Preparation and characterization of mixed anhydrides of O ...
Enhancing the Sustainability of Epoxy Resins and their Fiber … · 2018. 12. 12. · Forming a...
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Enhancing the Sustainability of Epoxy Resins and theirFiber Composites
Daniel F. Schmidt*
Associate Professor of Plastics Engineering
University of Massachusetts Lowell
*Lead Research & Technology Associate
Department of Materials Research and Technology
Luxembourg Institute of Science & Technology
(since September 1, 2017)
Luxinnovation Greater Region Plastics WorkshopLuxembourg
December 4th, 2018
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Introduction
Epoxy resins find many uses Adhesives and binders
Composites
Coatings
Encapsulants and potting compounds
Nearly all epoxies are petroleum derived
Health and safety can be a concern Acute toxicity (hardeners especially)
Chronic toxicity (hardeners, bisphenols, etc.)
Recycling and reuse are extremely challenging
Many opportunities to improve sustainability!
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Selecting a Sustainable Epoxy Resin
Epoxidized Linseed Oil (ELO)
Clean, single-step synthesis Good availability (multiple large suppliers) Inexpensive (<€2/kg) Low viscosity (~1,000 cps) High functionality (f ~ 6, EEW ~ 170-180) Minimally toxic (FDA approved for food contact) Derived from a non-food crop Low reactivity (all secondary epoxies)
http://dawnofthenewage.com/wp-content/uploads/2013/01/linseed-oil-and-flax-seeds.jpg
O
O
O
O
O
O
O
O
O
CH3
O
O
CH3
CH3
O
O
H2O2
RCOOH
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Forming a Network:Anhydride Cure
Found workable with a range of liquid anhydrides Catalysis required for curing to proceed High curing temperatures necessary Homogeneous, void-free material produced Highest hardness, modulus values realized
ELO +
Ex.: Nadic Methyl Anhydride(NMA)
O
O
O
CH3
Variouscatalysts
160-200°C2-24 hr.
For more, see: Ind. Eng. Chem. Res., 2017, 56 (10), pp 2658–2666
Ind. Eng. Chem. Res., 2017, 56 (10), pp 2673–2679
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Anhydride-cured ELO:DMA & Tensile Properties
Methyltetrahydrophthalic anhydride (MTHPA) identified as optimal hardener; two catalysts studied: DBU = 1,8-Diazabicyclo(5.4.0)undec-7-ene – liquid, cures well but induces voiding during composite formation 2E4MI = 2-Ethyl-4-methylimidazole – requires pre-heating, similar cure levels to DBU but no void formation
Standard (9.6% oxirane oxygen) and high oxirane (10.4% oxirane oxygen) ELO used Control was Hexion RIM 145, a high performance anhydride-cured epoxy used in wind energy
DBU
cat
.
2E4M
I cat
.
2E4M
I cat
., high
ox.
Con
trol (
RIM
145
)
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Tem
pera
ture
(°C
)
Main relaxation (from E")
DBU
cat
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2E4M
I cat
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I cat
., high
ox.
Con
trol (
RIM
145
)
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80
100
Tem
pera
ture
(°C
)
Main relaxation (from E")
Width of main relaxation
DBU
cat
.
2E4M
I cat
.
2E4M
I cat
., high
ox.
Con
trol (
RIM
145
)
0.0
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4.0
Tensile
Modulu
s (
GP
a)
DBU
cat
.
2E4M
I cat
.
2E4M
I cat
., high
ox.
Con
trol (
RIM
145
)
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90
Bre
ak S
tress (M
Pa)
0.0
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4.0
Tensile
Modulu
s (
GP
a)
DBU
cat
.
2E4M
I cat
.
2E4M
I cat
., high
ox.
Con
trol (
RIM
145
)
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ak S
tress (M
Pa)
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Modulu
s (
GP
a)
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ak S
train
(%)
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Anhydride-cured ELO:Composite Production
Vacuum Assisted Resin Transfer Molding (VARTM) gives test coupons
Bioepoxies are ELO cured with MTHPA or NMA, catalyzed with DBU or 2E4MI
Conventional controls are Hexion RIM 135 (amine-cured) and RIM 145 (anhydride-cured), both used in wind energy
Unidirectional (UD) stitched E-glass (Saertex 955) provides reinforcement
Constituent component analysis: Fiber fraction = 52-57 vol%
Resin fraction = 42-46 vol%
Void fraction = 0.7-1.4 vol% (5.5 vol% for ELO-MTHPA-DBU)
Pump
Resin Trap
ResinMold
180°C
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UD E-glass Composites:Flexural Properties
Resin dominates transverse properties
Axial modulus is fiber-dominated, while strength is more sensitive to interface
Excessive voiding compromises properties of ELO-MTHPA-DBU in particular
ELO
-NM
A-D
BU
ELO
-MTH
PA-D
BU
ELO
-NM
A-2
E4M
I
ELO
-MTH
PA-2
E4M
I
RIM
145
RIM
135
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Fle
xu
ral S
tre
ng
th (
MP
a)
Axial
Transverse
ELO
-NM
A-D
BU
ELO
-MTH
PA-D
BU
ELO
-NM
A-2
E4M
I
ELO
-MTH
PA-2
E4M
I
RIM
145
RIM
135
0
10
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30
40
Fle
xu
ral M
od
ulu
s (
GP
a)
Axial
Transverse
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UD E-glass Composites:Flexural Properties
0.00 0.01 0.02 0.03 0.04 0.05
0
100
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600
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900
1000
1100 ELO-MTHPA-2E4MI
Str
ess (
MP
a)
Strain (mm/mm)
0
5
10
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20
25
Work
of D
efo
rmation (
MJ/m
3)
Post-fracture
Pre-fracture
ELO-N
MA-D
BU
ELO-M
THPA-D
BU
ELO-N
MA-2
E4MI
ELO-M
THPA-2
E4MI
RIM
145
RIM
135
Axial
Transverse Post-fracture
Pre-fracture
0.00 0.01 0.02 0.03 0.04 0.05
0
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Str
ess (
MP
a)
Strain (mm/mm)
RIM145
Conventional systems show catastrophic failure
Bioepoxies provide greater damage tolerance
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UD E-glass Composites:Post-fracture Analysis
RIM145 ELO-MTHPA-2E4MI
Conventional control shows strong matrix adhesion, fiber breakage
Bioepoxy shows much more debonding, implying a weaker interface
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Adding Reworkability
Montarnal et al achieve reworkability in epoxies via transesterification – Science 334 965 (2011) DGEBA / dicarboxylic acid / tricarboxylic acid
Modulus = 4 MPa
Failure stress = 9 MPa
Failure strain = 180%
DGEBA / glutaric anhydride Modulus = 1.8 GPa
Failure stress = 55 MPa
Tg ~ 80°C
Zinc acetylacetonate used as transesterification catalyst
Implication is that excess hydroxyls are needed
We successfully apply this approach to systems withoutsignificant quantities of excess hydroxyls
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Assessing Reworkability:Catalyst Screening
Static load applied to RIM 145 specimens for 4 hours
In the absence of catalysts, <4% strain is observed
In the presence of catalysts, can see up to ~70% strain
No significant changes in hardness after testing
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Assessing Reworkability:Stress Relaxation
Characteristic relaxation time (τ*) defined according to Brutman et al.(ACS Macro Lett., 2014, 3, 607)
G/G0 = 1/e τ*
Values of τ* follow Arrhenius relation in RIM 145 control
Ea ~ 95-170 kJ/mol
τ* ~ 80-500 s @ 270°C
Correlation between ln τ* and strain under static load
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Using Reworkability:Mechanical Recycling
Mechanical grinding
Reprocessing via compression molding
25 mm
Regrind 0.2 mm Regrind Composite
25 mm
Regrind 2 mm
25 mm
Regrind 5 mm
25 mm
Pristine cast resin
Regrind 5 mm
Regrind 2 mm
Regrind 0.2 mm
Regrind Composite
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Using Reworkability:Mechanical Recycling
Pris
tine
Cas
t Res
in
Reg
rind
5 m
m
Reg
rind
2 m
m
Reg
rind
0.2
mm
Reg
rind
Com
posi
te
Reg
rind
Com
posi
te +
2 m
m
0
1
2
3
4
5
6
7
8
9
E' a
t 2
3°C
(G
Pa
)Pr
istin
e C
ast R
esin
Reg
rind
5 m
m
Reg
rind
2 m
m
Reg
rind
0.2
mm
Reg
rind
Com
posi
te
Reg
rind
Com
posi
te +
2 m
m
0
1
2
3
4
5
6
7
8
9
E' a
t 2
3°C
(G
Pa
)
0
10
20
30
40
50
60
70
T (°C
)
Modulus and Tα are mostly retained regardless of particle size(similar results in bioepoxy systems)
Stress and strain at failure are highest with finest particle size
Pris
tine
Cas
t Res
in
Reg
rind
5 m
m
Reg
rind
2 m
m
Reg
rind
0.2
mm
0
10
20
30
40
50
60
70
Str
es
s a
t F
ailu
re (
MP
a)
Pris
tine
Cas
t Res
in
Reg
rind
5 m
m
Reg
rind
2 m
m
Reg
rind
0.2
mm
0
10
20
30
40
50
60
70
Str
es
s a
t F
ailu
re (
MP
a)
0
1
2
3
4
Stra
in a
t Fa
ilure
(%)
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Using Reworkability:Chemical Recycling
Composite: RIM145 / E-glass
Solvent: 1-Dodecanol
Catalyst: n-butyltin tris(2-ethylhexanoate)
Heated for 12 hours
Cleaned in solvent, then water
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Using Reworkability:Chemical Recycling
Reclaimed E-glass composite
Reclaimed E-glass fibers
Stiffness entirely retained
Strength reduced, likely due to changes in fiber sizing
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Using Reworkability:Chemical Recycling
0
100
200
300
400
500
600
700
0
10000
20000
30000
40000
50000
60000
Fle
xura
l Str
en
gth
[M
Pa]
Fle
xura
l Mo
du
lus
[MP
a]
Flexural Modulus and Flexural Strength
Flexural Modulus
Flexural Strength
Bioepoxy / E glass
Bioepoxy /
carbon
Can improve properties with reclaimed fibers in bioepoxies(!)
Rate of chemical recycling is much faster as well
Fle
xu
ral
Mo
du
lus (
MP
a) F
lex
ura
l Stre
ng
th (M
Pa
)
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Using Reworkability:Reuse via thermoforming
Flat sheet of RIM 145 epoxy resin preparedin the presence of transesterification catalyst
Sample placed in tooling, heated to rework temperature, pressure applied
Sample cooled in water to yield rigid, permanently deformed epoxy part!
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Summary & Conclusions
Anhydride-cured structural thermosets successfully produced based solely on epoxidized linseed oil (ELO)
Bioepoxy composites provide good mechanical properties
Results are competitive with highly optimized controls
Bioepoxy composites are more damage tolerant than controls
Interfacial debonding, lower axial strength imply weak interface
Performance may be improved via optimization of fiber sizing
Transesterification catalysts enable recycling and reuse
Mechanical recycling demonstrated, particle size effect noted
Chemical recycling demonstrated, reclaimed fibers give high performance composites, especially effective with bioepoxies
Thermoforming demonstrated, promises reuse of existing parts
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AcknowledgementsCollaborators and Group Members
Assoc. Prof. Emmanuelle Reynaud (UML Mechanical Engineering)
Chris Kuncho (PhD), Wenhao Liu (PhD), Johannes Möller (PhD),Julia Kammleiter (MS), Julia Stehle (MS), Dr. Akshay Kokil
Financial Support
National Science Foundation (Award #1230884)
Massachusetts Toxics Use Reduction Institute
Materials and Analytical Support
ACS Technical Products (Epoxidized linseed oil)
Huntsman Advanced Materials (MTHPA)
Hexion (RIM 135 & 145)
General Support
W. Liu, Dr. A. Kokil & the Reynaud-Schmidt Research Group
P. Casey, Dr. E. Ada & the UML Core Research Facilities
D. Rondeau, M. Shone, Dr. X. Chen, Prof. S. Johnston,UML Plastics Engineering and the UML Composites Lab
FOR MORE INFORMATION:ACS Symp. Ser., 2018, vol. 1310, ch. 18, pp 281-295
THANK YOU FOR YOUR ATTENTION!