CHAPTER 1

1.1 Introduction
New materials are kept on being developed for enhanced the performance as per
the need from engineering field. Out of them there is group of material which has
properties to give a respond for a particular stimulus. Thermo response and
magneto response materials. Thremoresponse material stimulates by providing
heat which changes the physical and/or chemical properties of the material. For
magneto responsive material stimulates by creating the magnetic field.
Technically speaking, these materials are known as the stimulus-responsive
materials which include shape memory alloys.
Shape-memory alloys (SMAs) are a unique class of metallic alloys that exhibit
two outstanding properties namely the shape-memory effect and superelasticity.
These properties which make them different from the ordinary materials are based
on the diffusionless transformation in solid. The shapememory effect allows the
material to recover its original geometry during heating, after being deformed.
Superelasticity enables the material to withstand large cyclic deformations,
without residual strains, while developing a hysteretic loop. The formation of this
hysteretic loop translates into the ability of the material to dissipate energy. Due
to these inherent wonderful properties, SMAs have been progressively introduced
in new technological applications related with energy dissipation in civil
engineering structural design and in vibration control devices. Technological
application built up of shape memory alloys are designed to take advantages of
their characteristics properties like shape memory effect and super elasticity. The
shape memory effect is a unique property of shape memory alloys that exhibit
martensitic transformation, which enables the material to recover its original
shape, after being deformed upon heating to a critical temperature. Super
elasticity is associated with large non-linear recoverable strains during a
1

mechanical cycle of loading and unloading. There are two types of shape memory
alloy SMA (Shape Memory alloy), one way shape memory and two way shape
memory alloy. In one way shape memory alloy the metal can be stretched or bend
when that metal is in cold state. This will retain the similar shape till the heating
level reaches the transition temperature. In two way shape memory type, the
materials reflect one of its properties when it is in cold condition and reflects
another property when it is heated.

1.2 Brief History

The discovery of martensite in steels in the 1890s by Adolf Martens was a major
step toward the eventual discovery of shape memory alloys. The martensitic
transformation was perhaps the most widely studied metallurgical phenomenon
during the early 1900s. The martensitic transformation, as observed in the Fe-C
system, was established as an irreversible process.
The concept of thermoelastic martensitic transformation, which explained the
reversible transformation of martensite, was introduced in 1949 by Kurdjumov
and Khandros , based on experimental observations of the thermally reversible
martensitic structure in CuZn and CuAl alloys.By 1953,the occurance of
thermoelastic martensitic transformation was demonstrated in other alloys such
as InTl and CuZn.

Table 1: Properties of different SMA alloys (by AMT)

The reversible martensitic transformation and the alloys that exhibited them
remained unutilized until 1963. The breakthrough for engineering applications
occurred with the discovery of Ni-Ti by Buehler and coworkers while
investigating materials useful for heat shielding. It was noticed that in addition to
its good mechanical properties, comparable to some common engineering metals,
the material also possessed a shape recovery capability. Following this
observation, the term NiTiNOL was coined for this Ni-Ti material in honor of
its discovery at the Naval Ordnance Laboratory (NOL). The term Shape Memory
Effect (SME) was given to the associated shape recovery behavior. The discovery
of Nitinol spearheaded active research interest into SMAs. 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 Ni-Ti 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
3

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. Meanwhile, 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.

Properties

Ni-Ti Alloy

Stainless Steel

Melting point(C)

1310

1450

Density(gm/cc)

6.5

Electrical
Resistivity(/cm)

76(M)/82(A)

72

Thermal
Expansion(10-6/C)

6.6(M)/11(A)

17.3

Thermal

18

16.3

Conductivity(W/m-C)

Elastic Modulus(Gpa)

40(M)/75(A)

193

Tensile Strength(Mpa) >1240

517(Annealed)/862(cold w

Corrosion Resistance

Extremely high

High

Wear Resistance

Exceptionally high

High

Cost ($./kg)

158.70-300

0.5-6.0

Since the initial discovery of Nitinol in 1963, many commercial applications have
been developed. During the 1970s, several uses of Ni-Ti in biomedical
applications appeared, but it wasnt until the 1990s that Ni-Ti 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.

1.3 OBJECTIVES OF STUDY

Our objective is to understand the effect of stress induced phase transtormation
on the system dynamics. We find that the stress induced phase transformation

within the material has two effects: the resonance frequency of the system is
lower and the peak response near the resonance is heavily suppressed.
Furthermore, both of these effects depend on the forcing amplitude and they are
more pronounced at large forcing amplitudes. We also find that nonlinearity
associated with the phase transformation gives rise to complicated dynamics. In
particular, period-three responses are found for some forcing parameters.
It the case of a biased load, period-doubling cascade and chaotic motion can
occur. However, this complicated dynamics disappears at large forcing
amplitudes, making the shape memory alloy vibration isolator an effective device
at large forcing amplitudes.
Cyclic loading is one of the generic characteristic features of many of the present
and potential future applications of Ni-Ti shape memory alloys, no matter
whether they exploit mechanical (pseudo-elasticity) or thermal shape memory
(one and two way effect). Cyclic loading may well be associated with structural
and functional fatigue, which both limit the service life of shape memory
components. By structural fatigue we mean the microstructural damage that
accumulates during cyclic loading and eventually leads to fatigue failure. There
is a need to understand how microstructures can be optimized to provide good
fatigue resistance. The term functional fatigue indicates that shape memory
effects like the working displacement in a one way effect (1WE) actuator or the
dissipated energy in a loadingunloading cycle of a pseudo-elastic (PE) damping
application decrease with increasing cycle numbers. This is also due to a gradual
change in microstructure. In both cases it is important to know how fatigue
cycling affects shape memory properties. The present paper considers structural
and functional fatigue of NiTi shape memory alloys. It discusses four cases of
fatigue in NiTi shape memory alloys:

(1) The evolution of the stressstrain hysteresis in low cycle pullpull fatigue of
pseudo-elastic Ni-Ti wires.
(2) Crystal structure and phase Diagram.
(3) Strain localization during the stress induced formation of martensite.
(4) Generic features of functional fatigue in Ni-Ti shape memory actuator springs.
The report shows that fatigue of shape memory alloys is a fascinating research
field and highlights the need for further work in this area.

CHAPTER 2

2. Characteristics of shape memory alloys

2.1Martensitic transformation
In near-equiatomic Ni-Ti alloys martensite forms on cooling from the body
centered cubic high temperature phase, know as austenite, by a shear type of
process. This martensitic phase is heavily twinned. The transformation which
yields super elasticity and the shape-memory effect is diffusion less phase
transformation in solids, called martensitic transformation. During this
transformation, the atoms are cooperatively rearranged into a different crystalline
structure with identical chemical composition, through a displacive distortion
process.

Figure 2.1 Temperature deformation curve of SMAs

In SMAs, the martensitic transformation changes the material from the parent
phase, a high-temperature (high-energy) phase called austenite, to a lowtemperature phase (low-energy) called martensite shows in Figure 2.1. During
the transformation from the high-temperature phase to the low temperature phase,
these martensitic variants are formed in a twinned pattern, in which the atoms
8

achieve displacements with mirror symmetry. This occurs since the crystal lattice
strives to achieve minimal potential energy states for a given temperature. If a
deformed martensite is now heated, it reverts to austenite. The crystallographic
restrictions are such that it transforms back to the initial orientation, thereby
restoring the original shape. The transformation from austenite to martensite and
the reverse transformation from martensite to austenite do not take place at the
same temperature. A plot of the volume fraction of martensite as a function of
temperatures shown in Figure 2.2.The complete transformation cycle is
characterized by the following temperatures: austenite start temperature (As),
austenite finish temperature (Af), martensite start temperature (Ms) and
martensite finish temperature (Mf)

Figure 2.2 Temperature % austenite composition graph

2.2 Shape memory effect

The other manifestation of the thermoelastic martensitic transformation in SMAs
is the so called shape memory effect. Whereas stressed induced martensite
consists of a single preferential variant according to the applied stress, martensite
produced by cooling consists of a random mixture of several variants (including
9

twins). Twin boundaries can be relatively easily moved by the application of

stress. When the twin boundaries of the crystal are moved due to application of
the stress it will results in the change of the lattice orientation this phenomenon
is known as detwinn. During the detwinning process of the martensitic crystal
structure, when facing a unidirectional loading, the stress remains almost constant
until the martensite is completely detwinned. Crystals favourably aligned to the
load direction deform first, at a lower stress level, (o-a-b) in Figure 2.3 Less
favourably aligned crystals deform later, at higher stresses (b-c). Further straining
causes the elastic loading of the detwinned martensite (c-d). Unloading from any
point in (o-d) initially results in elastic unloading of the detwinned material. The
deformation recovered is much smaller than the one supplied by detwinning,
giving the apparent impression of permanent deformation. This deformation can
be recovered by raising the temperature above Af, transforming the detwinned
martensite back to austenite. This shape is maintained during cooling below Mf,
when the material re-transforms to twinned martensite. Straining further than
point (d) will first cause the slipping of the martensite lattices and eventually lead
the specimen to failure, corresponding to point (e). The force exerted by a
specimen when it transforms from martensite to austenite is associated with a
first-order phase transition, involving enthalpy of transformation. During this
transition, the system absorbs an amount of energy, through heating. This force
may be much higher than the force needed to deform the martensite specimen,
causing it to detwinn.

10

Figure 2.3 Shape memory effect

There are two categories of shape memory effect namely one way shape memory
effect and two way shape memory effect. In one way memory effect material
remembers its shape only in cold state where as in two way shape memory effect
it will remembers their original shape in both cold and heat condition.

2.3 Super elasticity

When a unidirectional stress is applied to an austenitic specimen, within a
temperature range between Af and Md (Md > Af), an elastic distortion of the
austenitic lattice starts to occur (o-a). There is a critical value (a) whereupon
austenite becomes unstable and a transformation from austenite to stress-induced
martensite (SIM) takes place; see Figure 5 in which stress strain curve shows as
the deformation proceeds the stress remains almost constant until the material is
fully transformed (a-b). During this part of the response the two phases coexist.
Upon stress removal, the elastic unloading of the detwinned martensite (b-c) takes
place. Since martensite becomes unstable below a critical stress (c) a reverse

11

transformation occurs as the unloading process continues. Detwinned martensite

reverts back to austenite, at a lower stress plateau than during loading (c-d).

Figure 2.4 Stress-strain curve of SMAs

When the material is fully transformed to the parent phase (d) further unloading
will follow the initial loading path, with full recovery of the deformation shows
in Figure.6. A hysteretic effect is hence produced. If the temperature is greater
than Af, the strain attained during loading is completely recovered at the end of
the unloading. This process is translated by an energy-absorption capacity with
zero residual strain, called super elasticity.

12

2.4 Crystal structure of Ni-Ti alloys

Equiatomic Ni-Ti may exhibit two polymorphic diffusionless martensitic
transformations upon cooling, involving three phases. The high temperature
phase is austenite. It may transform to an R-phase and a martensite phase upon
cooling. Figure 2.5 shows the crystal structures of the three phases, where the
black and white lattice points represent Ni and Ti atoms, respectively. The
austenite has a B2 structure. It has two atoms in the unit cell, with each Ni and Ti
has the equal chance to occupy the black and white locations. The lattice
parameter of austenite is a = 0.301 nm.
Martensite phase (B19) has monoclinic crystal structure. Its lattice parameters
are a = 0.289 nm, b = 0.412 nm, c = 0.462 nm and = 96.8. Martensite may form
from the austenite by either lowering the temperature or by the application of
force.
The R-phase was known to have rhombohedral structure initially but later proven
to be trigonal structure with lattice parameters of a = 0.738 nm and c = 0.532 nm.
This R-phase appears upon cooling prior to the martensite phase with sequence
transformation of ARM. Upon heating, this R-phase appears prior to the
austenite phase with sequence of transformation of MRA. This intermediate
R-phase can appear under certain conditions. These include aging treatment at
temperatures between 400C-500C for materials having nickel content greater
than 50.5at%, addition of third elements such as iron (Fe) or aluminium (Al)
which suppress a martensitic transformation, and cold working followed by
annealing at temperatures between 400C-500C.

13

Figure 2.5 Crystal structures of (a) B2 NiTi (austenite) phase (b) B19 NiTi (martensite) phase (c) R-trigonal
phase

In Ni-Ti binary system, there are two other stable intermetallic phases exist i.e.
Ti2Ni and TiNi3. Ti2Ni has a cubic crystal structure with lattice parameter of a =
1.132 nm. The unit cell contains 96 atoms, with 64 Ti atoms and 32 Ni atoms. In
conjunction, Ti2NiOx may also form. This phase has practically identical structure
and contains minor amount of oxygen, thus extremely difficult to differentiate
from Ti2Ni. This phase has caused much confusion and has often been
misinterpreted as Ti2Ni in the literature. A subtle difference between these two
phases is that Ti2NiOx has a slightly larger lattice parameter (a = 1.133 nm), since
it accommodates oxygen atoms.
TiNi3 has a hexagonal crystal structure with lattice parameters of a = 0.51 nm and
c = 0.832 nm. The unit cell contains 16 atoms with four Ti atoms and twelve Ni
atoms. These Ti2Ni and TiNi3 have more complex structures compared to the NiTi crystal structure.
As mentioned above, Ni-rich B2-NiTi may undergo diffusive reactions to form
precipitates. There are three forms of Ni-rich precipitates, including Ti3Ni4,
Ti2Ni3 and TiNi3, with the former two being metastable. Ti3Ni4 forms as
precipitates in the early stage of aging. It is coherent to the matrix. It has
rhombohedral structure with lattice parameters of a = 0.670 nm and = 113.8.
14

Ti2Ni3 is known to form as an intermediate phase prior to the formation of the

final product, TiNi3. This phase has 3 different crystal structures with each
formation dependent on temperature. The high, intermediate and low temperature
structures have tetragonal, orthorhombic and monoclinic structures, respectively.
Much attention has been given to Ti3Ni4 instead of Ti2Ni3 since this phase has
direct influence on the shape memory behaviour of Ni-Ti.

2.5 Phase diagram of Ti-Ni alloy system

Although there are many SMAs, such as Ti-Ni, Cu-Al-Ni, Cu-Zn-Al, Au-Cd, MnCu, Ni-Mn-Ga, and Fe-based alloys, most of the practical SMAs are Ti-Ni-based
alloys, since other SMAs are usually not ductile (or not ductile enough) or are of
low strength and exhibit grain-boundary fracture. Ti-Ni-based alloys are superior
to other SMAs in many respects. They exhibit 5060% elongation and tensile
strength as high as 1000 MPa. To our knowledge, they possess the best
mechanical properties among intermetallics and can be used as structural
materials as well. They also have a very high resistance to corrosion and abrasion.
In this section, we will describe the phase diagram of Ti-Ni, martensitic
transformations in Ti-Ni-based alloys, and other characteristics of the alloy
system.
The phase diagram of the Ti-Ni alloy shown in Figure 6 is essentially based on
Massalskis diagram although the dotted line for eutectoid decomposition at
650C is deleted. The presence or absence of the eutectoid decomposition was
controversial for many years, but its absence is now established. In the diagram,
we see a triangular region designated Ti-Ni near the equiatomic composition.
This phase has a bcc structure at temperatures above 1090C (dotted line), and a
B2 (cubic) ordered structure below that temperature.29 If an alloy is quenched
from the B2 region, a martensitic transformation occurs from B2 to
B19_(monoclinic)30 martensite below the respective Ms temperature (the bcc-toB2
15

orderdisorder transformation is insuppressible during quenching). If a ternary

element is added to the binary alloy, or the binary alloy is subjected to suitable
heat treatments, other martensitic transformations also occur. Thus, if a few
percent of Fe or Al is added, or if a Ni-rich Ti-Ni alloy is aged, a B2 to R (trigonal,
or

R-phase)

transformation

occurs

prior

to

the

subsequent

to

B19transformation. This B2R martensitic transformation is especially

important, since it is associated with a temperature hysteresis as small as 12 K.
Thus, this transformation is extremely important for actuator applications,
although the associated strain is small (0.51%, depending upon temperature).
Similarly, if more than 7.5% Cu is added to the binary alloy, a B2 to B19
(orthorhombic)32 martensitic transformation occurs prior to the subsequent B19
B19_ transformation. This B2B19 transformation is also important, since it is
associated with a small temperature hysteresis of 410C, depending upon Cu
content. Thus, we have three martensite structures in Ti-Ni-based alloys,
dependent upon composition and heat treatment. Among these, B19is the most
stable at 0 K. Thus, the other two martensites have a tendency to transform to
B19 with decreasing temperature.
One of the characteristics of the phase diagram in Figure 6 is that the solubility
in Ti-Ni changes with temperature on the Ni-rich side. This means that
precipitationhardening may be used on the Ni-rich side. On this side, the stable
precipitate phase is TiNi3, but other metastable phases, Ti3Ni4 and Ti2Ni3, also
exist, and the Ti3Ni4 phase appears at shorter aging times and at lower aging
temperatures.37 This Ti3Ni4 phase is especially important for improving shapememory characteristics and strength, since it precipitates on a very fine scale.
Furthermore, the precipitation process can be used to adjust transformation
temperatures which is extremely important to the practical application of SMAs,
since the Ms temperature changes more than 100 K for a 1% change in
composition. For that purpose, the metastable equilibrium between Ti-Ni and

16

Ti3Ni4 phases (see inset of Figure 2.6), which has been determined recently is
very useful.

Figure 2.6 Phase diagram of Ti-Ni alloy by Massalski et al.

Precipitation-hardening cannot be used on the Ti-rich side in bulk alloys, since

the solubility limit is nearly vertical with temperature on this side. However, in
sputter-deposited thin films, precipitationhardening is also usable, since thin
films are fabricated through the amorphous state. For this reason, the Ti-rich
region has attracted attention recently in research on thin films. This will be
discussed in detail in the article by Ishida and Martynov in this issue. To
summarize, the Ti-Ni alloy system is very interesting, since the alloy can be
improved by utilizing various phase transformations, both diffusional and
diffusionless, in addition to its many other advantages. In this respect, the Ti-Ni
alloy system is very similar to steels, in that various phase transformations can be
successfully utilized to improve it.

17

2.6 Ductile nature of intermetallic Ti-Ni alloys

The ductility of Ti-Ni alloys is quite remarkable among many intermetallics,
which are usually brittle. As typically shown in Fig. 8 elongation more than 50%
is easily obtained. Thus, the discussion will be useful for improving ductility in
other intermetallics. The temperature dependence of elongation is important, as
shown in Fig. 2.8. It indicates that elongation becomes maximum around the Ms
temperature. This is a clear manifestation that the high ductility is closely related
with the presence of the martensitic transformation. We now raise various factors,
which assist the high ductility in the alloy system.
2.

There are 24 habit plane variants upon stress-induced martensitic

transformation. This means that there are 24 deformation modes upon
stress-

induced transformation.
2. There are many twinning modes in the martensite.
3. Anisotropy factor A is as low as _2 in Ti-Ni alloys. Thus the grain boundary
fracture due to elastic anisotropy may be avoided.
4. Grain size is usually very small. Typically <30 mm. This is in sharp contrast
to those of b-phase alloys, which are typically >1 mm.

Figure 2.7 Tensile stress-strain curves of Ti50.6Ni alloy deformed at 243K (>Af). Dotted lines represent
the recovered strain upon heating to 373 K. The symbol (x) represents the fracture point.

18

5. The critical tensile stress for slip is very low at Ms (less than 50MPa), while
that in the parent phase for the same single crystal is about 400Mpa.
In fact, the combination of these factors make the Ti-Ni very ductile, e.g. If
only the item 1 is important, then we can expect that all b-phase alloys exhibiting
the martensitic transformation are ductile.

Figure 2.8 Temperature dependence of the elongation of Ti-51Ni alloy

However, most of the b-phase alloys are quite brittle, because the anisotropy
factor is usually as high as 1015, the grain size are large and the critical stress
for slip are usually high. Thus, we can now understand that the ductility of Ti-Ni
alloy system is based on the availability of these various factors. According to
Fig. 9, the ductility decreases at high temperatures

CHAPTER 3
19

3.Production of porous Ti-Ni shape memory alloys

Experimental procedure
3.1. Materials used
Prealloyed, spherical Ti-Ni powders (Ti-50.6 at. %Ni, 99.9% purity), shown in
Figure 1a, were used to produce porous Ti-Ni specimens, while spherical Mg
powders (Figure 3.1a) (99.82% purity) were employed to provide a nonoxidizing
atmosphere upon vaporization during sintering. The Ti-Ni powders exhibited
Gaussian (log-normal) particle size distribution with a mean diameter of 21,
while the particle size of the Mg powders was in the range of 250 to 600m,
averaging 450m.The Ti-Ni powders were completely austenitic at ambient
temperature (22 2 C), as confirmed by X-ray diffraction (XRD) (Figure 3.1a)
and scanning electron microscopy (SEM) (Figure 3.1b) techniques.

Figure 3.1 Microstructure of Ni-Ti powder(a) and (b)

3.2. Production technique

The production method used in the present study was as follows: Ti-Ni powders
were blended using a 5% wt polyvinyl alcohol (PVA) solution (2.5% wt PVA +
water) as the binder prior to compaction. Blended prealloyed Ti-Ni powders and
20

binder mixtures were consolidated in a double-ended steel die using a hydraulic

press at a pressure of 770 MPa, which was determined to be optimum from
preliminary experiments conducted at different pressures in the range of 1901150 MPa. The amount of Mg added into the crucible alongside the compacted
specimen before sintering was 12% of the weight of the Ti-Ni compact. The
sintering process was conducted at 1100 C for 1 h in a purified argon atmosphere.
Titanium was used as the getter to clean the Ar gas. Sintered porous specimens
were cooled in the cold zone of the furnace at a rate of approximately 60-75
C/min, sufficient to prevent formation of intermetallics other than Ti-Ni due to
possible oxidation problems that may occur during furnace cooling.

3.3. Heat treatment

A few samples were aged at 400 C for 1 h under a protective, inert Ar gas
atmosphere in a tube furnace subsequent to the sintering process. Solutionizing
prior to aging was not required since preliminary experiments showed that the assintered samples did not contain secondary phases to be dissolved. Aging
temperature and time employed were chosen on the basis of optimizing the
superelastic properties, considering the literature survey results for bulk Ti-Ni
alloys with the same composition. To minimize the oxidation during aging,
porous Ti-Ni alloys were embedded in Mg powders before processing. Porous
Ti-Ni alloys held in the cold zone initially were placed into the hot zone of the
furnace when it reached the aging temperature. After aging for 1 h at 400C,
samples were moved again to the cold zone and cooled there for 3 min. They were
then removed from the furnace and cooled by spraying alcohol onto them
immediately. The total cooling time was less than 4 min. Quenching was not
performed, since it results in considerable oxidation.

4.4. Characterization methods

Density and porosity content of the green compacts and porous Ti-Ni specimens
produced were determined employing Archimedes principle. A Rigaku D/Max
2200/PC model X-ray diffractometer was used for phase analysis. The pore
21

characteristics and microstructure of the produced specimens were revealed using

a JEOL JSM 6400 scanning electron microscope equipped with Noran System 6.
Pore sizes were determined using a Quantachrome PoreMaster 60 mercury
porosimeter. Phase transformation temperatures of the Ti-Ni powders and porous
Ti-Ni alloys were measured with a PerkinElmer Diamond differential scanning
calorimeter (DSC) through the temperature range of 60 to 150 C, with a heating
and cooling rate of 10 C/min and under nitrogen atmosphere. Superelasticity
tests were conducted cyclically at a constant stress of 380 MPa in compression at
room temperature, using a 30-Kn capacity Instron 3367 mechanical testing
system at a constant crosshead speed of 0.1 mm/min, and cylindrical specimens
of 10 mm in both diameter and height.

Figure 3.2 XRD pattern showing ordered B2 austenite peaks

in the parent phase significantly, but it is still higher (>20%) compared to those
of most intermetallics. Since stress-induced transformations and twinning in
martensites do not contribute to ductility at such high temperatures the high
ductility may be explained as follows. Firstly, items 3 and 4 are still valid at high
temperatures. Secondly, we focus attention on the low value of elastic constant
c44 in Ti-Ni based alloys. In fact, c44 in Ti-Ni based alloys are smaller than 1/3
of that of other B2 type intermetallics with similar melting point such as Ni-Al.
The abnormally low c44 leads to a low Peierls stress for {110}h001i slip system,
which is the operating system in Ti-Ni alloy. Thus, the combination of items 3
22

and 4, and the low value of c44 may be the origin for the high ductility at high
temperatures. Besides, there is a report that {112} and {114} twinning modesare
present even in the parent phase, which increase the available deformation modes.
Apparently these also assist to increase in ductility in the parent phase. However,
there may be a possibility that these twins were introduced by stress-induced
transformation, since mechanical twinning in ordered alloys do usually not
operate easily. These points should be examined more carefully.

CHAPTER 4
23

Applications of shape memory alloys

Since SMAs have unique properties which ordinary metals do not have, they have
high potentiality for many applications. In fact, more than 10,000 patents have
been proposed in the past, and it is difficult to classify all the applications. Thus,
in the following we introduce only successful applications utilizing shape
memory effect and superelasticity, respectively.

4.1. Applications using shape memory effect

This type of applications may be summarized as follows.
1. couplings;
2. actuators;
3. smart materials.
Couplings are the first most successful applications of SMAs, which were
developed by Raychem Corp. to hydraulic systems of F-14 jet fighters. Electric
connectors for IC developed by the same company belong to the same category.
Applications as actuators were carried out in various fields such as in electric
appliances, automobile devices, robotics etc. We introduce one recent example
of application for a thermostatic mixing value in Fig. 22. The apparatus consists
of a SMA coil spring and a bias spring, which are opposing to each other. When
the temperature of mixed water is too high, the SMA expands and the bias spring
shrinks, since SMA spring is stronger than the bias spring, resulting in a smaller
opening for hot-water and a larger opening for cool water, while when the
temperature of mixed water is low, vice versa.

24

Figure 4.1 Mixing valve

In fact, it is possible to control the temperature linearly due to the ClausiusClapeyron relationship, shows the appearance of this type of mixing value. For
the above purpose, wax type actuators were used in the past, but the thermal
conductivity of wax is very bad, thus resulting in slow response and overshooting.
On the other hand, thermal conductivity of SMA is good, resulting in excellent
thermal response. Thus, the superiority of SM actuator over wax one is apparent.
SMA used as an actuator described in the above has a role as a sensor as well as
an actuator. Thus, SMAs are smart (or intelligent) materials. The possession of
the dual function leads to the miniaturization of actuators, and thin films are
expected from this point of view. Another type of smart materials are composites
of Ti-Ni SMAs with polymer or metal matrix. The Ti-Ni wires embedded in
polymers may be used for vibration control of space vehicles, since the elastic
constants can be changed widely by changing the temperature in the
transformation temperature range [111]. The Ti-Ni wires embedded in Al matrix
may be used to strengthen Al matrix by the same mechanism of prestressed
concrete.

4.2. Applications using superelasticity

Superelasticity, which is a non-linear pseudoelasticity as much as 78%, was also
successfully applied in various fields. The first application was to orthodontic
arch wire, which made the orthodontic therapy much easier and effective. The
second quite successful one was to brassieres for women. The third one is to the
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antennas for cellular phones as shown in Fig. 4.2. This is quite popular all over
the world now, since superelastic wire is quite flexible and is not subject to
damage. The fourth, which is actually the third in time sequence, is guide wires
for catheters in medical use, as shown in Fig. 4.3.A catheter, which is a tube made
of plastics, is a standard tool for diagnosing the circulatory system by injecting a
contrast medium into vessels or for medical treatment by dilating a lumen of
blood vessel at the site of the obstruction. To introduce the catheter in a required
place of the vessel in brain, heart, lever etc., a guide wire is necessary. Previously
a thin stainless steel wire was used for this purpose. However, it is being
overtaken by Ti-Ni super elastic wire recently, since the latter is more flexible
and is not permanently bent. Thus, this application is expanding rapidly. The
above descriptions on applications of SMAs were rather sketchy.
In the above, we tried to review most of the recent developments of SMAs, but
we omitted some, since one of the purposes of the present overview is to introduce
this field to the readers of Intermetallics in general. Modeling of SMAs' is such a
missed topic. We also omitted the developments on Fe-based and Cu-based
SMASs.

Figure 4.2 Superelastic antenna for a cellular phone.

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Figure 4.3 Superelastic guide wire for a catheter in medical use. (a)Applications for brain; (b) appearance
of a guide wire. See text for details. (Courtesy of Terumo Corp.).

4.3 Ni-Ti SMAs in orthopedic applications

Shape memory alloys are a group of metallic materials with some unusual
properties such as one-way and two-way shape memory effects, superelastic
effect, high damping property and rubber-like effect. These characteristics make
the material suitable for different orthopedic applications such as load-bearings,
plates for bone fracture repair, internal fixators for long bone shafts, spinal
correctors, vertebral spacers and bone distraction devices. Some of these
applications are explained in the following subsections.

4.3.1. Spinal vertebral spacer

The spinal vertebral spacer is one of the applications of this material in
orthopedics. The insertion of the spacer (disc) between two vertebrae provides
the local reinforcement of the spinal column, avoiding any traumatic motion
during the healing process. The employ of a shape memory spacer enables the
use of a constant load regardless of the patient position with some degree of
motion. This device is used to treat scoliosis. Figure 4.4 presents spinal vertebrae
spacer in the in the original shape (right) and martensitic state (left).

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Figure 4.4 Spinal vertebrae spacer (Duerig, Melton et al. 1990)

4.3.2. Spinal rod

Shape memory rod has been applied as a tool to help the scoliosis correction
(Figure 3). NiTi is used in this application due to its ability to return to some
predefined shape when subjected to a thermal treatment. It is expected that the
spinal rod has the ability to keep the spine force loaded postoperatively, and it
appears that this will take the advantage of spine viscous behavior to obtain extra
correction. Furthermore, a postoperative fusion may prevent the long term failure
of the system. The additional postoperative correction is expected to be obtained
before the occurrence of this vertebral fusion.

Figure 4.5 Spinal rod; (A) The original rod shape in the cold condition, (B) The straightened rod before
insertion and heat treatment, (C) The implantation of straightened rod with anchorage system, (D) The
recovered original curve of the rod with anchorage system after heat treatment.

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4.3.3. Medical staples

Another application of Ni-Ti is related to the healing process of broken and
fractured bones, using the shape memory effect. The shape memory orthopedic
staples (Figure 4.6) are placed directly into the region of the break to compress
the two parts of the bone. These staples, in their opened shape, are implanted to
the fractured site of the bone, while through heating the staples tend to close,
compressing the separated part of fracture. In this application, the heating is
performed by an external device, and not due to the body temperature.

Figure 4.6 Medical staple before and after distraction

4.3.4. Plates for fractured bone

Shape memory plates also have been used to heal and recover the fractured bones,
in the injured area where it is not possible to apply cast such as facial areas, nose,
jaw, and eye socket. They are inserted to the fracture and fixed with intermediate
screws (Figure 4.7). This maintains the original alignment of the bone and enables
cellular regeneration. When these plates are heated, they tend to recover their
previous shape (because of the shape memory effect) and exert a constant and
uniform force on the two broken sections, which causes to join separated parts of
fractures and helps in the healing process.

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Figure 4.7 SMA plate for fractured human jaw bone and details of the plate and the screw (Machado and
Savi 2003)

4.4 Aircraft maneuverability

Maneuverability is defined as the ability to change the speed and flight direction
of an airplane in space. A highly maneuverable airplane, such as a fighter, has a
capability to accelerate or slow down very quickly, and also to turn sharply. Quick
turns with short turn radii place high loads on the wings as well as the pilot. These
loads are referred to as "g forces" and the ability to "pull g's" is considered one
measure of maneuverability. One g is the force acting on the airplane in level
flight imposed by the gravitational pull of the earth. Five g in a maneuver exerts
5 times the gravitational force of the earth.
An aircrafts maneuverability is determined by its ability to:
1. Change ATTITUDE around the aircrafts three axes (longitudinal, lateral,
and vertical).
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2. Change VELOCITY on the aircrafts three axes, and in the three spatial
dimensions (1 vertical and 2 horizontal).

Figure 4.8 Aircraft manueverability

Aircraft maneuverability depends heavily on the movement of flaps found at the

rear or trailing edge of the wings. The efficiency and reliability of operating these
flaps is of critical importance. Most aircraft in the air today operate these flaps
using extensive hydraulic systems. These hydraulic systems utilize large
centralized pumps to maintain pressure, and hydraulic lines to distribute the
pressure to the flap actuators. In order to maintain reliability of operation,
multiple hydraulic lines must be run to each set of flaps. This complex system of
pumps and lines is often relatively difficult and costly to maintain.
Many alternatives to the hydraulic systems are being explored by the aerospace
industry. Among the most promising alternatives are piezoelectric fibers,
electrostrictive ceramics, and shape memory alloys. The flaps on a wing generally
have the same layout shown on the left, with a large hydraulic system attached to
it at the point of the actuator connection. "Smart" wings, which incorporate shape
memory alloys, are typically like the wing this system is much more compact and
efficient, in that the shape memory wires only require an electric current for
movement

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4.5 Heat Engine

In the last years other shape memory heat engines with different function
principles were being developed at the HTWG and led 2009 to a new idea based
on the described tilted heat engine, see Fig. 4.10. The main difference of the new
heat engine is based in the function principle that will facilitate the conversion of
the complete phase change energy into mechanical energy. One of the approaches
consists in a revolving energy storage that could be realized in form of springs
that are blocked after the contraction of the shape memory wires in the water bath.
In the air the springs will be guided in their compressed form along a ring that
enables the springs to release their complete energy just in the moment before the
wires will dive again in the warm water bath. For sure, in this case the whole
system has to be tracked over an outside force (and not by the wires themselves
during their contraction). But with this new idea a considerable increase in the
efficiency of the energy conversion is expected that shall facilitate an effective
energy recovery of low-temperature waste energy of industrial processes.

Figure 4.10 Possible design of the novel heat engine

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CHAPTER 5

5.1 Conclusion
Shape memory alloys represent a very encouraging material to be used as active
elements for actuator and/or sensor applications in numerous technical fields.
Their advantages when using them as functional materials are undisputable and
widely recognized, e.g.: they offer a high working performance per volume, are
easily miniaturizable, allow noiseless and vibration-free motions in different
movement types and do not show susceptibility to electromagnetic fields. The use
of shape memory elements therefor enables the assembly of simple and compact
systems that economize weight, volume and costs. But in spite of this huge
potential their industrial use is still limited to very few applications in series or
volume production.
The many uses and applications of shape memory alloys ensure a bright future
for these metals. Research is currently carried out at many robotics departments
and materials science departments. With the innovative ideas for applications of
SMAs and the number of products on the market using SMAs continually
growing, advances in the field of shape memory alloys for use in many different
fields of study seem very promising. Future Applications There are many possible
applications for SMAs. Future applications are envisioned to include engines in
cars and airplanes and electrical generators utilizing the mechanical energy
resulting from the shape transformations. Nitinol with its shape memory property
is also envisioned for use as car frames. (Kauffman and Mayo, 7) Other possible
automotive applications using SMA springs include engine cooling, carburetor
and engine lubrication controls.

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5.2 References
[1]

Chopade Jayesh,Barjibhe Rahul and Kumar Bimlesh, Critical Review On

Shape Memory Alloy, International Journal of Engineering Research &
Technology

(IJERT) Vol. 2 Issue 2, February- 2013

[2] Kazuhiro Otsuka, Xiaobing Ren, Recent developments in the research of
shape memory alloys, Institute of Materials Science, University of
Tsukuba, Tsukuba, Ibaraki, 305-8573, Japan 6 May 1998.
[3] P. K. Kumar and D. C. Lagoudas, Introduction to Shape Memory Alloys
D.C. Lagoudas (ed.),Shape Memory Alloy, DOI: 10.1007/978-0-38747685-8 1, Springer Science+Business Media, LLC 2008.
[4] K. Otsuka and X. Ren, Physical metallurgy of TiNi-based shape
memory alloys, Progress in Materials Science 50 (2005) 511678.
[5] Tark Aydogmusand Ali Sakir BOR, Production and
characterization of porous TiNi shape memory alloys, Turkish J. Eng.
Env. Sci.35 (2011), 69 82.c_Tubitak doi:10.3906/muh-1007-127.
[6] Kazuhiro Otsuka and Tomoyuki Kakeshita, Science and Technology of
Shape-Memory Alloys: New Developments, MRS BULLETIN,
February 2002.
[7] J. Strittmatter, P. Gmpel , V. Gheorghita , Shape memory actuators
potentials and specifics of their technical use and electrical activation
Journal Of achievement in materials and manufacturing engineering,
vol.55 issue 2 december 2012.
[8] Marjan Bahraminasab and Barkawi Bin Sahari, NiTi Shape Memory
Alloys, Promising Materials in Orthopedic Applications, Chapter 10.
[9] Shape Memory Alloy, Shape Memory Alloy Suppliers and Manufacturer
Website, http://www.alibaba.com/showroom/shape-memory-alloy.html
[10] Shape Memory Effect, website,
http://www.aem.umn.edu/~shield/hane/shape.memory.html
[11] Material Science and Engineering An Introduction by William D.
Callister,Jr

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