Green’ Bio Composites: Moving Towards More Eco … More Eco-friendly Structural Automotive Parts....

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


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


“SUSTAINABLE” GREEN MATERIALS

TriggeredBiodegradableRecyclableRenewable

Commercial Viability &Environmental Acceptability

SUSTAINABLE


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


Factors Necessary for Development Factors Necessary for Development of a BioComposite Systemof a BioComposite System

Reinforcement Matrix

Process

SurfaceTreatment

REINFORCEMENTS


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


NATURAL FIBERSNATURAL FIBERS

FLAXFLAX HEMPHEMP

COIRCOIR

WOODWOOD

JUTEJUTE HENEQUENHENEQUEN

KENAFKENAF

Woven JUTE Cloth

GRASSGRASSCORNCORN


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


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


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


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)


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


Factors Necessary for Development of a BioComposite System


Process

SurfaceTreatment

MATRICES


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


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


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.


EPOXIDIZED OIL: A SOURCE OF PLASTIC RESIN TO REPLACE PETRO-BASED SYNTHETIC THERMOSET RESIN

CH3 CH CH = CHCH CH2(CH2)4O

(CH2)7 COOCH2


(CH2)7 COOCH2


(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


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


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


Factors Necessary for Development of a BioComposite System


Process

SurfaceTreatment

PROCESSING


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


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)


POWDERED PolyPROPYLENE

PROFAX 6501

Average size: 550 µm

EQUISTAR FP-800-00

Average size 40 µm


Mixing of PP powder and Paper Stock

Hollander Beater


Fourdrinier (Wet) Continuous Process: 160 lb/h


Thin sheets of Cellulose fiber-pp sheet composite

Stored for furtherCompression molding


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


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


Factors Necessary for Development Factors Necessary for Development of a BioComposite Systemof a BioComposite System


Process

SurfaceTreatment

SURFACE TREATMENT


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


ESEM pictures of Kenaf - PP Compositesscale bar 450 µm

Hybrid coupling agent treated Kenaf-PP 100XRaw Kenaf-PP 100X


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


ACCEPTANCE CRITERIA ACCEPTANCE CRITERIA for BIOCOMPOSITESfor BIOCOMPOSITES

1. Performance1. Cost2. Natural Resource Based3. Renewable4. Recyclable

etc.


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


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

)


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

)


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


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


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


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

Green’ Bio Composites: Moving Towards More Eco … More Eco-friendly Structural Automotive Parts....

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