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
ProteinProtein OilOil HullsHullsCarbohydrateCarbohydrate OtherOther43%43% 20%20% 26%26% 8%8% 3%3%
Soy proteinSoy protein Protein content Cost/lb.Protein content Cost/lb.
Defatted Flour 50Defatted Flour 50--55% $0.2055% $0.20Protein Concentrate 65Protein Concentrate 65--72% $0.5572% $0.55Protein Isolate 90+% $1.10Protein Isolate 90+% $1.10
Soy Oil: $0.20Soy Oil: $0.20--0.250.25
EpoxidizedEpoxidizedSoy Oil : $0.60Soy Oil : $0.60--0.650.65
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
CH3 CH CH = CHCH CH2(CH2)4O
(CH2)7 COOCH2
CH3 CH CH = CHCH CH2(CH2)4O
(CH2)7 COOCH2
CH3 CH CH = CHCH CH2(CH2)4O
(CH2)7 COOCH
VERONIAN OIL (VO) : Naturally epoxidized vegetable oil
VO has a lower average epoxy functionality of 2.4
CH3 CH CH CH2(CH2)4O
(CH2)7 COOCH2CH CHO
CH3 CH CH CH2(CH2)4O
(CH2)7 COOCHCH CHO
CH3 CH CH(CH2)7O
(CH2)7 COOCH2
EPOXIDIZED SOYBEAN OIL (ESO)
ESO has a higher average epoxy functionality (4.5)
• Triacylglycerol oil, very much similar to other vegetable oils, such as corn oil, soybean oil, sunflower oil, coconut oil, castor oil etc.
• VO contains triglycerols in which the fatty acid moieties are mostly epoxidized – thus VO is nature made epoxidized vegetable oil.
Vernonian Oil (VO): Natural made Epoxidized Vegetable OilAbundantly Available in Tropical Parts of AFRICA
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Biopolymers Are Becoming Commercial Products
Poly(lactic acid) Cargill-Dow & Mitsui ChemicalsStarch plastics Novamont, National StarchCellullosic Plastic Eastman ChemicalAliphatic / aliphatic-aromatic copolyester
Easter Bio EastmanBiomax DuPontEcoflerx BASFBAK BayerBionolle Showa High Polymer
PLA300 million lb./yr. –
Nebraska1 billion lb./yr. -World by 2006
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Natural/BioNatural/Bio--Fiber Composites (Fiber Composites (BioCompositesBioComposites))
Partial Biodegradable Completely Biodegradable(Optional)
ThermoplasticBioComposites(Biofiber+Poly
-propylene/Poly-ethylene etc.)
ThermosetBioComposites
(Biofiber+Epoxy,Polyester, etc.)
Biofiber-BiopolymerBioComposites
(Biofiber+Soy plastic/Starch plastic/
Cellulosic Plastic/PLA
Biofiber-PetroPolymerBioComposites
(Biofiber+aliphaticco-polyester
Polyesteramides
HYBRID BIO-COMPOSITESThermoplastic/Thermoset/bio-polymers
Reinforced with Two or more Bio-fibers toManipulate BioComposite Properties & To
Maintain Balance Among Ecology-Economy-Technology
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Factors Necessary for Development of a BioComposite System
Reinforcement Matrix
Process
SurfaceTreatment
PROCESSING
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
BioComposite Process BioComposite Process Requirements Requirements
• Preserve BioFiber Mechanical Properties– minimize attrition – minimize mixing degradation
• 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
Powder Impregnation TechnologyPowder Impregnation Technology
ADVANTAGESEnvironmentally BenignNo organic solvent (WET or DRY)Low Void-composites - better propertiesMixing and dispersion of multiple
components of is easyLow cost processes Low energy consumptionHigh Process SpeedPowders are recyclable
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
SURFACE TREATMENT
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Surface Modification of BioFibersWhy surface modification?
Improve: Improve: WettabilityWettabilityAdhesionAdhesionStrengthStrengthImpactImpactDurabilityDurability
Modification Strategies?* Alkali treatment* Silane treatment* Maleated Polyolefins* Ammonia ExplosionIsocyanate,Bleaching,Plasma, Grafting,Acetylation
BioComposites utilizing
EngineeredNatural Fibers
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
ESEM pictures of Kenaf - PP Compositesscale bar 450 µm
Hybrid coupling agent treated Kenaf-PP 100XRaw Kenaf-PP 100X
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
80.0985.3
39.84
4.2
7.49
8.48
0102030405060708090
100
60% (Raw) 60% 65%
Kenaf Fiber weight%
Flex
ural
Stre
ngth
0
4
8
12
16
20
MO
E
FS (MPa)MOE (GPa)
Optimum Surface Treatment forHIGH FIBER CONTENT BIO-COMPOSITES
UsedOptimumContent
OfCouplingAgent:
3% MAPP
Result: (High Fiber content) FS: 85 MPA, MOE: 8.5 GPa
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
ACCEPTANCE CRITERIA ACCEPTANCE CRITERIA for BIOCOMPOSITESfor BIOCOMPOSITES
1. Performance1. Cost2. Natural Resource Based3. Renewable4. Recyclable
etc.
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
BIOFIBER – POLYPROPYLENE COMPOSITES(40 wt.% Fiber –Powder Processing)
43.82
54.9548.9 51.25 50.17
35.6 35.65
52.85
41.87
63.99
75.62
1.85 2.03
5.5
3.72 4.24
7.4
4.544.71 4.654.25
1.78
0
20
40
60
80
PP JU-PP KE-PP HP-PP FX-PP HQ-PP SL-PP GL-PP HYB-PP
SizedKE-PP
SizedGL-PP
0.5
4.5
8.5
12.5
F.S (MPa)MOE (GPa)
E-GlassFlexural Strength & MOE
HYB: 15% KE, 15%FX, 10% SLSized: Hybrid water-based sizing (Silane + Maleated PP Emulsion)
Bio-composites show: Comparable FS & superior MOE over Glass Fiber Composites
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
IMPACT STRENGTH OF HENEQUEN BIO-COMPOSITESCOMPARABLE TO GLASS FIBER COMPOSITES
44.14
99.67
229.3 233.09
106.83124.18
68.7
156.87
17.89
105.75
0
50
100
150
200
250
300
PPJU
-PP
KE-P
PHP-
PPFX
-PP
SL-P
PHQ-P
PGL-P
PHYB
-PP
Size
d KE
-PP
Impa
ct s
tren
gth
(J/m
)
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
Natural Fiber (40 wt.%) PP Vs. Cellulose Acetate (CA)
Green Bio-Composites(Powder Processing --
Short fiber)
Need for more Eco-friendlyGreen Composite materials
Bioceta/Cellulosic plastic shows better Impact over PP
KE/Cellulose–based composites: best flexural and modulus
Ultimate Goal: EngineeredNatural Fiber and Continuous
BCSS Process
40.6348.9
50.94
43.82
0
20
40
60
80
PP CA KE-PP KE-CA
Flex
ural
Str
engt
h ( M
Pa)
0.5
1.52.5
3.54.5
5.5
MO
E ( G
Pa)
17.9
46.61
68.798.4
020406080
100120
PP CA KE-PP KE-CA
Impa
ct s
tren
gth
( J/m
)
Professor Lawrence T. Drzal, MICHIGAN STATE UNIVERSITY
PLAPLA--BASED BIOBASED BIO--COMPOSITESCOMPOSITES
20.14119.7194.1383.55 55.77 85.45
5.6110.84
8.14
3.76 6.350.89
-10.00
10.0030.00
50.0070.00
90.00
110.00130.00
150.00
100%PLA
Kenaf-PLA
Jute PLA
Coir PLA
Coir-JutePLA
Hemp-KenafPLA
-5.00
0.00
5.00
10.00
15.00
Flexural Strength(MPa)MOE (GPa)
132.33 111.65
83.9395.00
115.00
135.00
h (J
/m)
Enhancement: 44% in FS and 188% in MOE
Encouraging !!!> 400% ImprovementIn Impact Strength
45 wt.%Bio-fiber Patent
Disclosed
26.08
72.83 67.88
-5.00
15.00
35.00
55.00
75.00
100% PLA Kenaf-PLA
Jute PLA
Coir PLA
Coir-JutePLA
Hemp-KenafPLA
Impa
ct S
tren
gt
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
Dr. A.Mohanty
Dr. M.Misra
Dr. S. Han
D. Hokens
L. Belcher B. Moore
B. RookB. J.Foster
A. WibowoP. Tummala
G. Mehta
MSU BIOCOMPOSITES RESEARCH GROUP