Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY ‘ ‘ Green’ Bio Green’ Bio - - Composites: Moving Composites: Moving Towards More Eco Towards More Eco - - friendly friendly Structural Automotive Parts Structural Automotive Parts Lawrence T. Drzal Dept of Chemical Engineering and Materials Science A.K. Mohanty, M. Misra Composite Materials & Structures Center Michigan State University
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Green’ Bio Composites: Moving Towards More Eco … More Eco-friendly Structural Automotive Parts. ... BioFibers as Reinforcements ... BIODEGRADABLE POLYMERS. Renewable
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Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
‘‘Green’ BioGreen’ Bio--Composites: Moving Composites: Moving Towards More EcoTowards More Eco--friendly friendly Structural Automotive PartsStructural Automotive Parts
Lawrence T. DrzalDept of Chemical Engineering and Materials Science
A.K. Mohanty, M. MisraComposite Materials & Structures Center
Michigan State University
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Contents of PresentationContents of Presentation
Introduction to BioCompositesBioFibers as ReinforcementsBioPolymers as Matrices Processing of BioCompositesSurface Modification to Enhance PropertiesBioComposite Properties
Modulus, Strength and Impact Properties
Summary
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
“SUSTAINABLE” GREEN MATERIALS
TriggeredBiodegradableRecyclableRenewable
Commercial Viability &Environmental Acceptability
SUSTAINABLE
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Why BioComposites?Why BioComposites?
• Natural Products have an inherent high variability– Composition, properties, quality
• EcoFriendly MUST be extended to structural applications– Beyond ‘picnic’ goods and garbage bags
• Bioplastics alone are ‘marginal’ materials• Addition of reinforcing fibers increases structural
potential • Control of fiber orientation ‘optimizes’ properties• Improve Thermal, Moisture and Mechanical Durability
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Factors Necessary for Development Factors Necessary for Development of a BioComposite Systemof a BioComposite System
Reinforcement Matrix
Process
SurfaceTreatment
REINFORCEMENTS
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
BIOFIBERS- Cellulose + Lignin
Structure of cellulose
OCH2OH
H
HO
H H
H
OH
OH
HO
H HOH
H
H
OH
HH
CH2OHO
H
H
OH
CH2OH
OH OH
CH2OH
H
OHH
O
HO
HO
H O
H
H
OH
n
OHOH
OOCH3
OH
OH
O
CH3O
OCH3O
OHOH
HO
HO
HOO
CH3O O
CH3O
O
OH
OCH3
OH
OH
OH
OCH3
HO
O
OH
OCH3
OCH3O
OH
OHOH
CH3O
OH
OH OH
OH
OOCH3
OH
OHCH3O
OCH3
OO
OCH3O
HO Structure of lignin
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
NATURAL FIBERSNATURAL FIBERS
FLAXFLAX HEMPHEMP
COIRCOIR
WOODWOOD
JUTEJUTE HENEQUENHENEQUEN
KENAFKENAF
Woven JUTE Cloth
GRASSGRASSCORNCORN
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
REINFORCING BIOFIBERS
Non-woodBioFibers
BAST LEAF SEED/FRUIT
Examples:Kenaf, Flax,Jute,Hemp
Examples:Sisal, Henequen,
Pineapple Leaf Fiber
Examples:Cotton, Coir
StrawBioFibers
Examples:Corn/Wheat/Rice Straws
WoodBioFibers
Soft &Hard Woods
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
BIOFIBERS vs. GLASS(Specific Strength/Modulus)
1750
700 800615
900750
1100786
0
500
1000
1500
2000
2500
Tens
ile p
rope
rties
E- Glass Kenaf Hemp PALF
TS( M pa)Specif ic Strength
Modulus
0
20
40
60
80
100
E-glass Hemp Flax
E-modulus (GPa) Specif ic modulus
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
REINFORCING BIOFIBERS
Non-woodBioFibers
BAST LEAF SEED/FRUIT
Examples:Kenaf, Flax,Jute,Hemp
Examples:Sisal, Henequen,
Pineapple Leaf Fiber
Examples:Cotton, Coir
StrawBioFibers
Examples:Corn/Wheat/Rice Straws
CelluloseNano-whiskers
Sources:Wood
& Non-woodFibers Through
Explosion
WoodBioFibers
Soft &Hard Woods
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Cellulose Nanowhiskers as Reinforcements for Polymer Composites
• Cellulose microfibrils – (5nm x 150-300nm)– monocrystalline cellulose domains
parallel to the microfibril axis composed of cellulose chains in a cellulose lattice bonded laterally and surrounded by surface chains forming a paracrystalline envelope
– devoid of defects, linked by amorphous domains having a strength of 10 GPa
– tensile modulus of 130 GPa– reinforcement for polymers
TEM micrograph of cellulose whiskers from tunicate (Favier, et. al)
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Motivation for BioFibersMotivation for BioFibers
Energy savings
6,500
23,500
05,000
10,00015,00020,00025,00030,000
Glass Kenaf
E (B
TUs)
/1 lb
. fib
er
Cost comparison in average
90
25
020406080
100120
Glass Biofiber
U.S
. Cen
ts/lb
.
Weight savings
1.3
2.6
0
1
2
3
4
Glass Biofiber
Den
sity
, g/c
m3
LTD,AKM,MM - MSU 2000- Biodegradability and Recyclability- EcoFriendly ‘GREEN’ Material- CO2 Sequesterization- Mechanical PERFORMANCE
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Factors Necessary for Development of a BioComposite System
Reinforcement Matrix
Process
SurfaceTreatment
MATRICES
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
BIODEGRADABLE POLYMERS
RenewableResource-based
Petro-basedsynthetic
Microbialsynthesized
•Aliphatic polyester
•Aliphatic-aromatic polyesters
•Polyesteramides
•Polyvinyl alcohols
•Polyhydroxy-alkanoate (PHA)
•Polyhydoxy-butyrate co-valerate(PHBV)
BIOPOL Polymers
•PLA Polymer
•Cellulosic plastics
•Soy-based plastics
•Starch plastics
•Starch blends
•Polyester
•other blends
Biopolymerblends
A. K. Mohanty, L. T. Drzal, R. Narayan, M. Misra, Progress in Polymer Science 2001
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Chemical Structure of some Biopolymers
H C
P oly(a lpha-hydroxy ac id )
C
R
C Hn
O
O
C
R
C Hn
O
O 2
P oly(be ta-hydroxy a lkanoate )
O
CC H
n
(O2 5)
P o ly(om ega-hydroxy a lkanoate)
O
x C
O
O CC H
n
(O2) yHC( 2 )
P o ly(a lkylene d icarboxyla te )
R = H , P o ly(g lyco lic ac id ), P G A
R = C H 3, P o ly(lac ticac id ), P LA
R = C H 3, P o ly(be ta-hydroxybu tyra te ), P H B
R = C H 3, C 2H 5, P o ly(be tahydroxybutyra te -co-va le ra te )P H B V (B IO P O L)
x = 5 , P o ly(eps ilon -capro lactone), P C L
x = 2 , y = 2 , P E Sx = 4 , y = 2 , P B Sx = 4 , y = 2 ,4 , P B S A
( B IO N O LLE )
C hem ica l S tructu re E xam ples
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Composition of Whole SoybeanComposition of Whole Soybean
Protein And Soybean Oil: Source of Plastic Resin For Bio-Composite
In 1924 In 1924 -- -- 5 million bushels of soybean5 million bushels of soybeanIn 2000 In 2000 -- -- 2.8 billion bushels processes in U.S.2.8 billion bushels processes in U.S.
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
EPOXIDIZED OIL: A SOURCE OF PLASTIC RESIN TO REPLACE PETRO-BASED SYNTHETIC THERMOSET RESIN
• Attain a High Degree of BioFiber Dispersion• Insure BioFiber Wettability• Maximize BioFiber Volume Fraction• Control BioFiber Orientation• High Speed• Low Cost
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
AA ll mm oo ss tt CC oo nn ss oo ll ii dd aa tt ee dd
UU nn cc oo nn ss oo ll ii dd aa tt ee dd
PP aa rr tt ll yy CC oo nn ss oo ll ii dd aa tt ee dd
FF uu ll ll yyCC oo nn ss oo ll ii dd aa tt ee dd
11
222
Various Stages of Consolidation
Drzal et al. US Patent, 5,102,690 (1992); 5,123,373 (1992); 5,128,199 (1992)
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
POWDERED PolyPROPYLENE
PROFAX 6501
Average size: 550 µm
EQUISTAR FP-800-00
Average size 40 µm
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Mixing of PP powder and Paper Stock
Hollander Beater
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Fourdrinier (Wet) Continuous Process: 160 lb/h
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Thin sheets of Cellulose fiber-pp sheet composite
Stored for furtherCompression molding
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Electrode plate
Aligned Discontinuous Biofibers+ PP
IR radiant heater
Sintering
Roller pressingVeil/polymer film
(Carrier film)
BF+PP feeder/pre-aligner
BCSSComposite Sheets for
Compression molding
Engineered chopped fiber(BF) inletNozzle
Aerosol generator
Powder PP
Orientation chamber
Environmentally Benign Powder (DRY) Processing
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
THE CONCEPT OFENGINEERED NATURAL / BIO- FIBERS
Bio
-fib
ers B
ast f
iber
Kenaf
PALF
Leaf
fibe
r
AT Kenaf
ST Kenaf
AT PALF
Different ratiosBlends of
Kenaf &
PALF:“EngineeredBio- fibers”ready for composite fabrications
Alkali-treatment (AT)
Silane treatment (ST)
ST PALF
THE CONCEPT OF ENGINEERED NATURAL/BIO-FIBERS
AT / ST
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
SUMMARYSUMMARYPlant Derived Fiber and Crop Derived Plastics ARE thePlant Derived Fiber and Crop Derived Plastics ARE the
Materials of 21st Century: EcoMaterials of 21st Century: Eco--friendly BioCompositesfriendly BioCompositesReplace/Substitute Glass Fiber Petroleum Based Composites Energy benefitRenewability, potential to replace/supplement of PP, PEBiodegradability, CO2 sequestrationReduce Dependence on Petroleum ResourcesValue-Added Opportunity for Agricultural Industry
ChallengesChallengesConsistent Material PropertiesStable during storage, shipment, use Biodegradable/Recyclable after disposalLarge-scale and new processing technology Hybridization of Matrix and ReinforcementDesign with Higher degree of variability
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY