A Study of the Degradation of the

Two-Way Effect in NiTi (Proposal

and Preliminary Results)
Scott Skirlo

*All data in presentation obtained from personal test setup

 Purpose
• To investigate the degradation of the two-
way effect introduced into NiTi shape
memory alloy with martensite deformation.
• The samples with the two-way strain
developed will undergo several thousand
thermal cycles with different cycling
temperatures.
• The data gathered will be used to better
understand the mechanisms of the
degradation and to find optimal cycling
temperatures.
 Discovery of Nitinol
• This NiTi alloy was discovered in 1958 by
Buehler at Naval Ordnance Lab (the “nol” in
nitinol).
• Noticed strange properties when he dropped it
when it was hot, verses when it was cold.
• When it was hot rung like a brass bell, when cold
it made a dull thud, like a piece of lead.
• Nitinol is the most useful current shape memory
alloy (SMA) for it’s relative high strength,
ductility, and strong shape memory effects.
 Martensite Transformation
• All interesting properties of SMAs come down to
one thing: the martensite transformation.
• A martensite transformation refers to a change in
crystal structure which occurs with a change in
temperature, stress or some other factor.
• This is also called a military transformation since
the transformation proceeds, at least locally, by
uniformly shifting rows of atoms relative to each
other (i.e. as opposed to shifting by diffusion).
• The high temperature state is called austenite while
the low temperature state is known as martensite.
• If the alloy is cooled from the austenite (or parent)
phase the martensite transformation occurs.
 Continued from martensite
• As a section of the material transforms, it
encounters stress from the rest of the crystal since
the transformation changes the crystal unit cell.
• To deal with this the rows of atoms shift in a
symmetric way, as to cancel the stress.
• This phenomena is called twinning.
• Twinning occurs on many different planes since
there are many different equivalent (at least by
default) directions for the rows to move in. The
potential orientations are called variants.
• As a result of twinning no significant length
change occurs on cooling by default.
Austenite(Parent Phase) to Twinned
Martensite

Transformation between austenite (parent phase) and martensite

Retrieved December 9, 2006 from
pg. 22 of http://www-personal.engin.umich.edu/~btrease/share/SMA-Shape-Training-Tutorial.pdf
 Transformation Temperatures

Retrieved December 11, 2006 from pg. 5 of http://gltrs.grc.nasa.gov/reports/2006/TM-2006-214356.pdf

• Transformation temperatures (Martensite Start (Ms),

Martensite Finish (Mf), etc.) describe the martensite
transformation and its hysteresis.
• At the middle of the transformation (between Ms and Mf),
the bulk of crystal is transforming, while at edges, sections
less stable or more stable transform.
 One-Way Effect

• When the twinned structure is stressed, initially it

deforms mostly elastically, like a spring.
• However at a certain critical stress, the crystal
structure will start to detwin (i.e. one variant that
points more in the direction of stress is selected at
the expense of others).
• This results in what is called a stress plateau in the
stress-strain curve for SMAs.
• Even though the diagram above the graph on the
following page represents only a single crystal, this
same idea extends to polycrystalline samples
which were used in this project.
 Twinned Martensite Deformation
(Data from my setup with structure diagrams from first website listed) T
T Stress vs. Strain for Annealed Sample

2.5

2
Stress(N)

1.5

1
T
0.5 T
0
0 1 2 3 4 5 6
Strain(%)
 Continued from one-way
• Heating the detwinned martensite after removing
the load will completely recover the initial shape
if no plastic deformation occurred.
• This happens because all the stress did was select a
different, ‘preferred’ variant.
• At the first cooling, a given section of austenite
could transform to any given variant of martensite;
they were all crystallographically equivalent with
respect to the parent phase (stress makes them
unequal thermodynamically however)
• Therefore on heating, all martensite variants will
go back to the same parent structure of austenite,
resulting in the original shape being recovered.
• On cooling from austenite, in the absence of stress,
the sample will have no visible length change,
forming the same twinned martensite structure.
 Continued from one-way
• The phenomena of being able to recover a shape
with heating is known as the one-way effect.
• Through the one-way effect along and
superelasticity (think rubber band), nitinol has
found many applications in the medical industry.
• Applications using the one-way effect as an
actuator have been less common and less
successful due to the relative small size of the one-
way strain(3-5% stable, higher is less stable).
• Additionally in any actuating application using the
one-way effect, some sort of bias stress, usually in
the form of an opposing spring, is necessary to
‘reset’ the wire.
 Example of Application and
Potential Application

Use of One-Way Effect of Nitinol in

Use of Nitinol as Vascular Stent Modifying Airfoil.
Retrieved October 27, 2008 from Retrieved December 9, 2006 from 1
http://www.wahchang.com/pages/outlook/html/ http://www.continuum-dynamics.com/solution-me-
bkissues/20_04.htm sma.html
 Two-Way Effect
• The Two-Way Effect is an effect where a length
change occurs automatically when changing
temperature.
• A two-way effect can be created by stressing and
heating the alloy repeatedly.
• These thermomechanical cycles introduce internal
stress, in the form of dislocations, which will
automatically select preferred variants on cooling,
resulting in the length change.
• A bias stress is not needed if the two-way effect is
used instead of the one-way effect, making it more
useful for small actuator applications, such as in
micromechanical devices.
Two-Way Effect Mechanism

Internal stress fields introduced by

‘training’ resulting in the selection
of a single variant on cooling
Retrieved from pg. 20 of Liu and Favier
See References
 Rationale for Project
• One of the downsides of the two-way effect is that
its degradation over thousands of cycles verses the
cycling temperatures and many other important
parameters is not well understood.
• The purpose of this study is to identify different
degradation trends of the two-way effect verses the
cycling temperatures (the temperatures reached
when cooling and when heating).
• By identifying these trends higher and more stable
two-way effects can be created, by tailoring the alloy
and transformation temperatures to the specific
application.
 Continued from rational
• The reason cycling temperatures are so important is that
they determine how much internal stress is generated every
thermal cycle.
• Stress is not the only thing that generates dislocations,
thermal cycles do also.
• This is apparent in the resistance-current curves in the next
pages for several annealed samples.
• The electric current was steady for two seconds, so for all
practical purposes the current correlates to temperature.
• The stress from dislocations introduced by thermal cycling
‘competing’ with the internal stress from the training
procedure is what causes the degradation of the two-way
effect over many thermal cycles.
• Perhaps by modifying the maximum and minimum
temperatures the material experiences during thermal
cycling, optimal operating conditions can be found.
 Impact of Thermal Cycling
Electrical Resistance vs. Current for Fully Annealed Sample

0.6

Resistance(Normalized
0.5
0.4 Cooling Af
Ohms) Ms
0.3
0.2
As
0.1
Mf Heating
0
0 0.05 0.1 0.15 0.2 0.25 0.3
Current(A)

Notice that the hysteresis loop is not closed, the ending resistance is
significantly higher than the starting. With cold work and or many
thermal cycles, which generate internal stress, the loop changes less,
but the full transformation still has negative consequences on the
two-way effect.
 Effects of Thermal Cycling on Resistance
Effect of Thermal Cycling on Resistance for Annealed
Sample
Development of R-phase peak
0.7
Resistance(Normalized

0.6 Resistance of wire increases

0.5
0.4 Cycle 1
each cycle. The reason
ohms)

0.3 Cycle 2 curves appear to go down on

0.2 Cycle 3 graphs w/ cycling is because
0.1
0 the resistance is
-0.1 0 0.05 0.1 0.15 0.2 0.25 renormalized every cycle.
Current(A)
R-phase peak already present
Effect of Thermal Cycling on Resistance for Annealed Sample
As a result of cycling,
generally the resistance 2.5

increases, because the 2

Resistance(normalized

1.5
dislocation density Cycle 1
ohms)

1
increases. Third phases also 0.5
Cycle 2
Cycle 3
can develop. Specifically 0
here the R-phase is -0.5 0 0.05 0.1 0.15 0.2 0.25

observed on cooling before -1

Current(A)
transformation to B19’.
 Uses of Resistance vs. Current Curves
R-phase transformation
Electrical Resistance vs. Current for Thermal Cycled Two-Way Electrical Resistance vs. Current for Partially Annealed
Trained Sample Sample

0.6 0.2
Resistance(Normalized

Resistance(Ohms)
0.4 0
0.2 -0.2
Ohms)

0 -0.4
-0.2 0 0.05 0.1 0.15 0.2 0.25 0.3
-0.6
-0.4 -0.8
-0.6 -1
0 0.05 0.1 0.15 0.2 0.25 0.3
Current(A)
Current(A)

Resistance vs. Current curves for a complete thermal cycle

communicate the locations of the material’s transformation
temperatures as well as a large amount of non-ambiguous
information concerning the internal structure. The curves in NiTi
are very responsive, entirely changing in their very character, with
significant changes in internal structure. (Notice 2nd martensite
candidate transformation (peak), R-phase, on cooling w/ curve on
right).
Detwinned Martensite
Two-Way Strain
Two-Way Strain

1.6
As
1.4
1.2
1 Heating
Strain(%)

0.8
Mf Cooling
0.6 Austenite
0.4 (below
Ms Af
0.2 Room T)
0
-0.2 0 0.05 0.1 0.15 0.2 0.25
Electrical Current(A)

The two-way strain represents the length change a shape memory

metal undergoes with a change in temperature without an applied
force. The gap between the heating and cooling directions is known as
the hysteresis (difference between As and Mf or Af and Ms).
 Resistance and Two-Way Strain Curves
Two-Way Strain and Corresponding Resistance vs. Current

1.5 As
Resistance(Normalized

1
Ohms), Strain(%)

0.5
Af Two-Way Strain
Resistance
0
0 0.05 0.1 0.15 0.2 0.25
-0.5

-1
Current (A)

On certain resistance verses temperature curves, transformation

currents (temps.) are hard to spot (Ms, and Mf in this case). In
field of SMAs, scientists typically use differential scanning
calorimetry (DSC) to locate transformation temperatures.
 Two-Way Strain Degradation
Depending on the Degradation of the Two-Way Strain with Thermal Cycling

thermomechanical 2

1.5
history different

Strain(%)
1 Martensite Strain

samples will have very 0.5

Two-Way Strain
Austenite Strain

different degradation 0
0 1000 2000 3000 4000
-0.5
paths. Number of Thermal Cycles

Degradation of the Two-Way Strain with Thermal Cycling

Varying the thermal
1.2
1
0.8
cycling temperatures is
0.6
0.4 Tw o-Way Strain
very likely to have a
Strain(%)

0.2
0
Austenite Strain
Martensite Strain
dramatic impact on the
-500-0.2 500 1500 2500 3500
-0.4
-0.6
degradation in both
-0.8
-1 positive and negative
Therm al Cycles
ways.
 Experimental Setup
• In order to complete this study a test rig was built
with the appropriate specifications.
• The setup has the ability to accurately and in an
automated way conduct temperature-strain, stress-
strain, and resistance-temperature tests.
• Setup uses a computer interface with analog
circuitry and instrumentation to check various
sensors, control motors, and adjust the current
going through the wire (joule heating is used to
control the wire temperature).
• This setup allows extended thermal cycling tests to
be conducted over the large portion of a day.
• Images on following pages are from earlier and
later version of setup.
 Tensile Setup
• This portion of my testing equipment includes the force
sensor (which consists of a cantilever w/ strain gages
mounted on each side), the linear potentiometer and the
displacement controller.
• This has the ability to make stress-strain curves (look to
martensite deformation curve at start of slides for reference).
• Additionally if the current control circuitry is included, the
setup has the ability to conduct strain vs. current tests, in
addition to two-way degradation tests.
• Two-way tests usually involve letting the wire reach an
equilibrium state after changing the temperature, then
exerting some minimum force to stretch the wire so that the
length can be measured.
• With the two-way degradation tests, every 50 thermal cycles
or so, a measurement cycle is conducted.
• The stress-strain tests take about 1 hour to run, the two-way
strain tests take about 30 minutes, and the degradation tests
upwards of 16 hours for 4000 cycles.
 Resistance Measurement Setup
• The resistance measurement system consists of
several mosfets to switch between the heating
current, and the small constant measurement
current.
• After heating for approx. 2 seconds at a given
current, the setup switches and lets the
measurement current through.
• b/c heat dissipates slowly, an accurate resistance
measurement can be made after the voltage drop is
amplified.
• These tests are quick and clean, since it takes less
than 10 minutes to get about 250 highly accurate
and precise data points from one thermal cycle.
 Functional Circuit Diagrams
Force Sensor Half-Bridge Circuit
Length measurement circuit
+20V
Phidget out INA101 Gain= 6
ADCs In+ In- Phidget

Comp. Tension ADCs

+5V Reference

In- out Gain on

Sample displacement order of
In+ INA101 1000
Bottom resistors unstressed,
provide for thermal noise
cancellation.
Current Measurement Circuit
Power amp Sample wire 1 ohm

Phidget ADCs out INA101 In+ Gain=12

In-
 Resistance Measurement Circuit
Comparators

2.5V
Power amp

2.5V Sample wire

+5V
Motor Control

13 mA Phidget DOs
+5V
Nulling resistance

13 mA

DOs In+ In-

Phidget ADCs out Gain=65
INA101

Voltage Control
DAC
Power amp Sample Wire

Phidget DOs
ADCs
Power supplies Pennies (made after 1982) used to calibrate force sensor.
In recent days I have tried to increase displacement control
and length measurement accuracy w/ new methods

Changes were needed because old methods though yielding

good results for a period of time, were not consistent in
performance and required constant adjustments (most
important for two-way strain tests). It’s not easy to get accurate
control on the scale of 3 um!
 Crosshead Reduction gears
Screw/worm gears

Current displacement control method bears greater

semblance to actual universal testing or tensile machines.
 Experimental Problems
• When building each sensor, though the construction of each
was relatively simple in concept, many sources of noise and
inaccuracy were encountered.
• Untangling the problems and finding a robust, lasting
solution to each was difficult and still is ongoing.
• The greatest problems were encountered with the
displacement control system, and the electrical/mechanical
bond between the wire and the setup.
• The following pages show the cleanest examples of some
general problems I encountered.
• Many times especially during my problems with the two-
way tests and resistance measurement tests multiple
problems existed simultaneously in strange add-mixtures
resulting in very bad data.
 Several Resistance Measurement Problems
Resistance vs. Current
Resistance Vs. Current
Crimp resistance 0.6
0.3
changes midway 0.5

Resistance(ohms)
0.2
through test 0.4
0.1
0.3
Multiple
Resistance(ohms)

0
0.2
0 0.05 0.1 0.15 0.2 0.25
-0.1 transient 0.1

-0.2 contacts at 0
0 0.05 0.1 0.15 0.2
-0.3
setup-wire Current(A)
-0.4
interface and
-0.5
Current(A) others
Resistance Vs. Current
Timing Issue 0.2
0
-0.2 0 0.1 0.2 0.3 0.4

Resistance Vs. Current -0.4

Resistance(ohms)
0.8 Effect of -0.6
0.6
-0.8
0.4
0.2
soldering -1

-0.2 0
0
0.05 0.1 0.15 0.2 0.25
crimps to -1.2
-1.4
-0.4
-0.6
sample -1.6
-0.8
(annealed -1.8
Current(A)
unevenly) Current(A)
 Stress vs. Strain Problems
Stress Vs. Strain

Stress Vs. Strain 4

3.5
3
3
2.5

Stress(Newtons)
Stress(Newtons)

2.5
2
2
1.5
1.5
1
1
0.5
0.5
0
0 2 4 6 8 0
0 1 2 3 4 5 6 7
Strain(%)
Strain(%)

Force noise on martensite plateau shown

Mechanical contact slipping (even
to be caused by inertial effects in
when did not slip large changes
cantilever in addition to mechanical
(10-30 ohms) seen in crimp
contact of wire at cantilever and
resistance after loading, making
crosshead.
impossible to continue testing)
 Two-Way Strain Measurement Problems
Tw o-Way Strain
0.7
Binding of slider (or Tw o-Way Strain
0.9
0.6 crosshead) causes 0.8
0.5

0.4
overstepping of 0.7
0.6

Strain(%)
0.3
stress, resulting in 0.5
0.4

0.2
steps, depending on 0.3
0.2
0.1

0
mechanical setup 0.1
0
-0.1
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18
can bind in both -0.1 0 0.05 0.1 0.15 0.2 0.25

Current(A) Current(A)
directions, one, etc.
Please note these are the clearest
examples of the problems. Tw o-Way Strain

0.8
Tw o-Way Strain
0.7

1.4 0.6

1.2 0.5

Strain(%)
1 0.4

0.8 0.3
Strain(%)

0.6 0.2

0.4 0.1

0.2 0
0 0.05 0.1 0.15 0.2 0.25 0.3
-0.1
0
Current(A)
-0.2 0 0.05 0.1 0.15 0.2 0.25 0.3

Current(A)
Noise at edges, slider ‘wiggles’ in
Directional Offset, due to crosshead moving orientation as changes direction to
slider to one side of path apply force
 Stress-Assisted Two-Way Memory Effect (SATWME)

2.9

2.4
0.05 N

1.9 0.1 N
Strain(%)

0.12 N
0.15 N
1.4
0.2 N
0.3 N
0.9
0.5 N

0.4

-0.1
0 0.05 0.1 0.15 0.2 0.25
Current(A)

In order to measure the length of the wire, a force has to be applied to straighten
it. The wire changes length without any force being applied at all, but when
applying a force to the wire to measure the change, the total change is actually
increased. This effect is known as the Stress-Assisted Two-Way Memory Effect
(SATWME). When conducting a study, a measurement force has to be selected
such that the SATWME is minimized, while keeping the displacement
measurement accurate and precise.
 Standard Testing Procedure for all
Tests
• The sample wire will be annealed first, for
example w/ 0.6 amps (approx. 500 C) for 30 min,
to remove dislocations. (This makes the material
soft and easy to develop a high two-way strain)
• Next the wire is ‘trained’ by undergoing multiple
thermomechanical cycles which involve cold or
martensite deformation followed by heating and
recovery into the austenite state.
• A typical training run would consist of 10 cycles
with deformation to 6% each time followed by a
heating w/ 0.2 amps (approx. 100 C).
• Following training the material would undergo thermal
cycles (from one current to another, for example 0.0 A
(room temp.) to 0.2 A) several thousand times to assess the
influence of cycling temperatures on the degradation of the
two-way strain.
• Every 20 to 50 thermal cycles, a ‘measurement’ cycle will
be conducted by the setup to calculate the two-way strain.
• Measurement cycles consist of holding the wire at a
temperature in a stress-free state, then a applying a
minimum load to straighten the wire and calculate the
change in length.
• For each major step of the procedure, a resistance vs.
current graph will be produced, to help determine internal
changes.
• Additionally a full strain verses current graph will be
produced at certain key parts (i.e. after training and after
cycling).
 Current Developments
• I received about $200 of wire with a custom
anneal free from Dynalloy (c) to help with my
project.
• I am still working on the displacement control
system. From looking at my old results, it seems
that the mechanical problems became more
prominent as the potentiometer wore down.
• Potentially the slider, as the moving parts wore
down, was allowed more freedom in orientation,
resulting in inconsistent length measurement.
• Currently I am obtaining two industry quality
potentiometers rated for 200,000 cycles.
Hopefully this will solve most of my problems.
 Acknowledgements
• I would like to thank my electronics teacher Mr.
Bell for taking the time to help me get started and
learn about the electronics for this project.
• Mr. Jones and Craig at NRL for helping me with
my force sensor by providing me with supplies
and expertise.
• Many people who I have talked to about this
project and who have all offered insight and
perspective.
• Jeff Brown and Dynalloy(c) for cooperating with
me and getting me what I needed at no charge.
• My parents for putting up with me and letting me
make the basement a mess. Without their support
and everyone else’s help I would have never been
able to make this happen.
 Useful References
• Liu, Y, and D Favier. "Stabilisation of martensite due to shear
deformation via variant reorientation in polycrystalline NiTi . ."
Acta Materialia 48.13 (2000): 3489-99.
• Liu, Y, J Laeng, T V. Chin, and T Nam. "Partial Thermal
Cycling of NiTi." Journal of Alloys and Compounds 449.1-2
(2006): 144-47.
• Miller, D.A., and Lagoudas, D.C., 2000, " Thermo-Mechanical
Characterization of NiTiCu and NiTi SMA Actuators: Influence
of Plastic Strains," Smart Materials and Structures, Vol. 9, No.
5, pp. 640-652.
• Paula, A S., K K. Mahesh, C.M.L dos Santos, and F.M Branz
Fernandes. "Thermomechanical Behavior of Ti-rich NiTi Shape
Memory Alloys ." Materials Science and Engineering A (2008):
146-50.
• Scherngell, H., & Kneissl, A. C. (2002). Generation,
devolpment and degradation of the intrinsic two-way shape
memory effect in different alloy systems. Acta Materialia, 50,
327-341.
• Stalmans, R, J Van Humbeeck, and L Delaey. "Degradition of
the Shape Memory effect in copper-base alloys." Scripta
Metallurgica et Materilia 31.11 (1994): 1573-76.
• Stalmans, R, J Van Humbeeck, and L Delaey.
"Thermomechanical Cycling, Two Way Memory and
Concomitant Effects in Cu-Zn-Al Alloys." Acta Metallurgica
Materialia 40.3 (1992): 501-11.
• Stalmans, R, J Van Humbeeck, and L Delaey. "The Two Way
Memory Effect in Copper-Based Shape Memory Alloys-
Thermodynamics and Mechanisms ." Acta Metallurgica
Materialia 40.11 (1992): 2921-31.
• Uchil, J, K K. Mahesh, and K G. Kumara. "Electrical
Resistivity and Strain Recovery Studies on the Effect of
Thermal Cycling under Constant Stress on R-phase in NiTi
Shape Memory Alloy." Physics B 324 (2002): 419-28.