C.

Suryanarayana, “Mechanical alloying and milling”, Progress in Materials Science 46

(2001) 1-184

D.B. Witkin, E.J. Lavernia, “Synthesis and mechanical behavior of nanostructured

materials via cryomilling”, Progress in Materials Science 51 (2006) 1–60

H. Gleiter, “Nanostructured materials: basic concepts and microstructure”, Acta mater. 48

(2000) 1-29

Horst Hahn, “Gas phase synthesis of nanocrystalline materials”, Nanostructured

Materials, Vol. 9, 1997, Pp 3-12

K.A. Padmanabhan and S. Balasivanandha Prabu, ‘On the Origins of Conflict in the
Experimental Results Concerning the Mechanical Properties of Ultra-Fine Grained and
Nanostructured Materials: Effects of Processing Routes and Experimental Conditions ‘,
Adv.Mech.Properties and Deform. Mechanism of Bulk Nanostr.Mat, Trans Tech
Publication,UK, ISBN-13::978-3-03785-105-0, pp.3-54,

K.A. Padmanabhan and S. Balasivanandha Prabu, ‘Reliability of Nanostructured

Materials’, in Nanostructured Materials, G. Wilde (Ed.), in the Series Frontiers of
Nanoscience (Series Editor R. E. Palmer) Elsevier, Oxford, U. K./ Amsterdam, The
Netherlands, ISBN-13: 978-0-08-044965-4, pp. 51 – 126,
M.A. Meyers, A. Mishra, D.J. Benson, “Mechanical properties of nanocrystalline
materials”, Progress in Materials Science 51 (2006) 427–556

N. Wang , Y. Cai , R.Q. Zhang, “Growth of nanowires”, Materials Science and Engineering
R 60 (2008) 1–51

Peter J.F. Harris, “Solid state growth mechanisms for carbon nanotubes”, Carbon 45
(2007) 229–239

S.C. Tjong, Haydn Chen, “Nanocrystalline materials and coatings”, Materials Science and
Engineering R 45 (2004) 1–88

Stan Veprek, Maritza G.J. Veprek-Heijman, Pavla Karvankova, Jan Prochazka, “Different
approaches to superhard coatings and nanocomposites”, Thin Solid Films 476 (2005) 1 –
29

V.V. Pokropivny , V.V. Skorokhod, “Classification of nanostructures by dimensionality and

concept of surface forms engineering in nanomaterial science”, Materials Science and
Engineering C xx (2006) xxx–xxx
 New Technologies: Risks and Benefits

The Public
Benefits Risks

DDT cured malaria Endangered birds

Pesticides improved crop yields Toxic to animals
Refrigerants made houses cool Lead to ozone hole
Semiconductor manufacturing High manufacturing costs
Asbestos improved insulation Liability expenses

WOW YUCK
Environmental costs are expensive, paid
long-term and can be social deal-breakers.
Courtesy of V. Colvin
 Nanotechnology: Benefits and Perceived Risks

den
f hid
o r s
F e a .
d . c e
o rl c ie n
Feature size in a transistor:
a l w o s
1970 tenth of a millimeter r e n a n ?
t h e n f i e d
1980 several microns
it h m o s t i
2000 tenth of a micron
d w r iu j u
lid e r a to a r s
c ol m o e fe
lo gy
or a e th
• > $1B federal US n o dollars l s f ar
c h ca l o r
t e n n
a no ted i a tio • Self-aware, invisible ‘Robots’
3: N
• Nanotechnologies su l … r m
e f o
20• 0Curing
e s r
r cancer mis i n
• Materials/Environmental Impact
an g i t
•d Faster computers Is
• Greener chemistry
Courtesy of V. Colvin
 Nanotechnology

“Nano” – From the Greek word for “dwarf” and means 10-9, or one billionth.
In this case it refers to 10-9 meters, or 1 nanometer (nm).

1 nanometer is about 3 atoms long.

“Nanotechnology” – Manufacturing materials, devices and machines at the nanometer,

or atomic/molecular, scale.
 How small is a nanometer? (and other small sizes)

Start with a centimeter. A centimeter is about the size of a bean.

1 cm

Each part is a millimeter long. About the

Now divide it into 10 equal size of a flea.
parts. 1 mm

Each part is 100 micrometers long. About

the size (width) of a human hair.
Now divide that into 10 equal parts. 100 m

Each part is a micrometer long. About the

size of a bacterium.
1 m
Now divide that into 100 equal parts.

Each part is a 100 nanometers long. About

Now divide that into 10 equal parts. the size of a virus.
100 nm

Each part is a nanometer. About the size of

Finally divide that into 100 equal parts. a few atoms or a small molecule.
1 nm
 T he Sc ale of Things -- Nanometers and More
T hings Natural T hings Manmade
1 cm
10 -2 m
10 mm
Head of a pin
1-2 mm

1,000,000 nanometers = 21 s t Century

Ant 10 -3 m 1 mill imeter (mm) MicroElectroMechanical devices Challenge
~ 5 mm 10 -100 m wide

Micro wave
Dust mite
200 m 10 -4 m 0.1 mm
100 m

Microworld
Fly ash
Human hair ~ 10-20 m
~ 10-50 m wide

The
0.01 mm
10 -5 m
10 m O
P
O
O

In frared
Red blood cells
O O O O

Red blood cells

Pollen grain
O O O O O O O O

with white cell O O O O O O O O

~ 2-5 m 1,000 nanometers = S S S S S S S S

10 -6 m 1 micrometer (m) Zone plate x-ray “lens”

Visib le
Outermost ring spacing
~35 nm

0.1 m
10 -7 m Combine nanoscale building
100 nm blocks to make novel
Ultravio let

functional devices, e.g., a

The Nanoworld

photosynthetic reaction
center with integral
semiconductor storage
10 -8 m 0.01 m
~10 nm diameter 10 nm Nanotube electrode Nanotube transistor

ATP synthase

10 -9 m 1 nanometer (nm)
So ft x-ray

DNA Carbon nanotube

~2-1/2 nm diameter 10 -10 m 0.1 nm Quantum corral of 48 iron atoms on copper surface
Atoms of silicon positioned one at a time with an STM tip ~2 nm diameter
Of fi ce of B asi cE nergy S ciences
spacing ~tenths of nm Corral diameter 14 nm Of fi ce of S ci ence, U.S . DOE
V ersi on 03-05-02
 NANOSTRUCTURED MATERIALS VIS-A-VIS NANOTECHNOLOGY
1m

BULK COMPONENTS
BULK SUB FINE NORMAL COARSE
NANO GRAINED MICRON GRAINED MATERIALS GRAINED
MATERIALS GRAINED MATERIALS CASTINGS
100 mm MATERIALS

10 mm
Component / Device Size

1 mm

NANO
COATINGS

SUB MICRON NORMAL

STRUCTURED COATINGS/ COATINGS/
100 m FILMS FILMS
COATINGS

NE
10 m 

ZO
NANO

EN
STRUCTURED
MEMS

DD
THIN FILMS
1 m

I
RB
FO
100 nm
s o
b e an

O S
Tu n N
NANO

N R
TECH

A DE
o
rb

N
Ca

W
10 nm PO

1 nm 10 nm 100 nm 1 m 10 m  100 m 1 mm 10 mm 100

mm
Microstructure Size
 Capability
Capabilityof
of Nanotechnology
Nanotechnology

Multi-Functional
Materials Revolutionary Aircraft
High S trength
Material (>10 GPa) Concepts (30% less
mass, 20% less emission,
25% increased range)

Reusable Launch
Vehicle (20% less
mass, 20% less noise)
Autonomous S pacecraft
(40% less mass)
Bio-Inspired Materials Adaptive S elf-Repairing
and Processes S pace Missions
Source: NASA Ames
 FUTURE AUTOMOBILE
Nano-scale
Carbon nanotubes in metal oxide
windshields & ceramic
frames to make catalysts to
them strong & almost
lightweight eliminate
Nano-powders
emissions
in paints
for high
gloss &
durability

Nano polymer composites for lightweight Fuel cells with nano-

high resistance bumpers catalysts and
membrane
technologies
 Then there are dreams…
Library of
Library of Congress?
Congress

• Library of Congress inside a sugar cube

• Bottom-up manufacturing
• M aterials (100x) stronger but lighter than steel
• Speed and efficiency of computer chips & transistors
• Nano contrast agents for cancer cell detection
• Contaminant removal from water & air
• Double energy efficiency of solar cells

*From Nanotechnology
Magazine (nanozine.com)
 How do you build something so small?

“Top-down” – building something by starting with a larger component

and carving away material (like a sculpture).
In nanotechnology: patterning (using photolithography) and etching
away material, as in building integrated circuits

“Bottom-up” – building something by assembling smaller components

(like building a car engine).
In nanotechnology: self-assembly of atoms and molecules, as in
chemical and biological systems
Top-down fabrication
 Limitations of top-down fabrication

• Due to diffraction effects, the practical limit for optical lithography is around
0.1 microns (100 nm).

• To define smaller features, electron beams, or “e-beams,” (which have

smaller wavelengths) can be used. Feature sizes smaller than 20 nm can be
patterned.

•But e-beam projection systems using masks have not been fully developed
yet – instead, “direct-write” e-beam lithography has been used.

• While optical lithography works in parallel over the wafer (with high
throughput), direct-write e-beam lithography works as a series process (with
low throughput).
 Bottom-up fabrication

“Self-assembly” of atoms and molecules (since top-down is very difficult for

manufacturing at nanoscale level).
Use of chemical and biological processes.

Current day examples: Growth of nanowires from vapor, using gold nano-dot
catalysts; Self-assembled monolayers (SAM) from solution.

Self-assembled organic monolayers for

SEM showing the vertical growth of nanowires molecular transistors, etc. (Yale)
for electronic devices (Stanford)

More extreme example: Self-replicating robots.

 Challenges of bottom-up fabrication
• Getting the structures to always grow exactly how and where you want them
to

• Making complicated patterns

• Fabricating robust structures

Some common strategies:

• Use catalysts, stress fields, diffraction gratings to achieve selective growth in

specific locations

• Use top-down processes in conjunction with bottom-up processes, and build

on silicon substrates
 Nanotechnology Defined

“The development and use of devices that have a size of only a few nanometres.”
physics.about.com

“Research and technology development at the atomic, molecular or macromolecular level in

the length scale of approximately 1 - 100 nm range, to provide a fundamental understanding
of phenomena and materials at the nanoscale and to create and use structures, devices and
systems that have novel properties and functions because of their small and/or intermediate
size.” www.nano.gov

“Branch of engineering that deals with things smaller than 100 nm (especially with the
manipulation of individual molecules).” www.hyperdictionary.com

“Nanotechnology, or, as it is sometimes called, molecular manufacturing, is a branch of

engineering that deals with the design and manufacture of extremely small electronic circuits
and mechanical devices built at the molecular level of matter.” www.whatis.com

“The art of manipulating materials on an atomic or molecular scale especially to build

microscopic devices.” Miriam Webster Dictionary
 Perspective of Size

Water molecules – 3 atoms

Protein molecules – thousands of atoms
DNA molecules – millions of atoms
Nanowires, carbon nanotubes – millions of atoms water molecule

Carbon nanotube

Molecule of DNA
Protein molecule
www.iacr.bbsrc.ac.uk/notebook/ courses/guide/dnast.htm
www.phys.psu.edu/~crespi/research/_carbon.1d/public
student.biology.arizona.edu/.../ group2/crystallography.htm
 How Small is a nm?

1 µm = one millionth of a meter

1 nm = one billionth of a meter
≈ 1/50,000 thickness of a hair!
≈ a string of 3 atoms

If we shrunk all distances by 110,000,000,000 X

The sun and earth would be separated by 1 m
Human hair thickness
A football field would be 1 nm ~ 50 µm

110 m

110,000,000 km
 Surface vs. Volume

Si has a diamond structure with a = 5.43 Å

a
A Si nanocube 10 nm on a side is composed of:
~6250 unit cells
~50,000 atoms
Each nanocube face is composed of:
~340 unit cells per face Diamond unit cell
~680 surface atoms per face
Total surface area is:
~4080 atoms (~10% surface atoms)
Si nanocube
A bulk Si film 1 µm thick on a 10 cm square:
~6.3 X 1019 unit cells
~5 X 1020 atoms
~1.4 X 1017 surface atoms (~0.03% surface atoms)

Bulk Si film

In a nanoscale material, the surface/boundary/interface plays an important role!

 More than just size…

Interesting phenomena:
Chemical – take advantage of large
surface to volume ratio, interfacial
and surface
chemistry important,
systems too small for statistical analysis

Electronic – quantum confinement,

bandgap engineering, change in STM of dangling bonds on a Si:H
density of states, electron surface
tunneling
b
Magnetic – giant magnetoresistance
by nanoscale multilayers, change in
magnetic susceptibility

http://pubweb.acns.nwu.edu/~mhe663/ Electron tunneling

 More than just size …

Interesting phenomena:
Mechanical – improved strength hardness in
light-weight nanocomposites and
nanomaterials, altered bending,
compression properties, nanomechanics of
molecular structures
Fluorescence of quantum dots of
Optical – absorption and fluorescence of various sizes
nanocrystals, single photon phenomena,
photonic bandgap engineering
Fluidic – enhanced flow properties with
nanoparticles, nanoscale adsorbed films
important
Thermal – increased thermoelectric
performance of nanoscale materials,
interfacial thermal resistance important.
Phonon tunneling
 Nanotech – The next new thing?

Old Nanotechnology New Nanotechnology

Vastly improved catalysts enhance
surface area to volume ratios

Stained-glass windows – Designer drugs

Silver-Halide Photography Cheap, sensitive medical

diagnostics
AR-coated lenses
Transparent Sunblock
Viruses are nanomachines
Nanotube-strengthened cables
The difference between
old and new nano:

Now, we are designing and manipulating at the molecular level whereas

before it was either evolution that did it for us or results happened which
we never really understood and so couldn’t optimize.
 Historical Development of Nanotechnology

3.5 billion The first living cells emerge. Cells house nanoscale biomachines that
years ago perform such tasks as manipulating genetic material and
supplying energy

30BC-640AD Pottery using nanosized particles which can be seen in the British
museum. It is made from glass which appears green in reflected
light, but when light is shown through the glass it appears
translucent red.
500-1450AD Medival Period- stained glass colored ruby red is due to gold
nanoparticles trapped with glass matrix, while the drop yellow
colour is due to silver nano particle
1450- Renaissance Period-Artisans coloring pottery by European-
1600AD copper and silver metal nanoparticles are used
400 B.C. Democritus coins the word “atom,” meaning “not cleavable” in
ancient Greek
18th and 19th Photography depends on the production of silver nanoparticles
Centuries: sensitive to light.
1883: Eastman (founder of Kodak) produces prototype of
photographic film.
1857: Faraday publishes paper in Phil. Trans. of the Royal Society
attempting to explain how metal particles affect the color of
stained glass windows found in ancient churches and
cathedrals.
1861: Graham coins the term colloid to describe a
suspension/dispersion containing 1 to 100 nm particles.
1905 Einstein publishes a paper that estimates the diameter of a
sugar molecule as about one nanometer.
1908: Mie explains color dependence of glass on metal particle size
and type.
1931 Knoll and Ruska develop the electron microscope, which
enables sub-nanometer imaging.
1947 Williams Shockley, Bardeen and Brattain invent the junction
transistor which replaced bulk vacuum tubes in electronic
circuits. The invention of the transistor and the integrated
circuits marks the beginning of microelectronics.
1951 Mueller invents the ‘Field-ion Electron Microscope’ which
makes individual atoms and their arrangement on a surface
visible. The instrument allows a magnification of more than 2
million times.
1953 Discovery of DNA- Watson and crick publish an article in
Nature describing the double helix structure of DNA.
1958 Tunneling phenomena- Esaki discovers that electrons could
some times ‘tunnel’ through a potential barrier formed at the
junctions of certain semiconductor even though classical theory
predicts that this is not possible.
1959 Feynman gives his famed talk “There’s Plenty of Room at the
Bottom,” on the prospects for miniaturization.
1960 Discovery of Ferro-fluids, NASA scientists discover that nano-
sized particles of iron that were given a chemical coating or
surfactant, which prevented them from clumping together could
be dispersed in oil or water. They could then control the
location of fluid (called a ferro- fluid) with a magnet.
1965 Moore predicts (Moore’s law) that the number of transistors per
integrated circuit doubles every two years.
1968 Cho, Arthur and their colleagues invent molecular-beam
epitaxy, a technique that can deposit single atomic layers on a
surface
1974 Taniguchi conceives the word “nanotechnology” to signify
machining with tolerances of less than a micrometer.
1974 Charles, Morrison, Ratner and Aviram propose that individual
molecules may exhibit the behaviour of basic electronic
devices, thus allowing computers to be built from the bottom up
by turning individual molecules into circuit components.
1977 Van Duyne discovers ‘surface enhanced Raman spectroscopy’
that makes nanoscale studies possible.
1980 Sagir discovers that molecules containing a chemical called
octadecyltrichlorosilane or OTS would spontaneously react with
glass surface to assemble by themselves into individual layers
(Self Assembled Monolayers).
1981 Binnig and Rohrer create the scanning tunneling microscope,
which can image individual atoms.
1983 Nuzzo and Allara discover self-assembled monolayers.
1985 Heath discovers Buckminster fullerenes, also known as
buckyballs, which measure about a nanometer in diameter. Curl
Jr., Kroto and Smalley are awarded the Nobel prize in 1995 for
--
1986 Drexler publishes “Engines of Creation,” a futuristic book that
popularizes nanotechnology.
1986 Atomic Force Microscope is invented by Binning, Gerber and
Quate.
1987 Averin and Likharev propose the idea of a new device called a
single Electron Tunneling Transistor. Two years later Fulton and
Dolan build such a device.
1988 Brus and his team of researchers discover that nano-sized crystal
semiconductor material made from the same substance exhibits
strikingly different colors. These nanocrystal semiconductors were
called ‘Quantum Dots’ and this work eventually contributes to the
understanding of the quantum confinement effect.
1989 Eigler writes the letters of his company’s name using individual
xenon atoms.
1991 Ijima discovers carbon nanotubes.
1993 Robinett and Williams devise a virtual-reality system connected to
a scanning tunneling microscope that lets the user see and touch
atoms.
1997 Chou and coworkers unveil a single-electron transistor that
operates at room temperature.
1997 Tour and Reed measure the resistance of a single molecule
placed between two electrodes.
1998 Dekker’s group creates a transistor from a single molecule: a
carbon nanotube.
1998 Heath, Williams and Kuekes design defect-tolerant
supercomputer from defective processors.
1999 Mirkin develops ‘Dip-Pen Nanolithography’.
1999 Reed and Tour demonstrate that single molecules can act as
molecular switches.
2000 Eigler and other researchers devise a quantum mirage. Placing a
magnetic atom at one focus of an elliptical ring of atoms creates a
mirage of the same atom at another focus, a possible means of
transmitting information without wires.
2000 The Clinton administration announces the National
Nanotechnology Initiative, which provides a big boost in funding
($700M/yr) and gives the field greater visibility.
2002 IBM announces the Millipede, a data storage device based on
the atomic force microscope that can write, read and erase 10
nm holes in a plastic film. The device can store data at a density
of 50 GB per square inch, which could more than double.
2002 Hewlett-Packard announces that it has created the highest
density electronically addressable memory yet, a 64-bit memory
using molecular switches as active components. The entire
device fits inside a square micrometer.
2002 Norris and coworkers encapsulate quantum dots inside a
biocompatible polymer enabling in-vivo imaging. They
successfully track cells as they divide and the embryo grows
from just a few cells
2003 Guyot-Sionnest’s group succeeds in doping semiconductor
nanocrystals.
2003 Ho’s group demonstrates how the properties of nanoscale
objects can change when they are assembled.
2004 The world’s first College of Nanotechnology is established at
Sony Albany, USA.
A single-electron transistor is made, which operates by using a
nanometer-scale vibrating arm. It was built by using a simple
two-step process and unlike previous devices of the kind, it
does not require cryogenic temperatures to be operational
Solid-state carbon-50 molecules are prepared by using an arc-
discharge technique involving chlorine
A light bulb with Carbon nanotube as the filament has been
designed and it is found to have several advantages over the
conventional tungsten filament.
Spin of an individual electron is imaged by combining MRI with
AFM. This could eventually lead to the production of three-
dimensional images on an atomic scale and as read out
devices for spin-based quantum computing.
2005 Nanoscale Motors: A working example
of a Brownian Motor is presented.
Thermal Brownian Motion in
combination with non-equilibrium noise
is used to exercise control over the
system with Nanoscale accuracy. This
provides an ideal pathway for
fabricating and operating Nanoscale
devices.
Categories of nanostructured materials
Gleiter's classification schema for NSM according to their chemical composition and the
dimensionality (shape) of the crystallites (structural elements) forming the NSM. H.
GLEITER
 Various size effects in nanomaterials
Property Influence of size reduction on properties of nanoparticle

Structural Decrease or increase of lattice parameter

Structure transformation

Mechanical Enhancement of hardness, strength, fracture, ductility

Arise of super plasticity
Raising of wear resistance

Thermal Decrease of melting point

Decrease of phase transition temperature
Decrease of melting entropy
Softening of phonon spectra

Thermo-dynamical Increase of heat capacity

Increase of thermal expansion
Decrease of Debye temperature
Stabilization of high temperature phases

Kinetic Increase of diffusion coefficient

Sharp drop of thermal conductance under some critical size d*
Oscillation of kinetic coefficients

Electrical Increase of conductivity for nanometals

Arise of conductivity for nanodielectrics
Increase of dielectric inductivity for ferroelectrics at d*

Electronic Increase of band gap

Arise of phonon generation
Raising of conductivity under low temperatures in semi-metallic Bi

Magnetic Increase or decrease of coercive force at d*

Decrease of Curie temperature
Rice of paramegnetism in ferromagnetic at some d*
Rice of gaint magneto resistance
Rise of maximal temperature of magnetorsistance
Increase of magnetic permeability in ferromagnetic at d*

Optical Diffraction and interference

Increase of absorption in ultraviolet range (blue shift)
Oscillation of optical absorption
Arise of nonlinear optical properties

Chemical Increase of catalytic activity

Increase of velocity of physico-chemical interactions
Swap of solubility
Lotus, the national flower of
India featured on a postage
Floating lotus leaves and a blooming flower in a pond (Left); Water drops forming
stamp issued on beads on the leaf surface (Right).
September 1, 1977.

Scanning electron microscope image of leaf

surface of Nelumbo nucifera.
 Lotus flower

The Lotus flower is a symbol

of cleanliness The surface of the Lotus flower
W. Barthlott, University of Bonn
The four classes of surface wettability
types of leaf surface based on
their interaction with aqueous droplets.

Physics of selfcleaning
property of lotus.
The large contact angle results
from nanoscopic
bumps that trap air between
the water and the surface
minimizing the contact with
the surface. A drop of water
rolls downwards on leaf
surface, picking up dirt
(Based on Forbes 2008).
 Learn from nature: Geckos

K. Autumn
http://www.lclark.edu/~autumn/dept
 The secret behind the Gecko‘s feet
Biological sticking mechanisms are observed in many
different animals (beetles, flies, spiders, geckos). The higher
the weight of the animal, the smaller the sticking contacts
and the larger their number.
 Applications as self adhesive tapes without polymeric
adhesives to complex climbing robotic systems

The sticking behavior of the animals can be described by

classical contact mechanics (used to describe sticking of
spheres on smooth surfaces, i.e. Van-der-Waals forces). The
sticking force of a single contact skales with the circumference,
thus the splitting of a single contact into subcontacts results in
a continuous increase of the efficiency of the contact system,
Beetle: diameter of sticking hair
approx. 10 µm (1/10 of human i.e. the decrease of the sticking force of a single contact is
hair); compensated by the increasing number of sticking sites.
Gecko: diameter of sticking hair The capability of animals to stick can be described in a weight
approx. 100 to 200 nm. range from 10 mg to 100 g (Faktor 105).
Technological products could be better than nature as artificial
E. Arzt, St. Gorb, R. Spolenak nano-hair can be manufactured with diameters in the range of 10
MPI Metallforschung, Stuttgart
to 20 nm.
 Technology based on Geckos

Geckos and future high-tech products

For a human to walk along the

ceiling, hands and feet have to
be covered by sticking structures
consisting of hairs with max. 10
nm diameter.
the nanoparticles are often built-up from a full-shell cluster of atoms having cubic or hexagonal
closed-packed structure. Such a structure can be constructed from a central atom surrounded by
a first shell of 12, a second of 42, a third of 92 atoms, etc. The number of atoms in nth shell is
10n2 + 2
STRUCTURES AND PROPERTIES OF NsM

The properties of a crystalline solid are known to depend on:

(i) The size of the crystalline regions and

(ii) On the atomic structure of the solid characterized by the average atomic density
and the coordination between nearest neighbors.

Computed atomic structure of a NsM. The computations were

performed by modelling the interatomic forces by a Morse
potential. The black (boundary) atoms are atoms the sites of
which deviate more than 10% from the corresponding lattice sites
 Effects controlling the properties of nanostructured materials

Size effects

Fig. 4. Schematic model of the structure of

Fig. 2. Two-dimensional model nanostructured Cu-Bi and W-Ga alloys. The
of a nanostructured material. open circles represent the Cu or W atoms,
The atoms in the centers of the respectively, forming the nanometer-sized
crystals are indicated in black. crystals. The black circles are the Bi or Ga
The ones in the boundary core atoms, respectively, incorporated in the
regions are represented as boundaries at sites of enhanced local free
open circles [13]. volume. The atomic structure shown was
deduced from EXAFS and X-ray diffraction
measurements [6].
Size Effects

Size effects result if the

characteristic size of the
building blocks of the
microstructure (e.g. the
crystallite size,) is reduced
to the point where critical
length scales of physical
phenomena (e.g. the mean
free paths of electrons or
phonons, a coherency
length, a screening length,
Absorption spectrum of CdS particles in aqueous solution as etc.) become comparable
Flow stress of Ni-13 at% Ni alloys as a function of the size of
the Ni3Al precipitates.
a function of particle size with the characteristic size
of the building blocks of the
microstructure. If the
thickness of the
layers of a super lattice is
comparable with the
wavelength of the electrons
at the Fermi edge, discrete
energy levels for electrons
and holes are formed in the
quantum wells. Such size
e.ects modifying the
mechanical and optical
properties are displayed in
Figs
Photoluminescense spectra of nanocrystalline Melting temperature versus reciprocal
ZnO with different crystal sizes in comparison particle radius for indium
to the bulk material (9). The detection wave
length was 550 nm
Changes of the Atomic Structure of a NsM Relative to a Perfect Crystal due to the High
Density of Interfaces

Atomic structure in the core of grain boundary between Coordination number (X-ray scattering) for nanocrystalline Pd (12
two NiO crystals tilted relative to one another by 36.9” run crystal size) relative to a Pd single crystal as a function of the
about a common [lOO] direction interatomic spacings

Changes in the atomic structure result if a high density of incoherent interfaces or other lattice defects such as
dislocations, vacancies, etc. is incorporated. The cores of lattice defects represent a constrained state of solid
matter differing structurally from (unconstrained) crystals and/or glasses. As a consequence, a solid containing a
high density of defect cores differs structurally from a defect-free solid with the same (average) chemical
composition.
 The misfit between adjacent crystallites changes the atomic structure (e.g. the average
atomic density, the nearest-neighbor coordination, etc.) in the boundary regions relative to
the perfect crystal. At high defect densities the volume fraction of defect cores becomes
comparable with the volume fraction of the crystalline regions. In fact, this is the case if the
crystal diameter becomes comparable with the thickness of the interfaces, i.e. for crystal
sizes on the order of one or a few nanometers as is the case in NsM.

Alloying of components (e.g. elements) that are immiscible in the solid and/or the molten state.

Schematic model of the structure of nanostructured

Cu±Bi and W±Ga alloys. The open circles represent the
Cu or W atoms, respectively, forming the nanometer-
sized crystals. The black circles are the Bi or Ga atoms,
respectively, incorporated in the boundaries at sites of
enhanced local free volume. The atomic structure
shown was deduced from EXAFS and X-ray diffraction
measurements
solute atoms with little solubility in the lattice of
the crystallites frequently segregate to the
boundary cores

The second case of nanostructured alloys results if

the crystallites of a NsM have
di.erent chemical compositions. Even if the con-
stituents are immiscible in the crystalline and/or
molten state (e.g. Fe and Ag), the formation of
solid solutions in the boundary regions of the NsM
Chemical binding effects.

The atomic structures of the boundary regions in NsM are expected

to depend on the type of chemical binding forces.
COUPLING BETWEEN ATOMIC STRUCTURE, INTERATOMIC BONDS AND
CHEMICAL COMPOSITION

Diffusivity of Ag in a Cu single crystal (S.C.) and in Raman spectra of nanocrystalline diamond in comparison to a
nanocrystalline Cu (N.C.) (10 nm average crystal size) single crystal . The sharp line originates from sp3 bonds. The
hatched areas indicated the presence of sp2 bonds in the
nanocrystalline diamond