Contents

Introduction ............................................................................................................................................ 2
History ..................................................................................................................................................... 3
Working................................................................................................................................................... 5
Shape Memory Effect ............................................................................................................................. 9
Commercial SME Alloys ........................................................................................................................ 10
Ni-Ti Alloy .......................................................................................................................................... 10
Copper Based Alloys.......................................................................................................................... 12
Applications........................................................................................................................................... 13
Biomedical......................................................................................................................................... 13
Introduction
Metals play a crucial role as structural materials. Techniques of smelting, alloying, and forging have
been changing with evolution of science and technology, and with a rise in the knowledge of the
effects of processing techniques and microstructure on material behaviour, the field of material
science has dramatically improved over the past decades. The capability to manipulate different
material properties (such as mechanical, thermal, electrical, etc.) for a different uses has enabled the
development of new composites and alloys. The demand for lighter, stronger materials with
engineered properties that address the stringent structural requirements and also provide additional
engineering functionality (example, sensing, actuation, electromagnetic shielding) has introduced
materials called multifunctional materials. A few multifunctional materials which exhibit sensing and
actuation capabilities are known as active materials.

Active materials exhibit a mechanical response when subjected to non-mechanical fields (example
thermal, electrical, magnetic, etc.). The mechanical response is typically of a greater magnitude than
that from a conventional material behaviour such as thermal expansion. Examples of active
materials include electrostrictives and piezoelectrics (electric fields), piezomagnetics and
magnetostrictives (magnetic fields), and shape memory materials (thermal field).

The shape memory effect (SME) is a property of certain alloys which undergo martensitic
transformations to revert back to their original shape upon heating to a critical temperature called
the reverse transformation temperature. Shape Memory Alloys (SMAs) are a class of shape memory
materials with the ability to recover their shape when the temperature is increased. An increase in
temperature can result in shape recovery even under high applied loads. In addition, under certain
circumstances, SMAs can absorb and dissipate mechanical energy by undergoing a reversible
hysteretic shape change when subjected to applied mechanical cyclic loading. These characteristics
of SMAs have made them popular for impact absorption, sensing and actuation and vibration
damping applications.

SMAs have found an application in many different industries and are currently being applied in high-
end glass frames, women’s brasseries, cryofit couplings, actuators, cables and are currently being
researched to be applied in biomedical engineering, aerospace science, automotive industry, and in
oil exploration. SMAs if researched and developed appropriately can be used in many fields which
will benefit various industries.
History
In 1890’s, Adolf Martens discovered martensite in steels. The martensitic transformation was the
key discovery which led to the development of SMAs. In the 1900’s, the study of martensitic
transformations became the most researched metallurgical phenomenon. While the study of
martensitic transformation in Fe-C was established as irreversible, successful trials were recorded
eventually.

The first recorded discovery was in 1932 by Chang and Read. It was found in a 47.5% Au-Cd alloy.
The concept of thermoelastic martensitic transformation was introduced in 1949 by Khardos and
Kurdjumov, based on experimental observations of thermally reversible martensitic structure of
CuZn and CuAl alloys. By 1953, the occurrence of thermoelastic martensitic transformation was
exhibited in other alloys such as InTl and CuZn. However, it wasn’t until the year 1962, when Buehler
and his colleagues discovered this effect in NiTi alloy, that research into both potential practical
applications and metallurgy of SMAs began. The United States Naval Ordnance Laboratory first
developed the nickel titanium alloy in 1962-1963 and commercialized it under the name Nitinol.
These alloys exhibit another property called “superelasticity” at higher temperatures. The term
Shape Memory Effect (SME) was given to the associated shape recovery behavior. The effects of
heat treatment, composition and microstructure were widely investigated and began to be
understood during this period. In 1965, studies showed that the addition of a third alloying element
such as Co or Fe to the existing NiTi system caused a dramatic decrease in the SMA transformation
temperatures. The new alloys inspired the first commercial SMA application, known as Cryofit,
where SMA material was used for pipe couplings in F-14 fighter aircraft. The transformation
temperatures for Cryofit were so low that, to prevent actuation from occurring before the assembly,
the pipe couplings were transported in liquid nitrogen. Continued research to address this issue led
to the development of the NiTiNb system in 1989, which was easier to handle due to its larger
temperature hysteresis, and found widespread applications in battle damage repairs and in repairs
for nuclear reactors. High Temperature SMAs (HTSMAs), such as TiPd, TiPt and TiAu (with
transformation temperatures greater than 100 ◦C), were also developed as early as 1970. Melton
and Mercier, while studying the fatigue properties of NiTi in 1978, showed that alloying the material
with Cu did not change the transformation temperatures considerably, but narrowed the stress
hysteresis. Later in 1999, Miyazaki showed improved fatigue life for NiTiCu alloys. The improved
fatigue life and the low cost associated with this material system made it suitable for a wide variety
of engineering applications.

Since the initial discovery of Nitinol in 1963, many commercial applications were developed. In 1975,
Andreasen, of Iowa University, made the first implant of a superelastic orthodontic device. In the
1990s, NiTi stents made their commercial breakthrough. By this time, SMAs had found additional
applications in air conditioning vents, electronic cable connectors, valves and a variety of other
products. In addition, over the last decade the demand for actuation under high temperature
operating conditions, driven by the aerospace and oil industries, has revived a great deal of interest
in the development of HTSMAs. Finally, alloys that exhibit shape change characteristics similar to
SMAs but under the influence of a magnetic field have recently been under investigation. The high
actuation frequencies and the large strains generated in Magnetic SMAs (MSMAs) have made these
materials a strong candidate for high frequency actuation devices.
Figure 1http://isites.harvard.edu/fs/docs/icb.topic474338.files/annurev-ShapeMemoryAlloys.pdf
Working
Within the typical operating temperature range, SMAs have two phases, each with a different crystal
structure and therefore different properties. One is the high temperature phase called austenite (A)
and the other is the low temperature phase called martensite (M). Austenite (generally cubic) has a
different crystal structure from martensite (tetragonal, orthorhombic or monoclinic). The
transformation from one structure to the other does not occur by diffusion of atoms, but rather by
shear lattice distortion. Such a transformation is known as martensitic transformation. Each
martensitic crystal formed can have a different orientation direction, called a variant. The assembly
of martensitic variants can exist in two forms: twinned martensite (Mt ), which is formed by a
combination of “self-accommodated” martensitic variants, and detwinned or reoriented martensite
in which a specific variant is dominant (Md). The reversible phase transformation from austenite
(parent phase) to martensite (product phase) and vice versa forms the basis for the unique behavior
of SMAs.

Upon cooling in the absence of an applied load, the crystal structure changes from austenite to
martensite. The phase transition from austenite to martensite is termed the forward transformation.
The transformation results in the formation of several martensitic variants, up to 24 for NiTi. The
arrangement of variants occurs such that the average macroscopic shape change is negligible,
resulting in twinned martensite. When the material is heated from the martensitic phase, the crystal
structure transforms back to austenite, and this transition is called reverse transformation, during
which there is no associated shape change.

Figure 2: Temperature-induced phase transformation of an SMA without mechanical loading

There are four characteristic temperatures associated with the phase transformation. During the
forward transformation, austenite, under zero load, begins to transform to twinned martensite at
the martensitic start temperature (Ms) and completes transformation to martensite at the
martensitic finish temperature (Mf ). At this stage, the transformation is complete and the material
is fully in the twinned martensitic phase. Similarly, during heating, the reverse transformation
initiates at the austenitic start temperature (As) and the transformation is completed at the
austenitic finish temperature (Af ).

If a mechanical load is applied to the material in the twinned martensitic phase (at low
temperature), it is possible to detwin the martensite by reorienting a certain number of variants. The
detwinning process results in a macroscopic shape change, where the deformed configuration is
retained when the load is released. A subsequent heating of the SMA to a temperature above Af will
result in a reverse phase transformation (from detwinned martensite to austenite) and will lead to
complete shape recovery. Cooling back to a temperature below Mf (forward transformation) leads
to the formation of twinned martensite again with no associated shape change observed. The
process described above is referred to as the Shape Memory Effect (SME).
The load applied must be sufficiently large to start the detwinning process. The minimum stress
required for detwinning initiation is termed the detwinning start stress (σs). Sufficiently high load
levels will result in complete detwinning of martensite where the corresponding stress level is called
the detwinning finish stress (σf ). When the material is cooled with a mechanical load greater than σs
applied in the austenitic phase, the phase transformation will result in the direct formation of
detwinned martensite, producing a shape change. Reheating the material will result in shape
recovery while the load is still applied.
Recognizing that the forward and reverse transformations occur over a range of temperatures (Ms
to Mf, As to Af) for a given SMA composition, we can construct transformation regions in the stress-
temperature space. The transformation temperatures strongly depend on the magnitude of the
applied load, with higher values of applied load leading to higher transformation temperatures. As a
consequence, the transformation regions representing the A→Md and Md→A transformations have
a positive slope in stress-temperature space. Irrespective of the nature of applied load (tension or
compression), the transformation temperatures increase with an increase in the magnitude of the
load. Under an applied uniaxial tensile load with a corresponding stress, σ, the new transformation
temperatures are represented as Mσf, Mσs, Aσs and Aσf for martensitic finish, martensitic start,
austenitic start and the austenitic finish temperatures, respectively.

The martensitic transformation that occurs in the shape memory alloys gives a thermoelastic
martensite and develops from a high-temperature austenite phase with long-range order. The
martensite occurs as alternately sheared platelets. The transformation does not occur at a single
temperature but over a range of temperatures that varies with each alloy system. Most of the
transformation occurs over a relatively narrow temperature range, although the beginning and end
of the transformation during heating or cooling actually extends over a much larger temperature
range. The transformation also exhibits hysteresis in that the transformation on heating and on
cooling does not overlap. This transformation hysteresis varies with the alloy system.

The martensite (low temperature phase) of SMA is easily deformed under low stress conditions to
several % strain. Upon heating, the SMA “remembers” its shape as it transforms back to its original
shape. However, this does not take place when the material is austenite (high temperature phase).
The martensite phase under higher stress conditions exhibits a behaviour known as pseudoelasticity.
Upon loading the stress, the martensite strains immediately and exhibits increasing stress under
constant strain. Upon unloading, the material reverts to austenite at a lower stress and shape
recovery occurs, not upon the application of heat but upon a reduction of stress. This effect, which
causes the material to be extremely elastic, is known as pseudoelasticity.

In most cases, heating is required for a shape memory alloy to transform its shape. However, there
are some cases, where shape change occurs both upon cooling and heating. This is called a two-way
SMA. However, the amount of shape change is less than that of the one way SMA.

Shape Memory Effect

An SMA exhibits the shape memory effect (SME) when it is deformed while in the twinned
martensitic phase and then unloaded while at a temperature below As. When it is subsequently
heated above Af , the SMA will regain its original shape by transforming back into the parent
austenitic phase. The nature of the SME can be better understood by following the
thermomechanical loading path in a combined stress-strain-temperature space. The stress σ is the
uniaxial stress on the specimen due to an applied load. The corresponding strain ε is the change in
the length of the specimen along the direction of applied load, normalized by the original length.

Starting from the parent phase (point A), the stress-free cooling of austenite below the forward
transformation temperatures (Ms and Mf ) results in the formation of twinned martensite (point B).
When the twinned martensite is subjected to an applied stress that exceeds the start stress level
(σs), the reorientation process is initiated, resulting in the growth of certain favourably oriented
martensitic variants that grow at the expense of other less favourable variants. The stress level for
reorientation of the variants is far lower than the permanent plastic yield stress of martensite. The
detwinning process is completed at a stress level, σf , that is characterized by the end of the plateau
in the σ-ε diagram. The material is then elastically unloaded from C to D and the detwinned
martensitic state is retained. Upon heating in the absence of stress, the reverse transformation
initiates as the temperature reaches As, (at E) and is completed at temperature Af (point F), above
which only the parent austenitic phase exists. In the absence of permanent plastic strain generated
during detwinning, the original shape of the SMA is regained (indicated by A). The strain recovered
due to the phase transformation from detwinned martensite to austenite is termed as the
transformation strain (εt ). Subsequent cooling to martensite will again result in the formation of
self-accommodated twinned martensitic variants with no associated shape change, and the whole
cycle of the SME can be repeated. The above described phenomenon is called one-way shape
memory effect, or simply SME, because the shape recovery is achieved only during heating after the
material has been detwinned by an applied mechanical load.

Sometimes an SMA can exhibit repeatable shape changes under no applied mechanical load when
subjected to a cyclic thermal load. This behavior is termed two-way shape memory effect (TWSME).
The TWSME can be observed in a SMA material which has undergone repeated thermomechanical
cycling along a specific loading path (training). Repetition along a loading path for a large number of
cycles can induce changes in the microstructure, which causes macroscopically observable
permanent changes in the material behavior.

Commercial SME Alloys

Currently, only two alloy systems have been exploited commercially. They are Ni-Ti alloys and
copper based alloys. Properties of the two systems are different. The Ni-Ti alloys have greater shape
memory strain (up to 8% versus 4 to 5% for the copper-base alloys), tend to be much more thermally
stable, have excellent corrosion resistance compared to the copper-base alloys' medium corrosion
resistance and susceptibility to stress-corrosion cracking, and have much higher ductility. On the
other hand, the copper-base alloys are much less expensive, can be melted and extruded in air with
ease, and have a wider range of potential transformation temperatures. The two alloy systems thus
have advantages and disadvantages that must be considered in a particular application.

Ni-Ti Alloy
The basis of the nickel-titanium system of alloys is the binary, equiatomic intermetallic compound of
Ni-Ti. This intermetallic compound is extraordinary because it has a moderate solubility range for
excess nickel or titanium, as well as most other metallic elements, and it also exhibits a ductility
comparable to most ordinary alloys. This solubility allows alloying with many of the elements to
modify both the mechanical properties and the transformation properties of the system. Excess
nickel, in amounts up to about 1%, is the most common alloying addition. Excess nickel strongly
depresses the transformation temperature and increases the yield strength of the austenite. Other
frequently used elements are iron and chromium (to lower the transformation temperature), and
copper (to decrease the hysteresis and lower the deformation stress of the martensite). Because
common contaminants such as oxygen and carbon can also shift the transformation temperature
and degrade the mechanical properties, it is also desirable to minimize the amount of these
elements.

One of the biggest challenges in using this family of alloys is in developing the proper processing
procedures to yield the properties desired. Because of the reactivity of the titanium in these alloys,
all melting of them must be done in a vacuum or an inert atmosphere. Methods such as plasma-arc
melting, electron-beam melting, and vacuum-induction melting are all used commercially. After
ingots are melted, standard hot-forming processes such as forging, bar rolling, and extrusion can be
used for initial breakdown. The alloys react slowly with air, so hot working in air is quite successful.
Most cold-working processes can also be applied to these alloys, but they work harden extremely
rapidly, and frequent annealing is required. Wire drawing is probably the most widely used of the
techniques, and excellent surface properties and sizes as small as 0.05 mm (0.002 in.) are made
routinely.

Fabrication of articles from the Ni-Ti alloys can usually be done with care, but some of the normal
processes are difficult. Machining by turning or milling is very difficult except with special tools and
practices. Welding, brazing, or soldering the alloys is generally difficult. The materials do respond
well to abrasive removal, such as grinding, and shearing or punching can be done if thicknesses are
kept small. Heat treating to impart the desired memory shape is often done at 500 to 800 °C (950 to
1450 °F), but it can be done as low as 300 to 350 °C (600 to 650 °F) if sufficient time is allowed. The
SMA component may need to be restrained in the desired memory shape during the heat treatment;
otherwise, it may not remain there.
Copper Based Alloys
They are available in ternary Cu-Zn-AI and Cu-AI-Ni alloys, or in their quaternary modifications
containing manganese. Elements such as boron, cerium, cobalt, iron, titanium, vanadium, and
zirconium are also added for grain refinement

The melting of Cu-base shape memory alloys is similar to that of aluminium bronzes. Most
commercial alloys are induction melted. Protective flux on the melt and the use of nitrogen or inert-
gas shielding during pouring are necessary to prevent zinc evaporation and aluminium oxidation.
Powder metallurgy and rapid solidification processing are also used to produce fine-grain alloys
without grain-refining additives. Copper-base alloys can be readily hot worked in air. With low
aluminium content (<6 wt%), Cu-Zn-AI alloys can be cold finished with interpass annealing. Alloys
with higher aluminium content are not as easily cold workable. Cu-Al-Ni alloys, on the other hand,
are quite brittle at low temperatures and can only be hot finished. Manganese depresses
transformation temperatures of both Cu-Zn-AI and Cu-AI-Ni alloys and shifts the eutectoid to higher
aluminium content. It often replaces aluminium for better ductility.
Applications
Biomedical
The blood-clot filter developed by M. Simon. The Ni-Ti wire is shaped to anchor itself in a vein and
catch passing clots. The part is chilled so it can be collapsed and inserted into the vein, then body
heat is sufficient enough to turn the part to its functional shape.

The atrial septal occlusion device is employed to seal the atrial hole. The atrial hole is located
between the two upper heart chambers upon the surface that splits the upper part of the heart into
the right and left atria. The anomaly occurring when this hole is open can reduce life expectancy.
The traditional surgery that fixes this anomaly is extremely invasive and dangerous. The thorax of
the patient is opened and the atrial hole is sewn. Because of the intrinsic risks of this surgery, several
problems might occur. The atrial septal occlusion device is an alternative to this surgery. This device
is composed of SMA wires and a waterproof film of polyurethane. As is the case for the Simon filter,
the surgery to place this device exploits the shape memory effect, being much less invasive than the
traditional one. First, one half of the device is inserted through a catheter by the vena cava up to the
heart, in its closed form. Then, it is placed on the atrial hole and opened, recovering its original
shape. Next, the second half of the device is placed by the same route as the first one, and then both
halves are connected. This procedure seals the hole, avoiding blood flow from one atrium to the
other. It is expected that the device will stay in the heart for an indefinite period of time since the
heart tissue regenerates.

Self-expanding stents, named after the dentist C.T. Stent, are another important cardiovascular
application that is used to maintain the inner diameter of a blood vessel. Actually, these devices are
used in several situations in order to support any tubular passage such as the esophagus and bile
duct, and blood vessels such as the coronary, iliac, carotid, aorta and femoral arteries. In this type of
application, a cylindrical scaffold with shape memory is placed, for example, inside a blood vessel
through a catheter. Initially, this scaffold is pre-compressed in its martensitic state. As the scaffold is
heated, due to the body temperature, it tends to recover its original shape, expanding itself. This
device can be used not only in the angioplasty procedure, in order to prevent another obstruction of
a vessel, but also in the treatment of aneurysms for the support of a weakened vessel

The spinal vertebra spacer is one. The insertion of this spacer between two vertebrae assures the
local reinforcement of the spinal vertebrae, preventing any traumatic motion during the healing
process. The use of a shape memory spacer permits the application of a constant load regardless of
the position of the patient, who preserves some degree of motion. This device is used in the
treatment of scoliosis.

Another application in the orthopedic area is related to the healing process of broken and fractured
bones. Several types of shape memory orthopedic staples are used to accelerate the healing
process of bone fractures, exploiting the shape memory effect. The shape memory staple, in its
opened shape, is placed at the site where one desires to rebuild the fractured bone. Through
heating, this staple tends to close, compressing the separated part of bones. It should be pointed out
that an external device performs this heating, and not the temperature of the body. The force
generated by this process accelerates healing, reducing the time of recovery. These plates are
primarily used in situations where a cast cannot be applied to the injured area, i.e., facial areas,
nose, jaw and eye socket. They are placed on the fracture and fixed with screws, maintaining the
original alignment of the bone and allowing cellular regeneration. Because of the shape memory
effect, when heated these plates tend to recover their former shape, exerting a constant force that
tends to join parts separated by fractures, helping with the healing process.
Orthopedic treatment also exploits the properties of SMA in the physiotherapy of semi-standstill
muscles. Wires reproduce the activity of hand muscles, promoting the original hand motion. The
two-way shape memory effect is exploited in this situation. When the glove is heated, the length of
the wires is shortened. On the other hand, when the glove is cooled, the wires return to their former
shape, opening the hand. As a result, semi-standstill muscles are exercised.