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

Professor Richard E. Smalley Nobel Prize in Chemistry 1996 A 6 week summer project in – page paper in Nature C60 Buckminster- fullerene: Buckyballs with Robert F. Curl and Harold Kroto

National Nanotechnology Program White House – November 2003

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

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

Energy-efficient Commuting

PRIMARY ENERGY SOURCES Alternatives 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 ?

165,000 TW of sunlight hit the earth every day

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

Solar Cell Land Area Requirements 6 Boxes at 3.3 TW Each = 20 TWe Nathan S. Lewis, California Institute of Technology

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

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

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

One World Energy Scheme for 30-60TW 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 x + low temp start. 5.Batteries and supercapacitors -- improve by x for automotive and distributed generation applications. 6.H 2 storage -- light weight materials for pressure tanks and LH2 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!

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. Why Single Wall Carbon Nanotubes?

Graphene Sheet Texas Chicken Wire

SWNT: ROLLED-UP SHEET OF GRAPHITE

World’s largest 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) RAJAT DUGGAL (inside giant SWNT model) Building a 1000-ft SWNT: Cost of the parts: $6,000 pRICEless

armchair (  = 30°) zigzag (  = 0°) intermediate (0    30°) –Cylindrical graphene sheet –Diameters of 0.7 – 3.0 nm Observed tubes typically < 2 nm –Both metallic and semi- conductor species possible –Length to diameter ratio as large as 10 4 – 10 5 can be considered 1-D nanostructures Types of SWNT

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, (1997). McEuen, et al, Phys.Rev.Lett.84, 6082

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

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

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

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 vector

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

SWNT Seeded Growth 1. Attach Catalyst2. Deposit on Inert Surface 3. “Dock” Catalyst 4. SWNT 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 !!

SWNTcat Growth 46 nm long 1.8 nm 0.6 nm 120 nm long 1.0 nm 0.6 nm Initial100 mtorr CH 4 – 10 min – 800 o C

SWNT Amplifier Process Flow Cut Grow Disperse Attach Dock

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

SWNT Growth Rates SWNT SampleGrowth Rate (  m/min) SWNTcat on HOPG0.005 SWNT Fiber Continued Growth0.3 Maruyama Carpet Growth1 Hata Carpet Growth250 Free SWNT Growth600 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

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

Producing Neat SWNT Fibers Dry-Spun from Oleum 6 to 14 Wt. % SWNT Dope Extruded as 50 µm Dia. Fibers 10 9 Tubes in Cross Section 100 Meters Long Prototype Wire - SWNT Fibers Science 305, , 3 September 2004!!!

Ultimate Properties of Polymers Hermann Staudinger, Die Hochmolekularen Organischen Verbindungen, Berlin: Springer p.111 (1932) Perfect orientation Perfect lateral order Few chain end defects (HMW) + INTRINSIC CHAIN PROPERTIES Staudinger Continuous Crystal Model

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

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 $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.

High Pressure CO (HiPCO) Process CO + CO C atm Fe, Ni Catalysts CO 2 + SWNT + impurities Rice Univ.  Carbon Nanotechnologies, Inc. & NASA NASA Success Stories Continuous process ’s g/day Small diameters (0.7nm) Company spin-off (CNI) Tuesday, April 26 th, 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!!!

Energy Fuel cells Fuel cells Supercapacitors and batteries Supercapacitors and batteries Photovoltaic cells Photovoltaic cells “Quantum Wires” “Quantum Wires” Electronics Field emission Field emission –Flat panel displays –Back light units –Electron device cathodes Sensors Sensors Printable electronics Printable electronics Logic and memory devices Logic and memory devices Interconnects InterconnectsComposites Electrically conductive composites Electrically conductive composites –Wide range of conductivities AntistaticAntistatic Electrostatic dissipationElectrostatic dissipation EMI/RFI shieldingEMI/RFI shielding –Bulk parts –Transparent conductive coatings –Anti-corrosion coatings Reinforced composites Reinforced composites Tougher, stronger, stiffer, wear resistant –Thermosets and thermoplastics Parts, coatingsParts, coatings –High performance fibers –High performance ceramics Thermally conductive composites Thermally conductive composites –Electronics packaging –Industrial applications Buckytubes Offer Incredible Opportunities

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 FY06-FY10 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 DoD. 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 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 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

The biggest single challenge for the next few decades: ENERGY for 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??

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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!!

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 ( Matt Simmons, web site: ( M.I. Hoffert et. al., Science, 2002, 298, 981, DOE BES Workshop Report on Hydrogen ( State of the Future, ( Nanotechnology and Energy, 2003 Report, ( National Nanotechnology Program, (