E-Learning Material - Nanotechnology and Nanogeoscience

6 Year Integrated M. Tech.
Geotechnology and
Geoinformatics
e-Learning Material
PAPER CODE: MTIGT1001
NANOTECHNOLOGY AND
NANOGEOSCIENCE
Dr. J. SARAVANAVEL
Assistant Professor
Centre for Remote Sensing
Bharathidasan University
Tiruchirappalli- 620023
Email: [email protected]
e-learning Material – Nanotechnology and Nanogeoscience
Dr.J.Saravanavel, Assistant Professor, Centre for Remote Sensing, Bharathidasan University. [email protected]
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MTIGT1001:NANOTECHNOLOGY - 4 Credits
1. Introduction to Nanotechnology and Nanogeoscience: 12hrs

Introduction to Nanotechnology - Consequences of the nanoscale for technology and society,
Introduction to Nanogeoscience.
2. Nanoremote Sensing 12hrs

Hyperspectral Remote Sensing and its application in Geotechnology – Ultraspectral Remote
Sensing and its significance in Geotechnology.
3. Nanocrystals, Nanominerals, Nanofossils and Nanostructures 16hrs

Nanocrystals, types, genesis and significance – Nanominerals, origin, mode of occurrence and its
significance – Microscope based nanostructures and their significance in structure and tectonic
mapping – Field based nanostructures and their significance in structure and tectonic studies -
Nanomagnetic particles and deduction of ancient magnetic fields and their application in regional
tectonics.
4. Nanotechnology in mineral, water and hydrocarbon exploration 12hrs

Nanotechnology in mineral exploration – Nanotechnology (Isotope) in water resources exploration
– Nanofossils in hydrocarbon exploration – Nanotechnology in marine mineral exploration.
5. Nanotechnology in Environmental Geotechnology 12hrs

Nanoparticle interactions in Sedimentary systems - Water and mineral interactions on the
nanoscale - Nanoterrain features in landslide vulnerability mapping – Nanogeosystem features in
seismotectonic and seismic vulnerability mapping– Nanotechnology in water pollution and marine
pollution
References:
1. Hari Singh Nalwa : Encyclopedia of Nanoscience and Nanotechnology, EditedVol. American
Scientific Publishers, ISBN 1-58883-001-2, March 2004
2. J. F. Banfield and A. Navrotsky : Nanoparticles and the environment: edited Vol . Reviews in
mineralogy and geochemistry, vol. 44, Mineralogical Society of America and the Geochemical
Society, Washington, DC 2001, (ISBN 0-939950-56-1)
3. Lynn E. Foster : Nanotechnology: Science, Innovation, and Opportunity, Published by
Prentice Hall Professional Technical Reference, Pub. Date: December 2005,ISBN-13:
9780131927568
4. Peter Baláz : Mechanochemistry in Nanoscience and Minerals Engineering:, Publisher:
Springer; 1 edition (December 8, 2008)ISBN-10:3540748547, ISBN-13: 978-3540748540
5. K E Drexler : Nanosystems: Molecular Machinery, Manufacturing and Computation, Wiley
(1992), ISBN 0471575186

Dr.J.Saravanavel, Assistant Professor, Centre for Remote Sensing, Bharathidasan University. [email protected]
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Dr.J.Saravanavel, Assistant Professor, Centre for Remote Sensing,
Bharathidasan University. email: [email protected]
NANOTECHNOLOGY AND
NANOGEOSCIENCE
e – Learning Material - Unit: 1
Nanoscience will change the

nature of almost every human-
made object in the next century.
National Science and Technology Council, 2000
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On Dec. 29, 1959, at the California Institute of Technology, Nobel

Laureate Richard P. Feynman gave a talk at the annual meeting of
the American Physical Society that has become one of the twentieth
century’s classic science lectures, titled “There’s Plenty of Room at
the Bottom”
What Is Nanotechnology?
(Definition from the NNI)
Research and technology development
aimed to understand and control matter at
dimensions of approximately 1 - 100
nanometer – the nanoscale
Ability to understand, create, and use
structures, devices and systems that have Nanoarea Electron Diffraction
fundamentally new properties and functions of DW Carbon Nanotube –
because of their nanoscale structure Zuo, et.al
Ability to image, measure, model, and

manipulate matter on the nanoscale to
exploit those properties and functions
Ability to integrate those properties and
functions into systems spanning from nano-
to macro-scopic scales Corral of Fe Atoms – D. Eigler
Source: Clayton Teague, NNI
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Why Nanotechnology?
At the nanoscale, the physical, chemical, and
biological properties of materials differ in
fundamental and valuable ways from the
properties of individual atoms and molecules or
bulk matter.
Nanotechnology R&D is directed toward

understanding and creating improved
materials, devices, and systems that exploit
these new properties.
• Examples AFM Image of DNA
- Carbon Nanotubes
- Proteins, DNA
- Single electron transistors
• Not just size reduction but phenomena

intrinsic to nanoscale
- Size confinement
- Dominance of interfacial phenomena
- Quantum mechanics
• New behavior at nanoscale is not

necessarily predictable from what we
know at macroscales.
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Nanotech Areas
Nanotechnology for structural applications
Nanotechnology for information processing, storage and transmission
Nano-biotechnology
Nanotechnology for chemical applications
Nanotechnology for sensor applications
Long term research with generic applications
Instruments and equipment, supporting sciences and technologies
Geo
science
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The Scale of the Earth Sciences
Nano
NanoGeoscience and Technology Laboratory
The nano-scale
Its difficult to grasp quite how small the nano-scale is.

To give some reference points one nanometre (nm) is
one billionth of a metre, or one millionth of a
millimetre. A human hair is 80,000nm thick, a redblood
cell is 5,000nm in diameter and a DNA molecule is
2.5nm wide.
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Nanoscale = billionths (10-9)
6 billion people 10 billion components

8000 mile diameter 8 inch diameter
Effects of Nanoscale
Structural differences:
Nanoscale Carbon
Bulk Carbon
C60 (Buckeyball)
Smalley, Curl, Kroto
1996 Nobel Prize
Graphite Diamond
Carbon Nanotubes
Sumio Iijima - 1991
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History of Nanotechnology
• ~ 2000 Years Ago – Sulfide nanocrystals used by Greeks and Romans
to dye hair
• ~ 1000 Years Ago (Middle Ages) – Gold nanoparticles of different
sizes used to produce different colors in stained glass
windows
• 1974 – “Nanotechnology” - Taniguchi uses the term nanotechnology
for the first time to describe the science and technology of
processing or building parts with nanometric tolerances.
• 1981 – IBM develops Scanning Tunneling Microscope
• 1985 – “Bucky ball” - Scientists at Rice University and University of
Sussex discover C60
• 1986 – “Engines of Creation” - First book on nanotechnology by K.
Eric Drexler. Atomic Force Microscope invented by Binnig, Quate
and Gerbe
• 1989 – IBM logo made with individual atoms
• 1991 – Carbon nanotube discovered by S. Iijima
• 1999 – “Nanomedicine” – 1st nanomedicine book by R. Freitas
• 2000 – “National Nanotechnology Initiative” launched gold nano particles.
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But something as small as an atom is impossible to

see with the naked eye. In fact, it’s impossible to see
with the microscopes typically used in a high school
science classes. The microscopes needed to see things
at the nanoscale were invented relatively recently—
about 30 years ago.
Once scientists had the right tools, such as

the scanning tunneling microscope (STM) and the
atomic force microscope (AFM), the age of
nanotechnology was born.
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Unique Properties of Nanoscale Materials
• Quantum size effects result in unique mechanical,

electronic, photonic, and magnetic properties of
nanoscale materials
• Chemical reactivity of nanoscale materials greatly

different from more macroscopic form, e.g., gold
• Vastly increased surface area per unit mass, e.g.,

upwards of 1000 m2 per gram
• New chemical forms of common chemical elements, e.g.,

fullerenes, nanotubes of carbon, titanium oxide, zinc
oxide, other layered compounds
Nanoscale Size Effect

• Realization of miniaturized devices and systems while
providing more functionality
• Attainment of high surface area to volume ratio
• Manifestation of properties, including changes in:

- Physical Properties (e.g. melting point)
- Chemical Properties (e.g. reactivity)
- Electrical Properties (e.g. conductivity)
- Mechanical Properties (e.g. strength)
- Optical Properties (e.g. light emission)
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What’s the BIG deal about something so SMALL?

Materials behave differently at this size scale.
It’s not just about miniaturization.
At this scale---it’s all about INTERFACES
Color depends on particle size

Quantum dots 3.2 nm in diameter have blue emission
Quantum dots 5 nm in diameter have red emission
Evident Technologies
evidot Quantum Dots
Ordinary light excites all color quantum dots.

(Any light source “bluer” than the dot of interest works.)
Quantum dots change color with size because additional

energy is required to “confine” the semiconductor
excitation to a smaller volume.
Source: Bala Manian, Quantum Dot Corp.
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Thermal Conductivity
Si phonon thermal conductivity: Bulk vs. Microscale
Room-temperature thermal conductivity data for Thermal conductivities of the silicon device
silicon layers as a function of their thickness. layers with thicknesses 0.42, 0.83, and 1.6 mm.
Asheghi, A., Touzelbaev, M.N., Goodson, K.E., Leung, Y.K., and Wong, S.S., 1998, “Temperature-
Dependent Thermal Conductivity of Single-Crystal Silicon Layers in SOI Substrates,” ASME
Journal of Heat Transfer, 120, 30-36.
The melting point of gold particles decreases dramatically

as the particle size gets below 5 nm
The well-known and industrially important melting point

of gold is 10640C. However, for gold grains 4 nm in
diameter, the melting point has been measured at only
4270C
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Solubility
increases
with
decreases of
grain size
APPLICATION OF NANOTECHNOLOGY
Consequences of the nano-scale for technology and society
Nanotechnology is helping to considerably improve, even
revolutionize, many technology and industry sectors:
information technology, energy, environmental science,
medicine, homeland security, food safety, and transportation,
among many others.
Using nanotechnology, materials can effectively be made to be

stronger, lighter, more durable, more reactive, more sieve-like,
or better electrical conductors, among many other traits. There
already exist over 800 everyday commercial products that rely
on nanoscale materials and processes
Nanotechnology Unit-1 J.Saravanavel 16

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Nanoscale additives in polymer composite materials for baseball bats, tennis

rackets, motorcycle helmets, automobile bumpers, luggage, and power tool
housings can make them simultaneously lightweight, stiff, durable, and
resilient.
Nanoscale additives to or surface treatments of fabrics help them resist
wrinkling, staining, and bacterial growth, and provide lightweight ballistic
energy deflection in personal body armor.
Nanoscale thin films on eyeglasses, computer and camera displays, windows,
and other surfaces can make them water-repellent, antireflective, self-cleaning,
resistant to ultraviolet or infrared light, antifog, antimicrobial, scratch-resistant,
or electrically conductive.
Nanoscale materials in cosmetic products provide greater clarity or coverage;
cleansing; absorption; personalization; and antioxidant, anti-microbial, and
other health properties in sunscreens, cleansers, complexion treatments,
creams and lotions, shampoos, and specialized makeup.
Nano-engineered materials in the food industry include nanocomposites in
food containers to minimize carbon dioxide leakage out of carbonated
beverages, or reduce oxygen inflow, moisture outflow, or the growth of bacteria
in order to keep food fresher and safer, longer. Nanosensors built into plastic
packaging can warn against spoiled food. Nanosensors are being developed to
detect salmonella, pesticides, and other contaminates on food before packaging
and distribution.
High-resolution image of
a polymer-silicate
nanocomposite. This
material has improved
thermal, mechanical, and
barrier properties and
can be used in food and
beverage containers, fuel
storage tanks for aircraft
and automobiles, and in
aerospace components.
(Image courtesy of
NASA.)
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Sporting Goods
Cosmetics, Clothes and Food
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Nano-engineered materials in automotive products include high-power

rechargeable battery systems; thermoelectric materials for temperature
control; lower-rolling-resistance tires; high-efficiency/low-cost sensors
and electronics; thin-film smart solar panels; and fuel additives and
improved catalytic converters for cleaner exhaust and extended range.
Nano-engineered materials make superior household products such as
degreasers and stain removers; environmental sensors, alert systems, air
purifiers and filters; antibacterial cleansers; and specialized paints and
sealing products.
Nanostructured ceramic coatings exhibit much greater toughness than
conventional wear-resistant coatings for machine parts. In 2000, the U.S.
Navy qualified such a coating for use on gears of air-conditioning units for
its ships, saving $20 million in maintenance costs over 10 years. Such
coatings can extend the lifetimes of moving parts in everything from
power tools to industrial machinery.
Nanoparticles are used increasingly in catalysis to boost chemical
reactions. This reduces the quantity of catalytic materials necessary to
produce desired results, saving money and reducing pollutants. Two big
applications are in petroleum refining and in automotive catalytic
converters.
Nanotechnology in Electronics and Information Technology

Nanotechnology is already in use in many computing, communications, and
other electronics applications to provide faster, smaller, and more portable
systems that can manage and store larger and larger amounts of information.
Nanoscale transistors that are faster, more powerful, and increasingly energy-
efficient; soon your computer’s entire memory may be stored on a single tiny
chip.
Magnetic random access memory (MRAM) enabled by nanometer-scale
magnetic tunnel junctions that can quickly and effectively save even encrypted
data during a system shutdown or crash, enable resume-play features, and
gather vehicle accident data.
Displays for many new TVs, laptop computers, cell phones, digital cameras, and
other devices incorporate nanostructured polymer films known as organic light-
emitting diodes, or OLEDs. OLED screens offer brighter images in a flat format, as
well as wider viewing angles, lighter weight, better picture density, lower power
consumption, and longer lifetimes.
Other computing and electronic products include Flash memory chips for iPod
nanos; ultraresponsive hearing aids; antimicrobial/antibacterial coatings on
mouse/keyboard/cell phone casings; conductive inks for printed electronics for
RFID/smart cards/smart packaging; more life-like video games; and flexible
displays for e-book readers.
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Nanotechnology in ENERGY
The difficulty of meeting the world’s energy demand is compounded by the
growing need to protect our environment. Many scientists are looking into ways
to develop clean, affordable, and renewable energy sources, along with means
to reduce energy consumption and lessen toxicity burdens on the environment.
Prototype solar panels
incorporating nanotechnology are
more efficient than standard
designs in converting sunlight to
electricity, promising inexpensive
solar power in the future.
Nanostructured solar cells already
are cheaper to manufacture and
easier to install, since they can use
print-like manufacturing processes
New solar panel films incorporate and can be made in flexible rolls
nanoparticles to create lightwieght, rather than discrete panels. Newer
flexible solar cells. (Image courtesy of research suggests that future solar
Nanosys converters might even be
“paintable.”
Clean and Cheap Energy
Solid oxide fuel cell

Computational Courtesy: Steve McIntosh, UVA
catalysis
Courtesy: Matthew
Neurock, UVA
Laser-textured silicon for solar cells

Courtesy: Mool Gupta, UVA
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Nanotechnology in ENERGY….
Nanotechnology is improving the efficiency of fuel production from normal and
low-grade raw petroleum materials through better catalysis, as well as fuel
consumption efficiency in vehicles and power plants through higher-efficiency
combustion and decreased friction.
Nano-bioengineering of enzymes is aiming to enable conversion of cellulose
into ethanol for fuel, from wood chips, corn stalks (not just the kernels, as
today), unfertilized perennial grasses, etc.
Nanotechnology is already being used in numerous new kinds of batteries that
are less flammable, quicker-charging, more efficient, lighter weight, and that
have a higher power density and hold electrical charge longer. One new lithium-
ion battery type uses a common, nontoxic virus in an environmentally benign
production process
Nanostructured materials are being pursued to greatly improve hydrogen
membrane and storage materials and the catalysts needed to realize fuel cells
for alternative transportation technologies at reduced cost. Researchers are
also working to develop a safe, lightweight hydrogen fuel tank.
Various nanoscience-based options are being pursued to convert waste heat in
computers, automobiles, homes, power plants, etc., to usable electrical power.
Nanotechnology in ENERGY….
An epoxy containing carbon nanotubes is being used to make windmill blades
that are longer, stronger, and lighter-weight than other blades to increase the
amount of electricity that windmills can generate.
Researchers are developing wires containing carbon nanotubes to have much
lower resistance than the high-tension wires currently used in the electric grid
and thus reduce transmission power loss.
To power mobile electronic devices, researchers are developing thin-film solar
electric panels that can be fitted onto computer cases and flexible piezoelectric
nanowires woven into clothing to generate usable energy on-the-go from light,
friction, and/or body heat.
Energy efficiency products are increasing in number and kinds of application. In
addition to those noted above, they include more efficient lighting systems for
vastly reduced energy consumption for illumination; lighter and stronger
vehicle chassis materials for the transportation sector; lower energy
consumption in advanced electronics; low-friction nano-engineered lubricants
for all kinds of higher-efficiency machine gears, pumps, and fans; light-
responsive smart coatings for glass to complement alternative heating/cooling
schemes; and high-light-intensity, fast-recharging lanterns for emergency crews.
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Nanotechnology in Environmental Application

There are many eco-friendly applications for nanotechnology, such as materials
that provide clean water from polluted water sources in both large-scale and
portable applications, and ones that detect and clean up environmental
contaminants
Nanotechnology could help meet the need
for affordable, clean drinking water through
rapid, low-cost detection of impurities in and
filtration and purification of water. For
example, researchers have discovered
unexpected magnetic interactions between
ultrasmall specks of rust, which can help
Nanorust cleans arsenic remove arsenic or carbon tetrachloride from
from drinking water water; they are developing nanostructured
filters that can remove virus cells from
water; and they are investigating a
deionization method using nano-sized fiber
electrodes to reduce the cost and energy
requirements of removing salts from water.
Nanoparticles will someday be used to clean industrial water pollutants in

ground water through chemical reactions that render them harmless, at much
lower cost than methods that require pumping the water out of the ground for
treatment.
Researchers have developed a nanofabric "paper towel," woven from tiny wires
of potassium manganese oxide, that can absorb 20 times its weight in oil for
cleanup applications.
Many airplane cabin and other types of air filters are nanotechnology-based
filters that allow “mechanical filtration,” in which the fiber material creates
nanoscale pores that trap particles larger than the size of the pores. They also
may contain charcoal layers that remove odors. Almost 80% of the cars sold in
the U.S. include built-in nanotechnology-based filters.
New nanotechnology-enabled sensors and solutions may one day be able to
detect, identify, and filter out, and/or neutralize harmful chemical or biological
agents in the air and soil with much higher sensitivity than is possible today.
Researchers around the world are investigating carbon nanotube “scrubbers,”
and membranes to separate carbon dioxide from power plant exhaust. And
researchers are investigating particles such as self-assembled monolayers on
mesoporous supports (SAMMS™), dendrimers, carbon nanotubes, and
metalloporphyrinogens to determine how to apply their unique chemical and
physical properties for various kinds of toxic site remediation.
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Nanotechnology in Medical and Biotechnology

Nanotechnology has the real potential to revolutionize a wide array of medical and
biotechnology tools and procedures so that they are more personalized, portable,
cheaper, safer, and easier to administer. Below are some examples of important
advances in these areas.
Quantum dots are semiconducting nanocrystals that can
enhance biological imaging for medical diagnostics. When
illuminated with ultraviolet light, they emit a wide
spectrum of bright colors that can be used to locate and
identify specific kinds of cells and biological activities.
These crystals offer optical detection up to 1,000 times
better than conventional dyes used in many biological
tests, such as MRIs, and render significantly more
information.
Nanotechnology has been used in the early diagnosis of
atherosclerosis, or the buildup of plaque in arteries.
Researchers have developed an imaging technology to
measure the amount of an antibody-nanoparticle complex
that accumulates specifically in plaque. Clinical scientists
are able to monitor the development of plaque as well as
its disappearance following treatment
Gold nanoparticles can be used to detect early-stage Alzheimer’s disease.
Molecular imaging for the early detection where sensitive biosensors

constructed of nanoscale components (e.g., nanocantilevers, nanowires, and
nanochannels) can recognize genetic and molecular events and have reporting
capabilities, thereby offering the potential to detect rare molecular signals
associated with malignancy.
Multifunctional therapeutics where a nanoparticle serves as a platform to

facilitate its specific targeting to cancer cells and delivery of a potent treatment,
minimizing the risk to normal tissues.
Research enablers such as microfluidic chip-based nanolabs capable of
monitoring and manipulating individual cells and nanoscale probes to track the
movements of cells and individual molecules as they move about in their
environments.
Research is underway to use nanotechnology to spur the growth of nerve cells,
e.g., in damaged spinal cord or brain cells. In one method, a nanostuctured gel
fills the space between existing cells and encourages new cells to grow. There is
early work on this in the optical nerves of hamsters. Another method is
exploring use of nanofibers to regenerate damaged spinal nerves in mice.
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"Nanominerals" Influence Earth Systems from Ocean to Atmosphere to

Biosphere
A bacteria cell living in a no-oxygen

environment "breathes" using mineral
nanoparticles
Nanotechnology in transportation infrastructure

In addition to contributing to building and maintaining lighter, smarter, more
efficient, and “greener” vehicles, aircraft, and ships, nanotechnology offers
various means to improve the transportation infrastructure:
Nano-engineering of steel, concrete, asphalt, and other cementitious
materials, and their recycled forms, offers great promise in terms of improving
the performance, resiliency, and longevity of highway and transportation
infrastructure components while reducing their cost. New systems may
incorporate innovative capabilities into traditional infrastructure materials,
such as the ability to generate or transmit energy.
Nanoscale sensors and devices may provide cost-effective continuous
structural monitoring of the condition and performance of bridges, tunnels,
rails, parking structures, and pavements over time. Nanoscale sensors and
devices may also support an enhanced transportation infrastructure that can
communicate with vehicle-based systems to help drivers maintain lane
position, avoid collisions, adjust travel routes to circumnavigate congestion,
and other such activities.
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Courtesy of NASA
Future sensor systems will be able to use multiple physical phenomena to sense
many analyses simultaneously for a variety of applications, some of which are
noted above.
Illustrated here are (left to right) an optical tranducer, which measures light; an
electro/chemical tranducer, which measures electrical properties; a magnetic
tranducer, which measures changes to the local magnetic field; and a mechanical
transducer, which detects changes in motion. (Image by N.R. Fuller, Sayo-Art.)
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NASA Nanotechnology Roadmap

C A P A B I L I T Y
Multi-Functional Materials
Adaptive
Autonomous Sel
Revolutionary Spacecraft f-Repairing
Aircraft Concepts (40 Space Missions
Reusable (30% less mass, % less mass)
High Strength Launch Vehicle 20% less emission,
(20% less mass, Bio-Inspired Materials
Materials 25% increased and Processes
(>10 GPa) 20% less noise) range)
Increasing levels of system design and integration
• Single-walled • Nanotube • Integral • Smart “skin” • Biomimetic

Materials nanotube fibers composites thermal/shape materials material
control systems
• Low-Power CNT • Molecular • Fault/radiation • Nano electronic • Biological

Electronics/
electronic computing/data tolerant “brain” for space computing
computing
components storage electronics Exploration
• In-space • Nano flight • Quantum • Integrated • NEMS flight

Sensors, s/c
nanoprobes system navigation nanosensor systems @ 1 µW
components
components sensors systems
2002 2004 2006 2011 2016

>
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NANOGEOSCIENCE
Nanogeoscience is broadly defined to include the study of
materials and processes at the nanoscale in their role in
geologic processes on the Earth and other planets.
Because many nanoscale phenomena are concentrated near

the Earth’s surface, in the region sometimes referred to as
the critical zone and comprising land, water, air, and the
immediate subsurface environment, these phenomena are
of crucial importance to humans
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Nanogeoscience addresses a number of issues crucial to the

geological sciences:
The transport of metals and organics in the near-surface

environment; global geochemical and climate cycles (including
the carbon cycle); ore genesis and exploitation, soil science;
microbial geochemical action; origin of life; space weathering
and planetary surfaces; atmospheric particle transport and ice
nucleation; and even deep Earth processes.
Nanogeoscience also addresses national needs: environmental

safety, national security, and human health; mining, minerals,
oil, and gas; environmentally friendly manufacturing and new
geomimetic materials; and agriculture and food.
The Venn diagram

below shows how
nanoscience is central
to many important
problems in Earth
science and how
nanogeoscience links
Earth science to other
disciplines.
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NANOSCIENCE plays out in the critical zone of the Earth.
Jordan (2001) defines in a NRC book entitled Basic Research

Opportunities in Earth Science , as the place where the land
meets the fluid and gas envelopes of the Earth, i.e., the
hydrosphere & atmosphere. Fresh water, agriculture & many
vital natural resources such as most mineral deposits &
timber are here. Geo & bio aspects make it most
heterogeneous.
Based on Physical, geochemical, and biologic processes,
four principal & overarching categories in critical zone of
the Earth identified.
1) biologic
2) weathering,
3) fluid transport, &
4) near-surface tectonics
Critical Zone Processes

1) Biologic Activity:
Due to organism s nutritional requirements, drives a significant
amount of chemical cycling within & between water, soil, rocks
&atmosphere;
2) Weathering:
Constantly at work in the critical zone, generating soil, destroying
& producing minerals in the process & redistributing elements
among water, rocks, & organic materials
3) Fluid transport:
the critical component in water resources supply & management,
as well as everything from flooding to landform development
4) Near-surface tectonics:
shapes the land surface through faulting, subsidence, uplift & mass
movement
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The Large-scale geological effects are beautifully Concealed in tiny

domains of rocks. These pieces of rock fragment are like memory
chips that may retain extraordinary potential information on
significant geological events or past history.
To explore the matter at nanoscale, we need to access a suite of

techniques and tools.
Most sophisticated tools relate to microscopy: e-g.,
 Transmission electron microscopy (TEM),
 Scanning electron microscopy (SEM),
 Atomic force microscopy (AFM),
 Scanning tunneling microscopy (STM)
 or in-situ analysis: e.g., Raman spectroscopy, Nuclear
magnetic
 Resonance (NMR) spectroscopy, Extended X-ray
absorption fine structure (EWS),
 X-ray absorption near edge structure (XANES),
 Differential scanning calorimetry (DSC),
 Thermal analysis, thermogravimetry, solution calorimetry,
etc
Various micro-analytical techniques (e.g., laser probes, electron

probes, and ion probes) employed in petrology help in constraining
the ages of the earth's most ancient rocks, chemical and isotopic
character of fluids that have altered the composition of the Earth's
crust, and the ages of minerals significant to the reconstruction of
Earth's past climate.
The quantum computers and new sensors/ detectors based on rapidly
emerging nano-technologies will certainly have major impact on how we
model and analyze the Earth and planets. Focused Ion Beam (FIB) is a
robust tool for advanced application of nanoanalysis in geosciences and
applied mineralogy (Wirth, 2004). The new technology, LEAP (Local
electrode atom probe) has tremendous application for exploring
nanoscale magnetic particles in rocks and sediments, which can serve
as recorders of the ancient magnetic fields and microbial biospheres on
Earth and even Mars. The capabilities of LEAP involve examining nano
size geological materials; e.g., single-domain magnetite crystals (in the
30-500 nm size range) that are the key carriers of remnant magnetization
in rocks (ct Kuhlman et al. 2001).
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Geologists have the unique privilege of looking at

the entire cross-section of rocks from the large-
scale mountain- belts to the thin-section scales
under microscopes. Infact, they are capable of
contemplating the phenomena occurring on a
vast range of scales, both in space (nanometers to
thousands of kilometers) and time (nanoseconds
to billion of years).
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Importance of Nanogeoscience
1. Iron in mineral nanoparticles is bioavailable to various

species of marine phytoplankton making them more
important source of Oceanic iron.
2. Also in toxic-metal transport in Earths near surface

terrestrial environment – Radionuclide transport by
groundwater over several kilometers in short periods of time
defies thermodynamics based predictions
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Nanogeoscience, Why?
Contamination of an area of 1600 km2 by Cu, Zn, As, Pb, and Cd due to
11/2 century of mining - the largest Superfund site – in western
Montana,USA. Metals moved many hundreds of km down the
hydrologic gradient & across floodplains in the Clark Fork River basin.
Carried chiefly by nanominerals and mineral nanoparticles of
manganese and iron oxyhydroxides (Hochella et al. 2005).
Currently mechanical properties much less studied; so impact on

working of Earth less known; so an area of exciting future research in
mineralogy.
Natural production of mineral nanoparticles by mechanical grinding

associated with earthquake generating faults in shallow crust & Earth s
surface is known.
Large volumes of mineral fragments of 10 20 nm in size noticed in

pulverized rock in fault zones of up to 100 m width. Suggesting
importance of mineral nanoparticles in fault mechanics
Nanogeoscience, Why?
Nanoparticles of high-pressure silicates (e.g., ringwoodite and

wadsleyite) may have key role in deep-focus earthquakes (300
700 km depth) in Earth s mantle
As nanoparticles easily move past each other without

mechanical shearing of individual grains (like talc) high pressure
does not restrict the movement.
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NANOFILIM in WEATHERING
Zhu et al. (2006) reported thick amorphous silica rich (leached

from feldspar or from ground water) layers of nanofilms (10-50
nm) on feldspar surfaces in the Jurassic Navajo Sandstone, Black
Mesa, Arizona, USA.
Weathering rate of K-feldspars is very slower under natural

conditions than under similar conditions in weathering
experiments. Nanofilm study explains difference the rate
weathering in the lab and under nature.
Amorphous nanofilms on uranium containing pyrochlore (a

calcium titanate considered for immobilizing fissile elements),
slows release of U (Stubbs et al. 2008). May play a crucial role in
dictating uranium s mobility through the vadose zone
The Clark Fork riverbed and Floodplains, Mo Reducing zones of

river bed with amorphous, aggregated Zn-sulfide nanoparticles.
Their environmental role almost completely unknown a research
opportunity.
Amorphous, metal-bearing, naturally occurring nanomaterials still

undocumented or completely unknown.
Recent studies showed secondary amorphous silica with toxic

heavy metals are relatively common.
37
NANO-MATERIALS OUTSIDE EARTH
38
39
Geoscientists study phenomena occurring on a vast range of

scales, both in space (nanometers to thousands of kilometers)
and time (nanoseconds to billions of years).
Such a multiscale approach to scientific problems is necessary in

monitoring and minimizing the effects of pollution, evaluating the
toxicity of materials, and ensuring the safety of water and food
supplies.
Research on processes at the nanoscale accelerates the healthy

evolution within Geosciences toward understanding geologic
process from the molecular to the global scale
Nanogeoscience is the study of nanoscale phenomena related

to geological systems. Predominantly, this is interrogated by
studying environmental nanoparticles between 1-100
nanometers in size.
 Nanoscale minerals - nanoparticles - are formed in the
environment as a result of microbial activity, inorganic
precipitation reactions and chemical weathering.
 Nanoparticles of many common mineral phases have been found,
including ferric iron oxyhydroxides, such as goethite; transition
metal sulfides, such as sphalerite; as well as less common
minerals such as ceria or gold.
 In addition, numerous common minerals are only found as
nanomaterials, including ferrihydrite, akaganeite, mackinawite,
and manganese hydroxides.
 Naturally-formed nanoparticles can be important components of
geochemical cycles in soils, groundwater, rivers and lakes because
they possess high surface areas for adsorption and reaction.
40
Nanosystems, such as nanocrystals and nanopores are ubiquitous in

geological environments, especially in the critical zone where fluids
meet the solid earth.
Geochemical reactions and processes in nano-systems are greatly

different from those in macroscopic bulk systems
NanoGeoScience is to understanding of the reactions between
natural materials and fluids for:
 Development of nano particles to remove specific pollutants
from ground water
 Development of nano particles that binds and neutralizes toxic
materials in waste
 Increasing the recovery of oil from lime
 Reducing the amount of CO2 in the atmosphere by incorporation
into solids
 Solving the mystery about the formation of shells, bones, and
teeth. This will give our medical colleagues new possibilities of
developing better and efficient treatments of bone diseases.
Eight years ago, features resembling bacteria and measuring 20 to 100

nanometers across were discovered in the Martian meteoriteALH84001.
NASA scientists interpreted these features to be the fossilized remnants of
ancient life, but many scientists rejected that conclusion.
Eight years ago, nanometer-sized features

resembling bacteria were discovered in the
Martian meteorite ALH84001. Although some Close-up of a Mars
scientists think nanometer-sized life can't meteorite, showing what
exist, others contend that nanobacteria are some have argued appears
the new frontier in life science. to be fossilized evidence of
ancient microbial life.
41
Significance of Nanoscience to the Geoscience (Samples)

Minerals in the troposphere, including nanominerals, with implications
for radiative forcing effects and consequently global heating/cooling
The general formation, growth, and nature of airborne nanoparticles,

with implications for human health effects and atmospheric chemistry,
including heterogeneous catalysis on nanoaerosols
Carbonaceous nano films in many crystalline rocks of deep crustal and

mantle origin, with implications for the relatively high electrical
conductivity of these rocks
organic nanofilms in volcanic rocks, with implications for complex

abiotic heterogeneous catalysis and synthesis
Mineral nucleation and growth in the nano domain, with implications

related to the initial growth of minerals
42
Significance of Nanoscience to the Geoscience ….

Heterogeneous nanoprecipitation at the mineral/water interface in
soils, with implications for the transport and distribution of toxic
metals in the environment
Mineral surface reactivity in the presence of nanofilms of water, with

implications to weathering reactions and the formation of secondary
phases
The complexation of aqueous solution components in polynuclear

complexes and nanoclusters, with fundamental applications in the
areas of aqueous geochemistry and biogeochemistry
Metal sorption on nanominerals in acid mine drainage environments,

with implications to toxic metal transport in surface and
groundwater systems
Significance of Nanoscience to the Geoscience ….

The characteristics of naturally occurring magnetic nanoparticles, with
implications for biological systems, remediation strategies, medicine,
and so on
Nanomolecular attachments between minerals and microbes, with

implications for bacterial attachment and electron transport between
living and non-living systems.
The above examples are now available in literatures
But just from above list, one can project that nanoscience will one day
account for significant portions of research in the subfields of
mineralogy, petrology, geochemistry and biogeochemistry, atmospheric
science, hydrogeoscience, geophysics, and perhaps other sub-
disciplines.
43
NANOMINERALS, NANOPARTICLES &

NANOMATERIALS
The mineral world includes in present about 4000 valid mineral

species of various compositions (from native elements to organic
compounds) and size. Some 400 or 500 of the existing mineral
species are known only as inclusions in other minerals
Generally, the crystal/grain size of minerals can vary between 102m and 10-9
m. The
A – Macrominerals 105 – 10-3 m (mineralogical methods)

B – Microminerals 10-4 – 10-6 m (optical mineralogy)
C – Inframinerals 10-7 – 10-8 m (EPMA, NGR, XRD)
D – Nanominerals less than 10-8 m (TEM/SAED)
The category A, the macrominerals, includes the majority of the
mineral species known worldwide (may be 3000 – 3500 in number).
The microminerals (category B) include a relatively large number of

minerals, which can be detected under the microscope and occur
mainly as inclusions in other minerals or form only fine to very fine
grained aggregates, e.g. clay minerals. Exsolution bodies belong
hitherto as well as the daughter minerals in the fluid inclusions.
44
The inframinerals (category C) cannot be seen or cannot

reasonably good be identified under the optical microscope. They
occur as ultrafine inclusions and/or as very fine intergrowths, a fact
preventing a reliable identification as a result of interfering
properties. The main and mostly used methods of identification
are EPMA (electron probe microanalysis), NGR (Natural gamma ray
measurements) and XRD (X-ray diffraction).
The nanominerals (category D) cannot be depicted by usual

Mineralogical / physical methods; even EPMA seems to be useless
in many cases. However, their presence can be
“seemed”/predicted (NGR) or visualized (TEM transmission
electron microscopy) /SAED selected area electron diffraction),
HRTEM High-resolution transmission electron microscopy).
45
46
Classification of Nanomaterials
Nanomaterials can be classified based on
(1) Their origin
(2) Based on phase composition
(3) Based on dimensions
Based on their origin, nanomaterials are broadly classified as
(a) Natural nanomaterials and

(b) Artificial nanomaterials
Natural nanomaterials are those which are obtained naturally.

Examples:- Carbon-nanotubes and fiber s
Artificial nanomaterials are those which are synthesized in laboratories

Examples:- Au/Ag np system and Gold nanoparticles, Polymeric
nanocomposites
47
48
49
50
51
Classification Based on Phase composition

Single- Phase solids - Crystalline, amorphous particles and layers, etc.
Multi-phase solids - Matrix composites, coated particles, etc.
Multi-phase system - Colloids, aerogels, ferrofluids, etc.
CuS amorphous nanoparticles are example for single-phase solids, and
its inhibit the proliferation of cancer cells rather than normal cells
Multi-phase solids: A method for coating magnetic nanoparticles with a

very thin layer of gold. Because many biological markers and linkers
have been adapted to attach to gold surfaces, a functional coating of gold
allows nanoparticles of other materials to be used with the established
markers and linkers. Magnetic nanoparticles are of particular interest
for in vivo imaging and treatment operations.
1) Image enhancement in magnetic based diagnostics (such as MRI or other proprietary
techniques). (2) Cancer imaging and treatment.
Advantages:-
(1) Avoids direct contact between biological tissue and the core nanoparticle material
(2) Permits a wide range of magnetic materials to be used in biological tissue
(3) Simple, rapid, and relatively inexpensive chemical process
Multi-phase system
Aerogel is a manufactured material with the lowest bulk density of any known
porous solid.
It is derived from a gel in which the liquid component of the gel has been
replaced with a gas. The result is an extremely low-density solid with
several remarkable properties, most notably its effectiveness as a thermal
insulator.
It is nicknamed frozen smoke, solid smoke, solid air or blue smoke due to its
translucent nature and the way light scatter s in the material
Eq:- Carbon aerogels are composed of particles with sizes in the nanometer
range, covalently bonded together. They have high porosity over 50%,
with pore diameter under 100 nm and surface areas ranging between 400-
1000 sq.km/g.
52
Nanomaterials (gold, carbon, metals, meta oxides and alloys) with variety
of morphologies (shapes) are depicted
The term nanoparticle is generally used to

encompass all 0D nanosized building
blocks (regardless of size and morphology),
or those that are amorphous and possess
a relatively irregular shape.
Nanoclusters should be used to describe
0D nanostructures of a homogeneous size
distribution
Any nanomaterial that is crystalline should be
referred to as a nanocrystal. Nanocrystals are
characterized by the presence of an ordered
lattice array of the constituent subunits, as
illustrated by a single nanocrystal of CdSe
A special case of nanocrystal that is comprised

of a semiconductor is known as a quantum
dot. Quantum dots currently find applications
as sensors, lasers, and LEDs.
Nanopowder is shown that consists of

microscopic grains, each comprised of nanoscale
amorphous units
53
Significance of Nanomaterial's
These materials have created a high interest in recent years by virtue of
their unusual mechanical, electrical, optical and magnetic properties.
 Nanophase ceramics are of particular interest because they are more ductile at
elevated temperatures as compared to the coarse-grained ceramics.
 Nanostructured semiconductors are known to show various non-linear optical
properties. Nanostructured semiconductors are used as window layers in solar
cells
 Nanosized metallic powders have been used for the production of gas tight
materials, dense parts and porous coatings. Cold welding properties combined
with the ductility make them suitable for metal-metal bonding especially in the
electronic industry.
 Single nanosized magnetic particles are having special properties in addition to
the superparamagnetism behaviour
 Nanostructured metal clusters and colloids of mono- or plurimetallic
composition have a special impact in catalytic applications.
 Nanostructured metal-oxide thin films are receiving a growing attention for the
realization of gas sensors (NOx, CO, CO2, CH4 and aromatic hydrocarbons) with
enhanced sensitivity and selectivity
 Nanostructured metal-oxide (MnO2) finds application for rechargeable batteries
for cars or consumer goods. Nanocrystalline silicon films for highly transparent
contacts in thin film solar cell
Nanomaterial - synthesis and processing

Nanomaterials deal with very fine structures: a nanometer is a
billionth of a meter. This indeed allows us to think in both the
‘bottom up’ or the ‘top down’ approaches to synthesize
nanomaterials, i.e. either to assemble atoms together or to dis-
assemble (break, or dissociate) bulk solids into finer pieces until
they are constituted of only a few atoms
Schematic illustration of the

preparative methods of
nanoparticles
54
Methods for creating nanostructures
There are many different ways of creating nanostructures: of

course, macromolecules or nanoparticles or buckyballs or
nanotubes and so on can be synthesized artificially for certain
specific materials.
They can also be arranged by methods based on equilibrium or

near-equilibrium thermodynamics such as methods of self-
organization and self-assembly (sometimes also called bio-
mimetic processes).
Using these methods, synthesized materials can be arranged into

useful shapes so that finally the material can be applied to a
certain application.
Mechanical grinding
Mechanical attrition is a typical example of ‘top down’ method of

synthesis of nanomaterials, where the material is prepared not by
cluster assembly but by the structural decomposition of coarser-
grained structures as the result of severe plastic deformation.
This has become a popular method to make nanocrystalline

materials because of its simplicity and the relatively inexpensive
equipment needed. Similarly, the serious problems that are
usually cited are
1. contamination from milling media and/or atmosphere, and
2. to consolidate the powder product without coarsening the

nanocrystalline microstructure.
55
Schematic
representation of
the principle of
mechanical milling
Schematic representation of the principle of mechanical milling

The energy transferred to the powder from refractory or steel
balls depends on the rotational (vibrational) speed, size and
number of the balls, ratio of the ball to powder mass, the time
of milling and the milling atmosphere. Nanoparticles are
produced by the shear action during grinding.
Wet Chemical Synthesis of Nanomaterials

In principle we can classify the wet chemical synthesis of
nanomaterials into two broad groups:
1. The top down method: where single crystals are etched in an

aqueous solution for producing nanomaterials, For example, the
synthesis of porous silicon by electrochemical etching.
2. The bottom up method: consisting of sol-gel method,

precipitation etc. where materials containing the desired
precursors are mixed in a controlled fashion to form a colloidal
solution.
56
Sol-gel process
The sol-gel process, involves the evolution of inorganic networks
through the formation of a colloidal suspension (sol) and gelation
of the sol to form a network in a continuous liquid phase (gel).
The precursors for synthesizing these colloids consist usually of a

metal or metalloid element surrounded by various reactive
ligands.
The starting material is processed to form a dispersible oxide and

forms a sol in contact with water or dilute acid.
Removal of the liquid from the sol yields the gel, and the sol/gel
transition controls the particle size and shape. Calcination of the
gel produces the oxide.
57
Schematic representation of sol-gel process of synthesis of

nanomaterials
1. Formation of different stable solutions of the alkoxide or solvated metal

precursor.
2. Gelation resulting from the formation of an oxide- or alcohol- bridged

network (the gel) by a polycondensation reaction that results in a dramatic
increase in the viscocity of the solution.
3. Aging of the gel (Syneresis), during which the polycondensation reactions

continue until the gel transforms into a solid mass, accompanied by
contraction of the gel network and expulsion of solvent from gel pores.
Ostwald ripening (also referred to as coarsening, is the phenomenon by which
smaller particles are consumed by larger particles during the growth process)
and phase transformations may occur concurrently with syneresis. The aging
process of gels can exceed 7 days and is critical to the prevention of cracks in
gels that have beencast.
58
4. Drying of the gel, when water and other volatile liquids are removed from
the gel network. This process is complicated due to fundamental changes in the
structure of the gel.
The drying process has itself been broken into four distinct steps: (i) the
constant rate period, (ii) the critical point, (iii) the falling rate period, (iv) the
second falling rate period. If isolated by thermal evaporation, the resulting
monolith is termed a xerogel. If the solvent (such as water) is extracted under
supercritical or near super critical conditions, the product is an aerogel.
5. Dehydration, during which surface- bound M-OH groups are removed, there
by stabilizing the gel against rehydration. This is normally achieved by calcining
the monolith at temperatures up to 8000C.
6. Densification and decomposition of the gels at high temperatures (T>8000C).

The pores of the gel network are collapsed, and remaining organic species are
volatilized. The typical steps that are involved in sol-gel processing are shown in
the schematic diagram below.
Gas Phase synthesis of nanomaterials
The gas-phase synthesis methods are of increasing interest because they allow
elegant way to control process parameters in order to be able to produce size,
shape and chemical composition controlled nanostructures
In conventional chemical vapour deposition (CVD) synthesis, gaseous products

either are allowed to react homogeneously or heterogeneously depending on a
particular application
Gas phase processes have inherent advantages, some of which are noted here:
An excellent control of size, shape, crystallinity and chemical

composition
Highly pure materials can be obtained
Multicomonent systems are relatively easy to form
Easy control of the reaction mechanisms
59
Furnace
The simplest fashion to produce nanoparticles is by heating the desired
material in a heat resistant crucible containing the desired material. This
method is appropriate only for materials that have a high vapour pressure at
the heated temperatures up to 2000°C
Disadvantages of Nanomaterials
(i) Instability of the particles - Retaining the active metal nanoparticles is highly
challenging, as the kinetics associated with nanomaterials is rapid. In order to retain
nanosize of particles, they are encapsulated in some other matrix.
(ii) Nanomaterials are thermodynamically metastable and lie in the region of high-energy
local-minima. Hence they are prone to attack and undergo transformation. These
include poor corrosion resistance, high solubility, and phase change of nanomaterials.
This leads to deterioration in properties and retaining the structure becomes
challenging.
(iii) Fine metal particles act as strong explosives owing to their high surface area coming in
direct contact with oxygen. Their exothermic combustion can easily cause explosion.
(iv) Impurity - Because nanoparticles are highly reactive, they inherently interact with
impurities as well.
(v) Biologically harmful - Nanomaterials are usually considered harmful as they become
transparent to the cell-dermis.
(vi) Difficulty in synthesis, isolation and application - It is extremely hard to retain the size
of nanoparticles once they are synthesized in a solution.
60
Carbon and Forms of Carbon
• Sixth element in the periodic table

• Atomic weight 12.011
• Three isotopes:
– C12 (99% of the naturally occurring carbon -reference for relative
atomic mass of 12),
– C13 (has magnetic moment, spin=1/2 – used as a probe in NMR),
– and C14 (radioactive isotope, half life 5730 years –used in dating of
artefacts and ‘label’ organic reaction mechanisms)
• Electronic ground state: 1s22s22p2
• C exhibits “catenation” = bonding to itself – limitless number of
chains, rings and networks
Objects that are Made From Carbon
Diamond Graphite Nanotube Coal
61
Allotropes of carbon have different covalent bonding arrangements.
diamond graphite buckyball nanotube

• Carbon atoms form covalent bonds by sharing outer shell electrons
with each other
• Diamond, graphite, buckyballs and carbon nanotubes all have different
covalent arrangements of carbon atoms
• The differing covalent arrangements of carbon atoms lead to the
different properties of carbon allotropes.
Covalent Bonds In Diamond

• Diamond is formed by a 3D
box-like network of carbon
atoms
• The continuous nature of the
covalent arrangements forms
a giant molecule
• Electrons are fixed.
carbon covalent
atoms bonds
62
Covalent Bonds In Graphite

• Graphite is formed by
hexagonally-arranged carbon
molecules forming 2D layers
of sheets
• Electrons are free to move

between each carbon sheet.
Types of Carbon
• Diamond and Graphite alotropes of C with 10928’ and
120 bonds until 1964
• Other bond angles:
– C8H8, 90, “cubane” (P. Eaton, University of Chicago, 1964)
– C20H20, dodecahedron shape (L. Paquette, Ohio State
University, 1983)
– Carbon Clusters (3, 11, 15, 19, 23, 40, 50, 60, 70, 80, 90) –
C60: fullerene
– Carbon Nanotubes (S. Iijima, 1991, Japan [Ref.1])
63
Covalent Bonds In Buckyballs

• Carbon atoms in buckyballs
are arranged in a soccer ball
shape
• C60 Buckyballs have 20
regular hexagon faces and
12 regular pentagon faces
- these faces come together
at 60 carbon atom vertices
• Electrons are localised
internally due to the
curvature of the structure.
Image: Mstroeck @ Wikipedia
A Bit More About Buckyballs

• Buckyballs are also called
fullerenes (after architect
Richard Buckminster Fuller)
• Buckyballs were discovered
in 1985 by Robert Curl,
Harold Kroto and Richard
Smalley
- these scientists won the
1996 Nobel Prize in
Chemistry for discovering
Buckyballs in crystalline form
this new allotrope of carbon.
Image: Wikipedia
64
Covalent Bonds In Carbon Nanotubes

• Carbon nanotubes are formed by a
layer of hexagonally-arranged
carbon atoms rolled into a cylinder
- usually have half buckyballs on
one or both ends
• Electrons are localised internally,
and some can move along the
length of the tube by ballistic
transport
• Carbon nanotube diameter ~ 1nm
• Carbon nanotube length can be a
million times greater than its width
• Nanotubes can be
- single-walled (d = 1-2 nm), or
- multi-walled (d = 5-80 nm).
Image: Wikipedia
Properties of Carbon Allotropes

Allotrope Hardness Tensile Conducts Conducts
strength heat electricity
Coal + + + no
Graphite ++ ++ +++++ +++++
Not
Diamond +++++ known +++ no
Buckyballs +++++ ++++ + +
Carbon
Nanotubes ++++++ +++++ +++++ ++++++
65
Carbon Nanotubes
Did
What You Know?
is it?
• Carbon nanotubes, composed of
interlocking carbon atoms, are 1000x
thinner than an average human hair –
but can be 200x stronger than steel.
Carbon Nanotubes
What is it?
• Sheet of graphite rolled into a tube
• Single-Walled (SWNT) and Multi-Walled (MWNT)
• Large application potential, metallic, semiconducting
armchair
SWNT zigzag
MWNT
chiral
66
Covalent Bonding - Carbon
Single-walled
carbon nanotubes:
• armchair - metallic
• zigzag - semiconducting
• chiral - semiconducting
• multi-walled - metallic
Types of Carbon nanotubes
Two main types of

carbon nanotubes:
Single-walled
nanotubes (SWNTs)
consist of a single
graphite sheet
seamlessly wrapped
into a cylindrical tube.
Multiwalled nanotubes
(MWNTs) comprise an
array of such nanotubes
(more than one wall)
that are concentrically
nested with in.
67
Unique Properties Of Carbon Nanotubes

• 200x stronger than steel of the same diameter
• The first synthetic material to have greater strength than spider silk
• Excellent conductors of electricity and heat
• Have huge potential for product development.
Why Carbon Nanotubes ?
Small Dimensions
Chemically Stable
Mechanically Robust
High Thermal Conductivity
High Specific Surface Area (Good

Adsorbents)
Low Resistivity (Ballistic Electron Conduction)
Ideal materials for applications in conductive and high-strength composites; energy
storage and energy conversion devices; sensors; field emission displays and
radiation sources; hydrogen storage media; and nanometer-sized semiconductor
devices, probes, and interconnects.
68
Structure of Single Walled Carbon Nanotubes
• Structure depends on rolling direction (chirality)

– Metallic
– Semi-conducting
Three Forms of CNTs
• Chiral
• Zigzag
• Armchair
• Vectors describe the rolling process that
occurs when a graphite sheet is transformed
into a tube
69
Properties of Nanotubes
• Electrical Properties
– Metallic – armchair structure – conductive
– Semi-conductors – zigzag and chiral
• Depends on diameter (quantum effects)
– Ropes of SWNTs (R=10-4cm-1 at 27C)
– Combinations – transistors
Zigzag
• Bent molecules
• Response to stretching
• Chirality and diameter of nanotubes are important
parameters!!!
Properties of Nanotubes
• Mechanical Properties
– Young’s modulus E = 1.28 – 1.8TPa (steel
0.21TPa)
– Strength Rm = 45,000 MPa (high strength steel
2,000 MPa)
– Buckling – no fracture – change in hybridization
(from sp2)
Molecular dynamics simulations of a (10,10) nanotube under axial tension (J. Bernholc, M. Buongiorno Nardelli
and B. Yakobson). Plastic flow behavior is shown after 2.5 ns at T = 3,000 K and 3% strain. The blue area indicates
the migration path (in the direction of the arrow) of the edge dislocation (green). This sort of behavior might help make
composite materials that are really tough (as measured by their ability to absorb energy).
70
Filling of Nanotubes
Figure 6.20. Transmission electron micrograph of a MWNT filled with Sm2O3. The interlayer separation
in the MWNT is c.a. 0.34 nm. Lattice planes in the oxide are clearly seen. (From Ref. 55 by permission of
The Royal Society of Chemistry.)
Application of Nanotubes
• Variety of Applications
– Cost dependent
• Field Emission and Shielding
– Flat panel displays TV and computer monitors)
– High electrical conductive armchair SWNTs – shield magnetic fields (protection)
• Computers
– Based on conductivity change (small V change can change conductivity 106 times – switch
on of faster than current)
• Fuel Cells
– Storage of charge carriers (Li, H)
• Chemical Sensors
– Sensitivity of vibration modes to the presence of other molecules (Raman)
• Catalysts
– hydrogenation
• Mechanical Reinforcement
– 5% (vol) increases strength of Al by factor 2
71
CNTs in Electronic Devices
Figure 5.16. Nanoscale electronic device connected with a nanotube (left). (Reproduced with kind
permission of Ph. Avouris.) La2@C80 trapped inside a single walled carbon nanotube. a.k.a PEAPODS
(right). (Reproduced with kind permission of D. E. Luzzi.)
Nanotubes In Efficient Solar Cells

• Scientists have developed
the ‘blackest black’ colour
using carbon nanotubes
• The carbon nanotubes are
arranged like blades of
grass in a lawn
- they absorb nearly all light
• Use of carbon nanotubes in
solar cells could vastly
improve their efficiency.
72
Nanotubes In Sporting Equipment

• Badminton racquet manufacturer
Yonex incorporates carbon
nanotubes into their cup stack
carbon nanotubes racquets
(www.yonex.com)
• American baseball bat
manufacturer Easton Sports has
formed an alliance with a
nanotechnology company Zyvex
to develop baseball bats
incorporating carbon nanotubes
• Tennis racquets also incorporate
carbon nanotubes
(www.babolat.com).
Nanotubes In Miniaturised Electronics

• Branching and switching
of signals at electronic
junctions is similar to
what happens in nerves
• A carbon nanotube
‘neural tree’ can be
trained to perform
complex switching and
computing functions
• Could be used to
detect/respond to
electronic, acoustic,
chemical or thermal
signals.
73
Nanotubes In AV Technology
• Carbon nanotubes
are being used to
develop flat screen
televisions with
higher resolution
than the human eye
can detect
• Your next TV screen
could be thin, ultra-
light and foldable…
Graphene Sheets
A new form of carbon with many potential uses.
• Professor Gordon Wallace and his team at the
University of Wollongong have been studying
this new form of carbon just one atom thick
“The very unusual electronic properties of

graphene sheets means they could be used in
solar cells or new battery technology,” he says
“Because of the biological affinity of carbon,

they might also be useful as electrodes for a
range of medical bionic devices such as
cochlear implants”
• Graphene sheets could also be used to create
transparent electrodes and coatings that
prevent the build up of static electricity.
74
Manufacturing Carbon Nanotubes

Molecular Engineering
• Carbon nanotubes can be made using molecular
engineering
• Molecular templates are created
- under the right chemical conditions carbon atoms
arrange themselves into nanotubes on the template
• This process is also known as chemical synthesis or
self-assembly, and is an example of the ‘bottom-up’
approach to molecular engineering.
Molecular Engineering
2 Approaches
• ‘Bottom-up’ approach: structures are built
atom by atom
- can use self-assembly or sophisticated
tools (eg scanning tunnelling microscope,
atomic force microscope) which can pick up,
slide or drag atoms or molecules around to
build simple nanostructures
• ‘Top-down’ approach: traditional
engineering techniques such as machining
and etching are used at very small scales
- products tend to be refinements of existing
products, such as electronic chips with more
and more components crammed onto them.
Image: [email protected]
75
NANOTECHNOLOGY
APPLICATIONS IN GEOSCIENCE
e – Learning Material - Unit: 3 & 4
NANODIAMONDS FROM AGB STARS: A NEW TYPE OF PRESOLAR

GRAIN IN METEORITES
Presolar nanodiamonds found in meteorites (Lewis et al. 1987)

and available for study in the laboratory are traditionally believed
to have been formed in association with Type II supernovae
(Clayton 1989) at some point before formation of the solar
system (4.6 Gyr ago)
The major argument for this is the presence within the diamonds
of xenon displaying an isotopic signature thought to arise from
supernovae
However, as has long been known, since only 1 out of 106

nanodiamond grains contains an atom of xenon, only a fraction
(106) of the total diamond population may actually arise from
supernovae
76
Indeed, it has been demonstrated that some nanodiamonds

probably formed in the solar nebula (Dai et al. 2002; Gilmour et al.
2005). Furthermore, the mechanism of the formation of diamonds,
which is supposed to be mostly a chemical vapor deposition (CVD)
process (Daulton et al. 1996).
Recently, nanodiamonds have been identified spectroscopically in a

few stars (Kerckhoven et al.2002) one of which (HR 4049) is at the
post-AGB phase of evolution.
This means that nanodiamonds from AGB stars could also be

present in meteorites
77
Deep Diamonds Shed Light on Ancient Continental Movements
Deep inside Earth, hellish heat and pressure have been cooking
rocks and altering their chemical structure since the planet
formed about 4.5 billion years ago.
But not everything gets roasted. Tiny part of mineral that

became trapped in diamonds billions of years ago remain
pristine, because diamonds are for the most part chemically
inert. "In essence, diamonds are time capsules from Earth's
mantle," says Steven Shirey, a geochemist at the Carnegie
Institution for Science in Washington, D.C.
Analyses of inclusions in diamonds, such as the garnet (red)

trapped inside this gem when it formed, suggest that modern-
style plate tectonics began about 3 billion years ago.
78
EXPECTED STORAGES OF NANO-DIAMONDS AND/OR DIAMONDS

IN THE LUNAR ROCKS.
Diamonds with large size formed at deeper mantle are main
characteristics of the active water-planet Earth due to main
sources of carbon from life-materials on the dynamic surface
and circulated plate-tectonics and mantle convection, though
there is still problem to explain to move down and up by light
element carbon.
Main carbon storage on the Moon without ocean and air is

mainly in the brecciated or metamorphosed rocks. The main
purpose of the paper is to discuss source of diamonds with
nano- and large sizes probably found in the lunar breccias.
Expected diamond crystal in the lunar rocks:

If carbon-bearing materials (such as carbon dioxides) are stored in
deeper Moon during giant impact event with air-planets of
primordial Earth, these carbon bearing materials are main sources
of diamond carbon of the lunar mantle.
Evidences of such deeper carbon are found by increased carbon

content of lunar breccaiated rocks, and deeper sources of
terrestrial diamonds which has big event of giant impact.
This suggests that smaller diamond crystal will be found at rim of

impact craters, some boundary of the highland and lunar Mare, or
deeper cliffs on the Moon in future explorations.
As nano-diamonds formed by shock-wave process with
quenched reaction can be found at lunar surfaces of meteoritic
impacts, and deeper interiors of moonquake explosions (i.e.
underground explosions similar with surface quake).
79
Magnetic nanostructures in organic gases –

Palaeotectonic Study
The studies were carried out
to produce nanostructures in
both permalloy (80:20 Ni:Fe)
and in iron (later oxidised to
magnetite Fe3O4) to test and
verify the theoretical
predictions used to
reconstruct the motion of
tectonic plates from the
magnetisation of rocks
containing natural magnetite
particles.
80
Nano-Resolution (parts-per-billion) Oceanic and Atmospheric

Pressure Sensors
81
82
FAULTS AND NANOCOATINGS
Geologists Discovery Slippery Rocks Coat the San Andreas Fault
In an underground observatory located on the San Andreas Fault,

geologists are studying samples of rock from deep inside the
Earthýs crust.
Most earthquakes are the result of tectonic plates unlocking from

one another in a sudden release of energy. Researchers found that
nano-coatings of clay on these rocks grease the faults, reducing
friction between plates, which changes the dynamics of
earthquakes. Understanding more about the fault allows geologists
to more deeply comprehend earthquake cycles
83
84
Earthquakes are most common along fault lines. The most famous
fault is the San Andreas Fault in California which marks the plate
boundary between the Pacific oceanic plate and the North
American continental plate. It is more than 650 miles long.
There are many different kinds of faults, but all of them involve
different plates of rock pushing tightly together and creating
friction as they move. The nanocoatings recently found by
geologists are changing how they understand the behavior of
faults. These slick nanocoatings, fractions of a millimeter thick,
have been found at fault boundaries, where they can make it
weaker and more susceptible to movement.
Layer-Block Tectonics, a New Concept of Plate

Tectonics - An Example from Nansha Micro-Plate,
Southern South China Sea
The Layer-block tectonics (LBT) is a new theory describing the layer-
slip structure of lithosphere (Liu et al., 2002, 1999; Sun et al., 1991).
According to this theory, a lithosphere plate, continental
lithosphere plate in particular, is considered a composite of sub-
plates connecting with each other horizontally and overlapping
with each other vertically.
The term “Layer” in the LBT emphasizes the rheological and
stratifying characteristics of the lithosphere and the guiding and
controlling role of mechanically “soft” layers with different
deepness in the layer-slip movement of the lithosphere during the
process of tectonic deformation.
The term “block”, on the other hand, emphasizes the discontinuity
of various types of geological bodies segmentalized by dip-slip or
strike-slip movement of lithosphere in horizontal direction.
85
The obvious different of the LBT from the from the plate tectonics theory, is
that the LBT emphasizes the geotectonic effect of multi-levels of gliding
surfaces within lithosphere upper mantle including rheospheric top surface,
Moho surface, mid-crust, top surface of sedimentary basement, and so on,
rather than only emphasized singular Moho gliding surface in flake tectonics or
the plate tectonics.
The lithosphere can be divided into different layers by the characteristics of

material, energy, structure, rheological and chemical stratification at different
depths (Su et al., 1996; Song et al., 1996; Wang et al., 1996; Wang, 1992;
Rushentsev and Trifonov, 1985; Oxburgh, 1972).
These layers interrelate with each other and stack-and-piece together to form
an integral lithospheric aggregate. As the manifestation of this nature of
stratification, the LBT is the result of bedding layer-slip, dip-slip (both in
positive and negative direction) and strike-slip (in slant direction, sinistral or
dextral) of geologic bodies under tectonic forces (vertically or horizontally).
86
Forming mechanisms of LBT
The cause why the upper crust can easily slide on the middle crust
surface is that there are nano-sized particle layers developped
between the upper-crust and mid-crust.
The nanoparticles are characteried by higher density, higher

strength, and lower rolling friction force (f2 in Fig); and exist in
almostly all faults and layer-slip surfaces in natural world. I
n the case with nano-particles, the friction is rolling friction. Under

the same normal pressure force (P in Fig), the rolling friction force is
far less than the sliding friction force (f1/f2 can be up to 18) (f1 in
Fig.11). So, the upper crust can easily move along the mid-crust
layer.
87
Biomineral Nanostructures of Manganese Oxides in Oceanic

Ferromanganese Nodules
Many Mn minerals, especially their finely dispersed oxides, are
distinguished by a low degree of structural ordering and unstable
structure
The study of structural transformations of finely dispersed minerals

is a clue to understanding the processes of noncrystalline material
transformation into the crystalline state and vice versa.
Manganese oxides, which are widespread and of great practical

importance, are formed and transformed by an active role of
microorganisms.
Finely dispersed Mn oxides are the most abundant in oceanic

ferromanganese nodules (FMNs) and in products of weathering
on land
The effect of biogenic factors on the formation and growth of FMNs

has been discussed from the moment of their discovery by the
Challenger expedition in 1873–1876.
In the land–sea transitional zone, ore material is absorbed by living

organisms. This leads to the formation of organometallic complexes
as abundant species of Fe, Cu, and Zn dissolved in seawater.
This leads to the formation of organometallic complexes as

abundant species of Fe, Cu, and Zn dissolved in seawater. Bacteria
play a certain role in the formation of major minerals in FMNs.
A part of soft organic matter reaches the ocean floor and the upper
sedimentary layer, where it is oxidized. As a result, the redox
potential decreases and the diagenetic redistribution of manganese
leads to the formation of todorokite
88
Chukhrov et al. (1978), vernadite is formed only as a product of

fast Mn 2+ oxidation to Mn+4
Finely dispersed Mn oxides (asbolane, todorokite, buzerite,

birnessite, and vernadite) are characterized by phase
transformations observed in nature and in experiments.
Formation of Gold Spheroidal Nanoparticles
Nanosized spheroidal gold particles are most abundant in

deposits of the volcanogenic type among the studied gold–silver
deposits of the Far East.
Among volcanogenic deposits, spheroidal particles of electrum

(Au and Ag) are the most abundant in the May deposit,
Primor’e.
89
Uraninite
nanocrystals in
carbonaceous
particles in the
atmosphere
90
Biologically Produced Iron Oxyhydroxide Nanoparticles
Recent investigations have explored nanoscale interactions

between microbially produced polymers and iron oxyhydroxides.
Banfield et al. (2000) and Nesterova et al. used transmission
electron microscopy to study polymer biomineralization reactions
in the environment
Nanoseismic monitoring
Microseismicity: Earthquakes below the level of human sensitivity,
say ML 3.0, recorded locally (within 100 km) or at regional scale
(up to 3000 km).
Nanoearthquake: Suggested phrase for earthquakes below ML 0.0;
however, not yet commonly accepted by the seismological
community (Butler, 2003).
Nanoseismic monitoring: Location and identification of low-SNR
fracture processes, e.g., nanoearthquakes by jackknife analysis of
tripartite array networks.
Passive seismics: Location of energy release from fracture
processes by means of seismic exploration-like equipment and
software tools, e.g., in the concept of instrumented oil fields.
Forensic seismology: Location and identification of nonseismic
sources by seismic networks, e.g., airplane crashes, submarine
explosions (Zucca, 1998).
91
Nanoseismic monitoring, acting like a moderate effort seismic

microscope of previously unavailable sensitivity, offers many new
chances to resolve ambient fracture processes.
Wust-Bloch and Joswig (2006) derive a process identification of

pending sinkhole collapses at the Dead Sea, Häge and Joswig
(2008) report on improved resolution of seismicity during an inter-
swarm period at Vogtland, Czech Republic, and Walter and Joswig
(2008), in a forthcoming issue of First Break, describe the first-time
discovery of cracks in a creeping, clayey landslide during heavy
rainfall in Vorarlberg, Austria.
92
Microstructures of experimental slipping zones. (a)

Experimental pseudotachylyte produced by frictional
melting of tonalite. A large biotite grain (pale gray in colour)
in the wall rock to the left undergoes to selective melting
resulting in lattice breakdown, biotite dehydration and
formation of vesicles (black in color). The Fe-rich melt from
the biotite is mingled in the friction melt (20 MPa normal
stress, 1.3 m/s slip rate and 3 m of slip, BSE-SEM image, Di
Toro et al., 2006a,b).
(b) Silicaegels decorating the sliding surface of
deformed novaculite (112 MPa normal stress, 3.2 mm/s slip
rate, 1.7 m of slip SEM image, Goldsby and Tullis, 2002:
photo courtesy of David Goldsby).
(c) Decarbonation products and porous microstructure in
deformed Carrara marble (100% calcite). The slip surface is
located 50 mm to the left (10 MPa normal stress, 6.5 m/s
slip rate, slip 13.45 m. BSE-SEM image).
(d) Sliding surface of dolomitic marble. The sliding surface
has a pavement of euhedral grains about 100 nm thick of
Mg-rich calcite. The pavement covers a 25e40 mm thick
layer made of nanoparticles of periclase and lime (10 MPa
normal stress, 6.5 m/s slip rate, slip 19.5 m. BSE-SEM image.
(e) Sliding surface on limestone made of nanoparticles of

probable calcite. Experimental conditions aimed at
investigate flash heating and weakening (3 and 5 MPa
normal stress, 0.3 m/s slip rate, slip 4 cm. SE-SEM image,
Tisato et al., in press).).
93
Micro-, Nano- and Picoearthquakes: Implications for

Fault Friction and Fault Mechanics
The deployment of instrumentation within seismically active crustal rocks in

deep boreholes and mines has opened a new window for the study of the
earthquake source. Advances in both sensors and high-temperature electronics
enable recording of seismic waves over a very broad frequency spectrum (D.C.
to several KHz) and amplitude spectrum (Earth noise floor to several g
acceleration) in these challenging underground environments.
By reducing the distance between source and receiver to a few hundred meters
or less, it becomes possible to observe dynamic processes on space and time
scales that approach those of laboratory experiments.
94
Using deep borehole seismometers in the main hole of the San Andreas Fault
Observatory at Depth (SAFOD) and in the Long Valley Exploratory Well (LVEW) in
the center of Long Valley Caldera, CA, we have observed earthquakes at the
lowest limit of magnitude detection
The smallest events have source dimensions < 1 m, indicating that if there is a
minimum earthquake size, it must lie at lower magnitude and spatial scales.
Mean displacements in the smallest events are on the order of 100 microns,
suggesting that the displacement weakening distance is smaller still. The rate of
fault weakening can be studied using the earliest part of the P-wave arrival.
95
Study of Nanocrystals in the Dynamic Slip Zone
Slickensides are smoothly ground or polished surfaces produced by the relative

frictional motion of the rocks on the opposite sides of the fault plane. The
grooves and stepped topography of these surfaces give an insight into the
kinematics of the motion of the blocks of the rock (Allaby, 1990). The slickensides
revealed in the zones of paleoseismic events allow correlating their origin to the
seismic cycle (Pover and Tullis, 1989).
Typically, slickensides are formed at a slip rate exceeding 1 m/s, when a

coefficient of friction of the sliding rocks decreases by at least an order of
magnitude. This phenomenon develops due to the formation of an intermediate
layer between the blocks, which is low resistant to shear. This layer is supposed
to be a product of the grinding of the rocks into a gouge of nanoparticles (Han et
al., 2011; Di Toroet al., 2011), or a fluid saturated mineral assembly (Wang and
Manga, 2010), or a mineral melt in the zone of friction (Fialko and Khazan, 2005;
Nielsen et al., 2008).
96
97
The IR and Raman spectroscopy showed that the slickenside on

the surface of arkosic sandstone and the bulk of the sample at a
depth of 3 mm from the surface have a different mineral
composition. The slickenside is composed of the crystals of
montmorillonite and anatase, which have an average linear size
of ≈15 and 3 nm, respectively.
Besides montmorillonite, also beidellite, nontronite, quartz,

anatase, and plagioclase are identified in the bulk of the
sandstone. The average size of the nanocrystals of anatase in the
bulk of the specimen is about 8 nm.
98
NANO FOSSILS
Nanobacterial fossils and grainy textures have been described in
the geological record (Camoin et al., 1999; Folk, 1993; Vasconcelos
et al., 1995), as well as in the Martian meteorite ALH84001 in
association with carbonate globules (McKay et al., 1996).
These micro sedimentary structures were initially considered as

possible evidence for past life, leading to a still-unresolved debate
concerning both the signifi cance of the grainy texture and the
existence of microbes measuring <200 nm (Nealson, 1997).
In addition, nanoforms and grainy texture have been observed in

modern natural environments, as well as in laboratory culture
experiments, in the presence of sulfate-reducing bacteria (SRB),
which mediate carbonate formation (van Lith et al., 2003a;
Vasconcelos and McKenzie, 1997; Warthmann et al., 2000).
99
Imaging Techniques
Confocal laser scanning
microscopy images of culture
experiment inoculated with
Desulfovibrio brasiliensis.
Sample was stained to
visualize relationship among
minerals (blue), bacterial
cells (green), and
extracellular polymeric
substances (EPS) (white).
A: Overview of the culture
experiment. B: Nanosize
minerals nucleating in EPS
aggregate.
C: Mineral globules
enveloped within EPS
surrounded by bacteria. D:
Section through
threedimensional
reconstruction of image C.
Note that bacterial cells are
not included within
globular structures.
In the specific case of microbial dolomite formation in laboratory

experiments, we have demonstrated that nanobacteria-like
particles represent mineral nucleation and growth within EPS
Similar structures present in the geological record may have been

formed through a similar process
A close association between SRB (Sulphate Reduction Bacteria)

and precipitation of lithified laminae has been documented in
modern microbial mats, which are regarded as possible analogues
for Precambrian stromatolites
Many of the current models predict that SRB induce carbonate

formation through the excretion of metabolites, which increase
the alkalinity and pH of the water solution (Castanier et al., 1999).
100
Paleoenvironmental Application of Calcareous Nannofossils

Biostratigraphers primarily use benthic foraminifera and palynological
assemblages for paleoenvironmental reconstruction; calcareous nannofossils
and planktonic foraminifera for detailed age dates.
Preliminary research comparing modern to Miocene coccoliths indicates that
broader application of calcareous nannofossils may be possible. Ocean depth
preferences of the modern calcareous nannoplankton can be extrapolated to
the fossil record, if we assume that morphological variability can imply
habitat.
The morphological variability between coccoliths of extant calcareous
nannoplankton species and the Miocene species, Minylitha convallis.
The morphology of the coccoliths of M. convallis remains constant through
time, with overall low intraspecific variability in all samples, indicating that it
may have lived in the deep photic zone. Following this assumption, greater
relative abundance of M. convallis, like that of the modern deep photic zone
species, should indicate a highly stratified paleo-ocean, deep nutricline, and
warmer climate, whereas reduced abundance relative to other calcareous
nannoplankton species should indicate a cooler climate and shallow nutricline.
101
102
103
Nanotechnology Applications in Petroleum Reservoirs
• Nanotechnology-enhanced materials that provide strength and endurance to

increase performance and reliability in drilling, tubular goods, and rotating parts.
• Improved elastomers, critical to deep drilling and to improve drilling in high-
temperature/high-pressure environments.
• Designer properties to enhance hydro-phobic or hydrophilic behavior, to
enhance materials for waterflood applications.
• Nanoparticulate wetting carried out using molecular dynamics, which shows
promise in solvents for heterogeneous surfaces and porous solids.
• Lightweight, rugged materials that reduce weight requirements on offshore
platforms, and more-reliable and more-energy-efficient transportation vessels.
• Nanosensors for improved temperature and pressure ratings in deep wells and
hostile environments.
• New imaging and computational techniques to allow better discovery, sizing,
and characterization of reservoirs.
• Nanosensors deployed in the pore space by means of “nanodust” to provide
data on reservoir characterization, fluid-flow monitoring, and fluid-type
recognition.
• Small drill-hole evaluation instruments to reduce drilling costs and to provide
greater environmental sensitivity because of less drill waste.
104
Nanotechnology Applications in Petroleum Reservoirs
A buckytube, or nanotube, is an
elongated cylinder of carbon
atoms having a diameter a bit
more than one nm and a length
ranging from one μm to several
millimeters. A nanotube also can
contain process-activated
molecules. Similar to a
buckyball’s behavior, the
reaction of a nanotube offers a
host of possibilities that may
provide diagnostic information
about reservoir flow and
connectivity.
105
Because nanotubes can be designed to become efficient electrical conductors,

electromagnetic (EM) measurements may be the branch of geophysics that first
develops applications of nanotechnology in reservoir characterization
106
Nanofluids and nanomaterials for drilling

Nanotechnology has opened the door to the development of a
new generation of fluids defined as “smart fluids” for drilling,
production and stimulation related applications.
Thanks to the exceptionally high surface to volume ratio,

nanofluids and nano-based additives exhibit major interaction
with the surrounding environment even at very low
concentrations. Such smart fluids will further enhance drilling
by adding benefits such as wettability alteration, advanced drag
reduction and sand consolidation (Chaaudhury, 2003; Wasan
and Nikolov, 2003).
Petroleum laboratory has developed an advanced fluid mixed

with nanosized particles and superfine powder that significantly
improves the drilling speed and can eliminate formation
damage in near wellbore zone (Esmaeili, 2009).
The use of two different types of polysilicon nanoparticles in

oil fields to enhance water injection and improve oil
recovery (Ju and Fa, 2009). Reportedly, one nanometer-scale
polysilicon material could change the wettability of porous
surfaces of sandstone and consequently affect the flow of
water and oil when injecting a suspension of nanoparticles
in an oil reservoir (Ju and Dai, 2002).
107
Anti-wear coating
• Goal is to increase durability in moving parts
• Increased durability gives added toughness, a longer
life span, and a lower equipment cost over time
• Coating is usually sprayed on and will bond with the
host material.
• Drilling materials need advances to be able to reach
hard to get oil reserves
Nanovar
• Produced by Integran
• Can be put on most any
composite metal
• Coatings custom made
for situation and
material being applied
to
108
Nanovar
• Much denser than
metal on an atomic
level
• Provides strength,
hardness, and thermal
resistance which are
three things needed in
oil drilling in the future
to reach reserves
Anti-corrosion
• Long lasting coatings are needed
to protect under sea pipes from
sea water
• Coatings used on rigs and other
platforms to prevent rust and
corrosion that can cause safety
issues
• More environmental friendly
than anti-corrosion paints and
cheaper
109
Anti-corrosion
• Metal surfaces are
imperfect
• Surface penetration
from the coating is vital
to performance
• Nanocoatings can be
custom made and out
perform traditional
coatings in this aspect
Nanofluids - lubricants
• Suspensions of nanoparticles in fluids that
enhance its properties
• Main advantage in the oil and gas field is the
enhanced thermal properties (performs well
at high/low temperatures, transfers heat well,
insulates well, etc)
• Highly customizable to the desired situation
110
Nanofluids – drilling mud

• Nanofluids used in drilling mud is being looked at as a solution to
ultra deep drilling fluid
• Nanoparticles added at a low weight percentage can have a big
impact in the fluid
• The suspension of nanoparticles can provide enhanced stability
against sedimentation along with better thermal, mechanical,
electrical, and magnetic properties
• Customizable for the situation and geography/region
• Improvements will enable access to deeper, hotter regions in high
grade formations where oil cannot currently be reached
Anti-fouling
• Big issue in the marine
industry
• These bacteria and
plants can increase a
ships fuel costs by 40%
• Environmental concerns
about current anti-
fouling paints
111
Anti-fouling
• AMBIO project is seeking a
nanocoating solution that
eliminates fouling
• Focuses on how microorganisms
attach to the surfaces of ships
• Seeks to combine a low drag
silicon coating with carbon
nanotubes
Wrap-up
• Still a lot of development occurring in this
field
• Development slowed by competing
companies. No free flow of information
• Will be greatly important as we seek harder to
reach oil and gas reserves
112
Reservoir Surveillance
• Purpose: To increase
knowledge about oil wells in
an attempt to recover more
oil from wells
• Rice University is working
on “nanoreporters”
• Made up of hundreds of
millions of carbon clusters
• Each reporter is
approximately 30,000 times
smaller than a human hair
• These “reporters” are designed to change their

molecular makeup depending on what they
encounter – water, petroleum, hydrogen sulfide, etc
• They are also given tags, similar to barcodes, that
can tell scientists how long they have been
underground
113
• Lastly, they are being designed to be able to report
properties about the material that they are currently
near
• With the ability to report temperature and pressure,
they can relay valuable information to scientists
• How does this increased knowledge help?
• With a better idea of the physical properties of an oil
reservoir, operators will have a much easier time
finding and recovering oil
• This would also allow easier placement of Enhanced
Oil Recovery (EOR) chemicals such as emulsifier and
foamer
114
Nanorobots
• Another new technology that
may have an impact on the oil
and gas industry is nano-
robots. The EXPEC Advanced
Research Center has been
looking into this new
technology
• They have coined the phrase
resbots, or reservoir robots
• These resbots are designed for Resbot lead technologist Mazen Kanj
a similar purpose as the illustrates that one drop of solution
nanoreporters; however, they contains more 600 billion Resbots. One
are proving to be difficult due milligram of the dry material holds 6
to their larger size trillion Resbots.
Nanorobots
• In order for any particle to
move through an oil
reservoir, it must be able to
pass through tiny pores in
the rock
• In order for resbots to be
able to pass through them,
EXPEC ARC had to
manipulate the physical Reservoir rock holds oil in tiny pores
and chemical properties of connected by “pore throats,” outlined in
the resbots until they were red, which are even smaller than the
able to pass through the pores. Nanorobots must be small enough
pores to pass through the pore throats.
115
NANOTECHNOLOGY
116
117
Removal of bacteria using nanotube

filter
a, The unfiltered water containing E. coli bacteria

b, The E. coli bacteria (marked by arrows) grown by the culture of the polluted water
c, The filtration experiment
d, The water filtered through nanotube filter
e, The filtrate after culture showing the absence of the bacterial
118
Polychlorinated biphenyls (PCBs) is a group of organic compounds used in

the manufacture of plastics, as lubricants, and dielectric fluids in
transformers, in protective coating for wood, metal and concrete, and in
adhesives, wire coating and so forth.
119
Nanotube filters
The Use of Carbon Nano-tubes as filtering devices
a. Schematic of the
process
b. Photograph of the
bulk tube.
c. SEM image of the
aligned tubes with radial
symmetry resulting in
hollow cylindrical
structure (scale 1 mm).
Nature Materials 3, 610–614 (2004) Carbon nanotube filters A. SRIVASTAVA,

O. N. SRIVASTAVA, S. TALAPATRA, R. VAJTAI and P. M. AJAYAN
Nature Materials AOP Published online: 1 August 2004 | doi:10.1038/nmat1192
How the Filter Works

The nano-tubes act as a kind of
molecular filter, allowing smaller
molecules (such as water) to pass
through the tubes, while
contaminants are too large to pass
through.
Due to their electronic configuration
smaller ions
that would
otherwise pass
through are
also blocked
120
Carbon Nanotubes
-nanosize cylinder carbon atoms that provide the basis for nanofiltration
and nanoreactive membranes, aiding the filtration process
-removes bacteria and viruses
Titanium Dioxide Nanoparticles

-with ultraviolet lights, they have improved total removal of organic
carbon
Nanofiltration Membranes
-removes dissolved salts and pollutants by a physical barrier
-softens water
Nanorust
-magnetic nanoparticles of iron oxide suspended in water to remove and
bind arsenic
Desalination Membranes
-combination of polymers and nanoparticles to draw in water ions and
repel salts
121
122
123
124
NANOTECHNOLOGY IN WATER
POLLUTION MANAGEMENT
Major Challenges Solutions offered by the Nanotechnology

Providing clean and Filtration via nano membranes would ensure much more precision and purity
safe water devoid of Filtration through nano electropositive media can ensure improved filtration of
virus, bacteria and pathogenic microbes, particularly those which are resistant to conventional depth
other elements which filters
the conventional Nanotechnology enabled filters also ensure filtration of those viruses and bacteria
methods can’t tackle which are too small to be filtered by conventional filters
Providing clean and Affordable desalination is the panacea to the water problem. The high cost of
safe water at a lower conventional desalination is mainly owing to the energy cost. By strategic use of
cost ultra thin membranes, thanks to nanotechnology, high pressure pumps, energy
recovery systems, pretreatment systems, back flushing and other maintenance
costs would be minimized substantially; some even eliminated. This would make
desalination affordable even for the developing nations
Increasing the usability Nano filtration membrane technology is widely used to remove dissolved salts
of unusable water from salty water, remove micro pollutants, soften water and treating waste water
through desalination, Nano filters can remove up to 99 per cent of ammonia from contaminated
recycling waterways and sewage outflows. This allows the water to be recycled while the
ammonia removed can be re-used as fertilizer
Conserving water Conserving water is as important as increasing the supply of usable water.
Nanotech has immense potential in this area since this precision technology has
strategic solutions to control waste of water flowing through canals through
better linings and coatings, better drip and sprinkler systems, more efficient
coatings to stop seepage in household and industrial water systems and less
requirement of back flush in filtration systems
Preserving the
Nanotechnology based filters can precisely select the substances and hence
essential nutrients in
retention of essential ones will be possible
water like calcium etc
Measuring and Nano filters can analytically and effectively measure and monitor contaminants
monitoring like arsenic, mercury and others even at the trace level, unlike the conventional
contaminants at the ones which can measure only the concentrated high level contaminants
trace level
New possibilities Nanotechnology enables various applications as under:
Purification applications, ranging from high purity semiconductor and medical
uses through home drinking water
Remediation of both waste water and polluted ground water
Desalination applications, including both sea water and brackish water
125
Nanotechnology May Result in

Breakthrough Technologies
“These nanotubes are so beautiful
that they must be useful for
something. . .”, Richard Smalley
(1943-2005).
Aligned Nanotubes as High Flux

Membranes for Desalination?
Hinds et al, “Aligned multi-walled carbon nanotube

membranes”, Science, 303, 2004.
126
Research on Nanotube Based

Membranes
Mauter and Elimelech,

Environ. Sci. Technol., 42
(16), 5843-5859, 2008.
Next Generation Nanotube

Membranes
Mauter and Elimelech,

Environ. Sci. Technol., 42
(16), 5843-5859, 2008.
Single-walled carbon nanotubes (SWNTs) with a pore

size of ~ 0.5 nm are critical for salt rejection
Higher nanotube density and purity
Large scale production?
127
Nanomaterials and
nanoparticles:
Sources and
toxicity
128
129
130
Satellite monitoring of aerosol concentration

and size
Aerosols play an important role in the global atmosphere, directly

influencing global climate and human health.
Dust, smoke, and haze locally impair visibility and health in both
urban and rural regions. Anthropogenic aerosol nanoparticles are
especially abundant in the atmosphere, and they constitute a
significant uncertainty factor in estimating the climatic change
resulting from human pollution
Satellite images clearly show particulate matter from both

anthropogenic and natural sources in industrialized and heavily
populated parts of the world
131
• Nanotechnology Program Elements

- Nanoelectronics and Computing
- Sensors
- Structural Materials
Nanoelectronics and Computing Sensors

•Molecular electronics & photonics •Life detection
•Computing architecture •Crew health & safety
•Assembly •Vehicle health
Structural Materials
•Composites
•Multifunctional materials
•Self healing
• Onboard computing systems for future autonomous intelligent

vehicles
- powerful, compact, low power consumption, radiation
hard
• High performance computing (Tera- and Peta-flops)
- processing satellite data
- integrated space vehicle engineering
- climate modeling
• Revolutionary computing technologies

• Smart, compact sensors, ultrasmall probes
• Advanced miniaturization of all systems
• Microspacecraft
• 'Thinking' spacecraft
• Micro-, nano-rovers for planetary exploration
• Novel materials for future spacecraft
132
NASA Nanotechnology Roadmap

C A P A B I L I T Y
Multi-Functional Materials
Adaptive
Autonomous Sel
Revolutionary Spacecraft f-Repairing
Aircraft Concepts (40 Space Missions
Reusable (30% less mass, % less mass)
High Strength Launch Vehicle 20% less emission,
(20% less mass, Bio-Inspired Materials
Materials 25% increased and Processes
(>10 GPa) 20% less noise) range)
Increasing levels of system design and integration
• Single-walled • Nanotube • Integral • Smart “skin” • Biomimetic

Materials nanotube fibers composites thermal/shape materials material
control systems
• Low-Power CNT • Molecular • Fault/radiation • Nano electronic • Biological

Electronics/
electronic computing/data tolerant “brain” for space computing
computing
components storage electronics Exploration
• In-space • Nano flight • Quantum • Integrated • NEMS flight

Sensors, s/c
nanoprobes system navigation nanosensor systems @ 1 µW
components
components sensors systems
2002 2004 2006 2011 2016

>
Nanoelectronics and Computing Roadmap

Impact on Space Transportation, Space Science and Earth Science
2002 2005 2010 2015
hn
e-
Sensor Web
Mission Complexity
Robot Colony
Nano-electronic
components
Europa Sub
Ultra high density

storage
RLV
Biomimetic,
radiation resistant
Biological Molecules molecular computing
CNT Devices Compute Capacity
133
Nanosensor Roadmap
Impact on Space Transportation, HEDS, Space Science and Astrobiology
2002 2005 2010 2015

Optical Sensors
for Synthetic
Vision
2020
Sensor Web
Mission Complexity
Nanotube Vibration
Sensor for Propulsion
Diagnostics
Mars Robot Colony Multi-sensor
Europa Sub Arrays (Chemical,
optical and bio)
Sharp CJV
Spacestation
Nanopore for in situ

2003 biomark-sensor
ISPP
Missions too early Sensor Capacity
1999 for nanotechnology
DSI RAX impact
Nano-Materials Roadmap
Impact on Space Transportation, Space Science and HEDS
2002 2005 2010 2015
Generation 3 RLV
HEDS Habitats
Mission Complexity
CNT Tethers
SELF-HEALING
MATERIALS
RLV Cryo Tanks SO - 3 H SO -3 H SO - H +
+ +
3
Ca++
-
SO3
Ca++
-
SO
3
-
SO3
Ca++
-
SO3
Production of
-
SO3
Ca++
SO3
- Non-tacky
temperature
Tacky
single CNT SELF-ASSEMBLING
MATERIALS
NANOTUBE MULTIFUNCTIONAL
COMPOSITES MATERIALS
Strong Smart Structures

Nanotextiles
CNT = Carbon Nanotubes
134
Biomimetics and Bio-inspired Systems

Impact on Space Transportation, Space Science and Earth Science
2002 2010 2020 2030
Mission Complexity
Embryonics Self Assembled Array Space Transportation
Biologically inspired
aero-space systems
Brain-like
Sensor Web computing
Extremophiles
Mars in situ
life detector Skin and Bone
Self healing structure

and thermal protection
systems
DNA
Computing
Biological nanopore Artificial nanopore Biological Mimicking
low resolution high resolution
135

E-Learning Material - Nanotechnology and Nanogeoscience

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6 Year Integrated M. Tech.

PAPER CODE: MTIGT1001

1. Introduction to Nanotechnology and Nanogeoscience: 12hrs

2. Nanoremote Sensing 12hrs

3. Nanocrystals, Nanominerals, Nanofossils and Nanostructures 16hrs

4. Nanotechnology in mineral, water and hydrocarbon exploration 12hrs

5. Nanotechnology in Environmental Geotechnology 12hrs

e-learning Material – Nanotechnology and Nanogeoscience

Nanoscience will change the

National Science and Technology Council, 2000

On Dec. 29, 1959, at the California Institute of Technology, Nobel

Ability to image, measure, model, and

Nanotechnology R&D is directed toward

• Examples AFM Image of DNA

• Not just size reduction but phenomena

• New behavior at nanoscale is not

The Scale of the Earth Sciences

NanoGeoscience and Technology Laboratory

Its difficult to grasp quite how small the nano-scale is.

Nanoscale = billionths (10-9)

6 billion people 10 billion components

But something as small as an atom is impossible to

Once scientists had the right tools, such as

Unique Properties of Nanoscale Materials

• Quantum size effects result in unique mechanical,

• Chemical reactivity of nanoscale materials greatly

• Vastly increased surface area per unit mass, e.g.,

• New chemical forms of common chemical elements, e.g.,

Nanoscale Size Effect

• Attainment of high surface area to volume ratio

• Manifestation of properties, including changes in:

What’s the BIG deal about something so SMALL?

Color depends on particle size

Ordinary light excites all color quantum dots.

Quantum dots change color with size because additional

Source: Bala Manian, Quantum Dot Corp.

Si phonon thermal conductivity: Bulk vs. Microscale

The melting point of gold particles decreases dramatically

The well-known and industrially important melting point

Using nanotechnology, materials can effectively be made to be

Nanotechnology Unit-1 J.Saravanavel 16

Nanoscale additives in polymer composite materials for baseball bats, tennis

Cosmetics, Clothes and Food

Nano-engineered materials in automotive products include high-power

Nanotechnology in Electronics and Information Technology

Clean and Cheap Energy

Solid oxide fuel cell

Laser-textured silicon for solar cells

Nanotechnology in Environmental Application

Nanoparticles will someday be used to clean industrial water pollutants in

Nanotechnology in Medical and Biotechnology

Gold nanoparticles can be used to detect early-stage Alzheimer’s disease.

Molecular imaging for the early detection where sensitive biosensors

Multifunctional therapeutics where a nanoparticle serves as a platform to

"Nanominerals" Influence Earth Systems from Ocean to Atmosphere to

A bacteria cell living in a no-oxygen

Nanotechnology in transportation infrastructure

NASA Nanotechnology Roadmap

Increasing levels of system design and integration