gerard tobias - universidad de sevillacatedras-etsi.us.es/.../workshopendesa-13-11-2013.pdf ·...
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Gerard Tobias ([email protected])
13th November 2013 Cátedra Endesa Red de la Universidad de Sevilla
Consejo Superior de Investigaciones Científicas
• Largest public research organization in Spain
• 126 centres
• Research Institutes spread across Spain
• Research lines: • Humanities and Social Sciences • Biology and Biomedicine • Natural Resources • Agrarian Sciences • Physic Science and Technology • Chemical Science and Technology • Materials Science and Technology • Food Science and Technology
Instituto de Ciencia de Materiales de Barcelona
ALBA SYNCHROTRON
25th years at the UAB campus
Instituto de Ciencia de Materiales de Barcelona
Research lines at ICMAB:
I. Biomaterials and materials for drug delivery,
therapy, diagnostics and sensing
II. Materials for energy and environment
III. Materials for information science and
electronics
IV. Methodologies for materials science and
nanotechnology
NANOTECHNOLOGY
iPod NANO TATA NANO
Why Nano?
NANOTECHNOLOGY
Outline
Nanotechnology Why?, Properties, History, Nanomaterials Applications State-of-the-art, Comercial, Technological Revolution? Energy Applications Sources, Change, Distribution, Storage, Usage
NANOTECHNOLGY - THE CONCEPT -
NANOTECHNOLOGY
Why Nano?
Titanic 1912
Early in the 21st century…
Au rotating on CNT
2,000 times smaller than a humar hair
300 nm
Motor blades
Nature 2003
Early in the 20th century…
NANOTECHNOLOGY
d ~1.5 x 10-9 m d ~1.7 x 10-1m d ~1.3 x 107 m
NANOMATERIALS NANOTECHNOLOGY
Nanometric scale: 10-9 m 10-9 m = 0.000000001 m
NANO scale
NANOTECHNOLOGY
Nanotechnology is the design, characterization, production and application of structures, devices and systems by controlling shape and size at the nanometer scale (RSC).
1 mm ≡ 1.000.000 nano-objects
Hair Thickness ≡ 100.000 nano-objects
A 10 mg sample contains 3.000.000.000.000.000 nano-objects
NANOTECHNOLOGY
The NanoScale
NANOTECHNOLOGY
The NanoScale
The scale that holds so much interest is
typically from 100 nm down to the atomic level (aprox. 0.2 nm)
NANOTECHNOLOGY – Why Nano?
Why Nano?
Biological processes are controlled at the nanoscale Properties differ from the bulk Optical, electrical and magnetic properties, melting point, strength Tunable properties (quantized) Larger surface area - More chemically reactive
PhysRevA 1976, 13, 2287
Gold melting point
Quantum effects
Photochem. Photobio. 85, 21-32, 2009
Coloidal gold
CdSe/ZnS QDs, OceanNanotech
PL spectra Quantum Dots
NANOTECHNOLOGY – Why Nano?
1 cm
1 cm
8 cubes x 6 faces x (1x1) = 48 cm2 6 faces x (2x2) = 24 cm2 48.000 m2
10-9 m
At the Nano scale?
2 cm
Surface are of the crystal
5 x
Surface Area
NANOTECHNOLOGY – Why Nano?
Nano in Nature
Nature Education Knowledge 3(10):30, 2012
Gecko Feet
PNAS 10792, 104, 2007 Magnetotactic Bacteria
Lotus leave
NANOTECHNOLOGY – Why Nano?
Nano in Nature Halloysite clay
Buterfly wings
NANOTECHNOLOGY – Why Nano?
NANOTECHNOLOGY – History
Damascus sword, s. XVII
Nature 444, 286, 2006
Previous to the NanoEra Stained-glass window
Red color – Au NPs (Milan Cathedral 1480)
1959 Richard P. Feynman
“There’s plenty of room at the bottom”
History – Why now?
“What would the properties of materials be if we could really arrange the atoms the way we want them? They would be very interesting to investigate theoretically. I can't see exactly what would happen, but I can hardly doubt that when we have some control of the arrangement of things on a small scale we will get an enormously greater range of possible properties that substances can have, and of different things that we can do.”
1974 Norio Taniguchi - Coins the term “Nanotechnology” “Nanotechnology mainly consists of the processing of, separation, consolidation, and deformation of materials by one atom or one molecule”
NANOTECHNOLOGY – History
History – Why now?
1981 Heinrich Rohrer and Gerd Binnig Scanning tunneling microscope (STM) - Nobel Prize in Physics 1986 -
NANOTECHNOLOGY – History
1985 Robert F. Curl, Sir Harold Kroto, Richard E. Smalley - Nobel Prize in Chemistry 1996 -
Discovery of C60 fullerenes
History – Why now?
1991 Sumio Iijima Carbon Nanotubes 2004 Andre Geim, Konstantin Novoselov - Nobel Prize in Physics 2010 - Graphene
Other carbon nanomaterials
R. Smalley H. Kroto R. Curl
S. Iijima
A. Geim K. Novoselov
NANOTECHNOLOGY – History
NANOTECHNOLOGY – Nanomaterials
How to make it Nano
Top-down Bottom-up
Nanotechnology will allow more efficient approaches to manufacturing in a cost-effective, reduced resource use and waste
Mechanical milling Chemical Etching Electro-explosion Sonication Sputtering Laser-ablation Electron Beam Lithography
Chemical precipitation Sol-gel Aerosol Chemical Vapour Deposition Supercritial Fluid Synthesis Spin Coating Use of templates Self-assembly Molecular Beam Epitaxy
Top-down Bottom-up
NANOTECHNOLOGY – Nanomaterials
How to make it Nano
Is it Nano? Characterisation
Spectroscopic techniques (FTIR, Raman, UV-vis, NMR) – bonds coordination Dynamic Light Scattering – particle size Diffraction (X-ray, neutron, electron) – structure BET (Brunauer Emmet Teller) – surface area
BULK TECHNIQUES
MICROSCOPY
Electron microscopy – TEM (transmission) SEM (scanning) Probe microscopy – AFM (atomic force microscopy), STM (scanning tunneling microscopy)
STEM (scanning transmission)
NANOTECHNOLOGY – Nanomaterials
Nature 56, 354, 1991 Ressolution ∼0.08 nm
Characterisation - TEM
Pt Nanoparticles Carbon Nanotubes
Chem. Commun. 6095, 2009
Graphene
NANOTECHNOLOGY – Nanomaterials
Characterisation - AFM
Gold nanoparticles
NANOTECHNOLOGY – Nanomaterials
Molecules
Nanoparticles
Nanowires Nanotubes
Atomic manipulation
Surfaces Thin Films
Networks
10-9 m
0D
1D 2D
3D
Nanomaterials
NANOTECHNOLOGY – Nanomaterials
Graphene - Carbon Nanomaterials
GRAPHITE
Layered Structure
CARBON NANOTUBE GRAPHENE
Hexagonal latice
NANOTECHNOLOGY – Nanomaterials
Graphene Synthesis
Nature 490, 192, 2012
NANOTECHNOLOGY – Nanomaterials
Graphene - Properties
PROPERTY GRAPHENE COMPARISON WITH OTHER MATERIALS
Size
1 atom thick
Electron beam lithography 20 nm thickness
Young’s Modulus ~ 1 TPa Steel 200 GPa
Density 1,8 - 2,2 g/cm3 Aluminium 2,7 g/cm3
Electrical Conductivity 0.96x106 Ω-1cm-1 Copper 0.60x106 Ω-1cm-1
Thermal Conductivity ~ 5300 W/mK Diamond 2320 W/mK Copper 429 W/mK Graphite 1000 W/mK
Thermal stability <2.000 °C vacuum 600 °C air
Metal contacts in microchips melt between 600 - 1000°C
NANOTECHNOLOGY – Nanomaterials
APPLICATIONS OF NANOTECHNOLOGY
Graphene
Graphene FlagShip
APPLICATIONS
EU funding 1000 M€ 10 years
Graphene and Carbon Nanotubes
Science 339, 535, 2013
APPLICATIONS
Composite Materials
Beijing Olympic Games 2008 Adidas, 400 m Jeremy Wariner USA
BMC 2006
Mercedes 2005 – antiscratch coating
APPLICATIONS
Clothes
APPLICATIONS
AgActive - Antibacterial Antibacterial
Science 309, 1215, 2005
Nanocomp Technologies Inc. has stopped 9 mm bullets with CNT fibers
(Research supported by the USA army)
Super- hydrophobic
Toiletries & Cosmetics
APPLICATIONS
TiO2 NPs Fullerene C-60
nigth cream
Food & Beverages
Liposomes
Lypo-Spheric Vitamin C
TiO2 NPs ZnO NPs
Chantecaille Nano Gold Energizing Cream
Paint
TiO2 NPs
Applications that are evolutionary rather than revolutionary
Universidad Carlos III, Acciona
SCF Technologies
Self-cleaning
Or due to Lotus effect …
APPLICATIONS
Photonic Crystals
APPLICATIONS
Periodic nanostructures that affect the motion of photons and therefore allow light manipulation These can be used for instance to guide light or to paint with no pigment (avoid toxicity)
APL 90, 093102, 2007
APPLICATIONS
Nanoelectronics
Nature 454, 495, 2008
Lighter and more resistant than silicon-based devices
APPLICATIONS
Flexible displays Miniaturization of computer chips (2016 - 22nm)
Nanosensors
APPLICATIONS
Mass sensor with a CNT resonator Detection limit = 10-24 g
Nat. Nanotech. 7, 301, 2012 Michigan State University, 2013
Graphene resistance decreases upon exposure to 5% ethanol vapor
Biomedicine
Dentistry
Implants
Scaffolds for tissue engineering
Drug delivery
Sensors
Diagnosis
Therapy
Towards personalized medicine
APPLICATIONS
Biomedicine – Drug Delivery o Improve delivery of poorly soluble drugs o Targeted delivery (reduce side-effects) o Co-delivery of two or more drugs (combinatory therapy) o Controlled delivery (pH, T, external stimuli) o Multifunctional nanoparticles (drug, contrast agent, …)
APPLICATIONS
Nanomedicines on the market or in clinical trials Product name Supplier Technology Indications Nanocarrier Status
Myocet Cephalon Liposomal doxorubicin
Breast cancer Liposome Approved
Oncaspar Enzon PEG-asparaginase Cancer-acute lymphocytic leukemia
Polymer Approved
Feridex Bayer SPION dextran coating
Liver imaging Iron oxide nanoparticles
Approved
Abraxane Abraxis Albumin-paclitaxel nanoparticles
Breast cancer Albumin nanoparticles
Approved
Aurimmune CytImmune Sciences
Gold coated TNF-PEG particles
Solid Tumors Gold nanoparticles
Phase II
AuroShell Nanospectra Biosciences
Silica nanoparticles- gold coating
Solid Tumors Silica nanoparticles
Phase I
BioVant BioSante Calcium phosphate -vaccine adjuvant
Vaccine adjuvant
Calcium phosphate nanoparticles
Phase I
APPLICATIONS
Periods of technological revolutions that developed in different regions throughout the world that correspond to the regions of global power for the given time period
A new Technological revolution?
First technological revolution (1780 to 1840) - steam engine, the textiles industry and mechanical engineering. Centered in the UK.
Second technological revolution (1840 to 1900) - railways, electricity, and the steel industry. Centered in England, Germany and the United States.
Third technology revolution (1900 to 1950) - electrical engines, heavy chemicals, automobiles, and mass production of consumer durables. Largely based in the USA.
Fourth technology revolution (1950 to present) - synthetics, organic chemicals, and computers. Pacific Basin, Japan, and the United States have been the epicenters.
Fifth technological revolution (present to …) - nanotechnology. Centered in ??
C. Perez, Technological Revolution and Financial Capital (Edward Elgar Publishing 2003)
APPLICATIONS – 5th Technological revolution?
J Nanopart Res 2009
Patents
APPLICATIONS – 5th Technological revolution?
Is Nanotechnology the 5th Technological Revolution?
J Nanopart Res 2009
APPLICATIONS – 5th Technological revolution?
Patents Who will be the leaders in the 5th Technological Revolution?
PRC - People’s Republic of China
Top 15 Assignees in 2011 Nanotechnology Patent Literature
APPLICATIONS – 5th Technological revolution?
Jordan, et al., Nanotechnology Patent Survey: Nanotechnology Law & Business 122 (Fall 2012)
Patents
Who will be the leaders in the 5th Technological Revolution?
APPLICATIONS IN THE ENERGY SECTOR
ENERGY APPLICATIONS
1. Energy Sources
2. Energy Change
3. Energy Distribution
4. Energy Storage
5. Energy Usage
Role of Nanotechnology in the Energy chain
ENERGY APPLICATIONS – 1. Sources
1. Energy Sources
Regenerative Photovoltaics – Thin films, flexible Biomass Energy – Nanosensors, controlled release of pesticides and nutrients Wind Energy – Wear and corrosion protection, nanocomposites lighter blades Geothermal – Wear resistant drilling equipment Hydro-/Tidal power – Corrosion protection
Wear and corrossion protection for oil and gas drilling equipment Catalyst for impurity removal
Nanocomposites radiation shielding and protection Cleaning of radionuclide spillage
Fossil Fuels
Nuclear
Regenerative – Photovoltaics
Photovoltaics Transform solar energy into electricity Price of silicon has risen by 500 % since 2004 Alternative and cheaper technologies are needed
ENERGY APPLICATIONS – 1. Sources
More solar energy strikes the earth on a single day than the world’s population uses in a year.
Source: solar-wirtschaft
Regenerative – Photovoltaics
Roll to roll - large production process of polymer solar cells
ENERGY APPLICATIONS – 1. Sources
Regenerative – Wind Energy
Lotus-effect
Lotus-effect TiO2 NPs coating
Nano-solutions
Nanocomposites
WS2 nanoparticles
Nanocomposite elastomer
Fuel storage, for start-up
MNT Network
ENERGY APPLICATIONS – 1. Sources
ENERGY APPLICATIONS – 2. Change
2. Energy Change
Gas Turbines Wear and corrosion protection of blades (ceramic, intermetallic nano-coatings)
Thermoelectrics
Fuel Cells
Hydrogen Generation
Combustion Engines
Electrical Motors
Nanosturctured compounds for efficient thermoelectrical power generation.
Nano-membranes and electrodes for efficient fuel cells
Nano-catalysts for more efficient generation
Wear and corrosion protection of engine components, NPs as fuel additive
Wear and corrosion protection, superconducting components
Thermoelectric materials provide: Electricity under a temperature gradient Cooling when passing current PbTe doped with Ag and Sb
AgSbTe2 domines in the PbTe matrix
Same stoichiometry Same XRD diffraction pattern
Effect of nanostructuring on AgPbmSbTem+2
Nanocrystals of AgSeTe2
Different ZT
J. Am. Chem. Soc. 127, 9177 (2005)
Thermoelectrics
ENERGY APPLICATIONS – 2. Change
Cooling of automobile seats Waste heat to elecricity Body heat – portable electronics (long term)
Thermoelectrics
Nat. Nanotech. 8, 471, 2013
ENERGY APPLICATIONS – 2. Change Desired material properties - Good electric conductivity - Low heat conductivity
Nano-catalysts
High surface area Efficient hydrogen generation Optimized fuel production (reforming, refining)
ENERGY APPLICATIONS – 2. Change
MoS2 catalysts are use to remove sulphur impurities at oil refineries
Nat. Nano. 1, 3, 2006
MoS2
ENERGY APPLICATIONS – 3. Distribution
3. Energy Distribution
Power Transmission High-Voltage Transmission - Nano-fillers for electrical isolation Superconductors - Nanoscale interface design for loss-less power transmission CNT Power Lines - Based on carbon nanotubes Wireless Power Transmission - by electromagnetic waves (long term)
Smart Grids
Heat Transfer
Nanosensors for intelligent and flexible grid management for highly descentralised power feeds
Efficient heat in and out-flow based on nano-optimized heat exchangers and conductors in industries and buildings (e.g CNT composites, graphene)
Power Transmission - CNT Power Lines Expected Features 10x Copper Conductivity 6x Lighter Stronger Than Steel Zero Thermal Expansion Key Grid Benefits Reduced Power Loss Low-to-No Variations in Voltage Lightweigth Higher Current-Carrying Capacity SWNT Technology Benefits Type Specific High Purity Low Cost Scalable Processing
2005 – NASA granted 16 M$ to RICE University
Electric loss of Conventional Power Grid 5-10%
ENERGY APPLICATIONS – 3. Distribution
Science 318, 1892, 2007 Science 304, 276 2004
Power Transmission - CNT Power Lines
ENERGY APPLICATIONS – 3. Distribution
But… there are different types (properties) of CNTs
CNT power lines…
Metal
Metal or Semiconductor
Metal or Semiconductor
ENERGY APPLICATIONS – 3. Distribution
Power Transmission - CNT Power Lines – State-of-the-art
Sci. Rep. 1, 83, 2011
I2-doped DWNTs • Electrical resistivity ~10-7 Ω.m.
• Specific conductivity (conductivity/weight) > Cu, Al
• High current-carrying capacity of 104, 105 A/cm2
Not yet 108 A/cm2 Armchair Quantum Wire
ENERGY APPLICATIONS – 3. Distribution
Power Transmission - CNT Power Lines – State-of-the-art
Sci. Rep. 1, 83, 2011
ENERGY APPLICATIONS – 3. Distribution
ENDESA Novare program Superconducting Cable 30 m long 3.200 A (vs 600 nowadays); 24 kV; 138 MVA
Source: ICMAB-CSIC
Power Transmission - Superconductors
ENERGY APPLICATIONS – 3. Distribution
4. Energy Storage
Electrical Energy Batteries – Nanostructured electrodes and separator-foils; flexible load management in power grids (short term). Supercapacitors – Nanomaterials for electrodes for higher energy densities
Chemical Energy Hydrogen – Nanoporous materials (organometals, metal hydrides, C-nanomaterials); applications in fuel cells. Fuel Tanks – Gas tight tanks with polymer nanocomposites to improve efficiency in transport and storage Fuel Reforming/Refining – Nano-catalysts for optimized fuel
Thermal Energy Phase Change Materials – Encapsulated PCM, absorve/release heat through a phase transition Adsorptive Storage – Nano-porous materials (e.g. zeolites)
ENERGY APPLICATIONS – 4. Storage
Electrical Energy – Batteries
Sony 2005 Chemisty of batteries along the years
Commercial Batteries
→ In bulk – isolating material → Nanoparticles covered with carbon – new generation of batteries –
Graphite anode replaced by tin nanopaticles coated with amorphous carbon Higher capacity
LiFePO4 (nanostructured cathode)
ENERGY APPLICATIONS – 4. Storage
Nat. Mater. 4, 366 (2005)
Electrochemical behaviour of α-Fe2O3 in bulk and as nanoparticles
Reversible intercalation of 0.6 Li per Fe2O3 (20 nm)
Irreversible transformation with 0.05 Li per Fe2O3
Electrical Energy – Batteries
ENERGY APPLICATIONS – 4. Storage
5. Energy Usage (Saving)
Thermal Insulation
Light/Air Conditioning
Industrial Processes
Lighting
Lightweight Construction
Nanoporous foms and gels (aerogels, polymer foams) for insulation of buildings, industrial processes.
Intelligent management of light and heat flux in building by electrochromic windows, mirror arrays, IR-reflectors
Nano-composites (CNTs, graphene, aerogels, polymer composites, etc.)
Substitution of energy intensive processes based on nanotech process innovations (catalysts, sensors, etc.)
Energy efficient lighting systems (e.g. LED, OLED)
ENERGY APPLICATIONS – 5. Usage
Thermal Insulation
Aerogels
Characteristics High efficient insulating materials Extremely lightweight 99% of pore volume Typically made from silicon, carbon, polymers or ceramics Applications Outside facedes of buildings Industrial processes
ENERGY APPLICATIONS – 5. Usage
Light/Air Conditioning – Electrochromic windows
Nanoparticles-in-glass composite material Windows that controllably and selectively absorb visible light and near-infrared light (heat). Optical transparency can be tuned independently of the near-infrared transparency
Nature, 500, 323, 2013 Absence of voltage Voltage Higher voltage
ENERGY APPLICATIONS – 5. Usage
NANOTECHNOLOGY
5th Technological revolution?
Gerard Tobias ([email protected])
13th November 2013 Cátedra Endesa Red de la Universidad de Sevilla
APPLICATIONS – 5th Technological revolution?
NANOTECHNOLOGY
Carbon Nanotubes
PROPIEDAD
NANOTUBO MONOCAPA
COMPARACIÓN CON OTROS MATERIALES
Tamaño
0,4 – 1,4 nm diámetro
Litografía de haz electrónico - líneas de 20 nm de ancho
Módulo de Young ~ 1 TPa Acero 200 GPa
Densidad 1,33 a 1,40 g/cm3 Aluminio 2,7 g/cm3
Transporte de corriente 1013 A/m2 1000 veces mayor que Ag, Cu Transmisión de calor ~ 2000 W/mK Diamante 2320 W/mK
Cobre 429 W/mK Estabilidad térmica 2.800 °C en el vacío;
500 °C en aire Los alambres metálicos en microchips funden entre 600 y 1000°C
Regenerative – Photovoltaics
Transform solar energy into electricity Price of silicon has risen by 500 % since 2004 Alternative and cheaper technologies are needed
ENERGY APPLICATIONS – 1. Sources
Efficiencies: Silicon – 25 % Polymer – 10 % QDs – 40%
Stack solar cell
More solar energy strikes the earth on a single day than the world’s population uses in a year.
Source: solar-wirtschaft