Nanotechnology and Energy Armchair Quantum Wires The Power

Nanotechnology and Energy: Armchair Quantum Wires The Power Conference ‘ 06 UH - GEMI June 29 , 2006 Wade Adams, Howard Schmidt, Bob Hauge, Amy Jaffe, and Rick Smalley* www. nano. rice. edu www. rice. edu/energy *deceased

Professor Richard E. Smalley 1943 - 2005 Nobel Prize in Chemistry 1996 A 6 week summer project in 1985 2 – page paper in Nature with Robert F. Curl and Harold Kroto C 60 Buckminsterfullerene: Buckyballs

National Nanotechnology Program White House – November 2003

Humanity’s Top Ten Problems for next 50 years 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. ENERGY WATER FOOD ENVIRONMENT POVERTY TERRORISM & WAR DISEASE EDUCATION DEMOCRACY POPULATION 2003 2050 6. 5 Billion People 8 -10 Billion People

The ENERGY REVOLUTION (The Terawatt Challenge) 14 Terawatts 210 M BOE/day Energy: The Basis of Prosperity 20 st Century = OIL 21 st Century = ? ? 30 -- 60 Terawatts 450 – 900 MBOE/day

Energy-efficient Commuting

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

165, 000 TW of sunlight hit the earth every day

PV Land Area Requirements Nathan S. Lewis, California Institute of Technology 3 TW 20 TW

Solar Cell Land Area Requirements Nathan S. Lewis, California Institute of Technology 6 Boxes at 3. 3 TW Each = 20 TWe

≥ 20 TWe from the Moon “Harvested Moon” David Criswell Univ. Houston

Renewable Resource Maps Renewable sources generally remote from major population centers Source: NREL

US Power Production Map Currently, power is generated close to population centers Source: DOE & Nate Lewis, Caltech

One World Energy Scheme for 30 -60 TW in 2050: The 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 solar…”EVERYBODY PLAYS” • Hydrogen, methanol, ethanol are transportation fuels • Transition technology – Plug-in Hybrids

Energy Nanotech Grand Challenges from Meeting at Rice University May 2003 Report available! 1. Photovoltaics -- drop cost by 100 fold. 2. Photocatalytic reduction of CO 2 to methanol. 3. Direct photoconversion of light + water to produce H 2. 4. Fuel cells -- drop the cost by 10 -100 x + low temp start. 5. Batteries and supercapacitors -- improve by 10 -100 x for automotive and distributed generation applications. 6. H 2 storage -- light weight materials for pressure tanks and LH 2 vessels, and/or a new light weight, easily reversible hydrogen chemisorption system 7. 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).

Carbon Nanotechnology Laboratory Making Buckytubes “Be 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 – Director Prof. Matteo Pasquali – Co-Director Dr. Howard K. Schmidt - Executive Director Dr. Robert H. Hauge - Technology Director

If it ain’t tubes, we don’t do it!

Why Single Wall Carbon Nanotubes? MOLECULAR PERFECTION & EXTREME PERFORMANCE The Strongest Fiber Possible. Selectable Electrical Properties Metallic Tubes Better Than Copper Semiconductors Better Than In. Sb or Ga. As Thermal Conductivity of Diamond. The Unique Chemistry of Carbon. The Scale and Perfection of DNA. The Ultimately Versatile Engineering Material.

Graphene Sheet Texas Chicken Wire

SWNT: ROLLED-UP SHEET OF GRAPHITE

World’s 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: p. RICEless

Types of SWNT – Cylindrical graphene sheet – Diameters of 0. 7 – 3. 0 nm armchair (a = 30°) • Observed tubes typically < 2 nm – Both metallic and semiconductor species possible – Length to diameter ratio as large as 104 – 105 zigzag (a = 0°) • can be considered 1 -D nanostructures intermediate (0 a 30°)

Conductivity of Metallic SWNT • Measurements on individual metallic SWNT on Si wafers with patterned metal contacts • Single tubes can pass 20 u. A 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). Mc. Euen, et al, Phys. Rev. Lett. 84, 6082

Quantum Tunneling Alper Buldum and Jian Ping Lu, Phys. Rev. B 63, 161403 R (2001).

Tunneling Evidence • Indirect indication of conductivity by measuring lifetimes of photoexcited electrons • Cooling mechanism is interaction with phonons – just like electrical resistivity • Anomalously long life-times yield mean free path of 15 microns (10 x 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 – 25 x better conductivity than copper Source: Tobias Hertl, et al, Phys. Rev. Lett. 84(21) (2000) 5002

SWNT Quantum Wire Expected Features • 1 -10 x Copper Conductivity • 6 x 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

CNL Armchair Quantum Wire Program (armchair swnt wire with electrical conductivity > copper) ( 5 years, $25 million ) • • • SWNT Sorting (the “signal” for the amplifier) SWNT Amplifier SWNT Purification SWNT Fiber Spinning & Processing SWNT Continuous Growth

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

Rolling Graphite - n, m Vectors Roll -up vect o r

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

SWNT Seeded Growth Current Results 1. Attach Catalyst 2. Deposit on Inert Surface Key Starting Materials • Have Fe. Mo. C Catalyst • Have Short SWNT Seeds • Have Soluble SWNT Key Process Steps • In-Solution Attachment • Controlled Deposition • Catalyst Docking • Reductive Etching • Growth is Next !! 4. SWNT Growth 3. “Dock” Catalyst

SWNTcat Growth Initial 100 mtorr CH 4 – 10 min – 800 o. C 120 nm long 46 nm long 0. 6 nm 1. 8 nm 0. 6 nm 1. 0 nm

SWNT Amplifier Process Flow Attach Disperse Grow Dock Cut

SWNTamp Production Concept Hydro-carbon feedstocks SWNT+ Fe. Mo. C Catalyst Seeded Growth 500 < T < 700 C Mono-Type SWNT (1000 lb / day ) Bulk Output “Inner Loop” Processing Seed Preparation. (1 lb/ day) Cut SWNT, Prep. Catalyst, Functionalize, Attach, Dock

SWNT Growth Rates SWNT Sample SWNTcat on HOPG SWNT Fiber Continued Growth Maruyama Carpet Growth Hata Carpet Growth Free SWNT Growth Rate (mm/min) 0. 005 0. 3 1 250 600 DNA Replication (Bacteria) 0. 340 Science 306, 1362 (2004). Nano Lett. 4, 1025 (2004).

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

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

Dispersion in Super-Acids • SWNT bundles swell in superacids • Dispersion due to “protonation” & intercalation of SWNTs in 102% H 2 SO 4 “Spaghetti” In Oleum V. A. Davis et. Al. , Macromolecues 37, 154 (2004) dried SWNT fiber W. -F Hwang and Y. Wang

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!!!

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)

SWNT Tensile Strength Predicted tensile strength of single-wall nanotubes >100 GPa Calculated strain-tofailure >30% Measurements on small bundles found strength ~30 -60 GPa Yakobson, et al. , Comp. Mat. Sci. 8, 341 (1997).

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

Grid Applications & Benefits • Eliminate Thermal-Sag Failure: Now a $100 B+ 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 $100 M 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 $1 M to $2 M per mile, plus about $250 M per AC/DC converter station. • Remote Power: Could enable utilization of large-scale renewables and remote nuclear.

NASA Success Stories th High Pressure Process , CN CO (Hi. PCO) 6 2 l i l r p L A , y A a d s c e u T ti+v b + impurities CO + CO ui-l d. NASCOA SWNT e l y i 5 n 0 M 0 6 g 2 co 1 $ w n e n s e l c w a n u o b nn oraict e Ato R i f o o u t t n n n a r s G d o w t d criti ersitth n a y i s – v c i n al r U prog SA Ceesneters a rdcehvelop NAram o t h ! c ! r a ! Rese Wire Fe, Ni Catalysts 900 -1200 C 10 -40 atm Continuous process 10 -100’s g/day Small diameters (0. 7 nm) Company spin-off (CNI) 2 Rice Univ. Carbon Nanotechnologies, Inc. & NASA W m u t n a u Q the

Buckytubes Offer Incredible Opportunities Composites l l l 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 Thermally conductive composites – Electronics packaging – Industrial applications Energy l l Fuel cells Supercapacitors and batteries Photovoltaic cells “Quantum Wires” Electronics l l l Field emission – Flat panel displays – Back light units – Electron device cathodes Sensors Printable electronics Logic and memory devices Interconnects

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

From the age of Space to the age of Medicine

New Energy Research Program (Smalley’s Nickel & Dime Solution) • For FY 06 -FY 10 collect 5 cents from every gallon of oil product Invest the resultant > $10 Billion per year as additional funding in frontier energy research distributed among DOE, NSF, NIST, NASA, and Do. D. • For the next 10 years collect 10 cents from every gallon; invest the >$20 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.

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!

But… • Are these ideas tough or aggressive enough? • NO! – Biofuels budget actually smaller than in FY 06 – No market signal for more efficient vehicles • Fuel economy standards – regulatory – 40 mpg in 10 years saves 2. 5 M BOE/day • Substantial gas tax – market mechanism • Up to Congress to execute programs – Incentives for alternate fuel production/vehicles – Funding for research initiatives

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

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

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

2999

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!!

Reading Assignments • • • • Twilight in the Desert, Matthew R. Simmons Winning the Oil Endgame, Amory Lovins Beyond Oil: The View from Hubbert’s Peak, Kenneth S. Deffeyes Out of Gas, Daniel Goodstein The End of Oil, Paul Roberts The Prize, Daniel Yergin Hubbert’s 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) National Nanotechnology Program, (www. nano. gov)