Nanotechnology and Energy:

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Nanotechnology and Energy Armchair Quantum Wires
The Power Conference 06 UH - GEMI June 29 ,
2006
BE A SCIENTIST -- SAVE THE WORLD
Wade Adams, Howard Schmidt, Bob Hauge, Amy Jaffe,
and Rick Smalley www.nano.rice.edu
www.rice.edu/energy deceased
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Professor Richard E. Smalley1943 - 2005Nobel
Prize in Chemistry 1996
A 6 week summer project in 1985 2 page paper in
Nature
C60 Buckminster- fullerene Buckyballs
with Robert F. Curl and Harold Kroto
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National Nanotechnology ProgramWhite House
November 2003
Lonely Academic
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Humanitys Top Ten Problemsfor next 50 years

1. ENERGY
2. WATER
3. FOOD
4. ENVIRONMENT
5. POVERTY
6. TERRORISM WAR
7. DISEASE
8. EDUCATION
9. DEMOCRACY
10. POPULATION

2003 6.5 Billion People 2050 8-10
Billion People
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The ENERGY REVOLUTION (The Terawatt Challenge)
14 Terawatts 210 M BOE/day
30 -- 60 Terawatts 450 900 MBOE/day
Energy The Basis of Prosperity 20st Century
OIL 21st Century ??
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Energy-efficient Commuting
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PRIMARY ENERGY SOURCESAlternatives to Oil

• TOO LITTLE
• Conservation / Efficiency -- not enough
• Hydroelectric -- not enough
• Biomass -- not enough
• Wind -- not enough
• Wave Tide -- not enough
• CHEMICAL
• Natural Gas -- sequestration?, cost?
• Gas Hydrates -- sequestration?, cost?
• Clean Coal -- sequestration?, cost?
• NUCLEAR
• Nuclear Fission -- radioactive waste?,
  terrorism?, cost?
• Nuclear Fusion -- too difficult?, cost?
• Geothermal HDR -- cost ? , enough?
• Solar terrestrial -- cost ?
• Solar power satellites -- cost ?
• Lunar Solar Power -- cost ?

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165,000 TW of sunlight hit the earth every day
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PV Land Area Requirements
Nathan S. Lewis, California Institute of
Technology
3 TW
20 TW
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Solar Cell Land Area Requirements
Nathan S. Lewis, California Institute of
Technology
6 Boxes at 3.3 TW Each 20 TWe
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20 TWe from the Moon
Harvested Moon
David Criswell Univ. Houston
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Renewable Resource Maps

• Renewable sources generally remote from major
  population centers

Source NREL
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US Power Production Map

• Currently, power is generated close to population
  centers

Source DOE Nate Lewis, Caltech
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One World Energy Scheme for 30-60TW in 2050The
Distributed Store-Gen Grid

• Energy transported as electrical energy over
  wire, rather than by transport of mass (coal,
  oil, gas)
• Vast electrical power grid on continental scale
  interconnecting 100 million asynchronous
  local storage and generation sites, entire
  system continually innovated by free enterprise
• Local house, block, community, business,
  town,
• Local storage batteries, flywheels, hydrogen,
  etc.
• Local generation reverse of local storage
  local solar and geo
• Local buy low, sell high to electrical power
  grid
• Local optimization of days of storage capacity,
  quality of local power
• Electrical grid does not need to be very
  reliable, but it will be robust
• Mass Primary Power input to grid via HV DC
  transmission lines from existing plants plus
  remote (up to 2000 mile) sources on TW scale,
  including vast solar farms in deserts, wind,
  NIMBY nuclear, clean coal, stranded gas, wave,
  hydro, space-based solarEVERYBODY PLAYS
• Hydrogen, methanol, ethanol are transportation
  fuels
• Transition technology Plug-in Hybrids

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Energy Nanotech Grand Challengesfrom Meeting at
Rice University May 2003Report available!

• Photovoltaics -- drop cost by 100 fold.
• Photocatalytic reduction of CO2 to methanol.
• Direct photoconversion of light water to
  produce H2.
• Fuel cells -- drop the cost by 10-100x low
  temp start.
• Batteries and supercapacitors -- improve by
  10-100x for automotive and distributed generation
  applications.
• H2 storage -- light weight materials for
  pressure tanks and LH2 vessels, and/or a new
  light weight, easily reversible hydrogen
  chemisorption system
• Power cables (superconductors, or quantum
  conductors) with which to rewire the electrical
  transmission grid, and enable continental, and
  even worldwide electrical energy transport and
  also to replace aluminum and copper wires
  essentially everywhere -- particularly in the
  windings of electric motors and generators
  (especially good if we can eliminate eddy current
  losses).

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CarbonNanotechnologyLaboratory Making
BuckytubesBe All They Can Be

• Founded by Rick Smalley in 2003 as a division of
  CNST
• Coordinates SWNT Research with 10 Faculty in 6
  Departments
• Prof. James M. Tour DirectorProf. Matteo
  Pasquali Co-Director
• Dr. Howard K. Schmidt - Executive DirectorDr.
  Robert H. Hauge - Technology Director

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If it aint tubes, we dont do it!
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Why Single Wall Carbon Nanotubes?
MOLECULAR PERFECTION EXTREME PERFORMANCE
The Strongest Fiber Possible. Selectable
Electrical Properties Metallic Tubes Better Than
Copper Semiconductors Better Than InSb or
GaAs Thermal Conductivity of Diamond. The Unique
Chemistry of Carbon. The Scale and Perfection of
DNA. The Ultimately Versatile Engineering
Material.
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Graphene SheetTexas Chicken Wire
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SWNT ROLLED-UP SHEET OF GRAPHITE
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Worlds largest SWNT model
RAJAT DUGGAL (inside giant SWNT model)

• 22 April 2005, Guinness World Record
• Model of a 5-5 SWNT
• 65,000 pieces
• 360 m long, 0.36 m wide
• about 100 builders
• over 1000 in attendance
• Supremely Silly (from Rick Smalley)

Cost of the parts 6,000
Building a 1000-ft SWNT
pRICEless
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Types of SWNT

• Cylindrical graphene sheet
• Diameters of 0.7 3.0 nm
• Observed tubes typically lt 2 nm
• Both metallic and semi-conductor species possible
• Length to diameter ratio as large as 104 105
• can be considered 1-D nanostructures

armchair (a 30)
zigzag (a 0)
intermediate (0 ? a ? 30)
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Conductivity of Metallic SWNT

• Measurements on individual metallic SWNT on Si
  wafers with patterned metal contacts
• Single tubes can pass 20 uA for hours
• Equivalent to roughly a billion amps per square
  centimeter!
• Conductivity measured twice that of copper
• Ballistic conduction at low fields with mean free
  path of 1.4 microns
• Similar results reported by many
• Despite chemical contaminants and asymmetric
  environment

Dekker, Smalley, Nature, 386, 474-477 (1997).
McEuen, et al, Phys.Rev.Lett.84, 6082
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Quantum Tunneling
Alper Buldum and Jian Ping Lu, Phys. Rev. B 63,
161403 R (2001).
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Tunneling Evidence

• Indirect indication of conductivity by measuring
  lifetimes of photo-excited electrons
• Cooling mechanism is interaction with phonons
  just like electrical resistivity
• Anomalously long life-times yield mean free path
  of 15 microns (10x single tubes)
• Based on bundles in buckypapers good local
  symmetry and clean, but still based on mixture of
  metals and semi-conductors
• Results imply 10 25x better conductivity than
  copper

Source Tobias Hertl, et al, Phys. Rev. Lett.
84(21) (2000) 5002
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SWNT Quantum Wire

• Expected Features
• 1-10x Copper Conductivity
• 6x Less Mass
• Stronger Than Steel
• Zero Thermal Expansion
• Key Grid Benefits
• Reduced Power Loss
• Low-to-No Sag
• Reduced Mass
• Higher Power Density
• SWNT Technology Benefits
• Type Class Specific
• Higher Purity
• Lower Cost
• Polymer Dispersible

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CNL Armchair Quantum Wire Program(armchair swnt
wire with electrical conductivity gt copper)( 5
years, 25 million )

• SWNT Sorting (the signal for the amplifier)
• SWNT Amplifier
• SWNT Purification
• SWNT Fiber Spinning Processing
• SWNT Continuous Growth

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Getting The Right Tube

• Often Need A Single Type of SWNT
• Current Growth Inadequate
• Mixtures 50 Types
• Mixed Metals, Semi-Metals Semiconductors
• Impure Inefficient
• N,M Control Critical
• Quantum Wire
• Electronics Sensors
• Biomedical Therapeutics
• Energy Conversion Storage
• Seeded Growth Required
• Separates Nucleation From Growth
• Eliminate By-Products Purification
• Vastly Improved Efficiency
• Sort Once at Small Scale

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Rolling Graphite - n,m Vectors
Roll-up vector
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SWNT Excitation Fluorescence

• Each peak comes from a specific semi-conducting
  SWNT n,m value

Valley of the Metals
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SWNT Seeded Growth

• Current Results
• Key Starting Materials
• Have FeMoC Catalyst
• Have Short SWNT Seeds
• Have Soluble SWNT
• Key Process Steps
• In-Solution Attachment
• Controlled Deposition
• Catalyst Docking
• Reductive Etching
• Growth is Next !!

1. Attach Catalyst
2. Deposit on Inert Surface
4. SWNT Growth
3. Dock Catalyst
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SWNTcat Growth
Initial
100 mtorr CH4 10 min 800 oC
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SWNT AmplifierProcess Flow
Attach
Disperse
Grow
Dock
Cut
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SWNTamp Production Concept
Hydro-carbon feedstocks
Seeded Growth 500 lt T lt 700 C
Mono-Type SWNT (1000 lb / day )
Bulk Output
SWNT FeMoC Catalyst
Inner Loop Processing
Seed Preparation. (1 lb/ day) Cut SWNT, Prep.
Catalyst, Functionalize, Attach, Dock
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SWNT Growth Rates
SWNT Sample Growth Rate (mm/min)
SWNTcat on HOPG 0.005
SWNT Fiber Continued Growth 0.3
Maruyama Carpet Growth 1
Hata Carpet Growth 250
Free SWNT Growth 600

DNA Replication (Bacteria) 0.340
Science 306, 1362 (2004). Nano Lett. 4, 1025
(2004).
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Production Scale-Up Path

• Rice made 1 mg / day in 1997
• Lab-scale reactor at 1 gm / hour (2002)
• CNI Pilot plant producing 20 lb /day
• CNI now testing 100 lb / day reactor

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Forming SWNT Wires

• Need macro-crystalline SWNT fiber/wire
• Starting material is tangled at several scales
• Starting material has variety of diameters and
  types
• Enormous Van der Waals forces make it hard to
  separate SWNT bundles

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Dispersion in Super-Acids

• SWNT bundles swell in superacids
• Dispersion due to protonation
  intercalation of SWNTs
• V. A. Davis et. Al., Macromolecues 37, 154 (2004)

in 102 H2SO4
Spaghetti In Oleum
dried SWNT fiber
W.-F Hwang and Y. Wang
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Prototype Wire - SWNT Fibers

• Producing Neat SWNT Fibers
• Dry-Spun from Oleum
• 6 to 14 Wt. SWNT Dope
• Extruded as 50 µm Dia. Fibers
• 109 Tubes in Cross Section
• 100 Meters Long

Science 305, 1447-1450, 3 September 2004!!!
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Ultimate Properties of Polymers
Staudinger Continuous Crystal Model
Perfect orientation Perfect lateral order Few
chain end defects (HMW) INTRINSIC CHAIN
PROPERTIES
Hermann Staudinger, Die Hochmolekularen
Organischen Verbindungen, Berlin Springer p.111
(1932)
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SWNT Tensile Strength
Predicted tensile strength of single-wall
nanotubes gt100 GPa Calculated strain-to-failure
gt30 Measurements on small bundles found
strength 30-60 GPa
Yakobson, et al., Comp. Mat. Sci. 8, 341 (1997).
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Quantum Wire on The Grid

• Key Grid Benefits
• Eliminate Thermal Failures
• Reduce Wasted Power
• Reduce Urban R.O.W. Costs
• Enable Remote Generation

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Grid Applications Benefits

• Eliminate Thermal-Sag Failure Now a 100B a
  year problem.
• Short-Distance AC AQW could increase throughput
  up to ten-fold without increasing losses while
  using only existing towers and rights-of-way.
  Avoid new construction in congested urban areas
  estimated over 100M per mile.
• Medium-Distance AC AQW could decrease resistive
  losses and voltage drop ten-fold if amperage were
  not increased. This would improve grid dynamics
  significantly in the range between 100 and 300
  miles, where voltage stability limits deliverable
  power.
• Long-Distance HVDC AQW could permit amperage
  throughput ten fold or reduce losses ten-fold.
  New conventional lines cost 1M to 2M per mile,
  plus about 250M per AC/DC converter station.
• Remote Power Could enable utilization of
  large-scale renewables and remote nuclear.

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High Pressure CO (HiPCO) Process
NASA Success Stories
Tuesday, April 26th, 2005 -- NASA Announces new
16M Grant to Rice University and two NASA
Centers Research to develop the Quantum Wire
CNL Actively building new collaborations to fund
this critical research program!!!
Fe, Ni Catalysts
CO CO
CO2 SWNT impurities
900-1200 C 10-40 atm
Rice Univ. ? Carbon Nanotechnologies, Inc. NASA
Continuous process 10-100s g/day Small
diameters (0.7nm) Company spin-off (CNI)
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Buckytubes Offer Incredible Opportunities

• Energy
• Fuel cells
• Supercapacitors and batteries
• Photovoltaic cells
• Quantum Wires
•  
• Electronics
• Field emission
• Flat panel displays
• Back light units
• Electron device cathodes
• Sensors
• Printable electronics
• Logic and memory devices
• Interconnects

• Composites
• Electrically conductive composites
• Wide range of conductivities
• Antistatic
• Electrostatic dissipation
• EMI/RFI shielding  
• Bulk parts
• Transparent conductive coatings
• Anti-corrosion coatings
• Reinforced composites
• Tougher, stronger, stiffer, wear resistant
• Thermosets and thermoplastics
• Parts, coatings
• High performance fibers
• High performance ceramics

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Roadblocks

• Vision without funding is hallucination.
• Da Hsuan Feng UT Dallas
• Vision without hardware is delusion.
• Lockheed engineer

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From the age of Space to the age of Medicine
Age of Energy?
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New Energy Research Program(Smalleys Nickel
Dime Solution)

• For FY06-FY10 collect 5 cents from every gallon
  of oil product
• Invest the resultant gt 10 Billion per year
  as additional funding in frontier energy research
  distributed among DOE, NSF, NIST, NASA, and
  DoD.
• For the next 10 years collect 10 cents from every
  gallon
• invest the gt20 Billion per year in frontier
  energy research.
• Devote a third of this money to New Energy
  Research Centers
• located adjacent to major US Research
  Universities, especially Zip Code 77005.
• At worst this endeavor will create a cornucopia
  of new technologies and new industries.
• At best, we will solve the energy problem before
  2020,
• and thereby lay the basis for energy
  prosperity peace worldwide.

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Leadership

• President Bush State of the Union Address Jan
  31, 2006
• America is addicted to oil
• Replace oil imports from Middle East by 75 by
  2025
• DOE Advanced Energy Initiative 22 increase in
  clean energy research
• Zero emission coal
• Solar and wind
• Clean, safe nuclear
• Batteries, Hydrogen, ethanol
• A BIG change from the 2001 Cheney Energy Report
  drill our way to independence!

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But

• Are these ideas tough or aggressive enough?
• NO!
• Biofuels budget actually smaller than in FY06
• No market signal for more efficient vehicles
• Fuel economy standards regulatory
• 40 mpg in 10 years saves 2.5M BOE/day
• Substantial gas tax market mechanism
• Up to Congress to execute programs
• Incentives for alternate fuel production/vehicles
• Funding for research initiatives

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• The biggest single challenge for the next few
  decades
• ENERGY
• for 1010 people
• At MINIMUM we need 10 Terawatts (150 M
  BOE/day)
• from some new clean energy source
  by 2050
• For worldwide energy prosperity and peace we
  need it to be cheap.
• We simply can not do this with current
  technology.
• We need Boys and Girls to enter Physical
  Science and Engineering as they did after
  Sputnik.
• Inspire in them a sense of MISSION
• ( BE A SCIENTIST --- SAVE THE WORLD )
• We need a bold new APOLLO PROGRAM
• to find the NEW ENERGY TECHNOLOGY

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By 2012, if current trends continue, over 90 of
all physical scientists and engineers in the
world will be Asians working in Asia.
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Education

• American Competitiveness Initiative
• Double physical sciences research funding in ten
  years (including nanotech, supercomputing,
  alternative energy sources)
• Permanent RD Tax Credit
• HS Math/Science teacher training (70,000) and add
  30,000 MS professional teachers
• YEA!
• But will Congress fund the initiatives?
• And will they sustain the funding??

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2999
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You
Your Children
Your Grandchildren
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What Can YOU Do Now?

• Learn as much as possible about energy
• Learn as much as possible about nanotechnology

• Encourage kids to study science and
  engineering!!

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Reading Assignments

• Twilight in the Desert, Matthew R. Simmons
• Winning the Oil Endgame, Amory Lovins
• Beyond Oil The View from Hubberts Peak, Kenneth
  S. Deffeyes
• Out of Gas, Daniel Goodstein
• The End of Oil, Paul Roberts
• The Prize, Daniel Yergin
• Hubberts Peak, Kenneth S. Deffeyes
• The Hydrogen Economy, Jeremy Rifkin
• Twenty Hydrogen Myths, Amory Lovins
• (www.rmi.org)
• Matt Simmons, web site (www.simmons-intl.com)
• M.I. Hoffert et. al., Science, 2002, 298, 981,
• DOE BES Workshop Report on Hydrogen
• (www.sc.doe.org/bes/hydrogen.pdf)
• 2003 State of the Future,
• (www.stateofthefuture.org)
• Nanotechnology and Energy, 2003 Report,
• (www.cnst.rice.edu)

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BE A SCIENTIST -- SAVE THE WORLD