Advanced Material:

The development and advancement of materials is an extensive need in modern systems that extract, distribute, store or use
energy. The performance of these systems depends on the materials structures and properties. Composite, semiconductors
and biomaterials are some of the broad classes of materials used in current industrial and biomedical applications.
Advancements in these materials optimize energy conversion processes, improve system efficiency, extend lifetime,
mechanical strength, etc. There is contentious search for engineered materials with improved properties for high tech
applications. Some of advanced materials are described here.

Shape memory alloy (SMA): It is an alloy which can memorizes its shape and can be returned to that shape after being
deformed on application of heat. It may also be called memory metal or memory alloy or smart metal or smart alloy. SMA
can be deformed into any new shape below its transformation temperature, which it will retain. When the material is heated
above its transformation temperature it undergoes a change in crystal structure which causes it to return its original shape.
This effect is known as shape memory effect (SME). The shape memory effect occurs due to a reversible solid-solid phase
change especially in metal alloys.
A solid-solid phase change is defined as the molecular rearrangement but the molecules remain closely packed so that the
substance remains a solid. SMA can bear large stress without undergoing permanent deformation. They can be formed into
various shapes like bars, wires, plates and rings thus serving various functions. The two most prevalent SMA are Copper-
Aluminum-Nickel and Nickel-Titanium (NiTi), but SMA can also be created by alloying Zinc, Copper, Gold and Iron.
Although Iron based and Copper based SMAs such as Fe-Mn-Si, Cu-Zn-Al and Cu-Al-Ni, are commercially available and
cheaper than NiTi but NiTi-based SMAs are preferable for most applications due to their stability, practicability and
superior thermo-mechanic performance.
Some of the techniques to produce NiTi alloys are vacuum melting technique such as electron beam melting,
vacuum arc melting or vacuum induction melting. These are specialist techniques used to keep impurities in the alloy to
minimum and ensure the metals are well mixed. The ingot is then hot rolled into longer section and then drawn to turn it
into wire. Hot working to this point is done at temperature between 7000C and 9000C.

Phases of SMA:
There are two solid stable phases which occur in shape memory alloys.
 Austenite phase: It is a high temperature phase and more ordered phase. The crystal structure is cubic. The cubic
crystal structure of Ni-Ti is shown in Fig. 1.

Fig.1: Austenite structure of Ni-Ti.

 Martensite Phase: It is a low temperature phase and in monoclinic crystal structure. Martensite is a crystallographic
less ordered phase and therefore is the softer and easily deformed phase of shape memory alloys. It can be in one of two
forms: twinned and detwinned as shown in Fig. 2.
 Fig.2: Martensite crystal structure of Ni-Ti in the form of twinned and detwinned structure.

The phase transformation which occurs between these Austenite and Martensite phases upon heating/cooling is the basis for
the unique properties of SMAs. The phase transformation may occur due to the temperature or mechanical load or due to the
both temperature and load. The key effects associated with phase transformation are shape memory effect and
pseudoelasticity .

Temperature induced phase change without mechanical load:

Fig.3: Temperature induced phase transformation of an SMA without mechanical loading.

If an SMA is cooled in the absence of applied load, the material changes from austenite into twinned martensite. Observable
macroscopic shape change does not occur during the transformation. The reverser transformation takes place on heating of
the material. The process is shown in Fig. 3.
Characteristic temperature:
There are four characteristic temperature characterizing the phase transformation, which are defined as
(i) Ms is the martensite temperature at which the material starts changing from austenite to martensite.
(ii) Mf is the martensite finish temperature at which the transformation is complete and the material is fully in the
martensite phase.
(iii) As is the austenite phase at which austenite phase first appear in the martensite.
(iv) Af is the austenite finish temperature at which the reverse phase transformation is completed and the material is in
the austenite phase.
Temperature induced transformation with applied mechanical load and shape memory effect:
At a temperature above Ms, the specimen is entirely in the austenite phase. When the specimen is cooled below Mf, it
transforms entirely to the twinned martensite phase but the macroscopic volume does not change which is a condition
known as self accommodation. By applying small loads the specimen can be easily detwinned or deformed and the
deformed shape remains after removing the loads. If the specimen is heated in the detwinned state to above temperature Af,
the original un-deformed shape can be recovered.

Fig.4: Deformation of martensite phase under application of load.

Shape memory effect: When a piece of shape memory alloy is cooled below the temperature Mf and the material is applied
a constant load, it gets deformed martensite phase. The original shape can be recovered simply by heating the specimen
above Af., when heated the deformed martensite is transformed to the cubic austenite phase. This effect is called shape
memory effect.

Fig. 5: Temperature Vs load curve (shape memory effect).

The molecular rearrangement occurs due to the heat transferred to the material. SMA undergoes phase changes while
remaining a solid as phase changes occur below its melting point. Thus the alloy can retain its shape without melting. Under
the transition temperature, the alloy is in the martensite phase and can be deformed into various shapes.
The transformation from austenite to martensite and the reverse transformation from martensite to austenite do not take
place at the same temperature. It occurs over a range of temperature which is shown in Fig. 6. Here Ꜫ (T) represents the
volume fraction of martensite phase. Most of the transformation occurs over a narrow temperature range. Further the
heating and cooling transformation exhibit hysteresis. That is the transformation on heating does not overlap on the
transformation on cooling. The magnitude of the hysteresis varies with the alloy type and is typically in the range 10-500C.
 Fig. 6: Transformation hysteresis.
The values of the MS, Mf, AS and Af are depend on the composition of each element of the alloy material (i.e., what amount
of each element are present). Secondly values of the temperatures vary with the load applied on the SMA.
Superelasticity:
Superelasticity is a mechanical type of shape memory as opposed to thermally induced shape memory. In this case, a small
force induces considerable deformation but when the force is removed, the material automatically recovers its original shape
without the need for heating. SMAs show a super elastic behavior if deformed at temperature which is slightly above their
transformation temperatures. The applied stress changes the austenite to martensite and significant deformations happens for
a quite small applied stress. When the stress is removed the martensite, returns to austenite and the material recovers its
original shape. The effect which makes the alloy appears extremely elastic is known as Superelasticity or pseudoelasticity.
Load-induced phase change at constant temperature-Pseudo elasticity (Super elasticty):
A phase transformation may be induced in a sample purely due to mechanical load and without a change in its temperature.
Let the alloy be in the austenite phase, the load on the shape memory alloy is raised till the austenite changed into
martensite. Once the loading is reduced, the martensite begins to change back to austenite. Thus the material behavior
resembles elasticity. This effect is known as Pseudoelastic Effect and the phenomenon pseudo-elasticity or super elasticity.
The pseudoelasticity stress-strain diagram is shown in Fig. 7.

Fig.7: Stress induced transformation.

Different kinds of shape memory effect:

Generally, there are two types of memory effects namely one way and two way shape memory.
(i) The one way shape memory effect:
Transformation to the desired shape occurs only upon heating, i.e.,
memory is with the austenite phase. When a shape memory alloy is below
As the metal can be bent or stretched into a variety of new shapes under
application of stress and will hold that shape until it is heated above the
transition temperature. The shape returns back to its original shape on
heating. When the metals cool again it will remain in the hot shape,
unless distorted again. One way SME is a onetime operation and will not
be repeated indefinitely. The schematic of a stress-strain-temperature Fig.8: One way memory effect: (a)
Material in martensite phase, (b) material
curve is shown in Fig. 8. deformed, (c) sampleheated and (d) sample

(ii) The two way shape memory effect:

In this effect, material remembers two different shapes; one at

low temperature and one at high temperature, i.e., memory is
with both austenite and martensitic phase. Fig. 9 shows a
schematic view of the effect which can be achieved by without
application of the load. In usual condition, a shape memory
alloy remembers its high temperature shape, but upon heating
to recover the high temperature shape, instantly forgets the low
temperature shape. But it can be trained to remember to leave
Fig.9: Two way memory effect: (a) Material in
some reminders of the deformed low temperature condition in martensite phase (b) material deformed (c)
the high-temperature phase. sample heated and (d) sample cooled again

Characterization Techniques:
There are number of methods to characterize shape memory alloy. Primarily two methods are described below.
 Differential scanning calorimetry (DSC), a direct method yields valuable characterization information on SMA
systems. The transformations occurring during cooling and heating are readily observed using DSC. The endotherm
and exotherm peaks are measured for the beginning and the end of phase change.
 The most direct method employed to characterize SMA is strain measurement. At constant stress, the sample is allowed
to undergo the cycle of transformation. The strain experienced by the sample is measured simultaneously. The
characteristic temperature obtained through this method is slightly higher than the DSC method. The strain
measurement is made by applying stress over the sample. On the other hand DSC test is made with no stress applied.
The increase in the stress is attributed to the increase in transformation temperature.

Examples of SMA
Nickel-Titanium (Ni-Ti) (NITINOL) Alloy: In 1962-63, the nickel-titanium alloys were first developed under the trade
name NITINOL by the Naval ordnance laboratory. Ni-Ti is an extraordinary intermetallic binary compound because it has
moderate solubility for excess Nickel or Titanium. This solubility enables alloying with many other elements there by
getting systems with modified mechanical and transformation properties. Its ductility is comparable to ordinary alloy. It has
greater shape memory strain and excellent corrosion resistance compared to copper-base alloys. Also it tends to be much
more thermally stable. Because of the reactivity of titanium, the melting of this alloy must be done in vacuum or in an inert
atmosphere. Methods like plasma arc melting, electron beam melting and vacuum induction melting are commonly adopted
for this purpose.
Copper-Zinc-Aluminum (CuZnAl) Alloys: The transformation temperature depends on the composition of the alloys and
the thermo mechanical treatments used in their preparation. These alloys is cheapest of the commercial SMAs but their
memory properties are modest with a maximum recoverable strain of about 5%. Copper based alloys have medium
corrosion resistance and they are susceptible to stress corrosion cracking. They can be melted in air and having wider range
of potential transformation temperatures. The thermal stability is limited of Cu-Zn-Al alloys is generally limited at higher
temperatures.
Copper –Aluminium-Nickel (CuAlNi) Alloys: CuAlNi have transformation temperature in the range 80-200 0C dependent
on their composition, [articular;y sensitive to the Al contents. The alloy [recessing is difficult; the final treatment has to be
tightly controlled to produce an alloy with the desired transformation temperature. The production is more expensive than
CuZnAl and chipper than NiTi. The major advantage of the CuAlNi alloy is the wide range of transformation temperature,
its stability, for application above 1000C , small hysteresis and relatively low cost.
Applications of SMA:
The shape memory effect and super elasticity behavior of these SMA are being utilized in wide Varity of applications in
various fields.
 Civil construction such as Bridge, building, etc.
 Medical applications such as Cardiovascular stents, Dental Wires, Bone repairing, etc.
 Piping for consumer/commercial applications such as water piping and oil piping.
 Optometry such as Eyeglass frames
 Technological applications such as automotive systems, Robotics, Aircraft, Actuators, etc.
Advantages of SMA:
 Biocompatibility
 Diverse fields of application
 Good mechanical properties (Strong, Corrosion, Resistant)
Disadvantages of SMA:
 Relatively Expensive
 Have poor fatigue properties
 Heat Dissipation need mechanism for cooling

Biomaterials:
Biomaterial may be natural or synthetic material which is used to make devices to replace a part or a function of the body in
a safe, reliable, economic and physiologically acceptable manner.
Biomaterials are used to make devices that would be in close or direct contact with the body to augments or replace faulty
materials. Biomaterials have a major impact on the contemporary medicine and patient care and in improving the quality of
human’s lives.
Classification of Biomaterials: These are classified on the basis of natural or biological and synthetic materials which are
shown below

Criteria:
The criteria of synthetic and modified natural materials are as follows
Biocompatibility:
• Safety in a biological organism.
• Absence of carcinogenicity (the ability or tendency to produce cancer)
• Absence of immunogenicity (absence of a recognition of an external factor which could create rejection)
• Absence of teratogenicity (ability to cause birth defects)
• Absence of toxicity (poisonous).

Biofunctionality: Biomaterial should play a specific function physically, biologically and mechanically.

Mechanical and performance requirements: Understanding of the biomaterials and devices require the design principles
from physics, chemistry, mechanical engineering, chemical engineering and material science. The major categories of
understanding are

(a) Mechanical Performance: Biomaterial must be strong and flexible; (e.g) a heart valve leaflet must be flexible and
tough.
(b) Mechanical Durability: Functionality of biomaterials should be maintained over its design lifetime without requiring
excessive maintenance or repair. (e,g) A bone plate may fulfill its function in 6 months or longer. A leaflet in heart
valve must flex 60 times per minute for at least for 10 or more years.
(c) Bulk physical properties: Bulk physical properties such as melting point, density, refractive index, lubricity, etc are
very important for biomaterials. (e,g) the dialysis membrane has a specified permeability, the articular cup of the hip
joint must have high lubricity, and the intraocular lens has clarity and refraction requirements.

Applications of Biomaterials:

Both natural and synthetic biomaterials are used in many today’s medical devices, including artificial skin, artificial blood
vessels, total artificial hearts, pacemakers, dental fillings, dental wires, plates and pins for bone repair, total artificial joint
replacements, intraocular lens, etc.