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http://nano.materials.drexel.eduDANOTECHNOLOGY
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Carbide-Derived Carbons for Energy-Related and Biomedical Applications
Yury GogotsiA.J. Drexel Nanotechnology Institute and
Dept. Materials Science & Engineering, Drexel University, Philadelphia
Polytechnic U, April 23, 2007
The A.J. Drexel Nanotechnology Institute oversees education, research, collaboration, commercialization, and communication activities in the interdisciplinary field of nanotechnology for Drexel University.
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Current Research Projects
• Nanotubes, Nanocones, and Nanowires Y. G., et al, Science, v. 290, 317 (2000)
• Nanotube-Based Nanofluidic DevicesY. G., J. Libera, A. Yazicioglu, et al., Appl. Phys. Lett.,v. 79, p.1021 (2001)
• Nanotube-Reinforced PolymersF. Ko, Y. G., A. Ali, et al., Adv. Mater., v. 15, 1161 (2003)
• Nanodiamond Powders and CompositesS. Osswald, G. Yushin, V. Mochalin, S. Kucheyev, Y. G., J. American Chemical Society, v. 128, 11635 (2006)
• Nanoindentation Testing Y. G., A. Kailer, K.G. Nickel, Nature, v. 401, 663 (1999)
• Raman Spectroscopy and Electron MicroscopyP.H. Tan, S. Dimovski, Y.G., Phil. Trans. Royal Soc. Lond. A, 362, 2289 (2004)
• Carbide-Derived Carbons for Energy-Related and Other ApplicationsY. G., S. Welz, D. Ersoy, M.J. McNallan, Nature, v. 411, 283 (2001) J. Chmiola, G. Yushin, Y.G., et al., Science, v. 313, 1760 (2006)
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Carbon Nanomaterials: Ternary Bonding Diagram
Nanodiamond
Nanotubes
Fullerenes
Hydrocarbons
spn
Corannulene
CumuleneAdamantane
Carbyne (sp1)Diamond (sp3)
Graphite (sp2)
Adapted from M. Inagaki, New Carbons, 2000Heimann et al., Carbon, 1997
sp3+sp2+spamorphous carbon,DLC, glassy carbon,
carbon black, etc.
sp3+sp2+spamorphous carbon,DLC, glassy carbon,
carbon black, etc.
spn, (1<n<3, n=2)
Classification based on:-hybridization type of C atoms -characteristic size of clusters
Classification based on:-hybridization type of C atoms -characteristic size of clusters
Fullerene family
sp2 +
Csp + 2sp3
=C=C=
Nanosizedmorphology of graphite-based
materials
Ovalene
Car
bon
whi
sker
s,
cone
s an
d
poly
hedr
al
crys
tals
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Nanotechnology
A new material, process, or device must offer a net increase in economic utility if it is to be considered successful.
John J. Gilman, Mater. Res. Innov., v. 5, 12 (2001)
“Ideal” Nanotechnology Process:
•Control over the structure on the atomic level •Ability to generate desirable structures•Self-assembly•Low-cost/high-volume production
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TiC(s) + 2 Cl2(g) = TiCl4(g) + C(s) (Gº = - 434.1 kJ/mol at 950°)
c(g)22c
ba MClaCbClCM ; M = metal (or Si or B)
Carbide-Derived Carbon (CDC) Process
2 nmSiC 2 nm
Carbide: Porosity = 0 % CDC: Porosity = 57 %
Cl2
( 200 - 1200oC)
2 methods of pore size control:1.) Precursor choice2.) Synthesis conditions
G. Yushin, A. Nikitin, Y. Gogotsi, in Nanomaterials Handbook Y. Gogotsi, Ed. (CRC Press, 2006)
Reaction valid for most carbides - huge number of possible precursors
B.D. Shaninaa, S.K. Gordeev , A.V. Grechinskaya et al., Carbon (2003) J. Leis, A. Perkson, M. Arulepp, M. Kaarik, G. Svensson, Carbon (2001)
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2
Cl2HCl
Ar
1 Flowmeters2 Resistance furnace3 Quartz reaction tube4 Quartz boat with sample5 Sulfuric acid
T=200-1200°C; Ambient pressure
Chlorination Set-up
Large-scale production alternatives: Fluidized-bed furnace or rotary kiln reactor
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CDC: Powders, Films, Fibers, Bulk
CDC coated SiC Tyranno fabric
Bulk CDCfrom sintered
SiC
CDC coateddynamic seals
d=3 cm
Amorphous Carbon Whisker
200nm CDC from SiC whisker
Powder
Z.G. Cambaz, G. Yushin, Y. Gogotsi, J. Am. Ceram. Soc., 89, 509 (2005)
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Market Opportunities* Supercapacitors – up to $ 2B
Gas storage (hydrogen, methane, chlorine, etc.) - $1-50B
Adsorption/separation of proteins (bio-fluids’ purification / blood cleansing etc.) - $0.2-10B
Poisoning treatment - $0.04-1B
Protective respiratory equipment and suits – up to $4B
Water purification / desalination membranes - up to $2B
Portable desalination units
Filters (gas separation / indoor air quality/ etc.) - up to $2B
Others (tribological applications, catalyst support, etc.)
* Addressable (not necessarily current) market. Data taken from Frost & Sullivan and other business databases
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Positions and spatial distribution of carbon atoms in the carbide affect the structure and pore size/shape of CDC
Carbide Lattice – Template for CDC
G. Yushin, A. Nikitin, Y. Gogotsi, Carbide Derived Carbon, in Nanomaterials Handbook., Y. Gogotsi, Editor. 2006, CRC Press
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G. Yushin, A. Nikitin, Y. Gogotsi, in Nanomaterials Handbook, ed. by Y. Gogotsi (CRC Press, 2005)
Carbide Lattice – Template for CDC
0 1 2 3 4 5 6 70.0
0.1
0.2
0.3
0.4
Por
e vo
lum
e (c
c/nm
/g)
Pore size (nm)
Ti3SiC2-CDC (1200°C) SiC-CDC (1200°C)
0 1 2 3 4 5 6 7
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Por
e vo
lum
e (c
c/nm
/g)
Pore size (nm)
Pore-size distributions calculated using DFT model
Ar sorption at 77 KAutosorb-1
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Gogotsi, Y., et al., Nature Materials, 2, 591 (2003)
0.1 1 10 100
Dm=0.51 nm
Dm=0.58 nm
300 400 500 600 700 8000.5
0.6
0.7
0.8
P
ore
siz
e (
nm
)
Temperature of synthesis (°C)
Po
re v
olu
me
(a
.u.)
Pore size (nm)
Dm=0.64 nm (T=700oC) dD/dT ~ 0.0005 nm/o C,
or: +/- 10o C temperature control - better than 0.1 Å pore control.
Tunable Pore Size in CDC
Choice of starting material and synthesis conditions gives an almost unlimited range of porosity distributions
High surface area Uniform pores
Ti3SiC2 -CDC
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R.E. Smalley MRS Bulletin 30, 412-417 (2005)
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H2 liquid at 20K
105 liters
H2 gas at 1 atm.
pressure,25oC
> 48,000 liters
DOE target67 liters
Volume of 4 kg of hydrogen stored in different ways
L. Schlapbach and A.Zuttel, Nature, 2001, v.,414, p. 353
DOE Target (by 2010)6.5 wt.%60 kg/m3
Note: DOE target is system target and will include the density of accessories depending on the materials requirement
CDC for H2 Storage
H2 at 5,000psi 200 liters
A hydrogen fuel cell (internal combustion engine) car will require 4 (8) kg or 225 (450) liters of hydrogen to travel 400 km.
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CDC for H2 Storage: Cryo-adsorption
50 55 60 65 70 75 800
2
4
6
8
10
12
14
assuming liquid H2
filling all the pores
Max
. H2 s
tora
ge p
ossi
ble,
wt.%
Carbon pore volume, %
assuming solid H2
filling all the pores
Weak interaction between H2 and adsorbent (e.g.
isosteric heat of H2 adsorption is ~ 5 kJ/mole on plan graphite and 5-7 kJ/mole on MOF, which is too weak for RT adsorption)
Challenges:
MOF*
Nanoporous Carbon
Candidates:
* O. Yaghi, et al. , J. Am. Chem. Soc., 128, 3494 (2006)
Y. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005)
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0 300 600 900 1200 1500 1800 2100 24000.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
Linear fit (y = 0.00118x +0.1053) R = 0.93
Activated carbon Activated carbon fibers Carbon nanotubes Carbon nanofibers
Gra
vim
etric
den
sity
, wt%
H2
Specific surface area, m2/g
“Hydrogen storage is proportional to specific surface area”Schlapbach et al. Nature 2001, Agarwal et al. Carbon 1987, Nijkamp et al. Applied Physics A 2001
77K1 atm
CDC for H2 Storage: Cryo-adsorption
Specific surface area of ~5750 m2/g will be required for reaching 6.5 wt.%.
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0 300 600 900 1200 1500 1800 21000.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
3.2 TiC-CDC ZrC-CDC SiC-CDC B
4C-CDC
Activated carbon Carbon nanotubesG
ravi
met
ric d
ensi
ty, w
t% H
2
Specific surface area, m2/g
Large variation for similar surface area
H2 storage is NOT proportional to SSA
Linear fit
77K1 atm
CDC for H2 Storage: Cryo-adsorption
Y. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005)
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0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6 TiC-CDC ZrC-CDC SiC-CDC B4C-CDC
H2
wt.
% p
er u
nit
SS
A,
Pore size, nm
.103
m2
wt%
.g Small pores are more efficient than large ones for a given SSA
SSA of ~3000 m2/g will be needed for 7wt% storage - FEASIBLE!
Empty symbols: H2 treated samples
Y. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005)
CDC for H2 Storage: Cryo-adsorption77K
1 atm
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CDC for H2 storage: Cryo-adsorption
0.1 0.2 0.3 0.4 0.5
1.0
1.5
2.0
2.5
3.0
Gra
vim
etr
ic c
ap
aci
ty,
wt.
% H
2
Volume of pores below 1 nm, cc/g
large volume and SSA of pores above 1 nm
0.0 0.2 0.4 0.6 0.8
1.0
1.5
2.0
2.5
3.0
Gra
vim
etr
ic c
ap
aci
ty,
wt.
% H
2
Volume of pores above 1 nm, cc/g
77K1 atm
Large volume of pores < 1 nm needed for high storage capacityDensity of gaseous H2 innano-pores can be higherthan density of liquid H2 J. Jagiello et al.,
J. Phys. Chem. B, in press (2006), Q. Wang et al., J. Chem. Phys. 110, 577-586 (1999)
Samples with modest SSA (< 1300 m2/g) but with small pores substantially outperformed others with SSA > 2300 m2/g but having wider PSD
if all these poresfilled with liquid H2
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CDC for H2 storage: Cryo-adsorption
20 40 60 80 100 120
5
6
7
8
9
10
11
TiC-CDC (1000oC)
TiC-CDC (800oC)
SWCNT
Isot
eric
Hea
t of
ads
orpt
ion,
KJ/
mol
Volume adsorbed, cc/g
MOF
stQRT
P
)(
)(ln12
)(ln
RT
H
T
P vap
Obtained from isotherms @ 77, 88, and 300K using Clausius-Clapeyron Equation
6.2 6.4 6.6 6.8 7.0 7.2 7.41.0
1.2
1.4
1.6
1.8
2.0
2.2
Heat of adsorption, kJ/mol
wt%
.g.1
0-3
m2
H2 w
t.% p
er B
ET
SS
A,
Small pores increase the interaction with H2 and thus result in higher H2 coverage of the sorbent surface
CDC demonstrate stronger interaction with H2 than CNT and MOF
G. Yushin et al., Advanced Functional Materials, 16, p. 2288-2293 (2006)
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S.K. Bhatia, A.L. Myers, Langmuir (22) 1688-1700 (2006)
Optimum Isosteric Heat of Hydrogen Adsorption Assumptions: (1) homogeneous adsorbent and Langmuir isotherm
(2) delivery and storage at the same temperature (RT) (3) minimal storage in adsorbent-free volume (justified at RT)
Delivery (K, Pdelivery, Pstorage) = storage
storage
delivery
delivery
KP
nKP
KP
nKP
11
where: n = number of sorb. sites; equilibrium constant 0
00 1)exp()exp(
PRTH
RSK
-ΔHo = heat of adsorption; ΔSo = entropy change relative to standard pressure (1 atm)
Max Delivery:
20
00 ln2 P
PPRTSTH storagedelivery
optimum
Pstorage=30 atm, Pdelivery=1.5 atm; ΔSo ~8R:
-ΔHooptimum= 15.1 kJ/mol 10 100 1000
6
8
10
12
14
16
18
1000 atm.Opt
imum
Hea
t of
Hyd
roge
n A
dsor
ptio
n
Storage pressure, atm.
storage and delivery at room temperature (298 K) delivery at 1.5 atm
30 atm.
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CDC for Protein Adsorption
Grand challenge - Sepsis
Severe sepsis kills 1,500 people/day (comparable to lung and breast cancer (~ 2,700 and ~ 1,100 people /day, respectively)
Sepsis > $ 17 billion / year in the US
Inflammatory response is driven by a complex network of cytokines, inflammatory mediators
Cytokine removal from blood brings under control the unregulated pro- and anti-inflammatory processes driving sepsis
Hydrogen
TNF-α 9.4 x 9.4 x 11.7 nm
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CDC for Protein Adsorption
5 10 15 20 25 30 350.0
0.1
0.2
Ti3AlC
2- CDC @ 600oC
dV, c
c/nm
/gdV
, cc/
nm/g
5 10 15 20 25 30 350.0
0.1
0.2
Ti3AlC
2 - CDC @ 800oC
5 10 15 20 25 30 350.0
0.1
0.2
0.3
0.4
Ti3AlC
2 - CDC @ 1200oC
5 10 15 20 25 30 350.0
0.1
0.2
Pore width, nmPore width, nmPore width, nm Pore width, nm
Ti2AlC - CDC @ 600oC
5 10 15 20 25 30 350.0
0.1
0.2
Adsorba
5 10 15 20 25 30 350.0
0.1
0.2
CXV
5 10 15 20 25 30 350.0
0.1
0.2
Ti2AlC - CDC @ 800oC
5 10 15 20 25 30 35 400.0
0.1
0.2
0.3
0.4
Ti2AlC - CDC @ 1200oC
PSD in the 1.5 - 36 nm range obtained from N2 sorption isotherms: commercial carbons and CDC from MAX phase ternary carbides
G. Yushin, et al. Biomaterials, 27, 5755 , 2006
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CDC for Cytokine* Adsorption
100
1000
Control TNF-
TN
F-
con
cent
ratio
n, p
g/m
l initial 5 min 30 min 60 min
Adsorba CXV Ti3AlC
2 - CDC Ti
2AlC - CDC
1200oC600oC 800oC 1200oC600oC 800oC
100
1000
1200oC600oC
IL-6
con
cent
ratio
n, p
g/m
l
initial 5 min 30 min 60 min
Adsorba CXV Ti3AlC
2 - CDC
800oC
Control IL-6
1200oC600oC 800oC
Ti2AlC - CDC
* cytokines are regulatory proteins that are released by cells of the immune system and need to be removed from the blood in case of an autoimmune disease.
TNF-α
IL-6
CDC outperformed commercial carbons in the efficiency of cytokine’s removal
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CDC for Cytokine Adsorption
Adsorption depends on the SSA of adsorbents accessible by cytokines
G. Yushin, et al. Biomaterials, 27, 5755 , 2006
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CDC for Cytokine Adsorption
proteins adsorbed on the surface proteins adsorbed on the surface and in the mesopores
G. Yushin, et al. Biomaterials, 27, 5755 , 2006
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• Store charge electrostatically as charged ions “adsorbed” to oppositely charged surfaces
• No charge transfer reactions take place, eliminating many shortcomings of traditional batteries
• High specific surface area that is accessible to the electrolyte is crucial - porosity control is a requisite for high performance
• ELECTRODE OPTIMIZATION CRUCIAL FOR MAXIMIZING PERFORMANCE
Supercapacitors
Supercap schematic
B. E. Conway, Electrochemical Capacitors: Scientific Fundamentals and Technological Applications, Kluwer, (1999).
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Supercapacitors bridge between batteries and conventional capacitors
Supercapacitors are able to attain greater energy densities while still maintaining the high power density of conventional capacitors.
Supercapacitors are a potentially versatile solution to a variety of emerging energy applications based on their ability to achieve a wide range of energy and power density.
*Halper, M.S., & Ellenbogen, J.C., MITRE Nanosystems Group, March 2006
Ragone plot of energy storage systems*
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Supercapacitors: Market Segmentation
Total addressable market size in 2012 ~$2 Billion The largest part – applications in Hybrid Electrical Vehicles
2005 2006 2007 2008 2009 2010 2011 2012 20130
200
400
600
800
1000
1200
1400
1600
1800
2000
EV Market Mobile Device Market UPS Market Military Market Specialty Market
Ma
rke
t ($
Mill
ion
s)
Year
Uninterruptible Power Supplies and Power Quality
Mobile devices
Aerospace applications
Defense applications
Vehicles with electrical or hybrid motors (EV)
CAGR = 50%
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Traditional View: Increasing Pore Size Increases Specific Capacitance
Energy ~ C
Power ~ RC
1
Car
bo
n
Ideal pore size (~ 3x solvated ion size)
Carbon2
Pore
Surface
3
Carbon
electrolyte ions + its solvation shells
Too large pore size
A3>A1; A3>A1
Too small pore size
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(CH3CH2)4N+
6.75 Å diameterBF4
-
3.25 Å diameter
Cell: 2-electrode cells (3-electrode cell experiments are in progress)
Electrode Preparation: 95% CDC (TiC-CDC initially), 5% PTFE cast onto treated Al current collectors
Electrolyte: 1.5 M (CH3CH2)4N BF4 in CH3CN (most conventional)
Tests: Cyclic Voltammetry (CV), EIS, Galvanostatic cycling
Characterization: Ar and N2 adsorption, TEM, SEM, XRD, SAXS (Prof. Fischer, Dr. Laudisio), four-probe conductivity measurements, Raman spectrometry
Our Study: Experimental Details
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0
0.5
1
1.5
2
2.5
3
0 50 100 150 200 250
Ce
ll vo
ltag
e (
V)
Time (s)
A
-0.08
-0.06
-0.04
-0.02
0
0.02
0.04
0.06
0.08
-0.5 0 0.5 1 1.5 2 2.5 3C
urr
en
t (A
)Voltage (V)
B
Charge-Discharge: linear profile and identical slopes: non Faradic response.CV: identical response and non-Faradic behavior. This shows CDC electrode cells stable up to at least 2.7 V.
CDC: Galvanostatic and Potentiostatic TestsTiC-CDC @ 700oC
20 mA/cm2
20 mV/s
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1000
1100
1200
1300
1400
1500
1600
1700
0.6
0.7
0.8
0.9
1.0
1.1
1.2
500 600 700 800 900 1000
BE
T S
SA
(m
2 /g)
Average
pore size (nm
)
Chlorination temperature (¼C)
CDC: SSA and pore size vs. synthesis T
Higher SSA and Pore size at higher temperature
Specific capacitance should increase with synthesis temperature
J. Chmiola, G. Yushin, Y. Gogotsi, et al., Science, 313,1760-1763 (2006)
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Sub-nanometer pore size control shows a new direction for research!!!
Electrolyte: 1.5 M (CH3CH2)4N BF4 in CH3CN (most conventional)
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Decreasing pore size allowed a 50% increase in specific capacitance above the most advanced activated carbons commercially available
The decrease in capacitance for small pore samples at high current densities is negligible - ion transport in small pores is still fast
CDC for Supercapacitors
J. Chmiola, G. Yushin, Y. Gogotsi, et al., Science, 313,1760-1763 (2006)
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Conclusions
Extraction of metals from carbides produces carbon with tunable:
• Structure• Pore size; Pore volume and Specific surface area
CDC process enables design and fine tuning of porous carbons for improved performance in applications
Move from trial-and-error tests to design of nanoporous carbons
CDC process allows one to perform fundamental studies of the effects of porous carbon parameters on adsorption- and transport related phenomena
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G. Yushin, Y. Gogotsi, and A. Nikitin, Carbide Derived Carbon, in Nanomaterials Handbook,Y. Gogotsi, Editor. 2006, CRC Press. p. 237-280.
Book chapter on CDC
AcknowledgementsStudents and post-docs at Drexel University: J. Chmiola, G. Yushin, C. Portet, E. Hoffman, R. DashProf. J.E. Fischer, University of PennsylvaniaProf. M. Barsoum, Drexel University, Prof. M.J. McNallan, UICProf. P. Simon, Paul Sabatier University, Toulouse, FranceProf. S. Mikhalovsky, U. Brighton, UKFinancial support: DOE, DARPA, NSF, Arkema