Nanotechnology : Recapitulation

Overview

 Introduction.
 Nanomaterials: Basics.
 Properties of Nanomaterials:
 Mechanical Properties
 Optical Properties
 Electrical Properties
 Magnetic Properties
 Nanofluidics
Introduction
 Nano Particles: Basic Definitions
 Nanometer is one billionth (10-9) of a meter.
 1 nm is only three to five atoms wide.
 Nano Particles have size between 1 nm to 100 nm.
 Nanometer is ~40,000 times smaller than the thickness of human hair.

At nanoscale, physical and chemical properties of materials differ

fundamentally from that of individual atoms (or molecules) or bulk matter.

Nanoparticles A solid particle having the size in range 1-100nm that could be
non-crystalline, an aggregate of crystallites or single crystallite.

Cluster A collection of atoms or reactive molecules up to 50 units.

Colloids A stable liquid phase containing particles of 1-100nm in size.

Nano Crystal A solid particle that is a single crystal in nanometer range.

Nanoparticles: Size Estimates

Hydrogen atom 0.04 nm

Computer chips 90 nm Proteins ~ 1-20 nm
Definitions (Royal Society of London,2004)

• Study of fundamental relationships

Nanoscience between physical properties and
material dimensions on the nano scale.

• Designing, Production, Characterization

Nanotechnology and Applications of Nanostructured
materials.
 Birth of Nano-Science Birth of Nanotechnology
 Richard P. Feynman (1918-1988), a US • Taniguchi of Tokyo Science University
Physicist, first introduced the concept of coined the word nanotechnology in
nano-science in his statement: 1974 to describe science and
 Why can’t we write the entire 24 volumes technology of processing (or building)
of the Encyclopedia Britannica on the parts with nanometric tolerance.
head of a pin? • Eric Drexler (1986) conceptualized the
 The problems of chemistry and biology Cell Repair Machines as:
can be greatly helped if we develop  By working along molecule by
o ability to see what we are doing molecule and structure by
& structure, repair machines will be
o do things on an atomic level able to repair whole cell. By
A development, which I think is working on cell by cell and tissue
unavoidable. by tissue, they will be able to repair
whole organ………they will restore
health.
Nanomaterials: Basics
 Low Dimensional Systems
The most universal classification scheme of low-
dimensional system is based on the number of
spatial directions along which the particle in a system
can move freely.
• Quantum Well Systems have the particles
confined in one direction but are free to move in
other two directions.
• Quantum Wire Systems have the particles
confined in two directions but free to move in
third direction.
• Quantum Dot Systems have the particles that
are confined in all the three directions and can’t
move freely in any direction.

 The spatial dimensions are comparable to de Broglie wavelength of

carriers which leads to their continuous reflections from bounds of matter.
 The carrier energy states and density of states are quantized, which
results in their quantum mechanical electronic and optical behavior.
Fundamental Properties of Nanomaterials
• Nanomaterials have larger surface area to volume ratio
relative to matter in bulk form.

Enhanced Surface • This enhances the chemical activity, mechanical strength

of nanomaterials and also brings marked changes in
electrical properties.

• Quantum effects begin to dominate the behaviour of matter

at the Nanoscale due to spatial confinement.
Quantum Confinement • This is the root cause of altogether different properties
exhibited by nanomaterials as compared to bulk matter.

Why QuantIzed behaviour ?

The spatial distances are smaller than de Broglie wavelength of carriers resulting in their quantized behavior.
Nanoscale: High Ratio of Surface Area to Volume

Repeat 24
times

5 cm3 cube (Edge = 1.7 cm) of material divided 24

times will produce 1nm3 cubes which can spread as
a single layer over a football field.
Quantum Wells

• One dimension is reduced to nano-range

while others remain large. Hence particle’s Substrate
motion is restricted in one direction, while it
is free to move in other two directions.
Semiconductor growth
• Quantum wells are formed in (single layer)
semiconductors by having a material like
GaAs (small band gap) sandwiched
between two layers of a material with wide
band gap such as AlGaAs.
• These structures can be grown by
molecular beam epitaxy or chemical vapor
deposition with thickness control down to
monolayers.
• Single Quantum Well structure is formed

by hetero-epitaxial growth of ultra thin

layer of binary, tertiary, quaternary

semiconductor alloys on a suitable

substrate. Examples are InP-on-GaAs,

Semiconductor growth Substrate
AlGaAs-on-GaAs and Si-on-Ge. (single layer)

• Double Quantum Well structure is

heterostructure in which a ultra-thin layer

of small band gap material is sandwiched

between layers of wide band gap material.

Often the wide band gap materials are of

same semiconductor. An example is the

AlGaAs/GaAs/AlGaAs DQW system.

• Multiple Quantum Well structure

is a heterostructure in which

alternating layers of small band

gap and wide band gap materials

are grown on each other. Often the

wide band gap materials form a

barrier to prevent communication

between electrons of various

quantum wells.
Quantum Wires
 In quantum wire, two dimensions are reduced while one dimension remains large.
 Ultra fine wires formed by self-assembly of Nano dots into linear arrays.
 Semiconductors Si, Ga, InP form nanowires.
 Conventional formula of resistance of wire no longer remains valid.
 General Properties of Nanowire
 Diameter ~10-100nm.
 Single crystal formation with crystallographic orientation along the nanowire axis.
 Minimal defects within wire.
 Minimal irregularities within nanowire arrays.
 Nanowires find applications in
 High-density data storage as magnetic read heads or patterned storage media.
 Metallic interconnects of quantum devices and Nano-devices.
Magnetic Nanowire

 Examples: Cobalt, gold,

copper and cobalt-copper
nanowire arrays.
 Important for storage device
applications.
 Nanowire arrays with
diameter < 20 nm can be
fabricated by electrochemical Cobalt nanowires on Si substrate

deposition.
Quantum Dots
Ordinary light excites all color
 The extreme case of size reduction in which all 3
quantum dots. Any light source
dimensions reach the nanometer range.
bluer than dot of interest works.
 It is nanostructure that confines the motion of
conduction electrons, valences holes or excitons in
all three spatial directions.
 If semiconductor particles are made small enough,
quantum effects come into play, which limit the
energies that electrons and holes can possess.
 These particles can be made to emit or absorb
specific colours of light merely by controlling their
size.
 Quantum dots (dia~2nm) find applications in
 Composites
Quantum dots change color with size
 Solar cells
 because additional energy is required to
Fluorescent biological labels.
confine the semiconductor excitation to a
smaller volume.
Effect of Quantum Confinement

dn
Density of States 
Hydrogen Spectrum dE
 Fullerenes (Carbon 60)

 In mid-1980s, a new class of carbon material

was discovered by Harry Kroto and Richard
Smalley which are termed Carbon 60 or
Fullerenes (C60).
 C60 are spherical molecules about 1nm in
diameter, comprising 60 carbon atoms arranged
as 20 hexagons and 12 pentagons in Harold Kroto from the

configuration of a football (such that no two University of Sussex,

Robert Curl and Richard
pentagons lie adjacent).
Smalley from Rice
 Several applications of fullerenes are:
University were awarded
 Miniature ball bearings to lubricate surfaces.
the Nobel Prize in
 Drug delivery vehicles.
Chemistry in 1996 for
 Electronic circuits. their discovery of C60.
Carbon Nanotubes

• A single-walled carbon nanotube (SWNT) is unique among solid

state materials that has every atom lying on the surface.

• Structurally, carbon nano-tubes are 100 times stronger than steel.

• They can conduct electricity better than copper but under different

configurations exhibit insulating and semiconducting behavior too.

• They are very potential materials for future technologies.

Dendrimers

 Dendrimers are spherical polymeric molecules,

usually several nanometres in size.
 These are man-made molecules, with branching
shape and subtending large surface area, about the
size of an average protein.
 Dendrimers are used in applications such as:
 Coatings and inks.

 Carrier molecules for disease detection, drug delivery

and biologically active molecules.
Properties of Nanomaterials
Nano Materials: Shapes & Size
o Nanoparticles
o Nanocapsules
o Nanofibers The remarkable transition of physical properties of
o Nanowires nanomaterials are related to different factors:
 Large fraction of surface atoms.
o Fullerenes (C60)  Large surface energy.
o Nanotubes  Spatial confinement.
 Reduced imperfections.
o Nanosprings
o Nanobelts
o Quantum dots
o Nanofluids
Size Dependent Properties

The structure of materials changes with respect to

size. Consequently the matter in nano-dimensions
offers exciting changes in many properties such as
 Melting point
 Band gap
 Optical properties
 Electrical properties
 Magnetic properties
 Physical Properties of Nanomaterials

 Reduced Melting Point: Nanomaterials may have a significantly

lower melting point or phase transition temperature and appreciably
reduced lattice constants (spacing between atoms is reduced), due
to a huge fraction of atoms lying on surface.

 Ultra Hard: Mechanical properties of nanomaterials may reach the

theoretical strength, which are one to two orders of magnitude higher
than that of single crystals in the bulk form. The enhancement in
mechanical strength is due to the reduced probability of defects.

 Optical properties of nanomaterials can be significantly different

from bulk crystals. These properties arise due to increased band gap
and quantum confinement of charge carriers.
 Electrical conductivity decreases as reduced dimensions
enhance surface scattering. However electrical conductivity
may increase due to the improved ordering resulting in
ballistic transport.

 Magnetic properties of nanostructured materials are

distinctly different from that of bulk materials. Ferromagnetism
disappears and gives way to super-paramagnetism in the
nanometer scale due to the huge surface energy.

 Self-purification is an intrinsic thermodynamic property of

nanostructures and nanomaterials due to enhanced diffusion
of impurities/defects/dislocations to the nearby surface.
Surface Area

The total surface area or

the fraction of total number
of atoms on surface
increases with reducing
size of the particles
Melting Point

The melting point lowers

dramatically as the particle
size gets below 5 nm.
 Melting Point Depression

 Melting-point depression is a phenomenon of fall of the melting point

of a material with reduction of its particle size.
 It is most evident in nanowires, nanotubes and nanoparticles, which
suffer depression of melting point by more than 100oC as compared to
bulk phase of the same material.
 Nanoparticles of metals, inert gases, semiconductors and molecular
crystals suffer melting point depression when particle size reduces
below 100 nm.
 Melting temperature depression occurs in nanomaterials because of :
 Larger surface-to-volume ratio, which drastically alters their thermodynamic and
thermal properties.
 Shape of the nanoparticle also plays role in determining the melting temperature
depression of nanoparticles. This is owing to the fact that nanoparticles of different
shapes but occupying same volume have different surface to volume ratio.
 Cohesive energy
 Melting temperature relates to cohesive energy (heat of sublimation)
which is the energy required to transform the metallic crystal into
individual atoms. It rises with the increase in particle size.
 Let a metallic particle has a diameter of D and is composed of n
atoms. The cohesive energy of article is given as:

 The melting temperature and cohesive energy of particle are related as:

o This is the general equation for the

size and shape dependent melting
temperature of crystals.
o The melting temperature depression
of nanoparticles is apparent only
below 100nm particle size.
Properties of Nanomaterials: Mechanical
 Mechanical Properties of Nanomaterial

 Mechanical properties of solids depend on the microstructure, which

includes the influence of :
 Chemical composition
 Arrangement of the atoms and the atomic structure
 The size of a solid in one, two or three dimensions

 The important aspects related to microstructure are:

 Distribution of atomic defects, dislocations and strains
 Shape and nature of grain boundaries and interfaces
 Degree of porosity
 Existing short range order
 Mechanical Properties

• The calculated strength of perfect crystals exceeds

that of real ones by one to two orders of magnitudes.
• The enhancement starts in the micrometer scale which
is different from other size dependent properties.
• Two possible mechanisms have been proposed to
explain the enhanced strength of nanowires or nano
rods (diameters < 10 microns).
 Increased Internal Perfection.
 Increased Surface Perfection.
First: Increased Internal Perfection
o Imperfections, such as dislocations, are often created to
accommodate various stress generated during the
synthesis and processing of bulk materials.
o These stress can’t be completely avoided but in
nanomaterials we have:
 Much reduced probability of stress to persist.
 Smaller cross-section of these materials enhances the
probability that imperfections precipitate.
 Thermodynamically, imperfections in crystals are highly
energetic and can be eliminated. Small sizes makes such
elimination of imperfections possible.

Second: Increased Surface Perfection

o Smaller structures have less surface defects specially when synthesized

following the bottom-up approach.
o Vapor grown whiskers with diameters < 10μm are devoid of detectable steps on
their surfaces as confirmed by electron microscopy.
 Stronger hardness than
Hall-Petch Model what has been predicted
by the Hall-Petch Model.

 This model treats grain boundaries

as barriers to the motion of
dislocations. Thus dislocations pile
up against the boundary.
 These dislocations cross over to the Bulk: More Room for Deformation
in bulk polycrystalline materials
neighboring grain when critical stress
is exceeded. This leads to yielding of
material.
 Hall-Petch Model predicts that the d=
micrometer
smaller the grain size, the stronger scale grain
size

the material. Yield Strength

 The model loses its validity for single
Hardness
crystal materials.
 Hall-Petch Relation
• Decreasing the grain size is one of the most effective strengthening
mechanism which results in :
 Enhancement of both strength and ductility.
 Improves the fracture resistance as the size of crack formed gets
limited to grain diameter.
 Yield stress decreases finally reaching lowest limit (i.e. yield
stress of amorphous materials).

• Grain boundary plays a critical role in the yield stress of materials as

there are different deformation modes associated with different
 Grain size and shape.
 Temperature.
 Stress state and grain boundary structures.
Properties of Nanomaterials: Optical
 Optical Properties

 The reduction of material dimension has pronounced effects

on the optical properties.
 The size dependence is generally classified into two groups:
• One is due to the increased energy level spacing as the
system becomes more confined.
• Other is related to Surface Plasmon Resonance (SPR).
 Red Shift Blue Shift
 Redshift occurs when EM radiation • Blue shift is any decrease in
from an object suffers increase in wavelength, with a corresponding
wavelength. This is irrespective of increase in frequency, of
whether or not the radiation is electromagnetic waves. In visible
within the visible spectrum. light, this shifts the color from the
 The term "redder" means an red end of spectrum to blue end.
increase in wavelength (equivalent • The term also applies when
to a lower frequency and a lower photons outside the visible
photon energy), in accordance with spectrum (X rays and radio
the wave and quantum theories of waves) are shifted toward shorter
light. wavelengths.
Surface Plasmon Resonance: Definition

 Plasmons are collective oscillations of the free electron gas

density, which occurs often at optical frequencies.
 Surface Plasmons are:
 Confined to surface (or interface) and interact with light resulting in
polaritons (quasiparticles resulting from strong coupling of EM waves
with an electric or magnetic dipole-carrying excitation).
 Also referred to the propagating electron density waves occurring at
the interface between metal and dielectric materials.
 Surface Plasmon Resonance (SPR) refers to light in
resonance with surface plasmon oscillations.
Surface Plasmon Resonance(SPR) : Process

Surface Plasmon Resonance (SPR) is the

coherent excitation of all free electrons in the
conduction band, leading to an in-phase oscillation.
 SPR in Nanoparticles
• When the size of a nanoparticle is much smaller
than the wave length of light, coherent
oscillations of the conduction band electrons are
induced on interaction with EM field of light.
This is called Surface Plasmon Resonance
(SPR).

• The electric field of incoming light polarizes

free electrons relative to the cationic lattice. The
Schematic of Plasmon oscillation for a
net charge difference occurs at boundaries of sphere, showing the displacement of
conduction electron charge cloud relative
nanoparticle, which generates a restoring force
to nuclei.
causing dipolar oscillation of electrons.

• Energy of SPR depends on the free electron

density as well as the dielectric medium
surrounding the nanoparticle.
Properties of Nanomaterials: Electrical
 Electrical Conductivity

The mechanisms influencing the electrical conductivity of

nanostructures can be generally grouped into five categories:
 Surface scattering including grain boundary scattering
 Change of electronic structure
 Change of microstructure
 Quantum Effects
 Increased Perfection and Ballistic Transport.
 Surface Scattering
 Matthiessen’s Rule: Electrical conduction in materials can be described by
the electron scattering from atoms of oscillating lattice (temperature
dependence causing Thermal resistivity) as well as from defects / impurities
(temperature independent causing Defect resistivity) in the crystal. The total
resistivity (ρ) of a metal is the sum of the contributions from two types of free
electron scattering.

 Phonon Contribution: Electron collisions with oscillating atoms (phonons)

displaced from their equilibrium lattice positions are the source of the thermal
or phonon contribution, which increases linearly with temperature.
 Defect Resistivity: Impurity atoms, defects such as vacancies and grain
boundaries locally disrupt the periodic electric potential of the lattice and

effectively cause electron scattering, which is temperature independent.

 Surface Scattering….. Cont’d
 The defect resistivity can be further divided into:
o Impurity resistivity
o Lattice defect resistivity
o Grain boundary resistivity.

 Considering individual electrical resistivity to be inversely proportional to the

respective mean free path (λ) between collisions, the Matthiessen’s rule can be

rewritten as =+

 When the critical dimension of thin films and nanowires is smaller than the
electron mean-free path, the motion of electrons will be interrupted through
collisions (elastic as well inelastic) with the surface. Hence the surface
scattering of electrons results in reduction of electrical conductivity.
 In a polycrystalline material, as the crystallite size becomes smaller than the
electron mean-free path, resistivity from grain boundary scattering also arises.
 Change in Electronic Structure
 A reduction in characteristic dimension
below a critical size, (i.e., the electron de The band gap increases with
reduction of the size of particles
Broglie wavelength), would result in a
change of electronic structure, leading to
widening and discreteness of band gap.
Such a change generally results in reduced
electrical conductivity.
 Some metal nanowires may undergo a
transition to become semiconducting and
subsequently insulating as their diameter is
reduced below critical size progressively.
 Such a change can be partially attributed to
the quantum size effects, i.e., increase in
electronic energy level spacing when the
dimensions of materials are reduced below
a certain size.
 Effect of Microstructure
 Ordered Microstructure: Electrical conductivity may
change due to the formation of ordered microstructure,
when the size is reduced to a nanometer scale.
Polymer fibres demonstrate an enhanced electrical conductivity which can be
explained by the ordered arrangement of the polymer chains.

 Alteration of Grain Size: The magnitude of the electrical

conductivity in nanocomposites can be changed by
altering the grain size of the electrically conducting
component.

Changing the volume fraction of iron particles in a nano-crystalline iron silica

system, the electrical conductivity can be changed by 14 orders of magnitude.
 Ballistic Conduction (or Transport)
 Ballistic Conduction is the transport of electrons in a
medium having negligible electrical resistivity caused by
scattering. Without scattering, electrons simply obey
Newton's second law of motion at non-relativistic speeds.
 For a given medium, a moving electron can be ascribed a
mean free path as being the average length that the
electron can travel freely, i.e., before a collision, which
could change its momentum. The mean free path can be
increased by:
o Reducing the number of impurities/defects in a crystal.
o Lowering temperature of the crystal.
 Ballistic transport is observed when the mean free path of the
electron is (much) longer than the dimension of the medium
through which the electron travels. The electron alters its
motion only upon collision with the walls.
 Ballistic conduction is the unimpeded flow of charge, or
energy-carrying particles, over relatively long distances in a
material. Normally, transport of electrons (or holes) is
dominated by scattering events, which relax the carrier
momentum.
 Ballistic conduction is observed in quasi-1D structures (CNT
or Si nanowires), owing of extreme size quantization effects.
 Coulomb Blockade
 Coulomb blockade occurs, when:
o The contact resistance is larger than the resistance of nanostructures
o The total capacitance of the object is so small that adding a single electron requires significant
charging energy.

 Metal or semiconductor nanocrystals of size few nanometers in

diameter exhibit quantum effects that gives rise to discrete
charging of the metal particles. Such a discrete electronic
configuration permits to pick up one electron at a time, at specific
voltage values.
 Coulomb blockade behavior, also known as Coulombic
staircase, has originated the proposal that nanoparticles with
diameters below 2-3 nm may become basic components of
single electron transistors (SETs). To add a single charge to a
semiconductor or metal nanoparticle requires energy.
 Coulomb Blockade
 For a nanoparticle surrounded by a dielectric medium

with a dielectric constant of εr, the capacitance of the

nanoparticle is solely dependent on its size as:

where r is the radius of the nanoparticle.

 The energy required to add a single charge to the particle
is given by the charging energy

 It is clearly revealed that charging energy is independent

of nature of material.
Figure shows a characteristic I-V curve for such a device with a
single gold nanoparticle, where the charging energy gives rise to a
barrier to a current flow known as Coulomb blockade.
 Tunelling Effect

 Tunnelling involves charge transport through an insulating

medium separating two conductors that are extremely closely
spaced.
 It is because the electron wave functions from two conductors
overlap inside the insulating material, when its thickness is
extremely thin.
 Under such conditions, electrons are able to tunnel through the
dielectric material when an electric field is applied.

It should be noted that Coulomb Charging and Tunnelling

Conduction are not material properties but system
properties dependent solely on characteristic dimension(s).
Properties of Nanomaterials: Magnetic
 Magnetic Nanoparticles

• Nanomaterials can be
compact nanostructured or
colloidal solutions.
• For Magnetic Nano Particles
(MNP), the magnetic
properties are affected by:
 Size.
 Composition.
 Defects.
 Shape & Morphology.
 Size Effects: Super Paramagnetism

• Ferromagnetic material attains domain

structure to minimize its energy.
• As the size of magnetic nanoparticle is
decreased, below a critical size (DSD), no
domain walls exist. This leads to the
formation of Single Domain Particle (SDP).
• The material undergoes a transition from
ferromagnetism to Super Paramagnetism,
characterized by zero coercivity and random
flipping of spins along easy axis of particle.
• The critical size of particle, at which transition
occurs, is strongly temperature dependent.
 Size Effects: Magnetisation
• In ferromagnetic oxides, the disorder
of surface spins reduces
magnetization.
• For FCC Cobalt with a lattice constant
0.355nm, particles having about 200
atoms will have diameter ~1.6nm with
60% of spins occupying the surface.
• In ultra small ferromagnetic metallic
nanoparticles/ clusters, magnetization
either remains same or gets
enhanced due to reduced size.
• The critical temperatures TC and TB
are strongly size dependent and
decrease as particle volume
decreases.
Hysteresis Loop
 Single Domain Particle (SDP)
• Single Domain Particle (SDP): As the grain size decreases, a
critical size will be reached where the grain can no longer
accommodate a wall and becomes a single domain. A SD grain is
uniformly magnetized to its saturation magnetization.
• Multi-domain Grains are magnetically soft with low values of
coercivity and remanance. SD grains can be derived from MD
grains by translating domain walls on application of relatively low
magnetic fields.
• SD grains are magnetically hard with high coercivity and
retentivity. It remains in a single-domain state throughout the
hysteresis cycle, including during the transition between two such
states.
• SD particle has lowest energy single domain state of all possible
states.
 Single Domain Hysteresis
 SD particle has its unidirectional internal magnetization resulting
in the largest possible magnetic moment (μ=VMs) for a particle
of that size and composition.
 The magnetization at any point in a ferromagnet can only change
by rotation. For more than one magnetic domain, the transition
between one domain and its neighbour involves a rotation of the
magnetization due to presence of a domain wall.
 Domain walls move easily within the magnet and have a low
coercivity. In contrast, a single domain particle in all magnetic
fields changes its state by rotation of all the magnetization as a
unit, resulting in a much larger coercivity.
 Superparamagnetism (SPM)
 For ferromagnetic materials constituted by small nanoparticles,
magnetization suffers thermal fluctuations. As the size of nanoparticle is
reduced, very rapid fluctuations occurs between two magnetic states
thereby resulting in vanishing magnetization. This causes the formation
of Single Domain Particle (SDP).
 As particle size continues to decrease within the SD range, another
critical threshold is reached, at which remanance and coercivity vanish
and the grain becomes superparamagnetic. Such materials have high
saturation magnetization while their coercivity and remanance vanish.
This feature distinguishes it from ferromagnetism and paramagnetism.
 An SD particle of volume v has a uniform magnetization along easy axis
of magnetization. If v is small enough, or the temperature is high enough,
thermal fluctuations will overcome anisotropic forces to cause a
spontaneous reversal of magnetization.
 In an applied field, there will be a net statistical alignment of
magnetic moments analogous to paramagnetism. Now the
magnetic moment pertains to an SD particle containing ~10 5
atoms. Hence superparamagnetic material (SPM) is
characterized by a much higher susceptibility value than that
for simple paramagnetic material.
 In response to a change in the applied field or temperature, an
ensemble of SPM particles will approach an equilibrium value
of magnetization with a characteristic Neel relaxation time
expressed as:
The exponential nature of the relaxation
f0 -frequency factor (109 Hz) time dependent on v and T makes it
𝐾𝑢 𝑣
1 −
𝑘𝑇 Ku -anisotropy constant possible to define a blocking temperature,
=𝑓 0 𝑒 TB (at constant volume), or blocking volume
𝑡 v -particle volume
k -Boltzmann constant vB, (at constant temperature) at which the
magnetization goes from an unstable
T -absolute temperature
condition (t<<T) to a stable condition
 Superparamagnetism is a size effect of ferromagnetism.
 Figure shows the influence of magnetic particle size on magnetic
properties. The coercivity changes with the particle size, and at small
enough size, the coercivity or coercive field become zero.

𝐾𝑢 𝑣
1 −
𝑘𝑇
=𝑓 0 𝑒
𝑡
τ – Average length of time taken for a ferromagnetic New Properties of SPM
cluster to randomly flip directions as a result of • Large MS: Small size and larger magnetic
thermal fluctuations
moment for each particle like Ferromagnetism.
τ0 – Attempt period (characteristic of the material)
• No Open Loop: Response to external field like
E =Anisotropic energy which is proportional to V= KV
paramagnetic response.
Blocking Temperature Tb • Superparamagnetic relaxation guided by Neel
E = KV = 25kBTb
Arrhenius Equation.

T>Tb τ < <τ0 Behave like Paramagnetic particle

T<Tb τ > >τ0 Magnetic ordering and open loops
Susceptibility and Grain Size of Magnetic Particles

Largest Grains,
Lowest Susceptibility

Smallest Grains,
Lowest Susceptibility

Smallest Grains,
Largest Susceptibility
Properties of Nanomaterials: Nano fluids

Nano fluids are engineered colloidal suspensions of

nanoparticles (metals, oxides, carbides, CNT) in a base fluid.
Nano-Fluids
Fluid flow in small structures is entirely laminar and dominated by the
chemical boundaries of the channel.

Reynolds number (Re), a dimensionless number quantifying the

ratio of inertial to viscous forces that act on the volume of a liquid.

Density Channel narrowest dimension

u L
Re 
 Viscosity

Re >> 1: Turbulence Regime

Re << 1: Viscous Regime
 
Kinematic viscosity 
u

For water: ν =10-6 m2s-1 (25°C)

Re in a L=100nm channel with <u> = 1mm/s does not exceeds 10-4

o Flow in nanoscale channels is dominated by viscosity.

o Fluids do not mix in a nano-fluidic device.

o The chemistry of the interface becomes critical and

aqueous fluids will not generally enter a channel with
hydrophobic surfaces.