primaire
Couche S1
Couche S2
Couche S3
Lumen
Lamelle moyenne
Paroisecondaire
Sub-layers Thickness (μm)
Number of MF layers
MFA
Primary 0,05 – 0,1 – – Secondary S1 0,1 – 0,3 3 – 6 50 – 70
Secondary S2 1 – 8 30 – 150 5 – 30 Secondary S3 < 0,1 < 6 60 – 90
ML 0,2 – 1,0 –
Stratified and multi-axial structural systemStratified and multi-axial structural system
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 8
Cellulose biosynthesis
• Cellulose is biosynthesized by terminal complexes (rosettes) embedded in the plasma membrane
• The number of cellulose chains composing the rosettes determines the size of the microfibrills (usually 18-36 chains in higher plants)
• It explains the parallel orientation of cellulose chains in nature (thermodynamically defavorable)
http://www.as.wvu.edu/~cbarth/BIOL%20754%20Lecture%202%20080821_Cell%20walls%20handouts.pdf
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 9
Supramolecular structure of cellulose microfibrils
http://www.as.wvu.edu/~cbarth/BIOL%20754%20Lecture%202%20080821_Cell%20walls%20handouts.pdf
Sugiyama et al. (1991), Macromolecules 24, 4168-4175
• Co-existence of crystalline and amorphous cellulose
Amorphous domains ? Or…Surface chains + minor crystal defects ?
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 10
Cellulose polymorphism
Isogai, Cellulosic Polymers, Blends and Composites, Allomorphs of cellulose and other polysaccharides, 1-24, 1994.
Cellulose I : Native celluloseParallel chain arrangement
Cellulose II : Recrystallized celluloseAnti-parallel chain arrangement
Cellulose III : Swollen cellulose, different orientation of C6Chains arrangement depends on initial cellulose allomorph
Cellulose IV (?)
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 11
Micro/nanofibrillated cellulose
• The isolation of crystalline zones asks for a combination of two characteristics prerequisites :
Controlled (bio-)chemical pretreatments to destroy the molecular bonds whereby microcrystals are hinged together in a network structure
Appropriate use of mechanical energy to disperse a sufficient amount of the unhinged microfibres in the aqueous phase
• The amorphous regions act as structural defects where the cleavage of the microfibrils into short monocrystals takes place
Samir et al., (2005) Biomacromolecules, 6 (2), 612 –626.
Marchessault et al. (1961) J Colloid Sci.16,327-344.
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 12
• Chemical pre-treatmentsControlled acid hydrolysis Alkaline swelling and/or hydrolysisSurface cellulose chemical modifications
• Enzymatic pre-treatmentsCellulasesHemicellulases
• Mechanical treatmentsFibers refining/beating/grinding
“Homogenizers”
Micro/nanofibrillated cellulose
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 13
Enzymatic treatments
XylanasesXylanasesMannanasesMannanases
Lignine
Hémicelluloses
Cellulose
ENZYMES AUXILIAIRESENZYMES AUXILIAIRESFéruloyl esterasesFéruloyl esterases……
ENZYMES ENZYMES LignolytiquesLignolytiquesLaccases, Laccases, MnPMnP,…,…
XylanasesXylanasesMannanasesMannanases
CellulasesCellulases
XylanasesXylanasesMannanasesMannanases
Lignine
Hémicelluloses
Cellulose
ENZYMES AUXILIAIRESENZYMES AUXILIAIRESFéruloyl esterasesFéruloyl esterases……
ENZYMES ENZYMES LignolytiquesLignolytiquesLaccases, Laccases, MnPMnP,…,…
XylanasesXylanasesMannanasesMannanases
CellulasesCellulases
Lignine
Hémicelluloses
Cellulose
ENZYMES AUXILIAIRESENZYMES AUXILIAIRESFéruloyl esterasesFéruloyl esterases……
ENZYMES ENZYMES LignolytiquesLignolytiquesLaccases, Laccases, MnPMnP,…,…
XylanasesXylanasesMannanasesMannanases
CellulasesCellulases
Endoglucanases: cleaves internal β-1,4-glucosylic bonds on cellulose molecule
Exoglucanases: cleaves ends of cellulose chains to formoligosaccharides (e.g. cellobiose)
β-glucosidases: hydrolyzes soluble oligosaccharides to glucose
Shaw J. (2006) Executive Office of Environmental Affairs Workshop http://www.mass.gov/Eoeea/docs/doer/alternative_fuels/cew061108-dartmouth-shaw.pdf
Tapin-Lingua, S., Fiche Inforamtions Forêts 753, 2007, AFOCEL.
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 14
Micro-/nanofibrillated cellulose – Homogenizers
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 15
Micro-/nanofibrillated cellulose – Homogenizers
Sidduqui et al., 2008 International Conference on Nanotechnology for the Forest Products
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 16
Micro-/nanofibrillated cellulose – Homogenizers
Source : Masuko (Japan)
Source : Cavitron (Germany)
Sidduqui et al., 2008 International Conference on Nanotechnology for the Forest Products
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 17
Selective oxidation of hydroxymethyl group at C6 position into carboxylic groups
Main advantages
High selectivity
Aqueous system
Grafting from COOH possible
NaClO
NaCl
NaBr
NaBrO
N OH
N O
N O
.
+ OOH
OHOH
O
OONa
OHOH
OO OH
* 2,2,6,6-tetramethyl-piperidine-1-oxil
de Nooy et al. Recl. Trav. Chim. Pays-Bas, 113, 165-166 (1994); Carbohydr. Res., 269, 89-98 (1995); Macromolecules, 29, 6541-6547 (1996).Chang and Robyt. J. Carbohydr. Chem., 15(7), 819-830 (1996).Isogai and Kato. Cellulose, 5, 153-164 (1998). Tahiri and Vignon. Cellulose, 7, 177-188 (2000). Da Silva Perez et al. Biomacromolecules, 4, 1417-1425 (2003).
Chemical modification
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 18
Micro-/nanofibrillated cellulose Visual aspect
1 passes(400 µm)
+ 6 passes(200 µm)
+ 12 passes(200 µm)
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 19
Micro-/nanofibrillated cellulose Microscopic characterization
• Optical microscopy
• Transmission electronic miscrocopy
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 20
Homonoff et al., 2008 International Conference on Nanotechnology for the Forest Products
Micro-/nanofibrillated cellulose II
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 21
• Swelling of cellulose in liquid NH3 (or other amines), a simple way to increase crystalline cellulose accessibility.
• Ammonia enters the cellulose crystals as guests and modify the conformation of the hydroxymethyl groups
• Upon release of guest molecules, CH2OH groups remain distorted
“Activated state”.
• Cellulose III allomorphs formation : Essentially a solid state process Keep the integrity of the cellulose microfibrils while achieving substantial decrystallizationReorganization of intra-crystalline hydrogen bonds
Micro-/nanofibrillated cellulose III
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 22
• Main features concerning the gel fractionNH3-treatment improves the production of gel fraction.
Gel fraction amount varies from 2 to 76 % depending on :
Cellulose originCellulose allomorph (III or III)Extent of oxidationInitial form of samples
Micro-/nanofibrillated cellulose III
Da Silva Perez et al., 2008 International Conference on Nanotechnology for the Forest Products
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 23
• Transmission Electronic Microscopy (TEM)
Gel fraction is essentially composed of nano-fibres of length varying between 60 and 250 nm and width between 10 and 20 nm
Micro-/nanofibrillated cellulose III
Da Silva Perez et al., 2008 International Conference on Nanotechnology for the Forest Products
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 24
Paper applicationsBarrier
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 25
Paper applicationsBarrier
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 26
Paper applicationsPhysical properties
Gregersen, Ǿ, 2008, Recent advances in fibrilar nanocellulose research
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 27
Nano-biocomposites applications
Azizi Samir et al., 2004
5
6
7
8
9
10
150 250 350 450 550
Temperature (K)
log
(E'/P
a)
Transmission electron micrographs of a dilutesuspension of sugar beet cellulose microfibrils: (a) CMF, (b)
CMF20, and (c) CMF60.
● Poly(S-co-BuA)● CMF● CMF20● CMF 60
6 wt%
1811.531P6CMF60
1021.755P6CMF20
326.3114P6CMF
> 30000.180.2Matrix
εB (%)σB (MPa)E (MPa)Sample
Microfibrillated cellulose x whiskers
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 28
20 nmvalonia tunicin
ramie wood Primary cellwall
Cellulose Nanocrystals (whiskers)
Bleached raw-material
Hydrolysis treatment (H2SO4, 60°C, 20 min)
Neutralization, washing, centrifugation, dialysis,
sonication
Disintegration in water
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 29
L = 0.5-2 µmd = 15 nmL/d = 67
Favier et al., 1995
Tunicate
L = 150-300 nmd = 5 nmL/d = 45
Helbert et al., 1996 Ebeling et al., 1999
L = 100-200 nmd = 15 nmL/d = 10
Courtesy of A. Dufresne - PAGORA
Cellulose Nanocrystals (whiskers)
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 30
Sisal
L = 250 nmd = 4 nmL/d = 60
Garcia et al., 2006
Sugar Beet
L = 210 nmd = 5 nmL/d = 42
Azizi Samir et al., 2004
200 nm
L = 200 nmd = 7 nmL/d = 29
Habibi et al., 2008
Ramie
Courtesy of A. Dufresne - PAGORA
Cellulose Nanocrystals (whiskers)
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 31
Dufresne, Encyclopedia of Nanoscience and Nanotechnology 2nd Edition, in press
Nature Source L (nm) D (nm) Ref.
Cellulose Algal (Valonia) > 1000 10-20 [140,141] Bacterial 100-several
1000 5-10 × 30-
50 [130,133,142]
Cladophora - 20 × 20 [143] Cotton 100-300 5-10 [111,144-147] Cottonseed
linter 170-490 40-60 [148]
MCC 150-300 3-7 [135] Sisal 100-500 3-5 [137] Sugar beet pulp 210 5 [112] Tunicin 100-several
1000 10-20 [139,149]
Wheat straw 150-300 5 [136] Wood 100-300 3-5 [113,124,127,144]
Chitin Crab shell 80-600 8-50 [150-152] Riftia tubes 500-10000 18 [153] Shrimp 50-300 5-70 [154,155] Squid pen 150-800 10 [156]
Courtesy of A. Dufresne - PAGORA
Cellulose Nanocrystals (whiskers)
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 32
Scaling-up technology : Main challenges
•Micro/Nanofibrillated celluloseScaling-up of homogenization technologiesReduction of energy consumptionReduction of enzymes consumptionReduction of clogging problemsSimplifying purification processesDevelopment of characterization routine methods Controlling M/NFC reaggregationConcentration/Drying M/NFC (major issue!)Controlling early biodegradabilityExchange water – organic solvents (biocomposites)Reduction of production costsGuarantee of non-toxicity at nano-scaleDevelop new markets
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 33
Scaling-up technology : Main challenges
• Cellulose NanocrystalsReduction of chemicals consumption
Find applications for co-products (sugars from hydrolysis)
Simplifying purification process (centrifugation 10000 rpm, dialysis, freeze-drying)Development of characterization routine methods
Concentration/Drying NC (major issue!)
Controlling early biodegradability
Exchange water – organic solvents (biocomposites)
Prove to be more than only “models” for fundamental studies
Reduction of production costs
Guarantee of non-toxicity at nano-scale
Develop new markets
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 34
Scaling-up technology : Main challenges
Health-related questions :
Micro/nano scales effect actual risks ? (CNT!) Processing : aqueous / gel media (no actual risks ?)End-products : can M/NFC detach from network ?Modified M/NFC : risks related to the nature of physico-chemical modifications ?
Environment-related questions :
Effluents quality of M/NFRecyclability of M/NFBiodegradability / bioassimilation of M/NFC ?
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 35
From science to technology
FundamentalR&D science
AppliedR&D science
Scale-up /Demonstrators
Industry /Markets
Pilot scale
MicrofibrillatedCellulose I
NanofibrillatedCellulose I
Micro/nanofibrillatedCellulose II
Micro/nanofibrillatedCellulose III
Cellulose Nanocrystals ?
FunctionnalisedM/NFCPaper
applications
Nanocompositesapplications
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 36
A European perspective
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 37
A European perspective
Overview of Cellulose Nanocrystals and Nanofibres: The Science and Technology OECD Conference on Potential Environmental Benefits of Nanotechnology- July 15th-17th 2009 - DdSP - 38
Acknowledgements
• Co-authors and colleagues for the information and material for this presentation
• EGIDE, AGRICE/ADEME, UE for financial support
• NMA staff involved in this research theme
• CERMAV, PAGORA and FCBA staff for nano-fibers analysis
• Professor Mohini Sain for the invitation