Biopolymer micro and nanocomposites: modification of interphasesDr Katherine Dean, S. Petinakis, C. Way, A. Scully, M. Do, P. Sangwan, L. Yu, X. Zhang, DY. Wu,
E. Palombo, G. Edward CSIRO Materials Science and Engineering, Gate 5 Normanby Rd, Clayton, 3168, Australia, Swinburne University
Melbourne Australia, Monash University Melbourne Australia
Rome 16th April 2009
CSIRO (Commonwealth Scientific and Industrial Research Organisation) Australia
• Australia’s national research organisation (similar to CNRS in some respects)
• multidisciplinary (materials - polymer, ceramics, metals, plant industries, entomology, sustainable ecosystems, bushfire research)
• Sites all over Australia and around 6000 staff
• Our site is located in Melbourne, Victoria• Dedicated program to sustainable
polymer materials with around 50 research scientists engineers, PhD and postdocs
Polymer classes
• Biodegradable and renewable• From a renewable resource (corn, wheat, soy etc)• 100% biodegradable and compostable
• Biodegradable and non-renewable• From a petrochemical resource• 100% biodegradable and compostable
CSIRO polymer processing and design facilities
• Extrusion• Single & twin screws, co-extrusion,
foaming, sheet dies etc• Screw design• Reactive extrusion (liquid injection and
multi gravimetric feeding)
• Thermoforming• Scale-up from technologies developed in
the laboratory
• Film Blowing• Fibre Spinning • Characterization
• mechanical and thermal properties, x-ray diffraction
• permeability• Transmission electron microscopy • Scanning electron microscopy
State-of-the-art biodegradation facilities (commissioned in 2007)
• Used for commercial and strategic science projects
• Fully automated matrix of bioreactors
• Testing to Australian and European Standard AS 4736-2006 and EN 13432
Respirometer schematic
Compressed Air
Water
Humidifer(90%RH,23C)
Flowmeter(0-1L/min)
Waterbath + Bioreactor(58C, dark) (3L, dif plate)
Condens. glassware
ElectronicSolenoid
1
156 lines
Flowmeter (0-1L/min)
IR 02/CO2
(02<22% CO2<8%)
Computer + Labview(datalogger) (controller)
Hardware interface (signals in + controls
out)
T H T F O2CO2I/O
Biopolymer structures
O CH2 C CH2 C
O
N O
O
n
m
polybutylene succinate adipate (PBSA)
Starch (amylose –linear and amylopectin –branched)
Poly(lactic acid) (PLA)
O
OO
O
O
O
O
HO OH
H
OHHOH
H
OH
HOH
HO
H
H
H
HO H
OH
H
OH
H
OH
H
HO
H
H
HOH
O
H
HH
H
1
1
1
O
OHH
HOH
H
OH
H
O
O
OH
HOH OH
H
O
O
OHH
HOH OH
H
O
O
O
OHH
HOH OH
H
O
O
OH
H
HO
HHO
H
O
OO
OH
H
HO
HH
HO
H
H
H
H
H
H
H
H
H
H
H
HOO
OOH
CH3
O CH3
O CH3
O
n
Biopolymer nanocomposites Dean, Yu, Wu Comp. Sci. Tech 67(3-4) 413-421 2007 Dean, Do, Petinakis, Yu Comp. Sci. Tech. 68(6) 1453-1462 2008
• Using techniques which do not involve the use of high toxicity chemicals or agents
• strong ion dipole interactions and edge hydroxy interactions between starch and montmorillonite (MMT) clay
• Interruption of recrystallization by MMT process increasing shelf-life of material
Na+
Na+Na+
OH H
Na+
OHH
Detail of possible interactions between clay platelets, water and poly(vinyl alcohol)
Na+
Na+Na+
OH H
Na+
OHH
Na+
Na+Na+
Na+
CH2
CHO
CH2CH
O
O
CH3
H
n
n
O
O
CH3
CH2
CHO
CH2H
n
n
O
H
HOH
H
17Å
9.8Å*
*Up to 12.77Å depending on the level of hydration
Biopolymer nanocompositesDean,K., Pas,S., Yu,L., Ammala,A., Hill,A., and Wu,D.Y Accepted J Applied Polymer Sci (2009).
PBSA: 5wt% Somasif MEE
PBSA:5wt% Somasif MAE
PBSA:5wt% Somasif MTE
PBSA: 5wt%unmodified clay
Tortuous path
60% reduction in oxygen permeability
Bio-polymer nanocomposites - improvement in tensile modulus
0
100
200
300
400
500
600
700
800
900
1000
0 1 2 5
clay (weight %)
Ten
sile
Mo
du
lus
(MP
a)
baseline PBSA (no Na-FHT)
neat Na-FHT
MEE modified Na-FHT
MAE modified Na-FHT
MTE modified Na-FHT
Biopolymer micro-composites compatibilising matrix and fibre Petinakis, Yu, Edward, Dean, Liu, Scully; submitted to Journal of Polymers and the
Environment (2009).
PLA
wood-flour
Matrix/particle interface PLA
wood-flour
Matrix/particle interface
compatibiliserCellulose OH O C N R
Cellulose O C
O
RNH
Biopolymer micro-composites compatibilising and biodegradation Way, Dean Wu et al publications planned for 2009
• Maple treated with• Glycidyloxy-propyl-trimethoxysilane (5%w/wt fibre)
• Hydrolysed silanol groups forms bonds with the OH-maple or PLA
• Acetic anhydride• Replace OH groups on maple to acetyl and make more
hydrophobic (dispersion, stability, interface)
Biodegradation in aerobic compost
• ISO AS 14855 / ASTM D5338
(samples in compost at 58C, biodegradation via CO2 evolution)
CO2 Evolution
0
20
40
60
80
100
0 10 20 30 40 50 60
Time (Days)
Cu
mu
lati
ve C
O2
(mL
/ves
sel)
Compost Sample + Compost
t
contentgasCOrateflowgastimeCO0 22 )( 100
)(
)()(
2
,22
T
MEANBTT COlTheoretica
COCODeg
CO2 Evolution
0
20
40
60
80
100
0 10 20 30 40 50 60
Time (Days)
Bio
de
gra
da
tio
n (
%)
Sample
3321
,TTT
MEANT
DegDegDegDeg
Lag
Degradation
Plateau
Degradation Traces
0
10
20
30
40
50
60
70
80
90
0 10 20 30 40 50 60 70 80 90
Time (Days)
Deg
rad
atio
n (
%, M
ean
)
Cellulose Powder neat 30% WPC glycidyloxy-silane 30% WPC acetylated 30% WPC
• Biodegradation (compost)
Biopolymer micro-composites compatibilising and biodegradation Way, Dean Wu et al unpublished work 2009
Reduced time to onset of biodegradation
Greater % degradation
Sample Day 0 Day 14 Day 28 Day 41 Day 56
Neat
30% WPC
Glycidyloxy silane
30% WPC
Acetylated 30% WPC
Biopolymer micro-composites compatibilising and biodegradation Way, Dean Wu et al unpublished work
Conclusions
• Composites, nanocomposites and blends of biodegradable polymers have been prepared and studied.
• range of chemical and physical interfacial modification methods.
• superior improvements in a range of properties:•modulus
•tensile strength
•oxygen barrier
•thermal properties.
• Increased interest from industry in this field• Future work – biomimetics, utilising synchrotron science,
developing high performance bio-based materials
Thank You
CSIRO Materials Science and Engineering
Name Katherine Dean
Title Research Scientist
Biopolymer Composites Stream Leader
Phone ( +61 3 9545 2686)
Email [email protected]
Contact CSIROPhone 1300 363 400
+61 3 9545 2176
Email [email protected]
Web www.csiro.au
CSIRO Materials Science and Engineering
Name Stuart Bateman
Position Research Scientist
Sustainable Polymeric Materials Theme Leader
Phone ( +61 3 9252 6128)
Email [email protected]
CSIRO Materials Science and Engineering
Name Phil Casey
Title Designed Polymer Interfaces Leader
Phone ( +61 3 9545 2684)
Email [email protected]