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
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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.
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
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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
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16.3
Conductivity(W/m-C)
Elastic Modulus(Gpa)
40(M)/75(A)
193
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.
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
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
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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)
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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.
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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.
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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.
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R-phase)
transformation
occurs
prior
to
the
subsequent
to
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Ti3Ni4 phases (see inset of Figure 2.6), which has been determined recently is
very useful.
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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.
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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.
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
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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
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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
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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.
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.
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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.).
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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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Figure 4.7 SMA plate for fractured human jaw bone and details of the plate and the screw (Machado and
Savi 2003)
2. Change VELOCITY on the aircrafts three axes, and in the three spatial
dimensions (1 vertical and 2 horizontal).
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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]
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