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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
