novel systems based on thermoplastic polysaccharides · novel systems based on thermoplastic...

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

mailto:[email protected]

Some information on Strasbourg

Paris Strasbourg

Some information on Strasbourg

Information about Univ. of Strasbourg


World ranking: n°17 in Chemistry


Information about ICPEES-ECPM

Institut de Chimie et Procédés pour l’Énergie,

l’Environnement et la Santé (ICPEES)

Information about ICPEES-ECPM

Department of Polymer Engineering

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)

Investigation Area :

Non-food valorization of

biomass for the elaboration

of polymer materials

General Topic (BioTeam):

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):

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

Introduction – Basics

Starch and plasticized Starch

Multiphase systems based on

plasticized Starch

Thermoplastic Chitosan


plasticized Chitosan

OUTLINE

From Native Starch to Polymer Materials for

different Applications

Polysaccharide: Starch

- 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)


- 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


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:


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)



Protein = Maillard reactions



Starch composition varies according the botanical source and also

with the plant growth (climatic) conditions.

Dimensions: 0.5 to 175 microns

e.g., wheat and pea

Variety of shape

Starch granules



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



~9-10 nm

Amylopectin



Source:

UBA

(amylase)



From native starch, we obtain different processable materials,

According to

- the water content

- the thermo-mechanical input

Destructuration of native Starch

Starch-based materials

Destructuring level

Plasticized

starch

Reinforced

Plastic

Bakery,

food…

Gelatinized

starch

Water content

Expanded

starch

Destructured

starch

Destructuration of native Starch:

towards Plasticized Starch



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

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


Plasticized Starch

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


Plasticized Starch


Plasticized Starch

Xie F., Pollet E., Halley P., Avérous L. (2013) Progress in Polymer Science. Vol. 38

► Properties strongly influenced by the plasticizer content




plasticized Starch




OUTLINE

► 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

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 …

►Lamellar

►Spherical Particles

►Fibres and Tubes

Whiskers (cellulose, chitin)


Nanofillers:

• 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.


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


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


Plasticized Starch + unmodified clay (MMT-Na)


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



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)



SAXS

Exfoliated nano-biocomposite

Starch/Glycerol + 3wt% MMT-CS

TEM characterization

F. Chivrac, E. Pollet, L. Avérous (2010), Carbohydrate Polymer


Plasticized Starch + organoclay (MMT-CS)

Effect of Nanofiller content

Storage: 57% HR - 23°C

Uniaxial Tensile Test


Mechanical Properties


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


Elo

ng

ati

on

at

bre

ak

(%

)


0

0.2

0.4

0.6

0.8

1

1.2

-1 0 1 2 3 4 5 6 7


En

erg

y a

t b

rea

k (

M J

/m3)


-Tensile tests-


Mechanical Properties





plasticized Starch




OUTLINE

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

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


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 …)


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


Pr. M.C. Heuzey

Ecole Polytechnique

Montréal

Pr. P. Halley

U. Queensland

Brisbane

Dr. K. Dean

CSIRO

Clayton (Melbourne)

International Consortium Collaborators


Post-processing ageing and

Mechanical properties

Epure V., Griffon M., Pollet E., Avérous L. (2011). Carbohydrate Polymers, Vol. 83 N°2 pp. 947-952.




Post-processing ageing:

Impact of %RH on the Water uptake

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


Impact of the %RH


Destructuration / Plasticization

Modification of the crystallinity (Content and Type)


Crystallinity


WAXS

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)


Crystallinity: Effect of the plasticizer content

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


Crystallinity: Effect of the type of plasticizer




plasticized Starch




OUTLINE

► 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:

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

Plasticized Chitosan

(BIOPOLYMER)

Nano-Filler

(NANO-Objects)

Processing

NANO-BIOCOMPOSITE

Based on Chitosan

Applications: Packaging, Biomedical …

Nano-Biocomposites based on Chitosan

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


Influence of clay organo-modification

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


Mechanical properties

> 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,


Aerobic Composting

Dr Eric POLLET

BioTeam ICPEES – UMR CNRS 7515



email : [email protected]

Slovenj Gradec - 23 September 2014

mailto:[email protected]

novel systems based on thermoplastic polysaccharides · novel systems based on thermoplastic...

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