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Smart Materials &

Devices

Dr. Pramod Kumar Singh


Department of Physics
School of Basic Sciences & Research
Sharda University, Greater Noida
Email: pramodkumar.singh@sharda.ac.in

Syllabus
7.01

SMDXXX.A

Unit A

Materials- Basic Concepts

7.02

SMDXXX.A1

Unit A Topic 1

Classification of Materials, Bonding in solids

7.03

SMDXXX.A2

Unit A Topic 2

Crystal structure, Bravais lattice, Miller Indices

7.04

SMDXXX.A3

Unit A Topic 3

Imperfections of crystals

7.05

SMDXXX.B

Unit B

Dielectrics, Superconductors and Magnetic Materials

7.06

SMDXXX.B1

Unit B Topic 1

Dielectic materials and their properties

7.07

SMDXXX.B2

Unit B Topic 2

Superconductors and their applications

7.08

SMDXXX.B3

Unit B Topic 3

Magnetic materials and their properties

Syllabus
7.09

SMDXXX.C

Unit C

Composite & Nanocomposite materials

7.10

SMDXXX.C1

Unit C Topic 1

Introduction of composite and Nanocomposite materials

7.11

SMDXXX.C2

Unit C Topic 2

Metal-Ceramic nanocomposite

7.12

SMDXXX.C3

Unit C Topic 3

Polymer based nanocomposites

7.13

SMDXXX.D

Unit D

Characterization Techniques

7.14

SMDXXX.D1

Unit D Topic 1

X-ray diffraction

7.15

SMDXXX.D2

Unit D Topic 2

UV-Visible spectroscopy

7.16

SMDXXX.D3

Unit D Topic 3

Infrared spectroscopy

7.17

SMDXXX.E

Unit E

Devices

7.18

SMDXXX.E1

Unit E Topic 1

Devices for energy conversion

7.19

SMDXXX.E2

Unit E Topic 2

Storage Devices

7.20

NSTXXX.E3

Unit E Topic 3

Sensors and Microelectronic devices

References
9

References

1. Material Science and Engineering An Introduction by: William D. Callister


9.1

Text book

2. Nanocomposite Science and Technology, P. M. Ajayan, L. S. Schadler, P. V. Braun

3. Chemistry of nanomaterials: Synthesis, properties and applications by CNR Rao (Taylor & Francis 2008)
9.2

Other
references

4.Structure and Properties of Engg. Materials by: V R S Murthy, A K Jena

SMART MATERIALS

SMART Materials are special solids which


can be tailored to develop desired
properties applied for fabrication of devices
leading to societal benefits

Materials Engineering
Materials, Materials Science and Materials Scientist play a
very vital role in the development of a country

Properties of materials are size dependent

Materials scientist claim that 21st century is the century of


materials and especially nanomaterials/smart materials

SMARTCOMPOSITES

Properties of materials are size dependent

COMPOSITE/NANOCOMPO
SITES

COMPOSITE/NANOCOMPO
SITES

Fundamentals of Materials Science and Engineering, William D. Callister, Jr.

Atlantis Space Shuttle Orbiter, USA

Fundamentals of Materials Science and Engineering, William D. Callister, Jr.

Fundamentals of Materials Science and Engineering, William D. Callister, Jr.

CLASSIFICATION OF MATERIALS
Solid materials have conveniently been grouped into
three classes
1.Metals
2.Ceramics
3.Polymers

Combination of above materials give variety of other


materials
Now most of the new materials come under the category of
Smart Materials or Future Materials

THREE MAJOR ENGINEERING MATERIALS

*Modern technologies require materials with unusual


combinations of properties that can not be met by the
conventional metal alloys, ceramics and polymeric
materials.

This is usually true for materials that are needed for


aerospace, underwater, and transportation applications.

For example aircraft engineers are increasingly searching


for structural materials that have low densities, are strong,
stiff and abrasion and impact resistant, and are not easily
corroded.
This is a formidable combination of characteristics.

Frequently strong materials are relatively dense; also,


increasing the strength or stiffness generally results in a
decrease in impact resistance.

Atlantis Space Shuttle Orbiter, USA

Fundamentals of Materials Science and Engineering, William D. Callister, Jr.

Fundamentals of Materials Science and Engineering, William D. Callister, Jr.

Composites
Composite is considered to be any multiphase material that
exhibits a significant proportion of the properties of both
constituents such that a better combination of properties is
realized.

*Better property combinations are fashioned by the judicious


combination of two or more distinct materials

Composites

*In addition, the constituent phases must be chemically


dissimilar and separated by a distinct interface.

Thus most metallic alloys and many ceramics do not fit this
definition because their multiple phases are formed as a
consequence of natural phenomena.

Composites

Composites are a combination of two or more organic or inorganic


components one of which serves as a matrix holding the materials
together and then other of which serves as reinforcement in the form
of fibers

Two inherently different materials that when combined together


produce a material with properties that exceed the constituent
materials.

Composites are lightweight and strong but they are complex to


manufacture, expensive and hard to inspect for flaws

Composites
Many composite materials are composed of just two
phases; one is termed the matrix, which is continuous
and surrounds the other phase, often called dispersed
phase.

The properties of composites are a function of the


properties of the constituent phases, their relative
amounts and the geometry of the dispersed phase.

Composites
Composites often have only two phases
Matrix phase
continuous - surrounds other phase

Dispersed phase
discontinuous phase

Matrix (light)
Dispersed phase (dark)

Classification of Artificial
Composites
Composites
Particulate

Fiber

Structural

Large
Dispersion
Laminates
Particle Strengthened
Continuous Discontinuous

Aligned

Random

Sandwich
Panels

Properties of Composites
Properties depend on:
constituent phases
relative amounts
geometry of dispersed phase
shape of particles
particle size
particle distribution
particle orientation

Parameters on which properties depend

Concentration

Distribution

Shape

Orientation

Size

Composites Offer
High Strength
Light Weight
Design Flexibility
Consolidation of Parts
Net Shape Manufacturing

Biocomposites
Biocomposites combine plant fibers with resins to create natural based
composite materials.
High tensile plant fibers including, kenaf, industrial hemp, and flax, can
be combined with traditional resins to create an alternative to
traditionally steel or fiberglass applications.
Some advantages over traditional composites:
Reduced weight
Increased flexibility
Greater moldability
Less expensive
Sound insulation
Renewable resource
Self-healing properties

NANOCOMPOSITE
S

A nanocomposite is as a multiphase solid material


where one of the phases has one, two or three
dimensions of less than 100 nanometers (nm),

OR

structures having nano-scale repeat distances


between the different phases that make up the
material.

NANOCOMPOSITE
S

Constituents have at least one dimension in the


nanometer scale.
Nanoparticles (Three nano-scale dimensions)
Nanofibers (Two nano-scale dimensions)
Nanoclays (One nano-scale dimensions)

Properties of
Nanocomposites
Tiny particels with very high aspect ratio, and hence
larger surface area.
Larger surface area enables better adhesion with the
matrix/surface.
Improvement in the mechanical performance of the
parent material.
Better transparency due to small size(>wavelength of
light).

Why Nanocomposites? Multifunctionality


Small filler size:
High surface to volume ratio
Small distance between fillers bulk interfacial material

Mechanical Properties
Increased ductility with no decrease of strength,
Scratching resistance

Optical properties
Light transmission characteristics particle size dependent
nanocomposite

Stress

Traditional

polymer

Strain

Scratch Resistant, Transparent, Filtering Coatings


Visible
Ultraviolet

TEM of the 16.7wt% nano


alumina filled gelatin film

Transmittance rate of 16.7wt.% nanoalumina filled


gelatin films coated on 0.1mm thick plastic substrate

Size limits for these effects have been


proposed
<

5nm for catalytic activity

< 20nm for making a hard magnetic


material soft
<

50nm for refractive index changes

< 100nm for achieving


superparamagnetism, mechanical
strengthening.

Nanoclays
Silicates layers separated by
an interlayer or gallery.
Silicates layers are ~ 1 nm
thick, 300 nm to microns
laterally.
Polymers as interlayers.
Tailor structural, optical
properties

Nanofibers - Nanotubes
~1000 GPa (SWCNT)
~1200 GPa (MWCNT)
Tensile Strength ~ 100 GPa

Nanotubes in metal, metal oxide


and ceramic matrix have also
been fabricated.

Nanotubes in polymer matrices


by mixing, then curing.

Most important filler category in


nanocpomposites

Modulus

Thermal
Conductivity
Density

2000 W/m/K

Length

up to microns

1300 1400 kg/cm3

Nanocomposite VS
Composite
In mechanical terms, nanocomposites differ from conventional
composite materials
*Exceptionally high surface to volume ratio of the reinforcing
phase and/or its exceptionally high aspect ratio.
The reinforcing material can be made up of particles (e.g.
minerals), sheets (e.g. exfoliated clay stacks) or fibres (e.g.
carbon nanotubes or electrospun fibres).
The area of the interface between the matrix and reinforcement
phase(s) is typically an order of magnitude greater than for
conventional composite materials.

Nano composites are found in nature also. It is found in


abalone (small or very large-sized edible sea snail) and
bones.
Advantage of using the nanocomposites:
Greater tensile /flexural strength
Reduced weight for the same performance
Flame retardant properties
Improved mechanical strength
Higher electrical conductivity
Higher chemical resistance

A simple example of a normal composite can be


considered we do have concrete for our houses.
What exactly is this concrete? Its a blend of cement,
sand, and metal rod. These composition changes the
total property of the material used. It becomes so
hard that it can withstand tonnes of weight equally.
Its from this concept we device the idea about the
nanocomposites.

Nanocomposite as a Multiscale System


Macroscale composite structures
Clustering of nanoparticles - micron
scale

diffusion/bulk diffusion

Interface - affected zones - several to


tens 1.5
of nanometers - gradient of
R
properties
g
unbonded
bonded

0.5
0

distance from the particle

Polymer chain immobilization at


particle surface is controlled by
electronic and atomic level
structure

This large amount of reinforcement surface area means that a relatively


small amount of nanoscale reinforcement can have an observable effect
on the macroscale properties of the composite. For example, adding
carbon nanotubes improves the electricaland thermal conductivity.
Other kinds of nanoparticulates may result in enhanced optical properties,
dielectric properties, heat resistance or mechanical properties such as
stiffness, strengthand resistance to wear and damage.
In general, the nano reinforcement is dispersed into the matrix during
processing. The percentage by weight (called mass fraction) of the
nanoparticulates introduced can remain very low (on the order of 0.5% to
5%) due to the low filler percolation threshold, especially for the most
commonly used non-spherical, high aspect ratio fillers (e.g. nanometer-thin
platelets, such as clays, or nanometer-diameter cylinders, such as carbon
nanotubes).

Synthesis of
Nanocomposites

Chemical Synthesis:

1.

Gas Phase Synthesis


Chemical Vapor
Condensation
Combustion Flame
Synthesis
Liquid Phase Synthesis

2.
3.
4.

Others

Mechanical Deformation
Thermal recrystallization

Gas Phase Synthesis

(Synthesis of ultra pure metal powders and compounds of metal


oxides(ceramics) )

The nano powder formed normally has the same


composition as the starting material.
The starting material, which may be a metallic or
inorganic material is vaporized using some source
of energy
The metal atoms that boil off from the source
quickly loose their energy. These clusters of atoms
grow by adding atoms from the gas phase and by
coalescence
A cold finger is a cylindrical device cooled by
liquid nitrogen. The nano particles collect on the
cold finger
The cluster size depends on the particle residence
time and is also influenced by the gas pressure,
the kind of inert gas, i.e. He, Ar or Kr and on the
evaporation rate of the starting material. The size
of the nano particle increases with increasing gas
pressure, vapor pressure and mass of the inert
gas used.

Chemical Vapor
Condensation

the precursor vapor is passed through a hot walled reactor.


The precursor decomposes and nano particles nucleate in the
gas phase. The nano particles are carried by the gas stream
and collected on a cold finger. The size of the nano particles is
determined by the particle residence time, temperature of the
chamber, precursor composition and pressure.

Nanocomposites

Combustion Flame
Synthesis

Energy to decompose the precursor may be supplied by burning a


fuel-air mixture with the precursor. In order to reduce
agglomeration of the particles in the flame, the flame is specially
designed to be low pressure.
If you have observed the flame of a candle, you would have
noticed that the flame consist of a blue center and a yellow to red
periphery. This is because the temperature in the flame varies with
position in the flame. Such a variation in the temperature profile of
the flame would cause nanoparticles of different sizes to grow in
the different regions of the flame. This is avoided by designing the
flame to have a 'flat temperature profile' i.e. a constant
temperature across its width.

Liquid Phase Synthesis

Two chemicals are chosen such that


they react to produce the material
we desire
An emulsion is made by mixing a
small volume of water in a large
volume of the organic phase. A
surfactant is added. The size of the
water droplets are directly related
to the ratio of water to surfactant.
The surfactant collects at the
interface between the water and
the organic phase. If more
surfactant were to be added,
smaller drops would be produced
and therefore, as will become
apparent, smaller nano-particles.

The progress in nano composites is varied and covers many industries.


Nano Composites can be made with a variety of enhanced physical,
thermal and other unique properties.
They have properties that are superior to conventional micro scale
composites synthesized using simple and inexpensive techniques.
Materials are needed to meet a wide range of energy efficient applications
with light weight, high mechanical strength, unique color, electrical
properties and high reliability in extreme environments.
Applications could be diverse as biological implant materials, electronic
packages and automotive or aircraft components. Although some of the
properties will be common between the applications, others will be quite
different.
An electronic package polymer composite must be electrically insulating,
while an aircraft component may need to be electrically conductive to
dissipate charge from lighting strikes.

The additions of small amounts of nano particles to polymers have been


able to enable new properties for the composite material, but results are
highly dependent on the surface treatment of the nano particles and
processing used.
It is important to determine whether nano materials could be integrated
into nano composite to enable multiple desirable properties for a given
application.
While industry is seeking materials to meet challenges with unique
properties, there are no rule of mixtures to identify how to mix multiple
nano materials in a composite structure and all required properties nano
materials often have unique properties that could enable composite
materials with multiple unique properties simultaneously; however, it is
often challenging to achieve these properties in large scale nano
composite materials.
Furthermore, it is important that nano materials have desirable properties
that cant be achieved through use of conventional chemicals and
materials.
To access the positional value of nano materials, it is important to
determine which nano materials can be effectively integrated into nano
composites and what new or improved properties this enables.

Then it will be important to determine the effectiveness of dispersion


of the nano particles in the matrix and how this affects the structure
of the polymer to enable optimization of the desired property.
Once the basic models of this are developed, it will be resulting
structure and properties of the nano composite.
One nano composite may be required to improve the mechanical
property, ad another may be required to change the electrical
properties; however the addition of electrical material may also
change the mechanical properties of the nano composite trough
interactions with the polymer and nano particles.
Thus, models of the interactions within the nano composite are
needed to enable development of effective rules of mixtures.
This may require a combination of numerical modeling,
characterization and informatics to enable this nano composite with
properties by design capability.

As this capability is developed, it will be important to characterize the


interactions of the nano particles with environmental effects including
moisture, temperature and stress to assess potentional degradation of the
nano composites properties through its life.
Thus, the nano composite must have multiple new and unique properties for
a specific application, but those properties must not degrade significantly
through the life of the material.
Developing these capabilities will require significant research into
interactions of the nano materials in the polymer matrix and how these are
changed with temperature, moisture and mechanical stress.
In general, two idealized polymer layered nano composite structures are
possible; intercalated and exfoliated. The greatest property enhancements
are generally observed for exfoliated nano composites. These consist of
individual nano meter filler layers suspended in a polymer matrix. In
contrast, intercalated hybrids consist of well ordered multilayers with
alternating polymer / nano mater filter layers with a repeat distance of a new
nano meters. In reality many systems fall short of the idealized exfoliated
morphology.

Engineering Properties of
Materials
The mechanical, electrical,
thermal, optical, electrochemical, catalytic
properties of the nanocomposite will differ markedly from that of the
component materials.

Normal stress is the state leading to expansion or


contraction. The formula for computing normal stress is:

P
L

P
L

Where, is the stress, P is the applied force; and A is the


cross-sectional area. The units of stress are Newtons per
square meter (N/m2 or Pascal, Pa). Tension is positive and
compression is negative.
Normal strain is related to the deformation of a body under
stress. The normal strain, , is defined as the change in length
of a line, L, over its original length, L.

Young's modulus of elasticity (E) is a measure of the stiffness of the


material. It is defined as the slope of the linear portion of the normal
stress-strain curve of a tensile test conducted on a sample of the
material.
Yield strength, y, and ultimate strength, u, are points shown on
the stress-strain curve below.
Stress

Rupture

E
1

Strain,

For uniaxial loading (e.g., tension in one direction only): = E

Shear stress, , is the state leading to distortion of the


material (i.e., the 90o angle changes). The corresponding
change in angle, in Radians, is called shear strain, . The
slope of the linear portion of the -is called shear
modulus of elasticity, G.

Stress

G
1

Strain,

54

Poissons ratio, , is another property defined


by the negative of the ratio of transverse strain,
2, over the longitudinal strain, 1, due to stress in
the longitudical direction, 1.
12
2

2
1
Original shape

55

Anisotropic materials have different properties


in different directions. In the most general case,
they are defined by 21 independent constants.
Special cases include:
Orthotropic: wood and some composites
Transversely isotropic: some continuous fiber reinforced
composites
Fibers

56

A group of Chinese researchers prepared dye synthesized solar using micro /


nano composite TiO2 porous films.
Bloo solar is developing and manufacturing revolutionary nano structured ultra
thin film solar PV products that will provide affordable clean renewable energy
for everyone.
In addition to a large potential impact on solar energy production, nano
composites also have an impact on nuclear energy.
Nano composites also can save energy when incorporated into paints; TAG
technology has developed a nano particle that when added to paint only
allows heat flow in one direction.

Other industries are also influenced by nano composites, including


computers, electronic magnetic, industrial components, water
remediation and medical devices.
Nano composite permanent magnet materials are a new type of
permanent magnet material consisting of magnetically hard and soft
grains, both in nano meter size.
Those materials have a high potential to be developed into high
performance permanent magnets with very high energy product.
The new magnets will have lower cost, high magnetic performance,
and better corrosion resistance as a result of the significantly
reduced rare earth content.
The new magnets will also have improved fracture toughness as a
result of fine nano grain structure and the existence of a relatively
soft -Fe.

Nano composites of cyanate esters were prepared


by dispersing organically modified layered silicates
(OLS) into the resin. Inclusion of only 2.5% by weight
of OLS led to a marked improvement in physical and
thermal properties.
The mechanical response of nano scale materials
and structure has important implications diverse
areas of science spanning topics that include
understanding of biological recognition, development
of light weight structural materials, to exploration of
new concepts for switches and chemical sensors.

Engineering Applications: Composite materials have been used in


aerospace, automobile, and marine applications (see Figs. 1-3). Recently,
composite materials have been increasingly considered in civil engineering
structures. The latter applications include seismic retrofit of bridge columns
(Fig. 4), replacements of deteriorated bridge decks (Fig. 5), and new bridge
structures (Fig. 6).

Figure 1

Figure 4

Figure 2

Figure 5

Figure 3

Figure 6

The nanocrystalline grains should have random


orientation (i.e. high angle grain boundaries) to
minimize incoherent strain and facilitate many
nanocrystalline grains to slide in amorphous matrix to
release strain and obtain high toughness.
The amorphous phase must possess high structural
flexibility in order to accommodate coherent strains
without forming dangling bonds, voids, or other
defects.
The presence of amorphous phase on the boundaries
helps to deflect and terminate nanocracks in addition
addition to the enhancement of grain boundary
sliding, thus
improving coating toughness.

To design a nanocomposite coating with both high


hardness and high toughness, one must take all the
above into consideration. Probably the best way is to
use ternary, quaternary or even more complex
systems, with high strength amorphous phase as
matrix (such as a-SiNx, a-BN, a-C, etc.) and hard
transition metal-nitride nanocrystals (such as TiN,
W2N, BN, etc.) as nanocrystalline phase to increase
grain boundary complexity and strength.
These nanocrystalline phases should be refractory
and immiscible with each other, and could result in
compositional modulation, segregation and high
thermal stability of the nanostructure.

Synthesis methods
Different
techniques
are
now
available
preparation of nanocomposite coatings.

for

The most promising methods are magnetron


sputtering and chemical vapor deposition
(CVD), although other methods, such as laser
ablation , thermal evaporation , ion beam
Deposition and ion implantation, are also used by
various researchers.
High deposition rate and uniform deposition for
complicated geometries are the advantages of CVD
method compared to sputtering.
However, the main concern for CVD method is that
the precursor gases TiCl4, SiCl4 or SiH4 may pose

Evaluation of mechanical properties


Good mechanical properties of a coating require high hardness,
high toughness, low friction, high adhesion strength on
substrate, good load support capability and chemical and
thermal stability, etc.
Of all these, hardness is probably of number one importance for
an industrial
coatings especially in tribological applications.
At present, nanoindentation is regarded as a good method in
hardness determination of thin films and coatings.
In nanoindentation test, a diamond indenter is forced into the
coating surface.
The load and depth of penetration (the indentation profile) is
recorded, from which the
hardness and elastic properties are calculated.