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Dr Eric POLLET
BioTeam ICPEES – UMR CNRS 7515
École Européenne de Chimie, Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : [email protected]
Novel systems based on
thermoplastic polysaccharides
- from starch to chitosan materials –
23 September 2014 – Slovenj Gradec
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Some information on Strasbourg
Paris Strasbourg
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Some information on Strasbourg
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Information about Univ. of Strasbourg
Université de Strasbourg (UniStra)
World ranking: n°17 in Chemistry
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École Européenne de Chimie, Polymères et Matériaux (ECPM)
Information about ICPEES-ECPM
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Institut de Chimie et Procédés pour l’Énergie,
l’Environnement et la Santé (ICPEES)
Information about ICPEES-ECPM
Department of Polymer Engineering
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BioTeam Members (18) :
Staff(4): • Pr. Luc Avérous (BioTeam leader)
• Dr. Eric Pollet (A/Prof.)
• Pr. Jean Marc Jeltsch (Vice-President UniStra)
• Dr. Vincent Phalip (A/Prof.)
Researchers (14):
Post-Doct. (3):
• Dr. Ernesto Oyervides (Funding Mexico, 2014-2015)
• Dr. Anna Meszynska (European Project, 2014-2016)
• Dr. Alexandru Sarbu (2014/2015)
PhD Students (8):
• Flavie Prévot (Government, 2011-2014)
• Camille Carré (Region + Company, 2011-2014)
• Alice Arbenz (CIFRE, 2011-2014)
• Stéphane Duchiron (Company, 2012-2015)
• Marie Reulier (CIFRE, 2012-2015)
• Thibaud Debuissy (European Project, 2013-2016)
• Amparo Jimenez-Quero (Government, 2013-2016)
• Rogerio Prataviera (Co-Direction w/ Brazil – UFSCar)
> Masters (3)
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Investigation Area :
Non-food valorization of
biomass for the elaboration
of polymer materials
General Topic (BioTeam):
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BioTeam
► Integration, from the biomass to final objects
Chemical
Synthesis
Characterization
Formulation
Process
Biomass: Triglycerides,
Ligno-cellulose,
Tannins, Starch,
Chitin, …
Final Objects: For automotive,
Building, Textile,
Packaging,
Agriculture …
Bio-
Production
Integration « Biochemistry/Chemistry & Process »
Biobased and/or Biodegradable Polymers,
for Environmental and Biomedical Applications
General Topic (BioTeam):
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Biorefinery from Biomass*
Seeds
Starch
Ligno-cellulosic
Fibers
Chitin, Chitosan
Mushroom, Crustaceans…
Vegetable Oils
Fractionation
Extraction
Thermoplastic
Starch
Biocomposites
Thermoplastic
Chitosan (BioMaterials)
Biobased
Thermosets and
Thermoplastics
Fermentation
PHAs, PLA
Lignins and Tannins
-based Materials
Clay
Nano-Biocomposites
Fractionation
(*) Biological material derived from living
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Introduction – Basics
Starch and plasticized Starch
Multiphase systems based on
plasticized Starch
Thermoplastic Chitosan
Multiphase systems based on
plasticized Chitosan
OUTLINE
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From Native Starch to Polymer Materials for
different Applications
Polysaccharide: Starch
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- Storage for energy production for vegetal (Starch is the
major carbohydrate reserve in higher plants)
- Mainly from corn (USA), from Cassava (Asia and South
America), from Wheat and Potatoes (Europe)
- Fully biodegradable and from renewable resources
- Large prod. (< 60% for food) and cheap (< 0.5 €/kg)
Polysaccharide: Starch
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- Storage for energy production for vegetal (Starch is the
major carbohydrate reserve in higher plants)
- Mainly from corn (USA), from Cassava (Asia and South
America), from Wheat and Potatoes (Europe)
- Fully biodegradable and from renewable resources
- Large prod. (< 60% for food) and cheap (< 0.5 €/kg)
- Processable with plastic processing machines
Polysaccharide: Starch
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Starch is composed of two macromolecules:
amylose and amylopectin
amylose: linear polymer (Mw=105-106)
Amylose is a sparsely branched
carbohydrate mainly based on
alpha(1–4) bonds.
α (1- 4)
Native starch structure:
Polysaccharide: Starch
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amylopectin: highly branched polymer (Mw=106-109)
Amylopectin is a highly multiple-branched biopolymer. It is based on
alpha(1–4) (around 95%) and alpha(1–6) links (around 5%).
Starch is composed of two macromolecules:
amylose and amylopectin
α (1- 4)
α (1- 6)
Native starch structure:
Polysaccharide: Starch
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Protein = Maillard reactions
Native starch structure:
Polysaccharide: Starch
Starch composition varies according the botanical source and also
with the plant growth (climatic) conditions.
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Dimensions: 0.5 to 175 microns
e.g., wheat and pea
Variety of shape
Starch granules
Native starch structure:
Polysaccharide: Starch
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Hilum
Amorphous
Amorphous
strips
Cristal strips
cluster
Source D.J. Gallant & B. Bouchet, Food Microstr. 1986
- Radial organization from hilum
- Macromolecules are mainly oriented according to the radial axis
- Structure = inter-macromolecules H bonds between OH groups + water molecules
- Amylose + branching regions = amorphous zones
Native starch structure:
Polysaccharide: Starch
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~9-10 nm
Amylopectin
Native starch structure:
Polysaccharide: Starch
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Source:
UBA
(amylase)
Native starch structure:
Polysaccharide: Starch
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From native starch, we obtain different processable materials,
According to
- the water content
- the thermo-mechanical input
Destructuration of native Starch
Starch-based materials
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Destructuring level
Plasticized
starch
Reinforced
Plastic
Bakery,
food…
Gelatinized
starch
Water content
Expanded
starch
Destructured
starch
Destructuration of native Starch:
towards Plasticized Starch
Starch-based materials
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Starch-based materials
Plasticized Starch
• The first patents and articles on these materials
(plasticized starch or PLS) were published at the
end of the eighties.
• The so-called “Thermoplastic Starch” or TPS
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Destructuration
Plasticization (Depolymerization)
Fragmentation Melting
Shear + Heating (Thermo-mechanical input)
homogeneous molten phase
L. Avérous, Journal of Macromolecular Science, Polymer Reviews. 2004
Plasticized starch
(PLS)
Native starch
+ polyols
+ water
= Dry-blend
Starch-based materials
Plasticized Starch
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Plasticized
Starch
Main parameters: Temperature (T) and Specific Mechanical Energy (SME)
Native starch
+ plasticizers = Dry-blend
(polyols, water)
Shear + Heating (Thermo-mechanical)
homogeneous molten phase
Starch-based materials
Plasticized Starch
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Starch-based materials
Plasticized Starch
Xie F., Pollet E., Halley P., Avérous L. (2013) Progress in Polymer Science. Vol. 38
► Properties strongly influenced by the plasticizer content
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Introduction – Basics
Starch and plasticized Starch
Multiphase systems based on
plasticized Starch
Thermoplastic Chitosan
Multiphase systems based on
plasticized Chitosan
OUTLINE
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► Elaboration of different structures
Plasticized
Starch
+ Biopolymers /
Biodegradable
Polymers
(Nano)Fillers
Process: (co)extrusion, injection,
compression molding
Blends Multilayers (Nano)
BioComposites
+
+ Foam / Expanded material
Multiphase systems based on Starch
Association strategy:
Xie F., Pollet E., Halley P., Avérous L. (2013) Progress in Polymer Science. Vol. 38
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Plasticized Starch
(BIOPOLYMER)
Nano-Filler
(NANO-Objects)
Processing
NANO-BIOCOMPOSITE
Based on Starch
Nano-biocomposites based on Starch
Chivrac, Pollet, Avérous (2009) Materials Science & Engineering R. Vol. 67, pp. 1-17
Applications: Packaging, Agriculture, Leisure, Biomedical …
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►Lamellar
►Spherical Particles
►Fibres and Tubes
Whiskers (cellulose, chitin)
Nano-biocomposites based on Starch
Nanofillers:
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• Lamellar structure
• Montmorillonite platelet: – Thickness ~ 1nm
– Length ~ 100-150nm
High aspect ratio
– Specific surface ~ 700 m²/g when fully exfoliated
Montmorillonite (MMT)
Book: Avérous & Pollet « Environmental Silicate Nano-biocomposites » Springer- 2012.
Nano-biocomposites based on Starch
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0
500
1000
1500
2000
2500
3000
0 2 4 6 8 10 12
2 theta (°)
Inte
nsit
y (
A.U
.)
WS/MMT-Na 6wt%
WS/MMT-Na 3wt%
WS/MMT-Na 1wt%
WS
MMT-Na
Intercalation
Plasticized Starch + unmodified clay (MMT-Na)
F. Chivrac, E. Pollet, L. Avérous (2008), Biomacromolecules
SAXS
Intercalated nanocomposites
Interlayer spacing of 18Å
Nano-biocomposites based on Starch
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Preferential intercalation of Glycerol + Water !!
0
500
1000
1500
2000
2500
3000
0 2 4 6 8 10 12
2 theta (°)
Inte
nsit
y (
A.U
.)
WS_MMT-Na 3wt%
WS
18Å
SAXS
F. Chivrac, E. Pollet, L. Avérous (2008), Biomacromolecules
Plasticized Starch + unmodified clay (MMT-Na)
Nano-biocomposites based on Starch
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MMT-Na
OMMT-CS
Ultra- sonic bath
Cationic starch
Filtration
Lyophilisation
Elaboration of a new hydrophilic organoclay
MMT modified by cationic starch (MMT-CS)
25Å
Clay organo-modifier content:
~ 40 wt% of cationic starch
F. Chivrac, E. Pollet, L. Avérous (2008), Biomacromolecules
Nano-biocomposites based on Starch
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0
500
1000
1500
2000
2500
3000
0 2 4 6 8 10 12
2 theta (°)
Inte
nsit
y (
A.U
.)
WS/OMMT-CS 6wt%
WS/OMMT-CS 3wt%
WS/OMMT-CS 1wt%
WS
OMMT-CS
No diffraction peak for 1 and 3wt%
A shoulder is observed at 6wt% Exfoliated Nano-biocomposite
Plasticized Starch + organoclay (MMT-CS)
F. Chivrac, E. Pollet, L. Avérous (2008), Biomacromolecules
Nano-biocomposites based on Starch
SAXS
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Exfoliated nano-biocomposite
Starch/Glycerol + 3wt% MMT-CS
TEM characterization
F. Chivrac, E. Pollet, L. Avérous (2010), Carbohydrate Polymer
Nano-biocomposites based on Starch
Plasticized Starch + organoclay (MMT-CS)
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Effect of Nanofiller content
Storage: 57% HR - 23°C
Uniaxial Tensile Test
F. Chivrac, E. Pollet, L. Avérous (2008), Biomacromolecules
Mechanical Properties
Nano-biocomposites based on Starch
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10
15
20
25
30
35
40
45
50
-1 0 1 2 3 4 5 6 7
Inorganic Content (wt%)
Yo
un
g M
od
ulu
s (
MP
a)
WS/MMT-Na WS/OMMT-CS
0
5
10
15
20
25
30
35
40
-1 0 1 2 3 4 5 6 7
Inorganic Content (wt%)
Elo
ng
ati
on
at
bre
ak
(%
)
WS/MMT-Na WS/OMMT-CS
0
0.2
0.4
0.6
0.8
1
1.2
-1 0 1 2 3 4 5 6 7
Inorganic Content (wt%)
En
erg
y a
t b
rea
k (
M J
/m3)
WS/MMT-Na WS/OMMT-CS
-Tensile tests-
F. Chivrac, E. Pollet, L. Avérous (2008), Biomacromolecules
Mechanical Properties
Nano-biocomposites based on Starch
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Introduction – Basics
Starch and plasticized Starch
Multiphase systems based on
plasticized Starch
Thermoplastic Chitosan
Multiphase systems based on
plasticized Chitosan
OUTLINE
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Chitin: second most abundant natural polymer after cellulose (109 T/y)
Main component of the cell walls of fungi, the exoskeletons of
arthropods such as crustaceans (e.g., crabs, lobsters and shrimps)
and insects, …
Mainly obtained from the processing waste of shellfish, krill, clams,
oysters, and fungi (Content ranges 8-33%)
Polysaccharide, which can be compared to cellulose
Highly crystalline structure (cf. chitin whiskers)
From Chitin to Chitosan
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Chemical Structures:
Substitution in position 2
-OH = Cellulose
-NHCOCH3 = Chitin
-NH2 = Chitosan
% Deacetylation in commercial chitosan: 60-100%
Mw=104-108 (according to the resource)
Polysaccharides: Cellulose/Chitin/Chitosan
From Chitin to Chitosan
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Chitosan has a number of commercial and possible
uses (Diet, Cosmetic …)
Production: 2 000 tons/Year
Agriculture: seed treatment and biopesticide,
helping plants to fight off fungal infections
(antifungal and antimicrobial prop.)
Water processing: part of filtration process
(flocculants …)
Industry: self-healing PU paint coating
Medicine/Biomedical: useful in bandages to
reduce bleeding and as an antibacterial agent.
Used as drug delivery system or for tissue
engineering (scaffold …)
From Chitin to Chitosan
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Till 2008: Plasticized chitosan is only obtained by solvent casting
Innovative process, development based on previous studies on TPS
Multistep process: - Chitosan destructuration/disruption: Glycerol (10 to 25 wt %) is
incorporated in the chitosan powder and mixed. Then, acetic acid
aqueous solution (2% v/v) is added to the mixture to obtain a paste.
- Plasticized chitosan melting:
The mixture was thermo-mechanically
blended by internal mixer or by extrusion.
- Final Processing: The material is
e.g., hot-pressed to obtain plates
Epure V., Griffon M., Pollet E., Avérous L. (2011). Carbohydrate Polymers, Vol. 83 N°2 pp. 947-952
The new Thermo-mechanical process
Thermoplastic Chitosan
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Pr. M.C. Heuzey
Ecole Polytechnique
Montréal
Pr. P. Halley
U. Queensland
Brisbane
Dr. K. Dean
CSIRO
Clayton (Melbourne)
International Consortium Collaborators
Thermoplastic Chitosan
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Post-processing ageing and
Mechanical properties
Epure V., Griffon M., Pollet E., Avérous L. (2011). Carbohydrate Polymers, Vol. 83 N°2 pp. 947-952.
Thermoplastic Chitosan
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Epure V., Griffon M., Pollet E., Avérous L. (2011). Carbohydrate Polymers, Vol. 83 N°2 pp. 947-952.
Thermoplastic Chitosan
Post-processing ageing:
Impact of %RH on the Water uptake
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b relaxations: motions of the side chains or lateral groups of
chitosan interacting with glycerol and water by hydrogen bonding
1st b relax.: Linked to glycerol relaxation process (as TPS)
2nd b relax.: Attributed to water-induced relaxation process.
Highlights the water/polymer interactions
a relaxation can be associated to the Tg of the Chitosan
DMTA
Epure V., Griffon M., Pollet E., Avérous L. (2011). Carbohydrate Polymers, Vol. 83 N°2 pp. 947-952.
Impact of the %RH
Thermoplastic Chitosan
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Destructuration / Plasticization
Modification of the crystallinity (Content and Type)
Epure V., Griffon M., Pollet E., Avérous L. (2011). Carbohydrate Polymers, Vol. 83 N°2 pp. 947-952.
Crystallinity
Thermoplastic Chitosan
WAXS
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Matet M, Heuzey MC, Pollet E, Ajjia A, Avérous L (2013) Carbohydrate Polymers Vol. 95, pp. 241-251
Crystallinity decreases with the glycerol content (@ same %RH)
Thermoplastic Chitosan
Crystallinity: Effect of the plasticizer content
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Lower crystallinity is obtained for Glycerol
Highest crystallinity for Sorbitol
Matet M, Heuzey MC, Pollet E, Ajjia A, Avérous L (2013) Carbohydrate Polymers Vol. 95, pp. 241-251
Thermoplastic Chitosan
Crystallinity: Effect of the type of plasticizer
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Introduction – Basics
Starch and plasticized Starch
Multiphase systems based on
plasticized Starch
Thermoplastic Chitosan
Multiphase systems based on
plasticized Chitosan
OUTLINE
Page 53
► Elaboration of different structures
Plasticized
Chitosan
+ Biopolymers /
Biodegradable
Polymers
(Nano)Fillers
Process: (co)extrusion, injection,
compression molding
Blends Multilayers (Nano)
BioComposites
+
+ Foam / Expanded material
Multiphase systems based on Chitosan
Association strategy:
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Innovative Biomaterials Based
on Chitosan and PCL:
Elaboration of Interconnected
Porous Structures for biomedical
applications: Tissue engineering, cell
regeneration, controlled release,
drug delivery, wound dressing …
Obtained after a one-step process
(plate/film extrusion)
Controlled dehydration during the
thermo-mechanical treatment.
Martino, Pollet, Avérous (2011) Journal of Polymers and the Environment Vol. 19, N°4, pp. 819-826
Blends based on Chitosan and PCL
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Plasticized Chitosan
(BIOPOLYMER)
Nano-Filler
(NANO-Objects)
Processing
NANO-BIOCOMPOSITE
Based on Chitosan
Applications: Packaging, Biomedical …
Nano-Biocomposites based on Chitosan
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Xie, Martino, Sangwan, Way, Cash, Pollet, Dean, Halley, Avérous (2013) Polymer, Vol 54, pp. 3654-3662
MMT-Na: "unmodified" sodium MMT
OMMT-Ch: Based on chitosan organo-modifier
=> Good dispersion and exfoliation
200 nm
200 nm
Nano-Biocomposites based on Chitosan
Influence of clay organo-modification
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When the OMMT-Ch nanofiller was incorporated:
Modulus E
Energy at break
εb was not reduced
Typical behavior of a truly
Exfoliated Nanocomposite
Uniaxial Tensile tests:
Xie, Martino, Sangwan, Way, Cash, Pollet, Dean, Halley, Avérous (2013) Polymer, Vol 54, pp. 3654-3662
Nano-Biocomposites based on Chitosan
Mechanical properties
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> 85% biodegradation respectively after 180 days in compost
biodegradability of chitosan with the addition of glycerol and MMT
(vs. neat chitosan)
Dean, Sangwan, Way, Zhang , Martino, Xie, Halley, Pollet, Avérous (2013) Polymer Degrad and Stability Vol. 98,
Nano-Biocomposites based on Chitosan
Aerobic Composting
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Dr Eric POLLET
BioTeam ICPEES – UMR CNRS 7515
École Européenne de Chimie, Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : [email protected]
Slovenj Gradec - 23 September 2014