In Search of Martensite: Titanium-Tantalum

Shape-Memory Alloy
by
Jeffry Disko
Submitted to the Department of Materials Science and Engineering
in partial fulfillment of the requirements for the degree of
Bachelor of Science in Materials Science and Engineering
at the
MASSACHUSETTS INSTITUTE OF TECHNOLOGY
June 2010

c Massachusetts Institute of Technology 2010. All rights reserved.

Author . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Department of Materials Science and Engineering
May 14, 2010

Certified by . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Samuel M. Allen
POSCO Professor of Physical Metallurgy
Thesis Supervisor

Accepted by . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Lionel C. Kimmerling
Chairman, Department Undergraduate Committee
2
In Search of Martensite: Titanium-Tantalum Shape-Memory
Alloy
by
Jeffry Disko

Submitted to the Department of Materials Science and Engineering

on May 14, 2010, in partial fulfillment of the
requirements for the degree of
Bachelor of Science in Materials Science and Engineering

Abstract
There is a broad range of life-saving medical implants and devices that rely on the
shape-memory (SME) and superelastic properties of various nickel-based alloys [8].
Unfortunately, there is also serious concern about the toxicity of nickel. Titanium
based shape-memory alloys have been noted as potentially non-toxic replacements
of the more traditional, nickel-based shape memory alloys. In this thesis I present
research concerning the potential of SME-capable titanium-tantalum alloys to replace
Ni-based alloys in medical implants. A method for heat treatment of Ti–Ta alloys of
varying compositions to induce formation of martensite was developed. Heat-treated
alloys were then tested for SME and superelastic behavior by means of hot oil recovery
tests and were characterized through optical microscopy. Metallographs of some of
the samples were taken throughout the processing and testing procedures in order to
directly observe changes in microstructure.

Thesis Supervisor: Samuel M. Allen

Title: POSCO Professor of Physical Metallurgy

3
4
Acknowledgments
I would like to thank Yinlin Xie, Samuel Allen, Mike Tarkanian, Mark Belanger, and
Tom Nizoleck for the advice and help they gave me while working on this project.

5
6
Contents

1 Introduction 13
1.1 Motivations for Nickel-Free Shape-Memory Alloys . . . . . . . . . . . 14
1.1.1 Motivation for Development of Titanium-Tantalum Shape-Memory
Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.2 Description of Shape-Memory and Superelasticity . . . . . . . . . . . 16
1.2.1 Shape-Memory . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.2.2 Superelasticity . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.3 Comparison to Nickel-Based Shape-Memory Alloys . . . . . . . . . . 19

2 Experimental 21
2.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.1.1 Heat-Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1.2 Metallography Specimens . . . . . . . . . . . . . . . . . . . . 28
2.2 The Lighter Test: Qualitative Test for Shape Memory Effect . . . . . 30
2.3 Hot Oil Recovery Tests: Determing Transformation Temperature and
Strain Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

3 Results 33
3.1 Micrographs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.1.1 Martensite Formation . . . . . . . . . . . . . . . . . . . . . . . 33
3.1.2 Inhomogeneity . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.1.3 Layering Induced by Inadvertant Suface Cooling . . . . . . . . 34
3.2 Hot Oil Recovery: Transformation Temperature and Strain Recovery 35

7
 3.2.1 Strain Measurements . . . . . . . . . . . . . . . . . . . . . . . 36
3.2.2 Martensitic Strain Recovery and Transformation Temperature 37

4 Discussion and Conclusions 41

4.1 Shape-Memory Potential . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.1.1 Two-Way Shape-Memory Effect . . . . . . . . . . . . . . . . . 42
4.2 Potential Superelasticity . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.3 Martensite Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.4 Conclusions and Future Research . . . . . . . . . . . . . . . . . . . . 44

8
List of Figures

2-1 Comparison of EDM vs. Diamond saw cut surfaces. . . . . . . . . . . 22

2-2 Cutting Procedure for Testing Specimens: schematics not to scale. . . 23
2-3 Improved sample preparation procedure. . . . . . . . . . . . . . . . . 27
2-4 Strong bands of martensite end near surface of 62 wt% Ta material. . 28
2-5 Comparision of martensite formation at surface and core of 60 wt%
heat treated and quenched specimens. . . . . . . . . . . . . . . . . . . 29

3-1 Comparison of martensite formation in as-received and austenized at

900◦ C, ice water quenched 60, 62, and 64 wt% Ta alloys . . . . . . . . 34
3-2 Martensite formation in 60, 62, and 64 wt% Ta alloys Quenched from
914◦ C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3-3 Inhomogeneous bands in heat treated 60, 62, and 64 wt% Ta alloys . 35
3-4 Details of the outer edges and core of a heat treated piece 60 wt% Ta. 36
3-5 Bending strain applied to samples of 60, 62, and 64 wt% Ta, austenized
at 900◦ C and ice water quenched. . . . . . . . . . . . . . . . . . . . . 37
3-6 Maximum elastic strain in 60, 62, and 64 wt% Ta, austenized at 900◦ C
and ice water quenched. . . . . . . . . . . . . . . . . . . . . . . . . . 37
3-7 Martensitic strain recovery vs. oil temperature of 60, 62, and 64 wt%
Ta, austenized at 900◦ C and ice water quenched immediately after
removal from oil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3-8 Relaxation of samples vs oil test temperature a few minutes after cooling. 38
3-9 Net shape memory effect vs. oil temperature of 60, 62, and 64 wt%
Ta, austenized at 900◦ C and ice water quenched. . . . . . . . . . . . . 39

9
10
List of Tables

1.1 Ni-Ti Shape-Memory Relevant Properties [1] . . . . . . . . . . . . . . 20

11
12
Chapter 1

Introduction

The shape-memory and superelastic effect rely on an austenite to martensite phase

transition to absorb energy that would otherwise be absorbed in the form of disloca-
tion motion, and therefore plastic deformation. Because this phase transition occurs
spontaneously on heating or cooling, deformation incurred in one phase can func-
tionally be erased by moving the material into the temperature regime of the other
phase, which forces the material to take on whatever shape the new phase was origi-
nally formed in. This unique ability, a physical ctrl+z, makes shape-memory alloy’s
potentially extremely useful for many applications. Shape-memory alloys have seen
use as virtually indestructable eyeglass frames, arterial stents, shape-changing wings,
heat-activated pipe clamps, dental arch wires, and more [10].
The medical field, in particular, has begun to make extensive use of shape-memory
and superelastic materials, both because of the heat-induced shape change associated
with SME and because of the nature of the stresses induced by shape-memory. For
example, dental wire makes use of the relatively large constant stress regime of su-
perelastic alloy’s stress strain curve to apply a constant force while straightening
out teeth [10]. Also, the typically nickel-based shape-memory alloys avaliable on the
market today tend to exhibit quite good biocompatability [10, 7, 9]; this combined
with SME’s remarkable physical properties make these alloys well suited for many
high-tech medical applications.
Unfortunately, because many of these materials are nickel-based alloys, they present

13
a risk to people with nickel allergies. Because of this, there is a push to develop nickel-
free shape-memory alloys that can compete, both economically, and functionally with
the traditional shape-memory alloys. This paper examines Ti–Ta alloys as potential
alternatives to nickel-based shape-memory alloys.
Chapter one introduces the motivation for producing nickel-free shape-memory
alloys and provides some background information on shape-memory and superelas-
ticity. Also, the method by which Ti–Ta alloys will be compared with nickel-based
shape-memory alloys is presented.
Chapter two describes the development of an acceptable heat-treatment and quench-
ing protocol for inducing martensite in Ti–Ta alloys and the experimental procedures
used to characterize the Ti–Ta alloys thus produced.
Chapter three presents the results of experiments performed.
Chapter four presents a discussion of the experimental results and offers an at-
tempt to explain those results. Finally, a strategy for further and more accurate
characterization and development of Ti–Ta SME will be presented.

1.1 Motivations for Nickel-Free Shape-Memory Al-

loys

As previously mentioned, shape-memory alloys have been singled out as uniquely

useful in a wide variety of medical applications; often in the form of implants. Im-
plantable shape-memory products include arterial stents, orthopedic braces and align-
ment devices, blood clot filters, heart patches, suture holders and catheters [10]. Most
of these devices are fabricated out of nickel-based alloys like Nitinol
c and Flexinol c

[10, 8].
Unfortunately, nickel is known to be toxic in high enough concentrations. Research
has shown that direct exposure to nickel concentrations of 0.5 mg cm−2 per week [9],
or ingestion of 0.4 to 0.6 mg of nickel can cause an allergic skin reaction in some peo-
ple [7]. Most skin-related nickel allergies result in eczema[11, 7, 4], a skin condition

14
characterized by a scaly, or blistered rash that produces strong itching [2]. In addition
to dermatological symptons, nickel ions generated by implants are thought to play a
role in various implant failure modes [4]. It is still not clear exacty how much nickel
leaches out of nickel-containing implants or how much leached nickel is necessary to
cause serious symptoms in hypersensitive patients. Considerations of implant place-
ment relative to skin or other tissues, fluid flow within the body, and simple diffusion
of leached nickel ions all combine to make a very complicated problem to explore.
Also, the percentage of the population exhibiting nickel hypersensitivity is not well
known (reports have indicated anywhere from 8 to 30% of the female population [7]
and 3-17% of the male population). However, there is sufficient evidence suggesting
that nickel-leaching medical implants can cause negative skin conditions and implant
failure in enough patients to spur on continued research into viable alternatives to
nickel-containing alloys.

1.1.1 Motivation for Development of Titanium-Tantalum Shape-

Memory Alloy

Titanium alloys are often used as nickel-alloy substitutes for implant devices used in
patients hypersensitive to nickel [4]. Titanium alloys are similarly biocompatable but
are less likely to cause allergic reactions (although even Ti can cause allergic reactions
in some people). In light of this, pursuing Ti-based shape-memory alloys could result
in viable materials that are significantly less likely to cause allergic reactions resulting
in skin disorder or implant failure.

A local Massachusetts company, Dynamet, has developed a novel way to produce

Ti–Ta alloys of varying compositions. Because certain compositions of Ti–Ta are
known to harbor metastable martensitic phases [14], Dynamet has expressed interest
in exploring the potential of their product as a shape-memory alloy. This economic
incentive, in addition to the potential for good shape-memory behavior and biocom-
patibility, fuel the motivation for exploring Ti–Ta SME.

15
1.2 Description of Shape-Memory and Superelas-
ticity

1.2.1 Shape-Memory

SME is made possible by the solid-solid phase transformation from a cubic austenite
to a martensite phase of relatively less symmetry. The austenitic phase exists at high
temperatures and the martensitic phase exists at low temperatures. Ti–Ta alloys
have a body-centered cubic (BCC) austenitic phase (β) and two different martensitic
variants, (α’ and α”). α’ is often seen in alloys with 10–20wt% Ta by weight and
exhibits a hexagonal structure while α” is often seen in alloys with 20–60% Ta by
weight and exhibits an orthorhombic structure [14].

Low temperature martensite can exist in multiple, energetically equivalent vari-

ants within a given block of material. For example, a rolled sheet of some material
exhibiting a martensitic phase may have some martensite with its unit cell’s long di-
mension (as martensitic forms generally exhibit anisotropy) aligned along the rolling
direction, immediately adjacent to a variant of martensite with its unit cell’s long
dimension aligned along the sheet’s transverse axis. These two variants of martensite
are energetically equivalent, and the transformation of one form to the other will
result in (or be caused by) a macroscopic change in the material’s shape because of
the anisotropic nature of martensite. Martensite can transition from one form to the
other by means of twin boundary movement [6]; this is how martensite accomodates
deformation. Because each form of martensite is energetically equivalent, it takes
relatively little stress to produce large strains in martensite. For example, one could
put the aforementioned rolled sheet of material in tension along the rolling direction,
and the martensitic sections aligned along the sheet’s transverse direction would tran-
sition to martensite aligned along the rolling direction, thereby allowing the sheet to
stretch. Because the twinning stress of austenite is relatively high, austenite can
not accomodate strain nearly as easily as martensite, and is therefore typically a
much stiffer and springier phase [6]. The following example illustrates how SME is

16
developed.

A device that utilizes SME is generally clamped into some desired shape and
heated to a temperature high enough to induce nucleation and growth of austenite
within the material. The part is given enough time to become completely austenitic;
this processing stage imparts the ’memory’, or shape, that the alloy will revert to
upon heating. While still clamped, the part is cooled down such that martensite
variants begin to nucleate throughout the part. This cooling is continued until the
part has been completely converted to martensite. To maintain the same macroscopic
part geometry (as the part is forced to since it is clamped) while transitioning from
austenite to martensite, it is neccessary for martensite of various variants to nucleate
all at the same time during this processing stage; so the cooled part is made up of
various, energetically equivalent martensitic variants separated by twin boundaries [6].
At this point the part can be unclamped and put into use. Once in the martensitic
phase, deformation of the part (up to a point) will be accomodated by conversion
of martensite from one variant to another as described in the preceding paragraph.
This deformation will seem permanent as long as the processing temperature is low
enough to prevent formation of austenite. To recover the ’memorized’ shape, the
part is heated through a temperature high enough to completely convert the part to
austenite. During heating, the martensite, no matter its variant (which may have
been changed during deformation), will convert to its original austenitic form, which
has only one geometrical conformation. Thus the transition from deformed martensite
to austenite will restore the part’s original shape. Once the heat source is removed
and the part cools, it will generally retain its austenitic shape while transforming
back to martensite, and the entire part will be reset.

In some materials however, the part will revert back to its deformed shape upon
cooling. This phenomonon is two-way shape-memory. In materials that exhibit two-
way shape-memory, the deformed martensitic variants re-nucleate in exactly the same
conformation they held before re-austenizing [6].

This process indicates that there are four key temperatures related to shape-
memory alloys that should be identified. These temperatures are commonly referred

17
to as the martensite start (Ms ), martensite finish (Mf ), austenite start (As ) and
austenite finish (Af ) temperatures [6]. Where Mf < Ms < As < Af , thus the austen-
ite start temperature is defined as the temperature at which austenite begins to form
when heating, and the martensite start temperature is defined as the temperature at
which martensite begins to form when cooling.

1.2.2 Superelasticity

Superelasticity utilizes the same principles as shape-memory, but in a slightly different

way. Superelasticity is exhibited when a part is used at a temperature greater than the
austenite finish temperature, so the part is composed completely of austenite during
use and at the onset of deformation. When stress is applied to the part, the absorbed
energy is used to convert austenite to martensite (an energetically unfavorable thing
to do in the absence of stress because the part is at a temperature wherein austenite
is stable and martensite is not)[6], thereby allowing the part to take advantage of
martensite’s easy deformability. As soon as the applied stress is removed from the
part, the unstable martensite converts back to its orginal austenitic form and the
part springs back into its original shape, as if no deformation had occured at all. It is
important to note that the higher the temperature of the part above the martensite
start temperature, the more unstable the martensitic phase is and the more activiation
energy is required to produce it. Thus if the operation temperature is too high, it will
be energetically favorable for the part to plastically deform by means of irreversible
slip deformation, rather than by the superelastic effect. The part will not exhibit
superelastic behavior above a certain temperature. The temperature above which
superelasticity becomes more energetically demanding than slip deformation is refered
to as Md .

18
1.3 Comparison to Nickel-Based Shape-Memory
Alloys
Because Ni–Ti alloys are what the medical industry typically uses [1, 10, 7, 9], and
because the Ti–Ta alloys discussed in this thesis are being developed as hypoallergenic
alternatives to Ni–Ti shape-memory alloys, enquiries directed into the properties of
Ti–Ta SME are made in a way to lend themselves to comparison with Ni–Ti shape-
memory alloys. I have identified, and this appears to be fairly common practice, ten
numbers of importance which should be used to compare the two systems.

• Martensitic finish temperature (Mf )

• Martensitic start temperature (Ms )

• Austenitic start temperature (As )

• Austenitic finish temperature (Af )

• Md

• Elastic modulus of the martensitic phase (Em )

• Yield strength of the martensitic phase (Ym )

• Elastic modulus of the austenitic phase (Ea )

• Yield strength of the austenitic phase (Ya )

• Martensitic strain recovery (Erec )

Table 1.1 presents this data for a typical Ni–Ti shape-memory alloy.
One group has shown that the α” martensitic variant has a Em of 106Gpa, the
austenitic β phase has a Ea of around 50Gpa, and Ti–Ta compositions from 50–
70wt% Ta have a yield strength between 300 and 600MPa[14, 12, 13]. Other studies
have provided similar information [3, 5]. The work presented in this thesis is aimed
at determining the martensitic strain recovery and transformation temperature of

19
 Table 1.1: Ni-Ti Shape-Memory Relevant Properties [1]

Elastic modulus of the martensitic phase (Em ) 28-41 GPA

Yield strength of the martensitic phase (Ym ) 70-140 MPA
Elastic modulus of the austenitic phase (Ea ) 83 GPA
Yield strength of the austenitic phase (Ya ) 195-690 MPA
Martensitic strain recovery (Erec ) < 8.5
Martensite to Austenite Transformation Temperature (Ttr ) −200 to 100◦ C

various Ti–Ta alloys. This is accomplished by performing hot oil recovery tests on
Ti–Ta compositions ranging from 60–64wt% Ta as described in Chapter 2.

20
Chapter 2

Experimental

Most of the experiments presented in this thesis are continuations of work started
by Tom Nizoleck and others in conjunction with Professor Samuel M. Allen. Sample
preparation and experimental testing described herein were performed between late
January and early May in 2010. All material was provided by Dynamet in the form
of extruded bars ranging from aproximately 1/3 to 1 1/3in diameter. Samples ex-
amined had compositions of Ti–50wt% Ta, Ti–55wt% Ta, Ti–60wt% Ta, Ti–62wt%
Ta, Ti–64wt% Ta, and included a set of non-homogenized Ti–60wt% Ta, Ti–62wt%
Ta, Ti–64wt% Ta, where homogenization implies an annealing process that promotes
diffusion of titanium and tantalum throughout the material, leading to a more even
distribution of the two elements. These compositions were targeted for further re-
search by Dynamet based on work done by Tom Nizoleck in the summer of 2009.
Both qualitative and quantitative tests were conducted in order to determine Erec ,
and Ttr of the alloys provided by Dynamet.
This chapter will describe the procedures undertaken and challenges faced in at-
tempting to determine the targeted properties.

2.1 Sample Preparation

Ti–Ta alloys are remarkably difficult to work with. As such, specialized processing
techniques and equipment used include diamond saws, composite abrasive wheels,

21
and electrical discharge machining (EDM). Samples prepared for mechanical testing
were cut from bars of material provided by Dynamet. Test specimens were machined
through the use of some combination of cutting on a Buehll, low speed diamond saw
or a Charmilles Robofil 240cc EDM. Specimens were generally cut into rectangular
slices approximately 0.5mm thick and 3mm wide. The length of samples ranged from
about 20 to 60mm. Specimens cut using the diamond saw were cooled using Isocut
lubricating oil. The EDM used operates with deionized water as the dielectric, and
so all specimens cut on the EDM were submerged in DI water during machining.

During testing, some questions were raised concerning the potential of EDM to
damage the specimens. However, micrographs examining surfaces of Ti–64wt% Ta
transverse to an EDM cut show no visible difference to those cut with the diamond
saw. A comparison of the two surfaces is presented in Figure 2-1.

(a) Surface Cut Using Diamond Saw (b) Surface Cut Using EDM

Figure 2-1: Comparison of EDM vs. Diamond saw cut surfaces.

Once machined into slices, most samples were heat-treated to induce the austenitic
memory and and metastable martensite phases necessary for shape-memory and su-
perelastic behaviour.

22
2.1.1 Heat-Treatment

Initial Procedure

Determining an effective heat-treatment procedure that consistently produced sam-

ples with a uniform distribution of martensite proved difficult. Based on research
done by Tom Nizoleck and [12, 13, 14], an austenizing temperature of 900◦ C was
chosen. Mr. Nizoleck had shown that heat-treatment of material at 900◦ C for aprox-
imately ten minutes followed by quenching in ice water induced α” martensite in a β
matrix in samples ranging from 50 to 64 wt% Ta. He also recorded that samples of
60 wt% Ta exhibited shape memory behavior if heat treated in the same way.
Initial heat-treatment was performed on 50 and 55 wt% Ta material in order to
re-create the results observed by Mr. Nizoleck. The samples were cut along the
transverse direction of the bar using the low speed diamond saw. Sample alignment
relative to the bar is shown in Figure 2-2a.

(a) Specimens Cut Using Diamond Saw (b) Specimens Cut Using EDM

Figure 2-2: Cutting Procedure for Testing Specimens: schematics not to scale.

These samples were approximately 20mm x 4mm x 2mm. One point of departure
from Mr. Nizoleck’s procedure was to heat-treat the samples after cutting them to
their final dimensions as opposed to heat-treating a large piece of material, and then
cutting samples out of that. It was thought that heat-treating and quenching thin
pieces would induce a more even effect throughout the specimen’s thickness than

23
heat-treating relatively thick pieces. Heat-treatment was conducted as follows. An
open topped boat was filled with specimens of the same composition. The boat was
placed into a furnace pre-heated to 900◦ C. The furnace was allowed a few seconds to
recover from being opened (the furnace interior would cool slightly upon opening the
furnace door and placing samples inside), before the ten minute austenization time
was started. Upon completion of the austenization step (ten minutes after placing
the samples inside the furnace), the furnace door was opened, the boat was taken
from the furnace and upended a few centimeters above a bucket of ice water. The
entire quenching procedure, from the opening of the furnace door to submersion of
the samples in ice water generally took less than five seconds. After heat-treatment of
these samples, they exhibited properties similar to those described by Mr. Nizoleck.
They were very springy and could be bent through angles of approximately 60◦ . Upon
heating deformed samples with a lighter, SME was often observed. These results were
taken as indication that the chosen heat-treatment procedure was effective.
In anticipation of the planned hot oil recovery tests, it was determined that sample
thickness should be minimized. This would allow test strips to be bent through larger
angles while minimizing the induced stress in the sample. This would not only make
it easier to quickly and reliably prepare deformed samples, but would help prevent
pre-mature breaking of brittle samples (it was known that heat treated samples with
little martensite could be very brittle) and would allow samples to be bent through
larger angles before breaking,, thereby making it possible to more accurately measure
the strain induced by bending. Because of this, all hot oil recovery specimens were
machined using the EDM. The EDM was capable of cutting very clean and precise
sub-millimeter thick strips quickly and efficiently.

Heat Treatment Mystery

A new round of samples of 50, 55, 60, 62, and 64 wt% Ta samples were fabricated
on the EDM. This time, sample size was 30mm x 2mm x 0.4mm. The alignment of
these specimens relative to the bar is illustrated in Figure 2-2b. After fabrication, the
samples were austenized at 900◦ C for ten minutes and then quenched in ice water

24
as described above. Surprisingly, the resulting samples composed of 50 and 55 wt%
Ta proved to be very brittle, and no visible SME was observed in any of the samples
when bent and then re-austenized by heating with a lighter. Hot oil recovery tests
were performed on these samples, but no measurable results could be obtained.
It was thought that the heat-treatment method being used was unreliable enough
(because of the the human variable inherent in the procedure) that such radically
different results could be expected from one batch of material to the other. In an
attempt to reduce the variability in heat-treatment, three modifications were made to
the heat-treatment procedure. The first modification was to quench material directly
into liquid nitrogen rather than ice water. It was thought that this would result in a
more severe quench than in ice water and would induce more metastable martensite
formation. This technique proved unsatisfactory, however, as the liquid nitrogen
bubbled so much during quenching that it could not effectively cool the material.
The second modification was to increase the austenizing temperature to 914◦ C as
another means to make the quench more severe. Again, no noticable change was
observed. The third modification was to cover the boat and samples with another,
upturned boat. This completely enclosed the samples during transfer from the furnace
to the quenchant and was intended to reduce the amount of air cooling of the samples
during the transfer. Unfortunately, this change did not yield an improved product.

The Plot Thickens

Finally, it was hypothesized that the effect of quenching could vary with the sample
thickness. For example, perhaps, near the surface of the material, quenching would
be more severe than in the core, and so the resulting microstructure would vary
from the surface of the sample to the core. Because the samples prepared by Mr.
Nizoleck, and the samples first prepared by myself were relatively thick compared to
the newer, unsuccessful samples being fabricated, it was thought that such a depth
dependence on quenching effect could explain why the same processing could result in
such radically different products. To test for this, three sets of ingots approximately
6mm x 11mm x 22mm were cut from the center (it is known that even the homogenized

25
bars of material provided by Dynamet tend to show large Ta concentration gradients
near the surface) of 60, 62, and 64 wt% Ta bars. One ingot from each composition
was heat-treated at 900◦ C for ten minutes before being quenched in ice water. To
identify if any layering seen was a product of the quenching or the austenizing steps,
another of the ingots from each composition was austenized at 900◦ and allowed to
air cool. To determine the effect of a more severe quench on any layering present,
one ingot from each composition was heat treated at 914◦ before being quenched
in ice water. The boat-lid method described above was used for quenching. After
heat treatment, the ingots were cut in half on the diamond saw to expose the cross
section of the piece, and micrographs of the cut surface were taken after polishing and
etching. The observed cross-sectional surfaces were normal to the direction of heat
flow in the sample during austenizing and quenching and could be used to observe
the quenching effect vs. depth within the material. Simultaneously heat treated
metallographic specimens were prepared that displayed the surface exposed during
heat treatment and quenching. It was thought that comparing micrographs of the
surface, and of the depth of the same material undergoing the same heat-treatment,
would reveal any depth dependent quench affects and/or surface effects. A schematic
detailing this procedure is presented in Figure 2-3.

Analysis of the resulting micrographs revealed that there was an approximately

400 µm thick layer near the surface of every quenched ingot wherein very little marten-
site formed during quenching. No such layer was noticed in samples that were aust-
enized and then air cooled, which indicates that the layering is a result of the quench-
ing step, not the austenizing step. A micrograph depicting strong bands of martensite
abruptly ending near the surface of a 900◦ austenized, water quenched, 62 wt% Ta
specimen is shown in Figure 2-4.

The sudden disappearance of martensite sear surfaces of quenched material as

shown in Figure 2-4 is typical of all quenched samples less than 1̃mm thick. Figure
2-5 compares micrographs of the surface of a 60 wt% Ta ingot and the core of of a
similar ingot heat treated at the same time.

It can be seen from Figure 2-5 that the surface of the material has significantly

26
 Figure 2-3: Improved sample preparation procedure.

less martensite than the core of the material. It is likely that samples less than 0.4
µm thick, after heat-treatment, are composed entirely of the martensite-lean surface
layer observed in the aforementioned test specimens even though the Ti–Ta alloy in
question has the ability to form martensite during quenching. Thicker samples (like
those prepared by Mr. Nizoleck and myself early on during testing), on the order
of 2mm thick, could form this outer, brittle shell composed of very little martensite,
while containting an inner, martensitic rich core capable of SME. This would explain
the strange variety of behaviors witnessed.

Development of Improved Heat Treatment Protocol

Based on the evidence provided in the preceding section , it was determined that the
layering was probably caused by air cooling of the surface during transfer of the ingots
from the furnace to the quenchant after austenization. Even enclosed in two boats,
enough air was able to circulate around the ingots during the transfer process to
significantly cool down the outer surface layer of the samples enough to eliminate the
effects of the quench. To alleviate this problem, a new heat treatment and fabrication

27
 Figure 2-4: Strong bands of martensite end near surface of 62 wt% Ta material.

method was developed for hot oil recovery specimens.

The new protocol calls for a large ingot, approximately 11mm x 9mm x 40mm
to be cut from the center of a bar of material on the EDM. The ingot is then heat
treated at 900◦ for ten minutes before being water quenched. After quenching, the
outer 0.5mm of every surface of the ingot is shaved off in the EDM. Finally, the ingot
is cut down into 0.2mm thick slices to be used for hot oil recovery tests.

2.1.2 Metallography Specimens

Metallographic specimens of both heat treated and as recieved material were made
throughout the testing procedures in order to visualize what microstructural changes
were being induced by processing and as a quality control measure. Metallographic
specimens were cut down to size using either the EDM or diamond saw, mounted in
a thermosetting epoxy and then polished on automated Struers polishing machines.
The diamond and EDM cut surfaces were generally fairly smooth to begin with and
seemed to leave extremely small deformation zones as evidenced by Figure 2-1. Be-

28
 (a) Surface Martensite (b) Core Martensite

Figure 2-5: Comparision of martensite formation at surface and core of 60 wt% heat
treated and quenched specimens.

cause of this, polishing was started using relatively fine abrasive discs. Polishing
generally followed the following procedure.

• 5 Minutes on a TBW diamond fine grind diamond polishing disk at 20N and
150RPM

• 5 Minutes on a TBW diamond rough polish diamond polishing disk at 20N and
150RPM

• 5 Minutes on a 4000 grit silicon carbide polishing pad at 20N and 150RPM

• 5 Minutes on a 4000 grit silicon carbide polishing pad at 20N and 150RPM

• 3 X 2 Minutes on a polishing cloth charged with colloidal silica (OP-S) at 20N

and 150RPM

After polishing, samples were etched by submerging in either a lactic acid based
etchant1 for two minutes, or a phosphoric acid based ethant2 for 100 seconds. This
polishing and etching procedure gave mixed results and often resulted in extensive
1
Lactic acid etchant consisted of 60 vol% DL-Lactic acid, 20 vol% 48 wt% Hydroflouric Acid in
water, and 20% Nitric Acid
2
Phosphoric acid etchant consisted of 31.25 vol% Phosphoric Acid 37.5 vol% Glycerol, 25 vol%
48 wt% Hydroflouric Acid in water, and 6.25% Nitric Acid

29
pitting, especially in samples that exhibited a large degree of inhomogeneity of Ta
concentration throughout the sample.

2.2 The Lighter Test: Qualitative Test for Shape

Memory Effect

The lighter test refers to placing a deformed, heat treated sample over an open flame
and looking for any visible martensitic strain recovery. This technique proved ex-
tremely useful in quickly determing the success or failure of a given heat-treatment,
and in roughly gauging the potential of a given Ti–Ta composition for SME. It is a
techique limited to observation of large strain recovery only as it is too difficult to
accurately observe small amounts of recovery.

2.3 Hot Oil Recovery Tests: Determing Transfor-

mation Temperature and Strain Recovery

Although the transformation temperatures relevant to shape memory alloys are gen-
erally determined using differential scanning calorimitry (DSC), previous attempts
at this type of characterization by Tom Nizoleck and researchers at Dynamet have
failed to indicated the presence or formation of martensite. The dynamet researchers
postulated that this may be caused by a broadening of martensite transformation
temperatures caused by inhomogeneity of Ta concentration throughout DSC sam-
ples. Mr. Nizoleck hypothesized that the transformation of martensite to austenite
is heating rate dependent, and the relatively slow heating rate achieved by DSC ap-
paratus is insufficient to induce martensite to austenite transformation. Because of
this, hot oil recovery tests were used to determine the transformation temperature on
a point by point basis.
Heat-treated samples were bent, at room temperature, around a mandrel of known
radius, and then submerged in pre-heated oil for ten seconds before being removed

30
and examined. If the samples contained martensite, some of this deformation should
have been accomodated by twin boundary movement in the martensite as described
in Chapter 1. Upon heating these deformed samples by submerging them in hot oil,
the martensite should convert to austenite and SME should be observed. The strain,
, induced by bending can be calculated by

t
=
2 ∗ rm

, where t is the thickness of the bent sample and rm is the radius of the sample. By
measuring the radius of the bend in a sample before and after heat-induced recovery,
the martensitic strain recovery vs. oil temperature can be calculated. Because the
samples are very thin (< 0.5mm), it is reasonable to assume that the oil tempera-
ture corresponds to the the temperature of the material itself during recovery. By
performing this procedure for multiple samples over a range of oil temperature, the
transformation temperature and maximum martensitic strain recovery of a material
can be determined.
The radius of a bent sample was determined by taking a digital photograph of the
bent sample with a length reference included in the picture. Mathematica code that
took the digital photographs as input was written to calculate the bending radius of
a sample based on three points selected along the bend by a user. The points along
the sample chosen for radius measurements were marked before testing with white
paint so that each measurement would be consistent. This technique worked well
for bends greater than 45◦ , but proved somewhat inaccurate for bends of smaller
magnitude. Photographs were taken of each sample before being bent, after being
bent, immediately after heating in oil, and then again a few minutes after being taken
form the oil to catch any delayed effects or relaxation.

31
32
Chapter 3

Results

Characterization of the Ti–Ta alloys studied includes metallographic studies of the

material at different stages during processing and hot oil recovery tests performed on
heat-treated and quenched specimens of 60, 62 and 64 wt% Ta.

3.1 Micrographs

3.1.1 Martensite Formation

By comparing micrographs taken of the 60, 62 and 64 wt% Ta material to images of

α” martensite [12, 13, 14], it can be seen that the heat-treatment procedure described
in Chapter 2 does induce α” martensite. The most martensite is seen in the 60 wt%
Ta material, less is seen in the 62 wt% Ta material, and almost no martensite is seen
in the 64 wt% Ta material. This is shown in Figure 3-1
It can be seen that quenching from a slightly higher temperature does not sig-
nificantly change the amount of quench-induced martensite; the results of quenching
material from 914◦ C are presented in Figure 3-2.

3.1.2 Inhomogeneity

It was also noted that bands exist within the material parallel to the extrusion direc-
tion of the bars. In quenched samples, martensite is generally found within alternating

33
 (a) 60 wt% Ta: as-recieved (b) 62 wt% Ta: as-recieved (c) 64 wt% Ta: as-recieved

(d) 60 wt% Ta: heat-treated (e) 62 wt% Ta: heat-treated (f) 64 wt% Ta: heat-treated

Figure 3-1: Comparison of martensite formation in as-received and austenized at

900◦ C, ice water quenched 60, 62, and 64 wt% Ta alloys

bands. Pitting and aggressive etching is also seen in alternating bands. This is an
effect seen in all tested materials, and is suspected to be a result of in-homogeneous
Ta concentration throughout the material. Images depicting this phenomonen are
presented in Figure 3-3

3.1.3 Layering Induced by Inadvertant Suface Cooling

As mentioned in Chapter 2. The initial heat-treatment and quenching strategy used

to induce martensite formation failed because the samples were so thin that they
would air cool during transfer from the furnace to the quenchant. This problem
was alleviated by increasing the thickness of heat-treatment samples by an order of
magnitude (from 0̃.5mm to 5mm) and then cutting those heat-treated ingots down
to the final sample size. Micrographs highlighting the typical layering pattern at
one edge, the center, and the opposite surface of an ingot of 900◦ austenized, water
quenched, 62 wt% Ta are presented in Figure 3-4

34
 (a) 60 wt% Ta (b) 62 wt% Ta (c) 64 wt% Ta

Figure 3-2: Martensite formation in 60, 62, and 64 wt% Ta alloys Quenched from
914◦ C

(a) 60 wt% Ta (b) 62 wt% Ta (c) 64 wt% Ta

Figure 3-3: Inhomogeneous bands in heat treated 60, 62, and 64 wt% Ta alloys

In Figure 3-4, it can be seen that the martensite concentration falls dramatically
near the surfaces of heat treated specimens.

3.2 Hot Oil Recovery: Transformation Tempera-

ture and Strain Recovery

Hot oil recovery tests were conducted on 60, 62, and 64 wt% Ta materials austenized
at 900◦ C and water quenched. These tests were intended to determine the maxi-
mum martensitic strain recovery of each material and the martensitic transformation
temperature of each material.

35
 Figure 3-4: Details of the outer edges and core of a heat treated piece 60 wt% Ta.

3.2.1 Strain Measurements

Before being tested, samples were bent around a mandrel of 2.5mm radius and then
photographed. The strain induced by the bending in each material is presented in
Figure 3-5.1 Different samples are identified by the temperature at which they were
immersed in oil, and so the temperature scale on the horizontal axis of Figure 3-5
should be used for sample identification only.
Figure 3-5 is included to provide the reader a metric by which to judge perfor-
mance of hot oil recovery tests and the measurements taken throughout those tests.
When bent around the mandrel, some of the strain thus induced was accomodated
elastically; this elastic strain can be calculated by subtracting the plastically accomo-
1
Temperature on the horizontal axis corresponds to sample identity only; the data presented in
Figure 3-5 was taken from samples that had not yet been heated.

36
 Strain Strain Strain
0.10 0.10 0.10

Average Strain: 1.65% Average Strain: 1.43% Average Strain: 1.47%

0.08 0.08 0.08
Standard Deviation: 0.0243% Standard Deviation: 0.0340% Standard Deviation: 0.0217%
0.06 0.06 0.06

0.04 0.04 0.04

æ æ
0.02 æ 0.02 æ 0.02 æ æ
æ æ æ æ æ æ æ æ æ æ æ æ
æ æ æ æ æ æ æ æ æ æ æ æ
æ æ æ

°C °C °C
150 200 250 300 350 150 200 250 300 350 150 200 250 300 350

(a) 60 wt% Ta (b) 62 wt% Ta (c) 64 wt% Ta

Figure 3-5: Bending strain applied to samples of 60, 62, and 64 wt% Ta, austenized
at 900◦ C and ice water quenched.

dated strain presented in Figure 3-5 from the strain of bending to a radius of 2.5mm
using equation 1. The results of this calculation for each material are presented in
Figure 3-6.1

Elastic Strain Elastic Strain Elastic Strain

0.10 0.10 0.10

Average Elastic Strain: 2.62% Average Elastic Strain: 2.84% Average Elastic Strain: 2.79%
0.08 0.08 0.08
Standard Deviation: 0.0234% Standard Deviation: 0.0206% Standard Deviation: 0.0220%
0.06 0.06 0.06

0.04 0.04 0.04

æ æ æ æ æ æ æ æ æ æ æ æ æ æ æ
æ æ æ æ æ æ æ æ æ æ æ
æ æ æ æ æ æ
0.02 æ 0.02 0.02

0.00 °C 0.00 °C 0.00 °C

150 200 250 300 350 150 200 250 300 350 150 200 250 300 350

(a) 60 wt% Ta (b) 62 wt% Ta (c) 64 wt% Ta

Figure 3-6: Maximum elastic strain in 60, 62, and 64 wt% Ta, austenized at 900◦ C
and ice water quenched.

The maximum elastic strain presented in Figure 3-6 was calculated to determine
if any dramatic superelasticity was exhibited by the material.

3.2.2 Martensitic Strain Recovery and Transformation Tem-

perature

After being deformed, samples were submerged in hot oil for ten seconds. Upon
removal from oil, samples were immediately photographed. The strain of each sample
was recorded, and the difference between strain measured after heating and the strain
induced by bending (as presented in Figure 3-5) was calculated to determine the
martensitic strain recovery vs. temperature for each material. This data is presented

37
in Figure 3-7.2 Strain recovery is given in absolute strain, not as a percentage of the
original bending strain.

Strain Recovery Strain Recovery Strain Recovery

0.020 0.020 0.020

Highest Strain Recovery: 0.78% Highest Strain Recovery: ~0.6% Highest Strain Recovery: ~0.3%
0.015 0.015 0.015

0.010 0.010 0.010

æ
æ æ
0.005 æ 0.005 æ 0.005
æ æ æ æ æ æ
æ æ æ æ æ æ
æ æ æ
æ æ æ æ æ æ æ
0.000 æ æ °C 0.000 æ °C 0.000 æ °C
æ 200 250 300 350 200 æ 250 300 350 200 250 300 350

-0.005 -0.005 -0.005

(a) 60 wt% Ta (b) 62 wt% Ta (c) 64 wt% Ta

Figure 3-7: Martensitic strain recovery vs. oil temperature of 60, 62, and 64 wt% Ta,
austenized at 900◦ C and ice water quenched immediately after removal from oil.

During testing, it was noted that a few minutes after being removed from the oil,
samples seemed to have relaxed slightly. In some cases samples seemed to revert back
slightly to their deformed shape, while others seemed to recover more strain. Because
of this, the strain of each sample was recorded again, a few minutes after removal
from the oil; this final strain was compared to the strain of each sample as recorded
upon removal from the oil to calculate the relaxation of samples after martensitic
recovery. This data is presented in Figure 3-8.3

Strain Recovery Strain Recovery Strain Recovery

0.010 0.010 0.010

0.005 0.005 0.005

æ æ æ
æ
æ æ æ æ
æ æ æ æ æ æ
0.000 æ æ æ °C 0.000 æ æ °C 0.000 æ °C
200 250 300 350 200 æ æ
250 300 350 200 250 300 350
æ æ
æ
-0.005 -0.005 -0.005 æ

-0.010 -0.010 -0.010

(a) 60 wt% Ta (b) 62 wt% Ta (c) 64 wt% Ta

Figure 3-8: Relaxation of samples vs oil test temperature a few minutes after cooling.

Finally, the relaxation strain presented in Figure 3-8 was compared to the initial
strain induced by bending to determine the net martensitic strain recovery of each
material tested. This data is presented in Figure 3-9, both in terms of absolute strain
recovered, and percent of initial bending strain recovered.
3
Negative strain recovery indicates a net increase in strain (two way shape memory), while positive
strain recovery indicates a net decrease in strain (relaxation)

38
Strain Recovery Strain Recovery Strain Recovery
0.020 0.020 0.020
Highest Strain Recovery: ~0.7% Highest Strain Recovery: ~0.4%
0.015 Highest Strain Recovery: ~0.78% 0.015 0.015
Average Strain Recovery: 0.14%
0.010 0.010 0.010 Standard Deviation: 0.02%
æ æ

0.005 0.005 æ 0.005

æ æ æ æ æ æ
æ æ æ æ æ æ
æ æ æ æ æ
æ æ æ æ æ æ °C
0.000 æ æ æ °C 0.000 °C 0.000 æ æ
200 250 300 350 200 250 300 350 200 250 æ 300 350
-0.005 -0.005 -0.005

-0.010 -0.010 æ -0.010

(a) 60 wt% Ta: (b) 62 wt% Ta (c) 64 wt% Ta

% Strain Recovery % Strain Recovery % Strain Recovery
100 100 100
Highest % Strain Recovery: ~ 45% Highest % Strain Recovery: ~43% Highest % Strain Recovery: 24%
80 80 80

60 60 60
æ æ
40 40 æ 40
æ æ
æ æ æ
æ æ æ
20 20 æ æ 20
æ æ æ
æ æ æ æ
æ æ æ æ æ æ
æ æ æ °C °C æ æ °C
200 250 300 350 200 250 300 350 200 250 300 350
æ
-20 -20 -20

(d) 60 wt% Ta: (e) 62 wt% Ta (f) 64 wt% Ta

Figure 3-9: Net shape memory effect vs. oil temperature of 60, 62, and 64 wt% Ta,
austenized at 900◦ C and ice water quenched.

39
40
Chapter 4

Discussion and Conclusions

In this chapter, the results presented in Chapter 3 will be examined and interpreted.
Finally the conclusions I have drawn from those interpretations will be presented along
with suggestions for future research which should be done to further characterize and
improve Ti–Ta shape memory alloys.

4.1 Shape-Memory Potential

The data presented in Figure 3-9 indicates that both the 60 and 62wt% Ta alloys have
potential for shape-memory applications. At least some samples of both alloys show
martensitic strain recovery of at least 0.8%, and the 60wt% Ta alloy seems to have
◦
the potential for greater martensitic recovery at temperatures higher than 370 C.
Unfortunately, hot oil recovery tests were not feasable at such high temperatures as
the oil had a tendency to ignite when agitated when heated above that temperature.
The 64wt% Ta material seems to exhibit very little shape memory behavior over
the the temperature range indicated (average martensitic strain recovery of 0.14%).
This is expected as micrographs like those presented in Figure 3-1 indicate a falling
martensite concentration with increasing Ta content. This makes sense as Ta is known
to be a β phase stabilizer [14]. It should be noted that all martensitic strain recovery
data is probably lower than the actual values because some two-way shape-memory
was observed, but occurred more quickly than samples could be photographed. This

41
two-way shape-memory effect was subtle and not visibly present in all samples.
The data presented in Figure 3-9 also shows that the martensitic transformation
temperature of these materials is somewhere between 300 and 400◦ C. The 62wt% Ta
material appears to have a slightly lower transition temperature than the 60wt% Ta
material as SME is seen to begin increasing at around 200◦ C as opposed to the low end
transition temperature of 250◦ C seen in the 60wt% material. There doesn’t appear
to be any clear rise in martensitic strain recovery in the 64wt% material, although an
average strain recovery of 0̃.14% can be extracted from the data presented. This may
indicate that the martensitic start temperature for the 64wt% Ta material is below
170 ◦ C, the lowest test temperature tested. Unfortunately, the noise level in the data
makes it very difficult to confidently conclude much about such a low strain recovery.
In any case, the transformation temperatures extracted from the data in Figure 3-9
are all well above the transformation temperature range of typical Ni-based shape
memory alloys (−200–100◦ )as presented in Table 1.
It is possible that the maximum strain recovery of these materials could be much
improved by better heat-treatment methods, especially by improvements in transfer
from the furnace to the quenchant. Micrographs like those presented in Figure 3-1
indicate that there is only a relatively small fraction of martensite induced in these
materials by quenching. Also, the layering effect described in Chapters 2 and 3 and
shown in Figures 3-4 and 2-4 indicates that martensite formation is very sensitive to
quench severity and cooling rate. Because of the very imprecise nature of the quench-
ing technique applied for this research, I suspect there is much room for improvement
in the amount of martensite that could be induced in this material by quenching.

4.1.1 Two-Way Shape-Memory Effect

Some two-way shape-memory was observed in the 60 and 62wt% Ta material recov-
ered at low temperatures or if submerged in hot oil for relatively short times. Unfor-
tunately, this effect could not be quantified particularly well as it occurred much more
quickly than photographs of samples could be taken. The relaxation effect quantified
in Figure 3-8a hints at this two-way shape-memory effect for the 60wt% Ta material

42
but doesn’t do it true justice.

4.2 Potential Superelasticity

A very surprising result of the experiments performed is the relatively large elastic
strain recovery measured. Data presented in Figure 3-6 indicates that all three tested
alloys exhibit elastic strain recovery of around 2.7%. Although the elastic modulus
of these samples was not measured, assuming an elastic modulus of 80GPa 1 , during
bending these materials withstood stresses of around 2Gpa without failure. This is
well above the measured tensile strengths of similar materials as reported in [14],
which where on the order of 0.7GPa. On the other hand, assuming the maximum
stress achieved by bending these samples was the ultimate tensile stress reported in
[14], the Young’s Modulus of the material examined in this thesis must be around
3Gpa, which is well below the Modulus of 80GPa used above, and is in fact well
below the modulus of any Ti–Ta composition betwen 0 and 90wt% Ta as reported in
[14]. Neither the abnormally large ultimate tensile strength nor the abnormally low
Young’s Modulus resulting from the preceding calculations seems likely; this indicates
that these materials may exhibit some superelasticity. Superelasticity would acount
for these abnormalities as the stress strain curves for superelastic alloys exhibit regions
of little to no change in stress state with strain changes upon unloading. As no stress
strain curves were developed for the materials examined in this thesis, no concrete
conclusions can be made from these observations. However, these calculations are not
intended to actually extrapolate any significant material properties and are merely
intended to point out that the elastic properties of these alloys are interesting and do
not easily conform to the properties of similar materials previously described [14, 12,
13].

1
Samples of 60wt% Ta quenched in ice water from 1000◦ produced by [14] were shown to exhibit
a Young’s Modulus of 80GPa.

43
4.3 Martensite Formation

As already mentioned, the amount of martensite induced by quenching of these mate-

rials seems to decrease with increasing Ta content. Also, as shown in micrographs like
those exhibited in Figure 3-3, martensite formation seems prevalant in periodically
spaced bands which run parallel to the extrusion direction of the raw stock recieved
by Dynamet for testing. This same pattern is seen in etching aberrations and is
suspected to be a direct manifestation of inhomogeneous Ta content throughout the
material. EDX analysis should be performed to determine if the bands seen in these
materials correlate to Ta content or not. If so, it is possible that the martensite
forming in these materials is actually forming in bands of relatively low Ta conent.
If true, martensite formed in 60wt% Ta may not be very different from martensite
formed in 64wt% Ta material: there will simply be more of it in the 60wt% material,
as was observed.

4.4 Conclusions and Future Research

The research presented in this thesis has shown that Ti–Ta alloys can indeed exhibit
significant SME. Martensitic strain recoveries of up to 0.8% have been measured in
both the 60 and 62wt% material ice water quenched from 900◦ C. Although signif-
icantly less than the maximum martensitic strain recovery noted for nickel alloys in
Table 1, most shape memory applications do not require more than 3% martensitic
strain recoveries, which is significantly closer to the strain recovery exhibited by the
Ti–Ta alloys examined here. Martensitic transformation temperatures range between
250 and 370◦ C, which is significantly higher than typical transformation tempera-
tures seen in Ni-based shape-memory alloys (-200–100◦ ). It has also been noted that
these Ti–Ta shape-memory alloys exhibit some two-way shape-memory. Experiments
capable of recording strain changes in the material in real time must be conducted to
accurately quantify this effect, however.
Based on micrographs showing relatively low amounts of martensite formation in

44
these quenched materials, it is hypothesized that improvements in the heat-treatment
process, and specifically in the cooling rate induced by quenching, could result in
significant improvements in the martensitic strain recovery measured in this study.
It has also been noted that induced martensite is very sensitive to this quenching
procedure and so the details of the process should be closely examinedl.
In addition to SME, data from Fig 3-6 showing elastic strain recoveries of up
to 2.8% indicate that the Ti–Ta alloys studied might exhibit some superelasticity.
Stress strain curves for the material should be measured to confirm this hypothesis
as the data presented here is not sufficient to conclude the presence of superelasticity.
It has also been noted that the material produced by Dynamet exhibits significant
inhomogeneities that run parallel to the extrusion direction of the material. This
inhomoegeneity may correspond to variations in Ta content throughout the material;
EDX analysis of the material should be performed to confirm or deny this hypothe-
sis. In conclusion, this thesis has demonstrated the potential of Ti–Ta alloys to be
applied as shape-memory alloys. The results presented in this thesis are vey limited,
however, and much work yet remains to refine the processing and characterization
of these materials. Top priorities of researchers studying this material should in-
clude the recording of stress strain curves for 60–64wt% Ta alloys at held at different
temperatures in order to confirm or deny the presence of superelasticity, and real
time strain monitoring during recovery tests like that afforded by fixation of strain
gauges directly to test specimens to quantify maximum martensitic strain recovery
and two-way shape-memory effect.

45
46
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