Part 3

1
5/7/2014
2003 by Glenn Fishbine
Basic Nanotechnology
Commercial Activity: Part 2
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Better Living Through Chemistry
People whom I have seen doing cooking
know nothing of chemistry,
and the people who know chemistry do
not cook
The conclusion seems to be, if one knows
chemistry one must not cook
-(adapted from) Ellen Henrietta Swallow Richards

Topics
Commercial activity 2: materials and industrial chemistry

Overall state of the sector (size, maturity, growth,
evolution of market structure)

Leading firms, foci

State of technology, product, and application
landscape (what's possible, what's being done, why
is it interesting)

Investment opportunities and strategic
considerations for entrants and incumbents

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Chemistry Sampler

Fuel Cells
Encapsulation
Nanoparticles
Nanocomposites
Self Assembly
Surface Chemistry

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Fuel Cells

2010 global market estimated at $100 billion

Automotive

Power Grid

Battery Replacement
Copyright 1996-2002 by Batteries Digest
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Fuel Cells
Fuel cells consist of an electrolyte
material sandwiched between
two electrodes
The input fuel passes over the anode
(and oxygen over the cathode)
where it catalytically splits into
ions and electrons.
The electrons go through an external
circuit to create electricity.
The ions move through the
electrolyte toward the oppositely
charged electrode where they
combine to create by-products,
primarily water and CO2.
what is it?
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Fuel Cells
Proton Exchange Membrane (PEM)
Direct Methanol (DMFC)
Solid Oxide Fuel Cells (SOFC)
Molten Carbonate Fuel Cells (MCFC)
Alkaline Fuel Cells (AFC)
Regenerative Fuel Cells (one unit can run as both a
fuel cell and electrolyzer)
Phosphoric Acid Fuel Cells
Enzymatic Fuel Cell Battery
Zinc-Air Batteries
what kinds are there?
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Fuel Cells
Where does nanotech come in?
Hydrogen atoms are stripped of their electrons at the
anode, and the positively charged protons diffuse
through one side of the porous membrane and
migrate toward the cathode
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Proton Exchange Membrane
GE's Russell Hodgdon with a polymer electrolyte in 1965
Fuel Cells
Air efficiency 30-60%
Oxygen efficiency 50-80%

light weight
durable
green
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Fuel Cells - Costs
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Fuel Cells - Companies (partial list)
Acumentrics Corporation, Massachusetts, USA (SOFC)
Advanced Measurements Inc., Alberta, CANADA (Fuel Cell Testing Systems)
Anuvu Incorporated, California, USA (PEM)
Apollo Energy Systems, Inc., Florida, USA (AFC)
Arbin Instruments, Texas, USA (Fuel Cell Testing Systems)
Argonne National Laboratory, Illinois, USA (PEM, MCFC and SOFC)
Astris Energi, Inc., Mississauga, Ontario, CANADA (AFC)
Avista Laboratories, Washington, USA (PEM)
Azienda Energetica Municipale (AEM spa Milano), Milano, ITALY (PAFC)
Ball Aerospace & Technologies Corp., Colorado, USA
Ballard Power Systems, Inc., British Columbia, CANADA (PEM)
BCS Technology, Inc., Texas, USA (PEM)
Case Western Reserve University, Ernest B. Yeager Center, Ohio, USA (PEM)
Celsius, Malmo, SWEDEN (PEM)
Ceramatec, Utah, USA (SOFC)
Ceramic Fuel Cells Ltd., Victoria, AUSTRALIA (SOFC)
Consejo Superior de Investigaciones Cientificas, Madrid, SPAIN (PEM, MCFC, SOFC)
Coval H2 Partners, California, USA (PEM)
CSIRO Energy Technology, New South Wales, AUSTRALIA
DAIS Corporation, Florida, USA (PEM)
DCH Technology, Inc., California, USA (PEM)
DE NORA s.p.a., ITALY (PEM)
Desert Research Institute, Nevada, USA (PEM, PAFC)
Draeger Safety, Colorado, USA (PEM)
EBARA Ballard Corporation, Tokyo, JAPAN (PEM)
Electric Power Research Institute, California, USA (PAFC and MCFC)
Electro-Chem-Technic, Oxford, UNITED KINGDOM (PEM, PAFC)
ElectroChem, Inc., Massachusetts, USA (PEM)
Element 1 Power Systems Inc., California, USA
Elf Atochem North America, Pennsylvania, USA (PEM)
Emprise Corporation, Georgia, USA
Energia Ltd., Virginia, USA
Energy Conversion Devices, Inc., Michigan, USA (RFC)
Energy Partners, L.C., Florida, USA (PEM)
Energy Visions Inc., Ottowa, Ontario, CANADA (DMFC)
Esoro AG, Faellanden, SWITZERLAND (PEM)

ETH Materials, Zurich, SWITZERLAND (SOFC)
eVionyx, New York, USA (Metal-Air FC)
Federal Energy Technology Center, West Virginia, USA (MCFC and SOFC)
FEV Motorentechnik GmbH, GERMANY (PEM, SOFC)
Florida Solar Energy Center, Florida, USA (PEM)
Forschungszentrum Julich, GERMANY (DMFC, SOFC & PEM)
FuelCell Energy, Connecticut, USA (DFC)
Fuel Cell Resources Inc. - Georgia, USA (PEM membranes)
Fuel Cell Systems - West Sussex, UNITED KINGDOM (AFC)
Fuel Cell Technologies, Ltd., Ontario, CANADA
Gas Technology Institute, Illinois, USA (MCFC, PAFC, , PEM and SOFC)
Gaskatel GmbH, Kassel, GERMANY (AFC & PEM)
Gaz De France, La Plaine, FRANCE (PAFC, PEMFC, SOFC)
GE Energy and Environmental Research Corp., California, USA (PEM, MCFC,
SOFC)
Global Thermoelectric Inc., CANADA (SOFC)
Greenlight Power Technologies, CANADA (Fuel Cell Testing Systems)
GreenVolt Power Corporation, CANADA (AFC)
H Power, New Jersey, USA (PEM)
Hitachi Works, Ibaraki, JAPAN (MCFC)
Hoku Scientific, Hawaii, USA (PEM)
HTceramix - Lausanne, SWITZERLAND (SOFC)
H-Tec - Wasserstoff-Energie-Systeme GmbH, Luebeck, GERMANY (PEM)
Hydro Quebec Research Institute, Quebec, CANADA
Hydrocell U.K., UNITED KINGDOM (AFC, PEM)
Hydrogenics Corporation, Toronto, CANADA
Hydrovolt Energy Systems, California, USA (SOFC)
ICP-CSIC, Madrid, SPAIN
ICTP-CSIC, Madrid, SPAIN (PEM)
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Fuel Cells & Nanotech
More efficient proton exchange

Higher density hydrogen (fuel) storage

lower cost ?????
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Fuel Cells Companies to Watch
Ballard Power Systems
General Motors
Hitachi
Honeywell
Mitsubishi
Motorola
NEC
Seimens AG
Sony
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Encapsulation

Embedding molecules within molecules
Physical Review Letters, Dec 18. 2000
A single gadolinium atom
encapsulated in a
gadolinium fullerene,
encapsulated in a single-
wall carbon nanotube
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Encapsulation - samples

Insect control
polymer microencapsulation
processes that permit
controlled release of
pheromone to suppress
insect mating
Harald D.H. Stver, McMaster University
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Encapsulation - market/players

Not distinct enough at this time to be a
market segment
Value unknown, could be large
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Nanoparticles
Sun screen
Catalysts (automotive)
Corrosion resistance
Solar conversion
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Nanoparticles
Richard Brotzman
Nanophase Technologies Corporation
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Nanoparticles
Properties
optical
chemical
mechanical
electronic
electromagnetic

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Nanoparticles
Optical

The interaction of electromagnetic fields with subwavelength
structures. SOEs (subwavelength optical elements)
Reflection, refraction, diffraction and interference
describe the behavior of traditional optical elements.
With SOEs the equations describing optical behavior
must include quantum-mechanical effects.
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Nanoparticles
Optical
Applications include:
fiber amplifiers
beam splitters
circulators and isolators
interleavers
optical switches
variable optical attenuators

Future Applications include:
polarizers
polarization beam splitters/combiners
filters
photodetectors
photonic bandgap devices
dynamic control for switching,
attenuation and tuning
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Nanoparticles
Optical Market Potential
> 1.1 Billion by 2004 through replacement & new products

Biotech component estimated at $150 million by 2005

No dominant players

watch Nanophase Technologies Corporation
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Nanoparticles
Chemical - sieve

magnetic nanospheres

With no magnetic field, the nanoparticles float about in a liquid.

When a magnetic field is applied, the particles line up following the field
lines, and form rigid columns creating a regular array of obstacles.

This creates a sieve which separates biological molecules based on size.
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Nanoparticles
Chemical - reaction
control

1. Select a particle size
2. Select an electrostatic property
3. Select a particle density
4. Select interaction medium

You now have a tunable chemical
reaction control system

Binding energies Eb of single hydrogen) atom adsorped on the flat and
sharp regions of a (8,0) nanotube versus elliptical deformation
Taner Yildirim
NIST Center for Neutron Research
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Nanoparticles
Paper
Improved coating hold out
Improved print quality
More uniformly hydrophobic sheet surface
Option to modify sheet surface coefficient of friction
Reduced linting and dusting on offset grades
David Osby, EKA Chemicals Inc.
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Nanoparticles
Market Size
The total market size is estimated at $14 billion
- Evolution Capital, Dec 2001

Or $9.2 billion in inorganic/ceramics/metal oxides/etc.
- IoN/NPL Nanotechnology Report Oct 2001
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Nanocomposites

Nanomaterials often have different properties than their bulk-scale counterparts
- nanocrystalline copper is five times harder than ordinary copper

Nanocomposites are materials where the constituents are mixed on a nanometer scale

- A nanoscale dispersion of sheet-like inorganic silicate particles in a polymer matrix is superior to
either constituent in such properties as optical clarity, strength, stiffness, thermal stability, reduced
permeability, and flame retardancy.

Abalone shell has alternating layers of calcium carbonate and a rubbery biopolymer. It is twice as hard
and a thousand times tougher than its components.
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Nanocomposites

Types
plastics
foams
aerogels
powders
membranes
coatings
films
catalysts
semiconductors
magnets
etc.
T/J Technologies, Inc.
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Nanocomposites

Market

$1.2 billion in 2009
- Principia Partners
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Self Assembly

coordinated action of independent entities

under distributed (i.e., non-central) control

to produce a larger structure or to achieve a desired group effect
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Self Assembly

The Holy Grail of Electronics
Moores 1st law Moores 2nd law
Complexity Doubles every 18 months Factory Costs Double every 18 months
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Self Assembly

The Holy Grail of Electronics

The basic idea of self-assembly is to use natural forces to form a device
feature, although its position may be determined by coarser lithography.
Thus, the less-expensive equipment associated with a previous
technology generation may be used, along with self-assembly
techniques, to fabricate circuits for the next generation of devices.

Alternatively, self-assembly can be used to form structures for molecular
electronics. A single molecular monolayer (or a controlled number of
monolayers) can be routinely formed on a substrate by techniques such
as Langmuir-Blodgett deposition.
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Self Assembly

How?
A Langmuir-Blodgett film is a set of monolayers, or layers of
organic material one molecule thick, deposited on a solid
substrate. It can consist of a single layer or many, up to a
depth of several visible-light wavelengths.
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Self Assembly

Making What?

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Self Assembly

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Self Assembly

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Self Assembly

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Self Assembly
Other Self Assembly Areas

Regular structured devices (optics)
Nanocomposite fabrication
Chemical sensors
Wiring matricies (high density RAM)
Chemical reactors
Modular positioners
Light-emitting diodes
Optical storage materials
Biosensors
Drug-delivery materials

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Self Assembly
Market
replacement technologies: > $100 billion
new technologies: large

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Surface Chemistry

Materials interact with their environments through
surfaces and interfaces.

A surface is a stable platform from which reactions
can be studied or controlled.
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Surface Chemistry

Catalysts
polymers (plastics)
methanol
ammonia
hydrogen
carbon monoxide

fertilizers
pharmaceuticals
gasoline
Chemistry
Adhesives
Film
Paint
Sun Screen
Soap
Coatings
Lubrication & wear
Medical devices
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Surface Chemistry

Market

Indirectly influences material production valued in excess of
$550 billion/year.

Petroleum Chemicals

Exxon BASF
BP DuPont
Royal Dutch/Shell Dow
ChevronTexaco Bayer
Total Fina Elf Degussa
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Surface Chemistry

Surface Area

4 pi r
2
6 a
2
pi r
2

a
2
<
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Surface Chemistry

A Fractal Capacitor

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Break
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Commercial Activity
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Brains
If the automobile had followed the same development
cycle as the computer

a Rolls-Royce would today cost $100

get a million miles per gallon

and explode once a year, killing everyone inside.
- Robert X. Cringely
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Brains
875 Abacus
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Brains
1600 Slide Rule - Oughtred
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Brains
1822 multi function calculator - Babbage
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Brains
1946 ENIAC - U.S. Army
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Brains
1971 Microprocessor Intel
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Brains
2000 Pentium IV Intel
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Brains
100 million to 100 billion MIPS

Moore's law predicts that the
upper-end estimate of the human
brain's processing power will be
reached before 2017
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Brains
Statistically speaking,
x x x x x x
The vast majority of life on this planet does
not have a brain
x x x x x x
The remainder doesnt use the one they have.
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Brains
Nanoscale devices

Quantum computing
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Nanoscale devices
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Nanoscale devices
Copyright Cees Dekker, 1997
Intel 20 nm transistor T.U. Delft: <1 nm SWCNT transistor
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Nanoscale devices
Copyright Ron Reifenberger, 1997
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Nanoscale devices
Matrix Semiconductor
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Nanoscale devices
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Nanoscale devices
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Nanoscale devices
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Nanoscale devices
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Nanoscale devices
Current Storage Density is 10,000,000,000
bits/inch
2
Current requirement for one bit = 100 atoms
Theoretical Storage Density may be 1,000 times
higher.
Cubic storage density could be:
100,000,000,000,000,000,000 bits/inch
3

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IBM Millipede
200,000,000,000 bits/inch
2

10 nm
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Nanoscale devices
As devices become smaller, quantum effects tend
to become more important
A single-electron transistor

According to classical physics, there is no way
that electrons can get from the 'source' to
the 'drain', because of the two barrier walls
either side of the 'island'.

However, the structure is so small that
quantum effects occur, and one electron at a
time can tunnel through the barriers.
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Nanoscale devices
Market = Current computer
market
> $100 billion / year

Target companies:
The usual suspects

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Quantum computing
A classical bit can store either a 1 or a 0
Quantum physics states that when we measure the
spin
1/2
particles state we will determine that it is in
the
+1/2
state, or the
-1/2
spin state. In this manner
our qubit is not different from a classical bit, for it can
be measured to be in the
+1/2
, or 1 state, or the
-1/2
,
or 0 state.

Spin is a vector -
It has length
It has direction
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Quantum computing
A quantum bit can have an arbitrary number of states.
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Quantum computing
A quantum particle can exist in two states at the same
time - a coherent superposition

This means that the particle is both in state 0 and state 1
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Quantum computing
Which results in means you dont know its state until
you measure it
One atom: process is totally random,
so you can't decide if a one-atom cat is
alive or dead without measuring it

Few atoms (2-20): process becomes
steadily more predictable

Many atoms (a complete cat):
constitutes an independent measuring
system, so the cat measures it's own
deadness
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Quantum computing
Which means a qubit is both 0 and 1 until measured
So if you could have a quantum computer where the
input and output is represented by 0s and 1s

All possible combinations could exist simultaneously

Which means you could have a massively parallel
computer that produces the answers in one clock
cycle

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Quantum computing
How much sci-fi is it?
IBM
Delft
Confinement of electrons to quantum corrals on a metal surface
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Quantum computing
POWER?
Searching the entire web (8 trillion bytes of data) for a keyword would take
a month using a classical computer.

Such a search might take less than half an hour on a quantum computer.

WHEN?

As things stand, no quantum computer has been built, nor looks likely to be
built in (my) lifetime.
- Andrew Steane
Department of Atomic and Laser Physics
Clarendon Laboratory, Oxford University
MARKET?
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Break
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Commercial Activity
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Power
Irrigation of the land with seawater desalinated by
fusion power

is ancient.

It's called 'rain'.
-Michael McClary
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Power & Energy
Creation
Storage
Transmission
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Power & Energy
Examples:
Solar

81
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Power & Energy
Creation - Solar

5-28% efficiency 80% efficiency
82
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Power & Energy
Creation - Solar

1 nanometer
83
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Power & Energy
Creation - Solar
Brudvig Lab, Yale
84
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Power & Energy
Creation - Solar
85
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Power & Energy
Chlorophyll Voltaic Cell
86
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Power & Energy
Chlorophyll Voltaic Cell

When the porphyrin (antennae) absorbs light, it donates
an electron to the fullerene.
87
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Power & Energy
Dye Sensitized Solar Cell

88
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Power & Energy
Solar Cell usage: > 3 Billion/year

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Power & Energy
Iowa Thin Film Technologies, Inc. -- Boone, IA -- Mfr. Of Flexible, Lightweight, Non-Fragile Solar Cells. Supporting OEM Applications.
BP Solar -- Linthicum, MD -- Mfr. Of Photovoltaic (PV) Products. With 5 Different PV-Technologies, Supplying Products To Turn Sunlight
Into Electricity...
ABCO - Atlantic Distribution Network -- Flushing, NY -- Dealers, Dist., Packaging. Specializing In Small Quantities
Ebara Solar, Inc. -- Belle Vernon, PA
Southwest Photovoltaic Systems Inc. -- Tomball, TX -- Solar Energy Equipment, Supplies & Custom Designed Turnkey Solar Power (PV)
Systems For Remote Power Applications Worldwide
PerkinElmer OptoElectronics -- Santa Clara, CA
Huygen Corp. -- Wauconda, IL -- Test Instruments For Pulp & Paper, Chemicals, Plastics & Power Industries
Solar Electric Specialties Div., Applied Power Corp. -- Willits, CA -- Mfr. / Dist. Photovoltaic Power Systems & Related Components, System
Integration
Solar World Div., Colorado Instruments, Inc. -- Colorado Springs, CO
Solar Converters Inc. -- Guelph, ON
AstroPower, Inc. -- Newark, DE -- Mfr. & Supplier Of High Efficiency Solar Electric Photovoltaic Cells
Optoelectronics, Textron -- Petaluma, CA -- Infrared
Infineon Technologies, Inc., Optoelectronics Div. -- Cupertino, CA -- Optoelectronic Components, Lamps, Optocouplers, Displays, IR
Emitters, Photodetectors
Spire Corp. -- Bedford, MA -- Thermophotovoltaic
United Solar Systems Corp. -- Troy, MI -- Solar Energy (Photovoltaic) Equipment & Systems
Siemens Power Corp., Siemens Solar Industries -- Camarillo, CA
Midnight Sun Energy -- Yellowknife, NT
Northern Communication & Navigation Systems -- Yellowknife, NT
EG & G, Inc. (Corporate) -- Wellesley, MA
International Energy Systems Corp. -- Barrington, IL
East Texas Integrated Circuits, Inc. -- Richardson, TX -- Manufacture Of Numerous Bipolar Integrated Circuits For Optical Sensing
Applications
Silonex, Inc. -- Montreal, QC
Centro Vision Inc. -- Newbury Park, CA
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Power & Energy - Storage
Examples:

batteries

volatiles
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Batteries
All batteries consist of two
electrodes, an anode and a
cathode, and an electrolyte
solution.

The tendency for Zn to loose
electron is stronger than that for
copper. When the two cells are
connected by a salt bridge and
an electric conductor form a
closed circuit for electrons and
ions to flow, copper ions actually
gains electron to become copper
metal.
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Batteries
If you can create both nano-
anodes and nano-cathodes, then
these electrodes are as much as
100 times more powerful than
traditional ones.

University of Florida
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Nuclear Batteries
Americium 241
half life of 432 years
$1,500 per gram

James P. Blanchard
Amit Lal
- U of Wisc
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Batteries Market
$15 Billion per year
Growing Fast
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Capacitors
Two electric plates are separated by an insulating
material (plastic, glass, air...)

These two plates are connected to two leads that
allow the current to flow in and out of the capacitor.

As the current flows, electrons build up on one plate.
At the same time, electrons flow out of the other
plate.

Eventually, the capacitor is completely "charged up"
and no more current will flow. There is a positive
charge on one plate and a negative charge on the
other plate.

Energy can be released if the leads are shorted
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Capacitors

If you can increase the total surface
area of the the two plates, your energy
storage increases.

Composite nanotube
Japan Science & Technology Corporation
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Capacitors

~ $2 Billion/year

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Hydrogen
A hydrogen gas tank that contained energy
equivalent to a gasoline tank would be more than
3,000 times bigger than the gasoline tank.
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Source
Normal m
3
/year
(billions)
Share
Natural gas 240 48%
Oil 150 30%
Coal 90 18%
Electrolysis 20 4%
Total 500 100%
$1.00-$2.00/lb

Hydrogen burns 50% more efficiently than
gasoline, and burning hydrogen creates
less air pollution
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Hydrogen

52,000 Btu per pound

To liquify one pound of hydrogen
requires 5 kWh of electrical
energy
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Hydrogen

Carbon nanotubes are capable of storing anywhere from
4.2% - to 65% of their own weight in hydrogen

Gas-on-Solid Adsorption

Adsorption of hydrogen molecules on activated carbon
has been extensively studied.

The amount of hydrogen stored can approach the
storage density of liquid hydrogen at low temperatures
(i.e., liquid nitrogen).

Carbon-based hydrogen storage materials that can store
significant amounts of hydrogen at room temperature
are under investigation.
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Carbon Scolls - 2630 m
2
/g

Lisa M. Viculis, Julia J. Mack, Richard B. Kaner
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Market Value

> $876,000,000,000/year

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Power & Energy - Transmission
3.8 Trillion Kilowatt-hours
5% - 10% lost in
transmission
200 Billion Kilowatt-hours
lost
=~
waste of > 300 coal fired
plants/year
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Nanocrystaline materials
New transmission materials
Superconductors
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Superconductors
An element or compound that
will conduct electricity
without resistance.
D. J. Bishop, Kent State
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Superconductors
Current is carried by pairs of electrons - Cooper
pairs
The binding energy of the pair opens a gap in
the energy spectrum at E
f
(the Fermi energy -
the highest occupied level in a solid), which
separates the pair states from the "normal" single
electron states.
The size of a Cooper pair is given by the
coherence length which is typically 1000.
The space occupied by one pair contains many
other pairs. There is interdependence of the
occupancy of the pair states.
At low temperatures there is insufficient thermal
energy to scatter the pairs, thus they carry
current unimpeded.
Superconductors.ORG and Ian Grant.
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A. Bollinger and A. Bezryadin
University of Illinois at Urbana-Champaign
MoGe
8 nm
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