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MATTEO PASQUALI

Department of Chemical & Biomolecular Engineering,Department of Chemistry,

Carbon Nanotechnology Laboratory,

The Smalley Institute for Nanoscale Science & Technology

Rice University, Houston, TXmp@rice.edu

QUANTUM WIRESFOR GRID APPLICATIONS

Advanced Electricity Infrastructure WorkshopGCEP, Stanford, CA, 1 November2007

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OUTLINE

Team

Energy challenge and power transmission

Carbon Nanotubes

Armchair Quantum Wire

Expected features

Progress so far

Production of

single-chirality nanotubes

Separation of nanotubesSpinning of nanotube fibers

Perspective

Rick Smalley

WadeAdams

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TEAM

Team effortThough process initiated by Rick Smalley & Wade Adams

Idea of the AQW: Rick Smalley et al.

Multidisciplinary, integrated projectChemistry, Physics, Chem. Eng., Materials Science

Jim Tour, MP, Boris Yakobson, Andy Barron, Jun Kono,

Bob Hauge, Howard Schmidt, Wen-Fang Hwang, et al

Hauge

Tour

Schmidt

Yakobson HwangBarron Kono

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Humanitys Top Ten Problemsfor next 50 years

1. ENERGY

2. WATER

3. FOOD4. ENVIRONMENT

5. POVERTY

6. TERRORISM & WAR

7. DISEASE

8. EDUCATION

9. DEMOCRACY

10. POPULATION

2007 6.6 Billion People

2050 9-11 Billion People

RICK SMALLEYS LECTURE QUIZ

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0

5

10

15

20

25

30

35

40

45

50

OilCo

alGas

Fission

Biom

ass

Hydroele

ctric

Sola

r,wind

,geoth

ermal

0.5

2003

05

10

15

20

25

3035

40

45

50

Oil

Coal

Gas

Fusion

/Fi

ssio

n

Biom

ass

Hyd

roelectri

c

Sola

r,wind,

geothe

rmal

2050

Smalleys Terawatt Challenge

14 Terawatts

210 M BOE/day 30 -- 60 Terawatts450 900 MBOE/day

Energy:The Basis of Prosperity

20st Century = OIL

21st Century = ??

THE ENERGY REVOLUTION

Source: International Energy Agency

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SOLAR CELL LAND AREA REQUIREMENTS

Nate LewisCal Tech

Total average daily solar flux: 165,000 TW

6 Boxes at 3.3 TW each = 20 TWBoxes are in deserts, far from population centers

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Source:NREL

US RENEWABLE RESOURCES MAP

Biomass potential: negative energy balance?

Harvesting of renewables far from population centers

GEO

BIO

SUN

WIND

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Source: DOE & Nate Lewis, Caltech

Currently, power is generated close to population centers

US POWER PLANT MAP

Currently, power plants are near population centers

Reason: limitations on long-distance power transmission

Nuclear is a potential alternative: undesirable near cities

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ALLOTROPES OF CARBON

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SWNT: ROLLED-UP SHEET OF GRAPHITE

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MichaelStrck

Chirality (n,m) identifiesthe species

(n,0) and (0,m): zig-zag(n,n): armchair

(n,m): chiral

Metallic: n = m(bandgap = 0 eV)Semi-metallic: nmis multiple

of 3 (mod 3 tubes, bandgap ~1-10 meV)Semiconducting: nmis not amultiple of 3 (bandgap ~0.5 - 1.0eV; HiPco 0.8-1.4 eV)

Current methods produce mixtures of

metallic/semi-metallic (1/3rd) and semiconductors (2/3rd)

Length is polydisperse

Physical and chemical polydispersity

SWNTs AS A CLASS OF MATERIALS

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SWNT PROPERTIES

Exceptional mechanical strengthTensile strength > 37 GPa

(Steel 2 GPa, PBO 5.7 GPa, Aluminum 0.3 GPa)

Young modulus ~ 0.62 1.25 TPa(Steel 0.3 TPa, PBO 0.36 TPa, Aluminum 0.07 TPa)

Low density ~ 1.4 g/cm3

(Steel ~8 g/cm3, PBO 1.6 g/cm3, Aluminum 2.7 g/cm3)

Electrical resistivity ~ 1 cm

(Copper 1.7 cm, Silver 1.55 cm, Al 2.7 cm)

Thermal conductivity ~ 3000 W / m K

(Diamond ~ 2000 W / m K)

The ultimate polymer

The ultimate carbon material

Review by Baughman et al., Science, 297, 787 (2002)

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CONDUCTIVITY OF SWNTs

Measurements on individual

metallic SWNT on Si wafers with

patterned metal contacts

Single tubes can pass 20 uA forhours

Equivalent to roughly a billion amps

per square centimeter!

Conductivity measured twice that ofcopper

Ballistic conduction at low fields

with mean free path of 1.4 microns

Similar results reported by othersDespite chemical contaminants and

asymmetric environment

Dekker, Smalley, Nature, 386, 474-477 (1997). McEuen, et al, Phys.Rev.Lett.84, 6082

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RESONANT QUANTUM TUNNELING

Conductance in parallel end-to-end contact ~ single SWNT

Misalignment reduces conductance (up to ~10 times)

Buldum and Lu,Phys. Rev. B 63,161403 R (2001).

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Cable of all-aligned armchair SWNTsExceptional potential current carrying capacity

Estimated >1 Billion Amps / cm2 (McEuen et al, IEEE Trans.

Nanotech., 1, 78, 2002)Current technology (steel reinforced aluminum) has

1000-5000 Amps / cm2

Combination ofHigh electrical conductivity (~ twice copper at RT)

High thermal conductivity (~ diamond)

High stiffness: Young Modulus ~0.6-1 TPaSteel 0.3 TPa, Aluminum 0.07 TPa

Low density: 1.4 g/cm3

Steel 8 g/cm3, Aluminum 2.7 g/cm3

THE ARMCHAIR QUANTUM WIRE

Review by Baughman et al., Science, 297, 787 (2002)

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ARMCHAIR QUANTUM WIRE PROJECT

Expected Features1-10x Copper Conductivity6x Less MassStronger Than Steel

Zero Thermal Expansion30x Power Density vs. Cu/Al

Key Grid BenefitsReduced Power LossLow-to-No SagReduced MassHigher Power Density

SWNT Technology BenefitsType & Class SpecificHigher PurityLower Cost

Polymer Dispersible

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EXPECTATIONS: AQW ON THE GRID

Key Benefits

Eliminate Thermal Failures Reduce Wasted Power

Reduce Urban R.O.W. Costs Enable Remote Generation

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MAKING THE AQW

What needs to be done:Go from single SWNT

to macroscopic material

All-armchair SWNTs

preferably all same type

Large quantityAlign and transform into fiber

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THREE WAYS OF GETTING IT DONE

Route #1:Sort large amount of armchair SWNTs

Process into fibers

Route #2:

Sort minute amount of armchair SWNTs

Clone

Process into fibers (maybe on the fly)

Route #3:

Grow directly SWNTs of single-chirality bytuning catalyst (variant of cloning)

Process into fibers (maybe on the fly)

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ARMCHAIR QUANTUM WIRE PROJECT

initialSWNTsupply

HiPcoCoMoCATLaser-oven

Carpets

sorting&

separations

1 ng

1 g(enriched)

cutting&

cloning100 X

7 pass:

100 kg

1%

99%

fiberspinning

modulusstrength

densityelectrical cond.

thermal cond.

property maps

y

x

applicationsprototype

applications

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Selective elimination by electrical breakdown Collins et al., Science 2001

Covalent functionalization Strano et al., Science 2003

Selective adsorption Chattopadhryay et al., JACS 2003

Ion exchange chromatography Zheng et al., Science 2003Electrophoresis Heller et al., JACS 2004

Density gradient ultracentifugation

Arnold et al., Nature Nanotech. 2006

DielectrophoresisKrupke et al., Science 2003

Separation very difficult

Low solubility

Minimal physicochemical differences (except DEP)Some methods appear scalable, but not highly selective

Other methods have high selectivity, poor scalability

Modeling may help scale-up

SOA: SWNT TYPE SEPARATION METHODS

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DENSITY GRADIENT ULTRACENTRIFUGATION

Sort by densitySWNTs of different diameter

have (slightly) different density

Does not quite sort by typePossible when few SWNTs present

(e.g., CoMoCAT)

Arnold et al, Nature Nanotech,1, 60 2006Hersam

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SOA: SINGLE-CHIRALITY CATALYTIC GROWTH

Growth of single type from specific catalystCurrent opinion: SWNTs grow out of liquid metal droplets (catalyst)

Droplet (particle) size controls SWNT size

Narrowest distribution: CoMoCAT

Templated substrate

Selectivity by diameter

How to go from diameter to type?

HiPco

CoMoCATResasco

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SOA: SEEDED GROWTH/CLONING

Amplification of SWNTsDocking: reduce catalyst particle at end

of SWNT with minimal etching,

leaving activated catalyst in intimate

contact with SWNT

Growth: cause the seed to grow

in a CVD chamber. Longer

SWNT should be identical to original

one (seed)

Smalley, Tour, Barron, et al, Rice U

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Smalley et al, JACS 2006

Seed: 200nm long; amplified: 6.7 m long

Seed and amplified SWNT have same diameter (~0.7 nm)

Same chirality not yet proven

Low yield: few seeds regrow on surfaces; looking for alternatives

SOA: SEEDED GROWTH/CLONING

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SOA: SPINNING OF SWNT FIBERS

Four main methods

From water-surfactant suspension (Poulin et al, CNRS Bordeaux)

General route; SWNT manufacturing unimportant

Some surfactant/polymer may remain in fiber

From a carpet/forest (Baughman et al, UT Dallas)

Will be great if cloning is done on carpets

Works for long CNTs (~1 mm OK)

Never demonstrated on SWNTsFrom gas-phase reactor (Windle et al, Cambridge)

Will be great if magic catalyst can be found

Will work for long SWNTs (~1 mm OK)

From LC solution (Rice U)

General route; SWNT manufacturing unimportant

Will work for medium-length SWNTs

(~1 m proven, maybe ~10 m)

Baughman

Poulin

Windle

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SPINNING FIBERS FROM WATER-SURFACTANT

Poulin et al, CNRS Bordeaux

Vigolo et al, Science 290, 1331 (2000)

25 m

hydrophobic(C-12 chain)

SWNT

charged group(sulfate)

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SPINNING FIBERS FROM A CARPET

Baughman et al, UT Dallas

Zhang et al, Science 306, 1358 (2004)

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DIRECT FIBER SPINNING FROM FURNACE

Windle et al, U Cambridge (UK)

Li et al, Science 304, 276 (2004)

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SWNT-ACID LIQUID CRYSTAL

Acid protonate the SWNTs: stabilizationA liquid crystal forms at high SWNT

concentration

Similarities with rodlike polymers (Kevlar)

Liquid crystal morphology depends on

type of acid (sulfuric vs. chlorosulfonic)

Stable for months; no chemical reactions

7% wt in ClHSO3, cross polars, 0 and 90

20 m

DILUTE SEMIDILUTE

ISOTROPIC

CONCENTRATED

LIQUID

CRYSTALLINE

Ramesh et al, J. Phys. Chem. B, 2004Davis et al, Macromolecules, 2004

600 ppm wt. 6% wt.

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FIBERS FROM SWNT/ACID

Highly aligned fibers; diameter ~20-70 m

Continuous process Ericson et al, Science, 2004

TYPICAL ACID SPUN SWNT FIBER

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TYPICAL ACID-SPUN SWNT FIBER

Excellent macrostructure

Poor mesostructure (bundles), will affect transport

=373m

=502m

ASSESS WAYS OF GETTING IT DONE

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ASSESS WAYS OF GETTING IT DONE

Route #1:Separate large amount of SWNTs

Process into fibers

Large scale separation for fiber spinning

We need a miracle (breakthrough)

We know a few places where to look

Flow-dielectrophoresis

Selective reactions

Fiber spinning

We have two routes: surfactant, acid

Each needs scientific engineering

Flow-DEP

ASSESS WAYS OF GETTING IT DONE

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Route #2:Separate minute amount of SWNTs

Clone

Process into fibers (maybe on the fly)

Small scale separation

We have a route: CoMoCAT

+ density gradient ultracentrifugation

Cloning

Concept ~ proven (on surfaces, chirality?)

We need a miracle (breakthrough)

We know where to lookFiber spinning

Two routes: surfactant, acid

Maybecarpet and/or direct

ASSESS WAYS OF GETTING IT DONE

ASSESS WAYS OF GETTING IT DONE

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Route #3:Grow directly SWNTs of single-chirality by

tuning catalyst (variant of cloning)

Process into fibers (maybe on the fly)

Most elegant route

Fundamental understanding of

SWNT growth still evolving

Current understanding:

liquid phase catalyst

diameter selectivity possible

type selectivity unlikely

Fiber spinning

Two routes: surfactant, acid

Maybecarpet and/or direct

ASSESS WAYS OF GETTING IT DONE

liquidC

gas

SUMMARY ASSESSMENT

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SUMMARY ASSESSMENT

Direct single-chirality growth

We need a miracle

We dont know where to look

Cloning

Sort-of proven (surface, chirality?)

We need a miracle

We know where to look

Fiber spinning

We have four routes

Need scientific engineering

Need

Bright, enthusiastic people

Funding

RICK SMALLEYS LECTURE QUIZ

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Humanitys Top Ten Problems for next 50 years

1. ENERGY

2. WATER3. FOOD

4. ENVIRONMENT

5. POVERTY

6. TERRORISM & WAR

7. DISEASE

8. EDUCATION

9. DEMOCRACY

10. POPULATION2003 6.5 Billion People2050 10-12 Billion People

RICK SMALLEY S LECTURE QUIZ

POPULATION

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National

GeographicNov 2002

POPULATION

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POPULATION

For the first time in history, we now live in a small islandFully connected, interdependent

Nowhere to go (for a long time)

Insular civilizations (Jared Diamond)

Expanded and overtaxed environment until they collapsed

Learned to control harvest rate and limited population

Technology only makes the problem worse

Creates transient excess of resources

Albert Bartlett, The Essential Exponential

If thenkxdt

dx=

0,)(lim >=

ktxt Bartlett

Diamond

POPULATION

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POPULATION

Quick mnemonic: at k% growth rate, the doubling timeis Td = 100 ln2/k = 70/k

At 1% population growth rate:

At 2 kW/person, we run out of solar power in

1) 100 years (AD 2100)

2) 1,000 years (AD 3000)

3) 10,000 years (AD 12000)

4) 100,000 years (AD 102,000)

5) Ridiculous: we cannot possibly run out of solar power!

POPULATION

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POPULATION

Quick mnemonic: at k% growth rate, the doubling timeis Td = 100 ln2/k = 70/k

At 1% population growth rate:

At 2 kW/person, we run out of solar power in

1) 100 years (AD 2100)

2) 1,000 years (AD 3000)

3) 10,000 years (AD 12000)

4) 100,000 years (AD 102,000)

5) Ridiculous: we cannot possibly run out of solar power!

At that time, we will have 2 m2/person of space!

At 0.5% population growth rate, we run out of solar

power (and space) in AD 4000!

POPULATION

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POPULATION

Current estimates predict that population growth will stopin about 70 years

Estimates of population growth

are highly inaccurate beyond

average life expectancy

(currently ~ 65 yr)

Situation is better now

than in the 1960s

We need to remain

conscious of it

PREDICTED

CONTRIBUTORS

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PhD Students: Virginia Davis, Lars Ericson, Hua Fan, Nick Parra-Vasquez,

Richard Booker, Yuhuang Wang, Naty BehabtuUG Students: J. Sulpizio, Valentin Prieto, Jason Longoria, Robby Pinnick, Jon Allison

Postdocs: Pradeep Rai, Haiquing Peng, S. Ramesh, Rajesh Saini, Micah Green

Scientists: Carter Kittrell , Wen-Fang Hwang, Howard Schmidt

Rice Faculty: Boris Yakobson, Ed Billups, Wade Adams, Robert Hauge, Rick SmalleyU. Penn: Jack Fischer, Karen Winey, Wei Zhou, Juray Vavro, Cszaba Guthy

ACKNOWLEDGEMENTS

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FUNDING

Office of Naval Research / DURINTAir Force Office of Scientific Research

Air Force Research Lab

National Science Foundation

NASA

Welch Foundation

Texas Advanced Technology Program

REFERENCES (email mp@rice.edu)

Phase Behavior and Rheology:

Davis et al., Macromolecules, 37, p. 154 (2004)Zhou et al., Phys. Rev. B, 72, 045440 (2005)

Pasquali et al., US Patent 6,962,092 (2005)

Parra-Vasquez et al., Macromolecules, 40, p. 4043 (2007)

Solubility and Protonation:

Ramesh et al., J. Phys. Chem B, 108, p. 8794 (2004)

Rai et al., J. Am. Chem. Soc., 128, p. 591 (2006)

Fiber Spinning and Properties

Ericson et al., Science, 305, p. 1447 (2004)

Wang et al., Chem. Mater., 17, p. 6361 (2005)Smalley et. al., US Patent 7,125,502 (2006)

RICK SMALLEY

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RICK SMALLEY

Be a scientist, save the world!