UNIT – 3

Material Science and Engineering, IGDTUW

Smart Materials –
1. Smart Materials:
Smart materials are a specific kind of materials operated to respond in the desired way, and the move is
reversible as well. Some of their properties such as mechanical stress can be modified through external
stimulation. The smart materials are also called responsive materials because of their responsiveness
towards some external ambient provocations. These materials are also termed active materials although
their behavior suits more accurately by the name reactive material. In a nutshell, these materials react to
external provocations and show a change in one or more properties. Smart materials can change shape or
behaviors with changes in pressure, hotness, change in a chemical environment, light, etc.

Here an example of sportswear can be taken. The sportswear with valves designed for ventilation
reactive to body temperature and the level of humidity. The valves open up when the body of the
wearer reaches a certain threshold of sweat or hotness and close when the body cools down.

Shape-Memory Alloys:

Nitinol is the most regularly presented Shape Memory Alloy (SMAs). This was natively developed at
Naval Ordinance Laboratory. The phase of SMAs changes with the temperature, and they exert force or
generate motion as a consequence. They move slowly but are proficient in fairly high energy. The materials
demonstrating the shape memory effect include thermal switches, transforming structures, and some
applications of applying high strain on the absorption of energy. Many advanced materials are still under
development which includes magnetically activated SMAs.

1. Introduction & Historical Background: Some metallic materials, return to their natural shape from the
deformed state when heated. In a certain temperature range, the materials get strained to a certain level
like 10 % but they regain their natural shape as soon as they are unloaded. Such an effect is known as
thermal shape memory and super-elasticity. Both of these effects depend upon the existence of a specific
type of phase change called thermoelastic martensitic transformation. Such shape-related memories and
superelastic alloys respond to the change in temperature and mechanical stresses in unconventional and
astonishing ways. The material that has a shape memory can also be named "smart materials". Recent
applications have mainly come from the medical line. Such fields utilize the superelasticity and
biocompatibility of Ni-Ti alloys. Smart materials were first reported in 1932 on gold-cadmium alloys.
Along with this, later in the year 1938, the phase transformation was detected in the copper-zinc alloy
 (brass). Later in 1962, Beehler and his coworkers found the transformation in Nickel-Titanium and
reported shape memory effect at the Naval Ordnance Laboratory and named these alloys as Nitinol after
their laboratory.

2. Shape Memory Effect As described in the above passage the "Shape Memory" defines the phenomenon
of regaining the natural shape of a physically distorted body to its original shape by heating it. This effect
occurs because of a crystalline phase-change termed as "thermo-elastic martensitic transformation". Shape
memory alloys are martensitic, below the transition temperature. In such a situation, the microstructure is
categorized by "self-accommodating twins". The manensite is a soft material and it can be easily be
deformed. Heating the material, above transformation temperature turns the material to its original shape
and it also recovers its high strength (Fig. 1).

Fig. 1: Schematic demonstration of the super-elasticity and shape memory effect

3. What are Shape Memory Alloys:

Shape memory alloys are the alloys that could be distorted when they are cold but they return to their
original or say remembered shape when heated. It seems that the alloys do have a memory. These are
also known as memory alloys, memory metals, or smart metals. Such alloys (Shape memory alloys -
SMAs) exhibit two very exclusive properties, one of which is the pseudo-elasticity, and the other one
is the shape memory effect. In 1938, Arne Olander was the one who observed these special properties,
but until 1960, but no advance research was made in the field of shape memory alloys. Some of the most
researched and extensively used alloys contain CuZnAl, NiTi (Nickel - Titanium), and CuAlNi.

4. Applications of Shape Memory Alloys:

The scarce properties described in the last section are applicable to a vast variety of applications in several
streams.

Bones: Shape memory alloys can mend the broken bones.

Opening of Arteries and Veins: In some cases, when the blood vessel has been clogged, an alloy tube is
squeezed and inserted into the clogged vein and then allowed to expand.

Dental wires: Such materials are used for making dental wires, and braces. Memory alloys maintain a
stressed condition, on the teeth to shape them in a certain way.

Anti-scalding protection: Memory metals are designed to restrict the flow of water by behaving
differently at different temperatures. This helps to control the temperature in baths and showers.

Similarly, there could be many uses of these materials based on the above-mentioned properties such as
switches, controllers, and somewhat temperature sensor-based applications.

5. How the Shape Memory Alloys Work:

Shape Memory Alloys (SMAs) are known to demonstrate a structure-based reversible martensitic
transition. At elevated temperatures, the SMAs exist as an austenite phase (described as memory phase)
with long-range order. As the temperature reduces, the austenite phase transforms into a thermoelastic
martensite phase. The thermoelastic martensite phase has several alternates, specially sheared platelets.
Since the martensitic structure is self-compliant, its deformation on transformation to martensite does not
exist. The martensite changing its shape through a twinning mechanism transforming different alternates
to the shape that can accommodate the thoroughgoing elongation uni-directional with the direction of the
applied force. The phase between platelets in the martensite structure slips very readily and the material
is deformed at a comparatively lower value of applied stresses.

In contrast, there is only one possible orientation in austenite phase, therefore, all the possible deformed
structures of the martensite phase return to the only possible orientation of the austenite phase (memorized
phase), and ultimately the material recovers its shape we started with. Now, the temperature of
transformation is dependent on the type of alloy. Besides its composition and other processing conditions
such as applied thermomechanical treatments. The change in behavior while heating the alloy and cooling
down the material does not match closely. Besides, such materials exhibit hysteresis. The extent of the
hysteresis also changes with the type of alloy and in the range of 10 - 50 oC. A representative
transformation curve is shown in the figure. In this case, the physical property of the alloy such as
electrical resistance is shown to follow the phase transformations.
 Fig.2 Thermal Transformation in SMAs

Where Ms is the temperature at which martensite starts to form Mf. The temperature at which conversion
to martensite is complete. ‘As’ is the temperature at which austenite starts to form ‘Af’ is the temperature
at which conversion to austenite. In this way, this is the Transformation of hysteresis as a whole.

6. Applications of Shape Memory and Superelastic Alloys:

There are a number of patents exploiting the properties of shape memory alloys. However, a very small
fraction of them has turned these properties into a successful device. Undoubtfully, the applications are
very wide in range from day-to-day user products to its medical achievements to its applications in space
exploration. Only a small number of these applications can be described here. In 1969, the very first
application happened when SMA-based joints were attached to the hydraulic pipes in the F-14 aircraft.
This property has been stretched to connect different kinds of pipes. In some conditions, it uses a liner
that is embraced onto a pipe to make a connection. Such connectors are cylindrical and these are cooled
to an ultra-low temperature to make the martensitic phase when they can easily move over the pipes.
Furthermore, on increasing the temperature above the transformation temperature, the joint returns back
to its original shape and size but it is still constrained by the pipes. The couplings made by these alloys
create enough stress to form a tight joint which sometimes is better than a normal welding process.

Another application of these devices is to provide protection against fire. The water sprinkler can be
smartly designed by the change in shape actuated by the heat generated in the fire. On the other hand, a
safety valve containing SMA based controller can switch off the flow of a flammable liquid or gas in the
case of a fire. Whereas, in the construction industry, an SMA-based clamp is used to hold the ceiling
plates at their place if there is an increase in the temperature above 60 oC. This action protects pipes,
cables, and the floor above from the fire.

Their shapes sensitive to temperature variation can be used as a modified bimetallic strip to regulate the
temperature of the water. Similarly, an anti-scald device is attached to a shower to adding cold water to
the pipeline if the temperature of the water turns out to be too high. This kind of device uses a spring of
SMA and a compensatory spring made up of steel. As the temperature increases, the SMA-based spring
expands and unlocks a needle valve leaving cold water to enter for mixing in with hot water. When the
temperature decreases, the SMA returns to martensite phase and the spring made up of steel counters the
effect and shuts the needle valve off.

7. Nickel-Titanium Alloys (NiTi):

Nickel-Titanium alloys are one of the famous SMAs used in many commercial applications. This
structure is based upon the equiatomic construct of titanium and nickel atoms. It can bear fairly large
numbers of shape memory strains. It is stable in structure, and resistant to corrosion as well. The
temperature of transformation is very much dependent on the composition and even a minute change in
the nickel content could cause ample change in the transformation temperature. This system also shows
a huge transformation temperature hysteresis loop, of about 50 oC. A third metal is generally induced to
such a binary alloy to modify its properties for commercial explorations. The shape memory effect almost
remains the same if copper is added at the place of nickel up to 30%. Whereas it just reduces the width
of the hysteresis to about 15 oC and it also makes it less sensitive towards the changes in the nickel
content.

Figure 3: Diagrammatic representation of the superelasticity effect of NiTi alloy

The addition of copper into the system is the most beneficial up to 10% of concentration. The addition of
copper beyond this level only adds a small modification to the system. The manufacturing of NiTi alloys
 is not that easy just because the melting of all the components and the reaction of titanium must be
performed in a vacuum or an inert atmosphere. That is also the reason because of which joining such
alloys using welding, or soldering is the most difficult task. When it is done in a cold environment, the
alloy becomes hard very quickly but it consists of a fine grain structure. In this case, very fine wires can
be made easily. It is very hard to do machining with NiTi alloys. In this way, the alloy becomes very
expensive to construct for a variety of applications. In spite of these drawbacks, its outstanding shape
memory properties and resistance towards corrosion have given rise to NiTi being used in a vast variety
of applications.

Composite Materials

Introduction: The mixing of two materials with different physical and chemical properties forms a
composite. In this way, the material is designed to outgrow providing the desired job. Sometimes they
become stronger, lighter, or electrically resistant. There are several other benefits to be pointed
responsible for the growth of the composite materials but the specific goal achieved by the composites is
that they are stronger in strength and lighter in weight. The utilization of composite materials is
widespread and connected to almost all the industries we can think of. With the industrial advancements
in time, in the past four decades, the conventional building materials were replaced by advanced materials
designed for specific applications. In general, the industries of composite materials can be classified into
the following categories: construction, marine corrosion-resistant equipment, aerospace, automotive,
consumer products, appliance/business equipment, etc.
Whereas, the materials available can be divided into these categories: polymers, ceramics, metals, and
inorganic glasses and composites. Generally, metals weaken in their strength as the ambient temperature
increases. Several polymers can only bear a low temperature. Ceramics surpass polymers and metals
because of their ability to bear high temperatures, excellent mechanical strength, and low thermal
expansion, but they are brittle which becomes the reason for its rejection from being a structural material.
All these points converge to a common need for composite materials.
The major benefit of these advanced composite materials is that they are lightweight as well as carry high
building strength. By selecting the appropriate recipe of the matrix and reinforcement materials, the new
material can be designed that precisely meets the necessities of a specific application. Composites can
also be designed in various ways because most of the composites can be molded into complex shapes.
Sometimes the costs of the raw materials are high which makes it hard to use such composite materials
at all places.

1. Polymer-Matrix Composites:

The automobile industry has been flourished by the structural applications of E-glass fiber. Likewise, resin
systems are most expected to dominate in recent times. High-performance resins will be used for its
specific application. The glass fiber foam is also of very specific use, and both continuous and chopped
glass fibers are of wide-ranging use.

Advanced composites and reinforced plastics are two main categories of polymer matrix composite
(PMC). The mechanical properties such as strength and stiffness of these materials are the basis of this
classification. Otherwise, the difference between them is defined quite clearly. Comparatively inexpensive
reinforced plastics, generally carry polyester resins are reinforced with low-stiffness glass fibers. Being
light weight is the main advantage of PMCs along with this they have good strength in the direction of the
reinforcement. Such a combination of properties is the reason for their usefulness. Besides, these materials
demonstrate excellent fatigue and corrosion resistance in comparison to metals. The only drawback is that
the matrix decomposes at high temperatures, so, the PMCs can only be used up to 600 °F (316 °C).

Applications of polymer-matrix Composite:

The automotive industry is a big scope for all such material research advancements. The multiple places
of utility accommodate many advanced composite materials, PMCs are one of them. PMCs provide light
weight and good strength material thus the efficiency of the automobiles can be increased. Along with
this, its corrosion resistance nature makes it durable to use for several applications. The development in
this field of materials would have a significant impact on new ways of its production, and it will also
emerge some new industries. The benefits of advanced materials to automotive structures requires:
The criteria of performance applicable to new materials like PMCs in automotive are
1. Fatigue (durability)
2. Energy absorption (during accident)
3. Material stiffness in terms of ride quality, vibration, and noise
4. Reduction of weight, which on the other side makes vehicle fuel economy and enhances its
performance.
5. Overall improvement in built quality and uniformity in manufacturing.
6. The reduction of overall manufacturing costs.
7. Resistance towards corrosion

2. Metal Matrix Composites (MMCs):

Metal matrix composites (MMCs), are not used as much as their plastic opponents, irrespective of their
vital interest in research groups. These materials offer high strength, and toughness comparative to those
presented by their polymer counterparts. They can bear high temperatures with much comfort rather than
polymer composites. The non-reactive and highly stable over a range of temperature reinforcement
materials are required to combine with a matrix usually made up of any metal or alloy. The matrix material
decides the guiding aspects of the structure of the matrix. Light metals are used to form the matrix for
temperature applications and the reinforcement material in addition to the above-mentioned reasons are
categorized by the high modulus of rigidity. Most metals and alloys make good matrices. But it cannot
be used for low-temperature applications. The use of light metals is advantageous in the manufacturing
of these materials. The metals such as aluminum, titanium, and magnesium are the popular matrix metals
presently being explored. These light metals are specifically useful for their application in aircraft
industries if matrix materials are made up of light materials and offer high strength. The high value of
strength-to-weight ratios is required for these properties.

Advantages: MMC is more preferred over polymer-matrix composites (PMCs) which can be operated at
higher temperatures, and have greater resistance to degradation caused by organic fluids. Whereas, higher
cost of MMCs over PMCs restricts their use to some extent.

Constitution: The Matrix materials cover super alloys as well as the alloys of magnesium, titanium,
aluminum, and copper. The reinforcement can be in the form of both continuous and discontinuous fibers.
Whose concentration normally ranges between 10 to 60 %vol. materials containing continuous fibers
comprise carbon, aluminum oxide, silicon carbide, and boron. Instead, silicon carbide whiskers, chopped
fibers of aluminum oxide and carbon, and particulates of silicon carbide and aluminum oxide are some
vital discontinuous reinforcements.

Application:

In the field of automobile production: the aluminum alloy matrix that is used as reinforcement consists
of aluminum oxide and carbon fibers. This is used to form the main engine components. This MMC
resists wear and very light in weight. These composites are also used in driveshafts as they required high
rotational speed and reduced vibrational noise levels. On the other hand, in the aerospace industry:
advanced aluminum alloy-based metal-matrix composites are formed for structural requirements; Space
Shuttle Orbiters are constructed using boron fibers as a reinforcer. In the Hubble space telescope,
continuous graphite fibers were used as a reinforcer.
The high-temperature creeps and rupture properties of some of the Ni- and Co-based superalloys alloys
are enhanced by fiber reinforcement using tungsten-like refractory metals. Excellent impact strength and
oxidation resistance at high temperatures are maintained. The designs consisting of these composites
permit better efficiencies and higher operating temperatures for turbine engines.

3. Ceramic Matrix Materials (CMM):

Ceramic materials are defined as solid materials exhibiting strong ionic bonding and covalent bonding in
some cases. They usually have a high melting point, good resistance towards corrosion, and high inertness
for chemicals. These materials also possess high compressive strength. That is the reason why ceramic-
based matrix materials are favorite for structural applications above a temperature of 1500 ºC. In general,
ceramic matrix materials are the obvious choice at elevated temperatures. Low tensile strain and high
modulus of elasticity are possessed by the ceramics. These properties in combination became the reason
for unsuccess in the attempts to add reinforcements in these materials to improve its material strength.
This may happen because the stress level at which a ceramic breaks, the elongation of the matrix is not
sufficient; which does not allow the composite from transferring the load to the reinforcement and it fails
until there is a sufficiently high percentage of fiber present in the material. On the other hand, the addition
of a heavy quantity of high-strength fiber weakens the ceramic most of the time. The reinforcement can
be used in a material with a high modulus of elasticity. It may work to some extent but not always.
Ceramic materials are inherently resistant to oxidation and degradation at high temperatures. Some of
these materials would be ideal for use in high temperature and stress conditions, especially in aircraft
engines and heat portions in automobiles. The values of fracture toughness for these ceramic materials
are not that high and generally lies between 1 to 5 MPa. On the other hand, these values are very high for
metals of the order of 15 to 150 or sometimes even more in MPa. Ceramic-matrix composites (CMCs)
are formed to increase the fracture toughness of these materials. In these materials, fibers, particulates, or
whiskers of one ceramic material are embedded into the matrix formed by another ceramic. The facture
toughness of CMCs has been extended about 6 to 20 MPa.

Applications of CMCs
CMCs find applications in many industrial applications. A suitable organization of the applications of
ceramic matrix composites (CMCs) is aerospace and non-aerospace. CMCs used in the field of aerospace
are:
• High stiffness and better material strength.
• Reduction in weight.
• Lower maintenance and fabrication cost.
• Highly thermal resistant.
• Longer service life.
• Valuable in stealth technology (reduces the distance at which a vehicle can be detected).

4. Carbon Matrix Composite :

Carbon fibers embedded in a carbonaceous matrix forms a special kind of composite called
carbon/carbon composite. Carbon is an excellent material that persists even up to high temperatures
when used in inert or non-oxidizing atmospheres. The major with carbon is that it easily reacts with
oxygen, forming oxides. Carbon/carbon composite materials are commercially very useful. Heat
shields, heating elements, load plates, and X-ray targets are made using this material. The nozzle of a
rocket exhaust must bear an extremely rapid increase in temperature in a highly corrosive environment
while sustaining its strength. This is a fascinating material used in many applications in the field of
aerospace technology, wind energy production, automotive engineering, mechanical engineering, medical
technology, and the sports industry.
Carbon composites have a wide range of advantages such as:
• Extremely light weight
• Long-lasting
• Non-corrosive
• Multifunctional
• High stability
• High energy absorption in an accident
• Attractive looks

Applications of Carbon-Carbon Composites

▪ High-performance braking system
▪ Turbojet engine components (rocket nozzles)
▪ Hot-press die
▪ Refractory material (protection tubes and grids)
▪ Heating elements

Implant Materials
Visit this webpage to study the construction of an LED –
[Link]

Visit these webpages for photoconductor and photodiode –

[Link]
[Link]

Photonic Crystals –
[Link]
[Link]

Chromic Materials –
[Link]

Consult notes for more details.