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Shape Memory Alloys: Part One

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Abstract:
Shape memory alloys (SMAs) are metals which exhibit two very unique properties, pseudo-elasticity
and the shape memory effect.
Because these materials are relatively new, some of the engineering aspects of the materials are
still not well understood. Many of the typical engineering descriptors, such as Young's modulus and
yield strength, do not apply to shape memory alloys since they are very strongly temperature
dependent. On the other hand, a new set of descriptors must be introduced, such as stress rate and
amnesia.

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Shape memory alloys (SMAs) are metals which exhibit two very unique properties, pseudo-elasticity
and the shape memory effect. Arne Olander first observed these unusual properties in 1938, but not
until the 1960s were any serious research advances made in the field of shape memory alloys.
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The basic phenomenon of the shape memory effect was widely reported a decade later by Russian
metallurgist G. Kurdjumov and also by Chang and Read. However, presentation of this property to the
wider public came only after the development of the nickel-titanium alloy (Nitinol) by Buehler and
Wang. Since then, research activity in this field has been intense, and a number of alloys have been
investigated, including Ag-Cd, Au-Cd, Cu-Zn, Cu-Zn-AI, Cu-AI-Ni, Cu-Sn, Cu-Au-Zn, Ni-AI, Ti-Ni, Ti-NiCu, Ni-Ti-Nb, Ti-Pd-Ni, In-Ti, In-Cd and others. The most effective and widely used alloys include Ni-Ti,
Cu-Zn-Al, and Cu-Al-Ni.
Crystallography of shape memory alloys have been studied for the last four decades. Because these
materials are relatively new, some of the engineering aspects of the materials are still not well
understood. Many of the typical engineering descriptors, such as Young's modulus and yield strength,
do not apply to shape memory alloys since they are very strongly temperature dependent. On the
other hand, a new set of descriptors must be introduced, such as stress rate and amnesia.
SMAs are useful for such things as actuators which are materials that change shape, stiffness,
position, and other mechanical characteristics in response to temperature or electromagnetic fields.
The potential uses for SMAs especially as actuators have broadened the spectrum of many scientific
fields. The diverse applications for these metals have made them increasingly important and visible to
the world.
The alloys that exhibit so-called shape memory can undergo surprisingly large amounts of strain and
then, upon temperature increase or unloading, revert to their original shape. Ni-Ti based shape
memory alloys have to date provided the best combination of materials properties for most commercial
applications. However they are very expensive compared with Cu-based shape memory alloys. In
many applications, Cu-based alloys provide a more economical alternative to Ni-Ti. Cu-Zn based
shape memory alloys have actually been used and Cu-AI based shape memory alloys have shown
promise.
The two unique properties described above are made possible through a solid state phase change that
is a molecular rearrangement, which occurs in the shape memory alloy. The two phases, which occur
in shape memory alloys, are martensite and austenite. Martensite is the relatively soft and easily
deformed phase of shape memory alloys, which exists at lower temperatures. The molecular structure
in this phase is twinned which the configuration is shown in the middle of Figure 1. Upon deformation
this phase takes on the second form shown in Figure 1, on the right. Austenite, the stronger phase of
shape memory alloys, occurs at higher temperatures. The shape of the Austenite structure is cubic, the
structure shown on the left side of Figure 1. The undeformed martensite phase is the same size and
shape as the cubic austenite phase on a macroscopic scale, so that no change in size or shape is
visible in shape memory alloys until the martensite is deformed.

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Figure 1: Microscopic and macroscopic views of the two phases of shape memory alloys
The temperatures at which each of these phases begin and finish forming are represented by the
following variables: Ms, Mf, As, Af. The amount of loading placed on a piece of shape memory alloy
increases the values of these four variables as shown in Figure 2. The initial values of these four
variables are also dramatically affected by the composition of the wire (i.e. what amounts of each
element are present).

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The shape memory effect is observed when the temperature of a piece of shape memory alloy is
cooled to below the temperature Mf. At this stage the alloy is completely composed of martensite
which can be easily deformed. After distorting the SMA the original shape can be recovered simply by
heating the wire above the temperature Af. The heat transferred to the wire is the power driving the

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molecular rearrangement of the alloy, similar to heat melting ice into water, but the alloy remains solid.
The deformed martensite is now transformed to the cubic austenite phase, which is configured in the
original shape of the wire.

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Figure 2: The dependency of phase change temperature on loading

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The shape memory effect is currently being implemented in:

The space shuttle
Hydraulic fittings for airplanes
Thermostats
Vascular stents
Coffeepots
Nickel-titanium alloys have been found to be the most useful of all SMAs. Other shape memory alloys
include copper-aluminum-nickel, copper-zinc-aluminum, and iron- manganese-silicon alloys. The
generic name for the family of nickel-titanium alloys is Nitinol. In 1961, Nitinol, which stands for Nickel
Titanium Naval Ordnance Laboratory, was discovered to possess the unique property of having shape
memory. William J. Buehler, a researcher at the Naval Ordnance Laboratory in White Oak, Maryland,
was the one to discover this shape memory alloy.
It was discovered that Nitinol had phase changes while still a solid. These phase changes, known as
martensite and austenite, involve the rearrangement of the position of particles within the crystal
structure of the solid. Under the transition temperature, Nitinol is in the martensite phase.

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The transition temperature varies for different compositions from about -50C to 166C. In the
martensite phase, Nitinol can be bent into various shapes. To fix the parent shape (as it is called), the
metal must be held in position and heated to about 500C. The high temperature causes the atoms to
arrange themselves into the most compact and regular pattern possible resulting in a rigid cubic
arrangement known as the austenite phase. Above the transition temperature, Nitinol reverts from the
martensite to the austenite phase which changes it back into its parent shape. This cycle can be
repeated millions of times.
Pseudo-elasticity occurs in shape memory alloys when the alloy is completely composed of austenite
(temperature is greater than Af). Unlike the shape memory effect, pseudo-elasticity occurs without a
change in temperature. The load on the shape memory alloy is increased until the austenite becomes
transformed into martensite simply due to the loading.

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Figure 3: Microscopic diagram of the shape memory effect

Among the shape memory alloys that have been developed, Au-Cd, Cu-Zn-Al, Cu-Al-Ni and the like
have been noted as being comparable with the Ti-Ni type alloys. Particularly, the latter two Cu-type
alloys are generally considered prominent in the view of their low cost. When comparing the two Cutype alloys with each other, Cu-Al-Ni alloy is superior both in the shape memory performance and heat
stability (heat resistivity). However, the defect in the Cu-Al-Ni alloy of low cold workability somewhat
hinders its application. It has already been found that the workability of the Cu-Al-Ni alloy can be
improved by blending Ti therewith to render the crystal grain finder.
Some of the main advantages of shape memory alloys include:
1. Bio-compatibility
2. Diverse fields of application
3. Good mechanical properties (strong, corrosion resistant).
There are still some difficulties with shape memory alloys that must be overcome before they can live
up to their full potential. These alloys are still relatively expensive to manufacture and machine
compared to other materials such as steel and aluminum. Most SMAs have poor fatigue properties;
this means that under same loading conditions (i.e. twisting, bending, compressing) a steel component
may survive for more than one hundred times more cycles than an SMA element.

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