recruiting trip 2010
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The Fundamentals of Advanced Materials: A Novel
Triazole Resin for
Low Temperature-Cure‑
Irene Gorman and Robson Storey
School of Polymers and High Performance Materials
The University of Southern Mississippi
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OutlineOutline IntroductionIntroduction Polymer basicsPolymer basics
Polymerization typesPolymerization types
CompositesComposites
MatricesMatrices
Click ChemistryClick Chemistry
Synthesis of azide resinSynthesis of azide resin Alkyne crosslinkersAlkyne crosslinkers
Reactivity differencesReactivity differences
Activation EnergyActivation Energy AverageAverage
Change with conversionChange with conversion Comparison to industry standardComparison to industry standard
ExothermExotherm
AdhesionAdhesion
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What is a Polymer? What is a Polymer?
Gasoline= 4 units
Wax= 12 units
Polyethylene= 40,000 units
EthyleneMonomer
CH2 CH2
Polymer- a macromolecule (large molecule) made of many small molecules linked chemically
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Polymer ClassificationPolymer Classification
PolymersPolymers
NaturalNatural SyntheticSynthetic
ChainChain
GrowthGrowth
StepStep
GrowthGrowth
FreeFree
RadicalRadicalCationicCationic AnionicAnionic
RingRing
OpeningOpeningCondensationCondensation
Chain Growth: A* + A AA* + A AAA* . . .
Step Growth: AA + BB AABB + AABBAA AABBAABBAA . .
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Natural PolymersNatural polymeric materials have been used
throughout history for clothing, decoration,shelter, tools, weapons and writing materials
Examples of natural polymeric materials StarchCelluloseProteinHair SilkDNA and RNARubber
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Synthetic Polymers
The first fully synthetic polymers werephenol-formaldehyde polymers,Bakelites, manufactured by Bakelandin the 1900s.
The 1930s and 1940s provided the backdrop for the discoveryof many important polymers Melamine Polymers (Formica)
Neoprene Rubber
Polystyrene
Polyethylene Nylon 6,6
Polytetrafluroethylene (Teflon)
Polymethylmethacrylate (Plexiglass)
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CondensationCondensation
PolymerizationPolymerization
CH3 O C
O
C O CH3
O
OH CH2 CH2 OH+
CH2 O C
O
C O CH2
O
CH2 O H
dimethly terephthlate ethylene glycol
polyester
2nCH3OHCH2HO
n
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Addition Polymerization Addition Polymerization
CH3
O
CH3
O
C C
OO
OO OO CC
CH3
CH3
CH3
CH3
H3C CH3
∆2 H3C C
CH3
CH3
O O C
O
OC
CH3
CH3
H3C2 2CO2+
OC
CH3
CH3
H3C OC
CH3
CH3
H3C
H2
C C
CH3
C
O
CH3
O
OC
CH3
CH3
H3CH2C C
CH3
C
O
CH3
O
CH3
O
CH3
O
H2C C
CH3
O
CH3
O
n
di-t -butly peroxyoxalate carboxyl radicals
methyl methacrylate acrylic radical
growing chain polymethyl methacrylate
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Describing PolymersDescribing Polymers
Molecular Weight:Molecular Weight:
Number Average
Mn =ΣniMi
Σni
Weight Average
Mw =ΣniMi
2
ΣniMi
Polydispersity Index
PDI =Mw
Mn
ThermalThermal
Transition:Transition:
Tg
Sharp Tm
Tg
Broad Tm
t e m p e r a
t u re
t e m p e r a
t u re
Crystalline polymer Amorphous polymer
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Polymer Applications
Sports Equipment
Military/Police
Protection
Fibers Plastics
Adhesives
Cosmetics
Oil Industry Rubber
Electronics
Textiles/Clothing
Water Treatment
Biomedical
Pharmaceutical
Automotive
Aerospace Coatings
Paper
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Medical, PharmaceuticalMedical, PharmaceuticalMedical, PharmaceuticalMedical, Pharmaceutical
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Electrical, ElectronicElectrical, ElectronicElectrical, ElectronicElectrical, Electronic
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Aerospace, Marine
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15
Composites
Composite: consisting of two or more distinctparts, which remainseparate and distinct on
a macroscopic level.
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Fiber-Polymer Composites
Matrix Material
Fiber
Types of Fibers:
•Glass
•Graphite
•Boron
•Silica
•Kevlar
Matrix Function:
•Bind the fibers together
•Transfer the load to the fibers
•Protect the fibers from environmental damage
•Enable the formation of materials stronger than the individual parts
{ 5-500μm
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Polymer Matrices
Thermoplastics High Mw chains
Association through
Hydrogen bonding, van der Waals forces,dipole-dipole, aromatic stacking
Flow upon heating
Polystyrene, polyethylene, nylons,polycarbonate, polyacetals
Thermosets Crosslinked network
Cannot be softened or melted
Epoxides, polyesters,phenolics, ureas, melamine,silicones, polyimides
13700 260 650 110
0Temperature Range °C
Polymer
Composites
Metal
Composites
Glass
Composites
Ceramic &
Carbon-
Carbon
Composites
Tuttle, M. E., Structural Analysis of Polymeric Composite Materials. Marcel Dekker: 2004; p 1-41.
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Elevated Cure
Initial Cure Post Cure
heat
Considerations
•Tg rises as crosslinking progresses
•Once Tg surpasses the temp of the reacting mass, crosslinking stops
•Elevated, post-cure, temperatures are needed for high crosslink density
•If the system’s temp could be increased, by virtue of highly exothermic
crosslinking reaction, then higher crosslink density would be achieved prior to
vitrification
Morgan, P., Carbon Fibers and Their Composites. Taylor and Francis: Boca Raton, 2005; p 501-544
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Click Reactions
R'
"RO R'OR"
O
R'
Nuc
HO
R'
N
R'
"RO
N
NN
R'
"R
R"-N3
Cu(I)
[O] Nuc
R"O-NH3
Requirements
•easy to perform
•work-up
•high yielding
•tolerant to oxygen & water
•high thermodynamic driving force
(>20 kcal/mol)
Kolb, H. C.; Finn, M. G.; Sharpless, K. B.; Angewandte Chemie International Edition 2001, 40, 2004-2021.
H i
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N N N
R1
H R2
N
N N
N
N N
R2
R1 R1
R2
+Thermal
Cu(I)
N
N N
R2
R1
1,4 regioisomer 1,5 regioisomer
R-N3 =
1 1a 1b 1c 1d
N
R N N
N
R N NN
R N N
N
R N N
•Proceeds at low temp,
even room temp•Extremely exothermic
•Azides are highlyenergetic,
explosive
•Easily dissociate intonitrene & dinitrogen
Brase, S.; Gil, C.; Knepper, K.; Zimmermann, V., Angew. Chem. Int. Ed. 2005, 44, 5188-5240.
Kolb, H. C.; Finn, M. G.; Sharpless, K. B., Angewandte Chemie International Edition 2001, 40, 2004-2021.
Huisgen1,3-Cycloaddition
i l
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Epoxy Triazole CureEpoxy Triazole Cure
(Azido/Alkyne Reaction)(Azido/Alkyne Reaction)
C O
CH2 CH
CH2
O
CH2CH
CH2
CH3
CH3
O O
Na N3+
C O
CH2 CH
CH2
O
CH2CH
CH2
CH3
CH3
O O
NH4Cl
+ H
+ NaCl + NH3
N3 N3
C O
CH2 CH
CH2
O
CH2CH
CH2
CH3
CH3
OH OH
N3 N3
70/30 v/v
2-Ethoxyethanol/H2O ∆ 130 C°
4 h Highly exothermicHighly exothermic
higher crosslinkhigher crosslinkdensity prior todensity prior tovitrificationvitrification
Proceeds at lowProceeds at low
temp, even roomtemp, even roomtemptemp Easy scale-upEasy scale-up
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Alkyne Crosslinkers
N
O
N
TPJeff (solid)
n
N
TPA (liquid)
TPEDA (liquid)
N N
OO
O
OO
O
TMBTP (solid)
O
O
O
O
4
TEGDP (liquid)
O
O
4
TEGDPE (liquid)
O
O
O
ODPA (liquid)
OO
O
TMTP (solid)
O
O
O
Amine Propargyl Propiolate
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Linear Chain ExtensionLinear Chain Extension
C O
CH2
CH
OO
CH2
CH
N
O
CH3
CH3
N
NN
H
C
NN
H
C O
CH2
CH
H2C
O
CH2
CH
CH2
CH3
CH3
HO OH
N3
N3
CH2
CH2
O
O
CH2
CH2
O
C
C
HC
O
C
C
CH
O
+
O
CH2
CH2
O
O
CH2
CH2
O
C
O
CH2
CH2
C
O
CH2
O
CH2
CH2
C
O
CH2
O
CH2
CH2
C
O
CH2
O
C
HC
CH2
CH2
C
O
CH2
C
CH
O
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Propiolate vs. Propargyl
A A i i
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Average ActivationEnergies
AE (kJ/mol)
TMBTP 69.21
HDA 70.03
TEGDP 72.28
TMPTP 73.55
DPA 82.32
TMPTPE 82.51
TPDDS 82.62
TEGDPE 83.33TPEDA 84.32
TPA 84.72
TPJeff 85.88
TPTM 86.37
Distinct difference betweenpropiolate x-linkers &amine, propargyl types Resonance structure
N
Amine
O
O
Propargyl
O
Propargyl Ether
O
O
Propiolate
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P
3
CuBr
NN
Cu
Cl Cl
Bromotris triphenylphosphine Cu(I)
Dichloro (1,10-phenanthroline) Cu(II)
Copper(II) ethylhexonate
H3C O
O
H3C2
Cu2+
Catalysis w/ Cu(I) &Cu(II)
Cu(I) &Cu(II) activity function of solubility,not oxidation state
-2
0
2
4
6
8
10
12
14
16
H e a t F l o w ( W
/ g )
-50 0 50 100 150 200 250 300
Temperature (°C)
un-catalyzed
1 mol % BTTPP
3.5 mol % BTTPP
5 mol % BTTPP
5 mol % CEH
5 mol % DCP
Exo Up Universal V4.3A TA Ins
Ch i A ti ti
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Changes in ActivationEnergy
Averaged kinetic data does notaccount for mechanistic changes Temperature, extent of conversion
Problematic for complex systemsEpoxy, catalyst
OOHO
N3
OH
N3
O
O
O
O
3
Tetraethylene glycol dipropiolate (TEGDP)
O
O
3
Tetraethylene glycol diproargyl ether (TEGDPE)
+ or Copper(II) ethylhexonate (CEH)
H3C O
O
H3C 2
Cu2+
Room Temperature5 min
CH3
CH3
A ti ti E
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Activation Energy vs.Conversion
0 50 100
68
70
72
74
76
78
80
82
84
86
88
90
92
94
96Catalyzed FWO Model
TEGDP
TEGDPE
E a
( k J / m o l )
α0 50 100
64
66
68
70
72
74
76
78
80
82
84
86
88
90
92
94
96
98
100
102Un-catalyzed FWO Model
TEGDP
TEGDPE
E a
( k J / m o l )
α
0 50 100
70
80
90
100
TEGDPE FWOModel Uncatalyzed
Catalyzed
E a
( k J / m o l )
α
0 50 100
64
66
68
70
72
74 TEGDP FWO ModelUncatalyzed
Catalyzed
E a
( k J / m o l )
α
C i D k
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Comparison: Derakane510A-40 to BPA Azide-TMPTP
77.88°C
255.54°C
126.25°C
-0.5
0.0
0.5
1.0
1.5
2.0
H e a t F l o w ( W / g )
0 50 100 150 200 250 300 350
Temperature (°C)
Azide EPON + TMPTP
Control Derakane
Exo Up Universal V4.2E TA Instruments
O
O
O
O
O
O
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Comparison: Isothermal 45°C
0.0
0.1
0.2
0.3
0.4
H e a t F l o w ( W / g )
0 20 40 60 80 100 120
Time (min)
Control Derakane
Epon Azide + TMPTP
Exo Up Universal V4.2E TA Instruments
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Adhesion to Glass
BPA-Azide
Derakane
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ConclusionsExothermic for low
temp cure
Customizable
catalystvariety of alkyne
crosslinkers
Superior adhesion to
glass (qualitative)
Future WorkDetermine
regioisomer linkage
Conduct mechanicaltest on cured resin &composite materials
Quantitativelymeasure adhesion
Synthesis of newazide compounds
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School of Polymers & HighSchool of Polymers & HighPerformance MaterialsPerformance Materials
Graduate degrees are in Polymer Science and Engineering
12.9 million in funding
2009-10 enrollment
59 B.S. majors
77 Graduate students23 Postdoctoral fellows
Tuition waived
Up to 25,000 dollar stipend
Health insurance
Preparing for
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Preparing forGraduate School
Seniors Prepare for & take the GRE
Research graduate programs Consider program focus
Read up on faculty research Scholarships/stipends
Apply Letters of recommendation
Personal statement
Visit schools Talk to graduate students
Is there a fit?
Under-classman Consider academic
requirements
Research Experience for
Undergraduates (REU) Graduate school test run
Research experience
Publications
PSC Ph D R dPSC Ph D R d
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PSC Ph.D. RoadmapPSC Ph.D. Roadmap
GuidelineGuideline
August2010
December 2014
Select
Advisor
RESEARCH
ResearchProspectus
ResearchProposal Defense
1 2 3 4
Exams
Sh lb F l d ThSh lb F l d Th
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Shelby Freland ThamesShelby Freland ThamesPolymer Science ResearchPolymer Science Research
CenterCenter
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$30MM Research Center Includes 6.6MM addition that opened April 2004
104,000 sq. ft.Teaching Facilities
Classrooms, auditorium, conference rooms Research laboratories Major scientific instrumentation Polymer processing and fabrication facility Coatings formulation, processing, and
characterization
PSRC AdditionPSRC Addition
I t e tatioInstrumentation
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500MHz Multi-Nuclear NMR 500MHz Multi-Nuclear NMR InstrumentationInstrumentation
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Composite FabricationComposite Fabrication
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Department of Polymer Science founded by Dr. ShelbyF. Thames in 1970
Elevated to School of
Polymers and HighPerformance Materials in 1999
History History
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Faculty Research AreasFaculty Research Areas
• Biopolymers and biomimetic
polymers• Pharmaceutical polymers
Polymer Engineering
Coatings and Films
Biomedical Research
Polymer Synthesis
Formulation Science
Water-SolublePolymers
• Polymer composites• Nanoengineered materials• Membranes and fuel cells• Polymer processing and
rheology• Stimuli/-Responsive Systems• High solids, waterborne and
solvent based systems• “Green” coatings• Polymer photochemistry
• Controlled free radical
polymerization• Living polymerization• Functional polymers• Biodegradable materials
• High throughput screening
• Controlled activity• Surface assembly
• Colloid science
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l d h
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Selected Research PartnersSelected Research Partners
Sports and High
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Sports and HighPerformance Materials
B i o m
e c h a n i c s &
K i n e s i o l o g y E x e
r c i s e &
H u
m a n
P h y
s i o l o g
y
Polymer Science
SHPM
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2010 REU Summer Program
To apply:Online application:
http://www.usm.edu/polymer/Summer_research.php
Official transcriptTwo letters of recommendation
2010 Research Experience for UndergraduatesJune 1st – August 6th, 2010
Deadline: March 19th, 2010
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Why Southern Miss?
− Polymer Science & Engineering
− School of Human Performance
− Synergistic Research Opportunity
− Carnegie Research Extensive University
− Leverage DoD Research Relationships
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Outdoor Activities
40 mi Paved Trail 41 mi Hiking Trail 12 Golf Courses Canoeing Coast
Desoto NationalForest
Disk Golf Paul B. Johnson
State Park
Zoo Hunting Fishing
Mardi Gras
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Mardi Gras
h i b llS h i b ll
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Southern Miss FootballSouthern Miss Football
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QUESTIONSQUESTIONS
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Anionic Polymerization Anionic Polymerization
KNH2NH3 K + H2N
H2N +
C
H2N
H2C C
CH2
C +
H H
H
H
H2C C
Hn
polystyrene
C
H
H
H H
growing chain
styrene
free ions
carbanion
potassiumamide
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Bio InspiredBio Inspired
BiomimeticBiomimetic
Drug DeliveryDrug Delivery
BiopolymersBiopolymersBiocompatibleBiocompatible
Poly-DrugsPoly-Drugs
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MarineMarineRoom Temperature Cure MatricesRoom Temperature Cure Matrices
Fire / Flame / Smoke RetardantsFire / Flame / Smoke Retardants
Matrix KineticsMatrix Kinetics
VARTMVARTMCarbon-Fiber CompositesCarbon-Fiber Composites
l
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Personal Care