ACCE 2002, September 13- Bio based Thermoset Resins and Their Composites€¦ ·  ·...

ACCE 2002, September 13ACCE 2002, September 13--14, 200214, 2002

BioBio--based based Thermoset Thermoset Resins and Resins and Their CompositesTheir Composites

M. M. MisraMisra, L. T. Drzal, A. K. , L. T. Drzal, A. K. MohantyMohanty, L. , L. BelchlerBelchler, , G. G. MehtaMehta, J, J--P. P. Latere DwanLatere Dwan’’sIsasIsa

Michigan State UniversityMichigan State University2100 Engineering Building, East Lansing, MI, 488242100 Engineering Building, East Lansing, MI, 48824

Presentation OutPresentation Out--linelineIntroduction and motivationIntroduction and motivation

BioBio--based resins, Biobased resins, Bio--fibers and Biofibers and Bio--CompositesComposites

BiobasedBiobased Epoxies and Their CompositesEpoxies and Their CompositesBiobased PolyurethanesBiobased Polyurethanes and Their Compositesand Their CompositesBiobasedBiobased Unsaturated Polyesters and Their Unsaturated Polyesters and Their CompositesComposites

ConclusionsConclusions

AcknowledgementsAcknowledgements

Motivation

BLENDof Functionalized Oil

WITH Thermoset Resins?(Thermoset Resins:

Brittle & Expensive)

ECONOMY:Economically Viable

HOW ? Example: Epoxy ResinCosts 126 cents/lb.

WhereasEpoxidized Oils

Costs ~ 60 Cents/lb

TECHNOLOGY:To ImproveToughness

ECOLOGICALBENEFIT:

Incorporation OfBio-resources

To the MaximumPermissible Extent

To achieve Required Properties

NATURAL FIBERSNATURAL FIBERS

FLAXFLAX HEMPHEMP

COIRCOIR

WOODWOOD

JUTEJUTE HENEQUENHENEQUEN

KENAFKENAF

Woven JUTE Cloth

GRASSGRASSCORNCORN

Natural/BioNatural/Bio--Fiber Composites (BioFiber Composites (Bio--Composites)Composites)

Thermoplastic basedThermoplastic based Thermoset Thermoset based based

BiofiberBiofiber-- ThermoplasticThermoplastic( Polypropylene/PVC/PS)( Polypropylene/PVC/PS)

Green: PLA, Cellulose esters etc.Green: PLA, Cellulose esters etc.

BiofiberBiofiber--ThermosetsThermosets(Epoxy, Polyesters, (Epoxy, Polyesters, PolyurethanesPolyurethanes))

BioBio--based: Blend with based: Blend with functionalizedfunctionalizedVegetable oilVegetable oil

HYBRID BIOHYBRID BIO--COMPOSITESCOMPOSITES(Fiber blending/Matrix blending)(Fiber blending/Matrix blending)

Thermoset vs. thermoplastic composites

• Use of reinforced thermoset composites: ~doubled in the last decade

• Expected to increase 47% during next 5 years through 2004

• ~ 65% of all composites use glass fiber - polyester composites.

• Natural fiber polyester composites: target is to replace glass-polyester composites

70%Reinforcedunsaturated polyester

15%otherthermosets

15%Reinforcedthermoplastics

Matrix patternin Polymer Composites

BioBio--based Epoxies based Epoxies and and

their Compositestheir Composites

ReagentsDGEBA (Diglycidylether of bisphenol A)

m = 0, 1, 2

O

CH OCH2

CH3

CH3

C O CCH2 CH CH2 O O CH2 CH CH2

O

CH3

CH3OH

m

J-T403 (Jeffamine T403) MPDA (m-phenylene diamine)

NH2

NH2

CH2CH CH3 NH2

CH2

CH2

CH3CH2 C CH2 O

CH2CH CH3 NH2O

CH2CH CH3 NH2O

X

Y

Z

Reagents: Epoxidized Soy(ESO)/Linseed Oils(ELO)

CH2 C CH2 7 CH CH CH2 CH CH CH2 4 CH3

CH2 O C CH2 4 CH CH CH2 CH CH CH2 CH CH CH2 4 CH3

CH2 O C 7 CH CH CH2 7 CH3CH2

O

OO

O OO

O O O

O

Epoxy equivalent wt. of ESO: 225-230

CH2 C CH2 7 CH CH CH2 CH CH CH2

CH2 O C CH2 4 CH CH CH2 CH CH CH2 CH CH CH3

CH2 O C 7 CH CH CH2 7 CH3CH2

O

OO

O OO

O O O

O

CH2 CH3

CH2

CH CH

O

Epoxy equivalent wt. of ELO: 173-178

Epoxy-Primary Amine Curing Reaction

O

CH OCH2

CH3

CH3

C O CCH2 CH CH2 O O CH2 CH CH2

O

CH3

CH3OH

m

C C

O

+ RNH2 HO C C NHR

+C C

O

HO C C NHR HO C N C C OH

R

C

* taken from Tensile Measurements

0

0.5

1

1.5

2

2.5

3

3.5

ESO(10) ESO(20) *ESO(30) ELO(10) ELO(20) ELO(30)Samples

Mod

ulus

(GPa

)Dynamic Mechanical Analysis of Bio-based Epoxy Resin with Jeffamine T403 at 30°C

Impact Strength and Glass Transition Temp. of Bio-based Epoxy Resin with T 403

0

100

200

300

400

ESO(10%) ESO(20%) ESO(30%) ELO(10%) ELO(20%) ELO(30%)Samples

Impa

ct S

tr. (J

/m)

0

20

40

60

80

Tg (°C

)

IS Tg

Modulus of Elasticity & Bending Strength of Epoxy Samples containing ELO and MPDA

0

1

2

3

4

0% ELO 30% ELO 40% ELO 50% ELO

Samples

Mod

ulus

of

Elas

tici

ty (G

Pa)

0

50

100

150

Bend

ing

Stre

ngth

(MPa

)MOEBending Str.

Impact Strength of Epoxy Samplescontaining MPDA and ELO

0

20

40

60

80

100

120

0% ELO 30% ELO 40% ELO 50% ELO Samples

Impa

ct S

tren

gth

(J/m

)

ESEMs of Impact Fractured Epoxy Resin containing MPDA and ELO

Scale: 5µm 10 µm 10 µm

30%ELO X 6000 50% ELO X 500040%ELO X 6000

Phase separation between epoxy-rich phase and ELO-rich phase

0

20

40

60

80

100

120

0 100 200 300 400 500 600Temperature (°C)

Wei

ght

%

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

Der

ivat

ive

Wei

ght

(%/°

C)

Water-Washed (WW)5%Alkali2%Silane (Z-6040)***Plasma*UV**Water-Washed (WW)5%Alkali2%Silane (Z-6040)***Plasma*UV**

*550 W with O2 for 10 min.

**120 sec. of UV at 60 °C

***Epoxy compatible silane

Thermogravimetric Analysis of Surface Modified Henequen (HQ)

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

No ELO or HQ ELO 30V%WW HQ

30V%5%Alkali HQ

30V%Plasma* HQ

30V%2%SilaneHQ

30V%UV** HQ

Samples

MOE

(GPa

)

0

20

40

60

80

100

120

140

160

Bend

ing

Str

engt

h (M

Pa)

MOE Bending Str.

Modulus of Elasticity (MOE) & Bending Strength of -Epoxy Composites containing 30% ELO and 30V% HQ

Conclusion

The impact strength was directly proportional to the concentration of the epoxidized oils when using J-T403.The modulus, bending strength, and Tgwere inversely proportional to the concentration of the epoxidized oils when using J-T403.The impact strength was directly proportional to the concentration of the ELO when using 30 or 40% ELO and MPDA.

BioBio--based based Polyurethanes Polyurethanes & their Composites& their Composites

Polyurethanes: Synthesis and Uses

HO OH + OCN NCO HO OH+

OCNH

ONCOH

OOCN

O

HNCOH

O

POLYOL DIISOCYANATE

POLYURETHANE

• Fast reaction, no by-product• Wide range of polyols and isocyanates ⇒ numerous uses

Distinguishing Characteristics of Polyols

250 to 1,00028 to 160Hydroxyl number

3.0 to 8.02.0 to 3.0Functionality

150 – 1,0001,000 to 6,500Molecular weight

Rigid coatings, Rigid foams

Elastomers, Coatings, Flexible foams

Characteristics

(SZYCHER’S HANDBOOK OF PURs), CRC Press (1999).

HOOH

OH

HO

O

O

O

OOH

HO

HO

OH

HO

POH

OHO

O

O

OHO

OH

O

O

O

O

OO

OH

HO

HO OH

OH

OP

HO OH

O

HO

HO

OH

HO

Soy phosphate ester polyol

Mw = 2304 g/molFunctionality = 20

492 mg KOH/g

2025181200142714312100

G’ (30˚C) (MPa)

1.064520 / 10061.0697125 / 7551.08811150 / 5041.05114275 / 2530.85515490 / 1021.072167100 / 01

Density (g/cm3)

Tg (˚C) (DMA)

Polyol OH ratio(JEFFOL / SOPEP)

Entry

Properties of Biobased Polyurethane's

Isocyanate / OH ratio = 1.1. Jeffol 495 polyol: polyether polyol(495 mg KOH /g) and SOPEP (154 mg KOH /g). Isocyanate: polymeric diphenylmethane diisocyanate (MDI).

“Polyol” Hybridization ⇒ Biobased PURs with acceptable properties (thermal, mechanical

performances) and effective cost

Effect of the (Jeffol / SOPEP) OH molar ratio on flexural properties

0

20

40

60

80

100

0/100 25/75 50/50 75/25 90/10 100/0

Flex

ural

ste

ngth

(MPa

)

0

500

1000

1500

2000

Mod

ulus

(MPa

)

Flexural Strength (MPa) Modulus (MPa)

0

10

20

30

40

50

60

70

80

0/100 25/75 50/50 75/25 90/10 100/0

OH molar ratio (Jeffol/SOPEP)

Impa

ct s

treng

th (J

/m)

Glass reinforced Polyurethanes from soy phosphate ester polyol: DMA Study

Effect of glass fiber on G' of soy phosphate ester PU

0

500

1000

1500

2000

2500

3000

-10 10 30 50 70 90 110 130 150

Temperature (C)

G' (

MPa

)

No fiber 15 wt % 30 wt % 50 wt %

0

20

40

60

80

100

120

No fiber 15 wt % 30 wt % 50 wt %

Flex

ural

stre

ngth

(MPa

)

0

1000

2000

3000

Flex

ural

mod

ulus

(MP

a)

Flexural strength (MPa) Modulus (MPa)0

100

200

300

400

500

600

No fiber 15 wt % 30 wt % 50 wt %Im

pact

stre

ngth

(J/m

) Partial break

Modulus of Elasticity (MOE),Bending Strength and Impact Strength of Glass reinforced

Polyurethanes

⇒ Improvement of mechanical properties (dynamic, flexural and impact)

10 wt %

50 wt %30 wt %

No fiber

100X

Impact Fractured surfaces of Glass reinforced Polyurethanes

Conclusions

Preparation of PURs from soy phosphate ester combined with petroleum-based polyol (tuning of properties).

Commercially available plant-based polyols: low OH content for preparation of RIGID polyurethanes ⇒ Glass reinforced PURs from SOPEP.

Unsaturated Polyester Resins and their Composites

ExteriorExterior (Natural Fiber(Natural Fiber--Polyester): Polyester): UnderUnder-- floor panels, engine & floor panels, engine & transmission covers

Ref.: DaimlerChrysler High Tech Report 1999

transmission covers

Classification

Unsaturated Polyester Resins

Orthoresins Isoresins

Bisphenol-Afumarates Vinyl ester

resinsChlorendics

General purpose polyester resins (Cheapest resin)

Nonwoven Hemp –Unsaturated Polyester Composites

0

10

20

30

40

50

60

70

A B C0

5

10

15

20

Tensile Strength (MPa) Tensile Modulus (GPa)

9.29

16.88

25.83

0

5

10

15

20

25

30

A B CIm

pact

Str

engt

h(J/

m)

A: Neat polyester, B: Raw Hemp (30 vol.%)-polyester, C: Surface treated Hemp-polyester

CONCLUSIONSCONCLUSIONSThermoset Thermoset resins can be effectively blended with resins can be effectively blended with functionalized functionalized

vegetable oil (Stiffnessvegetable oil (Stiffness--toughness balance)toughness balance)Different BioDifferent Bio--based based polyurethanes polyurethanes can be designed and can be designed and

engineered engineered -- -- ReinformentReinforment with biowith bio--fiber/glass fiber result fiber/glass fiber result superior superior physicophysico--mechanical properties.mechanical properties.

BioBio--Composites can Replace/Substitute Glass Fiber CompositesComposites can Replace/Substitute Glass Fiber Composites–– Energy benefitEnergy benefit–– RenewabilityRenewability, biodegradability, CO, biodegradability, CO22 sequestrationsequestration–– Independent of dwindling petroIndependent of dwindling petro--sourcessources–– ValueValue--Added Opportunity for Agriculture IndustryAdded Opportunity for Agriculture Industry

AcknowledgementsAcknowledgements

NSF-PATH (2001 Award No. 0122108)

Project GREEEN (GR01 Project GREEEN (GR01 –– 037)037)

Bayer AG, Huntsman, Johnson & Manville Bayer AG, Huntsman, Johnson & Manville

ATOFINA Chemicals ATOFINA Chemicals

Flaxcraft & HemplineFlaxcraft & Hempline

KemliteKemlite

Composite Materials & Structures Center Composite Materials & Structures Center -- MSUMSU