A CASE STUDY REPORT

On

STUDY OF PHYSICAL METALLURGY AND SHAPE

MEMORY EFFECT OF Ti-Ni BASED ALLOYS

BY
P.ROSHAN (13118051)
AND
FAVAS K (13118024)
DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY, ROORKEE

Under the Esteemed Guidance of

Dr. K.S. SURESH
ASSISTANT PROFESSOR
DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING
IIT ROORKEE

LIST OF CONTENT:

Introduction
Shape memory alloys
Phase diagram of Ti-Ni- based alloys
Martensitic transformation in Ti-Ni- based alloys
Crystal structures of martensite in Ti-Ni- based alloys

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Shape memory and superelastic effect

2
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Applications of Ti-Ni- based alloys

4
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Reference

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Introduction:

Ti-Ni- based alloys are one of the most important shape memory alloys owing
to its good mechanical properties and lot of phase transformations taking place
in the alloy system. The phase transformation may be diffusion less martensitic
transformation which gives shape memory effect and super elastic effect or
diffusional transformation which can be used to improve the shape memory
property of the alloy. The equiatomic Ti-Ni based alloys also known as nitinol
whose properties depend on exact composition of the alloy, processing history
and small ternary additions in the alloy system. Titanium nickel is quite
sensitive to alloying element additions. Addition of Fe, Al, Cr, Co and V is used
to create a cryogenic shape memory alloy or to increase the separation of R
phase from martensite. Addition of copper is done to reduce hysteresis for
actuators applications. Ti-Ni- based alloys are extremely sensitive to the Ti to Ni
ratio for applications. For shape memory effect it has to be maintained in a
range of 49.7 o 50.7 in binary alloys. The density of equiatomic binary Ti-Ni
alloy is 6.45 to 6.5 gram per cubic centimeter.
Ti-Ni- based alloys exhibit lot of common characteristics with other shape
memory alloy exhibiting shape memory effect, superelasticity, 2 way shape
memory effect etc, they also exhibit properties which is uniquely restricted to
the alloy. The alloy has very low elastic anisotropy (of the order of 2) and the
structure of B19 martensite appears only in Ti-Ni- based alloys. The alloy has
excellent mechanical properties including good ductility (can be cold worked
upto 60%). Ti-Ni alloys forms TiO2 (rutile) passive layer which makes the alloy
resistant to severe corrosion. Because of these excellent properties exhibited, TiNi based alloys are commonly used in shape memory effect and superelasticity
applications.
The reason for such exceptionally good properties lie in the phase diagram of
Ti-Ni system which consists of many diffusional and diffusionless martensitic
transformations. Because of such good properties these alloys are widely used
for bio medical, superelastic and shape memory effects compared to other shape
memory alloys.

Shape memory alloys:

A shape-memory alloy is an alloy that remembers its original shape and that
when deformed returns to its pre-deformed shape when heated. The TiNi based
alloys are the most important practical shape memory alloys (SMA) with
excellent mechanical properties. SMAs can exist in two different phases, with
three different crystal structures (i.e. twinned martensite, detwinned martensite
and austenite) and six possible transformations can exist. Figure 8 represents the
hysteresis curve obtained on cooling and heating with martensite fraction. The
difference between the heating transition and the cooling transition gives rise
to hysteresis where some of the mechanical energy is lost in the process. The
shape of the curve depends on the material properties of the shape-memory
alloy, such as the alloying, and work hardening. NiTi alloys change
from austenite to martensite upon cooling; Mf is the temperature at which the
transition to martensite completes upon cooling. Accordingly, during
heating Asand Af are the temperatures at which the transformation from
martensite to austenite starts and finishes. The maximum temperature at which
SMAs can no longer be stress induced is called Md, where the SMAs are
permanently deformed. The transition from the martensite phase to the austenite
phase is only dependent on temperature and stress, not time, as most phase
changes are, as there is no diffusion involved. Similarly, the austenite structure
receives its name from steel alloys of a similar structure. It is the reversible
diffusionless transition between these two phases that results in special
properties. While martensite can be formed from austenite by rapidly
cooling carbon-steel, this process is not reversible, so steel does not have shapememory properties.

Figure 1 show plot of martensite fraction on heating and cooling.

A variety of alloys exhibit the shape-memory effect. Alloying constituents can

be adjusted to control the transformation temperatures of the SMA. Some
common systems include the following

Ni-Ti approx. 5560 wt% Ni

Ag-Cd 44/49 at.% Cd

Au-Cd 46.5/50 at.% Cd

Cu-Al-Ni 14/14.5 wt% Al and 3/4.5 wt% Ni

Cu-Sn approx. 15 at% Sn

Cu-Zn 38.5/41.5 wt.% Zn

Cu-Zn-X (X = Si, Al, Sn)

Fe-Pt approx. 25 at.% Pt

Mn-Cu 5/35 at% Cu

Fe-Mn-Si

Co-Ni-Al

Co-Ni-Ga

Ni-Fe-Ga

Ti-Nb

Ni-Ti-Hf

Ni-Ti-Pd

Ni-Mn-Ga

Shape-memory alloys have different shape-memory effects. Two common

effects are one-way and two-way shape memory. A schematic of the effects is
shown in figure 2.

One-way memory effect

When a shape-memory alloy is in its cold state (below As), the metal can be
bent or stretched and will hold those shapes until heated above the transition
temperature. Upon heating, the shape changes to its original. When the metal
cools again it will remain in the hot shape, until deformed again.
With the one-way effect, cooling from high temperatures does not cause a
macroscopic shape change. A deformation is necessary to create the lowtemperature shape. On heating, transformation starts at As and is completed at Af
(typically 2 to 20 C or hotter, depending on the alloy or the loading
conditions). As is determined by the alloy type and composition and can vary
between 150 C and 200 C.

Figure 2 illustrates one way and two way shape memory effect.

Two-way memory effect

The two-way shape-memory effect is the effect that the material
remembers two different shapes: one at low temperatures, and one at the hightemperature shape. A material that shows a shape-memory effect during both
heating and cooling is said to have two-way shape memory. This can also be
obtained without the application of an external force (intrinsic two-way effect).
The reason the material behaves so differently in these situations lies in training.

Training implies that a shape memory can "learn" to behave in a certain way.
Under normal circumstances, a shape-memory alloy "remembers" its lowtemperature shape, but upon heating to recover the high-temperature shape,
immediately "forgets" the low-temperature shape. However, it can be "trained"
to "remember" to leave some reminders of the deformed low-temperature
condition in the high-temperature phases. There are several ways of doing this.
A shaped, trained object heated beyond a certain point will lose the two-way
memory effect.

Phase diagram of Ti-Ni- based alloys:

The phase diagram of this system had been controversial for 30 years before its
establishment. The phase diagram of this system is important for heat treatments
of the alloy and improvement of shape memory characteristics. Our interests to
shape memory property of the alloy have restricted the phase diagram to the
central portion bound by Ti2Ni and TiNi3.

Figure 3 showing central portion of Ti-Ni phase diagram.

Figure 3 shows the central portion of Ti-Ni system relevant for shape memory
characteristics. On conducting extensive study on the system, presence of TiNi
phase was found out close to 50% atomic Ni. The compositional range of Ni at

which TiNi phase is found increased with temperature. Later, from the XRD
patterns it was concluded that TiNi decomposes eutectoidally to Ti2Ni and
TiNi3. The first martensitic transformation observed in Ti-Ni alloys was
transformation of TiNi phase to phase. This transformation was reversible and
occurred at a temperature low enough to prohibit diffusion controlled process.
Upon conducting extensive study of diffusion controlled transformation at
higher temperature three phases Ti3Ni4, Ti2Ni3 and TiNi3 appeared depending
upon the aging temperature and time. At lower aging temperature and shorter
aging time Ti3Ni4 is obtained while at higher aging temperature and time TiNi 3
is obtained. Ti2Ni3 is obtained at intermediate aging temperature and time. It
was observed that on prolonged heating Ti3Ni4 dissolves into the matrix and
Ti2Ni3 size increases and on further prolonged heating Ti2Ni3 dissolves into the
matrix and TiNi3 is formed. From the following observations it was concluded
that Ti3Ni4 and Ti2Ni3 are intermediate phases in a diffusional transformation
with TiNi3 as the equilibrium phase.
Ti3Ni4

Ti2Ni3

TiNi3

The TiNi phase has a B2 (CsCl) type ordered structure with a lattice constant of
0.3015 nm at room temperature. There is an order disorder transition from B2 to
BCC at 1090oC. The B2 phase retains upon quenching or slow cooling to room
temperature. B2 phase plays an essential role in martensitic transformation and
related shape memory effects. Ti2Ni is cubic structure with a space group of
Fd3m and lattice constant of 1.132 nm. The unit cell contains 96 atoms, oxides
appearing in the present alloy are mostly Ti4Ni2O has nearly the same structure
as Ti2Ni. The TiNi3 phase has hexagonal DO24 type ordered structure with lattice
constants a = 0.51010 nm and c = 0.83067 nm. Ti2Ni3 has two phases as a
function of temperature, and one phase changes martensitically to other phase
upon cooling. The higher temperature phase has a tetragonal structure with
space group of I4/mmm and lattice parameters a = 0.3095 nm and c = 1.3585
nm (at 373K), and lower temperature phase has an orthorhombic structure with
Bbmm space group and lattice parameter a = 0.4398, b = 0.4370 and c =1.3544
nm. With respect to shape memory characteristics Ti3Ni4 phase is very
important. It has a rhombohedral structure with R3 space group and lattice
parameter a = 0.670 nm and = 113.8o.

Martensitic transformation in Ti-Ni- based alloys:

A brief description of the types of martensitic transformation occurring in Ti-Nibased alloys is made here. There are 3 distinct martensitic transformations
occurring in Ti-Ni system. These transformations are indicated in electrical
resistivity vs temperature graph shown in figure 4. The martensitic
transformations are detected via the hysteresis loop present in electrical
resistivity vs temperature graph.

Figure 4 shows the electrical resistivity vs temperature graph for (a) B2 B19
transformation (b) B2 R B19 transformation and (c) B2 B19 B19
transformation in Ti-Ni- based alloys.

The curve in figure 4(a) is obtained when binary Ti-Ni alloys are quenched from
high temperature B2 parent phase. The martensite obtained in this case is B19
with a monoclinic structure. There is a gradual growth and shrinkage of
martensites upon cooling and heating respectively. This confirmed that
transformation is thermoelastic and was evidence for martensitic
transformation. In figure 4(a) Ms denotes martensitic transformation start
temperature that is temperature at which upon cooling the transformation starts,
the end of martensitic transformation is represented by M f. the temperature at
which reverse transformation starts is As and temperature at which reverse
transformation completes is Af.
Figure 4(b) shows presence of two hysteresis loops, one characterised by M s,
Mf, As, Af and the other indicated by Tr. The transformation indicated by Tr is
the first transformation to occur. It is characterised by a sharp increase in
electrical resistance upon cooling and extremely small hysteresis loop (1-2K).
This transformation is known as R phase transformation since the product
phase was considered to have rhombohedral structure at one time, although it
turned out to be triclinic later. R phase transformation was considered to be a
pre-martensitic transformation prior to the martensitic transformation but now it
is established that it is a martensitic transformation itself which competes with
subsequent martensitic transformation. The second transformation represented
by large temperature hysteresis R phase to B19 martensitic transformation.
This B2 R B19 transformation occurs when small ternary additions of Fe,
Al is made in the Ti-Ni binary alloy, similar transformations are obtained for Ni
rich Ti-Ni binary alloys when heat treated at proper temperature to produce
Ti3Ni4 precipitates. R phase transformation is available in binary Ti-Ni alloys
when cold worked and heat treated at proper temperature (673K) so that high
density of rearranged dislocations is left in the specimen. The conditions under
which martensitic transformation occur are to suppress B19 transformation
relative to R phase transformation.
The third type of transformation shown in figure 4(c) is obtained when Ni in TiNi binary alloy is substituted with Cu. The first transformation is represented by
Ms is the transformation of B2 phase to B19 phase and the second
transformation represented by Ms is the subsequent transformation of B19 phase
to B19 phase. The martensitic transformations in Ti50Ni50-xCux have
compositional dependence on Cu as shown in figure 5. When x > 7.5 B2 B19
B19 martensitic transformation occurs as described however whether the

second transformation occurs when x>16 is unknown. From the figure it is

noted that Ms and Ms are closer in range when 5<x<7.5, the transformation
occurs as described but the second transformation occurs immediately so B19
phase cant be observed in the transformation.
Figure 6 summarizes the three martensitic transformations occurring in Ti-Nibased alloys. Solution treated binary Ti-Ni alloys have tendency to B2 to B19
transformation. While for the upper and lower cases two successive
transformations occur. Depending on the composition and heat treatment only
the first transformation may take place and the second one may be lost.

Figure 5 Cu content dependence on transformation temperatures for Ti50Ni50xCux alloys.

Figure 6 summarizes the three types of martensitic transformations in Ti-Nibased alloys.

Crystal structure of martensite in Ti-Ni based alloys:

First the crystal structure of B19 martensite obtained on quenching solution
treated binary Ti-Ni alloy is discussed. The structural analysis of B19
martensite took a long time due to the lack of martensite single crystal. The
structure of the B19 martensite is monoclinic as shown in figure 7. From zero
layer X-ray precession photographs the space group of B19 phase was deduced
to be P21/m. The tests were carried out assuming crystal has centre of symmetry.
Lattice parameters a = 0.2898 nm, b = 0.4108 nm, c = 0.4646 nm and =
97.78o. The structure is not of two dimensional close packed planed, as usually
observed in phase alloys such as Cu-Al, Cu-Zn, Au-Sn, Au-Cd etc instead it is
a three dimensionally close packed system. The e/a ratio of phase alloys is 1.5
but e/a ratio of Ti-Ni alloys are not even close to 1.5 hence Ti-Ni alloys should
not be classified in phase alloys. This the reason why the martensites have
different than of the phase alloys.

Figure 7 illustrates the structure of B19 martensite.

The crystal structure of first martensitic transformation in Ti50Ni50-xCux was

reported to be orthorhombic. The lattice parameters are a function of
composition. The lattice parameters are a = 0.3030 nm, b = 0.4279 nm and c =
0.4514 nm. The crystal structure of B19 martensite is shown in figure 8.

Figure 8 shows the B19 martensite structure.

The transformation of R phase is characterised by sharp increase in electrical

resistance and extremely small hysteresis loop and the appearance of sharp
super lattice reflections in diffraction patterns at 1/3 positions along <110> * and

<111>* parent phase of the reciprocal space. Shape memory and super elasticity
effect which are characteristics of thermoelastic martensitic transformation is
observed in R phase transformation. The lattice of R phase can be described
by stretching the parent cubic lattice in the <111> diagonal direction and by
defining a corner angle as shown in figure 9. The angle is an acute angle and
has temperature dependence. increases with increasing temperature limiting at
90o. The space group of R phase was determined to be P3.

Figure 9 shows structure of R Phase.

Shape memory and super elasticity effects:

Shape memory effect(SME) and superelasticity (SE) are associated with the
crystallographically reversible nature of the martensitic transformation that
appears in shape memory alloys.
The deformation behavior of SMAs is strongly temperature sensitive , because
the deformation is associated with martensitic transformation . Schematic
stress-strain curves of a Ti-Ni alloy obtained at various temperatures are shown
in figure 10.
In the temperature range of T<M f , the specimen is fully transformed before
applying stress so that the elastic deformation take place in the in the
martensitic phase (the low temperature phase) at first as shown in figure 10(a).
In the temperature range Mf<T< Ms , the parent and martensitic phase coexist so
that yielding occurs due to twinning in the martensite phase and/or stressinduced martensitic transformation in the parent phase(the high temperature

phase).The stress-strain curve in figure 10(a) and (b) are essentially the same,
except the yield stress is a little lower in figure 10(b) than in figure 10(a).
In the temperature range of Ms<T<As, the parent phase elastically deforms at
first and yielding occurs owing to the stress-induced martensitic transformation.
Therefore,the yield stress linearly increase with increasing temperature
satisfying the Clausius-Clapeyron relationship . The stress-induced martensite
remains after unloading , because temperature is below As . The shape of the
stress-strain curve of figure 10(c) is similar to those of figure 10(a) and figure
10(b), where the shape of the specimen recovers to the original one by heating
above Af as shown by the dashed line revealing the shape memory effect.
In the temperature range As<T<Af , the deformation induced by the stressinduced martensitic transformation recovers partially upon unloading as shown
in figure 10(d) resulting in partial superelasticity and partial shape memory
effect by subsequent heating.
In the temperature range Af<T<Ts , perfect superelasticity appears as shown in
figure 10(e), where Ts stand for the critical temperature above which the
martensitic transformation does not take place and deformation occurs by slip.
If T is above Ts, plastic deformation occurs as in conventional metal and alloys
as shown in figure 10(f).
If we plot the critical stress in each SS curve as a function of temperature, we
obtain figure 11 where open circles represent the critical stresses upon loading,
and closed ones those upon unloading. We note that Ms determined by electrical
resistivity measurement roughly corresponds to the minimum of the critical
stress curve upon loading. The former pseudoelastic behavior is called
superelasticity, while the latter behavior, i.e. the phenomena that the apparent
plastic strain recovers by the reverse transformation upon heating is called the
shape memory effect. Superelasticity occurs by the stress-induced
transformation upon loading, and the subsequent reverse transformation upon
unloading.

Figure 10 shows schematic stress stain curves at various temperatures in a TiNi alloy.

Figure 11 shows Critical stress as a function of temperature for inducing

martensites (T > Ms) and for yielding (T <Ms) (open circles) and for reverse
transformation (solid circles)
Applications of Ti-Ni- based alloys:
Applications for titanium-nickel alloys can be conveniently divided into four
categories.
(1) Free recovery (motion) applications are those in which a shape memory
component is allowed to freely recover its original shape during heating,
thus generating a recovery strain.
(2) Constrained recovery (force) applications are those in which the recovery
is prevented, constraining the material in its martensitic, or cold, form
while recovering. Although no strain is recovered, large recovery stresses

are developed These applications include fasteners and pipe couplings

and are the oldest and most widespread type of practical use.
(3) Actuators (work) applications are those in which there is both a recovered
strain and stress during heating, such as in the case of a titanium-nickel
spring being warmed to lift a ball. In these cases, work is being done.
Such applications are often further categorized according to their
actuation mode, e.g.,electrical or thermal.
(4) Superelasticity (energy storage) refers to the highly exaggerated elasticity,
or springback, observed in many Ti-Ni alloys deformed above and below.
The function of the material in such cases is to store mechanical energy.
Although limited to a rather small temperature range, these alloys can
deliver over 15 times the elastic motion of a spring steel.

Reference:

Otsuka, K.,& Ren, X. (2005). Physical metallurgy of Ti-Ni based shape

memory alloys. Progress in materials science, 50(5), 511-678.
Lagoudas, D.C (Ed). (2008). Shape memory alloys: modeling and
engineer applications. Springer science and business Media.

 Yoneyama, T, S., & Miyazaki. (2008). Shape memory alloys for

Biomedical applications, Woodhead Publishing in Materials.
Duerig, T, W., & Pelton, A,R. (1994). Ti-Ni shape memory alloy. material
property handbook: Titanium alloys, 1035-1048.
http://ocw.mit.edu/courses/materials-science-and-engineering/3-22mechanical-behavior-of-materials-spring-2008/projects/superelastic_2/
www.wikipedia.com